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 materials, e.g. electroluminescent or chemiluminescent
  • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
  • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B14/02—Granular materials, e.g. microballoons
  • C04B14/30—Oxides other than silica
  • C04B14/303—Alumina
• • 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 materials, e.g. electroluminescent or chemiluminescent
  • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
• • 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 materials, e.g. electroluminescent or chemiluminescent
  • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
  • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
  • C09K11/7783—Luminescent materials, e.g. electroluminescent or chemiluminescent 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
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/80—Optical properties, e.g. transparency or reflexibility
  • C04B2111/807—Luminescent or fluorescent materials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/80—Optical properties, e.g. transparency or reflexibility
  • C04B2111/82—Coloured materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives

Definitions

• Colored luminescent pigment process for its preparation and uses thereof
• the present invention relates to colored luminescent pigments, processes for their preparation, compositions comprising them, coatings comprising them, and their uses, in particular in hydraulic binder compositions.
• luminescent pigments in materials, in order to provide visibility in low light or zero brightness (night, shadow, darkness, interior unlit due to an electrical failure ...), is sought.
• the goal is to provide good visibility over a long period, typically over several hours. This is particularly of interest for signaling type applications, for example vertical or horizontal; extra lighting, improvement of the aesthetics of a material, for example graphic visualization, decoration ...
• the color of the material when the material is in the light and when the material is in a low light or zero brightness location typically for illuminations less than 100 Ix or even 10 Ix or even less than 1 Ix.
• JP201240596 the application of at least two successive coatings on the material.
• this technology requires the application of different coatings, time consuming and economically unprofitable.
• the present invention aims in particular the treatment of composition based on hydraulic binder and in particular concretes.
• This particular application can bring additional stress due to the alkaline pH of the hydraulic binder compositions.
• the introduction of luminescent pigments into concretes is already described, in particular in FR2168685, FR2990204 and WO2010134805. However, these documents do not describe the possibility of introducing a particular dye to choose and control the color of concrete in light and low light or zero brightness.
• An object of the present invention is to provide a colored luminescent pigment, especially usable in the mass of the material, which allows the control of a coloration of the material in the light and by luminescence in low light or in the absence of brightness.
• Another object of the present invention is to provide a process for the preparation of such a pigment.
• compositions comprising the colored luminescent pigment.
• Still another object of the present invention is to provide a material, for example paint, hydraulic binder composition comprising the colored luminescent pigment or the composition comprising the colored luminescent pigment.
• the present invention provides a colored luminescent composite pigment comprising at least one luminescent pigment and at least one dye, the composite pigment having an average particle size of between about 50 and about 2000 ⁇ .
• the composite pigment of the present invention may also be defined as a colored luminescent composite pigment comprising, in combination, at least one luminescent pigment and at least one dye, and having an average particle size of from about 50 to about 2000 ⁇ .
• the colored luminescent composite pigment according to the present invention (or colored luminescent pigment or composite pigment or luminescent composite pigment) has an average particle size of between about 60 and about 2000 ⁇ , preferably between about 60 and about 500 ⁇ , for example between about 75 and about 200 ⁇ .
• the term "luminescent pigment” is understood to mean any compound capable of absorbing photons emitted by natural or artificial light and render a light emission in the case of reduced brightness or in the absence of luminosity. .
• Luminescence includes phosphorescence and fluorescence.
• the luminescent pigment is a photoluminescent pigment.
• the luminescent pigment will be chosen according to the color, in reduced brightness or in the absence of brightness, which is desired.
• the luminescent pigment will be selected to have a remanence of several hours after exposure to natural or artificial light.
• the luminescent pigment may be organic or inorganic, the mineral pigments being preferred because of their greater durability, especially in the open air.
• the luminescent organic pigments are chosen in particular from naphthalimides, coumarins, xanthenes, thioxanthenes, naphtholactams, azlactones, methines, oxazines and thiazines, or their mixture.
• the luminescent inorganic pigments are especially chosen from:
• M (II) is at least one divalent metal selected from barium, strontium, lead and calcium
• M (lll) is chosen from lanthanum, gadolinium, yttrium, cerium, lutetium and bismuth, 0 ⁇ x ⁇ 0.2
• the luminescent pigment is chosen from zinc sulphide and strontium or calcium aluminates doped with rare earths, or mixtures thereof.
