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
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0041—Digital printing on surfaces other than ordinary paper
  • B41M5/007—Digital printing on surfaces other than ordinary paper on glass, ceramic, tiles, concrete, stones, etc.
• • 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
  • C03C10/0018—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 containing SiO2, Al2O3 and monovalent metal oxide as main constituents
  • C03C10/0027—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 containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
• • 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
  • 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
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
  • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
  • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container 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
  • 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
  • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
• • 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
  • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
  • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form 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
  • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
  • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
  • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
  • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
  • C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
• • 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
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/29—Mixtures
• • 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
  • C03C2217/72—Decorative coatings
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • 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 a mineral ink for inkjet printing on mineral substrate. It also relates to a method of manufacturing a vitreous ceramic plate enamelled with such a mineral ink.
• inkjet printing methods are particularly suitable for enameling complex decorations on any type of glass or glass-ceramic support.
• Inkjet printing methods have two main technical variants:
• continuous jet a synchronous technical variant, called “continuous jet", based on the emission of a continuous stream of drops of ink towards the substrate;
• drop-on-demand an asynchronous technical variant, called “drop-on-demand", based on the emission of drops strictly necessary for printing the pattern.
• the size of drops is mainly dependent on the diameter of the orifice and the speed of the jet.
• the ink in which is stored the ink is insufficient to overcome the surface tension.
• the ink then forms a convex or concave meniscus at the reservoir orifice.
• the ink can be extracted from the reservoir either by electrostatic extraction or by mechanical extraction.
• electrostatic extraction an electrostatic field is applied between the orifice of the reservoir and the nozzle so as to deform the convex surface of the meniscus.
• electrostatic force outweighs the capillary force, one or more drops are ejected from the orifice whose size and number depend on the intensity of the applied electrostatic field.
• the pressure in the ink tank is lower than the atmospheric pressure.
• the meniscus formed by the ink at the orifice is concave.
• a rapid variation of the volume of the reservoir for example due to the effect of the displacement, by means of a piezoelectric element, of a membrane constituting a wall of the reservoir causes the expulsion of a drop of ink.
• enamel be prepared in the form of a suspension or a colloidal dispersion of a finely divided mineral solid phase in a generally organic liquid phase.
• This mineral ink must have a density, a viscosity and a surface tension compatible with the methods of ink jet printing. The values of these parameters depend on the devices
• the mineral solid phase of the colloidal suspension comprises
• the size of the grains constituting the mineral solid phase is generally micrometric, or even sub-micrometric.
• the liquid phase mainly comprises a solvent, which is generally organic. The type and amount of solvent partly conditions the rheological properties, the surface tension and the drying behavior of the mineral ink. It is also possible to add a dispersing agent to prevent flocculation and / or sedimentation of the solid phase, as well as a surfactant to adjust the surface tension of the mineral ink.
• the mineral ink After deposition on a mineral substrate, the mineral ink is dried and then subjected to a heat treatment baking.
• the drying of the ink can be carried out at room temperature. The drying time depends on the amount of ink deposited.
• Industrial production lines can sometimes include
• drying devices to reduce the drying time and increase production rates of enamelled parts.
• convection drying devices are generally suitable.
• electromagnetic radiation drying devices such as the air dryer. infrared radiation whose drying temperatures are generally between 100 ° C and 150 ° C.
• an enamel must in particular adhere to the substrate on which it is deposited and withstand the mechanical and chemical stresses it is likely to undergo under the conditions of use of said substrate.
• inkjet printing on inorganic substrates do not make it possible to obtain enamels that are resistant to food products and detergents.
• the combined effects of repeated exposure to these products and heating cycles cause their degradation in the medium or long term.
• these mineral inks are not resistant to high temperatures that the mineral substrates on which they are deposited can undergo during their manufacture. In particular, they do not withstand temperatures above 800 ° C.
• these enamels have the same disadvantages as those described above.
