Classifications

• • 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
  • C09D5/03—Powdery paints
  • C09D5/031—Powdery paints characterised by particle size or shape
• • 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
  • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
  • C09K11/7792—Aluminates
• • 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
  • C09D5/004—Reflecting paints; Signal paints
• • 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
  • C09D5/03—Powdery paints
  • C09D5/032—Powdery paints characterised by a special effect of the produced film, e.g. wrinkle, pearlescence, matt finish
• • 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
  • C09D5/03—Powdery paints
  • C09D5/033—Powdery paints characterised by the additives
• • 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
  • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor

Definitions

• the present invention relates to a method for manufacturing a reflective photoluminescent coating of any color and long phosphorescence time.
• the invention also relates to durable and resilient coating, which during the day has the phosphor's natural color, while at night glows with phosphorescence color of the phosphor (green-yellow, blue-green, blue, purple, yellow, white or other).
• the invention includes preparing a composition for making a reflective photoluminescence powder coating giving effects of luminescence and glare, in a formula of a dry binder mixed with the phosphor and suitably-sized glass reflective beads, and with the additives improving the coating properties. Thanks to the increased value of phosphorescence re- emission in relation to the absorbed light, a sustained, long and strong glow has been obtained.
• the invention also presents a method of applying a reflective photoluminescent coating on the steel or aluminum sheets, profiles of varying shapes, or plastic components.
• known methods have been used: a high voltage electrostatic spray of 40-100 kV, or an electrokinetic spray using a triboelectrization phenomenon.
• the invention is applicable for vertical signs on roads, bridges and other road facilities, on protective barriers, elements of architecture, and the like.
• the layer of paint retains its color in daylight, but due to the phosphorescence effect invisible in high insolation, a significant reduction in polarization of the reflected light and reduction of blinding white glow is achieved. Glare reduction significantly improves safety.
• Luminance characteristics of photoluminescent powder coating achieved according to the invention is many times better than what can be achieved currently in the prior art.
• the proposed reflective photoluminescent coating is designed primarily for application on the plates, sheets, closed and open profiles made from raw materials such as steel, aluminum, plastics, ceramics, glass, as well as cloth or wood-based materials.
• Photoiuminescent products made of luminescent material comprising a binder with various additives, as well as methods for their preparation are known in the art.
• European patent application EP1708825 A1 discloses a method of manufacturing a photoiuminescent non-slip element, wherein a phosphor, a binder and a non-slip component are applied. A feeding device for coating material is also disclosed.
• US patent US7713590 B2 describes a method for applying a base coat of powder paint, which is heated to a temperature of 200-400 °C and which is coated with a further layer of luminescent powder, without cooling a substrate.
• the operator changes the value of the electrostatic charge, the two layers are heated again to a temperature of 200-450 °C, a transparent powder coating is then applied, and the coated substrate is heated again.
• the method of preparing the powder consists of heating the binder to the softening temperature and adding the phosphor in a mixing procedure in the molten state. Extrusion in an extruder is followed by pulverization, grinding, classification and sieving of the obtained powder paint.
• a powder paint is used for electrostatic high voltage spraying.
• the paint has been obtained by mixing a phosphor with a transparent dry powder carrier.
• the phosphor layer is applied in a wet process on a wet layer of lacquer, and then the coated object is annealed.
• the next international patent application WO2013173451 A2 proposes a photoiuminescent composition.
• the material of the phosphor is mixed with a two- component epoxy resin, and the resultant binder is applied to the surface.
• US patent application US20030227002 A1 describes a method of making the thermoplastic compositions containing one or more thermoplastic resins and a phosphor, by mixing of these substances and extruding.
• US patent application US2012233895 A1 proposes another method of condensation of the phosphor mixed with the binder, by the phosphor's heavy particles deposition in the mold when the phosphor and binder mixture is poured into the form.
• mixing of the phosphor particles with the binder reduces distances between the phosphor grains, there is still a surplus of empty space between the grains, filled with the binder, which is a cause of decreased strength of illumination.
• the disclosed methods lead to relatively low levels of luminescence of the coatings, insufficient for use in road construction and other fields.
• Structure of the luminescent layer causes the phosphor particles not adhere one to another at a suitable distance, which in turn resulted in significant decrease in luminance of the phosphor used.
• the phosphor particles are surrounded by a binder during mixing. This resulted in that it was not possible to obtain a high density of phosphor particles with a small distance between the individual particles in the phosphor layer.
• the methods used so far do not ensure a multi-step transfer of excitation energy between molecules under the influence of light. It should be added that the coatings produced with the methods known in the prior art resulted in the layer thickness as big as 1.0 to 3.0 mm.
