EP3755667A1 - Glass-ceramic article - Google Patents

Glass-ceramic article

Info

Publication number
EP3755667A1
EP3755667A1 EP19710060.5A EP19710060A EP3755667A1 EP 3755667 A1 EP3755667 A1 EP 3755667A1 EP 19710060 A EP19710060 A EP 19710060A EP 3755667 A1 EP3755667 A1 EP 3755667A1
Authority
EP
European Patent Office
Prior art keywords
enamel
glass
coated
coating
substrate
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP19710060.5A
Other languages
German (de)
French (fr)
Inventor
Nicolas Roux
Caroline Faillat
Amélie BONTEMPS
Thibault GUEDON
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eurokera SNC
Original Assignee
Eurokera SNC
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 Eurokera SNC filed Critical Eurokera SNC
Publication of EP3755667A1 publication Critical patent/EP3755667A1/en
Pending legal-status Critical Current

Links

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
    • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • C03C17/04—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
    • 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
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition having a superconducting crystal 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
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/006—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24C—DOMESTIC STOVES OR RANGES ; DETAILS OF DOMESTIC STOVES OR RANGES, OF GENERAL APPLICATION
    • F24C15/00—Details
    • F24C15/10—Tops, e.g. hot plates; Rings
    • 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
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/16—Microcrystallites, e.g. of optically or electrically active material
    • 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
    • C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
    • C03C2217/485—Pigments
    • 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
    • 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
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/119—Deposition methods from solutions or suspensions by printing

