WO2020239785A1 - Solid composition for forming surface coatings - Google Patents

Solid composition for forming surface coatings Download PDF

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Publication number
WO2020239785A1
WO2020239785A1 PCT/EP2020/064607 EP2020064607W WO2020239785A1 WO 2020239785 A1 WO2020239785 A1 WO 2020239785A1 EP 2020064607 W EP2020064607 W EP 2020064607W WO 2020239785 A1 WO2020239785 A1 WO 2020239785A1
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WO
WIPO (PCT)
Prior art keywords
weight
forming
coating
composition according
composition
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Application number
PCT/EP2020/064607
Other languages
French (fr)
Inventor
Dany WIRTH
Original Assignee
Stoelzle Masnieres Parfumerie
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Publication of WO2020239785A1 publication Critical patent/WO2020239785A1/en

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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
    • C09D5/033—Powdery paints characterised by the additives
    • C09D5/035—Coloring agents, e.g. pigments
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/41—Organic pigments; Organic dyes
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • C08K2003/3036—Sulfides of zinc

Definitions

  • the invention relates to a solid composition of powder type capable of forming a surface coating on a support, in particular formed of a material of glass, ceramic, metal or plastic.
  • the invention also relates to a process for preparing this composition and a process for preparing a coating from this composition.
  • Solid compositions dedicated to forming surface coatings on supports of all types of wood, steel, plastic, glass are today recognized as being advantageous alternatives to liquid formulations of the paint and varnish type.
  • the powder type compositions do not require the use of a solvent. Their use is easy and clean. Thus, they are most often applied by electrostatic spraying or by a triboelectric process. Depending on the nature of the support considered, heating of the part or of its surface to be treated can sometimes be carried out before or after the immobilization of the solid composition on the surface to be treated.
  • these solid compositions consist essentially of an organic material of synthetic resin (s) type capable of forming the expected coating and of an inorganic material of mineral fillers and pigments type, the latter having more particularly the vocation of imparting a translucent and / or colored effect to the final coating.
  • the transparent or translucent appearance is adjusted by the choice of these inorganic materials and most often, the pigment retained for this purpose is titanium dioxide.
  • White in color it increases the whiteness or brilliance of coatings.
  • These pigments also have interesting opacity and covering power and satisfactory mechanical properties.
  • the titanium dioxide pigments are thus very particularly considered to impart a decorative effect of the opaline type, that is to say translucent to coatings of area. These coatings are particularly very useful for imparting decorative effects to articles of architectural type in public building works, in the glass industry, for example for the ornamentation of hollow glasses, perfume bottles, bottles, containers. cosmetics, and also in the ceramics industry as with regard to tableware and sanitary ware.
  • These titanium dioxide pigments are also widely used to modify the color tints provided by other organic or inorganic coloring agents.
  • titanium dioxide pigments are used in many different ways because their harmlessness with regard to living organisms because their harmlessness with regard to living organisms is now called into question.
  • An alternative pigment to titanium dioxide is zinc sulfide.
  • the dispersion of this second pigment in an organic material such as synthetic resin (s) proves to be more difficult.
  • the raw materials constituting the solid compositions dedicated to forming coatings are conventionally combined by considering successively the production of premixes of certain raw materials, the mixing of these premixes by extrusion, their grinding and a micronization of the final mixture thus obtained for the transform into a fine powder.
  • this method of preparation is not completely satisfactory in terms of modulation of coloration.
  • the color effect is not always reproduced optimally. It can therefore be difficult to faithfully reproduce a specific effect such as a shade using currently available powders.
  • the object of the present invention is precisely to provide novel solid compositions for coating which make it possible to overcome the aforementioned problems.
  • the present invention provides access to solid compositions of powder type capable of forming coatings endowed with improved surface qualities.
  • the present invention provides access to solid compositions of powder type capable of forming translucent and / or colored coatings and whose visual effect is uniform and optimized.
  • the present invention also aims to provide solid compositions of powder type capable of forming coatings endowed with increased mechanical strength.
  • the present invention further aims to provide a solid composition of powder type for forming coatings, having a reduced and preferably zero amount of titanium dioxide.
  • the present invention relates to a solid composition in the form of a powder capable of forming a surface coating on a support, said composition comprising at least one film-forming organic material, zirconium hydrogenphosphate. and at least one material chosen from organic coloring materials and pigments.
  • a "translucent coating” is a coating which allows part of visible light to pass through and scatter it. As opposed to a transparent coating, it does not make it possible to clearly visualize an object placed in a mirror. It is also distinguished from an opaque coating which does not allow light to pass through, and therefore which does not allow you to see what is behind the coating. Such a coating may further be qualified as endowed with a so-called “opaline” effect, or “opaline tint” when it also exhibits iridescent effects and the coating is then generally of a milky, white or colored appearance.
  • the present invention is most particularly aimed at a solid composition in the form of a powder capable of forming a surface coating on a support, said composition comprising at least one film-forming organic material, zirconium hydrogenphosphate and at least one chosen material. from organic dyestuffs and pigments, and comprising less than 3% by weight of titanium dioxide relative to its total weight and preferably devoid of titanium dioxide.
  • the coatings obtained from the compositions according to the invention are advantageous in several ways.
  • zirconium hydrogenphosphate advantageously makes it possible to improve the resistance of such coatings on the surface of a support, in particular a glass support.
  • the color effect it is optimized in terms of dispersion, depth of intensity, uniformity and durability in the coating.
  • the combination of at least one film-forming organic material, zirconium hydrogenphosphate and zinc sulphide, favored over titanium dioxide gives the coating a translucent appearance, in particular of an opaline hue, which is durable due to its high resistance to mechanical stresses, as well as to temperature or chemical stresses.
  • such a composition is useful for forming a translucent or opaline-effect coating.
  • the present invention relates to a process for preparing a composition in accordance with the invention comprising at least the steps consisting of:
  • a film-forming particulate material and G zirconium hydrogen phosphate with at least one premix comprising ancillary components of said composition including at least one organic coloring material or a pigment and preferably distinct from titanium dioxide,
  • the method of the invention does not implement an extrusion step.
  • the present invention also relates to the use of at least one composition according to the invention for forming a surface coating, in particular transparent or translucent and colored or not, on a support.
  • a coating is translucent or has an opaline effect. It also relates to a method for forming a coating on the surface of a support comprising at least the steps consisting in
  • Such a process makes it possible in particular to form a translucent coating or a coating with an opaline effect.
  • the term film-forming is intended to describe the fact that the material in question is capable of being organized in the form of a film when it is applied to a support.
  • This film is also advantageously capable of constituting a matrix for the materials which are combined with it in order to give it particular properties.
  • These properties can be qualities of adhesion, mechanical resistance, UV resistance, thermal resistance and also be related to the manifestation of aesthetic effect, for example decorative.
  • the film-forming organic materials which are particularly suitable for the invention are preferably synthetic resins.
  • thermo- or photo-curable or thermoplastic can be thermo- or photo-curable or thermoplastic. This type of material is well known and the conditions required to transform them into a film are well documented.
  • film-forming organic materials suitable for the invention may need to be stimulated by a trigger, heating, UV exposure or the like to form the film constituting the expected coating.
  • the film-forming organic material can incorporate a crosslinking agent.
  • the film-forming organic material can also be used without a crosslinking agent.
  • film-forming organic materials are used in particulate form and their particulate size advantageously ranges from 1 to 100 ⁇ m.
  • these resins mention may very particularly be made of epoxy resins, of polyurethanes, of polyacrylates, of polyesters, modified or not, and their mixtures.
  • the film-forming organic material is at least one polyurethane resin or at least one polyester resin.
  • a composition according to the invention may contain at least 90% by weight of film-forming material relative to its total weight.
  • a composition according to the invention may contain from 90 to 95% by weight of film-forming material relative to its total weight.
  • the weight of film-forming material is expressed in dry weight in the context of the present description.
  • this film-forming organic material is combined with zirconium hydrogen phosphate.
  • the zirconium hydrogenphosphate content varies from 0.5 to 10% by weight and in particular from 1 to 5% by weight relative to the total weight of the composition. In particular, the zirconium hydrogen phosphate content varies from 1 to 3.5% by weight, or even from 1.5 to 3% by weight relative to the total weight of the composition.
  • G zirconium hydrogenphosphate and the film-forming organic material are used in a weight ratio varying from 1/20 to 1/200 and preferably less than 1/20.
  • this zirconium hydrogenphosphate increases the mechanical strength of the coating formed according to the invention and gives it an optimized decorative effect in terms of intensity and homogeneity.
  • Zirconium hydrogen phosphate is not charged with metallic element, in particular does not contain silver.
  • a composition according to the invention further contains at least one organic coloring material or a pigment.
  • these materials are present for the purpose of imparting particular properties to the expected coating.
  • these materials generally have a particle size of between 30 microns and 100 microns, better still between 20 and 60 microns, even better between 5 and 40 microns.
  • a composition according to the invention advantageously contains less than 3% by weight, in particular less than 2% by weight, in particular less than 1% by weight, of titanium dioxide relative to its total weight and preferably is devoid of it.
  • the level of organic coloring matter or pigment in the composition may vary depending on the use for which it is intended.