• the prior art discloses a solution, wherein the binder with adhesion promoters, improvers, and coloring powder was subjected to the mixing process at a predetermined temperature together with the phosphor particles, and the resulting mass was extruded, cooled and milled to the desired granulation, and thus the photoluminescent coating was obtained. As a result of mixing, extruding and milling all substrates together the luminance of the phosphor crystals was decreased because of formation of a thin outer layer limiting absorption of light.
• the aim of the invention is to obtain a reflective photoluminescent powder paint, and a method of preparation of the reflective photoluminescent coating characterized by long-lasting luminance and phosphorescence, to be used as a renewable source of light for illumination of the surroundings without the need for electric energy supply to activate this effect.
• the aim of the invention is therefore a composition of photoluminescent coating devoid of a coloring pigment used commonly for paints which shall be replaced by a phosphor pigment so that in daylight the coating has a color of the phosphor powder used, while in the evening and at night it shines with color of luminescence of the luminescent powder.
• the reflective photoluminescent coating combines the effect of the phosphor luminance and the reflective effect, greatly improving the visibility of the coating.
• the proposed coating can be used for painting metal, glass, ceramic and plastic objects, for example furniture, auto parts, aluminum joinery, electrical equipment, housings of machines and various devices, lighting fixtures, household appliances, heating radiators, bicycles, ships, items for road safety such as barriers, signs, posts and other passive elements of road safety, as well as for painting elements of infrastructure of the human environment.
• Proposed invention results in a greater percentage of the phosphor attained by replacing the commonly used paint pigments with the photoluminescent powder consisting of one or more color compositions, depending on the specific requirements, thereby resulting in the ability to produce an ultra-thin coat of paint in just one cycle of the coating fusing.
• a method for producing a reflective photoluminescent coating according to the invention comprises: mixing a resin with an adhesion promoter and additives, heating the mixture to the molten state, extruding the mixture in a liquid state, cooling the mixture, pulverizing the extruded mixture to form a powder, milling the powder and finally adding the phosphor in powder form with mixing.
• Resin powder particles are selected, preferably of polyester, polyurethane, epoxy, mixed with the adhesion promoter and additives, that have a thickness of 10-350 ⁇ m (microns), preferably 10-200 ⁇ m, more preferably 33-195 ⁇ m. Also the phosphor powder particles having a thickness of 10-300 ⁇ m, preferably 30- 150 ⁇ m are selected.
• Addition of reflective glass beads preferably having a thickness of 10-300 ⁇ m, more preferably 30-150 ⁇ m, increases the reflective properties of the coating.
• the particles of pigments have a thickness of preferably 10-350 ⁇ m, more preferably 10-300 ⁇ m, most preferably 24-150 ⁇ m.
• the total volume fraction of the phosphor particles in the mixture was 30-65%, preferably 35%.
• an inner zone characterized by increased concentration of the phosphor particles is attained by reducing the distance between the grains until their mutual adhesion in the coating on the substrate side.
• This process is based on electrostatic interactions between electrically charged particles of the phosphor and the oppositely charged substrate. Both make an electric dipole.
• the volume fraction of the phosphor particles in the mixture in the inner zone of the coating is 70-98% and preferably 90-98%, especially 92- 98%.
• the coating After application of the powder mixture to the substrate, the coating is turned to the liquid state, and then back from the liquid state to the solid state.
• An article coated with the coating is annealed in a chamber furnace or continuous furnace at 200 °C for 10 min., or at 180 °C for 15 min., or at 160 °C for 20 min. Then it is cooled, preferably at a temperature of 20 °C.
• a reflective photoluminescent powder paint according to the invention comprises the powdered resin with the adhesion promoter and additives, and the phosphor powder mixed together.
• the powder particles of the resin preferably a polyester, polyurethane, epoxy, mixed with the adhesion promoter and additives, have a thickness of 10-350 ⁇ m, preferably 10-200 ⁇ m, more preferably 33-195 ⁇ m, and the phosphor powder particles have
• powder paint contains reflective glass beads, preferably with a thickness of 10- 300 ⁇ m, more preferably 30-150 ⁇ m.
• Powder paint can also contain pigments, preferably phosphors providing the coating with the desired color.
• the pigment particles have a thickness of preferably 10-350 ⁇ m, more preferably 10-300 ⁇ m, most preferably 24-150 ⁇ m.
• the total volume fraction of the phosphor particles in the mixture forming the powder paint is 30-65%, preferably 35%.
• a method for producing a reflective photoluminescent coating allows for making its inner zone with high packing density of the phosphor particles and such an arrangement of these particles that they adhere to one another.
