WO2014099579A1 - Procédé de préparation d'une composition de revêtement en poudre - Google Patents

Procédé de préparation d'une composition de revêtement en poudre Download PDF

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Publication number
WO2014099579A1
WO2014099579A1 PCT/US2013/074576 US2013074576W WO2014099579A1 WO 2014099579 A1 WO2014099579 A1 WO 2014099579A1 US 2013074576 W US2013074576 W US 2013074576W WO 2014099579 A1 WO2014099579 A1 WO 2014099579A1
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WO
WIPO (PCT)
Prior art keywords
powder coating
coating composition
polyurethane resin
component
total weight
Prior art date
Application number
PCT/US2013/074576
Other languages
English (en)
Inventor
Carmen Flosbach
Stefanie Matten
Jennifer Donnermeyer
Original Assignee
Axalta Coating Systems IP Co. LLC
Coatings Foreign Ip Co. Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Axalta Coating Systems IP Co. LLC, Coatings Foreign Ip Co. Llc filed Critical Axalta Coating Systems IP Co. LLC
Publication of WO2014099579A1 publication Critical patent/WO2014099579A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/20—Compositions for powder coatings

Definitions

  • the present invention refers to a process for the preparation of a powder coating composition useful for coatings with anti-graffiti properties.
  • polyurethane resins are known to the person skilled in the art; in particular, they may be produced by reacting polyol(s) with polyisocyanate(s).
  • Coatings with anti-graffiti properties can also be based on powder coating compositions comprising a mixture of polyester binder resins having different hydroxyl numbers and number-average molar masses (Mn), see for example EP-A 2214917.
  • WO 2007059133 discloses a powder coating composition containing hydrophobic agents such as functional alkyl silanes, alkyl siloxanes, fluorine alkyl silanes and fluorine alkyl siloxanes, perfluorinated hydro carbons.
  • EP-A 772 514 describes surfaces having specific structure consisting of elevations and depths with specific distances, the elevations are made of hydrophobic polymers providing a self-cleaning surface.
  • WO 02/064266 describes coatings providing a particle-based surface structure wherein the particles have an average diameter lower 100 nm, and wherein the coating is at least partially hydrophobic.
  • the present invention relates to a process for the preparation of a powder coating composition the composition comprising
  • the at least one polyurethane resin is produced by reacting the isocyanate component and the alcohol component comprising the at least one ⁇ , ⁇ -hydroxy organo functional polydimethylsiloxane with one another in substance or in the presence of a solvent and/or water.
  • the process according to the invention based on the at least such polyurethane resin provides coatings with highly improved anti-graffiti properties and a stable self-cleaning effect of the coatings.
  • the present invention refers to a process for the preparation of a powder coating composition
  • a powder coating composition comprising as component A) 30 to 99.5 wt%, based on the total weight of the powder coating composition, of at least one polyurethane resin as binder resin which is produced from an isocyanate component and an alcohol component comprising at least one ⁇ , ⁇ -hydroxy organo functional
  • the powder coating composition a silicon content (calculated as elementary silicon with molecular mass 28) in a range of 0.2 to 5 wt%, the wt% based on the total weight of the powder coating composition.
  • the powder coating composition of the invention comprises as component A) 50 to 99.5 wt%, more preferably 80 to 99.5 wt%, of the at least one polyurethane resin, the wt% based on the total weight of the powder coating composition, particularly in case the powder coating composition of the invention is cured by high energy radiation, for example, ultra violet (UV) irradiation.
  • high energy radiation for example, ultra violet (UV) irradiation.
  • the powder coating composition of the invention comprises as component A) 30 to 90 wt%, more preferably 50 to 80 wt%, of the at least one polyurethane resin, the wt% based on the total weight of the powder coating composition, particularly in case the powder coating composition of the invention is cured by thermal energy.
  • the at least one polyurethane resin according to this invention can be selected from the group consisting of amorphous, crystalline and/or semi-crystalline polyurethane resins.
  • the at least one polyurethane resin according to this invention is selected from the group consisting of crystalline and/or semi-crystalline polyurethane resins.