  • a composition according to the invention can contain up to 10% by weight of organic coloring material or pigment, preferably up to 6%, more preferably from 0.5% to 5%, or even less than 4%, relative to its total weight.
  • a composition according to the invention contains as a pigment at least zinc sulphide.
  • a pigment is very particularly advantageous for accessing so-called colorless or even transparent or even translucent coatings.
  • zinc sulphide is particularly interesting for obtaining coatings with an opaline effect or even milky appearance.
  • a composition according to the invention contains at least 90 to 95% by weight of at least one film-forming organic material, preferably at least one polyurethane or polyester resin, from 0.5% to 10 % and in particular from 1 to 5% by weight of zirconium hydrogen phosphate and preferably from 1% to 10%, in particular from 2.5% to 6% by weight of zinc sulphide relative to its total weight.
  • composition according to the invention may further comprise at least one coloring material other than titanium dioxide or zinc sulphide.
  • this coloring material which is different from titanium dioxide and zinc sulphide, can be chosen from fluorescent, phosphorescent or even interference pigments.
  • They may for example be phosphorescent pigments based on alkaline earth aluminates doped with rare earths, in particular covered at least partially by smaller grains of a metal oxide, in particular ferrous. These metal oxide grains can be used to color and modify the luminescence color, which can thus, if desired, be different from the green or yellow light most frequently encountered in phosphorescence.
  • organic dyestuffs they can in particular be chosen from organic pigments conventionally used in surface coatings, such as, for example, those considered in the examples below.
  • composition according to the invention comprises at least one material chosen from organic dyestuffs, for example perylene, or even perylene black.
  • composition according to the invention can comprise at least
  • Such a composition is very particularly effective in forming a coating with an opaline effect, that is to say translucent and with a milky white appearance.
  • composition according to the invention can comprise at least
  • Such a composition is very particularly effective for forming a colored coating.
  • compositions in accordance with the invention can be obtained and in particular by mixing different compositions according to the invention.
  • composition according to the invention can contain at least
  • Such a composition is very particularly effective for forming a coating with a colored opaline effect.
  • the mixtures mentioned above can in particular be prepared directly during the preparation of the surface coating.
  • compositions in accordance with the invention to adjust a particular color or decorative effect at the level of the surface coating to be developed.
  • composition according to the invention can also contain other additional components and in particular chosen from the usual additives of solid compositions dedicated to forming surface coatings.
  • a composition according to the invention contains at least one material, also called a mineral filler according to the invention, chosen from clays, pyrogenic silicas, calcium carbonate, barium sulphate and their mixtures, and preferably contains at least less calcium carbonate.
  • a mineral filler chosen from clays, pyrogenic silicas, calcium carbonate, barium sulphate and their mixtures, and preferably contains at least less calcium carbonate.
  • the presence of calcium carbonate makes it possible to increase the performance in terms of slip failure, and therefore sag, of the coating on the support during its deposition.
  • These compounds can represent from 0.1 to 10% by weight of the total weight of the composition.
  • a composition according to the invention can also comprise between 0.5 and 2% by dry weight of gelling agent relative to its total weight. This makes it possible to obtain better resistance of the composition on the substrate on which it is sprayed. Furthermore, a composition according to the invention is advantageously devoid of carbon nanotubes.
  • a composition according to the invention advantageously has a particle size of less than or equal to 100 ⁇ m and preferably less than or equal to about 60 ⁇ m.
  • compositions according to the invention can be prepared according to a process comprising at least the steps of
  • the film-forming particulate material and the zirconium hydrogen phosphate with, if present, at least one premix of ancillary components of said composition including at least one organic coloring material or a pigment and preferably distinct from titanium dioxide,
  • the process considered according to the invention does not require an extrusion step to form a composition according to the invention.
  • the inventors have observed that mechanical grinding of a mixture of all the raw materials provides a very homogeneous composition thanks to the presence of zirconium hydrogenphosphate.
  • the mixture obtained at the end of the grinding step according to the invention and before sieving has particles of size varying from 1 to 100 pm.
  • the process according to the invention makes it possible to obtain a composition having a particle size of less than or equal to 100 ⁇ m and preferably less than or equal to about 60 ⁇ m.
  • premixes can be prepared by mechanical grinding of their components and preferably in the presence of zirconium hydrogenphosphate to form homogeneous premixes which are easier to disperse homogeneously according to the process of the invention.
  • zirconium hydrogenphosphate is used with all the compounds which are combined with it at a rate varying between 0.1 and 5% by weight, expressed relative to the total weight of the corresponding mixture.
  • a premix comprises at least one mineral filler, zinc sulphide and zirconium hydrogenphosphate, preferably in an inorganic material / zirconium hydrogenphosphate weight ratio varying from 1/100 to 1/20.
  • a premix comprises at least one organic coloring material and zirconium hydrogen phosphate preferably in a coloring material / zirconium hydrogen phosphate weight ratio varying from 1/1000 to 1/20.
  • Mechanical grinding operations can be carried out in a ball mill.
  • the number and size of the beads are adjusted therein as a function of the volume to be ground and the desired particle size.
  • a particulate premix as identified above can be made by mechanically grinding these components and zirconium hydrogen phosphate, to form particles ranging in size from 1 to 100 ⁇ m.
  • a suitable sieving operation can be carried out following the grinding.
  • the powder obtained after grinding and sieving can be fluidized in a fluidization bed.
  • composition according to the invention can also be prepared by simply mixing several compositions according to the invention. It is thus possible to obtain a wide range of compositions according to the invention capable of respectively providing distinct color effects of great diversity.
  • compositions according to the invention are particularly useful for forming a transparent surface coating, translucent and colored or not on a support or even substrate.
  • These supports can be formed from a wide variety of materials such as metal, ceramic, plastic or glass and preferably is glass.
  • the compositions according to the invention can be used in very different technical fields such as that of metallurgy, the hollow glass and flat glass industry, the wood and ceramics industry.
  • compositions according to the invention are in particular useful for forming surface coatings endowed with a decorative effect on glass articles, such as for example bottles, perfume bottles, cosmetic receptacles, articles of the art of table, glazing.
  • the coating obtained is colored or not. It can thus be only translucent or even transparent in the absence of any material capable of providing a colored effect.
  • compositions according to the invention have also been found to be suitable for being mixed to form new compositions either before their use or at the time of their implementation to form a surface coating on a support.
  • a further subject of the invention is a method for forming a surface coating on a support, in particular glass, comprising
  • the electrostatic spraying is carried out according to an electrostatic process or Corona effect or else a triboelectric process or even fluidization.
  • the film-forming organic material present in the solid composition and / or the nature of the support considered, for example metallic or not, it may be necessary to expose the deposit to a trigger element to form the expected coating.
  • This trigger can be in particular heating, UV exposure.
  • the deposit can be formed at room temperature, that is to say between 18 and 25 ° C.
  • the support is made of glass
  • the method according to the invention makes it possible to form the coating directly in contact with the substrate.
  • the coating obtained is formed from a single deposit of composition.
  • the coating obtained by the process of the invention may have a thickness varying from 50 to 120 ⁇ m.
  • the composition according to the invention contains at least 3% by weight of zinc sulphide and the coating formed from this composition is translucent or else said to have an opaline effect.
  • Resin-type materials are thermoplastic resins.
  • N ° 2 a polyester base varnish called N ° 2 marketed under the trade name GZ C642C8202 from Protech Oxyplast
  • the powder mixes are made in a grinding jar using ceramic balls as detailed below.
  • the volume of the jar is distributed in 1/3 balls, 1/3 air and 1/3 mixture of materials.
  • the mechanical strengths are checked according to the methods defined by the ISO 8113 standard.
  • Adhesive tape having an adhesive power of between 350 and 450 N / cm 2 and a width of 19mm (for example reference 616M from the Company 3M)
  • Product G1 (70% ethyl alcohol + 20% turpentine ⁇ 10% ethyl phthalate) and a soft white cloth.
  • the tested surface is then rubbed lightly with the thumb or the white cloth.
  • Example 1 preparation of a composition according to the invention.
  • Preparation of a premix A 20 g (15.38%) zirconium hydrogen phosphate, 50 g (38.46%) zinc sulfide, 50 g (38.46%) calcium carbonate and 10 g (07.69%) silica pyrogenic (Aerosil 200 from the company EVONIK) are introduced into a ceramic jar containing ceramic balls with a diameter of 10 to 30 mm. The mixture is ground there for 30 minutes and then sieved at 100 pm.
  • the pulverulent composition obtained is suitable for forming a translucent coating of opaline tint.
  • Example 2 Formation of a coating on a support from a composition according to the invention.
  • the composition of Example 1 obtained with the premix A is sprayed by an electrostatic process onto a glass vial to form a surface coating thereon having a thickness of 50 to 80 microns.
  • the surface qualities of the coating are tested as follows.
  • the treated glass bottle is immersed for 20 minutes in hot water at a temperature of 60 ° C. and then collected.
  • the glass bottle is first rubbed with your finger on the coating. No alteration of the applied coating was observed. This is not entrained and remains fully attached to the container. Its color aspect also remains intact.
  • the grid test is then carried out according to the standard (scotch Ref 3M brand 616 Made in USA 5704 - 1) detailed in material and method. After this treatment, a visual examination of the coating on the glass container is carried out. No degradation of this coating was also observed.
  • Example 3 Coating formation according to the invention and witnesses.
  • Table 1 gives an account of the solid compositions tested. They were prepared by reproducing the operating protocol described in Example 1 with the amounts specified in this table. Their surface qualities were tested according to the water test and the G1 test described in Example 2. The results are also shown in Table 1.
  • Example 4 Preparation of coatings in accordance with the invention Coatings were formed according to the protocol described in Example 2 from the compositions detailed in Table 2.

