EP3515997A1 - Item at least partially coated with at least one layer of luminescent coating - Google Patents

Item at least partially coated with at least one layer of luminescent coating

Info

Publication number
EP3515997A1
EP3515997A1 EP17772681.7A EP17772681A EP3515997A1 EP 3515997 A1 EP3515997 A1 EP 3515997A1 EP 17772681 A EP17772681 A EP 17772681A EP 3515997 A1 EP3515997 A1 EP 3515997A1
Authority
EP
European Patent Office
Prior art keywords
luminescent
phosphorescent
microns
pigment
size
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
EP17772681.7A
Other languages
German (de)
French (fr)
Inventor
Benoît Claude BOUTON
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.)
Stoelzle Masnieres Parfumerie
Original Assignee
Stoelzle Masnieres Parfumerie
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 Stoelzle Masnieres Parfumerie filed Critical Stoelzle Masnieres Parfumerie
Publication of EP3515997A1 publication Critical patent/EP3515997A1/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02Use of particular materials as binders, particle coatings or suspension media therefor
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7706Aluminates
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/22Luminous paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/40Coatings comprising at least one inhomogeneous layer
    • C03C2217/42Coatings comprising at least one inhomogeneous layer consisting of particles only
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/40Coatings comprising at least one inhomogeneous layer
    • C03C2217/43Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/445Organic continuous phases
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/40Coatings comprising at least one inhomogeneous layer
    • C03C2217/43Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/48Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
    • C03C2217/485Pigments

Definitions

  • the present invention relates to the manufacture of various luminescent articles and the articles thus produced.
  • US 2004/0064989 discloses a container for receiving a drink, which is affixed a decorative phosphorescent coating in the form of adhesive phosphorescent film.
  • a decorative phosphorescent coating in the form of adhesive phosphorescent film.
  • CN 104417845 discloses a bottle of wine coated with a coating of a phosphorescent material. A sieve of 250-400 mesh is mentioned, which involves the use of small luminescent pigments.
  • CN 102133977A teaches to screen a phosphorescent composition on a glass.
  • the composition can be deposited by screen printing using a 100 mesh screen, which corresponds to a little less than 150 microns sieve size. No information is given on the thickness of the deposit or the size of the luminescent pigments.
  • the screen must pass the pigments, which must be much smaller particle size. As a result, in this prior application, the size of the luminescent pigments is much less than 150 microns.
  • No. 1,637,963 describes a phosphorescent varnish based on zinc sulphide.
  • the matrix may be colored by introducing a dye such as aniline.
  • the invention aims to further improve the production of luminescent areas on an article, for decoration or other purposes.
  • the invention seeks in particular to have, if desired, a lasting effect of remanence in the case of phosphorescence and to have solutions compatible with the coating application technologies that are lacquering, screen printing, enamelling or dusting.
  • luminescence it is understood in the sense of the present invention any phenomenon of photoluminescence, that is to say, re-emission of light after a light excitation, the photons being emitted following electronic transitions. It includes fluorescence and phosphorescence, the latter corresponding to a residual emission of light by the material after being illuminated.
  • the luminescent element simply by exposing it to a light source, visible or not, as the case may be. It also does not include luminescent elements where excitation is substantially produced by ionizing radiation.
  • the luminescence according to the invention is not produced using a radioactive element, and an article according to the invention does not contain radium.
  • the luminescent producing compound (s) are in the invention purely mineral.
  • the luminescence may be green or yellow in color or in a color other than green and yellow, for example white, blue, orange or violet.
  • the invention relates to an article comprising a substrate at least partially covered by at least one layer of a luminescent coating whose thickness is greater than 30 microns, better at 50 microns, more preferably at 80 microns , always better at 100 microns, even better at 150 microns, preferably between 150 and 1500 microns.
  • larger grains may have stronger luminescence and longer duration if phosphorescence occurs. Moreover, it makes it easier to color the grains to give the coating a color in the visible and above all it makes it possible to color the luminescence light more easily, and thus to obtain interesting effects of color changes visible light / color of the light. luminescence.
  • the relatively large coating thickness makes it possible to increase the thickness of the matrix which links the grains to the substrate and thus to improve the mechanical strength of the coating. This also helps to get when the coating thickness is greater than the thickness of the pigment grains a smooth coating, which may be desirable for many applications.
  • the luminescent coating may be fluorescent.
  • the luminescent coating is phosphorescent.
  • the luminescent coating is preferably of a thickness of between 30 and
  • the luminescent charge can be evenly distributed in this thickness.
  • the coating may comprise luminescent grains, in particular phosphorescent, of size between 15 and 400 microns, better still between 30 and 300 microns, and still more preferably between 30 and 180 microns.
  • the coating may comprise a luminescent charge comprising a mixture of luminescent grains, in particular phosphorescent grains, having different sizes, preferably average mass sizes D 50 which differ from each other by more than 30%, taking as a reference the grains of smallest size. .
  • the coating comprises, for example, a phosphor charge comprising a mixture of a first luminescent pigment, in particular a phosphorescent pigment, of a size of between 30 and 70 microns, of a second luminescent pigment, especially a phosphorescent pigment, of a size of between 70 and 110 microns, and a third luminescent pigment, especially phosphorescent, of size between 130 and 170 microns, each of the three pigments preferably representing between 20 and 40% by weight of the filler.
  • a phosphor charge comprising a mixture of a first luminescent pigment, in particular a phosphorescent pigment, of a size of between 30 and 70 microns, of a second luminescent pigment, especially a phosphorescent pigment, of a size of between 70 and 110 microns, and a third luminescent pigment, especially phosphorescent, of size between 130 and 170 microns, each of the three pigments preferably representing between 20 and 40% by weight of the filler.
  • the size of a pigment is defined as the mass size D50.
  • the coating may comprise a luminescent charge comprising at least one phosphor-based pigment based on alkaline earth aluminate doped with one or more rare earths.
  • the coating may comprise a phosphor charge comprising at least one composite phosphorescent pigment comprising a grain of a phosphorescent material, especially a rare earth aluminate, at least partially covered by smaller grains of a metal oxide, in particular ferrous or non-ferrous oxide. , having when not ferrous material preferably a decomposition temperature greater than or equal to 550 ° C, better 600 ° C when the pigment must be compatible with enamelling.
  • Metallic oxides, in particular ferrous or non-ferrous make it possible to color the pigments and to act on the luminescence color.
  • the size of the oxide (s) metal (s), including non-ferrous, may be less than or equal to 1 micron.
  • the mass proportion of the grains of metal oxide (s) may be less than or equal to 1% within the luminescent charge.
  • the coating comprises a transparent matrix.
  • luminescent pigments examples include the composite pigments described in the French patent application FR 1559270, and in particular those defined by the wording of claim 1 of the application as filed, which is incorporated herein by reference.
  • the substrate may be glass, metal, plastic or a material of plant or animal origin, including wood.
  • the article may be a container, a lamp, a tableware item, a signaling device, among others.
  • the coating can be formed in different ways on the article, in particular by lacquering, screen printing, enameling, dusting.
  • a luminescent lacquering composition comprising, by dry weight relative to the total weight of the composition:
  • a luminescent charge between 30 and 75% of a luminescent charge, better more than 50%, between 25 and 50% of a binder, preferably transparent.
  • Such a composition makes it possible to obtain a strong luminescence, with regard to the concentration of luminescent charge, and allows the realization of a coating as defined above.
  • the binder may be based on polyurethane.
  • the composition preferably comprises between 0.5 and 2% by dry weight of gelling agent. This makes it possible to obtain a better hold of the composition on the substrate on which it is sprayed, while waiting for the composition to dry.
  • the filler has a particle size of between 30 microns and 400 microns, better still between 30 and 300 microns, more preferably between 30 and 200 microns.
  • the phosphor charge comprises a mixture of at least two luminescent pigments, in particular phosphorescent pigments, of different particle sizes, preferably differing from each other by at least 30%, taking as a reference the most granulometry. low.
  • the phosphor charge thus comprises a mixture of a first luminescent pigment, especially a phosphorescent pigment, of between 30 and 70 microns in size, of a second luminescent pigment, especially a phosphorescent pigment, of size between 70 and 110 microns, and a third luminescent pigment, especially phosphorescent, of size between 130 and 170 microns, each of the three pigments preferably representing between 20 and 40% by weight of the filler.
  • the luminescent charge may comprise a mixture of at least two luminescent pigments, in particular phosphorescent, of different particle sizes, preferably differing from each other by at least 30%, taking as a reference the smallest particle size.
  • the luminescent charge may comprise at least one phosphor-based pigment based on alkaline earth aluminate doped with one or more rare earths.
  • the luminescent charge may comprise at least one composite phosphorescent pigment comprising a grain of a phosphorescent material, especially an alkaline earth aluminate doped with one or more rare earths, at least partially covered by smaller grains of a coloring agent, for example a metal oxide, ferrous or non-ferrous.
  • a coloring agent for example a metal oxide, ferrous or non-ferrous.
  • the coloring agent is chosen to withstand the baking temperature of the composition, for example around 200 ° C.
  • the size of the coloring agent grains, and in particular of the metal oxide (s), may be less than or equal to 1 micron.
  • the mass proportion of the coloring agent, and in particular the grains of metal oxide (s), may be less than or equal to 1% within the luminescent charge.
  • the subject of the invention is also a process for lacquering a substrate, in particular made of glass, comprising spraying the substrate with a composition as defined above so as to obtain after cooking a deposit thickness greater than 30 microns, preferably a thickness between 100 and 600 microns, better between 200 and 400 microns.
  • the substrate is treated in several passes, which can increase the thickness of the coating formed.
  • an application of a lacquer without phosphorescence can be carried out on the already formed deposit containing the phosphor charge.
  • the invention further relates, in another of its aspects, independently or in combination with the foregoing, to a composition
  • a composition comprising a colorless transparent glass flux and a luminescent charge comprising at least one luminescent pigment, in particular phosphorescent pigment.
  • Such a composition by the use of a colorless transparent flux reduces the absorption of excitation light or re-emits and contributes to obtaining a high afterglow in the case of a phosphorescent pigment.
  • composition is thus particularly suitable for producing a coated article as defined above, according to the first aspect of the invention.
  • the glass flux consists of glass microbeads.
  • the particle size of the flux may be between 100 and 200 microns.
  • the proportion by dry weight of the phosphor load is preferably between 35 and 55% relative to the total weight of the composition, better still between 40 and 50%.
  • the proportion by dry weight of the flux is preferably between 35 and 55% relative to the total weight of the composition, more preferably between 40 and 50%.
  • the luminescent charge preferably comprises a mixture of at least two luminescent pigments, in particular phosphorescent pigments, of different particle sizes, preferably differing from each other by at least 30%, taking as a reference the smallest particle size. This allows to obtain a strong luminescence while reducing the pixelation effect, as mentioned above.
  • the luminescent charge may comprise a mixture of a first luminescent pigment, especially phosphorescent, of size between 30 and 70 microns, a second luminescent pigment, in particular phosphorescent, of size between 70 and 110 microns, and a third luminescent pigment, in particular phosphorescent, of size between 130 and 170 microns, each of the three pigments preferably representing between 20 and 40% by weight of the filler.
  • the luminescent charge may comprise at least one phosphor-based pigment based on alkaline earth aluminate doped with one or more rare earths.