Definitions

  • the present invention relates to the field of glass-ceramics. More specifically, it relates to an article, or product, glass-ceramic, including a glass-ceramic plate for (e) serving as a furniture surface and / or cooking surface.
  • glass-ceramic article or glass-ceramic means an article based on a substrate (such as a plate) of glass-ceramic material, said substrate may optionally be provided with accessories or additional elements, decorative or functional, required for its final use, the article may designate both the substrate alone and that provided with additional equipment (for example a cooking plate provided with its control panel, its heating elements, etc.).
  • a glass-ceramic is originally a glass, said precursor glass or mother glass or green-glass, whose specific chemical composition can cause by suitable heat treatments, called ceramization, a controlled crystallization. This specific partly crystallized structure gives the glass ceramic unique properties.
  • a glass-ceramic plate in particular, to be used as a hob, a glass-ceramic plate must generally have a transmission in the wavelengths of the visible range both low enough to mask at least a portion of Underlying heating elements at rest and sufficiently high so that, depending on the case (radiant heating, induction heating, etc.), the user can visually detect the heating elements in working order for the purpose of security ; it must also have a high transmission in the wavelengths of the infrared range in the case in particular radiant hob plates.
  • the vitroceramic plates must also have sufficient mechanical strength as required in their field of use.
  • a ceramic hob must have good resistance to pressure, shock (support and fall of utensils, etc.), etc. .
  • vitroceramic hotplates are dark in color, in particular black or brown or orange-brown in color, but there are also plates with a lighter appearance (in particular white in color, for example with a blur of at least 50% as described in patent FR2766816), or transparent plates generally provided with opacifying coatings or provided with filters for particular color effects.
  • glass-ceramic plates are used as hotplates, or they can also be associated with heating elements in other applications, for example to form chimney inserts.
  • ceramic plates can be used as furniture surfaces, especially to form worktops, central islands, consoles, etc. the surface they occupy in these new applications being larger than in the past.
  • they may be provided with keys, touch zones, buttons or other commands, their surface being in all cases (even in the case of a single piece of furniture) subject to multiple contacts related to their uses, causing usually the appearance of unsightly fingerprints at contact areas, resulting in repeated cleaning if necessary, especially when the plates are dark and shiny.
  • These traces or soiling can also cause interference with other components (heating elements, light sources, displays, etc.) of the glass ceramic product.
  • coatings are generally not suitable for systematically remedying fingerprint problems.
  • the coatings most frequently used are mainly coatings chosen to resist high temperature, such as enamels, used locally to form decorative patterns or signaling for example heating zones, or paints used rather flat as opacifiers.
  • these traditional coatings do not generally hinder fingerprints related to the handling and use of the coated substrates, the enamels can also locally reduce the mechanical strength of the glass-ceramic plates and peel, and the paints are not suitable for all heating modes for the hobs due to their lower resistance, including thermal.
  • the present invention has therefore sought to develop improved glass-ceramic products to limit the visibility of fingerprints on their surface, especially new glass-ceramic plates for use with one or more heating elements such as hotplates. , or intended to serve as a furniture surface, these plates having anti-fingerprint properties, without harming other properties sought for their use, including without impairing their ease of maintenance and cleaning, or their resistance, in particular mechanical, scratch and abrasion, and if necessary thermal, and without being detrimental to their life, while ensuring a simple solution and if possible flexible allowing the presence of decorations or additional functions as needed.
  • the glass-ceramic product developed according to the invention in which the visibility of the fingerprints on the surface is reduced by the application of a specific enamel coating, said coating and said enamel being selected according to precise criteria so to obtain the desired anti-fingerprint effect.
  • the inventors have in fact demonstrated that by choosing an enamel and applying it according to the criteria listed below, the anti-fingerprinting effect was visibly obtained for different types of glass-ceramic substrates (more or less dark or having different compositions, etc.), while keeping a certain flexibility in the enamel composition (to obtain, for example, different dyes) as long as the enamel and coating deposited remain within the limits defined below.
  • the present invention therefore relates to a new glass-ceramic article, comprising at least one substrate, such as a plate, glass-ceramic, said substrate being coated in at least one zone of at least one enamel coating (or deposit or layer of enamel ) such as :
  • said enamel has a gloss (or a degree of gloss) at 60 ° less than
  • the coverage rate of said enamel (or said enamel coating) in said zone coated with said coating is 40 to 80%
  • said enamel comprises pigments in the form of mica particles and / or aluminum oxide and / or silica coated with metal oxides or combinations of metal oxides,
  • said enamel has a roughness Ra greater than or equal to 0.4 miti
  • said enamel has a roughness Rt greater than 4 prn.
  • the enamel coating thus selected and applied makes it possible to generate, in the zone coated with said coating, a reduction in the visibility of the fingerprints, or in other words to give the said zone anti-fingerprint properties (or functionality). fingers.
  • the article (or product) vitroceramic according to the invention is in particular a cooking plate or any furniture article integrating (or comprising, or formed de) at least one glass-ceramic substrate (the substrate being most commonly in the form of a plate, integrating or mounting in the furniture and / or combined with other elements to form the furniture), said substrate may optionally have display areas (in combination for example with light emitting sources) or decorated areas or combined with heating elements.
  • the article according to the invention is intended to serve as a cooking plate, this plate being generally intended to be integrated in a hob or cooker also comprising heating elements, for example radiant heaters or halogen or induction heating elements.
  • the article according to the invention is a vitroceramic worktop or central island, where appropriate with different displays and without necessarily cooking zones, or even a console type furniture (the substrate forming by example the upper part), etc.
  • the substrate (or the article according to the invention itself if it is formed only of the substrate) is generally (in the form of) a plate, intended in particular to be used with, in particular to cover or receive, the minus a light source and / or a heating element or intended to serve as a furniture surface.
  • This substrate (or respectively this plate) is generally of geometric shape, in particular rectangular, even square, even circular or oval, etc., and generally has a face turned towards the user in the use position (or visible or external face, generally the upper face in the use position), another generally hidden face, for example in a frame or cabinet of furniture, in the use position (or inner face, generally the lower face in the use position), and a slice (or edge or thickness).
  • the upper or outer face is generally flat and smooth but may also present locally at least one raised area and / or at least one hollow area and / or at least one opening and / or bevelled edges, these shape variations constituting in particular continuous variations of the plate.
  • the lower or inner face may also be flat and smooth or provided with pins.
  • the thickness of the glass-ceramic substrate is generally at least 2 mm, in particular at least 2.5 mm, and is advantageously less than 15 mm. mm, in particular is of the order of 3 to 15 mm, in particular of the order of 3 to 8 mm or of the order of 3 to 6 mm.
  • the substrate is preferably a flat or quasi-flat plate (in particular with an arrow less than 0.1% of the diagonal of the plate, and preferably of the order of zero).
  • the substrate may be based on any glass-ceramic, this substrate advantageously having a zero or almost zero CTE, in particular lower (in absolute value) at 30 ⁇ 10 7 K 1 between 20 and 700 ° C., in particular less than 15 ⁇ 10 7 K 1 , even less than 5.10 7 K 1 between 20 and 700 ° C.
  • the invention more particularly targets substrates of dark appearance, weakly transmissive and not very diffusing, in particular based on any vitroceramic having, intrinsically, a light transmission TL less than 40%, in particular less than 5%, in particular 0.2 at 2% for vitroceramics up to 6 mm thick, and an optical transmission (determined in a known manner by relating the transmitted intensity to the incident intensity at a given wavelength) between 0.5 and 3 % for a wavelength of 625 nm in the visible range.
  • an optical transmission determined in a known manner by relating the transmitted intensity to the incident intensity at a given wavelength
  • the TL light transmission is measured according to the EN 410 standard using the D65 illuminant, and is the total transmission (notably integrated in the visible range and weighted by the curve. sensitivity of the human eye), taking into account both the direct transmission and the possible diffuse transmission, the measurement being made for example using a spectrophotometer provided with an integrating sphere (in particular with the spectrophotometer marketed by Perkin Elmer under the reference Lambda 950).
  • a substrate of black or brown appearance is used, which, in combination with light sources placed underneath, makes it possible to display light areas or decorations, while masking any underlying elements. It may in particular be based on a black glass ceramic comprising crystals of b-quartz structure within a residual vitreous phase, the absolute value of its coefficient of expansion being advantageously less than or equal to 15 ⁇ 10 7 K 1 , or even to 5.10 7 K 1 , such as the glass-ceramic plates sold under the name Kerablack + by the Eurokera company.
  • It may be in particular an arsenic-refined glass-ceramic of composition as described in the patent application EP0437228 or US5070045 or FR2657079, or a tin-refined glass-ceramic having a degree of oxides of arsenic preferably less than 0.1%, for example of composition as described in the patent application WO 2012/156444, or further refined with the sulphide (s) as described in the patent application WO20080531 10.
  • the present invention can also be applied in the case where the substrate is lighter, for example for a transparent substrate, optionally coated with an opacifying coating, generally in paint, on its underside, such as a commercialized plate. under the name Keralite® by Eurokera.
  • the glass-ceramic substrate considered is coated in at least one zone (or at least one zone of said substrate is coated), more particularly at the surface, on at least a part of a face, advantageously on at least a part of of the face facing the user in the use position and / or requiring a reduction in the visibility of fingerprints, generally the upper or outer face in the use position, or may be coated on several areas on one or more faces, even on the whole of one or more faces.
  • the zone coated with the enamel coating according to the invention is preferably (or preferably occupies a surface) at least 5 cm by 5 cm, in particular at least 10 cm by 10 cm, in particular at least 20 cm by cm. cm by 20 cm.
  • the thickness of said enamel coating is preferably between 1.5 ⁇ m and 3.5 ⁇ m.
  • the enamel is thus chosen so as to have a gloss (or a degree of gloss) at 60 ° less than 40 (value expressed in "gloss unit” or without unit), this brightness being measured at spectro-guide 45-0 marketed by the company BYK Gardner, according to the ISO 2813 standard on enamel deposited in flat (with a recovery rate of 100%).
  • Gloss is the optical characteristic of a light-reflecting surface and is measured along an axis inclined to the surface normal (here an axis of 60 ° to the normal to the surface) of the enamel deposited on the surface. flat.
  • the enamel selected (by simple measurement of the gloss of the enamels tested and selection of those which fulfill the criterion) according to the invention thus has a gloss (or a degree of gloss) at 60 ° according to the ISO 2813 standard between 0 and 40.
  • the recovery rate (or coverage rate) of the enamel or coating in the zone (coated with said coating) for which the anti-fingerprinting effect is sought and obtained according to FIG. invention is 40 to 80% (or between 40 and 80%, limits included), this rate being defined as the area actually covered by the enamel divided by the area of said area, the recovery rate being in practice measurable on any analysis surface of 15 by 10 mm in the zone provided with the coating for which the anti-fingerprint effect is sought and obtained according to the invention, said zone being at least 5 cm by 5 cm.
  • the recovery rate is measured using an optical bench with 1024 pixel SVS EC0267 reference camera marketed by the company SVS Vistek and backlighting by light-emitting diode (LED Backlight compact SBACKII 51x51 mm marketed by the company TPL Vision) placed under the sample for taking pictures and using free software ImageJ for image analysis.
  • the recovery rate of said enamel coating is from 50% to 80%, particularly preferably from 55% to 80%, and in particular from 58% to 79%, in particular of the order of 59% or 60% to 75% or 76%.
  • the profile or the weft (mixture or alternation of covered and uncovered portions in the area on which the enamel coating has been deposited) of the enamel coating according to the invention is in particular, and advantageously, random and isotropic.
  • This recovery rate (which can be adjusted according to the chosen method of deposit, the deposit of enamel being generally operated in the present invention by screen printing - one can then choose a screen of screen printing more or less covering - or jet of enamel - we can then choose a projection more or less important) combined with the choice of the other aforementioned criteria makes it possible to obtain particularly satisfactory and improved results (with respect in particular to uncovered zones, or with respect to zones which are more weakly or strongly coated, for example coated with a solid surface-deposit continuous- said enamel, or compared to areas coated with a glossier enamel) in terms of anti-fingerprint effect on the desired areas.
  • enamel (and enamel coating) includes in particular pigments:
  • mica particles coated (or coated) with metal oxides or combinations of metal oxides in particular particles of mica coated with Ti0 2 or coated with Fe 2 O 3 , or coated with a TiO 2 - Fe combination 2 0 3 or a combination Ti0 2 - Sn0 2 or a combination Ti0 2 - Fe 2 0 3 - Sn0 2; and or
  • Al 2 O 3 aluminum oxide coated with metal oxides or combinations of metal oxides, in particular particles of Al 2 O 3 coated with a TiO 2 -Si 2 2 combination or with a combination Ti0 2 - Sn0 2 - Si0 2 ; and or
  • silica particles coated with metal oxides or combinations of metal oxides particularly silica particles coated with a combination of Ti0 2 - Sn0 2 or a combination Fe 2 0 3 - Zr0 2;
  • any other "effect” pigment ie metallic effect pigment (s) also called interferential pigment (s) or pearlescent (s) or pearlescent (s) pigment (s)
  • metallic effect pigment (s) also called interferential pigment (s) or pearlescent (s) or pearlescent (s) pigment (s)
  • enamel coating is an enamel coating (respectively an enamel) aspect said "metallized”.
  • the aforementioned pigments are for example sold, inter alia, by Merck under the references Iriodin 120, 300, 500, 520, 9602 or Pyrisma T40-23, T81 -23, M40-58, or Colorstream F10-00, T10- 01 or T10-02, where Xi joins F60-25, T60-23 or T60-10
  • the proportion of pigments chosen in the form pigments of mica particles and / or aluminum oxide and / or silica coated with metal oxides or combinations of metal oxides in the enamel composition in dry form is from 10 to 30% by weight of said composition, the enamel composition being essentially constituted, in dry form, of a glass frit to which, if appropriate, pigments are added, a medium is then added to allow the coating to be applied, this medium being subsequently removed during the heat treatment to achieve the final coating (heat treatment ceramization of the plate or heat treatment in recovery).
  • particles also includes the terms flake or platelet according to the usual forms of the pigments concerned.
  • the enamel used also advantageously comprises (in the dry composition including the frit and the pigments) a proportion of B 2 0 3 less than or equal to 25%, especially less than 20%, and preferably less than 15%, especially less than 10%, or even less than 6% by weight.
  • the enamel coating In combination with the choice of an enamel or an enamel coating having the aforementioned pigments, the enamel coating must also have a roughness Ra greater than or equal to 0.4 ⁇ m and a roughness Rt greater than 4 ⁇ m (roughness of the enamel deposited in flat (with a recovery rate of 100%))
  • the roughness Ra is a well-known roughness parameter and is the arithmetic average roughness of the profile (arithmetic mean of the absolute values of the differences between the successive peaks and troughs), defined over an evaluation length, and the roughness Rt is the height. total of the profile between the deepest valley and the highest peak over the evaluation length.
  • the roughness Ra and the roughness Rt as considered here are measured according to the ISO 4287 standard over a measurement length of 4 mm using a reference probe SJ401 from Mitutoyo.
  • the roughness Ra is 0.4 to 0.7 ⁇ m (or between 0.4 and 07 ⁇ m, limits included), and preferably, the roughness Rt is between 4 and 8 ⁇ m.
  • the enamel coating selected according to the invention is devoid of hydrophobic character (the contact angle of the water on this coating being less than 90 °) and devoid of oleophobic character (the contact angle of the diiodomethane on this coating being less than 90 °).
  • the area for which the anti-fingerprinting effect is desired is coated with the selected enamel coating, without the need for any prior treatment (eg quenching or application of the coating). a primer), to obtain both a good adhesion of the coating and the desired effect.
  • the substrate according to the invention may optionally be coated with other coatings or layers with functional and / or decorative effect, deposited in particular in other areas than the areas coated with anti-fingerprint enamel, such as conventional patterns based on other enamels or a layer of opacifying paint on another part of the substrate, or one or more functional layers of the anti-scratch layer, anti-overflow layer, opacifying layer, etc.
  • the article according to the invention may further comprise, associated with or combined with the substrate, one or more light sources and / or one or more heating elements (or heating elements, such as one or more radiant or halogen elements and / or one or more atmospheric gas burners and / or one or more induction heating means), generally placed on the underside of the substrate.
  • the source or sources may be integrated in or coupled to one or more structure (s) display type (s), an electronic control panel with sensitive keys and digital display, etc., and are advantageously formed by light-emitting diodes, plus or less spaced, possibly associated with one or more optical guides.
  • the article may also be provided with (or associated with) additional functional element (s) (frame, connector (s), cable (s), control element (s), etc.
  • the invention has thus made it possible to develop a surface-coated glass-ceramic product at the desired locations (for example on the areas more exposed to handling or soiling, such as control or display zones or heating zones, etc.) of a selected composition to obtain an anti-fingerprint effect, while respecting the constraints, including thermal and mechanical, specific to the uses of said products, and maintaining glass ceramic products perennial and easy maintenance.
  • the solution according to the present invention thus makes it possible to obtain in a simple and economical manner, without complex operation (coating that can be deposited by traditional enamel deposition techniques, such as screen printing, as indicated later), in a sustainable way and with great flexibility, zones with anti-fingerprint effect in any desired area of the product, even when these areas are intended to be subjected to high temperatures.
  • the article according to the invention has in particular a good thermal resistance compatible with the use of various types of heating, and does not pose maintenance problems, scratches or abrasion as indicated above.
  • the product according to the invention is not subject to thermal degradation at temperatures greater than or equal to 400 ° C. which can be attained in particular in applications such as the use as hotplates.
  • the article according to the invention also has a good adhesion of the coating to the glass-ceramic substrate (without the need for prior treatment of the support and / or the use of an adhesion promoter, an adhesion layer or an adhesion promoter. a primary).
  • This coating shows in particular no delamination after a thermal shock (for example around 600 ° C), and withstands high temperatures.
  • the coating also has good scratch resistance.
  • the coated substrate can be easily cleaned and has a long life.
  • the present invention also relates to a method of manufacturing the glass-ceramic article according to the invention, from a glass substrate (the mother-glass substrate for forming the ceramic-ceramic substrate by ceramization) in which at least one a part of said glass substrate (parent glass), before ceramization, at least one enamel coating as selected according to the invention (fulfilling the criteria previously indicated in the definition of the article according to the invention), then performs the ceramization of the glass substrate (mother-glass substrate) thus coated, this ceramization thus making it possible to obtain a glass-ceramic substrate at least in part (in at least one zone) coated with at least one anti-trace coating of fingers as previously described.
  • the enamel coating may optionally be deposited on the substrate already ceramized and cooked in recovery, for example in an annealing arch.
  • at least one coating of an enamel as selected according to the invention is applied to at least a portion of a glass-ceramic substrate and the enamel is then baked, for example at a temperature of the order of 850 ° C. .
  • the manufacture of the glass-ceramic plates generally takes place as follows: in a melting furnace, the glass of the chosen composition is melted to form the glass-ceramic, and then the molten glass is rolled into a standard ribbon or sheet by passing the glass melted between rolling rolls and cut the glass ribbon to the desired dimensions.
  • the plates thus cut are then ceramized in a manner known per se, the ceramization of baking the plates according to the thermal profile chosen to transform the glass into the polycrystalline material called "glass-ceramic" whose expansion coefficient is zero or almost zero and which withstands a thermal shock that can be up to 700 ° C in particular.
  • the ceramization generally comprises a step of gradual raising of the temperature to the nucleation range, a step of crossing in several minutes (for example between 5 and 60 minutes) of the nucleation interval (for example between 650 and 830 ° C. C), a new rise in temperature to allow the crystals to grow (ceramizing in a range of, for example, 850 to 1000 ° C., with maintaining the temperature of the ceramic bearing for several minutes (for example from 5 to 30 minutes ) then rapid cooling to room temperature.
  • the application or deposition, before ceramization, of enamel coating on parent glass can be carried out by any suitable and fast technique for the deposition of enamels, the application being preferably by screen printing or enamel spray.
  • the coated substrate is then subjected to the ceramizing heat treatment (at temperatures of up to 850 ° C. to 1000 ° C.) for a period generally of several tens of minutes, as indicated previously.
  • the method also comprises a cutting operation (generally before ceramization), for example by water jet, mechanical tracing with the wheel, etc. followed by a shaping operation (grinding, beveling, ).
  • an enamel composition selected from the following composition was used: Al 2 O 3 : 12.5 - 13.4%; U 2 0 + Na 2 O + K 2 O: 3.8 - 5.9%; B 2 O 3 : 18 - 19.8%, CaO + BaO + MgO: 1.7 - 2.3%, ZrO 2 : 1.4 - 2%, mixture of TiO 2 -coated mica particles, Fe 2 0 3 -coated mica particles, and mica particles coated by a combination Ti0 2 - Fe 2 O 3 - SnO 2 (pigments with metallized effect): 30%, the balance (at 100% by weight) being silica Si0 2 , this enamel having a gloss (in flat) of 26.3, a roughness Ra 0.5 ⁇ m, and roughness Rt 4.5 ⁇ m, and being tested with different coating coverage rates of 2.5 ⁇ m thick.
  • the recovery rates tested were respectively: 10%, 36%, 42%, 46%, 48%, 58%, 59%, 60%, 72%, 74%, 78%, 80% and 100%. Ratings (averages) of less than 1 to 0 were given for 42-80%, with the lowest and lowest scores being observed for rates ranging from 55-78%, with an optimum at 60%.
  • the enamel was then compared, at the same thickness (2.5 ⁇ m) and with a recovery rate of 80% for each enamel tested, with a metallized enamel not according to the invention having a gloss (in flat) of 66, a roughness Ra of 0.2 ⁇ m, and a roughness Rt of 2.8 ⁇ m, of composition chosen from the following composition: Al 2 O 3 : 15.2 - 16.2%; Li 2 O + Na 2 O + K 2 O: 4.6 - 7.1%; B 2 O 3 : 21.8 - 24.1%, CaO + BaO + MgO: 2 - 2.8%, ZrO 2 : 1.7 - 2.5%, Xirallic F60-25 pigments marketed by Merck (pigments with a metallic effect): 15%, complement (at 100% by weight) being silica Si0 2 . The average score obtained was of the order of 2.
  • the enamel was then compared, at a coverage ratio of 80% and the same thickness as above, with a non-metallized enamel not according to the invention having a brightness (in flat) of 15.7, a roughness Ra of 0.3 pm , and a roughness Rt of 4.4 ⁇ m, of composition selected from the following composition: Al 2 O 3 : 5.4 - 6.5%; Li 2 O + Na 2 O + K 2 O: 4.8 - 7.4%; B 2 O 3 : 3.6 - 5.4%, CaO + BaO + MgO: 17 - 20.3%, ZrO 2 : 1 - 1.7%, ZnO: 5.9 - 7.4%, mixture of TiO 2 , Fe 2 O 3 , Fe-Cr-Co-Ni oxides, and Al-Co oxides (pigments with no metallised effect): 15%, the balance (at 100% by weight) being silica Si0 2 .
  • the average score obtained was of the order of 2.
  • the enamel was then compared, at a coverage ratio of 80% and the same thickness as before, with another metallized enamel according to the invention having a brightness (in flat) of 38.4, a roughness Ra of 0.6 ⁇ m, and a roughness Rt of 4.6 ⁇ m, of composition chosen from the following composition: Al 2 O 3 : 12.5 - 13.4%; Li 2 O + Na 2 O + K 2 O: 3.8 - 5.9%; B 2 O 3 : 18.0 - 19.8%, CaO + BaO + MgO: 1.7 - 2.3%, ZrO 2 : 1.4 - 2%, Colorstream F10-00 pigments marketed by Merck (pigments with metallic effect): 30%, the balance (at 100% by weight) being SiO 2 silica. The average score obtained was of the order of 0.
  • the enamel was then compared, at a coverage ratio of 80% and the same thickness as above, with another metallized enamel according to the invention having a brightness (in flat) of 37.6, a roughness Ra of 0.4 ⁇ m, and a roughness Rt of 6 ⁇ m, of composition chosen from the following composition: Al 2 O 3 : 14.3 - 15.3%; Li 2 O + Na 2 O + K 2 O: 4.3 - 6.7%; B 2 0 3 : 20.5 - 22.7%, CaO + BaO + MgO: 1.9 - 2.6%, ZrO 2 : 1.6 - 2.3%, mixture of TiO 2 -coated mica particles, Fe 2 0 3 -coated mica particles, and mica particles coated with a combination TiO 2 - Fe 2 O 3 - SnO 2 (pigments with metallized effect): 20%, the balance (at 100% by weight) being SiO 2 silica.
  • the average score obtained was of the order of 0.
  • the enamel was then compared, at a coverage ratio of 80% and the same thickness as above, with a metallized enamel not according to the invention having a gloss (in flat) of 80, a roughness Ra of 0.2 ⁇ m, and a roughness Rt of 2.5 ⁇ m, of composition chosen from the following composition! Al 2 0 3! 16.1 - 17.2%; Li 2 O + Na 2 O + K 2 O: 4.9 - 7.6%; B 2 0 3!
  • the enamel coatings fulfilling the conditions of the invention have shown anti-fingerprint properties as opposed to other coatings not fulfilling these conditions. In addition, there were no significant differences in scoring when the tests were performed 7 or 14 days after the application of the fingers.
  • the resulting substrate and coatings showed no delamination after thermal shock of 620 ° C and showed no appearance degradation after 100 h at 580 ° C.
  • the articles according to the invention can in particular be used with advantage to achieve a new range of cooking plates for stoves or hobs or a new range of work tables, consoles, credence, central islands, etc..