Abstract

The present invention relates to a solid composition in powder form capable of forming a surface coating on a substrate, said composition comprising at least one film-forming organic material, zirconium hydrogen phosphate and at least one material selected from the organic colouring materials and pigments. It also relates to a method for preparing this composition and to the use thereof for the purpose of forming surface coatings on substrates, in particular glass substrates.

Description

Description Description
Titre : COMPOSITION SOLIDE POUR FORMER DES REVETEMENTS DE SURFACE Title: SOLID COMPOSITION FOR FORMING SURFACE COATINGS
Domaine technique Technical area
L 'invention concerne une composition solide de type poudre apte à former un revêtement de surface sur un support, notamment formé d’un matériau en verre, céramique, métal ou plastique. L'invention concerne également un procédé de préparation de cette composition et un procédé de préparation d’un revêtement à partir de cette composition. The invention relates to a solid composition of powder type capable of forming a surface coating on a support, in particular formed of a material of glass, ceramic, metal or plastic. The invention also relates to a process for preparing this composition and a process for preparing a coating from this composition.
Technique antérieure Prior art
Les compositions solides dédiées à former des revêtements de surface sur des supports de tout type bois, acier, plastique, verre sont aujourd’hui reconnues comme étant des alternatives avantageuses aux formulations liquides de type peintures et vernis. Par opposition à ces formulations liquides, les compositions de type poudre ne requièrent pas la mise en œuvre d’un solvant. Leur utilisation est aisée et propre. Ainsi, elles sont le plus souvent appliquées par pulvérisation électrostatique ou par un procédé triboélectrique. Selon la nature du support considéré, un chauffage de la pièce ou de sa surface à traiter peut parfois être réalisé préalablement ou consécutivement à l’immobilisation de la composition solide sur la surface à traiter. Solid compositions dedicated to forming surface coatings on supports of all types of wood, steel, plastic, glass are today recognized as being advantageous alternatives to liquid formulations of the paint and varnish type. As opposed to these liquid formulations, the powder type compositions do not require the use of a solvent. Their use is easy and clean. Thus, they are most often applied by electrostatic spraying or by a triboelectric process. Depending on the nature of the support considered, heating of the part or of its surface to be treated can sometimes be carried out before or after the immobilization of the solid composition on the surface to be treated.
D’une manière générale, ces compositions solides sont constituées pour l’essentiel, d’un matériau organique de type résine(s) synthétique(s) apte à former le revêtement attendu et d’un matériau inorganique de type charges minérales et pigments, ces derniers ayant plus particulièrement pour vocation de conférer un effet translucide et/ou coloré au revêtement final. In general, these solid compositions consist essentially of an organic material of synthetic resin (s) type capable of forming the expected coating and of an inorganic material of mineral fillers and pigments type, the latter having more particularly the vocation of imparting a translucent and / or colored effect to the final coating.
Ainsi, dans le cas d’une formulation dédiée à former un vernis de surface, l’aspect transparent ou translucide est ajusté par le choix de ces matériaux inorganiques et le plus souvent, le pigment retenu à cette fin est le dioxyde de titane. De teinte blanche, il permet d’augmenter la blancheur ou la brillance des revêtements. Ces pigments possèdent un outre des pouvoir d’opacité et couvrant intéressants et des propriétés mécaniques satisfaisantes. Les pigments de dioxyde de titane sont ainsi tout particulièrement considérés pour conférer un effet décoratif de type opaline c’est-à-dire translucide à des revêtements de surface. Ces revêtements sont particulièrement très utiles pour conférer des effets décoratifs à des articles de type architectural dans les travaux publics du bâtiment, dans l’industrie du verre par exemple pour l’ornementation de verres creux, de flacons en parfumerie, les bouteilles, de contenants cosmétiques, et également dans l’industrie de la céramique comme à l’égard de la vaisselle et des articles sanitaires. Ces pigments de dioxyde de titane sont également largement utilisés pour modifier les teintes colorées procurées par d’autres agents de coloration organiques ou inorganiques. Thus, in the case of a formulation dedicated to forming a surface varnish, the transparent or translucent appearance is adjusted by the choice of these inorganic materials and most often, the pigment retained for this purpose is titanium dioxide. White in color, it increases the whiteness or brilliance of coatings. These pigments also have interesting opacity and covering power and satisfactory mechanical properties. The titanium dioxide pigments are thus very particularly considered to impart a decorative effect of the opaline type, that is to say translucent to coatings of area. These coatings are particularly very useful for imparting decorative effects to articles of architectural type in public building works, in the glass industry, for example for the ornamentation of hollow glasses, perfume bottles, bottles, containers. cosmetics, and also in the ceramics industry as with regard to tableware and sanitary ware. These titanium dioxide pigments are also widely used to modify the color tints provided by other organic or inorganic coloring agents.
Or, il existe une volonté de diminuer significativement voire de s’affranchir de l’utilisation des pigments de dioxyde de titane car leur innocuité à l’égard du vivant est aujourd’hui mise en question. Un pigment alternatif au dioxyde de titane est le sulfure de zinc. Toutefois, la dispersion de ce second pigment au sein d’un matériau organique de type résine(s) synthétique(s) s’avère plus difficile. However, there is a desire to significantly reduce or even eliminate the use of titanium dioxide pigments because their harmlessness with regard to living organisms is now called into question. An alternative pigment to titanium dioxide is zinc sulfide. However, the dispersion of this second pigment in an organic material such as synthetic resin (s) proves to be more difficult.
En effet, les matières premières constitutives des compositions solides dédiés à former des revêtements sont classiquement combinées en considérant successivement la réalisation de prémélanges de certaines matières premières, le mélange de ces prémélanges par extrusion, leur broyage et une micronisation du mélange final ainsi obtenu pour le transformer en une poudre fine. Or, ce mode de préparation ne donne pas totale satisfaction en termes de modulation de coloration. En particulier, l’effet coloriel n’est pas toujours reproduit de manière optimale. Il peut être donc difficile de reproduire fidèlement un effet spécifique telle une nuance à l’aide des poudres actuellement disponibles. Indeed, the raw materials constituting the solid compositions dedicated to forming coatings are conventionally combined by considering successively the production of premixes of certain raw materials, the mixing of these premixes by extrusion, their grinding and a micronization of the final mixture thus obtained for the transform into a fine powder. However, this method of preparation is not completely satisfactory in terms of modulation of coloration. In particular, the color effect is not always reproduced optimally. It can therefore be difficult to faithfully reproduce a specific effect such as a shade using currently available powders.
La présente invention a précisément pour objet de proposer de nouvelles compositions solides pour revêtement permettant de s’affranchir des problèmes précités. The object of the present invention is precisely to provide novel solid compositions for coating which make it possible to overcome the aforementioned problems.
Exposé de l’invention Disclosure of the invention
Plus précisément, la présente invention permet d’accéder à des compositions solides de type poudre aptes à former des revêtements dotés de qualités de surfaces améliorées. More precisely, the present invention provides access to solid compositions of powder type capable of forming coatings endowed with improved surface qualities.
En particulier, la présente invention permet d’accéder à des compositions solides de type poudre aptes à former des revêtements translucides et/ou colorées et dont l’effet visuel est uniforme et optimisé. In particular, the present invention provides access to solid compositions of powder type capable of forming translucent and / or colored coatings and whose visual effect is uniform and optimized.
La présente invention vise également à proposer des compositions solides de type poudre aptes à former des revêtements dotés d’une résistance mécanique accrue. La présente invention vise en outre à proposer une composition solide de type poudre pour former des revêtements, possédant une quantité réduite et de préférence nulle en dioxyde de titane. The present invention also aims to provide solid compositions of powder type capable of forming coatings endowed with increased mechanical strength. The present invention further aims to provide a solid composition of powder type for forming coatings, having a reduced and preferably zero amount of titanium dioxide.
Résumé de l’invention Summary of the invention
Ainsi selon un premier de ses aspects, la présente invention se rapporte à une composition solide sous forme d’une poudre apte à former un revêtement de surface sur un support, ladite composition comprenant au moins un matériau organique filmogène, de l’hydrogénophosphate de zirconium et au moins un matériau choisi parmi les matières colorantes organiques et les pigments. Thus according to a first of its aspects, the present invention relates to a solid composition in the form of a powder capable of forming a surface coating on a support, said composition comprising at least one film-forming organic material, zirconium hydrogenphosphate. and at least one material chosen from organic coloring materials and pigments.
Contre toute attente, les inventeurs ont en effet constaté que l’association d’hydrogénophosphate de zirconium à un matériau organique filmogène s’avère tout particulièrement efficace pour améliorer les performances des revêtements formés à partir de ces compositions. Against all expectations, the inventors have in fact observed that the association of zirconium hydrogenphosphate with a film-forming organic material proves to be very particularly effective in improving the performance of the coatings formed from these compositions.
Il s’avère possible d’accéder à des revêtements de surface translucide, coloré ou non, sans dioxyde de titane. De tels revêtements peuvent être encore qualifiés comme étant de teinte opaline. It is possible to access translucent surface coatings, colored or not, without titanium dioxide. Such coatings can be further qualified as being opaline tint.
Au sens de l’invention, un « revêtement translucide » est un revêtement qui laisse passer une partie de la lumière visible et la diffuse. Par opposition à un revêtement transparent, il ne permet pas de visualiser avec netteté un objet disposé en miroir. Il se distingue également d’un revêtement opaque qui ne permet pas de laisser passer la lumière, et donc qui ne permet pas de voir ce qui est présent derrière le revêtement. Un tel revêtement peut être en outre qualifié comme doté d’un effet dit « opaline », ou de « teinte opaline » lorsque qu’il manifeste en outre des effets irisés et le revêtement est alors généralement d’aspect laiteux, blanc ou coloré. For the purposes of the invention, a "translucent coating" is a coating which allows part of visible light to pass through and scatter it. As opposed to a transparent coating, it does not make it possible to clearly visualize an object placed in a mirror. It is also distinguished from an opaque coating which does not allow light to pass through, and therefore which does not allow you to see what is behind the coating. Such a coating may further be qualified as endowed with a so-called "opaline" effect, or "opaline tint" when it also exhibits iridescent effects and the coating is then generally of a milky, white or colored appearance.