• the present invention solves these problems. It concerns an ink
• mineral for ink jet printing on mineral substrate comprising:
• the mineral ink according to the invention is suitable for depositing by inkjet printing methods on inorganic substrates made of glass, ceramic and glass-ceramic.
• Each primary color can then be formulated using the mineral ink according to the invention by selecting a suitable mineral pigment.
• the production of the gamut can then be carried out, for example and without limitation, by four-color process according to the model of four primary CMYK colors (Cyan, Magenta, Yellow, Black) or by a set of five primary colors according to the five-color model.
• Primary CMYKB (Cyan, Magenta, Yellow, Black, White).
• the mineral ink according to the invention is particularly suitable for primary color models making it possible to obtain different levels of gray.
• the mineral ink according to the invention When used in inkjet printing methods, it advantageously makes it possible to produce enamel patterns with graphic elements that are particularly fine compared with those that can be obtained.
• the mineral ink according to the invention makes it possible to create homogeneous lines with a width of the order of 0.05 mm or homogeneous points of a diameter of the order of 0.05 mm.
• the thickness of the enamel obtained can reach an order of 1 ⁇ m.
• the printing nozzles In the jet printing methods of entry, the printing nozzles
• the weight proportions of the organic solvent, the dispersing agent, the surfactant and the glass frit are adjusted so that the properties of the mineral ink are adapted to the device used for jet printing. ink.
• the surface tension is preferably between 20 and 50 mN.m -1, preferably between 25 and 32 mN m -1 at 25 ° C.
• the mineral ink has shear thinning properties, also called shear thinning, that is to say that the viscosity decreases with the shear rate.
• the viscosity is 20 to 100 mPa.s, preferably 20 to 30 mPa.s at 25 ° C.
• the mass fraction of the sinter of the glass in the mineral ink is
• the organic solvent is preferably 80% by weight of the organic solvent mixture, dispersing agent and mineral ink surfactant.
• the type and amount of organic solvent can be adjusted according to the technical constraints of the inkjet printing device used and the production constraints.
• the enamels that can be obtained after drying and firing a mineral ink according to the invention are particularly resistant to soiling and mechanical stress such as metal friction.
• the temperature at which the mineral ink is dried is preferably between 25 and 150 ° C.
• the temperature of the baking heat treatment is preferably equal to or greater than 650 ° C.
• the temperature will not exceed 1100 ° C.
• the adhesion of the enamel on the mineral substrate may not be optimal. In particular, he may become less resistant to mechanical stresses such as abrasion or friction.
• the organic solvent advantageously represents between 70 to 90% by weight of the sum of the mass percentages of the organic solvent, of the dispersing agent and of the surfactant. Such an amount of solvent is suitable for most inkjet printing devices.
• the organic solvent may be a liquid organic compound at room temperature or a mixture of organic compounds which are liquid at room temperature and comprise at least one alcohol functional group.
• the choice of the organic compound comprising an alcohol functional group depends on the method and / or the device used for inkjet printing. If the deposition of the mineral ink on the mineral substrate is slow, it is advantageous to use a solvent or a solvent mixture with a low saturation vapor pressure under the conditions of pressure and temperature of use of the method and or the device. In other words, under standard temperature and pressure conditions, in order to prevent the solvent or solvent mixture from evaporating too rapidly, its boiling temperature may be higher.
• Nonlimiting examples of organic solvent are: methylene glycol, ethylene glycol, propylene glycol, butylene glycol, methanol, ethanol, propanol, butanol, glycol ethers such as methyl ether, propylene glycol or dipropylene glycol methyl ether.
• the dispersing agent is preferably a copolymer or a mixture of copolymers comprising at least one acid functional group.
• the dispersing agent makes it possible to prevent flocculation and / or sedimentation of the solid phase. It preferably represents 3 to 7%, at most 10%, by weight of the sum of the mass percentages of the organic solvent, of the dispersing agent and of the surfactant.