  • the phosphorescent charge may comprise at least one composite phosphorescent pigment comprising a grain of a phosphorescent material, in particular an alkaline earth aluminate doped with one or more rare earths, at least partially covered by smaller grains of a non-ferrous metal oxide. , having a decomposition temperature greater than or equal to 550 ° C, more preferably 600 ° C.
  • the size of the non-ferrous metal oxide (s) grains is preferably less than or equal to 1 micron.
  • the mass proportion of the grains of metal oxide (s) may be less than or equal to 1% within the luminescent charge.
  • the subject of the invention is also a process for enameling a substrate, comprising the application of the enameling composition according to the invention as defined above on the substrate and the firing of the composition at a sufficient temperature. to cause melting of the flux, especially a temperature greater than or equal to 550 ° C, better than or equal to 600 ° C.
  • the enameling composition may be deposited by screen printing or otherwise on the substrate, for example by spraying.
  • the invention further relates, in another of its aspects, independently or in combination with the foregoing, to a composition intended for screen printing application, comprising a two-component resin, in particular an epoxy resin, and a luminescent charge, in particular phosphorescent, in a mass proportion by dry weight greater than or equal to 50% relative to the total weight of the composition, better still between 50 and 75% by dry weight.
  • a composition intended for screen printing application comprising a two-component resin, in particular an epoxy resin, and a luminescent charge, in particular phosphorescent, in a mass proportion by dry weight greater than or equal to 50% relative to the total weight of the composition, better still between 50 and 75% by dry weight.
  • Such a composition is suitable for producing a coated article as defined above.
  • the luminescent charge may comprise a mixture of at least two luminescent pigments, in particular phosphorescent pigments, of different particle sizes, preferably differing from one another by at least 30%, taking as a reference the most granulometry. low. This reduces the pixelation effect while having intense luminescence, as mentioned above.
  • the phosphor charge preferably comprises a mixture of a first luminescent pigment, in particular a phosphorescent pigment, ranging in size from 30 to 70 microns, a second luminescent pigment, especially a phosphorescent pigment, of size between 70 and 110 microns, and a phosphorescent phosphor.
  • the phosphor charge preferably comprises at least one phosphor-based pigment based on alkaline earth aluminate doped with one or more rare earths.
  • the phosphor charge preferably comprises at least one phosphorescent composite pigment comprising a grain of a phosphorescent material, in particular an alkaline earth aluminate doped with one or more rare earths, at least partially covered by smaller grains of a coloring agent. , especially a ferrous or non-ferrous metal oxide.
  • the coloring agent is preferably chosen to withstand the baking temperature of the composition, for example about 160 ° C.
  • the size of the oxide (s) metal (s) is preferably less than or equal to 1 micron.
  • the mass proportion of the grains of metal oxide (s) is preferably less than or equal to 1% within the luminescent charge.
  • the invention also relates, in another of its aspects, to a process for the application by screen printing of an enameling composition or a screen printing composition as defined above, the screen printing being performed with a screen having 40 to 80 threads / cm and with a capillary film 100 to 900 microns thick, better 300 to 9700 microns, more preferably 300 to 700 microns.
  • the invention further relates, independently or in combination with the foregoing, to a luminescent composition, in particular a phosphorescent composition, comprising a luminescent charge comprising a mixture of at least two luminescent pigments, in particular phosphorescent, of different particle sizes, preferably differing from each other by at least 30%, taking as a reference the smallest particle size.
  • a luminescent composition in particular a phosphorescent composition, comprising a luminescent charge comprising a mixture of at least two luminescent pigments, in particular phosphorescent, of different particle sizes, preferably differing from each other by at least 30%, taking as a reference the smallest particle size.
  • Such a composition makes it possible, as explained above, to use large, particularly luminescent pigments, while reducing the rasterization effect.
  • the phosphor charge comprises a mixture of a first luminescent pigment, especially phosphorescent, preferably of size between 30 and 70 microns, of a second luminescent pigment, especially phosphorescent pigment, preferably of size between 70 and 110 microns , and a third luminescent pigment, especially phosphorescent, preferably of size between 130 and 170 microns, each of the three pigments preferably representing between 20 and 40% by weight of the filler.
  • a first luminescent pigment especially phosphorescent, preferably of size between 30 and 70 microns
  • a second luminescent pigment especially phosphorescent pigment, preferably of size between 70 and 110 microns
  • a third luminescent pigment especially phosphorescent, preferably of size between 130 and 170 microns
  • the phosphor charge comprises at least one phosphor-based pigment based on alkaline earth aluminate doped with one or more rare earths.
  • the luminescent charge comprises at least one composite phosphorescent pigment comprising a grain of a phosphorescent material, especially an alkaline earth aluminate doped with one or more rare earths, at least partially covered by smaller grains of a metal oxide.
  • ferrous or non-ferrous having when non-ferrous preferably when an enameling application is referred, a decomposition temperature greater than or equal to 550 ° C, more preferably 600 ° C.
  • the size of the oxide (s) metal (s) may be less than or equal to 1 micron.
  • the mass proportion of the grains of metal oxide (s) is preferably less than or equal to 1% within the luminescent charge. This makes it possible to color without unduly impairing the luminescence.
  • the composition may comprise when it is an enameling composition a flux or a binder capable of constituting after baking or drying a transparent matrix.
  • the luminescent charge may comprise a mixture of luminescent pigments of different remanence times.
  • an article in particular a containing, comprising a body made of a transparent material, in particular glass, having two opposite faces, coated with respective images each formed with a phosphorescent coating, in particular with the aid of a composition according to the invention as defined above, the images being applied with respect to each other.
  • the subject of the invention is, according to another of its aspects, independently or in combination with the foregoing, an article, in particular a container, comprising a body made of a transparent material, in particular glass, having a face on which is printed a non-luminescent image, and having a luminescent coating at least partially covering the image, the latter being observable from an opposite face of the article through said body, the luminescent coating being in particular made using a composition according to the invention as defined above.
  • the invention also relates, independently or in combination with the foregoing, to a process for producing a luminescent coating, in particular a phosphorescent coating, on a substrate, in which at least a first layer and then a second layer are successively deposited on the substrate, the first layer comprising a luminescent charge comprising a luminescent pigment of a first average size, and the second layer comprising a luminescent pigment of a second average size less than the first.
  • the deposition of the second layer smooths the first, while providing luminescence and decreasing the pixelation effect.
  • More than two layers can be deposited successively, including three layers or more.
  • the subject of the invention is also, independently or in combination with the foregoing, a method for producing a phosphorescent, in particular phosphor coating, on a substrate, in which at least one layer of a substrate is deposited. a luminescent coating, and wherein ultraviolet (UV) radiation is used to polymerize the substrate coated with the at least one layer.
  • UV radiation ultraviolet
  • the luminescent coating may be a composition in the form of an ink or a powder, in particular printed by screen printing.
  • UV radiation allows a long afterglow and obtaining a satisfactory finish, especially for screen printing.
  • UV radiation can initiate the reaction of photoinitiators in the formulation of the compositions.
  • the UV wavelengths chosen for polymerizing the substrate are advantageously between 200 and 400 nanometers.
  • An aqueous lacquering composition is prepared by mixing (mass proportions) 60% of phosphorescent filler consisting of luminescent composite pigments as described in the French patent application FR 1559270, based on rare earth aluminates stained with metal oxides. % of binder PU for lacquering, and 0.5%> of a viscosity providing agent, the remainder being demineralised water.
  • the charge comprises 1/3 luminescent pigments of 150 microns in average size, 1/3 of 100 micron luminescent pigments and 1/3 of 50 micron luminescent pigments.
  • composition is sprayed on glass containers to obtain a dry thickness of 300 microns and the containers thus coated are cured in an oven.
  • Phosphorescent containers having a smooth coating having a persistence of more than six hours are obtained without pixelation effect.
  • a screen printing composition is prepared with the same pigment load as in Example 1, by mixing it with a two-component epoxy resin for screen printing, the rate of hardener having been doubled compared with the usual recommendation.
  • the filler constitutes 60% by weight of the composition, by dry weight.
  • the composition is screen printed onto a glass container using a screen having 60 threads per cm and a capillary film 500 microns thick. The pattern was computer generated.
  • the baking is then carried out at 160 ° C. to initiate the polymerization.
  • a pattern-reproducing container is obtained, which appears luminescent at night, with no raster effect, and with a persistence of more than six hours.
  • An enameling composition is prepared with the same phosphorescent filler as in Examples 1 and 2, at a level of 45% by weight. It is mixed with a flux consisting of transparent and colorless glass microbeads, also 45%. 10% of conventional enamel binder is added in the aqueous phase.
  • the size of the glass microbeads is 150 microns.
  • composition is deposited on a glass and the enamel is baked at 600 ° C.
  • the luminescence lasts more than six hours.
  • a monochrome image with a non-luminescent ink is printed by screen printing on one side of a bottle. Then, a lacquering composition according to Example 1 is applied to this image.
  • the image illuminated by the luminescent coating can be observed in the dark, through the thickness of the bottle.
  • a glass vial is produced whose walls are honeycombed.
  • the cells are printed by serigraphy using compositions according to Example 2.
  • Three layers of lacquer are deposited successively on a glass container, respectively containing phosphorescent pigments of sizes 150 microns, 100 microns and 50 microns.
  • a composition is prepared by mixing a maximum of 60% of phosphor and at least 40% of a mixture of ultraviolet-type high viscosity inks.
  • the filler comprises 70% of 35 micron luminescent pigments of medium size and 30% of 25 micron luminescent pigments of medium size.
  • the composition is applied by screen printing to a glass container, with a frame composed of a mesh of 32 threads per cm and a capillary film with a thickness ranging from 40 microns to 100 microns. Then, it is irradiated with a UV lamp which can thus create an overlayer and increase the luminescence.
  • the baking is then carried out at 140 ° C. to trigger the complete polymerization of the coating.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Composite Materials (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Wood Science & Technology (AREA)
  • Luminescent Compositions (AREA)

Abstract

The invention relates to an item comprising a substrate at least partially coated with at least one layer of a luminescent coating having a thickness greater than 30 microns.

Description

ARTICLE RECOUVERT AU MOINS PARTIELLEMENT PAR AU MOINS UNE COUCHE DE REVETEMENT LUMINESCENT  ARTICLE COVERED AT LEAST PARTIALLY BY AT LEAST ONE LUMINESCENT COATING LAYER
La présente invention concerne la fabrication d'articles luminescents divers et les articles ainsi fabriqués.  The present invention relates to the manufacture of various luminescent articles and the articles thus produced.
II a déjà été proposé d'utiliser des matériaux phosphorescents sur des contenants destinés à recevoir des liquides.  It has already been proposed to use phosphorescent materials on containers for receiving liquids.
US 2004/0064989 divulgue ainsi un contenant destiné à recevoir une boisson, sur lequel est apposé un revêtement phosphorescent décoratif sous forme de film phosphorescent adhésif. La possibilité d'introduire des pigments dans la masse avant moulage du contenant est évoquée, mais dans la pratique une telle incorporation pose de nombreux problèmes.  US 2004/0064989 discloses a container for receiving a drink, which is affixed a decorative phosphorescent coating in the form of adhesive phosphorescent film. The possibility of introducing pigments into the mass before molding the container is mentioned, but in practice such incorporation poses many problems.