Ainsi, la présente invention vise tout particulièrement une composition solide sous forme d’une poudre apte à former un revêtement de surface sur un support, ladite composition comprenant au moins un matériau organique filmogène, de l’hydrogénophosphate de zirconium et au moins un matériau choisi parmi les matières colorantes organiques et les pigments, et comprenant moins de 3% en poids de dioxyde de titane par rapport à son poids total et de préférence dénuée de dioxyde de titane. Les revêtements obtenus à partir des compositions selon l’invention sont avantageux à plusieurs titres. Thus, the present invention is most particularly aimed at a solid composition in the form of a powder capable of forming a surface coating on a support, said composition comprising at least one film-forming organic material, zirconium hydrogenphosphate and at least one chosen material. from organic dyestuffs and pigments, and comprising less than 3% by weight of titanium dioxide relative to its total weight and preferably devoid of titanium dioxide. The coatings obtained from the compositions according to the invention are advantageous in several ways.
Ainsi, ils possèdent une résistance mécanique nettement supérieure à celles manifestées par des revêtements dénués en hydrogénophosphate de zirconium. La présence d’hydrogénophosphate de zirconium permet avantageusement d’améliorer la tenue de tels revêtements en surface d’un support, en particulier un support en verre. Thus, they have a mechanical resistance markedly greater than those exhibited by coatings devoid of zirconium hydrogen phosphate. The presence of zirconium hydrogenphosphate advantageously makes it possible to improve the resistance of such coatings on the surface of a support, in particular a glass support.
Quant à l’effet coloriel, il s’avère optimisé en termes de dispersion, de profondeur d’intensité, d’homogénéité et de pérennité au niveau du revêtement. Notamment, la combinaison d’au moins un matériau organique filmogène, de l’hydrogénophosphate de zirconium et du sulfure de zinc, privilégié au dioxyde de titane, procure au revêtement un aspect translucide, notamment de teinte opaline, qui est durable du fait de sa résistance élevée aussi bien à des contraintes mécaniques, que des contraintes en température ou chimique. As for the color effect, it is optimized in terms of dispersion, depth of intensity, uniformity and durability in the coating. In particular, the combination of at least one film-forming organic material, zirconium hydrogenphosphate and zinc sulphide, favored over titanium dioxide, gives the coating a translucent appearance, in particular of an opaline hue, which is durable due to its high resistance to mechanical stresses, as well as to temperature or chemical stresses.
En particulier, une telle composition est utile pour former un revêtement translucide ou à effet opaline. In particular, such a composition is useful for forming a translucent or opaline-effect coating.
Selon un autre de ses aspects, la présente invention vise un procédé de préparation d’une composition conforme à l’invention comprenant au moins les étapes consistant à : According to another of its aspects, the present invention relates to a process for preparing a composition in accordance with the invention comprising at least the steps consisting of:
mélanger par broyage mécanique, un matériau particulaire filmogène et G hydrogénophosphate de zirconium avec au moins un prémélange comprenant des composants annexes de ladite composition dont au moins une matière colorante organique ou un pigment et de préférence distinct du dioxyde de titane, mixing by mechanical grinding, a film-forming particulate material and G zirconium hydrogen phosphate with at least one premix comprising ancillary components of said composition including at least one organic coloring material or a pigment and preferably distinct from titanium dioxide,
le cas échéant, tamiser le mélange homogène pulvérulent ainsi obtenu à une taille inférieure ou égale à 150pm et de préférence inférieure ou égale à environ lOOpm et where appropriate, sieve the homogeneous pulverulent mixture thus obtained to a size less than or equal to 150 μm and preferably less than or equal to approximately 100 μm and
le cas échéant, fluidiser ledit mélange tamisé. where appropriate, fluidizing said sieved mixture.
Avantageusement, le procédé de l’invention ne met pas en œuvre une étape d’extrusion. Advantageously, the method of the invention does not implement an extrusion step.
La présente invention vise en outre G utilisation d’au moins une composition selon l’invention pour former un revêtement de surface, notamment transparent ou translucide et coloré ou non, sur un support. De préférence un tel revêtement est translucide ou à effet opaline. Elle vise également un procédé pour former un revêtement en surface d’un support comprenant au moins les étapes consistant à The present invention also relates to the use of at least one composition according to the invention for forming a surface coating, in particular transparent or translucent and colored or not, on a support. Preferably, such a coating is translucent or has an opaline effect. It also relates to a method for forming a coating on the surface of a support comprising at least the steps consisting in
former par pulvérisation électrostatique un dépôt d’au moins une composition selon l’invention en surface de la zone à traiter dudit support, et si nécessaire, exposer ledit dépôt à des conditions efficaces pour le transformer en un revêtement adhérent à ladite zone. forming by electrostatic spraying a deposit of at least one composition according to the invention on the surface of the area to be treated of said support, and if necessary, exposing said deposit to conditions effective to transform it into a coating adhering to said area.
Un tel procédé permet notamment de former un revêtement translucide ou à effet opaline. Such a process makes it possible in particular to form a translucent coating or a coating with an opaline effect.
Description détaillée detailed description
Matériau organique filmogène Film-forming organic material
Au sens de l’invention, le terme filmogène entend qualifier le fait que le matériau considéré est apte à s’organiser sous la forme d’un film lorsqu’il est appliqué sur un support. Ce film est en outre avantageusement apte à constituer une matrice pour les matériaux qui lui sont combinés en vue de lui conférer des propriétés particulières. Ces propriétés peuvent être des qualités d’adhésion, de résistance mécanique, de résistance UV, de résistance thermique et également être liées à la manifestation d’effet esthétique par exemple décoratif. For the purposes of the invention, the term film-forming is intended to describe the fact that the material in question is capable of being organized in the form of a film when it is applied to a support. This film is also advantageously capable of constituting a matrix for the materials which are combined with it in order to give it particular properties. These properties can be qualities of adhesion, mechanical resistance, UV resistance, thermal resistance and also be related to the manifestation of aesthetic effect, for example decorative.
Ainsi, il est tout particulièrement considéré dans le cadre de la présente invention, l’obtention de revêtements de surface qui sont transparents ou translucides et colorés ou non. Thus, it is very particularly considered in the context of the present invention, the obtaining of surface coatings which are transparent or translucent and colored or not.
Les matériaux organiques filmogènes convenant tout particulièrement à l’invention sont des résines de préférence synthétiques. The film-forming organic materials which are particularly suitable for the invention are preferably synthetic resins.
Ces résines peuvent être thermo- ou photo-durcissables ou thermoplastiques. Ce type de matériaux est bien connu et les conditions requises pour les transformer en un film sont bien documentées. These resins can be thermo- or photo-curable or thermoplastic. This type of material is well known and the conditions required to transform them into a film are well documented.
Ainsi, des matériaux organiques filmogènes convenant à l’invention peuvent nécessiter d’être stimulés par un élément déclencheur, chauffage, exposition UV ou autre pour former le film constituant le revêtement attendu. Ainsi si nécessaire, le matériau organique filmogène peut incorporer un agent de réticulation. Le matériau organique filmogène peut également être mis en œuvre sans agent de réticulation. Thus, film-forming organic materials suitable for the invention may need to be stimulated by a trigger, heating, UV exposure or the like to form the film constituting the expected coating. Thus, if necessary, the film-forming organic material can incorporate a crosslinking agent. The film-forming organic material can also be used without a crosslinking agent.
Ces matériaux organiques filmogènes sont mis en œuvre sous une forme particulaire et avantageusement leur taille particulaire varie de 1 à 100 pm. A titre représentatif et non limitatif de ces résines peuvent tout particulièrement être citées les résines époxy, de polyuréthanes, de polyacrylates, de polyesters modifiées ou non et leurs mélanges. These film-forming organic materials are used in particulate form and their particulate size advantageously ranges from 1 to 100 μm. By way of representation and without limitation of these resins, mention may very particularly be made of epoxy resins, of polyurethanes, of polyacrylates, of polyesters, modified or not, and their mixtures.
Avantageusement, le matériau organique filmogène est au moins une résine polyuréthane ou au moins une résine de polyester. Advantageously, the film-forming organic material is at least one polyurethane resin or at least one polyester resin.
Une composition selon l’invention peut contenir au moins 90% en poids en matériau filmogène par rapport à son poids total. De préférence, une composition selon l’invention peut contenir de 90 à 95% en poids en matériau filmogène par rapport à son poids total. A composition according to the invention may contain at least 90% by weight of film-forming material relative to its total weight. Preferably, a composition according to the invention may contain from 90 to 95% by weight of film-forming material relative to its total weight.
Le poids en matériau filmogène est exprimé en poids sec dans le cadre de la présente description. The weight of film-forming material is expressed in dry weight in the context of the present description.
Comme énoncé précédemment, ce matériau organique filmogène est combiné avec de l’hydrogénophosphate de zirconium. As stated above, this film-forming organic material is combined with zirconium hydrogen phosphate.
La teneur en hydrogénophosphate de zirconium varie de 0,5 à 10% en poids et notamment de 1 à 5% en poids par rapport au poids total de la composition. En particulier, la teneur en hydrogénophosphate de zirconium varie de 1 à 3,5% en poids, voire de 1,5 à 3% en poids par rapport au poids total de la composition. The zirconium hydrogenphosphate content varies from 0.5 to 10% by weight and in particular from 1 to 5% by weight relative to the total weight of the composition. In particular, the zirconium hydrogen phosphate content varies from 1 to 3.5% by weight, or even from 1.5 to 3% by weight relative to the total weight of the composition.
Avantageusement, G hydrogénophosphate de zirconium et le matériau organique filmogène sont mis en œuvre dans un rapport pondéral variant de 1/ 20 à 1/ 200 et de préférence inférieur à 1/20. Advantageously, G zirconium hydrogenphosphate and the film-forming organic material are used in a weight ratio varying from 1/20 to 1/200 and preferably less than 1/20.
Comme illustré dans les exemples ci-après, la présence de cet hydrogénophosphate de zirconium permet d’ accroître la résistance mécanique du revêtement formé selon l’invention et de lui conférer un effet décoratif optimisé en termes d’intensité et d’homogénéité. As illustrated in the examples below, the presence of this zirconium hydrogenphosphate increases the mechanical strength of the coating formed according to the invention and gives it an optimized decorative effect in terms of intensity and homogeneity.
De préférence, G hydrogénophosphate de zirconium n’est pas chargé en élément métallique, en particulier ne contient pas d’argent. Preferably, Zirconium hydrogen phosphate is not charged with metallic element, in particular does not contain silver.
Une composition selon l’invention contient en outre au moins une matière colorante organique ou un pigment. A composition according to the invention further contains at least one organic coloring material or a pigment.