  • Amorphous substances can be defined by glass transition temperatures (Tg), and crystalline and/or semi-crystalline substances can be defined by melting temperatures (Tm).
  • Tg is the glass transition temperature of the solid component(s) measured by means of differential scanning calorimetry (DSC) according to ISO 1 1357-2 standard.
  • Tm is the melting temperature of the solid component(s) measured by means of DSC at heating rates of 10 K/min according to DIN 53765-B-10 standard.
  • the melting temperature is not in general a sharp melting point, but instead the upper end of melting range with a breadth, as known by a skilled person.
  • the at least one polyurethane resin of the invention may have a number- average molar mass (Mn) in the range of, for example, 500 to 15000, preferably 1000 to 12000.
  • the number-average molar mass (Mn) stated herein is the number average molar mass determined or to be determined by gel permeation chromatography (GPC; divinylbenzene-cross-linked polystyrene as the immobile phase,
  • polystyrene standards determined according to ISO 13885-1 standard.
  • the at least one polyurethane resin of the invention may have functional groups such as hydroxyl, carboxyl, alkoxy, (meth)acryl, blocked isocyanate groups and/or may have free-radically polymerizable olefinic double bonds in the form of (meth)acryloyl within its resin structure.
  • (meth)acryloyl groups can be introduced by transesterifying hydroxy functional polyurethane resin with alkyl esters of (meth)acrylic acid;
  • esterifying hydroxy functional polyurethane resin with (meth)acrylic acid reacting hydroxyl functional polyurethane resin with isocyanate-functional (meth)acrylates or reacting carboxy functional polyurethane resin with epoxy-fu notional (meth)acrylates, reacting isocyanate functional polyurethane resin with hydroxyalkyl (meth)acrylates.
  • the hydroxyl groups may be introduced using measures known to the person skilled in the art, for example, by reacting isocyanate groups still present in the
  • (meth)acryloyl is respectively intended to mean acryloyl and/or methacryloyl.
  • (meth)acryl is respectively intended to mean acryl and/or methacryl.
  • the at least one polyurethane resin of the invention may have a hydroxyl number in the range of, for example, 30 to 150 mg KOH/g resin, preferably 30 to 120 mg KOH/g resin.
  • the carboxyl functional polyurethane resin of the invention may have an acid number in the range of, for example, 30 to 150 mg KOH/g resin, preferably 30 to 120 mg KOH/g resin.
  • the at least one polyurethane resin of the invention may have a number of blocked isocyanate groups, calculated as latent NCO-content in a range of 5 to 15, preferably 5 to 10.
  • latent NCO-content is intended to mean grams free NCO (with molecular mass 42) after deblocking / 100g resin.
  • the isocyanate groups are incorporated in blocked form.
  • Blocking may proceed as known in the art with conventional agents, e.g., with monoalcohols, glycol ethers, ketoximes, lactams, malonic acid esters, acetoacetic acid esters, for example, ethylene glycol monobutyl ether, butanone oxime, phenol, ethyl
  • hydroxyl number in this document is defined as the number of mg of potassium hydroxide (KOH) which is equal to the number of milligrams (mg) acetic acid for acetalizing of 1 g of the resin, determined according to DIN 53240 standard.
  • acid number in this document is defined as the mg of potassium hydroxide required to neutralise the acid groups of the polyester, described in DIN EN ISO 21 14 standard.
  • the person skilled in the art selects the nature and proportion of the components of the polyurethane resin of the invention in such a manner providing the polyurethane resin of the invention the functional groups as described above.
  • the isocyanate component for the production of the polyurethane resin of this invention comprises isocyanate(s) as known by a skilled person as such for the production of polyurethanes.
  • isocyanate(s) as known by a skilled person as such for the production of polyurethanes.
  • diisocyanates such as 1 ,6-hexane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, the isomeric diphenylmethandiisocyanates, dicyclohexylmethane diisocyanate and cyclohexane diisocyanate, but also polyisocyanates derived from these
  • diisocyanates like for example, uretidione or isocyanurate type polyisocyanates produced by di- or trimerization of these diisocyanates or polyisocyanates produced by reaction of these diisocyanates with water and containing biuret groups or urethane group containing polyisocyanates produced by reaction of these diisocyanates with polyols.
