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 coatingInfo
- 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
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 59
- 239000011248 coating agent Substances 0.000 title claims abstract description 58
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 239000000049 pigment Substances 0.000 claims description 118
- 239000000203 mixture Substances 0.000 claims description 96
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 36
- 239000011521 glass Substances 0.000 claims description 24
- -1 aluminate aluminate Chemical class 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 229910044991 metal oxide Inorganic materials 0.000 claims description 20
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 19
- 238000007650 screen-printing Methods 0.000 claims description 18
- 239000000945 filler Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 150000004645 aluminates Chemical class 0.000 claims description 15
- 230000004907 flux Effects 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 12
- 238000004534 enameling Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- 239000011325 microbead Substances 0.000 claims description 4
- 239000012780 transparent material Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000003349 gelling agent Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 3
- 239000002253 acid Substances 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 238000004544 sputter deposition Methods 0.000 claims 1
- 238000004020 luminiscence type Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 239000010410 layer Substances 0.000 description 11
- 239000003086 colorant Substances 0.000 description 7
- 210000003298 dental enamel Anatomy 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000002688 persistence Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000010410 dusting Methods 0.000 description 2
- 238000001033 granulometry Methods 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005415 bioluminescence Methods 0.000 description 1
- 230000029918 bioluminescence Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7706—Aluminates
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface 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
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/42—Coatings comprising at least one inhomogeneous layer consisting of particles only
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/445—Organic continuous phases
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
- C03C2217/485—Pigments
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)
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- Luminescent Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1658788A FR3056327B1 (en) | 2016-09-20 | 2016-09-20 | ARTICLE COVERED AT LEAST PARTIALLY BY AT LEAST ONE LUMINESCENT COATING |
PCT/EP2017/073813 WO2018054995A1 (en) | 2016-09-20 | 2017-09-20 | Item at least partially coated with at least one layer of luminescent coating |
Publications (1)
Publication Number | Publication Date |
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EP3515997A1 true EP3515997A1 (en) | 2019-07-31 |
Family
ID=57485683
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP17772681.7A Pending EP3515997A1 (en) | 2016-09-20 | 2017-09-20 | Item at least partially coated with at least one layer of luminescent coating |
Country Status (3)
Country | Link |
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EP (1) | EP3515997A1 (en) |
FR (1) | FR3056327B1 (en) |
WO (1) | WO2018054995A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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TR201611238A2 (en) * | 2016-08-10 | 2018-02-21 | Tuerkiye Sise Ve Cam Fabrikalari Anonim Sirketi | GLAZING GLASS CONTAINER AND PRODUCTION METHOD IN THE DARK |
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2016
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- 2017-09-20 WO PCT/EP2017/073813 patent/WO2018054995A1/en unknown
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Also Published As
Publication number | Publication date |
---|---|
FR3056327B1 (en) | 2020-11-06 |
WO2018054995A1 (en) | 2018-03-29 |
FR3056327A1 (en) | 2018-03-23 |
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