Ces matériaux sont présents à des fins de conférer des propriétés particulières au revêtement attendu. En ce qui concerne les pigments, ces matériaux ont généralement une granulométrie comprise entre 30 microns et 100 microns, mieux entre 20 et 60 microns, encore mieux entre 5 et 40 microns. These materials are present for the purpose of imparting particular properties to the expected coating. As regards the pigments, these materials generally have a particle size of between 30 microns and 100 microns, better still between 20 and 60 microns, even better between 5 and 40 microns.
Une composition selon l’invention contient avantageusement moins de 3% en poids, en particulier moins de 2% en poids, notamment moins de 1% en poids, de dioxyde de titane par rapport à son poids total et de préférence en est dénuée. A composition according to the invention advantageously contains less than 3% by weight, in particular less than 2% by weight, in particular less than 1% by weight, of titanium dioxide relative to its total weight and preferably is devoid of it.
Le taux en matière colorante organique ou en pigment dans la composition peut varier selon l’usage auquel elle est destinée. The level of organic coloring matter or pigment in the composition may vary depending on the use for which it is intended.
En général, une composition selon l’invention peut contenir jusqu’à 10% en poids de matière colorante organique ou pigment, de préférence jusqu’à 6%, plus préférentiellement de 0,5 % à 5%, voire moins de 4%, par rapport à son poids total. In general, a composition according to the invention can contain up to 10% by weight of organic coloring material or pigment, preferably up to 6%, more preferably from 0.5% to 5%, or even less than 4%, relative to its total weight.
En particulier, une composition selon l’invention contient à titre de pigment au moins du sulfure de zinc. Un tel pigment est tout particulièrement avantageux pour accéder à des revêtements dits incolores ou encore transparents voire translucides. Ainsi, en termes d’effet décoratif, le sulfure de zinc est tout particulièrement intéressant pour obtenir des revêtements à effet opaline ou encore d’aspect laiteux. In particular, a composition according to the invention contains as a pigment at least zinc sulphide. Such a pigment is very particularly advantageous for accessing so-called colorless or even transparent or even translucent coatings. Thus, in terms of decorative effect, zinc sulphide is particularly interesting for obtaining coatings with an opaline effect or even milky appearance.
Selon une variante de réalisation, une composition selon l’invention contient au moins de 90 à 95% en poids d’au moins un matériau organique filmogène, de préférence au moins une résine de polyuréthane ou de polyester, de 0,5% à 10% et notamment de 1 à 5% en poids d’hydrogénophosphate de zirconium et de préférence de 1 % à 10% en particulier de 2.5 % à 6% en poids de sulfure de zinc par rapport à son poids total. According to one embodiment variant, a composition according to the invention contains at least 90 to 95% by weight of at least one film-forming organic material, preferably at least one polyurethane or polyester resin, from 0.5% to 10 % and in particular from 1 to 5% by weight of zirconium hydrogen phosphate and preferably from 1% to 10%, in particular from 2.5% to 6% by weight of zinc sulphide relative to its total weight.
Bien entendu, une composition selon l’invention peut comprendre en outre au moins une matière colorante distincte du dioxyde de titane ou du sulfure de zinc. Of course, a composition according to the invention may further comprise at least one coloring material other than titanium dioxide or zinc sulphide.
Selon une variante de réalisation, cette matière colorante différente du dioxyde de titane et du sulfure de zinc, peut être choisie parmi les pigments fluorescents, phosphorescents ou encore interférentiels. According to an alternative embodiment, this coloring material, which is different from titanium dioxide and zinc sulphide, can be chosen from fluorescent, phosphorescent or even interference pigments.
Il peut par exemple s’agir de pigments phosphorescents à base d’aluminates d’alcalinoterreux dopés par des terres rares, notamment recouverts au moins partiellement par des grains plus petits d’un oxyde métallique, notamment ferreux. Ces grains d’oxydes métalliques peuvent servir à donner une couleur et à modifier la couleur de luminescence, laquelle peut ainsi, si on le souhaite, être différente de la lumière verte ou jaune la plus fréquemment rencontrée en phosphorescence. En ce qui concerne les matières colorantes organiques, elles peuvent notamment être choisies parmi les pigments organiques classiquement utilisés dans les revêtements de surface comme par exemple ceux considérés dans les exemples ci-après. They may for example be phosphorescent pigments based on alkaline earth aluminates doped with rare earths, in particular covered at least partially by smaller grains of a metal oxide, in particular ferrous. These metal oxide grains can be used to color and modify the luminescence color, which can thus, if desired, be different from the green or yellow light most frequently encountered in phosphorescence. As regards the organic dyestuffs, they can in particular be chosen from organic pigments conventionally used in surface coatings, such as, for example, those considered in the examples below.
En particulier, une composition selon l’invention comprend au moins un matériau choisi parmi les matières colorantes organiques, par exemple du pérylène, voire du noir de pérylène. In particular, a composition according to the invention comprises at least one material chosen from organic dyestuffs, for example perylene, or even perylene black.
Selon une variante de réalisation, une composition selon l’invention peut comprendre au moins According to an alternative embodiment, a composition according to the invention can comprise at least
90 à 92% en poids d’au moins matériau organique filmogène en particulier de résine polyuréthane 90 to 92% by weight of at least film-forming organic material, in particular polyurethane resin
2,5 à 4% en poids d’hydrogénophosphate de zirconium, 2.5 to 4% by weight of zirconium hydrogen phosphate,
2 à 4% en poids de sulfure de zinc, 2 to 4% by weight of zinc sulphide,
2 à 4% en poids de carbonate de calcium et 2 to 4% by weight of calcium carbonate and
le cas échéant jusqu’à 1% en poids de silice pyrogénée par rapport à son poids total. optionally up to 1% by weight of fumed silica relative to its total weight.
Une telle composition est tout particulièrement efficace pour former un revêtement à effet opaline c’est-à-dire translucide et d’aspect blanc laiteux. Such a composition is very particularly effective in forming a coating with an opaline effect, that is to say translucent and with a milky white appearance.
Selon une autre variante de réalisation, une composition selon l’invention peut comprendre au moins According to another variant embodiment, a composition according to the invention can comprise at least
90 à 95% en poids d’au moins matériau organique filmogène en particulier de résine polyuréthane, 90 to 95% by weight of at least film-forming organic material, in particular polyurethane resin,
2.5 à 4% en poids d’hydrogénophosphate de zirconium et 2.5 to 4% by weight of zirconium hydrogen phosphate and
3 à 6% en poids d’une matière colorante différente du dioxyde de titane et du sulfure de zinc et en particulier apte à procurer une couleur distincte du blanc par rapport à son poids total. 3 to 6% by weight of a coloring matter different from titanium dioxide and zinc sulphide and in particular capable of providing a color distinct from white relative to its total weight.
Une telle composition est tout particulièrement efficace pour former un revêtement coloré. Such a composition is very particularly effective for forming a colored coating.
Bien entendu, d’autres compositions conformes de l’invention peuvent être obtenues et notamment par mélange de différentes compositions selon l’invention. Of course, other compositions in accordance with the invention can be obtained and in particular by mixing different compositions according to the invention.
Ainsi, une composition selon l’invention peut contenir au moins Thus, a composition according to the invention can contain at least
90 à 95% en poids d’au moins matériau organique filmogène en particulier de résine polyuréthane 90 to 95% by weight of at least film-forming organic material, in particular polyurethane resin
2.5 à 4% en poids d’hydrogénophosphate de zirconium 2 à 4% en poids de sulfure de zinc, 2.5 to 4% by weight of zirconium hydrogen phosphate 2 to 4% by weight of zinc sulphide,
2 à 4% en poids de carbonate de calcium et 2 to 4% by weight of calcium carbonate and
3 à 6% en poids d’une matière colorante de teinte différente du blanc, par rapport à son poids total. 3 to 6% by weight of a coloring matter of a different shade from white, relative to its total weight.
Une telle composition est tout particulièrement efficace pour former un revêtement à effet opaline coloré. Such a composition is very particularly effective for forming a coating with a colored opaline effect.
Les mélanges évoqués ci-dessus peuvent notamment être préparés directement lors de la confection du revêtement de surface. The mixtures mentioned above can in particular be prepared directly during the preparation of the surface coating.
L’utilisateur peut ainsi à sa guise associer plusieurs compositions conformes à l’invention pour ajuster un effet coloriel ou décoratif particulier au niveau du revêtement de surface à élaborer. The user can thus at will combine several compositions in accordance with the invention to adjust a particular color or decorative effect at the level of the surface coating to be developed.
Bien entendu, une composition selon l’invention peut également contenir d’autres composants annexes et notamment choisis parmi les additifs usuels des compositions solides dédiées à former des revêtements de surface. Of course, a composition according to the invention can also contain other additional components and in particular chosen from the usual additives of solid compositions dedicated to forming surface coatings.
Ces composants sont bien entendu compatibles avec une formulation à un état solide c’est-à-dire sous la forme d’une poudre selon l’invention. These components are of course compatible with a formulation in a solid state, that is to say in the form of a powder according to the invention.
Avantageusement, une composition selon l’invention contient au moins un matériau, dit encore charge minérale selon l’invention, choisi parmi les argiles, les silices pyrogénées, le carbonate de calcium, le sulfate de baryum et leurs mélanges, et de préférence contient au moins du carbonate de calcium. Advantageously, a composition according to the invention contains at least one material, also called a mineral filler according to the invention, chosen from clays, pyrogenic silicas, calcium carbonate, barium sulphate and their mixtures, and preferably contains at least less calcium carbonate.
Comme illustré dans les exemples qui suivent, la présence du carbonate de calcium permet d’augmenter les performances en termes de défaut de glissement, et donc d’affaissement, du revêtement sur le support lors de son dépôt. As illustrated in the examples which follow, the presence of calcium carbonate makes it possible to increase the performance in terms of slip failure, and therefore sag, of the coating on the support during its deposition.
Ces composés peuvent représenter de 0,1 à 10% en poids du poids total de la composition. These compounds can represent from 0.1 to 10% by weight of the total weight of the composition.
Une composition selon l’invention peut également comprendre entre 0,5 et 2% en poids sec d’agent gélifiant par rapport à son poids total. Cela permet d’obtenir une meilleure tenue de la composition sur le substrat sur lequel elle est pulvérisée. Par ailleurs, une composition selon l’invention est avantageusement dénuée de nanotubes de carbone. A composition according to the invention can also comprise between 0.5 and 2% by dry weight of gelling agent relative to its total weight. This makes it possible to obtain better resistance of the composition on the substrate on which it is sprayed. Furthermore, a composition according to the invention is advantageously devoid of carbon nanotubes.
Une composition selon l’invention possède avantageusement une taille particulaire inférieure ou égale à 100 pm et de préférence inférieure ou égale à environ 60pm. A composition according to the invention advantageously has a particle size of less than or equal to 100 μm and preferably less than or equal to about 60 μm.