  • Preferred examples of the isocyanate component are isophorone diisocyanate, 1 ,6-hexane diisocyanate and dicyclohexylmethane diisocyanate.
  • the alcohol component for the production of the polyurethane resin of this invention comprises the at least one ⁇ , ⁇ -hydroxy organo functional
  • the silicon content of the powder coating composition of the invention is provided by the content of the at least one
  • polyurethane resin of the invention in the powder coating composition and particularly by the amount of the at least one ⁇ , ⁇ -hydroxy organo functional polydimethylsiloxane used for the preparation of the polyurethane resin of the invention.
  • the ⁇ , ⁇ -hydroxy organo functional polydimethylsiloxane can be a linear ⁇ , ⁇ -hydroxy organo functional polydimethylsiloxane, for example, linear ⁇ , ⁇ - dihydroxyalkylpolydimethylsiloxane having a hydroxyl number in the range of, for example, 30 to 150, preferably 35 to 120, providing a calculated hydroxy equivalent weight of 375 to 1900, preferably 470 to 1600.
  • the alkyl residue can be, for example, C1 to C6 alkyl group.
  • the alcohol component for the production of the polyurethane resin of the invention further comprises alcohols which are diols or polyols in the form of low molar mass compounds defined by empirical and structural formula and/or oligomeric or polymeric polyols with number-average molar masses of, for example, up to 800, for example, corresponding hydroxyl-functional polyethers, hydroxyl- functional polyesters and/or hydroxyl-functional polycarbonates.
  • Examples of such low molar mass diols are ethylene glycol, the isomeric propane- and butanediols, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,10-decanediol, 1 ,12- dodecanediol, 1 ,4-cyclohexanedimethanol, hydrogenated bisphenol A, dimer fatty alcohol, neopentyl glycol, butylethylpropanediol, the isomeric cyclohexanediols, the isomeric cyclohexanedimethanols, tricyclodecanedimethanol.
  • polyols are polyols with more than two hydroxyl groups such as glycerol, trimethylolpropane, trimethylolethane and pentaerythrite.
  • Preferred examples of such further diols and polyols are trimethylolpropane and glycerol.
  • polyurethane resin of the invention in such a manner providing the powder coating composition of the invention a silicon content (calculated as elementary silicon with molecular mass 28) in a range of 0.2 to 5 wt%, the wt% based on the total weight of the powder coating composition.
  • a perfluoroalkyl alcohol can be used in the production of the at least one polyurethane resin of the invention, resulting in a fluoro-modified polyurethane resin based on the isocyanate component, the alcohol component comprising the at least one ⁇ , ⁇ -hydroxy organo functional polydimethylsiloxane and the perfluoroalkyl alcohol, providing a fluorine content (calculated as elementary fluorine with molecular mass 19) of the powder coating composition of the invention in the range of 0.1 to 3 wt%, preferably 0.1 to 2 wt%, the wt% based on the total weight of the powder coating composition.
  • the fluorine content of the powder coating composition of the invention is provided by the content of the fluoro-modified polyurethane resin in the powder coating composition and particularly by the amount of the perfluoroalkyl alcohol used for the production of the fluoro-modified
  • the perfluoroalkyl alcohol can be a perfluoroalkyl containing polymeric polyol and/or a perfluoroalkyl containing monoalcohol.
  • the fluorine-containing polyether polyol has a fluorine content provided by its -OCH2CnF2n+1 groups in the range of, for example, 24 to 40 wt%, and it may have a number-average molar mass (Mn) in the range of, for example, 470 to 5000.
  • the fluorine-containing monoalcohol has a fluorine content provided by its F-(CF2)n- groups in the range of, for example, 65 to 70 wt%, and it may have a number-average molar mass (Mn)in the range of, for example, 416-528.