CN 104417845 décrit une bouteille de vin recouverte d'une enduction d'un matériau phosphorescent. Un tamis de 250-400 mesh est mentionné, ce qui implique l'utilisation de pigments luminescents de petite taille.  CN 104417845 discloses a bottle of wine coated with a coating of a phosphorescent material. A sieve of 250-400 mesh is mentioned, which involves the use of small luminescent pigments.
CN 102133977A enseigne d'appliquer par sérigraphie une composition phosphorescente sur un verre. La composition peut être déposée par sérigraphie à l'aide d'un écran de 100 mesh, ce qui correspond à un peu moins de 150 microns de taille de tamis. Aucune information n'est donnée sur l'épaisseur du dépôt ni la taille des pigments luminescents. L'écran doit laisser passer les pigments qui doivent donc être de granulométrie bien inférieure. Il en résulte que dans cette demande antérieure, la taille des pigments luminescents est bien inférieure à 150 microns.  CN 102133977A teaches to screen a phosphorescent composition on a glass. The composition can be deposited by screen printing using a 100 mesh screen, which corresponds to a little less than 150 microns sieve size. No information is given on the thickness of the deposit or the size of the luminescent pigments. The screen must pass the pigments, which must be much smaller particle size. As a result, in this prior application, the size of the luminescent pigments is much less than 150 microns.
US 1 637 963 décrit un vernis phosphorescent à base de sulfure de zinc. La matrice peut être colorée par introduction d'un colorant tel que de l'aniline.  No. 1,637,963 describes a phosphorescent varnish based on zinc sulphide. The matrix may be colored by introducing a dye such as aniline.
Il est connu de la demande EP 0 540 390 de mélanger des billes de verre et des pigments pour obtenir un revêtement luminescent, dédié en particulier à des revêtements, par exemple de sol, dont il est nécessaire de garantir une longue durée de vie.  It is known from application EP 0 540 390 to mix glass beads and pigments to obtain a luminescent coating, dedicated in particular to coatings, for example of soil, which must be guaranteed a long service life.
L'invention vise à perfectionner encore la réalisation de zones luminescentes sur un article, à des fins de décoration ou autres.  The invention aims to further improve the production of luminescent areas on an article, for decoration or other purposes.
L'invention cherche notamment à pouvoir disposer, si cela est souhaité, d'un effet durable de rémanence dans le cas de phosphorescence et à disposer de solutions compatibles avec les technologies d'application d'un revêtement que sont le laquage, la sérigraphie, l'émaillage ou le poudrage. Par « luminescence » il faut comprendre au sens de la présente invention tout phénomène de photoluminescence, c'est-à-dire de réémission de lumière après une excitation lumineuse, les photons étant émis suite à des transitions électroniques. Elle englobe la fluorescence et la phosphorescence, cette dernière correspondant à une émission rémanente de lumière par la matière après avoir été éclairée. Elle n'englobe pas les phénomènes de chimie-luminescence ou de bio luminescence, où la lumière est émise par des réactions chimiques d'oxydation par exemple, ou des réactions biologiques, qui présentent l'inconvénient de ne pas permettre de « recharger » l'élément luminescent simplement en l'exposant à une source de lumière, visible ou non, selon les cas. Cela n'englobe pas non plus les éléments luminescents où l'excitation est produite de façon substantielle par un rayonnement ionisant. Ainsi, la luminescence selon l'invention n'est pas produite à l'aide d'un élément radioactif, et un article selon l'invention ne contient pas de radium. De préférence, le ou les composés produisant la luminescence sont dans l'invention purement minéraux. La luminescence peut être de couleur verte ou jaune ou d'une couleur autre que le vert et le jaune, par exemple blanche, bleue, orangée ou violette. The invention seeks in particular to have, if desired, a lasting effect of remanence in the case of phosphorescence and to have solutions compatible with the coating application technologies that are lacquering, screen printing, enamelling or dusting. By "luminescence" it is understood in the sense of the present invention any phenomenon of photoluminescence, that is to say, re-emission of light after a light excitation, the photons being emitted following electronic transitions. It includes fluorescence and phosphorescence, the latter corresponding to a residual emission of light by the material after being illuminated. It does not include chemiluminescence or bio-luminescence phenomena, where the light is emitted by chemical oxidation reactions, for example, or biological reactions, which have the disadvantage of not being able to "recharge" the light. luminescent element simply by exposing it to a light source, visible or not, as the case may be. It also does not include luminescent elements where excitation is substantially produced by ionizing radiation. Thus, the luminescence according to the invention is not produced using a radioactive element, and an article according to the invention does not contain radium. Preferably, the luminescent producing compound (s) are in the invention purely mineral. The luminescence may be green or yellow in color or in a color other than green and yellow, for example white, blue, orange or violet.
Article revêtu  Article coated
Selon un premier aspect, l'invention a pour objet un article comportant un substrat recouvert au moins partiellement par au moins une couche d'un revêtement luminescent dont l'épaisseur est supérieure à 30 microns, mieux à 50 microns, encore mieux à 80 microns, toujours mieux à 100 microns, encore mieux à 150 microns, de préférence entre 150 et 1500 microns.  According to a first aspect, the invention relates to an article comprising a substrate at least partially covered by at least one layer of a luminescent coating whose thickness is greater than 30 microns, better at 50 microns, more preferably at 80 microns , always better at 100 microns, even better at 150 microns, preferably between 150 and 1500 microns.
Le fait de déposer une épaisseur importante de revêtement permet à celui-ci de contenir des grains luminescents de taille relativement importante, ce qui présente de multiples avantages.  The fact of depositing a large thickness of coating allows it to contain luminescent grains of relatively large size, which has multiple advantages.
Tout d'abord, les grains plus gros peuvent avoir une luminescence plus forte et sur une durée plus longue en cas de phosphorescence. Par ailleurs, cela permet de colorer plus facilement les grains pour donner au revêtement une couleur dans le visible et surtout cela permet de colorer la lumière de luminescence plus facilement, et ainsi d'obtenir des effets intéressants de changements de couleur lumière visible/couleur de luminescence.  First, larger grains may have stronger luminescence and longer duration if phosphorescence occurs. Moreover, it makes it easier to color the grains to give the coating a color in the visible and above all it makes it possible to color the luminescence light more easily, and thus to obtain interesting effects of color changes visible light / color of the light. luminescence.
De plus, l'épaisseur de revêtement relativement grande permet d'augmenter l'épaisseur de matrice qui lie les grains au substrat et donc d'améliorer la résistance mécanique du revêtement. Cela permet aussi d'obtenir lorsque l'épaisseur de revêtement est supérieure à l'épaisseur des grains de pigment un revêtement lisse, ce qui peut être souhaitable pour de nombreuses applications. In addition, the relatively large coating thickness makes it possible to increase the thickness of the matrix which links the grains to the substrate and thus to improve the mechanical strength of the coating. This also helps to get when the coating thickness is greater than the thickness of the pigment grains a smooth coating, which may be desirable for many applications.
Le revêtement luminescent peut être fluorescent. De préférence, le revêtement luminescent est phosphorescent.  The luminescent coating may be fluorescent. Preferably, the luminescent coating is phosphorescent.
Le revêtement luminescent est de préférence d'épaisseur comprise entre 30 et The luminescent coating is preferably of a thickness of between 30 and
1500 microns, mieux 50 et 900 microns, encore mieux 100 et 900 microns, par exemple entre 100 et 800 microns. La charge luminescente peut être distribuée de façon homogène dans cette épaisseur. 1500 microns, better 50 and 900 microns, even better 100 and 900 microns, for example between 100 and 800 microns. The luminescent charge can be evenly distributed in this thickness.
Le revêtement peut comporter des grains luminescents, notamment phosphorescents, de taille comprise entre 15 et 400 microns, mieux entre 30 et 300 microns, encore mieux entre 30 et 180 microns.  The coating may comprise luminescent grains, in particular phosphorescent, of size between 15 and 400 microns, better still between 30 and 300 microns, and still more preferably between 30 and 180 microns.
Le revêtement peut comporter une charge luminescente comportant un mélange de grains luminescents, notamment phosphorescents, ayant des tailles différentes, de préférence des tailles moyennes en masse D50 qui diffèrent entre elles de plus de 30% en prenant comme référence les grains de taille la plus faible.  The coating may comprise a luminescent charge comprising a mixture of luminescent grains, in particular phosphorescent grains, having different sizes, preferably average mass sizes D 50 which differ from each other by more than 30%, taking as a reference the grains of smallest size. .
L'utilisation d'un mélange de grains de différentes tailles permet de réduire l'effet de pixellisation de la lumière émise sans avoir à utiliser un trop forte proportion de grains de taille élevée, tout en ayant une durée de rémanence importante.  The use of a mixture of grains of different sizes makes it possible to reduce the rasterization effect of the emitted light without having to use an excessively high proportion of grains of high size, while having a significant duration of remanence.
Le revêtement comporte par exemple une charge luminescente comportant un mélange d'un premier pigment luminescent, notamment phosphorescent, de taille comprise entre 30 et 70 microns, d'un deuxième pigment luminescent, notamment phosphorescent, de taille comprise entre 70 et 110 microns, et d'un troisième pigment luminescent, notamment phosphorescent, de taille comprise entre 130 et 170 microns, chacun des trois pigments représentant de préférence entre 20 et 40 % en masse de la charge.  The coating comprises, for example, a phosphor charge comprising a mixture of a first luminescent pigment, in particular a phosphorescent pigment, of a size of between 30 and 70 microns, of a second luminescent pigment, especially a phosphorescent pigment, of a size of between 70 and 110 microns, and a third luminescent pigment, especially phosphorescent, of size between 130 and 170 microns, each of the three pigments preferably representing between 20 and 40% by weight of the filler.
La taille d'un pigment est définie comme étant la taille D50 en masse. The size of a pigment is defined as the mass size D50.
Le revêtement peut comporter une charge luminescente comportant au moins un pigment phosphorescent à base d'aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares. The coating may comprise a luminescent charge comprising at least one phosphor-based pigment based on alkaline earth aluminate doped with one or more rare earths.
Le revêtement peut comporter une charge luminescente comportant au moins un pigment phosphorescent composite comportant un grain d'un matériau phosphorescent, notamment un aluminate de terres rares, recouvert au moins partiellement par des grains plus petits d'un oxyde métallique, notamment ferreux ou non ferreux, ayant lorsque non ferreux de préférence une température de décomposition supérieure ou égale à 550°C, mieux à 600°C lorsque le pigment doit être compatible avec un émaillage. Les oxydes métalliques, notamment ferreux ou non ferreux, permettent de colorer les pigments et d'agir sur la couleur de luminescence. The coating may comprise a phosphor charge comprising at least one composite phosphorescent pigment comprising a grain of a phosphorescent material, especially a rare earth aluminate, at least partially covered by smaller grains of a metal oxide, in particular ferrous or non-ferrous oxide. , having when not ferrous material preferably a decomposition temperature greater than or equal to 550 ° C, better 600 ° C when the pigment must be compatible with enamelling. Metallic oxides, in particular ferrous or non-ferrous, make it possible to color the pigments and to act on the luminescence color.
La taille des grains d'oxyde(s) métallique(s), notamment non ferreux, peut être inférieure ou égale à 1 micron.  The size of the oxide (s) metal (s), including non-ferrous, may be less than or equal to 1 micron.
La proportion massique des grains d'oxyde(s) métallique(s) peut être inférieure ou égale à 1% au sein de la charge luminescente.  The mass proportion of the grains of metal oxide (s) may be less than or equal to 1% within the luminescent charge.