• the luminescent pigment is chosen from zinc sulphide and strontium aluminates doped with rare earths.
• the luminescent pigments according to the present invention are not covered with a protective layer, that is to say they have not been covered with a polymeric matrix (for example polyethylene), wax ... to protect them from external aggressions, especially to protect them from reactions to water.
• a polymeric matrix for example polyethylene
• wax ... to protect them from external aggressions, especially to protect them from reactions to water.
• the luminescent pigments coated with a protective layer are used in the invention, when the composite pigment obtained is washed with water, the water is found colored dye color, thus highlighting leaching of the dye.
• the luminescent pigment has an average particle size of between about 60 and about 2000 ⁇ , preferably between about 60 and about 500 ⁇ , for example between about 75 and about 200 ⁇ .
• the luminescent pigment particles are porous and have a percentage of pores by volume, in particular measured by mercury porosity according to the IS015901-1: 2005 standard, of between 1 and 90%, preferably between approximately 2 and approximately 50%.
• the term "dye” is understood to mean a substance, or a mixture of substances, allowing, when it is used in a material, to give color to this material by absorbing or reflecting specific wavelength radiation. This substance or mixture may be soluble or insoluble in the material in question.
• the dye will make it possible to fix the color of the material in the light, in particular in the light of the day.
• the dye will be chosen according to the desired color, it is also possible to use dye mixtures.
• the dye may be organic or inorganic in nature.
• the dye may especially be in the form of a powder, a powder in suspension.
• This composite dye may be composed in particular of particles comprising an inorganic core, at least one binder for fixing the organic dyes on the core, and at least one organic dye at least partially covering the core.
• the dye may also be a special effects dye.
• Special effects dyes are dyes which generally create a colored appearance (characterized by a certain shade, a certain liveliness and a certain clarity) which is non-uniform and changeable according to the conditions of observation (light, temperature , observation angles ). They are therefore opposed to white or colored dyes that provide a uniform opaque, semi-transparent or conventional transparent tint.
• pearlescent pigments such as white pearlescent pigments such as titanium mica, or mica-bismuth oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, mica titanium with in particular ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride.
• inorganic dyes mention may be made of titanium oxides such as anatase and rutile, the various iron oxides (yellow, red, brown, etc.), chromium oxides, barium oxides, oxides of cadmium, nickel oxides, copper oxides, cobalt oxides, zinc oxides, cobalt stannate, cobalt aluminates, quartz powder, talc, carbon black, calcium carbonate and barite.
• the dye may also be a fluorescent dye (or brightener).
• fluorescent dyes may be of interest, especially for safety displays.
• the effect of the dye can be enhanced by combination with an optical brightener for example.
• This brightener (or combination of brighteners) may for example be chosen from stilbene derivatives.
• the addition of a fluorescent dye (or an optical brightener) advantageously also makes it possible to modulate the night color of the luminescent pigment.
• the dye is chosen from oxides of iron, barium, chromium, cadmium, zinc, cobalt, nickel and titanium and carbon black.
• the size of the dye particles is smaller than the size of the luminescent pigment particles.
• the average size of the dye particles is at least 10 times smaller than that of the luminescent pigment.
• the dye has an average particle size of between about 0.1 and about 10 ⁇ .
• the mean size of the particles or aggregates the mean diameter of the particles.
• This size can be measured in volume by laser granulometry for particles having a size of less than or equal to 500 ⁇ (ISO 13320: 2009 standard) or in weight by sieving for particles having a size greater than 500 ⁇ (measured according to the NF standard EN 933-1 of May 2012).
• control of the coloring with light and control of the luminescence in low light or in the absence of luminosity is understood to mean having a homogeneous color in the light and having a homogeneous color by luminescence under low illumination (or low light) or in the absence of illumination (or in the absence of brightness), these colors being identical or different and being chosen independently of one another. Thus, it is possible to have a color of day (dye) different from the color of night (luminescent pigment).