  • F-(CF2)n- groups F-(CF2)n- groups
  • Mn number-average molar mass
  • Examples of commercially available products are POLYFOXTM 636 (Omnova Solutions), POLYFOXTM 656 (Omnova Solutions) and ZONYL® BA-types (DuPont).
  • the person skilled in the art selects the nature and proportion of the isocyanate component and the polyol component comprising the ⁇ , ⁇ -hydroxy organo functional polydimethylsiloxane and the perfluoroalkyl alcohol for the production of the fluoro-modified polyurethane resin in such a manner providing the powder coating composition of the invention a fluorine content (calculated as elementary fluorine with molecular mass 19) in a range of 0.1 to 3 wt%, the wt% based on the total weight of the powder coating composition of the invention.
  • a fluorine content (calculated as elementary fluorine with molecular mass 19) in a range of 0.1 to 3 wt%, the wt% based on the total weight of the powder coating composition of the invention.
  • the isocyanate component and the polyol component comprising the at least one ⁇ , ⁇ -hydroxy organo functional polydimethylsiloxane, and, if desired, the perfluoroalkyl alcohol, can be reacted with one another in substance or in the presence of a solvent and/or water.
  • solvent means an organic solvent or mixture of organic solvents, as known in the art.
  • solvent may be used, in general, for example, in an amount of 0 to 50 wt%, the wt% based on the total amount of the polyurethane resin solution which, however, makes it necessary to remove the solvent from the resulted resin.
  • the production of the polyurethane resin according to the invention is carried out without solvent and without subsequent purification operations.
  • the reactants may all be reacted together simultaneously or in two or more synthesis stages. When the synthesis is performed in multiple stages, the reactants may be added in the most varied order, for example, also in succession or in alternating manner.
  • the polyol component may be divided into two or more partial amounts, for example, or into the individual polyols, for example, such that the isocyanate component is reacted first with a portion of the polyol component, e.g. ⁇ , ⁇ -hydroxy organo functional polydimethylsiloxane, and finally with the remaining proportion of the polyol component.
  • the isocyanate component may also be divided into two or more partial amounts, for example, such that the polyols are reacted first with a portion of the isocyanate component and finally with the remaining proportion of the isocyanate component. That means, that the individual reactants may be added in their entirety or in two or more portions.
  • the reaction is exothermic and proceeds at a temperature above the melting temperature of the reaction mixture.
  • the reaction temperature is, for example, 60 to 140°C.
  • the rate of addition or quantity of reactants added is accordingly determined on the basis of the degree of exothermy and the liquid (molten) reaction mixture may be maintained within the desired temperature range by heating or cooling.
  • solid polyurethane resin is obtained.
  • the polyurethane resin assumes the form of a mixture exhibiting a molar mass distribution.
  • the polyurethane resin does not, however, require working up and may be used directly as a powder coating binder resin.
  • the resulted polyurethane resin may be used in the powder coating composition of the invention as binder resin in combination with, as component B), 0 to 70 wt%, preferably 0 to 60%, based on the total weight of the powder coating composition, of at least one co-binder resin to cross-link (cure) with one another.
  • Examples of the at least one co-binder resin of component B) are binders known as such in the art of paints and coatings by a skilled person which are different from the polyurethane resin of component A) and which are able to crosslink with the polyurethane resin of component A).
  • Examples are compounds curable by free-radical polymerization of olefinic double bonds, such as unsaturated polyesters, and/or resins based on polyesters, polyurethanes, phenolic resins, polyester epoxy resins, epoxy resins and/or (meth)acrylic copolymer resins such as glycidyl functionalized (meth) acrylic copolymers, polymer hybrid resins derived from these classes of resin binders, with a number-average molar mass (Mn) in the range of, for example, 500 to 10000.
  • Mn number-average molar mass
  • Examples are also compounds containing amino, amido groups, for example hydroxyl alkylamide compounds, further, dimerized isocyanates (uretidiones), triglycidyl isocyanurate (TGIC); polyglycidyl ethers based on diethylene glycol.
  • dimerized isocyanates uretidiones
  • TGIC triglycidyl isocyanurate
  • the powder coating composition of the invention comprises at least one pigment, filler and/or coating additive known at a skilled person in a range of 0.5 to 60 wt%, preferably 1 to 60 wt%, based on the total weight of the powder coating composition of the invention.