De préférence, le revêtement comporte une matrice transparente.  Preferably, the coating comprises a transparent matrix.
Des exemples de pigments luminescents pouvant être utilisés sont les pigments composites décrits dans la demande de brevet français FR 1559270, et notamment ceux définis par le libellé de la revendication 1 de la demande telle que déposée, libellé qui est incorporé ici par référence.  Examples of luminescent pigments that can be used are the composite pigments described in the French patent application FR 1559270, and in particular those defined by the wording of claim 1 of the application as filed, which is incorporated herein by reference.
Le substrat peut être en verre, en métal, en matière plastique ou en une matière d'origine végétale ou animale, notamment en bois.  The substrate may be glass, metal, plastic or a material of plant or animal origin, including wood.
L'article peut être un contenant, une lampe, un article de vaisselle de table, un dispositif de signalisation, entre autres.  The article may be a container, a lamp, a tableware item, a signaling device, among others.
Le revêtement peut être formé de différentes façons sur l'article, notamment par laquage, sérigraphie, émaillage, poudrage.  The coating can be formed in different ways on the article, in particular by lacquering, screen printing, enameling, dusting.
Composition de laquage  Lacquering composition
L'invention a encore pour objet, selon un autre de ses aspects, indépendamment ou en combinaison avec ce qui précède, une composition de laquage luminescente, comportant en poids sec par rapport au poids total de composition :  The subject of the invention is, according to another of its aspects, independently or in combination with the foregoing, a luminescent lacquering composition comprising, by dry weight relative to the total weight of the composition:
- entre 30 et 75% d'une charge luminescente, mieux plus de 50%, - entre 25 et 50% d'un liant, de préférence transparent.  between 30 and 75% of a luminescent charge, better more than 50%, between 25 and 50% of a binder, preferably transparent.
Une telle composition permet d'obtenir une forte luminescence, eu égard à la concentration en charge luminescente, et permet la réalisation d'un revêtement tel que défini plus haut.  Such a composition makes it possible to obtain a strong luminescence, with regard to the concentration of luminescent charge, and allows the realization of a coating as defined above.
Le liant peut être à base de polyuréthane.  The binder may be based on polyurethane.
La composition comporte de préférence entre 0,5 et 2% en poids sec d'agent gélifiant. Cela permet d'obtenir une meilleure tenue de la composition sur le substrat sur laquelle elle est pulvérisée, dans l'attente du séchage de la composition. De préférence, la charge est de granulométrie comprise entre 30 microns et 400 microns, mieux entre 30 et 300 microns, encore mieux entre 30 et 200 microns. The composition preferably comprises between 0.5 and 2% by dry weight of gelling agent. This makes it possible to obtain a better hold of the composition on the substrate on which it is sprayed, while waiting for the composition to dry. Preferably, the filler has a particle size of between 30 microns and 400 microns, better still between 30 and 300 microns, more preferably between 30 and 200 microns.
De préférence, pour éviter le phénomène de pixellisation, la charge luminescente comporte un mélange d'au moins deux pigments luminescents, notamment phosphorescents, de granulométries différentes, de préférence différant entre elles d'au moins 30% en prenant comme référence la granulométrie la plus faible.  Preferably, in order to avoid the pixelation phenomenon, the phosphor charge comprises a mixture of at least two luminescent pigments, in particular phosphorescent pigments, of different particle sizes, preferably differing from each other by at least 30%, taking as a reference the most granulometry. low.
De préférence, la charge luminescente comporte ainsi un mélange d'un premier pigment luminescent, notamment phosphorescent, de taille comprise entre 30 et 70 microns, d'un deuxième pigment luminescent, notamment phosphorescent, de taille comprise entre 70 et 110 microns, et d'un troisième pigment luminescent, notamment phosphorescent, de taille comprise entre 130 et 170 microns, chacun des trois pigments représentant de préférence entre 20 et 40 % en masse de la charge. La charge luminescente peut comporter un mélange d'au moins deux pigments luminescents, notamment phosphorescents, de granulométries différentes, de préférence différant entre elles d'au moins 30% en prenant comme référence la granulométrie la plus faible.  Preferably, the phosphor charge thus comprises a mixture of a first luminescent pigment, especially a phosphorescent pigment, of between 30 and 70 microns in size, of a second luminescent pigment, especially a phosphorescent pigment, of size between 70 and 110 microns, and a third luminescent pigment, especially phosphorescent, of size between 130 and 170 microns, each of the three pigments preferably representing between 20 and 40% by weight of the filler. The luminescent charge may comprise a mixture of at least two luminescent pigments, in particular phosphorescent, of different particle sizes, preferably differing from each other by at least 30%, taking as a reference the smallest particle size.
La charge luminescente peut comporter au moins un pigment phosphorescent à base d'aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares.  The luminescent charge may comprise at least one phosphor-based pigment based on alkaline earth aluminate doped with one or more rare earths.
La charge luminescente peut comporter au moins un pigment phosphorescent composite comportant un grain d'un matériau phosphorescent, notamment un aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares, recouvert au moins partiellement par des grains plus petits d'un agent de coloration, par exemple un oxyde métallique, ferreux ou non ferreux. De préférence, l'agent de coloration est choisi pour résister à la température de cuisson de la composition, par exemple autour de 200°C.  The luminescent charge may comprise at least one composite phosphorescent pigment comprising a grain of a phosphorescent material, especially an alkaline earth aluminate doped with one or more rare earths, at least partially covered by smaller grains of a coloring agent, for example a metal oxide, ferrous or non-ferrous. Preferably, the coloring agent is chosen to withstand the baking temperature of the composition, for example around 200 ° C.
Lorsque l'agent de coloration est particulaire, la taille des grains d'agent de coloration, et notamment du ou des oxyde(s) métallique(s) peut être inférieure ou égale à 1 micron.  When the coloring agent is particulate, the size of the coloring agent grains, and in particular of the metal oxide (s), may be less than or equal to 1 micron.
La proportion massique de l'agent de coloration, et notamment des grains d'oxyde(s) métallique(s), peut être inférieure ou égale à 1% au sein de la charge luminescente.  The mass proportion of the coloring agent, and in particular the grains of metal oxide (s), may be less than or equal to 1% within the luminescent charge.
L'invention a encore pour objet, selon un autre de ses aspects, un procédé de laquage d'un substrat, notamment en verre, comportant la pulvérisation sur le substrat d'une composition telle que définie plus haut de façon à obtenir après cuisson une épaisseur de dépôt supérieure à 30 microns, de préférence une épaisseur comprise entre 100 et 600 microns, mieux entre 200 et 400 microns. According to another of its aspects, the subject of the invention is also a process for lacquering a substrate, in particular made of glass, comprising spraying the substrate with a composition as defined above so as to obtain after cooking a deposit thickness greater than 30 microns, preferably a thickness between 100 and 600 microns, better between 200 and 400 microns.
Le cas échéant, le substrat est traité en plusieurs passes, ce qui peut permettre d'accroître l'épaisseur du revêtement formé.  If necessary, the substrate is treated in several passes, which can increase the thickness of the coating formed.
Selon l'état de surface souhaité, une application d'une laque sans charge luminescente peut être effectuée sur le dépôt déjà formé contenant la charge luminescente.  Depending on the desired surface condition, an application of a lacquer without phosphorescence can be carried out on the already formed deposit containing the phosphor charge.
Composition d'émaillage luminescente  Luminescent enameling composition
L'invention a encore pour objet selon un autre de ses aspects, indépendamment ou en combinaison avec ce qui précède, une composition comportant un fondant de verre transparent incolore et une charge luminescente comportant au moins un pigment luminescent, notamment phosphorescent.  The invention further relates, in another of its aspects, independently or in combination with the foregoing, to a composition comprising a colorless transparent glass flux and a luminescent charge comprising at least one luminescent pigment, in particular phosphorescent pigment.
Une telle composition, de par l'emploi d'un fondant transparent incolore réduit l'absorption de la lumière d'excitation ou réémise et contribue à l'obtention d'une durée de rémanence élevée dans le cas d'un pigment phosphorescent.  Such a composition, by the use of a colorless transparent flux reduces the absorption of excitation light or re-emits and contributes to obtaining a high afterglow in the case of a phosphorescent pigment.
Une telle composition convient ainsi tout particulièrement à la réalisation d'un article revêtu tel que défini plus haut, selon le premier aspect de l'invention.  Such a composition is thus particularly suitable for producing a coated article as defined above, according to the first aspect of the invention.
De préférence, le fondant de verre est constitué de microbilles de verre.  Preferably, the glass flux consists of glass microbeads.
La granulométrie du fondant peut être comprise entre 100 et 200 microns. La proportion en poids sec de la charge luminescente est de préférence comprise entre 35 et 55 % par rapport au poids total de la composition, mieux entre 40 et 50 %.  The particle size of the flux may be between 100 and 200 microns. The proportion by dry weight of the phosphor load is preferably between 35 and 55% relative to the total weight of the composition, better still between 40 and 50%.
La proportion en poids sec du fondant est de préférence comprise entre 35 et 55% par rapport au poids total de la composition, mieux entre 40 et 50 %.  The proportion by dry weight of the flux is preferably between 35 and 55% relative to the total weight of the composition, more preferably between 40 and 50%.
La charge luminescente comporte de préférence un mélange d'au moins deux pigments luminescents, notamment phosphorescents, de granulométries différentes, de préférence différant entre elles d'au moins 30% en prenant comme référence la granulométrie la plus faible. Cela permet d'obtenir une forte luminescence tout en réduisant l'effet de pixellisation, comme mentionné plus haut.  The luminescent charge preferably comprises a mixture of at least two luminescent pigments, in particular phosphorescent pigments, of different particle sizes, preferably differing from each other by at least 30%, taking as a reference the smallest particle size. This allows to obtain a strong luminescence while reducing the pixelation effect, as mentioned above.
En particulier, la charge luminescente peut comporter un mélange d'un premier pigment luminescent, notamment phosphorescent, de taille comprise entre 30 et 70 microns, d'un deuxième pigment luminescent, notamment phosphorescent, de taille comprise entre 70 et 110 microns, et d'un troisième pigment luminescent, notamment phosphorescent, de taille comprise entre 130 et 170 microns, chacun des trois pigments représentant de préférence entre 20 et 40 % en masse de la charge. In particular, the luminescent charge may comprise a mixture of a first luminescent pigment, especially phosphorescent, of size between 30 and 70 microns, a second luminescent pigment, in particular phosphorescent, of size between 70 and 110 microns, and a third luminescent pigment, in particular phosphorescent, of size between 130 and 170 microns, each of the three pigments preferably representing between 20 and 40% by weight of the filler.
La charge luminescente peut comporter au moins un pigment phosphorescent à base d'aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares.  The luminescent charge may comprise at least one phosphor-based pigment based on alkaline earth aluminate doped with one or more rare earths.
La charge luminescente peut comporter au moins un pigment phosphorescent composite comportant un grain d'un matériau phosphorescent, notamment un aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares, recouvert au moins partiellement par des grains plus petits d'un oxyde métallique non ferreux, ayant une température de décomposition supérieure ou égale à 550°C, mieux à 600°C.  The phosphorescent charge may comprise at least one composite phosphorescent pigment comprising a grain of a phosphorescent material, in particular an alkaline earth aluminate doped with one or more rare earths, at least partially covered by smaller grains of a non-ferrous metal oxide. , having a decomposition temperature greater than or equal to 550 ° C, more preferably 600 ° C.