• the volume fraction of the phosphor powder in the inner zone of the coating is from 70% to 98%, and the remaining part is a binder and other additives.
• the invented method allows to increase photoluminescence of the phosphor layer used from 50% to 340% and at least from 50% to 90%. Prolonged phosphorescence and luminescence in comparison with prior art coatings is also achieved.
• This method makes possible to produce white paint coating without the use of white pigment (eg. Titanium dioxide TiO 2 ) as this pigment can be replaced with a white phosphor (luminescent white).
• the coating method according to the invention by specifying a selected temperature in a chamber furnace or a continuous furnace the coating is fused, wherein the phosphor particles are arranged as close as possible in the inner zone with a volume concentration ranging from 70% to 98% of this zone. Transition of the binder from solid state in powder form into liquid state and back to a solid is applied, and the volume reduction accompanied by shrinkage of the coating is one of the mechanisms of concentration of the phosphor in the coating.
• a photoluminescent coating one has to mix the two components of the binder, ie. a resin with a catalyst (promoter) of binding, f!uidizers and improvers.
• the prepared material is melted, extruded, and cooled to ambient temperature, and it is then ground to a predetermined grain thickness, preferably between 10 ⁇ m and 350 ⁇ m, more preferably from 30 ⁇ m to 150 ⁇ m. Finally the phosphor particles of a selected thickness are added to the powder.
• the reflective beads are added, prepared e.g. from glass, and having a thickness of 10 to 350 ⁇ m, and preferably from 24 to 150 ⁇ m.
• the proportion of the reflective beads to the volume of the phosphor and binder particles ranges from 10% to 25%.
• the coated element After application of prepared mixture on the coated object it is heated to a temperature of 160-200 °C and annealed for 10-20 minutes. It is also possible to apply the coating in liquid form by melting the powder in a gas flame or using a flameless method, and moving it in a liquid state on the coated item by means of compressed air.
• the painted element shall be placed in an air fluidized bed of powder at a temperature higher than the melting point of the powder.
• a suitable electrostatic charge is supplied to the powder during its application, and then it is heated to the liquid state in the chamber furnace or the continuous furnace. Electrically charged particles are deposited on the grounded object due to electrostatic induction.
• the phosphor particle charged with positive charge (frictional charging) or negative charge (voltage powder charging) is attracted by induced charge of opposite sign and deposited on the painted material. The particles remain charged and are suspended in the structure of dry binder grains. Concentration of phosphorescent particles in the inner zone of the coating may reach 70% to 98% and is based on mutual attraction of the substrate and the phosphorescent particles making an electric dipole.
• deposited dry coating is heated until it is liquefied.
• the phosphor particles having a larger unit weight than the melted binder are deposited on the substrate first, because they are attracted to its surface by electrostatic charges. This results in a full absorption of the phosphor particles in the coating layer.
• next step of contraction of the binder the phosphor particles are further brought together. This process in combination with the interaction of electrostatic charges leads to a laminated composite fused by heating.
• the next step is removing the element outside the firing chamber and cooling at ambient temperature.
• the photoluminescent paint is finally contracted acting on the phosphor particles suspended in the binder.
• the phosphor has a thermal resistance exceeding many times the temperature applied for annealing.
• the method of forming a coating with use of the powder paint consists in applying the powder photoluminescent or reflective photoluminescent layer by electrostatic coating in one or two processes of layering the powder, and its consolidation takes place in a single thermal process.
• Fig. 1 shows a cross section through the reflective photoluminescent coating after electrostatic concentration of phosphor particles in a zone close to the substrate, wherein the state prior to densification, immediately after application of the coating to a substrate is shown in Fig. 2.
• the applied powder coating of photoluminescent layer (Fig. 2) contains the phosphor particles mixed with particles of binder in the first phase after application with contact-and- friction charging. A positively-charged powder is deposited on the painted material. When placed in a chamber and heated to an appropriate temperature the processes occur as follows:
• a process of energy transfer between the phosphor particles is faster as a result of packing of these particles, and this in turn increases the life time of molecules in the excited state and the strength of the lighting luminance (quantum efficiency) of produced coating with specified molar absorption coefficient, the integral absorption coefficient and value of transmittance.
• the reflective photoluminescent coating ultra-thin with a thickness of 35 microns, a transparent binder has been used, plus additives and phosphor of white base color (luminescence white), which gives off a light green color in the dark.
• the coating in application had a thickness of 40-60 ⁇ (microns), and was applied on a steel plate approximately 30 cm x 50 cm.
• the object surface was prepared for application of the powder paint with photoluminescent and reflective properties.
• the steel plate has been treated with pneumatic blasting-abrasive method and whitened.