  • the pigments can be transparent pigments, color-imparting and/or special effect-imparting pigments and/or fillers (extenders), for example, corresponding a pigment plus filler: resin ratio by weight in the range from 0:1 to 2:1 .
  • inorganic or organic color-imparting pigments are titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, quinacridone or pyrrolopyrrole pigments.
  • special effect-imparting pigments are metal pigments, for example, made from aluminum, copper or other metals; interference pigments, such as, for example, metal oxide coated metal pigments, for example, titanium dioxide coated or mixed oxide coated aluminum, coated mica, such as, for example, titanium dioxide coated mica.
  • Examples of usable fillers are silicon dioxide, aluminum silicate, barium sulfate, calcium carbonate and talcum.
  • Coating additives are, for example, inhibitors, catalysts, levelling agents, degassing agents, wetting agents, anticratering agents, initiators, antioxidants and light stabilizers.
  • the coating additives are used in conventional amounts known to the person skilled in the art.
  • the powder coating composition consists of
  • the components of the powder coating composition are mixed, extruded and ground by conventional techniques employed in the powder coatings art familiar to a person of ordinary skill in the art. Typically, all of the components of the present powder coating formulation are added to a mixing container and mixed together. The blended mixture is then melt blended, for example, in a melt extruder. Also, components can be melt blended with the molten polyurethane resin. The melt blended, for example extruded, composition is then cooled and broken down and ground to a powder. The ground powder is subsequently screened to achieve the desired particle size, for example, an average particle size (mean particle diameter) of 20 to 200 ⁇ , determined by means of laser diffraction.
  • an average particle size mean particle diameter
  • the powder coating composition may also be prepared by spraying from supercritical solutions, NAD "non-aqueous dispersion” processes or ultrasonic standing wave atomization process.
  • specific components of the powder coating composition may be processed with the finished powder coating particles after extrusion and grinding by a "bonding" process using an impact fusion.
  • the specific components may be mixed with the powder coating particles.
  • the individual powder coating particles are treated to softening their surface so that the components adhere to them and are homogeneously bonded with the surface of the powder coating particles.
  • the softening of the powder particles' surface may be done by heat treating the particles to a temperature, e.g., 40 to 100°C, dependent from the melt behaviour of the powder particles.
  • the desired particle size of the resulted particles may be proceed by a sieving process.
  • the powder coating composition of the invention can be readily applied to metallic and non-metallic substrates, in a dry-film thickness of 10 to 300 ⁇ , preferably 20 to 100 ⁇ , particularly from 10 to 50 ⁇ for thin film coatings.
  • the powder coating composition of the invention can be used to coat metallic substrates including, but not limited to, steel, brass, aluminum, chrome, and mixtures thereof, and also to other substrates including, for example, heat-sensitive substrates, such as, substrates based on wood, plastics and paper, and other substrates based, for example, on glass and ceramics.
  • the surface of the substrate may be subjected to a mechanical treatment, such as, blasting followed by, in case of metal substrates, acid rinsing, or cleaning followed by chemical treatment.
  • the powder coating composition of the invention may be applied by, e.g., electrostatic spraying, electrostatic brushing, thermal or flame spraying, fluidized bed coating methods, flocking, tribostatic spray application and the like, also coil coating techniques, all of which are known to those skilled in the art.
  • the substrate Prior to applying the powder coating composition of the invention the substrate may be grounded but not pre-heated, so that the substrate is at an ambient temperature of about 25°C.
  • the substrate to be coated may be pre-heated before the application of the powder coating composition, and then either heated after the application of the powder composition or not.
  • gas is commonly used for various heating steps, but other methods, e.g., microwaves, infra red (IR), near infra red (NIR) and/or ultra violet (UV) irradiation are also known.
  • the pre-heating can be to a temperature ranging from 60 to 260°C using means familiar to a person of ordinary skill in the art.