La taille des grains d'oxyde(s) métallique(s) non ferreux est de préférence inférieure ou égale à 1 micron.  The size of the non-ferrous metal oxide (s) grains is preferably less than or equal to 1 micron.
La proportion massique des grains d'oxyde(s) métallique(s) peut être inférieure ou égale à 1% au sein de la charge luminescente.  The mass proportion of the grains of metal oxide (s) may be less than or equal to 1% within the luminescent charge.
L'invention a encore pour objet un procédé d'émaillage d'un substrat, comportant l'application de la composition d'émaillage selon l'invention telle que définie ci-dessus sur le substrat et la cuisson de la composition à une température suffisante pour provoquer la fusion du fondant, notamment une température supérieure ou égale à 550°C, mieux supérieure ou égale à 600°C.  The subject of the invention is also a process for enameling a substrate, comprising the application of the enameling composition according to the invention as defined above on the substrate and the firing of the composition at a sufficient temperature. to cause melting of the flux, especially a temperature greater than or equal to 550 ° C, better than or equal to 600 ° C.
La composition d'émaillage peut être déposée par sérigraphie ou autrement sur le substrat, par exemple par pulvérisation.  The enameling composition may be deposited by screen printing or otherwise on the substrate, for example by spraying.
Composition pour sérigraphie  Silkscreen composition
L'invention a encore pour objet, selon un autre de ses aspects, indépendamment ou en combinaison avec ce qui précède, une composition destinée à une application par sérigraphie, comportant une résine bi-composant, notamment une résine époxy, et une charge luminescente, notamment phosphorescente, en une proportion massique en poids sec supérieure ou égale à 50% par rapport au poids total de la composition, mieux entre 50 et 75 % en poids sec.  The invention further relates, in another of its aspects, independently or in combination with the foregoing, to a composition intended for screen printing application, comprising a two-component resin, in particular an epoxy resin, and a luminescent charge, in particular phosphorescent, in a mass proportion by dry weight greater than or equal to 50% relative to the total weight of the composition, better still between 50 and 75% by dry weight.
Une telle composition convient à la réalisation d'un article revêtu tel que défini ci-dessus.  Such a composition is suitable for producing a coated article as defined above.
La charge luminescente peut comporter un mélange d'au moins deux pigments luminescents, notamment phosphorescents, de granulométries différentes, de préférence différant entre elles d'au moins 30% en prenant comme référence la granulométrie la plus faible. Cela permet de réduire l'effet de pixellisation tout en ayant une luminescence intense, comme mentionné plus haut. The luminescent charge may comprise a mixture of at least two luminescent pigments, in particular phosphorescent pigments, of different particle sizes, preferably differing from one another by at least 30%, taking as a reference the most granulometry. low. This reduces the pixelation effect while having intense luminescence, as mentioned above.
La charge luminescente comporte de préférence un mélange d'un premier pigment luminescent, notamment phosphorescent, de taille comprise entre 30 et 70 microns, d'un deuxième pigment luminescent, notamment phosphorescent, de taille comprise entre 70 et 110 microns, et d'un troisième pigment luminescent, notamment phosphorescent, de taille comprise entre 130 et 170 microns, chacun des trois pigments représentant de préférence entre 20 et 40 % en masse de la charge.  The phosphor charge preferably comprises a mixture of a first luminescent pigment, in particular a phosphorescent pigment, ranging in size from 30 to 70 microns, a second luminescent pigment, especially a phosphorescent pigment, of size between 70 and 110 microns, and a phosphorescent phosphor. third luminescent pigment, especially phosphorescent, of size between 130 and 170 microns, each of the three pigments preferably representing between 20 and 40% by weight of the filler.
La charge luminescente comporte de préférence au moins un pigment phosphorescent à base d'aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares.  The phosphor charge preferably comprises at least one phosphor-based pigment based on alkaline earth aluminate doped with one or more rare earths.
La charge luminescente comporte de préférence au moins un pigment phosphorescent composite comportant un grain d'un matériau phosphorescent, notamment un aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares, recouvert au moins partiellement par des grains plus petits d'un agent de coloration, notamment un oxyde métallique ferreux ou non ferreux.  The phosphor charge preferably comprises at least one phosphorescent composite pigment comprising a grain of a phosphorescent material, in particular an alkaline earth aluminate doped with one or more rare earths, at least partially covered by smaller grains of a coloring agent. , especially a ferrous or non-ferrous metal oxide.
L'agent de coloration est de préférence choisi pour résister à la température de cuisson de la composition, par exemple 160°C environ.  The coloring agent is preferably chosen to withstand the baking temperature of the composition, for example about 160 ° C.
La taille des grains d'oxyde(s) métallique(s) est de préférence inférieure ou égale à 1 micron.  The size of the oxide (s) metal (s) is preferably less than or equal to 1 micron.
La proportion massique des grains d'oxyde(s) métallique(s) est de préférence inférieure ou égale à 1% au sein de la charge luminescente.  The mass proportion of the grains of metal oxide (s) is preferably less than or equal to 1% within the luminescent charge.
Procédé d'application par sérigraphie d'une composition luminescente L'invention a encore pour objet, selon un autre de ses aspects, un procédé d'application par sérigraphie d'une composition d'émaillage ou d'une composition pour sérigraphie telles que définies ci-dessus, la sérigraphie étant effectuée avec un écran ayant de 40 à 80 fils/cm et avec un film capillaire de 100 à 900 microns d'épaisseur, mieux de 300 à 9700 microns, encore mieux de 300 à 700 microns.  The invention also relates, in another of its aspects, to a process for the application by screen printing of an enameling composition or a screen printing composition as defined above, the screen printing being performed with a screen having 40 to 80 threads / cm and with a capillary film 100 to 900 microns thick, better 300 to 9700 microns, more preferably 300 to 700 microns.
Composition luminescente à effet de pixellisation réduit  Luminescent composition with reduced pixelation effect
L'invention a encore pour objet, indépendamment ou en combinaison avec ce qui précède, une composition luminescente, notamment phosphorescente, comportant une charge luminescente comportant un mélange d'au moins deux pigments luminescents, notamment phosphorescents, de granulométries différentes, de préférence différant entre elles d'au moins 30% en prenant comme référence la granulométrie la plus faible. The invention further relates, independently or in combination with the foregoing, to a luminescent composition, in particular a phosphorescent composition, comprising a luminescent charge comprising a mixture of at least two luminescent pigments, in particular phosphorescent, of different particle sizes, preferably differing from each other by at least 30%, taking as a reference the smallest particle size.
Une telle composition permet, comme expliqué ci-dessus, d'utiliser des pigments de grande taille, particulièrement luminescents, tout en réduisant l'effet de pixellisation.  Such a composition makes it possible, as explained above, to use large, particularly luminescent pigments, while reducing the rasterization effect.
De préférence, la charge luminescente comporte un mélange d'un premier pigment luminescent, notamment phosphorescent, de préférence de taille comprise entre 30 et 70 microns, d'un deuxième pigment luminescent, notamment phosphorescent, de préférence de taille comprise entre 70 et 110 microns, et d'un troisième pigment luminescent, notamment phosphorescent, de préférence de taille comprise entre 130 et 170 microns, chacun des trois pigments représentant de préférence entre 20 et 40 % en masse de la charge.  Preferably, the phosphor charge comprises a mixture of a first luminescent pigment, especially phosphorescent, preferably of size between 30 and 70 microns, of a second luminescent pigment, especially phosphorescent pigment, preferably of size between 70 and 110 microns , and a third luminescent pigment, especially phosphorescent, preferably of size between 130 and 170 microns, each of the three pigments preferably representing between 20 and 40% by weight of the filler.
De préférence, la charge luminescente comporte au moins un pigment phosphorescent à base d'aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares.  Preferably, the phosphor charge comprises at least one phosphor-based pigment based on alkaline earth aluminate doped with one or more rare earths.
De préférence, la charge luminescente comporte au moins un pigment phosphorescent composite comportant un grain d'un matériau phosphorescent, notamment un aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares, recouvert au moins partiellement par des grains plus petits d'un oxyde métallique ferreux ou non ferreux, ayant lorsque non ferreux de préférence lorsqu'une application en émaillage est visée, une température de décomposition supérieure ou égale à 550°C, mieux à 600°C.  Preferably, the luminescent charge comprises at least one composite phosphorescent pigment comprising a grain of a phosphorescent material, especially an alkaline earth aluminate doped with one or more rare earths, at least partially covered by smaller grains of a metal oxide. ferrous or non-ferrous, having when non-ferrous preferably when an enameling application is referred, a decomposition temperature greater than or equal to 550 ° C, more preferably 600 ° C.
La taille des grains d'oxyde(s) métallique(s) peut être inférieure ou égale à 1 micron.  The size of the oxide (s) metal (s) may be less than or equal to 1 micron.
La proportion massique des grains d'oxyde(s) métallique(s) est de préférence inférieure ou égale à 1% au sein de la charge luminescente. Cela permet de colorer sans pour autant nuire outre mesure à la luminescence.  The mass proportion of the grains of metal oxide (s) is preferably less than or equal to 1% within the luminescent charge. This makes it possible to color without unduly impairing the luminescence.
La composition peut comporter lorsqu'il s'agit d'une composition d'émaillage un fondant ou un liant apte à constituer après cuisson ou séchage une matrice transparente.  The composition may comprise when it is an enameling composition a flux or a binder capable of constituting after baking or drying a transparent matrix.
La charge luminescente peut comporter un mélange de pigments luminescents de durées de rémanence différentes.  The luminescent charge may comprise a mixture of luminescent pigments of different remanence times.
Article à images au repère  Article with images at the landmark
L'invention a encore pour objet, selon un autre de ses aspects, indépendamment ou en combinaison avec ce qui précède, un article, notamment un contenant, comportant un corps en une matière transparente, notamment en verre, présentant deux faces opposées, revêtues d'images respectives formées chacune avec un revêtement phosphorescent, notamment à l'aide d'une composition selon l'invention telle que définie plus haut, les images étant appliquées de façon repérée l'une par rapport à l'autre. Another subject of the invention, according to another of its aspects, independently or in combination with the foregoing, an article, in particular a containing, comprising a body made of a transparent material, in particular glass, having two opposite faces, coated with respective images each formed with a phosphorescent coating, in particular with the aid of a composition according to the invention as defined above, the images being applied with respect to each other.
Cela peut permettre d'obtenir des effets particulièrement attractifs, notamment de donner une impression de profondeur à l'observateur.  This can provide particularly attractive effects, including giving an impression of depth to the observer.
Article à image éclairée par luminescence  Luminous Illuminated Article Article
L'invention a encore pour objet, selon un autre de ses aspects, indépendamment ou en combinaison avec ce qui précède, un article, notamment un contenant, comportant un corps en une matière transparente, notamment en verre, présentant une face sur laquelle est imprimée une image non luminescente, et comportant un revêtement luminescent recouvrant au moins partiellement l'image, cette dernière étant observable depuis une face opposée de l'article à travers ledit corps, le revêtement luminescent étant notamment réalisé à l'aide d'une composition selon l'invention telle que définie plus haut.  The subject of the invention is, according to another of its aspects, independently or in combination with the foregoing, an article, in particular a container, comprising a body made of a transparent material, in particular glass, having a face on which is printed a non-luminescent image, and having a luminescent coating at least partially covering the image, the latter being observable from an opposite face of the article through said body, the luminescent coating being in particular made using a composition according to the invention as defined above.