Abstract

The present invention relates to a glass-ceramic article comprising at least one substrate, such as a plate, made of glass-ceramic, said substrate being coated in at least one zone with at least one enamel coating, such that: 1) the enamel has a 60° gloss value of less than 40; 2) the percentage of enamel coverage in the area coated with the coating is between 40 and 80%; 3) the enamel comprises pigments in the form of particles of mica and/or aluminium oxide and/or silica, which are coated with metal oxides or combinations of metal oxides; 4) the enamel has a roughness Ra greater than or equal to 0.4 μm; and 5) the enamel has a roughness Rr greater than 4 μm.

Description

ARTICLE VITROCERAMIQUE  GLASS-CERAMIC ARTICLE
La présente invention concerne le domaine des vitrocéramiques. Plus précisément, elle concerne un article, ou produit, en vitrocéramique, notamment une plaque vitrocéramique destiné(e) à servir de surface de meuble et/ou de surface de cuisson. Par article vitrocéramique ou en vitrocéramique, on entend un article à base d’un substrat (tel qu'une plaque) en matériau vitrocéramique, ledit substrat pouvant le cas échéant être muni d’accessoires ou d'éléments supplémentaires, décoratifs ou fonctionnels, requis pour son usage final, l’article pouvant désigner tout aussi bien le substrat seul que celui muni d’équipements supplémentaires (par exemple une plaque de cuisson munie de son bandeau de commande, de ses éléments de chauffage, etc). The present invention relates to the field of glass-ceramics. More specifically, it relates to an article, or product, glass-ceramic, including a glass-ceramic plate for (e) serving as a furniture surface and / or cooking surface. By glass-ceramic article or glass-ceramic, means an article based on a substrate (such as a plate) of glass-ceramic material, said substrate may optionally be provided with accessories or additional elements, decorative or functional, required for its final use, the article may designate both the substrate alone and that provided with additional equipment (for example a cooking plate provided with its control panel, its heating elements, etc.).
Une vitrocéramique est à l’origine un verre, dit verre précurseur ou verre- mère ou green-glass, dont la composition chimique spécifique permet de provoquer par des traitements thermiques adaptés, dits de céramisation, une cristallisation contrôlée. Cette structure spécifique en partie cristallisée confère à la vitrocéramique des propriétés uniques.  A glass-ceramic is originally a glass, said precursor glass or mother glass or green-glass, whose specific chemical composition can cause by suitable heat treatments, called ceramization, a controlled crystallization. This specific partly crystallized structure gives the glass ceramic unique properties.
Il existe actuellement différents types de plaques en vitrocéramique, chaque variante étant le résultat d’études importantes et de nombreux essais, étant donné qu’il est très délicat de faire des modifications sur ces plaques et/ou sur leur procédé d’obtention sans risquer un effet défavorable sur les propriétés recherchées : en particulier, pour pouvoir être utilisée comme plaque de cuisson, une plaque vitrocéramique doit généralement présenter une transmission dans les longueurs d’onde du domaine du visible à la fois suffisamment basse pour masquer au moins une partie des éléments de chauffage sous-jacents au repos et suffisamment élevée pour que, selon les cas (chauffage radiant, chauffage par induction, etc), l’utilisateur puisse détecter visuellement les éléments de chauffage en état de marche dans un but de sécurité ; elle doit également présenter une transmission élevée dans les longueurs d’onde du domaine de l’infrarouge dans le cas notamment des plaques à foyers radiants. Les plaques vitrocéramiques doivent également présenter une résistance mécanique suffisante telle qu’exigée dans leur domaine d’utilisation. En particulier, pour pouvoir être utilisée comme plaque de cuisson dans le domaine de l’électroménager ou comme surface de meuble, une plaque vitrocéramique doit présenter une bonne résistance à la pression, aux chocs (support et chute d’ustensiles, etc), etc. There are currently different types of glass ceramic plates, each variant being the result of important studies and numerous tests, since it is very difficult to make modifications on these plates and / or on their method of obtaining without risking an adverse effect on the properties sought: in particular, to be used as a hob, a glass-ceramic plate must generally have a transmission in the wavelengths of the visible range both low enough to mask at least a portion of Underlying heating elements at rest and sufficiently high so that, depending on the case (radiant heating, induction heating, etc.), the user can visually detect the heating elements in working order for the purpose of security ; it must also have a high transmission in the wavelengths of the infrared range in the case in particular radiant hob plates. The vitroceramic plates must also have sufficient mechanical strength as required in their field of use. In particular, to be used as a hob in the field of household appliances or as a furniture surface, a ceramic hob must have good resistance to pressure, shock (support and fall of utensils, etc.), etc. .
Les plaques de cuisson vitrocéramiques les plus répandues sont de couleur sombre, en particulier de couleur noire ou brune ou brun-orangé, mais il existe également des plaques d’aspect plus clair (en particulier de couleur blanche, présentant par exemple un flou d’au moins 50% comme décrit dans le brevet FR2766816), voire des plaques transparentes munies généralement de revêtements opacifiants ou encore munies de filtres pour des effets de couleur particuliers.  The most common vitroceramic hotplates are dark in color, in particular black or brown or orange-brown in color, but there are also plates with a lighter appearance (in particular white in color, for example with a blur of at least 50% as described in patent FR2766816), or transparent plates generally provided with opacifying coatings or provided with filters for particular color effects.
Traditionnellement, les plaques vitrocéramiques sont utilisées comme plaques de cuisson, ou elles peuvent aussi être associées à des éléments de chauffage dans d'autres applications, par exemple pour former des inserts de cheminées. Depuis peu, leur utilisation s'étend à d'autres domaines de la vie quotidienne : les plaques vitrocéramiques peuvent ainsi servir de surfaces de meuble, notamment pour former des plans de travail, des ilôts centraux, des consoles, etc. la surface qu'elles occupent dans ces nouvelles applications étant plus importante que par le passé. Selon leur usage, elles peuvent être munies de touches, zones tactiles, boutons ou autres commandes, leur surface étant dans tous les cas (même dans le cas d'une simple surface de meuble) soumise à de multiples contacts liés à leurs utilisations, occasionnant généralement l'apparition de traces de doigts peu esthétiques aux endroits de contact, entraînant le cas échéant des nettoyages répétés, en particulier lorsque les plaques sont sombres et brillantes. Ces traces ou salissures peuvent également entraîner des interférences avec les autres composants éventuels (éléments de chauffage, sources lumineuses, affichages, etc.) du produit vitrocéramique.  Traditionally, glass-ceramic plates are used as hotplates, or they can also be associated with heating elements in other applications, for example to form chimney inserts. Recently, their use extends to other areas of daily life: ceramic plates can be used as furniture surfaces, especially to form worktops, central islands, consoles, etc. the surface they occupy in these new applications being larger than in the past. Depending on their use, they may be provided with keys, touch zones, buttons or other commands, their surface being in all cases (even in the case of a single piece of furniture) subject to multiple contacts related to their uses, causing usually the appearance of unsightly fingerprints at contact areas, resulting in repeated cleaning if necessary, especially when the plates are dark and shiny. These traces or soiling can also cause interference with other components (heating elements, light sources, displays, etc.) of the glass ceramic product.
Pour éviter les empreintes de doigts à le surface des produits, il est connu dans d'autres domaines (par exemple dans le domaine des écrans à fenêtre en verre) d'appliquer des revêtements hydrophobes (qui repoussent l'eau) et oléophobes (qui repoussent l'huile) permettant de limiter la quantité de liquide(s) (eau, sébum) déposé(s) lors du contact avec le doigt. Cependant, de tels revêtements, qui doivent être appliqués sur la totalité de la surface à protéger, ne sont pas résistants thermiquement, ce qui pose des problèmes pour des applications de type plaques de cuisson. To avoid fingerprints on the surface of products, it is known in other fields (for example in the field of window screens with glass) to apply hydrophobic coatings (which repel water) and oil repellant (which repel oil) to limit the amount of liquid (s) (water, sebum) deposited (s) during contact with the finger. However, such coatings, which must be applied over the entire surface to be protected, are not thermally resistant, which poses problems for hob-type applications.
Il est également connu de texturer la surface vitrée de produits pour limiter la visibilité des traces de doigts. Cependant les texturations généralement opérées sont fragiles et résistent mal aux sollicitations mécaniques (nettoyage, abrasion).  It is also known to texture the glazed surface of products to limit the visibility of fingerprints. However texturations generally operated are fragile and poor resistance to mechanical stress (cleaning, abrasion).
Dans le domaine des vitrocéramiques, les texturations ou revêtements existants ne sont généralement pas appropriés pour remédier systématiquement aux problèmes de traces de doigts. Les revêtements les plus fréquemment utilisés sont surtout des revêtements choisis pour résister à haute température, tels que les émaux, utilisés localement pour former des motifs décoratifs ou signalant par exemple des zones de chauffe, ou bien des peintures utilisées plutôt en aplat comme opacifiants. Cependant ces revêtements traditionnels ne font généralement pas obstacle aux traces de doigts liées à la manipulation et l'utilisation des substrats revêtus, les émaux pouvant en outre diminuer localement la résistance mécanique des plaques vitrocéramiques et s’écailler, et les peintures ne convenant pas à tous les modes de chauffage pour les plaques de cuisson en raison de leur moindre résistance, notamment thermique. Il est également connu d'utiliser d'autres revêtements à base notamment de couches minces métalliques déposées en aplat sur une grande partie de la surface du substrat, mais de telles couches contribuent parfois à contrario aux problèmes de traces de doigts.  In the field of glass-ceramics, existing texturations or coatings are generally not suitable for systematically remedying fingerprint problems. The coatings most frequently used are mainly coatings chosen to resist high temperature, such as enamels, used locally to form decorative patterns or signaling for example heating zones, or paints used rather flat as opacifiers. However, these traditional coatings do not generally hinder fingerprints related to the handling and use of the coated substrates, the enamels can also locally reduce the mechanical strength of the glass-ceramic plates and peel, and the paints are not suitable for all heating modes for the hobs due to their lower resistance, including thermal. It is also known to use other coatings based in particular thin metal layers deposited flat on a large part of the surface of the substrate, but such layers sometimes contribute contrario to the problem of fingerprints.
La présente invention a donc cherché à mettre au point des produits vitrocéramiques améliorés permettant de limiter la visibilité des traces de doigts à leur surface, en particulier de nouvelles plaques vitrocéramiques destinées à être utilisées avec un ou des éléments de chauffage telles que des plaques de cuisson, ou destinées à servir de surface de meubles, ces plaques présentant des propriétés anti-traces de doigts, sans nuire aux autres propriétés recherchées pour leur usage, notamment sans nuire à leur facilité d'entretien et de nettoyage, ni à leur résistance, en particulier mécanique, aux rayures et à l'abrasion, et le cas échéant thermique, et sans être préjudiciable à leur durée de vie, tout en veillant à proposer une solution simple et si possible flexible autorisant la présence de décors ou de fonctions additionnelles en fonction des besoins. The present invention has therefore sought to develop improved glass-ceramic products to limit the visibility of fingerprints on their surface, especially new glass-ceramic plates for use with one or more heating elements such as hotplates. , or intended to serve as a furniture surface, these plates having anti-fingerprint properties, without harming other properties sought for their use, including without impairing their ease of maintenance and cleaning, or their resistance, in particular mechanical, scratch and abrasion, and if necessary thermal, and without being detrimental to their life, while ensuring a simple solution and if possible flexible allowing the presence of decorations or additional functions as needed.
Ce but est atteint grâce au produit vitrocéramique mis au point selon l'invention dans lequel la visibilité des empreintes digitales en surface est réduite par l'application d'un revêtement en émail spécifique, ledit revêtement et ledit émail étant sélectionnés suivant des critères précis afin d'obtenir l'effet anti-traces de doigts recherché. Les inventeurs ont en effet mis en évidence qu'en choisissant un émail et l'appliquant suivant les critères listés ci-après, l'effet anti-traces de doigts était visiblement obtenu pour différents types de substrats en vitrocéramique (plus ou moins foncés ou présentant des compositions différentes, etc.), tout en gardant une certaine flexibilité dans la composition d'émail (pour obtenir par exemple différentes colorations) tant que l'émail et le revêtement déposés restent dans les limites définies ci-après.  This object is achieved thanks to the glass-ceramic product developed according to the invention in which the visibility of the fingerprints on the surface is reduced by the application of a specific enamel coating, said coating and said enamel being selected according to precise criteria so to obtain the desired anti-fingerprint effect. The inventors have in fact demonstrated that by choosing an enamel and applying it according to the criteria listed below, the anti-fingerprinting effect was visibly obtained for different types of glass-ceramic substrates (more or less dark or having different compositions, etc.), while keeping a certain flexibility in the enamel composition (to obtain, for example, different dyes) as long as the enamel and coating deposited remain within the limits defined below.