• low luminosity or low illumination
• absence of luminosity or absence of illumination
• association is understood to mean an interaction, in particular an intimate one, between the luminescent pigment and the dye which allows, when the colored luminescent pigment is rinsed with water not to remove the dye as was shown by the inventors.
• the composite pigment according to the invention comprises from 0.00001 to 99.99999% by weight of luminescent pigment and from 99.99999 to 0.00001% by weight of dye, preferably from 50 to 99.99% by weight of luminescent pigment and from 50 to 0.01% by weight. by weight of dye.
• the present invention also relates to a process for preparing a colored luminescent composite pigment comprising the steps of:
• step b) providing a composition comprising one or more dyes in a fluid; b) mixing with the composition of step a) at least one luminescent pigment; and c) drying the mixture obtained in step b).
• the composition of step a), when the dye is non-soluble in the fluid is a dye suspension (s) in the fluid.
• the fluid is selected from water, alcohols (preferably ethanol) and acetone, or mixtures thereof.
• the fluid is water and in particular purified water (by distillation or passage over an ion exchange resin) in order to avoid the appearance of whitish deposit on the colored luminescent pigment and to limit the phenomena of agglomeration detrimental.
• the dye may be suspended or solubilized in the fluid by any means known to those skilled in the art, in particular by mechanical means.
• the suspension may also be carried out in the presence of a dispersant of surfactant type or other polymers, for example acrylic polyacid, comb polymer, in particular of the PCP type, structured polymer such as those described in the patent application EP0877765.
• composition of step a) may optionally contain a wetting agent.
• wetting agents are described in particular in the reference: The formulation of paints, J.C.Laout, Ed. Engineering Techniques, page J 2 270-16 of September 10, 2005.
• the composition of step a) comprises from 0.0001 to 50%, preferably from 0.05 to 1%, preferably from 0.1 to 0.5%, by weight of dye (s) relative to the total weight of the composition. This advantageously makes it possible to control the viscosity of the composition of step a).
• the Brookfield dynamic viscosity of the composition of step a), measured at 20 ° C. is less than 1000 mPa.s, preferably less than 100 mPa.s, in particular between about 1 mPa.s and 1000 mPa. .s, preferably between about 1 mPa.s and about 100 mPa.s.
• the inventors have pointed out that the more the composition of step a) was viscous, the more the composite pigment was leachable with loss of the dye, revealing a less good association, or even a gap between the luminescent pigment and the dye at viscosities. greater than 1000 mPa.s.
• the composition of step a) is an aqueous dye composition.
• the luminescent pigment is as defined above.
• the amount of dye is chosen so that the loss of luminescence of the final colored luminescent pigment with respect to the luminescent pigment alone is not greater than 10% (loss measured according to NF X 08-050-1 and DIN 67510-1).
• the mixture obtained comprises 1 to 90%, preferably 15 to 60%, preferably 25 to 35%, by weight of luminescent pigment relative to the total weight of the mixture.
• Color enhancers may be chosen in particular from fatty acids.
• the antioxidants may especially be chosen from phenol derivatives, aromatic secondary amines, quinones, amines of the HALS type (Hindered Amine Light Stabilizers).
• the mixture of step b) is carried out for 30 seconds to 1 hour, preferably for 1 to 10 minutes.
• the agitation, during step b), should preferably not be shearing so as not to change the size of the luminescent pigments and dyes. Stirring greater than 10 minutes may cause a risk of luminescent pigment breaking and risk of agglomeration. Stirring less than 1 minute can cause a less good association between the luminescent pigment and the dye and thus a possible leaching of the composite pigment obtained.
• step b) the dye is associated with the luminescent pigment to form the colored luminescent pigment.
• step b) can be carried out in the presence of a binder.
• binders include latexes, epoxy resins, polyurethane resins.
• the composite pigment of the invention may not comprise a binder for fixing between them the luminescent pigment and the dye.
• the composite pigment of the invention does not comprise a silica layer.
• the drying step c) can be carried out at room temperature (about 20 to 25 ° C), however the temperature must be controlled in order not to degrade luminescent pigments and dyes. Those skilled in the art, in view of the luminescent pigments and dyes used, are able to determine the drying limit temperature. Preferably, the drying temperature is below 400 ° C.