• the alkylammonium salts of a copolymer comprising one or more acid functional groups are nonlimiting examples of dispersing agent.
• the surfactant is preferably a polyether or a mixture of
• polyethers It preferably represents 0.05% to 0.5% by weight of the sum percentages by weight of the organic solvent, the dispersing agent and the surfactant.
• the mineral ink according to the invention can be used without adding mineral pigment dye.
• the color of the enamel that can be obtained using the mineral ink of the invention when it does not comprise a mineral coloring pigment depends on the color of the mineral substrate on which it is deposited.
• the mineral ink may be any suitable mineral ink. In one embodiment of the invention, the mineral ink may be any suitable mineral ink.
• the mineral pigment makes it possible to adjust the color of the mineral ink and the enamel.
• the inorganic pigment may be based on metal oxides and / or metals or metal alloys that can oxidize during heat treatment of the mineral ink to form the enamel.
• Non-limiting examples of inorganic pigments are titanium oxide, cerium oxide, cobalt oxide, iron oxide, zirconium oxide, manganese oxide, spinels, or the like. doped aluminas.
• the sum of the mass percentages of the glass frit and the mineral pigment advantageously represents 50 to 80% by weight of the mineral ink. Above about 80%, the solid fraction in the mineral ink may become too large and be a source of technical difficulties for an implementation of the ink inkjet ink. Below about 50%, there is a risk that the solid fraction is too dispersed on the substrate after inkjet deposition and that the enamel obtained is not uniformly distributed on the substrate. The color of the enamel obtained may not be uniform.
• the weight percentage of the glass frit represents 65% to 90% by weight of the sum of the mass percentages of the glass frit and the mineral pigment. It has been found experimentally that this value range is an optimal interval to obtain a homogeneous enamel with a satisfactory color. A mass percentage of glass frit of less than 65% may cause poor enamel adhesion to the substrate. The limits indicated are indicative. They depend in particular on the intensity or saturation of the color provided by the mineral pigment and aesthetic effects sought for the enamel.
• the particle size of the mixture of the glass frit and the inorganic pigment is between 1 ⁇ m and 2 ⁇ m.
• the D90 is calculated from the particle size distribution determined by laser granulometry methods according to ISO 13320: 2009. It corresponds to the size of the particles which represent 90% of the total volume of particles of the mixture. In other words, 90% of the particle volume of the mixture of the glass frit and the inorganic pigment consists of particles having a size of between 1 ⁇ m and 2 ⁇ m.
• the mineral ink ink-jet inks on a mineral substrate may contain a binder or a mixture of organic and / or inorganic binder capable of serving to maintain the structure and the shape of the deposits on the mineral substrate until the enamel formation after cooking.
• binders are organic sol-gel binders or acrylic resins.
• the mineral ink does not include such an organic binder and / or inorganic. Indeed, although it is not excluded that it may contain, the mineral ink of the invention does not require such an organic binder and / or inorganic to form an enamel with precise contours and devoid of deformation.
• the invention also relates to a method of manufacturing an ink
• the method includes the following steps:
• a glass frit comprising the following constituents in the weight limits defined below expressed in percentages by weight of the glass frit:
• step (b) adding an organic solvent and a dispersing agent to the mixture obtained in step (b);
• step (c) grinding by recirculation of the mixture obtained in step (c) until the D90 of the particle size distribution of the mixture of the glass frit and the mineral pigment is between 1 and 2 ⁇ m;
• step (d) adding a surfactant to the ground preparation obtained in step (d).
• the glass frit supplied in step (a) is generally obtained according to the glass product manufacturing methods known from the state of the art. In particular, it can be obtained by quenching with water a liquid silicate having the desired composition.
• This liquid silicate is generally formed by the melting at high temperature of a mixture of vitrifiable raw materials.
• the raw materials of the mixture carry the elements used in the composition of the glass frit. They are in such proportions that once the melted mixture the molten silicate has the desired composition for the glass frit.