• Polyester resin e.g. POLICEN 3660 T
• Liquidation improving additive polyacrylate-based anti-crater; supplier: e.g. BYK-366 P KRAHN CHEMIE
• This example was made to a product based on the starting preparation prepared in accordance with the following procedures.
• the thus prepared material was milled in a planetary ball mill PM 100 to produce a grain of 35 microns.
• a phosphor of particle size of 15-35 ⁇ m, and reflective glass beads of particle size of 25 ⁇ m were added with stirring to the resulting powder.
• a mixer Plasmec TRL was used to mix all the basic ingredients, and the resulting substance was applied to the prepared substrate by frictional triboelectrization.
• the substrate was fired in the chamber furnace or the continuous furnace at 200 °C for 10 min. A well-fixed paint coating was obtained.
• the plate surface was prepared for application of the powder paint with photoluminescent and reflective properties.
• the treatment of the aluminum plate was made by degreasing and mechanical cleaning with fine grit sandpaper and then washed with isopropyl alcohol and dried.
• Polyester resin e.g. POLICEN 3660 T
• Liquidation improving additive polyacrylate-based anti-crater; supplier: e.g. BYK-366 P KRAHN CHEMIE
• This example was made to a product based on the starting preparation prepared in accordance with the following procedures.
• the thus prepared material was milled in a planetary ball mill PM 100 to produce a grain of 35-80 microns.
• a phosphor having a particle size of 65-75 microns was added with stirring to the resulting powder, mixer Plasmec TRL was used for mixing.
• the resultant powder paint was applied to the prepared surface using high voltage electrostatic air-spray method of 40-100 kV.
• the material was then fired in the chamber furnace or continuous furnace at a temperature of 180 °C for 15 min. A ready well-fixed paint coating was obtained.
• the surface was prepared for application of the powder paint with photoluminescent and reflective properties.
• the treatment of the aluminum plate was made by degreasing and mechanical cleaning with fine grit sandpaper, and then the plate was then washed with isopropyl alcohol and dried.
• Polyester resin e.g. POLICEN 3660 T
• Liquidation improving additive polyacrylate-based anti-crater; supplier: e.g. BYK-366 P KRAHN CHEMIE
• a coating was pre-prepared for the use of two phosphors:
• the thus prepared material was milled in a planetary ball mill PM 100 to produce a grain of 35-80 microns.
• a phosphor having a particle size of 65-75 microns (The phosphor MSGG-4D 10 28 ⁇ m ) was added with stirring to the resulting powder, mixer Plasmec TRL was used for mixing.
• the resultant powder paint was applied to the prepared surface using high voltage electrostatic air-spray method of 40-100 kV.
• the resultant paint was applied to the prepared material.
• the method of applying was the high voltage of 40-100 kV electrostatic method.
• the mold surface was prepared by a known method.
• a binder with additives and a phosphor MGH 6 BA 50-150 ⁇ m Lanxi Minhui Photoluminescent was sprayed with a spray gun using electrostatic method on the prepared mold for powder casting.
• Vacuum forming was based on placing over the form of a shaped sheet of polymer in any, preferably light color, heating it and turning on the vacuum system, which removes air from the space between the mold and the material, thus injecting the heated material into the mold by means of air pressure.
• the layer of phosphor with binder and additives has been moved this way on the shell- shaped element. Finished piece was covered with a layer of luminescent powder on 1 % to 100% of the surface. It can be further processed by painting, varnishing, imposing an additional color with traditional paints, etc.
• the powder layer thickness was 50-150 ⁇ m in 1 % volume of 300 ⁇ , the applied thickness was 1.5 mm.
• the phosphor applied was MGH 6 BA with molecular formula: SrAI 2 O 4 :Eu+2,Dy+3.
• the phosphor particles are arranged spatially to one another, so that there is energy transfer between all particles which results in a longer, non-exponential decay of luminescence in the luminescent matrix.
• Phosphor photoluminescent powder
• any substance or material having photoluminescent properties usually a mixture of oxides, sulfides, selenides, silicates and orthophosphates (V) of alkaline earth metals, zinc and cadmium, including activators, e.g.: SrAI 2 O 4 :Eu+2,Dy+3.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Inorganic Chemistry (AREA)
• Paints Or Removers (AREA)
• Luminescent Compositions (AREA)

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• 2015
  • 2015-06-16 PL PL412732A patent/PL412732A1/pl unknown
• 2016
  • 2016-06-10 WO PCT/PL2016/000062 patent/WO2016204636A1/en active Application Filing
  • 2016-06-10 EP EP16739281.0A patent/EP3371259A1/en not_active Withdrawn

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