• the drying can be carried out by any method known to those skilled in the art and in particular by static drying (for example drying in a fixed thin layer), atomizer, fluidized bed, etc.
• the drying step can be carried out under a gaseous flow, for example air flow, nitrogen.
• the drying step c) can also be carried out under vacuum. Advantageously, this reduces the drying time.
• the process according to the present invention may comprise, before step c), a step b ') of decanting the mixture obtained in step b) and of separating:
• a liquid phase comprising the dye which has not been associated with the luminescent pigment and which can be reused in the process of the invention as a composition of stage a).
• the process for preparing the colored luminescent pigment according to the present invention may also comprise a step b "), before or after step c), and if appropriate before or after step b '), of depositing a coating on the surface of the colored luminescent pigment
• This step which advantageously makes it possible to protect the colored luminescent pigment, particularly with respect to water, can be carried out hot or cold, in particular up to a temperature of 400 ° C., by any method known to a person skilled in the art, such as spraying or quenching in a bath,
• the coating may be chosen by those skilled in the art depending on the application and the end material concerned.
• the colored composite luminescent pigment of the invention in particular, be a polymeric coating (chosen in particular from polyurethanes, epoxy resins, acrylic polymers, polyamides, polyesters, silicone resins, polyalkylenes or fluorinated polymers) or a wax (chosen especially among naturally occurring waxes such as carnauba wax or synthetic waxes such as paraffins).
• a polymeric coating Chosen in particular from polyurethanes, epoxy resins, acrylic polymers, polyamides, polyesters, silicone resins, polyalkylenes or fluorinated polymers
• a wax chosen especially among naturally occurring waxes such as carnauba wax or synthetic waxes such as paraffins.
• step b can be carried out before step b ') and before step
• the invention also relates to the colored luminescent pigment obtainable by the process of the invention.
• the colored luminescent pigment of the present invention may be introduced into a matrix, preferably transparent.
• the present invention therefore relates to a luminescent composition (C) comprising a transparent matrix and a luminescent composite pigment according to the invention.
• the transparent matrix is in particular compatible with the alkaline pH of the hydraulic binder compositions, and is preferably chosen from polymethyl methacrylate (PMMA), polycarbonate (PC), polyvinyl chloride (PVC), polyurethane (PU), styrene acrylonitrile (SAN) copolymers and their derivatives such as ABS (acrylonitrile / butadiene / styrene) or glass.
• PMMA polymethyl methacrylate
• PC polycarbonate
• PVC polyvinyl chloride
• PU polyurethane
• SAN styrene acrylonitrile copolymers and their derivatives such as ABS (acrylonitrile / butadiene / styrene) or glass.
• ABS acrylonitrile / butadiene / styrene
• the luminescent composition (C) may be a liquid composition or a solid composition at room temperature (approximately 20 to 25 ° C.), that is to say that the transparent matrix that it contains is either a transparent liquid matrix at ambient temperature is a transparent matrix solid at room temperature.
• the luminescent composition (C) is a solid composition, the solid transparent matrix notably making it possible to ensure durability and to avoid degradation, in particular by contact with water, of the colored luminescent composite pigment.
• the luminescent composition (C) may be obtained by dispersing the colored luminescent pigment obtained in step c) in a liquid transparent matrix solution or in a transparent liquid matrix capable of generating the solid transparent matrix, in particular by solidification, crosslinking or polymerization. .
• the luminescent composition (C) When the luminescent composition (C) is solid, it can be molded, for example the mold can be filled by an injection press, or shaped by extrusion. Rotational molding techniques can also be implemented.
• solution capable of generating the transparent matrix is meant the transparent matrix in the molten state (which can therefore generate the transparent matrix by solidification), or a solution comprising monomers capable of generating the transparent matrix by polymerization, or a solution comprising a prepolymer capable of generating the transparent matrix by crosslinking.
• the solution capable of forming the transparent matrix is a solution of molten polymer or molten glass, preferably molten polymer.
• molten polymer preferably molten polymer.