Procédé de dépose multicouche  Multilayer removal process
L'invention a encore pour objet, indépendamment ou en combinaison avec ce qui précède, un procédé pour réaliser un revêtement luminescent, notamment phosphorescent, sur un substrat, dans lequel on dépose successivement au moins une première couche puis une deuxième couche sur le substrat, la première couche comportant une charge luminescente comportant un pigment luminescent d'une première taille moyenne, et la deuxième couche comportant un pigment luminescent d'une deuxième taille moyenne inférieure à la première.  The invention also relates, independently or in combination with the foregoing, to a process for producing a luminescent coating, in particular a phosphorescent coating, on a substrate, in which at least a first layer and then a second layer are successively deposited on the substrate, the first layer comprising a luminescent charge comprising a luminescent pigment of a first average size, and the second layer comprising a luminescent pigment of a second average size less than the first.
Le dépôt de la deuxième couche permet de lisser la première, tout en apportant de la luminescence et en diminuant l'effet de pixellisation.  The deposition of the second layer smooths the first, while providing luminescence and decreasing the pixelation effect.
Plus de deux couches peuvent ainsi être déposées successivement, notamment trois couches ou plus.  More than two layers can be deposited successively, including three layers or more.
Utilisation de radiations ultra- violettes  Use of ultraviolet radiation
L'invention a encore pour objet, indépendamment ou en combinaison avec ce qui précède, un procédé pour réaliser un revêtement luminescent, notamment phosphorescent, sur un substrat, dans lequel on dépose au moins une couche d'un revêtement luminescent, et dans lequel on utilise des radiations ultra- violettes (UV) pour polymériser le substrat revêtu de ladite au moins une couche. The subject of the invention is also, independently or in combination with the foregoing, a method for producing a phosphorescent, in particular phosphor coating, on a substrate, in which at least one layer of a substrate is deposited. a luminescent coating, and wherein ultraviolet (UV) radiation is used to polymerize the substrate coated with the at least one layer.
Le revêtement luminescent peut être dans ce cas une composition sous forme d'encre ou de poudre, notamment imprimée par sérigraphie.  In this case, the luminescent coating may be a composition in the form of an ink or a powder, in particular printed by screen printing.
L'utilisation de radiations UV permet une durée de rémanence importante et l'obtention d'une finition satisfaisante, en particulier pour l'impression par sérigraphie.  The use of UV radiation allows a long afterglow and obtaining a satisfactory finish, especially for screen printing.
Dans le mécanisme de séchage, les radiations UV permettent d'amorcer la réaction des photoinitiateurs dans la formulation des compositions.  In the drying mechanism, UV radiation can initiate the reaction of photoinitiators in the formulation of the compositions.
Les longueurs d'ondes UV choisies pour polymériser le substrat sont avantageusement comprises entre 200 et 400 nanomètres.  The UV wavelengths chosen for polymerizing the substrate are advantageously between 200 and 400 nanometers.
Exemples  Examples
Exemple 1  Example 1
On prépare une composition aqueuse de laquage en mélangeant (proportions massiques) 60% de charge phosphorescente constituée de pigments composites luminescents tels que décrits dans la demande de brevet français FR 1559270, à base d'aluminates de terres rares colorés par des oxydes métalliques, 20% de liant PU pour laquage, et 0,5%> d'un agent apportant de la viscosité, le reste étant constitué d'eau déminéralisée.  An aqueous lacquering composition is prepared by mixing (mass proportions) 60% of phosphorescent filler consisting of luminescent composite pigments as described in the French patent application FR 1559270, based on rare earth aluminates stained with metal oxides. % of binder PU for lacquering, and 0.5%> of a viscosity providing agent, the remainder being demineralised water.
La charge comporte 1/3 de pigments luminescents de 150 microns de taille moyenne, 1/3 de pigments luminescents de 100 microns et 1/3 de pigments luminescents de 50 microns.  The charge comprises 1/3 luminescent pigments of 150 microns in average size, 1/3 of 100 micron luminescent pigments and 1/3 of 50 micron luminescent pigments.
La composition est pulvérisée au pistolet sur des contenants de verre pour obtenir une épaisseur à sec de 300 microns puis les contenants ainsi revêtus sont mis à polymériser à l'étuve.  The composition is sprayed on glass containers to obtain a dry thickness of 300 microns and the containers thus coated are cured in an oven.
On obtient des contenants phosphorescents ayant un revêtement lisse, ayant une durée de rémanence de plus de six heures, sans effet de pixellisation.  Phosphorescent containers having a smooth coating having a persistence of more than six hours are obtained without pixelation effect.
Exemple 2  Example 2
On prépare une composition de sérigraphie avec la même charge pigmentaire qu'à l'exemple 1, en la mélangeant à un résine époxy bi-composant pour sérigraphie dont on a doublé le taux de durcisseur par rapport à la préconisation habituelle. La charge constitue 60%> en masse de la composition, en poids sec. On applique la composition par sérigraphie sur un contenant en verre en utilisant un écran ayant 60 fils par cm et un film capillaire de 500 microns d'épaisseur. Le motif a été généré par ordinateur. A screen printing composition is prepared with the same pigment load as in Example 1, by mixing it with a two-component epoxy resin for screen printing, the rate of hardener having been doubled compared with the usual recommendation. The filler constitutes 60% by weight of the composition, by dry weight. The composition is screen printed onto a glass container using a screen having 60 threads per cm and a capillary film 500 microns thick. The pattern was computer generated.
On procède ensuite à une cuisson à 160°C pour déclencher la polymérisation. The baking is then carried out at 160 ° C. to initiate the polymerization.
On obtient un contenant reproduisant le motif, lequel apparaît luminescent la nuit, sans effet de pixellisation, et avec une durée de rémanence de plus de six heures. A pattern-reproducing container is obtained, which appears luminescent at night, with no raster effect, and with a persistence of more than six hours.
Exemple 3  Example 3
On prépare une composition d'émaillage avec la même charge phosphorescente qu'aux exemples 1 et 2, à hauteur de 45 % en masse. On la mélange à un fondant constitué de microbilles de verre transparentes et incolores, à hauteur de 45 % également. On ajoute 10 % de liant d'émaillage conventionnel, en phase aqueuse.  An enameling composition is prepared with the same phosphorescent filler as in Examples 1 and 2, at a level of 45% by weight. It is mixed with a flux consisting of transparent and colorless glass microbeads, also 45%. 10% of conventional enamel binder is added in the aqueous phase.
La taille des microbilles de verre est de 150 microns.  The size of the glass microbeads is 150 microns.
La composition est déposée sur un verre puis on procède à une cuisson de l'émail à 600°C.  The composition is deposited on a glass and the enamel is baked at 600 ° C.
On obtient un article émaillé phosphorescent, sans effet de pixellisation, et avec une forte résistance mécanique de l'émail.  We obtain a phosphorescent enamelled article, without pixelation effect, and with a strong mechanical strength of the enamel.
La luminescence dure plus de six heures.  The luminescence lasts more than six hours.
Exemple 4  Example 4
On imprime par sérigraphie sur une face d'un flacon une image monochrome avec une encre non luminescente. Puis on applique sur cette image une composition de laquage selon l'exemple 1.  A monochrome image with a non-luminescent ink is printed by screen printing on one side of a bottle. Then, a lacquering composition according to Example 1 is applied to this image.
On peut observer dans le noir, à travers l'épaisseur du flacon, l'image éclairée par le revêtement luminescent.  The image illuminated by the luminescent coating can be observed in the dark, through the thickness of the bottle.
Exemple 5  Example 5
On réalise un flacon en verre dont les parois sont alvéolées.  A glass vial is produced whose walls are honeycombed.
On imprime dans les alvéoles par sérigraphie à l'aide de compositions selon l'exemple 2.  The cells are printed by serigraphy using compositions according to Example 2.
On obtient des décors sur chacune des faces qui se superposent et créent un effet particulièrement attractif lorsque l'angle d'observation change. Exemple 6 Decorations are obtained on each of the overlapping faces and create a particularly attractive effect when the viewing angle changes. Example 6
On dépose successivement sur un contenant en verre trois couches de laque, renfermant respectivement des pigments phosphorescents de tailles 150 microns, 100 microns et 50 microns.  Three layers of lacquer are deposited successively on a glass container, respectively containing phosphorescent pigments of sizes 150 microns, 100 microns and 50 microns.
On obtient un revêtement final relativement lisse et sans effet de pixellisation. A relatively smooth final finish with no raster effect is obtained.
Exemple 7 Example 7
On prépare une composition en mélangeant 60% maximum de matière luminescente et au moins 40% d'un mélange d'encres haute viscosité de type ultra-violet.  A composition is prepared by mixing a maximum of 60% of phosphor and at least 40% of a mixture of ultraviolet-type high viscosity inks.
La charge comporte 70%> de pigments luminescents de 35 microns de taille moyenne et 30% de pigments luminescents de 25 microns de taille moyenne.  The filler comprises 70% of 35 micron luminescent pigments of medium size and 30% of 25 micron luminescent pigments of medium size.
On applique la composition par sérigraphie sur un contenant en verre, avec un cadre composé d'une maille de 32 fils par cm et un film capillaire d'une épaisseur allant de 40 microns à 100 microns. Ensuite, on irradie avec une lampe UV pouvant ainsi créer une surcouche et augmentant la luminescence.  The composition is applied by screen printing to a glass container, with a frame composed of a mesh of 32 threads per cm and a capillary film with a thickness ranging from 40 microns to 100 microns. Then, it is irradiated with a UV lamp which can thus create an overlayer and increase the luminescence.
On procède ensuite à une cuisson à 140 °C pour déclencher la polymérisation complète du revêtement.  The baking is then carried out at 140 ° C. to trigger the complete polymerization of the coating.
Bien entendu, l'invention n'est pas limitée aux exemples qui viennent d'être décrits. On peut par exemple utiliser des pigments ayant des durées de rémanence différentes pour varier les effets optiques observés dans le temps.  Of course, the invention is not limited to the examples which have just been described. It is possible, for example, to use pigments having different persistence periods to vary the optical effects observed over time.
L'expression « compris entre » s'entend bornes incluses.  The expression "between" means included limits.

Claims

REVENDICATIONS
1. Article comportant un substrat recouvert au moins partiellement par au moins une couche d'un revêtement luminescent dont l'épaisseur est supérieure à 30 microns. An article comprising a substrate at least partially covered by at least one layer of a luminescent coating having a thickness greater than 30 microns.
2. Article selon la revendication 1, le revêtement luminescent étant phosphorescent.  2. Article according to claim 1, the luminescent coating being phosphorescent.
3. Article selon l'une des revendications précédentes, le revêtement luminescent étant d'épaisseur comprise entre 30 et 1500 microns, mieux 50 et 900 microns, encore mieux 100 et 900 microns.  3. Article according to one of the preceding claims, the luminescent coating having a thickness between 30 and 1500 microns, better 50 and 900 microns, more preferably 100 and 900 microns.
4. Article selon l'une quelconque des revendications précédentes, le revêtement comportant des grains luminescents, notamment phosphorescents, de taille comprise entre 15 et 200 microns, mieux entre 30 et 180 microns.  4. Article according to any one of the preceding claims, the coating comprising luminescent grains, especially phosphorescent, size between 15 and 200 microns, better between 30 and 180 microns.