• the mineral ink according to the invention is particularly suitable for depositing decorative enamels on a glass-ceramic plate.
• a glass-ceramic is a composite material comprising an amorphous phase in which crystalline phases or crystals are dispersed. It is generally obtained by the heat treatment of a glass, called “mother glass”, in order to crystallize, in a controlled manner, crystals in its volume. This treatment by which a glass crystallizes partially is called “ceramization treatment” or simply “ceramization”. The final physicochemical properties of the glass-ceramic depend on the composition of the parent glass and the ceramization treatment.
• the mineral ink of the invention can be deposited by inkjet printing directly on a mother glass plate glass ceramic before the ceramization treatment. It is not necessary that a method of Manufacture of a glass-ceramic plate implementing the mineral ink according to the invention comprises a thermal treatment step specific to the formation of an enamel from the mineral ink. In this sense, the invention also relates to a method of manufacturing an enameled vitroceramic plate comprising the following steps:
• the mineral ink of the invention can also be deposited by inkjet printing directly on a glass ceramic plate before being dried and then fired at a temperature of about 850 ° C for 30 minutes.
• the exposure of the dried mineral ink to temperatures lower than those of the method described above can give the enamel certain special properties, especially those relating to color.
• the inkjet printing method is a method of ink jet printing type drop-on-demand.
• the mineral ink is suitable for a drop-on-demand ink jet printing method by mechanical extraction.
• the mechanical extraction is carried out using a piezoelectric element which, under the effect of electrical impulse, displaces a membrane constituting a wall of the reservoir in which the ink is stored.
• the vitroceramic mother glass plate of the method for manufacturing an enameled glass-ceramic plate is formed in FIG. from a glass of lithium aluminosilicate comprising the following constituents within the weight limits defined below expressed in percentages by weight of the glass:
• the invention also relates to an enamelled ceramic hob
• an enamelled plate can be advantageously used as a cooking surface of a cooking device.
• the enamels formed on its surface from a mineral ink according to the invention are particularly suitable for this type of application. They have a high resistance to metal friction, including metal friction related to the movement of pots, and a chemical and mechanical durability advantageous for repeated exposure to food products and heating cycles.
• the invention also relates to a cooking device comprising an enameled glass-ceramic plate obtained by a method of manufacturing an enameled vitroceramic plate according to one of the embodiments described above.
• the solid fraction of the mineral ink represents 65% of the mass of mineral ink.
• the liquid fraction represents 35% of the mass of mineral ink.
• Frit 1 glass frit The nature and proportions of the constituents of the Frit 1 glass frit are shown in Table 2 below. The proportions are expressed in percentages by weight of the glass frit.
• the mineral ink of Example E1 was manufactured according to the following protocol: a. providing a Frit 1 glass frit obtained by quenching a vitrifiable liquid silicate mixture; b. mixing the glass frit with the mineral pigment;
• step (b) adding the organic solvent and the dispersing agent to the mixture obtained in step (b);
• step (c) wet milling by recirculation of the mixture obtained in step (c) until the D90 of the particle size distribution of the mixture of the glass frit and the mineral pigment is between 1 and 2 ⁇ m;
• step (d) adding the surfactant to the ground preparation obtained in step (d).
• the surface tension was measured using a Kibron EZPi tensiometer according to the methods of Wilhelmy and Noüy-Paddaa. Viscosity was measured by the Brookfield method for two shear rates, 50s-1 and 100s-1.
• the D90 is calculated from the particle size distribution determined by laser granulometry methods according to ISO 13320: 2009.
• the mineral inks were printed to form textures of random sinuous protrusions.
• the thicknesses vary randomly between 2 ⁇ m and 3 ⁇ m and the widths vary randomly between 0.2 mm and 1 mm.
• the projections may be in the form of dots, lines and / or curves.