• this makes it possible, because of the high viscosity of the molten polymer, to avoid settling of the composite pigment according to the invention and thus to obtain homogeneous compositions.
• the luminescent composition according to the invention comprises from 0.001% to 99.999% by weight of luminescent composite pigment and 99.999% to 0.001% by weight of transparent matrix.
• the luminescent composition comprises between 0.5% and 60% by weight of luminescent composite pigment and 99.5% and 40% of transparent matrix, and preferably between 5% and 50% of luminescent composite pigment and 95% and 50% by weight of transparent matrix.
• the solid luminescent composition (C) obtained can be milled to form aggregates.
• the grinding can be carried out by any method known to those skilled in the art depending on the size of the desired aggregates.
• the invention therefore also relates to a granulate comprising a transparent matrix and a composite pigment according to the invention.
• the aggregates Preferably, the aggregates have an average particle size of between about 0.1 and 125 mm (size measured according to the standards ISO 13320: 2009 or NF EN 933-1 of May 2012).
• the average particle size corresponds to the average particle diameter.
• the transparent matrix is PMMA and the solution capable of forming the transparent matrix is a molten PMMA solution.
• the mixture of molten PMMA and composite pigment according to the invention is poured into a mold, in particular using an injection molding machine.
• the composition (C) obtained is milled to obtain aggregates of desired size.
• the process for preparing the composition (C) of the invention or a granulate of the invention comprises the steps of:
• step 2) optionally formatting the dispersion obtained in step 2), in particular in a mold;
• step 2) optionally solidifying the mixture obtained in step 2) or 3);
• step 5) optionally grinding the composition obtained in step 4) to obtain aggregates.
• the method may comprise a step of preparing the colored luminescent composite pigment according to the invention before step 1), in particular the preparation method described above.
• the invention relates to a method for preparing a granulate according to the invention in which the transparent matrix is PMMA, comprising the steps of:
• step 2) shaping the dispersion obtained in step 2) in a mold, in particular using an injection molding machine or by rotational molding;
• the method may comprise a step of preparing the colored luminescent composite pigment according to the invention before step 1), in particular the preparation method described above.
• composition (C) according to the invention can also comprise additives, in particular additives of flame retardant type; additives which improve the hardness, for example quartz.
• additives are preferably added during the preparation of the luminescent composition (C) or the granulate, especially in the dispersion comprising the composite pigment of the invention and the solution capable of forming the transparent matrix.
• the colored luminescent composite pigment and the luminescent composition (C) according to the present invention can be used for coloring materials such as hydraulic binder compositions (plaster, concrete, mortar, screed), plastics, plaster, coatings, varnishes and paints, inks, paper and cardboard, cosmetic compositions, textiles, glasses, enamels, ceramics, tile adhesives, tile joints ...
• the coloration with the colored luminescent pigment of the invention, the composition (C) of the invention or the granulate of the invention can be made both in the mass and on the surface of the material to be colored.
• the composite pigment according to the invention can be used:
• a two-component mixture comprising, on the one hand, the composite pigment, the composition (C) or the granulate and, on the other hand, a binder, the mixture of the two components being made just before application
• composition (C) in a one-component mixture comprising the composite pigment, the composition (C) or the granulate dispersed in a binder, in particular of the acrylic, epoxy, styrene-acrylic, silicate or polyurethane type,
• the surface application may be by spraying, by deposition for example by roller or with a brush, by pouring, by sprinkling (in particular dusting of the composite pigment on the surface of the material).
• the composition (C) is liquid, it can be applied by spraying, by deposition for example by roll or deposition on the surface of the material and crosslinking or polymerization to form a solid coating.
• the composite pigment can be dispersed in a solution of a monomer capable of polymerizing after deposition on the surface of the material.
• the surface application can be done for example by nailing (insertion of a composition (C) or granulate on the surface of the material before setting) ...
• the invention also relates to a material comprising the colored luminescent composite pigment or the luminescent composition (C) or the granulate according to the invention.
• the material is chosen from hydraulic binder compositions (plaster, concrete, mortar, screed), plastics, varnishes and paints, coatings, coatings, inks, paper and paperboard, cosmetic compositions, textiles, glass, tile adhesives, tile joints ...