5. Article selon l'une quelconque des revendications précédentes, le revêtement comportant une charge luminescente comportant un mélange de grains luminescents, notamment phosphorescents, ayant des tailles différentes, de préférence des tailles moyennes en masse D50 qui diffèrent entre elles de plus de 30% en prenant comme référence les grains de taille la plus faible.  5. Article according to any one of the preceding claims, the coating comprising a phosphor charge comprising a mixture of luminescent grains, in particular phosphorescent, having different sizes, preferably average mass sizes D 50 which differ from each other by more than 30%. taking as reference the grains of the smallest size.
6. Article selon l'une quelconque des revendications précédentes, le revêtement comportant une charge luminescente comportant un mélange d'un premier pigment luminescent, notamment phosphorescent, de taille comprise entre 30 et 70 microns, d'un deuxième pigment luminescent, notamment phosphorescent, de taille comprise entre 70 et 110 microns, et d'un troisième pigment luminescent, notamment phosphorescent, de taille comprise entre 130 et 170 microns, chacun des trois pigments représentant de préférence entre 20 et 40 % en masse de la charge.  6. Article according to any one of the preceding claims, the coating comprising a phosphor charge comprising a mixture of a first luminescent pigment, especially phosphorescent, of size between 30 and 70 microns, a second luminescent pigment, especially phosphorescent, of size between 70 and 110 microns, and a third luminescent pigment, especially phosphorescent, of size between 130 and 170 microns, each of the three pigments preferably representing between 20 and 40% by weight of the filler.
7. Article selon l'une quelconque des revendications 1 à 6, le revêtement comportant une charge luminescente comportant au moins un pigment phosphorescent à base d'aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares.  7. Article according to any one of claims 1 to 6, the coating comprising a phosphorescent charge comprising at least one phosphor-based pigment alkaline earth aluminate doped with one or more rare earths.
8. Article selon l'une quelconque des revendications 1 à 7, le revêtement comportant une charge luminescente comportant au moins un pigment phosphorescent composite comportant un grain d'un matériau phosphorescent, notamment un aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares, recouvert au moins partiellement par des grains plus petits d'un oxyde métallique, notamment ferreux ou non ferreux. 8. Article according to any one of claims 1 to 7, the coating comprising a phosphorescent charge comprising at least one phosphorescent pigment composite comprising a grain of a phosphorescent material, in particular an aluminate alkaline earth doped with one or more rare earths, at least partially covered by smaller grains of a metal oxide, in particular ferrous or non-ferrous.
9. Article selon la revendication 8, la taille des grains d'oxyde(s) métallique(s), notamment non ferreux, étant inférieure ou égale à 1 micron.  9. Article according to claim 8, the size of the oxide (s) metal (s), including non-ferrous, being less than or equal to 1 micron.
10. Article selon l'une des revendications 8 et 9, la proportion massique des grains d'oxyde(s) métallique(s) étant inférieure ou égale à 1% au sein de la charge luminescente.  10. Article according to one of claims 8 and 9, the mass proportion of oxide grains (s) metal (s) being less than or equal to 1% within the luminescent charge.
11. Article selon l'une quelconque des revendications précédentes, le revêtement comportant une matrice transparente.  11. Article according to any one of the preceding claims, the coating comprising a transparent matrix.
12. Article selon l'une quelconque des revendications précédentes, le substrat étant en verre.  12. Article according to any one of the preceding claims, the substrate being made of glass.
13. Article selon l'une quelconque des revendications 1 à 11, le substrat étant en métal, en matière plastique ou en une matière d'origine végétale ou animale, notamment en bois.  13. Article according to any one of claims 1 to 11, the substrate being metal, plastic or a material of plant or animal origin, including wood.
14. Composition de laquage luminescente, notamment pour la réalisation d'un revêtement d'un article selon l'une quelconque des revendications 1 à 13, comportant en poids sec :  14. Luminescent lacquering composition, in particular for producing a coating of an article according to any one of claims 1 to 13, comprising in dry weight:
- entre 30 et 75% d'une charge luminescente,  between 30 and 75% of a luminescent charge,
- entre 25 et 50% d'un liant, de préférence à base de polyuréthane.  - Between 25 and 50% of a binder, preferably based on polyurethane.
15. Composition selon la revendication 14, comportant entre 0,5 et 2% en poids sec d'agent gélifiant. 15. Composition according to claim 14, comprising between 0.5 and 2% by dry weight of gelling agent.
16. Composition selon l'une des revendications 14 et 15, la charge étant de granulométrie comprise entre 30 microns et 400 microns, mieux entre 30 et 300 microns, encore mieux entre 30 et 200 microns.  16. Composition according to one of claims 14 and 15, the load being of particle size between 30 microns and 400 microns, better between 30 and 300 microns, more preferably between 30 and 200 microns.
17. Composition selon l'une quelconque des revendications 14 à 16, la charge luminescente comportant un mélange d'au moins deux pigments luminescents, notamment phosphorescents, de granulométries différentes, de préférence différant entre elles d'au moins 30% en prenant comme référence la granulométrie la plus faible.  17. Composition according to any one of claims 14 to 16, the phosphor charge comprising a mixture of at least two luminescent pigments, in particular phosphorescent, of different particle sizes, preferably differing from each other by at least 30%, taking as a reference the smallest particle size.
18. Composition selon l'une quelconque des revendications 14 à 17, la charge luminescente comportant un mélange d'un premier pigment luminescent, notamment phosphorescent, de taille comprise entre 30 et 70 microns, d'un deuxième pigment luminescent, notamment phosphorescent, de taille comprise entre 70 et 110 microns, et d'un troisième pigment luminescent, notamment phosphorescent, de taille comprise entre 130 et 170 microns, chacun des trois pigments représentant de préférence entre 20 et 40% en masse de la charge, la charge luminescente comportant de préférence au moins un pigment phosphorescent à base d'aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares, la charge luminescente comportant de préférence au moins un pigment phosphorescent composite comportant un grain d'un matériau phosphorescent, notamment un aluminate d'alcalinoterreux dopé par une ou plusieurs e terres rares, recouvert au moins partiellement par des grains plus petits d'un oxyde métallique, la taille des grains d'oxyde(s) métallique(s) étant de préférence inférieure ou égale à 1 micron, la proportion massique des grains d'oxyde(s) métallique(s) étant de préférence inférieure ou égale à 1% au sein de la charge luminescente. 18. Composition according to any one of claims 14 to 17, the luminescent charge comprising a mixture of a first luminescent pigment, in particular phosphorescent pigment, of size between 30 and 70 microns, of a second luminescent pigment, especially phosphorescent, of size between 70 and 110 microns, and a third luminescent pigment, in particular a phosphorescent pigment, of size between 130 and 170 microns, each of the three pigments preferably representing between 20 and 40% by weight of the filler, the phosphor load preferably comprising at least one phosphorescent pigment based on alkaline earth aluminate aluminate doped with one or more rare earths, the phosphor feed preferably comprising at least one composite phosphorescent pigment comprising a grain of a phosphorescent material, in particular an alkaline earth aluminate doped with one or more rare earths, at least partially covered by smaller grains of a metal oxide, the size of the oxide (s) metal (s) being preferably less than or equal to 1 micron, the mass proportion of oxide grains (s) metal (s) being preferably less than or equal to 1% within the luminescent charge.
19. Procédé de laquage d'un substrat, notamment en verre, comportant la pulvérisation sur le substrat d'une composition telle que définie à l'une quelconque des revendications 14 à 18, de façon à obtenir après cuisson une épaisseur de dépôt supérieure à 30 microns, de préférence une épaisseur comprise entre 100 et 1500 microns, mieux entre 200 et 900 microns.  19. A method of lacquering a substrate, in particular glass, comprising sputtering onto the substrate of a composition as defined in any one of claims 14 to 18, so as to obtain after coating a deposit thickness greater than 30 microns, preferably a thickness between 100 and 1500 microns, better between 200 and 900 microns.
20. Composition d'émaillage luminescente, notamment pour la réalisation d'un revêtement d'un article selon l'une quelconque des revendications 1 à 13, comportant un fondant de verre transparent incolore et une charge luminescente comportant au moins un pigment luminescent, notamment phosphorescent, le fondant de verre étant de préférence constitué de microbilles de verre, la granulométrie du fondant étant de préférence comprise entre 100 et 200 microns.  20. Luminescent enameling composition, in particular for the production of a coating of an article according to any one of claims 1 to 13, comprising a colorless transparent glass flux and a luminescent charge comprising at least one luminescent pigment, in particular phosphorescent, the glass flux being preferably constituted by glass microbeads, the particle size of the flux being preferably between 100 and 200 microns.
21. Composition selon la revendication 20, la proportion en poids sec de la charge luminescente étant comprise entre 35 et 55 % par rapport au poids total de la composition, mieux entre 40 et 50 %, la proportion en poids sec du fondant étant de référence comprise entre 35 et 55% par rapport au poids total de la composition, mieux entre 40 et 50%.  21. Composition according to claim 20, the proportion by dry weight of the phosphor load being between 35 and 55% relative to the total weight of the composition, more preferably between 40 and 50%, the proportion by dry weight of the flux being reference between 35 and 55% relative to the total weight of the composition, more preferably between 40 and 50%.
22. Composition selon l'une des revendications 20 et 21, la charge luminescente comportant un mélange d'au moins deux pigments luminescents, notamment phosphorescents, de granulométries différentes, de préférence différant entre elles d'au moins 30% en prenant comme référence la granulométrie la plus faible, la charge luminescente comportant de préférence un mélange d'un premier pigment luminescent, notamment phosphorescent, de taille comprise entre 30 et 70 microns, d'un deuxième pigment luminescent, notamment phosphorescent, de taille comprise entre 70 et 110 microns, et d'un troisième pigment luminescent, notamment phosphorescent, de taille comprise entre 130 et 170 microns, chacun des trois pigments représentant de préférence entre 20 et 40 % en masse de la charge, la charge luminescente comportant de préférence au moins un pigment phosphorescent à base d'aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares, la charge luminescente comportant de préférence au moins un pigment phosphorescent composite comportant un grain d'un matériau phosphorescent, notamment un aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares, recouvert au moins partiellement par des grains plus petits d'un oxyde métallique non ferreux, ayant une température de décomposition supérieure ou égale à 550°C, mieux à 600°C, la taille des grains d'oxyde(s) métallique(s) non ferreux étant de préférence inférieure ou égale à 1 micron, la proportion massique des grains d'oxyde(s) métallique(s) étant de préférence inférieure ou égale à 1% au sein de la charge luminescente. 22. Composition according to one of claims 20 and 21, the phosphor load comprising a mixture of at least two luminescent pigments, especially phosphorescent pigments, of different particle sizes, preferably differing from each other by at least 30% by taking as a reference the the smallest particle size, the luminescent charge preferably comprising a mixture of a first luminescent pigment, in particular phosphorescent, of size between 30 and 70 microns, a second luminescent pigment, especially phosphorescent, size between 70 and 110 microns, and a third luminescent pigment, including phosphorescent, size between 130 and 170 microns , each of the three pigments preferably representing between 20 and 40% by weight of the filler, the phosphor load preferably comprising at least one phosphor-based pigment based on alkaline earth metal aluminate doped with one or more rare earths, the luminescent filler comprising preferably at least one composite phosphorescent pigment having a grain of a phosphorescent material, in particular an alkaline earth aluminate doped with one or more rare earths, at least partially covered by smaller grains of a non-ferrous metal oxide, having a decomposition temperature greater than or equal to 550 ° C, better at 600 ° C, the size of the oxide grains (s) metal the non-ferrous acid (s) being preferably less than or equal to 1 micron, the mass proportion of the oxide (s) metal (s) being preferably less than or equal to 1% within the luminescent charge.