Procédé de préparation des compositions selon l’invention. Process for preparing the compositions according to the invention.
Comme énoncé précédemment, les compositions solides selon l’invention peuvent être préparées selon un procédé comprenant au moins les étapes consistant à As stated above, the solid compositions according to the invention can be prepared according to a process comprising at least the steps of
mélanger par broyage mécanique, le matériau particulaire filmogène et l’hydrogénophosphate de zirconium avec si présent, au moins un prémélange de composants annexes de ladite composition dont au moins une matière colorante organique ou un pigment et de préférence distinct du dioxyde de titane, mixing by mechanical grinding, the film-forming particulate material and the zirconium hydrogen phosphate with, if present, at least one premix of ancillary components of said composition including at least one organic coloring material or a pigment and preferably distinct from titanium dioxide,
le cas échéant, tamiser le mélange homogène pulvérulent ainsi obtenu à une taille inférieure ou égale à 150pm et de préférence inférieure ou égale à environ lOOpm et where appropriate, sieve the homogeneous pulverulent mixture thus obtained to a size less than or equal to 150 μm and preferably less than or equal to approximately 100 μm and
le cas échéant, fluidiser ledit mélange tamisé. where appropriate, fluidizing said sieved mixture.
Avantageusement, le procédé considéré selon l’invention ne requiert pas d’étape d’extrusion pour former une composition selon l’invention. Advantageously, the process considered according to the invention does not require an extrusion step to form a composition according to the invention.
Les inventeurs ont constaté qu’un broyage mécanique d’un mélange de l’ensemble des matières premières permet d’accéder à une composition très homogène grâce à la présence de l’hydrogénophosphate de zirconium. The inventors have observed that mechanical grinding of a mixture of all the raw materials provides a very homogeneous composition thanks to the presence of zirconium hydrogenphosphate.
Le mélange obtenu à l’issu de l’étape de broyage selon l’invention et avant tamisage possède des particules de taille variant de 1 à lOOpm. The mixture obtained at the end of the grinding step according to the invention and before sieving has particles of size varying from 1 to 100 pm.
Le procédé selon l’invention permet d’obtenir une composition dotée d’une taille particulaire inférieure ou égale à 100 pm et de préférence à inférieure ou égale à environ 60pm. The process according to the invention makes it possible to obtain a composition having a particle size of less than or equal to 100 μm and preferably less than or equal to about 60 μm.
Il a également été constaté qu’il est avantageux de disposer d’un ou plusieurs prémélanges des ingrédients destinés à être associés au matériau organique filmogène. It has also been found that it is advantageous to have one or more premixes of the ingredients intended to be combined with the film-forming organic material.
Ces prémélanges peuvent être préparés par broyage mécanique de leurs composants et de préférence en présence d’hydrogénophosphate de zirconium pour former des prémélanges homogènes qui sont plus faciles à disperser de manière homogène selon le procédé de l’invention. These premixes can be prepared by mechanical grinding of their components and preferably in the presence of zirconium hydrogenphosphate to form homogeneous premixes which are easier to disperse homogeneously according to the process of the invention.
D’une manière générale, l’hydrogénophosphate de zirconium est mis en œuvre avec l’ensemble des composés qui lui sont combinés à un taux variant entre 0.1 et 5% en poids exprimé par rapport au poids total du mélange correspondant. In general, zirconium hydrogenphosphate is used with all the compounds which are combined with it at a rate varying between 0.1 and 5% by weight, expressed relative to the total weight of the corresponding mixture.
Selon une variante de réalisation, un prémélange comporte au moins une charge minérale, du sulfure de zinc et de l’hydrogénophosphate de zirconium de préférence dans un rapport pondéral matériaux inorganiques/hydrogénophosphate de zirconium variant de 1/100 à 1/20. According to an alternative embodiment, a premix comprises at least one mineral filler, zinc sulphide and zirconium hydrogenphosphate, preferably in an inorganic material / zirconium hydrogenphosphate weight ratio varying from 1/100 to 1/20.
Selon une autre variante de réalisation, un prémélange comporte au moins une matière colorante organique et de l’hydrogénophosphate de zirconium de préférence dans un rapport pondéral matière colorante /hydrogénophosphate de zirconium variant de 1/1000 à 1/20. According to another variant embodiment, a premix comprises at least one organic coloring material and zirconium hydrogen phosphate preferably in a coloring material / zirconium hydrogen phosphate weight ratio varying from 1/1000 to 1/20.
Les opérations de broyage mécanique peuvent être réalisées au sein d’un broyeur à billes. Le nombre et la taille des billes y sont ajustés en fonction du volume à broyer et la taille particulaire souhaitée. Mechanical grinding operations can be carried out in a ball mill. The number and size of the beads are adjusted therein as a function of the volume to be ground and the desired particle size.
Par exemple, un prémélange particulaire tel qu’identifié ci-dessus peut être réalisé par broyage mécanique de ces composants et de G hydrogénophosphate de zirconium, pour former des particules de taille variant de 1 à 100 pm. Une opération de tamisage adéquate peut-être réalisée consécutivement au broyage. For example, a particulate premix as identified above can be made by mechanically grinding these components and zirconium hydrogen phosphate, to form particles ranging in size from 1 to 100 µm. A suitable sieving operation can be carried out following the grinding.
Si nécessaire, la poudre obtenue à l’issue du broyage et de son tamisage, peut être fluidisée dans un lit de fluidisation. If necessary, the powder obtained after grinding and sieving can be fluidized in a fluidization bed.
Comme énoncé précédemment, une composition selon l’invention peut également être préparée par simple mélange de plusieurs compositions selon l’invention. Il est ainsi possible d’obtenir une large gamme de compositions selon l’invention aptes à procurer respectivement des effets coloriels distincts de grande diversité. As stated above, a composition according to the invention can also be prepared by simply mixing several compositions according to the invention. It is thus possible to obtain a wide range of compositions according to the invention capable of respectively providing distinct color effects of great diversity.
Utilisation use
Les compositions solides selon l’invention sont particulièrement utiles pour former un revêtement de surface transparent, translucide et coloré ou non sur un support ou encore substrat. Ces supports peuvent être formés de matériaux très divers comme un métal, une céramique, du plastique ou du verre et de préférence est du verre. Au regard de cette diversité de supports envisageables, les compositions selon l’invention peuvent être employées dans des domaines techniques très différents comme celui de la métallurgie, l’industrie du verre creux et verre plat, l’industrie du bois et de la céramique. The solid compositions according to the invention are particularly useful for forming a transparent surface coating, translucent and colored or not on a support or even substrate. These supports can be formed from a wide variety of materials such as metal, ceramic, plastic or glass and preferably is glass. In view of this diversity of supports that can be envisaged, the compositions according to the invention can be used in very different technical fields such as that of metallurgy, the hollow glass and flat glass industry, the wood and ceramics industry.
Les compositions selon l’invention sont notamment utiles pour former des revêtements de surface dotés d’un effet décoratif sur des articles en verre, comme par exemple des bouteilles, des flacons de parfum, des réceptacles cosmétiques, des articles de l’art de la table, du vitrage. The compositions according to the invention are in particular useful for forming surface coatings endowed with a decorative effect on glass articles, such as for example bottles, perfume bottles, cosmetic receptacles, articles of the art of table, glazing.
Selon la nature des pigments et matières colorantes présents dans la composition utilisée, le revêtement obtenu est coloré ou non. Il peut ainsi n’être que translucide voire transparent en absence de tout matériau apte à procurer un effet coloré. Depending on the nature of the pigments and coloring materials present in the composition used, the coating obtained is colored or not. It can thus be only translucent or even transparent in the absence of any material capable of providing a colored effect.
Les compositions selon l’invention s’avèrent en outre adaptées à être mélangées pour former de nouvelles compositions soit avant leur utilisation ou au moment de leur mise en œuvre pour former un revêtement de surface sur un support. The compositions according to the invention have also been found to be suitable for being mixed to form new compositions either before their use or at the time of their implementation to form a surface coating on a support.
Procédé pour former un revêtement Process for forming a coating
L’invention a encore pour objet, un procédé pour former un revêtement de surface sur un support, notamment en verre, comprenant A further subject of the invention is a method for forming a surface coating on a support, in particular glass, comprising
former par pulvérisation électrostatique un dépôt d’au moins une composition selon l’invention en surface de la zone à traiter dudit support, et forming by electrostatic spraying a deposit of at least one composition according to the invention on the surface of the area to be treated of said support, and
si nécessaire, exposer ce dépôt à des conditions efficaces pour le transformer en un revêtement adhérent à ladite zone. if necessary, exposing this deposit to conditions effective to transform it into a coating adherent to said zone.
La pulvérisation électrostatique est réalisée selon un procédé électrostatique ou effet Corona ou encore un procédé triboélectrique voire fluidisation. The electrostatic spraying is carried out according to an electrostatic process or Corona effect or else a triboelectric process or even fluidization.
Selon la nature du matériau organique filmogène présent dans la composition solide et/ou la nature du support considéré par exemple métallique ou non, il peut être nécessaire d’exposer le dépôt à un élément déclencheur pour former le revêtement attendu. Depending on the nature of the film-forming organic material present in the solid composition and / or the nature of the support considered, for example metallic or not, it may be necessary to expose the deposit to a trigger element to form the expected coating.
Cet élément déclencheur peut être notamment un chauffage, une exposition UV. This trigger can be in particular heating, UV exposure.
Par exemple dans le cas d’un support métallique, le dépôt peut être formé à température ambiante c’est-à-dire entre 18 et 25 °C. For example in the case of a metal support, the deposit can be formed at room temperature, that is to say between 18 and 25 ° C.
Lorsque le support est en verre, il est préférable de former le dépôt en surface du verre porté à une température de 100 à 180 °C. Le procédé selon l’invention permet de former le revêtement directement au contact du substrat. When the support is made of glass, it is preferable to form the deposit on the surface of the glass brought to a temperature of 100 to 180 ° C. The method according to the invention makes it possible to form the coating directly in contact with the substrate.
Avantageusement, le revêtement obtenu est formé à partir d’un unique dépôt de composition. Advantageously, the coating obtained is formed from a single deposit of composition.
Le revêtement obtenu selon le procédé de l’invention peut posséder une épaisseur variant de 50 à 120 pm. The coating obtained by the process of the invention may have a thickness varying from 50 to 120 μm.