• hydraulic binder compositions plaster, concrete, mortar, screed
• plastics varnishes and paints
• coatings coatings
• coatings inks
• paper and paperboard cosmetic compositions
• textiles glass, tile adhesives, tile joints ...
• the use of the composite pigment according to the invention, of the composition (C) according to the invention or of the aggregates according to the invention makes it possible to obtain materials of homogeneous color with good control of the color at the light and in reduced brightness or in the absence of brightness while reducing the necessary amount of dye compared to the usual techniques.
• the present invention also relates to a coating comprising the colored luminescent composite pigment or the composition (C) or the granulate according to the present invention.
• the coatings may for example be organic coatings, for example example acrylic varnish, or inorganic coatings, for example silicate paint.
• the coatings can also be obtained by a sol / gel process.
• the present invention relates to the use of composite pigments according to the invention and / or aggregates according to the invention for the coloration of hydraulic binder compositions, especially for the coloring of concrete.
• hydraulic binder is understood to mean any compound having the property of hydrating in the presence of water and whose hydration makes it possible to obtain a solid having mechanical characteristics.
• the hydraulic binder can comprise or consist of a cement according to the EN 197-1 standard and in particular a CEM I, CEM II, CEM III, CEM IV or CEM V type cement according to the NF EN 197-1 (2012) cement standard.
• the cement can therefore in particular comprise mineral additions.
• composition based on hydraulic binder means a composition comprising a hydraulic binder. It may be a composition based on fresh hydraulic binder, which then corresponds to a “hydraulic binder composition”, or a composition based on hardened hydraulic binder, such as concrete.
• the hydraulic binder can also be a hydraulic binder based on calcium sulphate.
• calcium sulfate hydraulic binders is meant according to the invention the hydraulic binders based on partially anhydrous or totally anhydrous calcium sulfate. This includes:
• freshness refers to such hydraulic binder-based compositions when they have been tempered with water, but have not yet hardened. They are then malleable enough to fill the mold or formwork.
• hardened is understood to mean such hydraulic binder-based compositions when cured.
• setting is meant the passage to the solid state by hydration reaction of the binder.
• crete is meant a mixture of hydraulic binders, aggregates, sands, water, optionally additives, and possibly mineral additions.
• cement also includes mortars and screeds.
• mineral additions refers to slags (as defined in NF Cement Standard EN 197-1 (2012) section 5.2.2), steelmaking slags, pozzolanic materials (as defined in NF Cement Standard).
• metakaolins such as type A metakaolins conforming to standard NF P 18-513
• siliceous additions such as the siliceous additions of mineralogy Qz conforming to standard NF P 18-509 (2012).
• aggregates is meant a set of mineral grains with a mean diameter of between 0 and 125 mm. Depending on their diameter, aggregates are classified into one of six families: fillers, sand, sand, gravels, chippings and ballast (standard XP P 18-545 of September 201 1).
• the most widely used aggregates are the following: fillers, which have a diameter of less than 2 mm and for which at least 85% of the aggregates have a diameter less than 1.25 mm and at least 70% of the aggregates have a diameter less than 0.063 mm, sands with a diameter between 0 and 4 mm (in standard 13-242, diameter up to 6 mm), lobes with a diameter greater than 6.3 mm, gravel diameters between 2 and mm and 63 mm. Sand is therefore included in the definition of granulate according to the invention.
• the fillers may in particular be of calcareous, siliceous or dolomitic origin.
• the present invention also relates to hydraulic binder compositions, preferably concrete, comprising the colored luminescent composite pigment of the invention and / or the aggregates of the invention.
• the colored luminescent composite pigment When used, it can be introduced into the mass of the hydraulic composition, especially concrete, or at the surface of the hydraulic composition.
• the composite pigment according to the invention can be added in premix with the standard aggregates and introduced to the mix or directly introduced, individually at the time of mixing.
• the quantities of composite pigment used depend on the color and in particular on the intensity that is desired. In general, they correspond to the amounts generally used for conventional dyes, that is to say between 1 and 10% by weight of the hydraulic binder.