  • the powder coating composition of the invention can be applied directly on the substrate surface as a primer coating or on a layer of a primer which can be a liquid or a powder based primer.
  • the powder coating composition can also be applied as a coating layer of a multilayer coating system based on liquid or powder coats, for example, as clear coat layer applied onto a color-imparting and/or special effect-imparting base coat layer or as pigmented one-layer coat applied onto a prior coating.
  • the powder After being applied, the powder can be melted by exposing by convective, gas and/or radiant heating, e.g., IR and/or NIR irradiation, as known in the art, to temperatures of, e.g. 100°C to 300°C, preferably, 120°C to 200°C, object
  • the applied and melted powder can be cured by thermal energy.
  • the coating layer may, for example, be exposed to convective, gas and/or radiant heating, e.g., infra-red (IR) and/or near infra-red (NIR) irradiation, as known in the art, to temperatures of, e.g., 100 to 300°C, preferably of 120 to 230°C for convective thermal curing and preferably 200 to 280°C for radiation heating processes (object temperature in each case).
  • convective, gas and/or radiant heating e.g., infra-red (IR) and/or near infra-red (NIR) irradiation, as known in the art, to temperatures of, e.g., 100 to 300°C, preferably of 120 to 230°C for convective thermal curing and preferably 200 to 280°C for radiation heating processes (object temperature in each case).
  • IR infra-red
  • NIR
  • Dual curing means a curing method of the powder coating composition according to the invention where the applied powder coating composition can be cured, e.g., both by high energy radiation such as, e.g. ultra violet (UV) irradiation, and by thermal curing methods known by a skilled person as described above.
  • high energy radiation such as, e.g. ultra violet (UV) irradiation
  • thermal curing methods known by a skilled person as described above.
  • UV (ultraviolet) radiation or electron beam radiation may be used as high- energy radiation. UV-radiation is the preferred high-energy radiation. Irradiation may proceed continuously or discontinuously.
  • thermally curable powder coating compositions may contain thermally cleavable free-radical initiators
  • the powder coating compositions curable by UV irradiation contain photoinitiators.
  • the initiators can be used, for example, in amounts of 0.1 to 7 wt%, preferably of 0.5 to 5 wt%, based on the total powder coating composition of the invention.
  • the initiators may be used individually or in combination.
  • thermally cleavable free-radical initiators are azo compounds, peroxide compounds and C-C-cleaving initiators, as known by a person skilled in the art.
  • photoinitiators are benzoin and derivatives thereof, acetophenone, benzophenone, thioxanthone and derivatives thereof, anthraquinone, 1 - benzoylcyclohexanol, organophosphorus compounds as known by a person skilled in the art.
  • the self-cleaning properties of the coatings provided by the powder coating composition of the invention can be determined by testing the initial self-cleaning ability of a coating layer on a panel by applying Leverkusen standard dirt 09 LD-40 (commercially available from wfk institute Krefeld, Germany) on the horizontally positioned coated panel, using a sieve, to the horizontally positioned panel. Then, 10 ml of water droplets are placed on the unsoiled area of the coated panel. The unsoiled end of the panel is slowly and continuously raised from the horizontal position to a more vertical position, and angle at which the water droplets begin to move is recorded. After the water droplets have reached the bottom end of the panel it is visually rated how much dirt the water droplets have removed from the surface.
  • Leverkusen standard dirt 09 LD-40 commercially available from wfk institute Krefeld, Germany
  • the coated panel is then carefully cleaned to remove any remaining dirt, and is subjected to artificial weathering conditions (1000h CAM 180 artificial weathering test).
  • artificial weathering conditions 1000h CAM 180 artificial weathering test.
  • the artificially weathered panel is then subjected to the same self-cleaning ability test as described above, and this is repeated again. Finally, a trend can be estimated, if or to what extent the self-cleaning ability reduces over time.
  • the mixture is heated to 60 °C, and 19.4 wt% of hydroxyethylacrylate is dosed in such a way that a temperature of 80 °C is not exceeded.
  • the mixture is kept at 80 °C till the target NCO-value is reached.
  • the molten resin is filled off and cooled down.