La présente invention concerne donc un nouvel article vitrocéramique, comprenant au moins un substrat, tel qu’une plaque, en vitrocéramique, ledit substrat étant revêtu en au moins une zone d’au moins un revêtement en émail (ou dépôt ou couche d'émail) tel que :  The present invention therefore relates to a new glass-ceramic article, comprising at least one substrate, such as a plate, glass-ceramic, said substrate being coated in at least one zone of at least one enamel coating (or deposit or layer of enamel ) such as :
1 ) ledit émail présente une brillance (ou un degré de brillance) à 60° inférieure à1) said enamel has a gloss (or a degree of gloss) at 60 ° less than
40, 40
2) le taux de recouvrement dudit émail (ou dudit revêtement en émail) dans ladite zone revêtue dudit revêtement est de 40 à 80%,  2) the coverage rate of said enamel (or said enamel coating) in said zone coated with said coating is 40 to 80%,
3) ledit émail comprend des pigments sous forme de particules de mica et/ou d’oxyde d’aluminium et/ou de silice revêtues par des oxydes métalliques ou combinaisons d'oxydes métalliques,  3) said enamel comprises pigments in the form of mica particles and / or aluminum oxide and / or silica coated with metal oxides or combinations of metal oxides,
4) ledit émail présente une rugosité Ra supérieure ou égale à 0.4 miti,  4) said enamel has a roughness Ra greater than or equal to 0.4 miti,
5) ledit émail présente une rugosité Rt supérieure à 4 prn.  5) said enamel has a roughness Rt greater than 4 prn.
Le revêtement en émail ainsi sélectionné et appliqué permet d'engendrer en la zone revêtue dudit revêtement une réduction de la visibilité des traces de doigts, ou en d'autres termes de conférer à ladite zone des propriétés (ou une fonctionnalité) anti-traces de doigts.  The enamel coating thus selected and applied makes it possible to generate, in the zone coated with said coating, a reduction in the visibility of the fingerprints, or in other words to give the said zone anti-fingerprint properties (or functionality). fingers.
L'article (ou produit) vitrocéramique selon l'invention est en particulier une plaque de cuisson ou tout article mobilier intégrant (ou comprenant, ou formé de) au moins un substrat en (matériau) vitrocéramique (le substrat étant le plus couramment sous forme d'une plaque, venant s'intégrer ou se monter dans le meuble et/ou combinée à d'autres éléments pour former le meuble), ledit substrat pouvant le cas échéant présenter des zones à caractère d'affichage (en combinaison par exemple avec des sources émettant de la lumière) ou des zones décorées ou être combiné avec des éléments chauffants. Dans son application la plus courante, l'article selon l'invention est destiné à servir de plaque de cuisson, cette plaque étant généralement destinée à être intégrée dans une table de cuisson ou cuisinière comprenant également des éléments chauffants, par exemple des foyers radiants ou halogènes ou des éléments de chauffage par induction. Dans une autre application avantageuse, l'article selon l'invention est un plan de travail en vitrocéramique ou un ilôt central, le cas échéant avec différents affichages et sans nécessairement de zones de cuisson, voire un meuble de type console (le substrat formant par exemple la partie supérieure), etc.. The article (or product) vitroceramic according to the invention is in particular a cooking plate or any furniture article integrating (or comprising, or formed de) at least one glass-ceramic substrate (the substrate being most commonly in the form of a plate, integrating or mounting in the furniture and / or combined with other elements to form the furniture), said substrate may optionally have display areas (in combination for example with light emitting sources) or decorated areas or combined with heating elements. In its most common application, the article according to the invention is intended to serve as a cooking plate, this plate being generally intended to be integrated in a hob or cooker also comprising heating elements, for example radiant heaters or halogen or induction heating elements. In another advantageous application, the article according to the invention is a vitroceramic worktop or central island, where appropriate with different displays and without necessarily cooking zones, or even a console type furniture (the substrate forming by example the upper part), etc.
Le substrat (ou l'article selon l'invention lui-même s'il n'est formé que du substrat) est généralement (sous forme de) une plaque, destinée notamment à être utilisée avec, en particulier à couvrir ou recevoir, au moins une source lumineuse et/ou un élément de chauffage ou destinée à servir de surface de meuble. Ce substrat (ou respectivement cette plaque) est généralement de forme géométrique, en particulier rectangulaire, voire carrée, voire circulaire ou ovale, etc, et présente généralement une face tournée vers l'utilisateur en position d’utilisation (ou face visible ou externe, généralement la face supérieure en position d'utilisation), une autre face généralement cachée, par exemple dans un châssis ou caisson de meuble, en position d’utilisation (ou face interne, généralement la face inférieure en position d'utilisation), et une tranche (ou chant ou épaisseur). La face supérieure ou externe est généralement plane et lisse mais peut aussi présenter localement au moins une zone en relief et/ou au moins une zone en creux et/ou au moins une ouverture et/ou des bords biseautés, ces variations de forme constituant notamment des variations continues de la plaque. La face inférieure ou interne peut également être plane et lisse ou munie de picots.  The substrate (or the article according to the invention itself if it is formed only of the substrate) is generally (in the form of) a plate, intended in particular to be used with, in particular to cover or receive, the minus a light source and / or a heating element or intended to serve as a furniture surface. This substrate (or respectively this plate) is generally of geometric shape, in particular rectangular, even square, even circular or oval, etc., and generally has a face turned towards the user in the use position (or visible or external face, generally the upper face in the use position), another generally hidden face, for example in a frame or cabinet of furniture, in the use position (or inner face, generally the lower face in the use position), and a slice (or edge or thickness). The upper or outer face is generally flat and smooth but may also present locally at least one raised area and / or at least one hollow area and / or at least one opening and / or bevelled edges, these shape variations constituting in particular continuous variations of the plate. The lower or inner face may also be flat and smooth or provided with pins.
L'épaisseur du substrat vitrocéramique est généralement d'au moins 2 mm, notamment d'au moins 2.5 mm, et est avantageusement inférieure à 15 mm, en particulier est de l'ordre de 3 à 15 mm, notamment de l'ordre de 3 à 8 mm ou de l'ordre de 3 à 6 mm. Le substrat est de préférence une plaque plane ou quasi-plane (en particulier avec une flèche inférieure à 0,1 % de la diagonale de la plaque, et de préférence de l’ordre de zéro). The thickness of the glass-ceramic substrate is generally at least 2 mm, in particular at least 2.5 mm, and is advantageously less than 15 mm. mm, in particular is of the order of 3 to 15 mm, in particular of the order of 3 to 8 mm or of the order of 3 to 6 mm. The substrate is preferably a flat or quasi-flat plate (in particular with an arrow less than 0.1% of the diagonal of the plate, and preferably of the order of zero).
Le substrat peut être à base de toute vitrocéramique, ce substrat présentant avantageusement un CTE nul ou quasi-nul, en particulier inférieur (en valeur absolue) à 30.10 7 K 1 entre 20 et 700 °C, notamment inférieur à 15.10 7K 1, voire inférieur à 5.10 7 K 1 entre 20 et 700 °C. The substrate may be based on any glass-ceramic, this substrate advantageously having a zero or almost zero CTE, in particular lower (in absolute value) at 30 × 10 7 K 1 between 20 and 700 ° C., in particular less than 15 × 10 7 K 1 , even less than 5.10 7 K 1 between 20 and 700 ° C.
L'invention vise plus particulièrement les substrats d'aspect sombre, faiblement transmissifs et peu diffusants, notamment à base de toute vitrocéramique ayant, de manière intrinsèque, une transmission lumineuse TL inférieure à 40%, en particulier inférieure à 5%, notamment de 0.2 à 2% pour des vitrocéramiques jusqu'à 6 mm d'épaisseur, et une transmission optique (déterminée de façon connue en faisant le rapport entre l’intensité transmise et l’intensité incidente à une longueur d’onde donnée) entre 0.5 et 3% pour une longueur d’onde de 625 nm comprise dans le domaine du visible. Par « de manière intrinsèque», on entend que le substrat possède une telle transmission en lui-même, sans la présence d’un quelconque revêtement. Les mesures optiques sont faites selon la norme EN 410. En particulier, la transmission lumineuse TL est mesurée selon la norme EN 410 en utilisant l’illuminant D65, et est la transmission totale (notamment intégrée dans le domaine du visible et pondérée par la courbe de sensibilité de l’œil humain), tenant compte à la fois de la transmission directe et de l’éventuelle transmission diffuse, la mesure étant faite par exemple à l'aide d'un spectrophotomètre muni d’une sphère intégrante (en particulier avec le spectrophotomètre commercialisé par la société Perkin Elmer sous la référence Lambda 950).  The invention more particularly targets substrates of dark appearance, weakly transmissive and not very diffusing, in particular based on any vitroceramic having, intrinsically, a light transmission TL less than 40%, in particular less than 5%, in particular 0.2 at 2% for vitroceramics up to 6 mm thick, and an optical transmission (determined in a known manner by relating the transmitted intensity to the incident intensity at a given wavelength) between 0.5 and 3 % for a wavelength of 625 nm in the visible range. By "intrinsically" is meant that the substrate has such a transmission in itself, without the presence of any coating. The optical measurements are made according to the EN 410 standard. In particular, the TL light transmission is measured according to the EN 410 standard using the D65 illuminant, and is the total transmission (notably integrated in the visible range and weighted by the curve. sensitivity of the human eye), taking into account both the direct transmission and the possible diffuse transmission, the measurement being made for example using a spectrophotometer provided with an integrating sphere (in particular with the spectrophotometer marketed by Perkin Elmer under the reference Lambda 950).
En particulier, on utilise un substrat d’aspect noir ou brun, permettant, en combinaison avec des sources lumineuses placées dessous, d'afficher des zones lumineuses ou des décors, tout en masquant les éventuels éléments sous-jacents. Il peut être notamment à base d’une vitrocéramique noire comprenant des cristaux de structure b-quartz au sein d’une phase vitreuse résiduelle, la valeur absolue de son coefficient de dilatation étant avantageusement inférieure ou égale à 15.10 7 K 1, voire à 5.10 7 K 1, telle que la vitrocéramique des plaques commercialisées sous le nom Kerablack+ par la société Eurokera. Il peut s’agir notamment d’une vitrocéramique affinée à l’arsenic de composition telle que décrite dans la demande de brevet EP0437228 ou US5070045 ou FR2657079, ou d’une vitrocéramique affinée à l'étain, présentant un taux d’oxydes d’arsenic préférentiellement inférieur à 0.1 %, par exemple de composition telle que décrite dans la demande de brevet WO 2012/156444, ou encore affinée au(x) sulfure(s) comme décrit dans la demande de brevet W020080531 10. In particular, a substrate of black or brown appearance is used, which, in combination with light sources placed underneath, makes it possible to display light areas or decorations, while masking any underlying elements. It may in particular be based on a black glass ceramic comprising crystals of b-quartz structure within a residual vitreous phase, the absolute value of its coefficient of expansion being advantageously less than or equal to 15 × 10 7 K 1 , or even to 5.10 7 K 1 , such as the glass-ceramic plates sold under the name Kerablack + by the Eurokera company. It may be in particular an arsenic-refined glass-ceramic of composition as described in the patent application EP0437228 or US5070045 or FR2657079, or a tin-refined glass-ceramic having a degree of oxides of arsenic preferably less than 0.1%, for example of composition as described in the patent application WO 2012/156444, or further refined with the sulphide (s) as described in the patent application WO20080531 10.
La présente invention peut également s'appliquer dans le cas où le substrat est plus clair, par exemple pour un substrat transparent, revêtu le cas échéant d'un revêtement opacifiant, généralement en peinture, sur sa face inférieure, tel qu'une plaque commercialisée sous le nom Keralite® par la société Eurokera.  The present invention can also be applied in the case where the substrate is lighter, for example for a transparent substrate, optionally coated with an opacifying coating, generally in paint, on its underside, such as a commercialized plate. under the name Keralite® by Eurokera.