Ses qualités de surface en termes d’effet esthétique, par exemple coloré ou non, translucide ou non sont directement liés à la nature des composants de la composition mise en œuvre. Its surface qualities in terms of aesthetic effect, for example colored or not, translucent or not, are directly linked to the nature of the components of the composition used.
Il est également envisageable de considérer la mise en œuvre simultanée de plusieurs compositions conformes selon l’invention pour créer des effets décoratifs au niveau d’un même revêtement. Ainsi, en ajustant de manière différente la pulvérisation de deux compositions selon l’invention, il est possible par exemple de créer un effet de dégradé au niveau du revêtement. It is also conceivable to consider the simultaneous use of several compositions in accordance with the invention to create decorative effects at the same coating. Thus, by adjusting the spraying of two compositions according to the invention in a different manner, it is possible, for example, to create a degraded effect in the coating.
Par exemple, selon un mode de réalisation la composition selon l’invention contient au moins 3% en poids de sulfure de zinc et le revêtement formée à partir de cette composition est translucide ou encore dit à effet opaline. For example, according to one embodiment, the composition according to the invention contains at least 3% by weight of zinc sulphide and the coating formed from this composition is translucent or else said to have an opaline effect.
Les exemples ci-après sont soumis à titre illustratif et non limitatif du domaine de l’invention. The examples below are submitted by way of illustration and not limiting the field of the invention.
Matériel et méthodes Material and methods
Les matériaux de type résine sont Resin-type materials are
- un vernis de base polyuréthane commercialisé série 44 par la société Tiger - a polyurethane base varnish sold in series 44 by the company Tiger
Coating, Coating,
- un vernis de base polyester dit N°1 commercialisé sous le nom Série 16 de la société Tiger Coating et - a polyester base varnish known as No. 1 marketed under the name Série 16 from the company Tiger Coating and
- un vernis de base polyester dit N°2 commercialisé sous la dénomination commerciale GZ C642C8202 de chez Protech Oxyplast - a polyester base varnish called N ° 2 marketed under the trade name GZ C642C8202 from Protech Oxyplast
Les mélanges de poudres sont réalisés dans une jarre de broyage à l’aide de boules céramiques telles que détaillées ci-après. Le volume de la jarre est distribué en 1/3 boules 1/3 air et 1/3 mélange de matières. Les résistances mécaniques sont contrôlées suivant les méthodes définies par la norme ISO 8113. The powder mixes are made in a grinding jar using ceramic balls as detailed below. The volume of the jar is distributed in 1/3 balls, 1/3 air and 1/3 mixture of materials. The mechanical strengths are checked according to the methods defined by the ISO 8113 standard.
a) Test d’arrachement au scotch sur surface quadrillée a) Tear-off test with tape on a grid surface
Matériel utilisé Equipment used
Ruban adhésif ayant un pouvoir adhésif compris entre 350 et 450 N/cm2 et d’une largeur de 19mm (par exemple référence 616M de la Société 3M) Adhesive tape having an adhesive power of between 350 and 450 N / cm 2 and a width of 19mm (for example reference 616M from the Company 3M)
Cutter pour le quadrillage Cutter for grid lines
Mode opératoire Procedure
Réaliser un quadrillage de 5 traits verticaux et 5 traits horizontaux sur une surface de 1 à 2 cm2, Make a grid of 5 vertical lines and 5 horizontal lines on a surface of 1 to 2 cm 2 ,
Appliquer soigneusement le ruban adhésif sur la surface quadrillée en appuyant avec le pouce, Carefully apply the adhesive tape to the grid surface by pressing with your thumb,
Attendre 1 minute et Wait 1 minute and
Arracher le ruban adhésif d’un coup sec en exerçant l’effort sous un angle compris entre 45° et 90° par rapport au support. Tear off the adhesive tape by exerting the effort at an angle of between 45 ° and 90 ° to the support.
Si le revêtement est satisfaisant, il ne doit y avoir aucun départ sur l’ensemble de la surface quadrillée. b) Test d’action au produit contenu ou G1 à froid If the coating is satisfactory, there should be no departure over the entire grid area. b) Action test on the product contained or G1 cold
Matériel Equipment
Un cristallisoir transparent, A transparent crystallizer,
Produit G1 (70% alcool éthylique + 20% essence de térébenthine† 10% phtalate d’éthyle) et un chiffon doux blanc. Product G1 (70% ethyl alcohol + 20% turpentine † 10% ethyl phthalate) and a soft white cloth.
Mode opératoire Procedure
Immerger les surfaces à tester pendant 24 Heures (+/- 1 heure) dans le produit à température ambiante. Immerse the surfaces to be tested for 24 hours (+/- 1 hour) in the product at room temperature.
La surface testée est ensuite frottée légèrement avec le pouce ou le chiffon blanc. The tested surface is then rubbed lightly with the thumb or the white cloth.
On ne doit pas observer d’entraînement ni de variation des nuances de teinte ni de dégorgement dans le liquide du bain. No carry-over or variation in color shades or bleeding in the bath liquid should be observed.
Exemple 1 : préparation d’une composition selon l’invention. Example 1: preparation of a composition according to the invention.
Préparation d’un pré-mélange A 20 g (15, 38%) d’hydrogénophosphate de zirconium, 50 g (38,46 %) de sulfure de zinc, 50 g (38, 46%) de carbonate de calcium et 10 g (07,69%) de silice pyrogénée (Aerosil 200 de la société EVONIK) sont introduits dans une jarre de céramique contenant des billes de céramique de diamètre de 10 à 30 mm. Le mélange y est broyé pendant 30 minutes puis tamisé à lOOpm. Preparation of a premix A 20 g (15.38%) zirconium hydrogen phosphate, 50 g (38.46%) zinc sulfide, 50 g (38.46%) calcium carbonate and 10 g (07.69%) silica pyrogenic (Aerosil 200 from the company EVONIK) are introduced into a ceramic jar containing ceramic balls with a diameter of 10 to 30 mm. The mixture is ground there for 30 minutes and then sieved at 100 pm.
Préparation d’un pré-mélange B Preparation of a pre-mix B
3 g de pigment Paliogen® NOIR L 0086 BASF ( perylene ) et 1 g d’hydrogénophosphate de zirconium sont introduits dans un pot en plastique (120ml) contenant des billes de zirconium diamètre de 2 à 20 mm. Le mélange y est broyé 30 minutes puis tamisé à 63pm. 3 g of Paliogen® BLACK L 0086 BASF pigment (perylene) and 1 g of zirconium hydrogen phosphate are placed in a plastic jar (120ml) containing zirconium beads with a diameter of 2 to 20 mm. The mixture is ground there for 30 minutes then sieved at 63 pm.
Préparation de compositions solides conformes à l’invention Preparation of solid compositions according to the invention
100g (90.5%) de résine polyuréthane (série 44 de la société TIGER) sont introduits dans un pot en plastique de diamètre de 80mm sur 10cm de haut contenant 5 billes de zirconium de diamètre de 30mm. 100g (90.5%) of polyurethane resin (series 44 from the TIGER company) are introduced into a plastic pot with a diameter of 80mm by 10cm high containing 5 zirconium balls with a diameter of 30mm.
7.5gr (6.79%) du pré mélange A et 3 g (2.71%) d’hydrogénophosphate de zirconium sont ajoutés et l’ensemble est broyé 10 minutes, tamisé à lOOpm puis fluidisé dans un bain de fluidisation. 7.5 g (6.79%) of premix A and 3 g (2.71%) of zirconium hydrogen phosphate are added and the whole is ground for 10 minutes, sieved at 100 pm and then fluidized in a fluidization bath.
Avec le prémélange A, la composition pulvérulente obtenue est appropriée pour former un revêtement translucide de teinte opaline. With the premix A, the pulverulent composition obtained is suitable for forming a translucent coating of opaline tint.
100g (96%) de résine polyuréthane (série 44 de la société TIGER) sont mélangés avec 1,2 gr (1.1%) le prémélange B et 3gr (2.9%) d’hydrogénophosphate de zirconium selon le protocole décrit précédemment. La composition solide de type poudre obtenue permet de former un revêtement translucide coloré. 100 g (96%) of polyurethane resin (series 44 from the company TIGER) are mixed with 1.2 g (1.1%) of the premix B and 3 g (2.9%) of zirconium hydrogen phosphate according to the protocol described above. The solid powder-type composition obtained makes it possible to form a colored translucent coating.
Exemple 2 : Formation d’un revêtement sur un support à partir d’une composition selon l’invention. La composition de l’exemple 1 obtenue avec le prémélange A est pulvérisée par un procédé électrostatique sur un flacon en verre pour y former un revêtement de surface possédant une épaisseur de 50 à 80 microns. Example 2 Formation of a coating on a support from a composition according to the invention. The composition of Example 1 obtained with the premix A is sprayed by an electrostatic process onto a glass vial to form a surface coating thereon having a thickness of 50 to 80 microns.
Les qualités de surface du revêtement sont testées comme suit. The surface qualities of the coating are tested as follows.
Le flacon en verre traité est immergé pendant 20 minutes dans une eau chaude de température 60°C puis récupéré. The treated glass bottle is immersed for 20 minutes in hot water at a temperature of 60 ° C. and then collected.
Le flacon en verre est tout d’abord frotté avec le doigt au niveau de son revêtement. Il n’est constaté aucune altération du revêtement appliqué. Celui-ci n’est pas entraîné et demeure intégralement fixé au contenant. Son aspect coloriel demeure en outre intact. The glass bottle is first rubbed with your finger on the coating. No alteration of the applied coating was observed. This is not entrained and remains fully attached to the container. Its color aspect also remains intact.
Il est ensuite réalisé le test quadrillage selon la norme (scotch Réf 3M brand 616 Made in USA 5704 - 1) détaillé dans matériel et méthode. A l’issue de ce traitement, il est procédé à un examen visuel du revêtement figurant sur le contenant en verre. Aucune dégradation de ce revêtement n’est également constatée. The grid test is then carried out according to the standard (scotch Ref 3M brand 616 Made in USA 5704 - 1) detailed in material and method. After this treatment, a visual examination of the coating on the glass container is carried out. No degradation of this coating was also observed.
Exemple 3 : Formation de revêtement conformes à l’invention et témoins. Example 3: Coating formation according to the invention and witnesses.
Le tableau 1 ci-après rend compte des compositions solides testées. Elles ont été préparées en reproduisant le protocole opératoire décrit en exemple 1 avec les quantités précisées dans ce tableau. Leurs qualités de surface ont été testées selon le test eau et le test G1 décrit en exemple 2. Les résultats sont également indiqués en tableau 1. Table 1 below gives an account of the solid compositions tested. They were prepared by reproducing the operating protocol described in Example 1 with the amounts specified in this table. Their surface qualities were tested according to the water test and the G1 test described in Example 2. The results are also shown in Table 1.
[Tableau 1] [Table 1]
Figure imgf000018_0001
Figure imgf000018_0001
Exemple 4 : préparation de revêtements conformes l’invention Des revêtements ont été formés selon le protocole décrit en exemple 2 à partir des compositions détaillées en tableau 2. Example 4: Preparation of coatings in accordance with the invention Coatings were formed according to the protocol described in Example 2 from the compositions detailed in Table 2.
Tous les revêtements obtenus sont translucides et de teinte opaline. De plus, comme démontré dans le tableau 2, les compositions selon l’invention permettent d’obtenir une résistance élevée lors des tests à l’eau chaude et du test G1 pour différentes teneurs en pigment. [Tableau 2] All the coatings obtained are translucent and opaline in color. In addition, as shown in Table 2, the compositions according to the invention make it possible to obtain high resistance during the hot water tests and the G1 test for different pigment contents. [Table 2]
Figure imgf000019_0001
Figure imgf000019_0001
Par ailleurs, l’affaissement est évalué visuellement à la sortie du four. Comme il ressort des résultats, la présence de carbonate de calcium au sein de la composition dédiée à former le revêtement, accroît les performances de ce revêtement. In addition, sag is visually assessed upon exiting the oven. As the results show, the presence of calcium carbonate in the composition dedicated to forming the coating increases the performance of this coating.