• Cleaners were evaluated using protocols simulating actual conditions of use of an enamelled plate as a cooking surface in a cooking device or as a work surface.
• the soil resistance was evaluated using the following protocol.
• An enamelled vitroceramic plate is first inserted on a cooking device in which it serves as a cooking surface.
• a mixture of minced meat, egg, milk, sugar, flour, gruyere and tomato paste is placed between a saucepan containing 100 ml of water and the enamelled area of the ceramic hob. The mixture is in contact with the enamelled area.
• the mixture is then heated until the water evaporates of the pan, then again for 10 minutes so that it starts to char and adhere to the ceramic hob.
• the steps of applying the mixture and heating are repeated five times.
• the degree of soiling is evaluated visually according to the following scale of degrees:
• This level of soiling can also be expressed using the following overall index:
• the mineral according to the invention is more resistant to soiling than enamels obtained using mineral inks according to the state of the art.
• the enamel obtained using the mineral ink E1 according to the invention does not stain. Its level of soiling, Ig, is less than 0.1. Little surface of enamel is covered with dirt.
• the enamels obtained using the mineral inks A and B according to the state of the art have a much higher level of soiling. A large part of the surfaces of these enamels are covered with important stains.
• a counterexample, CEx1, glazed vitreous ceramic plate comprising a screen-printed enamel was also manufactured in order to compare the resistance to metal friction of an enamel that can be obtained using a mineral ink. according to the invention and an enamel obtained by screen printing.
• a mineral paste for screen printing comprising an enamel powder and a medium based on pine oil has been prepared.
• the enamel powder is composed of about 70% by weight of a glass frit of the same composition as that used for the mineral ink of the invention, and about 30% by weight of a black mineral pigment based on a mixture of iron oxides, chromium, nickel, silicon and cobalt.
• the D90 of the particle size distribution of the email powder is between 1 ⁇ m and 2 ⁇ m.
• the mineral paste was then deposited on a glass ceramic motherboard using the usual methods of screen printing. Then, the whole was subjected to a heat treatment according to the following cycle:
• Example E2 glazed vitreous ceramic plate comprising an enamel obtained using the mineral ink of the invention was also carried out according to the same method as that used for Example E1.
• a mineral ink identical to that of Example E1 was used except for the mineral pigment which was replaced by the same mineral pigment as that of the enamel paste of the counterexample ECx1.
• vitroceramic is successively rubbed with a back and forth movement using several metal elements such as coins and metal and / or enamelled pans.
• the surface is then cleaned with various detergents specially designed for cleaning the hobs and available commercially.
• the degradation of the enamelled surface is evaluated visually on a scale of 0 to 20; the degree 0 corresponds to a total degradation of the enamelled surface and the degree 20 corresponds to a total absence of degradation. In other words, the higher the degree, the more the enamel is resistant to metal friction.
• the mineral ink according to the invention makes it possible to form enamels having a resistance to metal friction and dirt and an ability to be cleanable greater than those of enamels obtained from mineral inks. or enamel pastes for screen printing of the state of the art.
• the effects of the achievable size of the graphic elements of the patterns on the local phenomena of microcracking of the enamel obtained and the substrate were evaluated for the mineral ink according to the invention.
• Table 7 summarizes the results obtained for three enamelled plates, one with the mineral ink according to the invention, the other two with a mineral ink of the state of the art. These two plates were manufactured according to the same protocol as that used for the previous comparative tests.
• the enamel pattern is a printed image consisting of mottling covering the entire surface of the plates.
• the thicknesses of the pattern are the minimum thicknesses attainable by each of the mineral inks.
• the local microcracking phenomena were evaluated by measuring the breaking strength (MOR) at the levels of the enamel patterns according to a three-point bending method with the enameled face of the plate in extension. Between 10 and 20 samples were measured for each of the plates.
• MOR breaking strength

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• 2018
  • 2018-05-15 FR FR1870565A patent/FR3081164B1/fr not_active Revoked
• 2019
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