Conformément à l'invention, le substrat vitrocéramique considéré est revêtu en au moins une zone (ou au moins une zone dudit substrat est revêtue), plus particulièrement en surface, sur au moins une partie d'une face, avantageusement sur au moins une partie de la face tournée vers l'utilisateur en position d'utilisation et/ou nécessitant une réduction de la visibilité des traces de doigts, généralement la face supérieure ou externe en position d'utilisation, voire peut être revêtu sur plusieurs zones sur une ou plusieurs faces, voire sur la totalité d'une ou plusieurs faces.  According to the invention, the glass-ceramic substrate considered is coated in at least one zone (or at least one zone of said substrate is coated), more particularly at the surface, on at least a part of a face, advantageously on at least a part of of the face facing the user in the use position and / or requiring a reduction in the visibility of fingerprints, generally the upper or outer face in the use position, or may be coated on several areas on one or more faces, even on the whole of one or more faces.
Il est revêtu d'au moins (ou par au moins) un revêtement en émail tel que défini selon l'invention, c'est-à-dire d'au moins un revêtement en émail présentant (ou sélectionné et appliqué de façon à présenter) les caractéristiques précédemment mentionnées. La zone revêtue du revêtement en émail selon l'invention est de préférence (ou occupe de préférence une surface) d'au moins 5 cm par 5 cm, en particulier d'au moins 10 cm par 10 cm, notamment d'au moins 20 cm par 20 cm. L'épaisseur dudit revêtement en émail est préférentiellement comprise entre 1.5 pm et 3.5 pm.  It is coated with at least (or at least) an enamel coating as defined according to the invention, that is to say at least one enamel coating having (or selected and applied to present ) the previously mentioned characteristics. The zone coated with the enamel coating according to the invention is preferably (or preferably occupies a surface) at least 5 cm by 5 cm, in particular at least 10 cm by 10 cm, in particular at least 20 cm by cm. cm by 20 cm. The thickness of said enamel coating is preferably between 1.5 μm and 3.5 μm.
Comme indiqué en premier lieu, l'émail est ainsi choisi de façon à présenter une brillance (ou un degré de brillance) à 60° inférieure à 40 (valeur exprimée en "unité de brillance" ou sans unité), cette brillance étant mesurée au spectro-guide 45-0 commercialisé par la société BYK Gardner, selon la norme ISO 2813 sur l'émail déposé en aplat (avec un taux de recouvrement de 100%). La brillance est la caractéristique optique d'une surface réfléchissant la lumière et est mesurée suivant un axe incliné par rapport à la normale à la surface (ici un axe de 60° par rapport à la normale à la surface) de l'émail déposé en aplat. L'émail sélectionné (par simple mesure de la brillance des émaux testés et sélection de ceux qui remplissent le critère) selon l'invention présente ainsi une brillance (ou un degré de brillance) à 60° selon la norme ISO 2813 comprise entre 0 et 40. As indicated firstly, the enamel is thus chosen so as to have a gloss (or a degree of gloss) at 60 ° less than 40 (value expressed in "gloss unit" or without unit), this brightness being measured at spectro-guide 45-0 marketed by the company BYK Gardner, according to the ISO 2813 standard on enamel deposited in flat (with a recovery rate of 100%). Gloss is the optical characteristic of a light-reflecting surface and is measured along an axis inclined to the surface normal (here an axis of 60 ° to the normal to the surface) of the enamel deposited on the surface. flat. The enamel selected (by simple measurement of the gloss of the enamels tested and selection of those which fulfill the criterion) according to the invention thus has a gloss (or a degree of gloss) at 60 ° according to the ISO 2813 standard between 0 and 40.
Comme indiqué également en second critère de sélection, le taux de recouvrement (ou taux de couverture) de l'émail ou du revêtement dans la zone (revêtue dudit revêtement) pour laquelle l'effet anti-traces doigts est recherché et obtenu selon l'invention, est de 40 à 80% (ou compris entre 40 et 80%, bornes incluses), ce taux étant défini comme la surface réellement couverte par l’émail divisée par la surface de ladite zone, le taux de recouvrement étant en pratique mesurable sur toute surface d'analyse de 15 par 10 mm dans la zone munie du revêtement pour laquelle l'effet anti-traces doigts est recherché et obtenu selon l'invention, ladite zone étant d'au moins 5 cm par 5 cm. Le taux de recouvrement est mesuré en utilisant un banc optique avec caméra 1024 pixels de référence SVS EC0267 commercialisée par la société SVS Vistek et rétroéclairage par diode électroluminescente (LED Backlight compact SBACKII 51x51 mm commercialisée par la société TPL Vision) placée sous l'échantillon pour la prise d'image et en utilisant un logiciel libre ImageJ pour l'analyse de l'image.  As also indicated in the second selection criterion, the recovery rate (or coverage rate) of the enamel or coating in the zone (coated with said coating) for which the anti-fingerprinting effect is sought and obtained according to FIG. invention, is 40 to 80% (or between 40 and 80%, limits included), this rate being defined as the area actually covered by the enamel divided by the area of said area, the recovery rate being in practice measurable on any analysis surface of 15 by 10 mm in the zone provided with the coating for which the anti-fingerprint effect is sought and obtained according to the invention, said zone being at least 5 cm by 5 cm. The recovery rate is measured using an optical bench with 1024 pixel SVS EC0267 reference camera marketed by the company SVS Vistek and backlighting by light-emitting diode (LED Backlight compact SBACKII 51x51 mm marketed by the company TPL Vision) placed under the sample for taking pictures and using free software ImageJ for image analysis.
De préférence, le taux de recouvrement dudit revêtement en émail (dans la zone pour laquelle l'effet anti-traces doigts est recherché), est de 50% à 80%, de façon particulièrement préférée de 55% à 80%, et en particulier de 58% à 79%, notamment de l'ordre de 59% ou 60% à 75% ou 76%.  Preferably, the recovery rate of said enamel coating (in the area for which the anti-fingerprint effect is desired) is from 50% to 80%, particularly preferably from 55% to 80%, and in particular from 58% to 79%, in particular of the order of 59% or 60% to 75% or 76%.
Le profil ou la trame (mélange ou alternance de portions couvertes et non couvertes dans la zone sur laquelle le revêtement en émail a été déposé) du revêtement en émail selon l'invention est en particulier, et avantageusement, aléatoire et isotrope.  The profile or the weft (mixture or alternation of covered and uncovered portions in the area on which the enamel coating has been deposited) of the enamel coating according to the invention is in particular, and advantageously, random and isotropic.
Ce taux de recouvrement (que l'on peut régler selon le mode de dépôt choisi, le dépôt d'émail étant généralement opéré dans la présente invention par sérigraphie - on peut alors choisir un écran de sérigraphie plus ou moins couvrant - ou jet d'émail - on peut alors choisir une projection plus ou moins importante) combiné au choix des autres critères précités permet d'obtenir des résultats particulièrement satisfaisants et améliorés (par rapport notamment à des zones non recouvertes, ou par rapport à des zones plus faiblement ou fortement revêtues, par exemple revêtues d'un aplat - dépôt continu- dudit émail, ou par rapport à des zones revêtues d'un émail plus brillant) en termes d'effet anti-traces de doigts sur les zones souhaitées. This recovery rate (which can be adjusted according to the chosen method of deposit, the deposit of enamel being generally operated in the present invention by screen printing - one can then choose a screen of screen printing more or less covering - or jet of enamel - we can then choose a projection more or less important) combined with the choice of the other aforementioned criteria makes it possible to obtain particularly satisfactory and improved results (with respect in particular to uncovered zones, or with respect to zones which are more weakly or strongly coated, for example coated with a solid surface-deposit continuous- said enamel, or compared to areas coated with a glossier enamel) in terms of anti-fingerprint effect on the desired areas.
Le revêtement en émail sélectionné est également un revêtement combinant les caractéristiques 3 à 5) précitées. Ainsi l'émail (et le revêtement en émail) comprend notamment des pigments :  The selected enamel coating is also a coating combining the above mentioned characteristics 3 to 5). Thus enamel (and enamel coating) includes in particular pigments:
- sous forme de particules de mica revêtues (ou enrobées) par des oxydes métalliques ou combinaisons d’oxydes métalliques, en particulier des particules de mica enrobées par Ti02 ou enrobées par Fe203, ou enrobées par une combinaison Ti02 - Fe203 ou par une combinaison Ti02 - Sn02 ou par une combinaison Ti02 - Fe203 - Sn02; et/ou in the form of mica particles coated (or coated) with metal oxides or combinations of metal oxides, in particular particles of mica coated with Ti0 2 or coated with Fe 2 O 3 , or coated with a TiO 2 - Fe combination 2 0 3 or a combination Ti0 2 - Sn0 2 or a combination Ti0 2 - Fe 2 0 3 - Sn0 2; and or
- sous forme de particules d’oxyde d’aluminium (Al203) revêtues par des oxydes métalliques ou combinaisons d'oxydes métalliques, en particulier des particules d'AI203 enrobées par une combinaison Ti02 - Sn02 ou par une combinaison Ti02 - Sn02 - Si02; et/ou in the form of particles of aluminum oxide (Al 2 O 3 ) coated with metal oxides or combinations of metal oxides, in particular particles of Al 2 O 3 coated with a TiO 2 -Si 2 2 combination or with a combination Ti0 2 - Sn0 2 - Si0 2 ; and or
- sous forme de particules de silice revêtues par des oxydes métalliques ou combinaisons d’oxydes métalliques, en particulier des particules de silice enrobées par une combinaison Ti02 - Sn02 ou par une combinaison Fe203 - Zr02; - in the form of silica particles coated with metal oxides or combinations of metal oxides, particularly silica particles coated with a combination of Ti0 2 - Sn0 2 or a combination Fe 2 0 3 - Zr0 2;
- voire tout autre pigment "à effet" (c'est-à-dire pigment(s) à effet métallique aussi appelés pigment(s) interférentiel(s) ou pigment(s) nacré(s) ou perlé(s), ces pigments conduisant à une réflexion élevée de la lumière incidente, du fait qu'ils ne sont pas absorbants mais réfléchissants contrairement aux pigments classiques), c'est-à-dire en d'autres termes que le revêtement en émail (respectivement l'émail) est un revêtement en émail (respectivement un émail) à aspect dit "métallisé".  - even any other "effect" pigment (ie metallic effect pigment (s) also called interferential pigment (s) or pearlescent (s) or pearlescent (s) pigment (s)) pigments leading to a high reflection of the incident light, because they are not absorbent but reflective unlike conventional pigments), that is to say in other words that the enamel coating (respectively enamel ) is an enamel coating (respectively an enamel) aspect said "metallized".
Les pigments précités sont par exemple commercialisés, entre autres, par la société Merck sous les références Iriodin 120, 300, 500, 520, 9602 ou Pyrisma T40-23, T81 -23, M40-58, ou Colorstream F10-00, T10-01 ou T10-02, ou Xi rallie F60-25, T60-23 ou T60-10  The aforementioned pigments are for example sold, inter alia, by Merck under the references Iriodin 120, 300, 500, 520, 9602 or Pyrisma T40-23, T81 -23, M40-58, or Colorstream F10-00, T10- 01 or T10-02, where Xi joins F60-25, T60-23 or T60-10
De préférence, le taux de pigments choisis dans les pigments sous forme de particules de mica et/ou d’oxyde d’aluminium et/ou de silice revêtues par des oxydes métalliques ou combinaisons d'oxydes métalliques dans la composition d'émail sous forme sèche est de 10 à 30% en poids de ladite composition, la composition d'émail étant essentiellement constituée, en sec, d'une fritte de verre à laquelle on rajoute le cas échéant des pigments, un médium étant ensuite ajouté pour permettre l'application du revêtement, ce médium étant éliminé ensuite lors du traitement thermique permettant de réaliser le revêtement final (traitement thermique de céramisation de la plaque ou traitement thermique en reprise). Preferably, the proportion of pigments chosen in the form pigments of mica particles and / or aluminum oxide and / or silica coated with metal oxides or combinations of metal oxides in the enamel composition in dry form is from 10 to 30% by weight of said composition, the enamel composition being essentially constituted, in dry form, of a glass frit to which, if appropriate, pigments are added, a medium is then added to allow the coating to be applied, this medium being subsequently removed during the heat treatment to achieve the final coating (heat treatment ceramization of the plate or heat treatment in recovery).
A noter que le terme particules englobe aussi les termes paillettes ou plaquettes selon les formes habituelles des pigments concernés.  It should be noted that the term particles also includes the terms flake or platelet according to the usual forms of the pigments concerned.
De préférence selon l'invention, l'émail utilisé comprend en outre avantageusement (dans la composition en sec incluant la fritte et les pigments) une proportion de B203 inférieure ou égale à 25%, notamment inférieure à 20%, et préférentiellement inférieure à 15%, notamment inférieure à 10%, voire inférieure à 6% en poids. Preferably according to the invention, the enamel used also advantageously comprises (in the dry composition including the frit and the pigments) a proportion of B 2 0 3 less than or equal to 25%, especially less than 20%, and preferably less than 15%, especially less than 10%, or even less than 6% by weight.
En combinaison avec le choix d'un émail ou d'un revêtement en émail présentant les pigments précités, le revêtement en émail doit également présenter une rugosité Ra supérieure ou égale à 0.4 pm et une rugosité Rt supérieure à 4 pm (rugosités de l'émail déposé en aplat (avec un taux de recouvrement de 100%))  In combination with the choice of an enamel or an enamel coating having the aforementioned pigments, the enamel coating must also have a roughness Ra greater than or equal to 0.4 μm and a roughness Rt greater than 4 μm (roughness of the enamel deposited in flat (with a recovery rate of 100%))