Claims

Revendications Claims
1. Composition solide sous forme d’une poudre apte à former un revêtement de surface sur un support, ladite composition comprenant au moins un matériau organique filmogène, de l’hydrogénophosphate de zirconium et au moins un matériau choisi parmi les matières colorantes organiques et les pigments, et comprenant moins de 3% en poids de dioxyde de titane par rapport à son poids total et de préférence dénuée de dioxyde de titane. 1. Solid composition in the form of a powder capable of forming a surface coating on a support, said composition comprising at least one film-forming organic material, zirconium hydrogenphosphate and at least one material chosen from organic coloring materials and organic dyestuffs. pigments, and comprising less than 3% by weight of titanium dioxide relative to its total weight and preferably devoid of titanium dioxide.
2. Composition selon la revendication précédente comprenant de 0,5 à 10% en poids et notamment de 1 à 5% en poids d’hydrogénophosphate de zirconium par rapport à son poids total, en particulier de 1 à 3,5% en poids, voire de 1,5 à 3% en poids par rapport au poids total de la composition. 2. Composition according to the preceding claim comprising from 0.5 to 10% by weight and in particular from 1 to 5% by weight of zirconium hydrogen phosphate relative to its total weight, in particular from 1 to 3.5% by weight, even from 1.5 to 3% by weight relative to the total weight of the composition.
3. Composition selon la revendication 1 ou 2, contenant au moins 90%, de préférence de 90 à 95%, en poids en matériau filmogène par rapport à son poids total. 3. Composition according to claim 1 or 2, containing at least 90%, preferably from 90 to 95%, by weight of film-forming material relative to its total weight.
4. Composition selon l’une quelconque des revendications précédentes, comprenant du sulfure de zinc à titre de pigment. 4. Composition according to any one of the preceding claims, comprising zinc sulphide as a pigment.
5. Composition selon l’une quelconque des revendications précédentes comprenant en outre au moins un matériau choisi parmi les argiles, les silices pyrogénées, le carbonate de calcium, le sulfate de baryum et leurs mélanges, de préférence au moins du carbonate de calcium. 5. Composition according to any one of the preceding claims further comprising at least one material selected from clays, fumed silicas, calcium carbonate, barium sulfate and mixtures thereof, preferably at least calcium carbonate.
6. Composition selon l’une quelconque des revendications précédentes dans laquelle le matériau organique filmogène est choisi parmi les résines époxy, de polyuréthanes, de polyacrylates, de polyester modifiées ou non et leurs mélanges, et en particulier est au moins une résine polyuréthane ou au moins une résine de polyester. 6. Composition according to any one of the preceding claims, in which the film-forming organic material is chosen from epoxy, polyurethane, polyacrylate and polyester resins, modified or not, and their mixtures, and in particular is at least one polyurethane resin or at least one resin. minus a polyester resin.
7. Composition selon l’une quelconque des revendications précédentes dans laquelle l’hydrogénophosphate de zirconium et ledit matériau organique filmogène sont mis en œuvre dans un rapport pondéral variant de 1/ 20 à 1/ 200, et en particulier inférieur à 1/20. 7. Composition according to any one of the preceding claims, in which the zirconium hydrogen phosphate and said film-forming organic material are used in a weight ratio varying from 1/20 to 1/200, and in particular less than 1/20.
8. Composition selon l’une quelconque des revendications précédentes comprenant au moins de 90 à 95% en poids d’au moins un matériau organique filmogène, de préférence au moins une résine de polyuréthane ou de polyester, de 0,5% à 10% en poids d’hydrogénophosphate de zirconium et de préférence de 1 % à 10% de sulfure de zinc par rapport à son poids total. 8. Composition according to any one of the preceding claims comprising at least 90 to 95% by weight of at least one film-forming organic material, preferably at least one polyurethane or polyester resin, from 0.5% to 10%. by weight of zirconium hydrogenphosphate and preferably from 1% to 10% of zinc sulphide relative to its total weight.
9. Composition selon l’une quelconque des revendications précédentes, utile pour former un revêtement translucide ou à effet opaline. 9. Composition according to any one of the preceding claims, useful for forming a translucent coating or having an opaline effect.
10. Procédé de préparation d’une composition selon l’une quelconque des revendications précédentes comprenant au moins les étapes consistant à : 10. A process for preparing a composition according to any one of the preceding claims comprising at least the steps of:
mélanger par broyage mécanique, le matériau particulaire filmogène et l’hydrogénophosphate de zirconium avec au moins un prémélange de composants annexes de ladite composition dont au moins une matière colorante organique ou un pigment, mixing by mechanical grinding, the particulate film-forming material and the zirconium hydrogen phosphate with at least one premix of ancillary components of said composition including at least one organic coloring material or a pigment,
le cas échéant tamiser le mélange homogène pulvérulent ainsi obtenu à une taille inférieure ou égale à lOOpm et de préférence inférieure ou égale à environ 60 pm et if necessary sieve the homogeneous pulverulent mixture thus obtained to a size less than or equal to 100 μm and preferably less than or equal to approximately 60 μm and
Le cas échéant, fluidiser ledit mélange tamisé. Where appropriate, fluidize said sieved mixture.
11. Procédé selon la revendication précédente dans lequel le broyage mécanique est réalisé dans un broyeur à billes. 11. Process according to the preceding claim, in which the mechanical grinding is carried out in a ball mill.
12. Procédé selon l’une des revendications 10 ou 11 dans lequel ledit prémélange est obtenu par broyage mécanique d’un prémélange comprenant au moins une charge minérale, du sulfure de zinc et de l’hydrogénophosphate de zirconium de préférence dans un rapport pondéral matériaux inorganiques/hydrogénophosphate de zirconium variant de 1/100 à 1/20. 12. Method according to one of claims 10 or 11 wherein said premix is obtained by mechanical grinding of a premix comprising at least one mineral filler, zinc sulphide and zirconium hydrogen phosphate preferably in a material weight ratio. inorganic / zirconium hydrogenphosphate varying from 1/100 to 1/20.
13. Utilisation d’au moins une composition selon l’une quelconque des revendications 1 à 9 pour former un revêtement de surface sur un support, et de préférence un revêtement translucide ou à effet opaline. 13. Use of at least one composition according to any one of claims 1 to 9 to form a surface coating on a support, and preferably a translucent or opaline effect coating.
14. Utilisation selon la revendication 13 dans laquelle le support est formé d’un matériau choisi parmi le plastique, la céramique, le verre et le métal et de préférence est un verre. 14. Use according to claim 13 wherein the support is formed of a material selected from plastic, ceramic, glass and metal and preferably is glass.
15. Procédé pour former un revêtement, notamment un revêtement translucide ou à effet opaline, en surface d’un support comprenant au moins les étapes consistant à former par pulvérisation électrostatique un dépôt, de préférence un unique dépôt, d’au moins une composition selon l’une quelconque des revendications 1 à 9 en surface de la zone à traiter dudit support, et si nécessaire, exposer ledit dépôt à des conditions efficaces pour le transformer en un revêtement adhérent à ladite zone, et possédant de préférence une épaisseur variant de 50 à 120 pm. 15. A method for forming a coating, in particular a translucent or opaline-effect coating, on the surface of a support comprising at least the steps of forming by electrostatic spraying a deposit, preferably a single deposit, of at least one composition according to any one of claims 1 to 9 on the surface of the area to be treated of said support, and if necessary, exposing said deposit to conditions effective to transform it into a coating adhering to said area, and preferably having a thickness varying from 50 at 120 pm.
16. Procédé selon la revendication 15 dans lequel le support est métallique et le dépôt est formé à température ambiante. 16. The method of claim 15 wherein the support is metallic and the deposit is formed at room temperature.
17. Procédé selon la revendication 15 dans lequel le support est en verre et le dépôt est formé en surface dudit verre porté à une température de 100 à 180 °C. 17. The method of claim 15 wherein the support is glass and the deposit is formed on the surface of said glass brought to a temperature of 100 to 180 ° C.
PCT/EP2020/064607 2019-05-27 2020-05-26 Solid composition for forming surface coatings WO2020239785A1 (en)

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CN108864905A (en) * 2018-05-31 2018-11-23 华南理工大学 A kind of lozenge bedded zirconium phosphate and the marine anticorrosion powdery paints of carbon nanotube and the preparation method and application thereof

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US20030096017A1 (en) * 1997-10-03 2003-05-22 Decker Owen H. Anti-microbial powder coatings

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CN108864905A (en) * 2018-05-31 2018-11-23 华南理工大学 A kind of lozenge bedded zirconium phosphate and the marine anticorrosion powdery paints of carbon nanotube and the preparation method and application thereof

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