23. Procédé d'émaillage d'un substrat, comportant l'application de la composition selon l'une quelconque des revendications 20 à 22 sur le substrat et la cuisson de la composition à une température suffisante pour provoquer la fusion du fondant, notamment une température supérieure ou égale à 550°C, mieux supérieure ou égale à 600°C.  23. A method of enameling a substrate, comprising applying the composition according to any one of claims 20 to 22 to the substrate and baking the composition at a temperature sufficient to cause melting of the flux, in particular a temperature greater than or equal to 550 ° C, better still greater than or equal to 600 ° C.
24. Composition destinée à une application par sérigraphie, notamment afin de réaliser un revêtement luminescent d'un article tel que défini dans l'une quelconque des revendications 1 à 13, comportant une résine bi-composant, notamment une résine époxy, et une charge luminescente, notamment phosphorescente, en une proportion massique en poids sec supérieure ou égale à 50% par rapport au poids total de la composition, mieux entre 50 et 75% en poids sec.  24. Composition intended for application by screen printing, in particular in order to achieve a luminescent coating of an article as defined in any one of claims 1 to 13, comprising a two-component resin, in particular an epoxy resin, and a filler. luminescent, in particular phosphorescent, in a mass proportion by dry weight greater than or equal to 50% relative to the total weight of the composition, better still between 50 and 75% by dry weight.
25. Composition selon la revendication 24, la charge luminescente comportant un mélange d'au moins deux pigments luminescents, notamment phosphorescents, de granulométries différentes, de préférence différant entre elles d'au moins 30% en prenant comme référence la granulométrie la plus faible, la charge luminescente comportant de préférence un mélange d'un premier pigment luminescent, notamment phosphorescent, de taille comprise entre 30 et 70 microns, d'un deuxième pigment luminescent, notamment phosphorescent, de taille comprise entre 70 et 110 microns, et d'un troisième pigment luminescent, notamment phosphorescent, de taille comprise entre 130 et 170 microns, chacun des trois pigments représentant de préférence entre 20 et 40 % en masse de la charge, la charge luminescente comportant de préférence au moins un pigment phosphorescent à base d'aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares, la charge luminescente comportant de préférence au moins un pigment phosphorescent composite comportant un grain d'un matériau phosphorescent, notamment un aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares, recouvert au moins partiellement par des grains plus petits d'un oxyde métallique ferreux ou non ferreux, ayant lorsque non ferreux de préférence une température de décomposition supérieure ou égale à 550°C, mieux à 600°C, la taille des grains d'oxyde(s) métallique(s) étant de préférence inférieure ou égale à 1 micron, la proportion massique des grains d'oxyde(s) métallique(s) étant de préférence inférieure ou égale à 1% au sein de la charge luminescente. 25. A composition according to claim 24, the phosphor charge comprising a mixture of at least two luminescent pigments, especially phosphorescent pigments, of different particle sizes, preferably differing from each other by at least 30%, taking as a reference the smallest particle size, the luminescent charge preferably comprising a mixture of a first luminescent pigment, in particular a phosphorescent pigment, ranging in size from 30 to 70 microns, a second luminescent pigment, in particular a phosphorescent pigment, of size between 70 and 110 microns, and a third pigment luminescent, in particular phosphorescent, of size between 130 and 170 microns, each of the three pigments preferably representing between 20 and 40% by weight of the filler, the phosphor load preferably comprising at least one phosphor-based pigment based on aluminum aluminate. alkaline earth doped with one or more rare earths, the phosphor feed preferably comprising at least one composite phosphorescent pigment comprising a grain of a phosphorescent material, in particular an alkaline earth aluminate doped with one or more rare earths, at least partially covered by smaller grains of a ferrous or non-ferrous metal oxide, having when preferably non-ferrous a decomposition temperature greater than or equal to 550 ° C, more preferably at 600 ° C, the size of the oxide (s) metal grains (s) ) is preferably less than or equal to 1 micron, the mass proportion of the grains of metal oxide (s) being preferably lower than 1% or less in the luminescent charge.
26. Procédé d'application par sérigraphie d'une composition d'émaillage selon l'une quelconque des revendications 20 à 22 ou d'une composition pour sérigraphie selon l'une des revendications 24 et 25, la sérigraphie étant effectuée avec un écran ayant de 40 à 80 fils/cm et avec un film capillaire de 100 à 900 microns d'épaisseur.  26. A method of application by screen printing an enameling composition according to any one of claims 20 to 22 or a screen printing composition according to one of claims 24 and 25, the screen printing being performed with a screen having from 40 to 80 threads / cm and with a capillary film 100 to 900 microns thick.
27. Composition luminescente, notamment phosphorescente, notamment pour la réalisation du revêtement luminescent d'un article tel que défini à l'une quelconque des revendications 1 à 13, comportant une charge luminescente comportant un mélange d'au moins deux pigments luminescents, notamment phosphorescents, de granulométries différentes, de préférence différant entre elles d'au moins 30% en prenant comme référence la granulométrie la plus faible, la charge luminescente comportant de préférence un mélange d'un premier pigment luminescent, notamment phosphorescent, de préférence de taille comprise entre 30 et 70 microns, d'un deuxième pigment luminescent, notamment phosphorescent, de préférence de taille comprise entre 70 et 110 microns, et d'un troisième pigment luminescent, notamment phosphorescent, de préférence de taille comprise entre 130 et 170 microns, chacun des trois pigments représentant de préférence entre 20 et 40% en masse de la charge, la charge luminescente comportant de préférence au moins un pigment phosphorescent à base d'aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares, la charge luminescente comportant de préférence au moins un pigment phosphorescent composite comportant un grain d'un matériau phosphorescent, notamment un aluminate d'alcalinoterreux dopé par une ou plusieurs terres rares, recouvert au moins partiellement par des grains plus petits d'un oxyde métallique ferreux ou non ferreux, ayant lorsque non ferreux de préférence une température de décomposition supérieure ou égale à 550°C, mieux à 600°C, la taille des grains d'oxyde(s) métallique(s) étant de préférence inférieure ou égale à 1 micron, la proportion massique des grains d'oxyde(s) métallique(s) étant de préférence inférieure ou égale à 1% au sein de la charge luminescente. 27. Luminescent composition, in particular phosphorescent composition, in particular for producing the luminescent coating of an article as defined in any one of Claims 1 to 13, comprising a phosphorescent filler comprising a mixture of at least two luminescent pigments, in particular phosphorescent pigments. of different particle sizes, preferably differing from each other by at least 30%, taking as a reference the smallest particle size, the phosphor load preferably comprising a mixture of a first luminescent pigment, in particular a phosphorescent pigment, preferably of a size between 30 and 70 microns, a second luminescent pigment, especially phosphorescent, preferably of size between 70 and 110 microns, and a third luminescent pigment, especially phosphorescent, preferably of size between 130 and 170 microns, each of three pigments preferably representing between 20 and 40% by weight of the charge, the charge light-emitting element preferably comprising at least one phosphor-based pigment based on alkaline earth metal aluminate doped with one or more rare earths, the phosphor charge preferably comprising at least one phosphorescent composite pigment comprising a grain of a phosphorescent material, in particular an aluminate d alkaline earth metal doped with one or more rare earths, covered at least partially by smaller grains of a ferrous or non-ferrous metal oxide, having when preferably non-ferrous a decomposition temperature greater than or equal to 550 ° C, more preferably at 600 ° C, the size of the oxide grains (s) metal (s) being preferably less than or equal to 1 micron, the mass proportion of the oxide grains (s) metal (s) being preferably less than or equal to 1% within the luminescent charge.
28. Composition selon la revendication 27, comportant un fondant ou un liant apte à constituer après cuisson ou séchage une matrice transparente.  28. The composition of claim 27, comprising a flux or a binder capable of constituting after baking or drying a transparent matrix.
29. Article, notamment contenant, comportant un corps en une matière transparente, notamment en verre, présentant deux faces opposées, revêtues d'images respectives formées chacune avec un revêtement phosphorescent, notamment à l'aide d'une composition selon l'une des revendications 20 à 22 ou 24 ou 25, les images étant appliquées de façon repérée l'une par rapport à l'autre.  29. Article, in particular containing, comprising a body made of a transparent material, in particular glass, having two opposite faces, coated with respective images each formed with a phosphorescent coating, in particular with the aid of a composition according to one of the claims 20 to 22 or 24 or 25, the images being applied in a manner marked with respect to each other.
30. Article, notamment contenant, comportant un corps en une matière transparente, notamment en verre, présentant une face sur laquelle est imprimée une image non luminescente, et comportant un revêtement luminescent recouvrant au moins partiellement l'image, cette dernière étant observable depuis une face opposée de l'article à travers ledit corps, le revêtement luminescent étant notamment réalisé à l'aide d'une composition selon l'une quelconque des revendications 14 à 18, 20 à 22 ou 24 ou 25.  30. Article, in particular a container, comprising a body made of a transparent material, in particular glass, having a face on which a non-luminescent image is printed, and comprising a luminescent coating at least partially covering the image, the latter being observable for a period of time. opposite side of the article through said body, the luminescent coating being in particular made using a composition according to any one of claims 14 to 18, 20 to 22 or 24 or 25.
31. Procédé pour réaliser un revêtement luminescent, notamment phosphorescent, sur un substrat, notamment pour réaliser un article tel que défini à l'une quelconque des revendications 1 à 13, dans lequel on dépose successivement au moins une première couche puis une deuxième couche sur le substrat, la première couche comportant une charge luminescente comportant un pigment luminescent d'une première taille moyenne, et la deuxième couche comportant un pigment luminescent d'une deuxième taille moyenne inférieure à la première.  31. A method for producing a luminescent coating, in particular a phosphorescent coating, on a substrate, in particular for producing an article as defined in any one of claims 1 to 13, in which at least a first layer and then a second layer are deposited successively. the substrate, the first layer comprising a luminescent charge comprising a luminescent pigment of a first average size, and the second layer comprising a luminescent pigment of a second average size less than the first.
32. Procédé pour réaliser un revêtement luminescent, notamment phosphorescent, sur un substrat, notamment pour réaliser un article tel que défini à l'une quelconque des revendications 1 à 13, dans lequel on dépose au moins une couche d'un revêtement luminescent, et dans lequel on utilise des radiations ultra- violettes pour polymériser le substrat revêtu de ladite au moins une couche. 32. Process for producing a luminescent coating, in particular a phosphorescent coating, on a substrate, in particular for producing an article as defined in any one of Claims 1 to 13, in which at least one layer of a luminescent coating is deposited, and wherein ultraviolet radiation is used to polymerize the substrate coated with said at least one layer.
33. Procédé selon la revendication précédente, dans lequel les longueurs d'ondes ultra- violettes choisies pour polymériser le substrat sont comprises entre 200 et 400 nanomètres. 33. Method according to the preceding claim, wherein the ultraviolet wavelengths chosen to polymerize the substrate are between 200 and 400 nanometers.
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