La rugosité Ra est un paramètre de rugosité bien connu et est la rugosité moyenne arithmétique du profil (moyenne arithmétique des valeurs absolues des écarts entre les pics et les creux successifs), définie sur une longueur d'évaluation, et la rugosité Rt est la hauteur totale du profil entre la vallée la plus profonde et le pic le plus haut sur la longueur d'évaluation. La rugosité Ra et la rugosité Rt telles que considérées ici sont mesurées selon la norme ISO 4287 sur une longueur d'évaluation de 4 mm à l'aide d'un palpeur de référence SJ401 de la société Mitutoyo.  The roughness Ra is a well-known roughness parameter and is the arithmetic average roughness of the profile (arithmetic mean of the absolute values of the differences between the successive peaks and troughs), defined over an evaluation length, and the roughness Rt is the height. total of the profile between the deepest valley and the highest peak over the evaluation length. The roughness Ra and the roughness Rt as considered here are measured according to the ISO 4287 standard over a measurement length of 4 mm using a reference probe SJ401 from Mitutoyo.
De préférence, la rugosité Ra est de 0.4 à 0.7 pm (ou comprise entre 0.4 et 07 pm, bornes incluses), et de préférence, la rugosité Rt est comprise entre 4 et 8 pm.  Preferably, the roughness Ra is 0.4 to 0.7 μm (or between 0.4 and 07 μm, limits included), and preferably, the roughness Rt is between 4 and 8 μm.
Cette rugosité de l'émail se substitue le cas échéant à toute microrugosité initiale à la surface du substrat. Il peut être observé que le revêtement en émail sélectionné selon l'invention est dénué de caractère hydrophobe (l'angle de contact de l'eau sur ce revêtement étant inférieur à 90°) et dénué de caractère oléophobe (l'angle de contact du diiodométhane sur ce revêtement étant inférieur à 90°). This roughness of the enamel is substituted where appropriate for any initial microroughness at the surface of the substrate. It can be observed that the enamel coating selected according to the invention is devoid of hydrophobic character (the contact angle of the water on this coating being less than 90 °) and devoid of oleophobic character (the contact angle of the diiodomethane on this coating being less than 90 °).
Il peut être observé également que la zone pour laquelle l'effet anti-trace de doigts est recherché est revêtue du revêtement en émail sélectionné, sans qu'il soit besoin d'effectuer aucun traitement préalable (par exemple une trempe ou l'application d'un primaire), pour obtenir à la fois une bonne adhérence du revêtement et l'effet recherché.  It can also be observed that the area for which the anti-fingerprinting effect is desired is coated with the selected enamel coating, without the need for any prior treatment (eg quenching or application of the coating). a primer), to obtain both a good adhesion of the coating and the desired effect.
Le substrat selon l'invention peut le cas échéant être revêtu d'autres revêtements ou couches à effet fonctionnel et/ou décoratif, déposés en particulier dans d'autres zones que les zones revêtues de l'émail anti-traces de doigts, tels que des motifs habituels à base d'autres émaux ou une couche de peinture opacifiante sur une autre partie du substrat, ou une ou des couches fonctionnelle de type couche anti-rayure, couche anti-débordement, couche opacifiante, etc.  The substrate according to the invention may optionally be coated with other coatings or layers with functional and / or decorative effect, deposited in particular in other areas than the areas coated with anti-fingerprint enamel, such as conventional patterns based on other enamels or a layer of opacifying paint on another part of the substrate, or one or more functional layers of the anti-scratch layer, anti-overflow layer, opacifying layer, etc.
L’article selon l’invention peut en outre comprendre, associés ou combinés au substrat, une ou plusieurs sources lumineuses et/ou un ou plusieurs éléments de chauffage (ou éléments chauffants, tels qu’un ou plusieurs éléments radiants ou halogènes et/ou un ou plusieurs brûleurs à gaz atmosphérique et/ou un ou plusieurs moyens de chauffage par induction), généralement placés en face inférieure du substrat. La ou les sources peuvent être intégrées dans ou couplées à une ou des structure(s) de type afficheur(s), à un bandeau de commande électronique à touches sensitives et affichage digital, etc, et sont avantageusement formées par des diodes électroluminescentes, plus ou moins espacées, éventuellement associées à un ou plusieurs guides optiques.  The article according to the invention may further comprise, associated with or combined with the substrate, one or more light sources and / or one or more heating elements (or heating elements, such as one or more radiant or halogen elements and / or one or more atmospheric gas burners and / or one or more induction heating means), generally placed on the underside of the substrate. The source or sources may be integrated in or coupled to one or more structure (s) display type (s), an electronic control panel with sensitive keys and digital display, etc., and are advantageously formed by light-emitting diodes, plus or less spaced, possibly associated with one or more optical guides.
L’article peut également être muni de (ou associé avec des) élément(s) fonctionnel(s) supplémentaire(s) (cadre, connecteur(s), câble(s), élément(s) de commande), etc.  The article may also be provided with (or associated with) additional functional element (s) (frame, connector (s), cable (s), control element (s), etc.
L’invention a ainsi permis la mise au point d'un produit vitrocéramique à surface revêtue aux endroits souhaités (par exemple sur les zones plus exposées aux manipulations ou salissures, telles que des zones de commande ou d'affichage ou des zones de chauffage, etc) d'une composition sélectionnée permettant d'obtenir un effet anti-traces de doigts, tout en respectant les contraintes, notamment thermiques et mécaniques, propres aux utilisations desdits produits, et en conservant des produits en vitrocéramique pérennes et d'entretien facile. La solution selon la présente invention permet ainsi d'obtenir de façon simple et économique, sans opération complexe (e revêtement pouvant être déposé par des techniques de dépôt traditionnelles pour émaux, telles que la sérigraphie, comme indiqué ultérieurement), de façon durable et avec une grande flexibilité, des zones à effet anti-traces de doigts dans toute zone souhaitée du produit, et ceci même lorsque ces zones sont destinées à être soumises à des températures élevées. L’article selon l'invention présente notamment une bonne tenue thermique compatible avec l’utilisation de divers types de chauffages, et ne pose pas de problèmes d'entretien, de rayures ou d’abrasion comme indiqué précédemment. Le produit selon l'invention ne subit en particulier pas de dégradation thermique à des températures supérieures ou égales à 400 °C pouvant être atteintes notamment dans des applications telles que l'utilisation en tant que plaques de cuisson. The invention has thus made it possible to develop a surface-coated glass-ceramic product at the desired locations (for example on the areas more exposed to handling or soiling, such as control or display zones or heating zones, etc.) of a selected composition to obtain an anti-fingerprint effect, while respecting the constraints, including thermal and mechanical, specific to the uses of said products, and maintaining glass ceramic products perennial and easy maintenance. The solution according to the present invention thus makes it possible to obtain in a simple and economical manner, without complex operation (coating that can be deposited by traditional enamel deposition techniques, such as screen printing, as indicated later), in a sustainable way and with great flexibility, zones with anti-fingerprint effect in any desired area of the product, even when these areas are intended to be subjected to high temperatures. The article according to the invention has in particular a good thermal resistance compatible with the use of various types of heating, and does not pose maintenance problems, scratches or abrasion as indicated above. In particular, the product according to the invention is not subject to thermal degradation at temperatures greater than or equal to 400 ° C. which can be attained in particular in applications such as the use as hotplates.
L'article selon l'invention présente également une bonne adhérence du revêtement au substrat vitrocéramique (sans avoir nécessité de traitement préalable du support et/ou l’utilisation d’un promoteur d’adhésion, d'une couche d’accrochage ou d'un primaire). Ce revêtement ne montre en particulier aucune délamination après un choc thermique (par exemple aux environs de 600 °C), et résiste à de hautes températures. Le revêtement présente également une bonne résistance à la rayure. Le substrat revêtu peut être facilement nettoyé et présente une durée de vie élevée.  The article according to the invention also has a good adhesion of the coating to the glass-ceramic substrate (without the need for prior treatment of the support and / or the use of an adhesion promoter, an adhesion layer or an adhesion promoter. a primary). This coating shows in particular no delamination after a thermal shock (for example around 600 ° C), and withstands high temperatures. The coating also has good scratch resistance. The coated substrate can be easily cleaned and has a long life.
La présente invention concerne également un procédé de fabrication de l'article vitrocéramique selon l'invention, à partir d'un substrat en verre (le substrat en verre-mère devant former le substrat vitrocéramique par céramisation) dans lequel on applique, sur au moins une partie dudit substrat en verre (verre-mère), avant céramisation, au moins un revêtement en un émail tel que sélectionné selon l'invention (remplissant les critères précédemment indiqués dans la définition de l'article selon l'invention), puis on effectue la céramisation du substrat en verre (substrat en verre-mère) ainsi revêtu, cette céramisation permettant alors d'obtenir un substrat vitrocéramique au moins en partie (en au moins une zone) revêtu d’au moins un revêtement anti traces de doigts comme précédemment décrit. The present invention also relates to a method of manufacturing the glass-ceramic article according to the invention, from a glass substrate (the mother-glass substrate for forming the ceramic-ceramic substrate by ceramization) in which at least one a part of said glass substrate (parent glass), before ceramization, at least one enamel coating as selected according to the invention (fulfilling the criteria previously indicated in the definition of the article according to the invention), then performs the ceramization of the glass substrate (mother-glass substrate) thus coated, this ceramization thus making it possible to obtain a glass-ceramic substrate at least in part (in at least one zone) coated with at least one anti-trace coating of fingers as previously described.
Alternativement le revêtement en émail peut éventuellement être déposé sur le substrat déjà céramisé et cuit en reprise, par exemple dans une arche de recuisson. Dans ce cas, on applique au moins un revêtement en un émail tel que sélectionné selon l'invention sur au moins une partie d'un substrat en vitrocéramique puis on cuit l'émail par exemple à une température de l'ordre de 850 °C.  Alternatively the enamel coating may optionally be deposited on the substrate already ceramized and cooked in recovery, for example in an annealing arch. In this case, at least one coating of an enamel as selected according to the invention is applied to at least a portion of a glass-ceramic substrate and the enamel is then baked, for example at a temperature of the order of 850 ° C. .
Pour mémoire, la fabrication des plaques vitrocéramiques s’opère généralement comme suit : dans un four de fusion, on fond le verre de composition choisie pour former la vitrocéramique, puis on lamine le verre fondu en un ruban ou feuille standard en faisant passer le verre fondu entre des rouleaux de laminage et on découpe le ruban de verre aux dimensions souhaitées. Les plaques ainsi découpées sont ensuite céramisées de manière connue en soi, la céramisation consistant à cuire les plaques suivant le profil thermique choisi pour transformer le verre en le matériau polycristallin appelé « vitrocéramique » dont le coefficient de dilatation est nul ou quasi-nul et qui résiste à un choc thermique pouvant aller en particulier jusqu’à 700 °C. La céramisation comprend généralement une étape d’élévation progressive de la température jusqu’au domaine de nucléation, une étape de traversée en plusieurs minutes (par exemple entre 5 et 60 minutes) de l’intervalle de nucléation (par exemple entre 650 et 830 °C), une nouvelle élévation de la température pour permettre la croissance des cristaux (céramisation dans un intervalle allant par exemple de 850 à 1000°C, avec maintien de la température du palier de céramisation pendant plusieurs minutes (par exemple de 5 à 30 minutes) puis un refroidissement rapide jusqu’à la température ambiante.  As a reminder, the manufacture of the glass-ceramic plates generally takes place as follows: in a melting furnace, the glass of the chosen composition is melted to form the glass-ceramic, and then the molten glass is rolled into a standard ribbon or sheet by passing the glass melted between rolling rolls and cut the glass ribbon to the desired dimensions. The plates thus cut are then ceramized in a manner known per se, the ceramization of baking the plates according to the thermal profile chosen to transform the glass into the polycrystalline material called "glass-ceramic" whose expansion coefficient is zero or almost zero and which withstands a thermal shock that can be up to 700 ° C in particular. The ceramization generally comprises a step of gradual raising of the temperature to the nucleation range, a step of crossing in several minutes (for example between 5 and 60 minutes) of the nucleation interval (for example between 650 and 830 ° C. C), a new rise in temperature to allow the crystals to grow (ceramizing in a range of, for example, 850 to 1000 ° C., with maintaining the temperature of the ceramic bearing for several minutes (for example from 5 to 30 minutes ) then rapid cooling to room temperature.