• the pigment composite of the invention can be sprinkled on the surface of the hydraulic binder composition before setting or applied, before or after setting dispersed in a composition of the paint type, varnish.
• the aggregates according to the invention When used, they can be used as a replacement for all or part of the aggregates typically used in hydraulic compositions, particularly of the concrete type or in addition to the aggregates typically used. Aggregates can also be inserted into the concrete surface before setting.
• FIG. 1 represents the particle volume in% as a function of the particle size in ⁇ and provides the particle size distribution measured by laser granulometry (Mastersizer 2000) (example 7).
• FIG. 2 represents the granulometric curve of the aggregates according to the standards NF EN 933-1 and NF EN 933-2 (example 8).
• Example 1
• the mixture decants rapidly and the decantate is spread on shelves to a thickness of 2 to 3 cm.
• the shelf is then placed for 4 hours in a chamber to be heated at 50 ° C. under a stream of hot air.
• the pigment is then in the form of a fluid powder that is not necessary to grind. In the light of day, the pigment has the beige color of the dye. In the dark, it emits a yellow / green light identical to that of the luminescent pigment.
• the colored pigment is available to be incorporated in materials such as for example cementitious materials (mortar, concrete, screed, ...) or plastic materials (PMMA, %), which after grinding to the desired size, can be used as aggregates in concretes.
• materials such as for example cementitious materials (mortar, concrete, screed, ...) or plastic materials (PMMA, %), which after grinding to the desired size, can be used as aggregates in concretes.
• PMMA plastic materials
• a and B composed of strontium aluminate (yellow in daylight, emitting in the blue in the dark, particle size 350 ⁇ ) are used. They differ only in the fact that A is untreated whereas B has been treated with a polyethylene wax to give it better resistance to water and moisture.
• the colored pigments 2 and 3 are prepared according to the procedure of Example 1 from the compositions described in the table below:
• the pigment content of the paste is 60% by weight.
• the colored pigment of Example 2 is in the form of a homogeneous powder of blue color in the light of day and emitting in the night blue.
• the colored pigment of Example 3 is not homogeneous, of generally less intense color, with the presence of dark blue agglomerates. This inhomogeneity is also noticeable when one looks at the light emitted in the dark by the sample 3.
• each of these two pigments are placed under agitation in 1 liter of tap water. After about 5 minutes, stirring is stopped.
• the pigment 2 decants leaving the water transparent.
• the pigment of Example 3 decants and leaves the water colored blue, indicating that the colored luminescent pigment of Example 3 would be very sensitive to leaching problems, which is detrimental in terms of durability.
• the comparison of these 2 examples shows the importance of having an untreated luminescent pigment in order to achieve an effective coloration.
• Untreated luminescent pigments of the same chemical composition as that of Example 2 and variable particle sizes are used. They are mixed with the same blue pigment paste and according to the same procedure as in Example 2.
• the brightness remanence is measured according to DIN 67510-1: 2009.
• the unit cd is the candela which is the unit of measure of the luminous intensity.
• the objective is to measure the luminance (mcd / m 2 ) restored by a composition (C) according to the invention after exposure under illumination produced by a Xenon arc.
• the sample is a material consisting of 30 parts of composite luminescent pigment according to the invention and 100 parts of PMMA.
• AFNOR sand is a standardized sand with a grain size between 0 and 2 mm (determined by sieving and complies with the requirements of EN 1 96-1 (2006) and ISO 679 (2009).)
• Mortar composition (with sand afnor substituted for 30% by weight with a luminescent material 0/2)
• the start time (DP), end of set (FP) and total set time (TP) are grouped in the table below
• the particle size of a luminescent pigment obtained according to Example 1 was determined by laser granulometry (Mastersizer 2000).
• Figure 1 shows the particle size distribution in volume.
• the luminescent powder has the following profile provided in FIG. 1 according to a volume distribution:
• the granulometry of the aggregates of size 6/10 comprising 20 parts of luminescent pigment and 100 parts of PMMA was determined according to the standards NF EN 933-1 and NF EN 933-2 and is provided in FIG.
• Figure 2 is a grain size curve representing the cumulative percentage by weight of sieve (mm).

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