L'application ou dépôt, avant céramisation, du revêtement en émail sur verre-mère peut s’effectuer par toute technique appropriée et rapide pour le dépôt d'émaux, l'application se faisant de préférence par sérigraphie ou jet d'émail.  The application or deposition, before ceramization, of enamel coating on parent glass can be carried out by any suitable and fast technique for the deposition of enamels, the application being preferably by screen printing or enamel spray.
Le substrat revêtu est ensuite soumis au traitement thermique de céramisation (à des températures pouvant atteindre entre 850 et 1000°C) pendant une durée généralement de plusieurs dizaines de minutes, comme indiqué précédemment. Le cas échéant, le procédé comprend également une opération de découpe (généralement avant céramisation), par exemple par jet d'eau, traçage mécanique à la molette, etc. suivie par une opération de façonnage (meulage, biseautage,...). The coated substrate is then subjected to the ceramizing heat treatment (at temperatures of up to 850 ° C. to 1000 ° C.) for a period generally of several tens of minutes, as indicated previously. If necessary, the method also comprises a cutting operation (generally before ceramization), for example by water jet, mechanical tracing with the wheel, etc. followed by a shaping operation (grinding, beveling, ...).
Les exemples suivants illustrent sans la limiter la présente invention.  The following examples illustrate without limiting the present invention.
Dans ces exemples, on a utilisé des plaquettes de 10 cm par 10 cm du même substrat formé d'une vitrocéramique noire translucide, commercialisée sous la référence KeraBlack+ par la société Eurokera, ces plaquettes présentant une face supérieure lisse et une face inférieure munie de picots et une épaisseur de 4 mm, ces plaquettes étant revêtues suivant les exemples de différents revêtements en émail à comparer, les revêtements en émail ayant été déposés par sérigraphie sur le substrat en verre-mère devant donner la vitrocéramique noire translucide, puis ledit substrat en verre-mère ayant été céramisé pour donner la vitrocéramique.  In these examples, 10 cm by 10 cm wafers of the same substrate formed of a translucent black glass-ceramic, marketed under the reference KeraBlack + by Eurokera, were used, these wafers having a smooth upper face and a lower face provided with pins. and a thickness of 4 mm, these wafers being coated according to the examples of different enamel coatings to be compared, the enamel coatings having been deposited by screen printing on the mother-glass substrate to give the translucent black glass-ceramic, then said glass substrate -mother having been ceramized to give the vitroceramic.
Plusieurs empreintes ont ensuite été effectuées sur les zones revêtues des émaux et sur la vitrocéramique comme référence. La notation suivante a été utilisée, le chiffre étant d'autant plus élevé que la trace devient plus visible, la note la plus élevée (4) étant celle de la référence (vitrocéramique non revêtue) : 0 correspondait à l'absence de trace de doigts visible, 1 correspondait à une trace que l'on devine à peine, 2 correspondait à une trace que l'on devine en observant plus attentivement, 3 correspondait à une trace visible sans effort immédiat mais moins prononcée que celle sur la vitrocéramique, et 4 correspondait à une trace de doigts identique à celle sur la vitrocéramique. Ces notes ont été attribuées pour chaque comparaison par un panel de 5 personnes, dans les mêmes conditions à chaque évaluation, par série d’une dizaine d’échantillons par émail, sous un angle de 60° par rapport à la normale, le jour même de l'application du doigt (sauf mention contraire), les notes attribuées par les différentes personnes étant ensuite comparées et moyennées.  Several impressions were then made on the enamelled areas and on the glass ceramic as a reference. The following notation was used, the figure being all the higher as the trace becomes more visible, the highest note (4) being that of the reference (uncoated glass-ceramic): 0 corresponded to the absence of trace of visible finger, 1 corresponded to a trace that we can hardly guess, 2 corresponded to a trace that we guess by observing more carefully, 3 corresponded to a visible trace without immediate effort but less pronounced than that on the glass-ceramic, and 4 corresponded to a trace of fingers identical to that on the glass-ceramic. These scores were assigned for each comparison by a panel of 5 people, under the same conditions for each evaluation, by a series of ten samples per enamel, at an angle of 60 ° to the normal, the same day. the application of the finger (unless otherwise stated), the scores assigned by the different people are then compared and averaged.
Pour les premières comparaisons, un émail de composition choisie dans la composition suivante a été utilisé: Al203 : 12.5 - 13.4%; U20 + Na20 + K20: 3.8 - 5.9%; B203 : 18 - 19.8%, CaO + BaO + MgO : 1.7 - 2.3%, Zr02 : 1.4 - 2%, mélange de particules de mica revêtues par Ti02, de particules de mica revêtues par Fe203, et de particules de mica revêtues par une combinaison Ti02 - Fe203 - Sn02 (pigments avec effet métallisé): 30%, le complément (à 100% en poids) étant de la silice Si02, cet émail présentant une brillance (en aplat) de 26.3, une rugosité Ra de 0.5 pm, et une rugosité Rt de 4.5 pm, et étant testé avec différents taux de recouvrement en revêtement de 2.5 pm d'épaisseur. Les taux de recouvrement testés étaient respectivement de : 10%, 36%, 42%, 46%, 48%, 58%, 59%, 60%, 72%, 74%, 78%, 80% et 100%. Des notes (moyennes) inférieures à 1 jusqu'à 0 ont été données pour les taux 42 à 80%, les notes les plus basses et avec la plus faible dispersion étant observées pour les taux allant de 55 à 78%, avec un optimum à 60%. For the first comparisons, an enamel composition selected from the following composition was used: Al 2 O 3 : 12.5 - 13.4%; U 2 0 + Na 2 O + K 2 O: 3.8 - 5.9%; B 2 O 3 : 18 - 19.8%, CaO + BaO + MgO: 1.7 - 2.3%, ZrO 2 : 1.4 - 2%, mixture of TiO 2 -coated mica particles, Fe 2 0 3 -coated mica particles, and mica particles coated by a combination Ti0 2 - Fe 2 O 3 - SnO 2 (pigments with metallized effect): 30%, the balance (at 100% by weight) being silica Si0 2 , this enamel having a gloss (in flat) of 26.3, a roughness Ra 0.5 μm, and roughness Rt 4.5 μm, and being tested with different coating coverage rates of 2.5 μm thick. The recovery rates tested were respectively: 10%, 36%, 42%, 46%, 48%, 58%, 59%, 60%, 72%, 74%, 78%, 80% and 100%. Ratings (averages) of less than 1 to 0 were given for 42-80%, with the lowest and lowest scores being observed for rates ranging from 55-78%, with an optimum at 60%.
L'émail a ensuite été comparé, à la même épaisseur (2.5 pm) et avec un taux de recouvrement de 80% pour chaque émail testé, avec un émail métallisé non conforme à l'invention présentant une brillance (en aplat) de 66, une rugosité Ra de 0.2 pm, et une rugosité Rt de 2.8 pm, de composition choisie dans la composition suivante : Al203 : 15.2 - 16.2%; Li20 + Na20 + K20: 4.6 - 7.1 %; B203 : 21.8 - 24.1 %, CaO + BaO + MgO : 2 - 2.8%, Zr02 : 1.7 - 2.5%, pigments Xirallic F60-25 commercialisés par la société Merck (pigments avec effet métallisé) :15 %, le complément (à 100% en poids) étant de la silice Si02. La note moyenne obtenue était de l'ordre de 2. The enamel was then compared, at the same thickness (2.5 μm) and with a recovery rate of 80% for each enamel tested, with a metallized enamel not according to the invention having a gloss (in flat) of 66, a roughness Ra of 0.2 μm, and a roughness Rt of 2.8 μm, of composition chosen from the following composition: Al 2 O 3 : 15.2 - 16.2%; Li 2 O + Na 2 O + K 2 O: 4.6 - 7.1%; B 2 O 3 : 21.8 - 24.1%, CaO + BaO + MgO: 2 - 2.8%, ZrO 2 : 1.7 - 2.5%, Xirallic F60-25 pigments marketed by Merck (pigments with a metallic effect): 15%, complement (at 100% by weight) being silica Si0 2 . The average score obtained was of the order of 2.
L'émail a ensuite été comparé, à un taux de couverture de 80% et la même épaisseur que précédemment, avec un émail non métallisé non conforme à l'invention présentant une brillance (en aplat) de 15.7, une rugosité Ra de 0.3 pm, et une rugosité Rt de 4.4 pm, de composition choisie dans la composition suivante : Al203 : 5.4 - 6.5%; Li20 + Na20 + K20: 4.8 - 7.4%; B203 : 3.6 - 5.4%, CaO + BaO + MgO : 17 - 20.3%, Zr02 : 1 - 1.7%, ZnO : 5.9 - 7.4%, mélange de particules de Ti02, de Fe203, d'oxydes Fe-Cr-Co-Ni, et d'oxydes Al- Co (pigments sans effet métallisé) : 15%, le complément (à 100% en poids) étant de la silice Si02. La note moyenne obtenue était de l'ordre de 2. The enamel was then compared, at a coverage ratio of 80% and the same thickness as above, with a non-metallized enamel not according to the invention having a brightness (in flat) of 15.7, a roughness Ra of 0.3 pm , and a roughness Rt of 4.4 μm, of composition selected from the following composition: Al 2 O 3 : 5.4 - 6.5%; Li 2 O + Na 2 O + K 2 O: 4.8 - 7.4%; B 2 O 3 : 3.6 - 5.4%, CaO + BaO + MgO: 17 - 20.3%, ZrO 2 : 1 - 1.7%, ZnO: 5.9 - 7.4%, mixture of TiO 2 , Fe 2 O 3 , Fe-Cr-Co-Ni oxides, and Al-Co oxides (pigments with no metallised effect): 15%, the balance (at 100% by weight) being silica Si0 2 . The average score obtained was of the order of 2.
L'émail a ensuite été comparé, à un taux de couverture de 80% et la même épaisseur que précédemment, avec un autre émail métallisé selon l'invention présentant une brillance (en aplat) de 38.4, une rugosité Ra de 0.6 pm, et une rugosité Rt de 4.6 pm, de composition choisie dans la composition suivante : Al203 : 12.5 - 13.4%; Li20 + Na20 + K20: 3.8 - 5.9%; B203 : 18.0 - 19.8%, CaO + BaO + MgO: 1.7 - 2.3%, Zr02 : 1.4 - 2%, pigments Colorstream F10-00 commercialisés par la société Merck (pigments avec effet métallisé) : 30%, le complément (à 100% en poids) étant de la silice Si02. La note moyenne obtenue était de l'ordre de 0. The enamel was then compared, at a coverage ratio of 80% and the same thickness as before, with another metallized enamel according to the invention having a brightness (in flat) of 38.4, a roughness Ra of 0.6 μm, and a roughness Rt of 4.6 μm, of composition chosen from the following composition: Al 2 O 3 : 12.5 - 13.4%; Li 2 O + Na 2 O + K 2 O: 3.8 - 5.9%; B 2 O 3 : 18.0 - 19.8%, CaO + BaO + MgO: 1.7 - 2.3%, ZrO 2 : 1.4 - 2%, Colorstream F10-00 pigments marketed by Merck (pigments with metallic effect): 30%, the balance (at 100% by weight) being SiO 2 silica. The average score obtained was of the order of 0.
L'émail a ensuite été comparé, à un taux de couverture de 80% et la même épaisseur que précédemment, avec un autre émail métallisé selon l'invention présentant une brillance (en aplat) de 37.6, une rugosité Ra de 0.4 pm, et une rugosité Rt de 6 pm, de composition choisie dans la composition suivante : Al203 : 14.3 - 15.3%; Li20 + Na20 + K20: 4.3 - 6.7%; B203 : 20.5 - 22.7%, CaO + BaO + MgO : 1.9 - 2.6%, Zr02 : 1.6 - 2.3%, mélange de particules de mica revêtues par Ti02, de particules de mica revêtues par Fe203, et de particules de mica revêtues par une combinaison Ti02 - Fe203 - Sn02 (pigments avec effet métallisé) : 20%, le complément (à 100% en poids) étant de la silice Si02. La note moyenne obtenue était de l'ordre de 0. The enamel was then compared, at a coverage ratio of 80% and the same thickness as above, with another metallized enamel according to the invention having a brightness (in flat) of 37.6, a roughness Ra of 0.4 μm, and a roughness Rt of 6 μm, of composition chosen from the following composition: Al 2 O 3 : 14.3 - 15.3%; Li 2 O + Na 2 O + K 2 O: 4.3 - 6.7%; B 2 0 3 : 20.5 - 22.7%, CaO + BaO + MgO: 1.9 - 2.6%, ZrO 2 : 1.6 - 2.3%, mixture of TiO 2 -coated mica particles, Fe 2 0 3 -coated mica particles, and mica particles coated with a combination TiO 2 - Fe 2 O 3 - SnO 2 (pigments with metallized effect): 20%, the balance (at 100% by weight) being SiO 2 silica. The average score obtained was of the order of 0.
L'émail a ensuite été comparé, à un taux de couverture de 80% et la même épaisseur que précédemment, avec un émail métallisé non conforme à l'invention présentant une brillance(en aplat) de 80, une rugosité Ra de 0.2 pm, et une rugosité Rt de 2.5 pm, de composition choisie dans la composition suivante ! Al203 ! 16.1 - 17.2%; Li20 + Na20 + K20: 4.9 - 7.6%; B203 ! 23.1 - 25.5%, CaO + BaO + MgO : 2.2 - 3%, Zr02 : 1.8 - 2.6%, pigments Xirallic T60- 10 commercialisés par la société Merck (pigments avec effet métallisé): 10%, le complément (à 100% en poids) étant de la silice Si02. La note moyenne obtenue était entre 1 et 2. The enamel was then compared, at a coverage ratio of 80% and the same thickness as above, with a metallized enamel not according to the invention having a gloss (in flat) of 80, a roughness Ra of 0.2 μm, and a roughness Rt of 2.5 μm, of composition chosen from the following composition! Al 2 0 3! 16.1 - 17.2%; Li 2 O + Na 2 O + K 2 O: 4.9 - 7.6%; B 2 0 3! 23.1 - 25.5%, CaO + BaO + MgO: 2.2 - 3%, Zr0 2 : 1.8 - 2.6%, Xirallic T60-10 pigments marketed by Merck (pigments with metallic effect): 10%, the complement (at 100% by weight) being SiO 2 silica. The average score obtained was between 1 and 2.
Les revêtements en émail remplissant les conditions selon l'invention ont montré des propriétés anti-traces de doigts par opposition aux autres revêtements ne remplissant pas ces conditions. Par ailleurs, il n'a pas été noté de différences significatives sur la notation lorsque les tests ont été effectués 7 ou 14 jours après l'application des doigts.  The enamel coatings fulfilling the conditions of the invention have shown anti-fingerprint properties as opposed to other coatings not fulfilling these conditions. In addition, there were no significant differences in scoring when the tests were performed 7 or 14 days after the application of the fingers.
En outre, le substrat et les revêtements obtenus n’ont montré aucune délamination après un choc thermique de 620 °C et n’ont montré aucune dégradation d’aspect après 100 h à 580°C.  In addition, the resulting substrate and coatings showed no delamination after thermal shock of 620 ° C and showed no appearance degradation after 100 h at 580 ° C.
Les articles selon l’invention peuvent notamment être utilisées avec avantage pour réaliser une nouvelle gamme de plaques de cuisson pour cuisinières ou tables de cuisson ou une nouvelle gamme de tables de travail, consoles, crédences, ilôts centraux, etc.  The articles according to the invention can in particular be used with advantage to achieve a new range of cooking plates for stoves or hobs or a new range of work tables, consoles, credence, central islands, etc..

Claims

REVENDICATIONS
1. Article vitrocéramique, comprenant au moins un substrat, tel qu’une plaque, en vitrocéramique, ledit substrat étant revêtu en au moins une zone d’au moins un revêtement en émail tel que :  A glass-ceramic article, comprising at least one substrate, such as a glass-ceramic plate, said substrate being coated in at least one zone with at least one enamel coating such that:
1 ) ledit émail présente une brillance à 60° inférieure à 40, 1) said enamel has a gloss at 60 ° less than 40,
2) le taux de recouvrement dudit émail dans ladite zone revêtue dudit revêtement est de 40 à 80%,  2) the recovery rate of said enamel in said zone coated with said coating is 40 to 80%,
3) ledit émail comprend des pigments sous forme de particules de mica et/ou d’oxyde d’aluminium et/ou de silice revêtues par des oxydes métalliques ou combinaisons d'oxydes métalliques,  3) said enamel comprises pigments in the form of mica particles and / or aluminum oxide and / or silica coated with metal oxides or combinations of metal oxides,
4) ledit émail présente une rugosité Ra supérieure ou égale à 0.4 miti,  4) said enamel has a roughness Ra greater than or equal to 0.4 miti,
5) ledit émail présente une rugosité Rt supérieure à 4 pm.  5) said enamel has a roughness Rt greater than 4 pm.
2. Article vitrocéramique selon la revendication 1 , caractérisé en ce que ledit substrat est à base d'une vitrocéramique ayant de manière intrinsèque une transmission lumineuse TL sous illuminant D65 inférieure à 40% et une transmission optique entre 0.5 et 3% pour une longueur d’onde de 625 nm.  2. Glass ceramic article according to claim 1, characterized in that said substrate is based on a glass-ceramic having intrinsically TL light transmittance under illuminant D65 of less than 40% and optical transmission between 0.5 and 3% for a length of 60 ° C. wave of 625 nm.
3. Article vitrocéramique selon l'une des revendications 1 à 2, caractérisé en ce que la zone revêtue dudit revêtement en émail est d'au moins 5 cm par 5 cm, en particulier d'au moins 10 cm par 10 cm, notamment d'au moins 20 cm par 20 cm.  3. Glass ceramic article according to one of claims 1 to 2, characterized in that the area coated with said enamel coating is at least 5 cm by 5 cm, in particular at least 10 cm by 10 cm, especially of at least 20 cm by 20 cm.
4. Article vitrocéramique selon l'une des revendications 1 à 3, caractérisé en ce que le profil ou la trame dudit revêtement en émail est aléatoire et isotrope.  4. Glass ceramic article according to one of claims 1 to 3, characterized in that the profile or the frame of said enamel coating is random and isotropic.
5. Article vitrocéramique selon l'une des revendications 1 à 4, caractérisé en ce que la rugosité Ra est de 0.4 à 0.7 pm.  5. Glass ceramic article according to one of claims 1 to 4, characterized in that the roughness Ra is 0.4 to 0.7 pm.
6. Article vitrocéramique selon la revendication 5, caractérisé en ce que la rugosité Rt est comprise entre 4 et 8 pm.  6. Glass ceramic article according to claim 5, characterized in that the roughness Rt is between 4 and 8 pm.
7. Article vitrocéramique selon l'une des revendications 1 à 6, caractérisé en ce que ledit émail comprend une proportion de B203 inférieure ou égale à 25%, notamment inférieure à 20%, préférentiellement inférieure à 15%, notamment inférieure à 10%, voire inférieure à 6% en poids. 7. Article vitroceramic according to one of claims 1 to 6, characterized in that said enamel comprises a proportion of B 2 0 3 less than or equal to 25%, especially less than 20%, preferably less than 15%, especially less than 20%. 10%, or even less than 6% by weight.
8. Article vitrocéramique selon l'une des revendications 1 à 7, caractérisé en ce que l'épaisseur dudit revêtement est comprise entre 1.5 pm et 3.5 pm. 8. Glass ceramic article according to one of claims 1 to 7, characterized in that the thickness of said coating is between 1.5 pm and 3.5 pm.
9. Article vitrocéramique selon l'une des revendications 1 à 8, caractérisé en ce que ledit revêtement en émail est dénué de caractère hydrophobe et dénué de caractère oléophobe. 9. Glass ceramic article according to one of claims 1 to 8, characterized in that said enamel coating is devoid of hydrophobicity and lack of oleophobic character.
10. Article vitrocéramique selon l'une des revendications 1 à 9, caractérisé en ce que ladite zone est revêtue dudit revêtement en émail sans traitement préalable de type trempe ou application de primaire.  10. Article vitroceramic according to one of claims 1 to 9, characterized in that said area is coated with said enamel coating without prior treatment type quenching or primer application.
1 1. Article vitrocéramique selon l'une des revendications 1 à 10, caractérisé en ce que ledit article ou ledit substrat est une plaque de cuisson ou un plan de travail ou un ilôt central ou une console.  1 1. Glass ceramic article according to one of claims 1 to 10, characterized in that said article or said substrate is a cooking plate or a worktop or a central island or a console.
12. Procédé de fabrication d'un article en vitrocéramique selon l'une des revendications 1 à 1 1 , dans lequel on applique au moins un revêtement en émail tel que :  12. A method of manufacturing a glass ceramic article according to one of claims 1 to 1 1, wherein applying at least one enamel coating such as:
1 ) ledit émail présente une brillance à 60° inférieure à 40,  1) said enamel has a gloss at 60 ° less than 40,
2) le taux de recouvrement dudit émail dans ladite zone revêtue dudit revêtement est de 40 à 80%,  2) the recovery rate of said enamel in said zone coated with said coating is 40 to 80%,
3) ledit émail comprend des pigments sous forme de particules de mica et/ou d’oxyde d’aluminium et/ou de silice revêtues par des oxydes métalliques ou combinaisons d'oxydes métalliques,  3) said enamel comprises pigments in the form of mica particles and / or aluminum oxide and / or silica coated with metal oxides or combinations of metal oxides,
4) ledit émail présente une rugosité Ra supérieure ou égale à 0.4 miti,  4) said enamel has a roughness Ra greater than or equal to 0.4 miti,
5) ledit émail présente une rugosité Rt supérieure à 4 miti, 5) said enamel has a roughness Rt greater than 4 miti,
soit sur au moins une partie d'un substrat en verre puis on effectue la céramisation du substrat en verre ainsi revêtu, either on at least a part of a glass substrate and then the ceramization of the glass substrate thus coated is carried out,
soit sur au moins une partie d'un substrat en vitrocéramique puis on cuit l'émail. or on at least a portion of a glass ceramic substrate and then the enamel is cooked.
EP19710060.5A 2018-02-19 2019-02-18 Glass-ceramic article Pending EP3755667A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1851396A FR3078066B1 (en) 2018-02-19 2018-02-19 Glass-ceramic anti-fingerprint article
PCT/FR2019/050362 WO2019158882A1 (en) 2018-02-19 2019-02-18 Glass-ceramic article

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KR (1) KR20200123418A (en)
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DE (1) DE202019003146U1 (en)
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WO (1) WO2019158882A1 (en)

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US20210188701A1 (en) 2021-06-24
JP2021513947A (en) 2021-06-03
FR3078066B1 (en) 2023-03-24
WO2019158882A1 (en) 2019-08-22
CN111670170A (en) 2020-09-15
KR20200123418A (en) 2020-10-29
CN111670170B (en) 2022-09-16
FR3078066A1 (en) 2019-08-23

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