  • HDI 1 ,6-hexandiisocyanate
  • the powder clear coats are applied with a film thickness of 80 ⁇ onto steel panels, molten for 10 min at 140 °C (oven temperature) and after that irradiated with UV-light with an intensity of 500 mW/cm2 and a UV-dose of 800 mJ/cm2.
  • the self-cleanability of a coating layer over time is determined by the following method.
  • Leverkusen standard dirt 09 LD- 40 commercially available from wfk institute Krefeld, Germany
  • the coated panel is sprayed with a commercial black spray-can lacquer. After the lacquer had dried, an adhesive strip was stuck on the surface. If the spray- can lacquer layer was also removed when the strip was torn-off the desired unsticking-property was achieved (rating satisfactory), whereas when the spray-can lacquer remained on the panel the test result was unsatisfactory.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un procédé de préparation d'une composition de revêtement en poudre qui inclut: A) 30 à 99,5% en poids d'au moins une résine de polyuréthanne en tant que résine servant de liant, qui est produite à partir d'un composant d'isocyanate et d'un composant d'alcool comprenant au moins un α,ω-hydroxypolydiméthylsiloxanne fonctionnel organique, fournissant à la composition de revêtement en poudre une teneur en silicium dans la plage de 0,2 à 5% en poids, le % en poids étant basé sur le poids total de la composition de revêtement en poudre, B) 0 à 70% en poids d'au moins un co-liant (agent de réticulation, durcisseur), et C) 0,5 à 60% en poids d'au moins un pigment, charge et/ou additif de revêtement, le % en poids étant basé sur le poids total de la composition de revêtement en poudre où la résine de polyuréthanne est produite par réaction du composant d'isocyanate et du composant d'alcool comprenant au moins un α,ω-hydroxypolydiméthylsiloxanne fonctionnel organique l'un avec l'autre dans une substance ou en présence d'un solvant et/ou d'eau.
PCT/US2013/074576 2012-12-17 2013-12-12 Procédé de préparation d'une composition de revêtement en poudre WO2014099579A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111057203A (zh) * 2019-12-31 2020-04-24 北京松井工程技术研究院有限公司 硅氟聚氨酯丙烯酸树脂及其制备方法与应用
CN114163907A (zh) * 2021-11-04 2022-03-11 广东省科学院化工研究所 一种自清洁涂料及其制备方法和应用
WO2022062402A1 (fr) * 2020-09-24 2022-03-31 浙江华彩新材料有限公司 Revêtement en poudre facile à nettoyer, de haute dureté, et procédé de préparation associé

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DE2610372A1 (de) 1976-03-12 1977-09-15 Pfersee Chem Fab Verfahren zum behandeln von textilien mit polymerisaten von acrylsaeure- und methacrylsaeureestern
US4929666A (en) 1987-05-14 1990-05-29 The Dow Chemical Company Fluorocarbon containing, reactive polymeric surfactants and coating compositions therefrom
US5426151A (en) 1992-11-28 1995-06-20 Herberts Gesellschaft Mit Beschrankter Haftung Polysiloxane-containing binders, manufacture thereof, coating agents containing them, and use thereof
EP0772514A1 (fr) 1994-07-29 1997-05-14 Wilhelm Barthlott Surfaces autonettoyantes d'objets et leur procede de production
US6187863B1 (en) * 1997-08-01 2001-02-13 Ppg Industries Ohio, Inc. Curable compositions based on functional polysiloxanes
WO2002064266A2 (fr) 2001-02-10 2002-08-22 Ferro Gmbh Revetement autonettoyant sous forme de peinture et procede et agent permettant de fabriquer ladite peinture
DE102004058069A1 (de) * 2004-12-01 2006-06-08 Basf Ag Kratzfeste strahlungshärtbare Beschichtungen
US20070112164A1 (en) * 2005-11-17 2007-05-17 Bayer Materialscience Llc Low surface energy, ethylenically unsaturated polyisocyanate addition compounds and their use in coating compositions
WO2007059133A2 (fr) 2005-11-14 2007-05-24 E.I. Du Pont De Nemours And Company Procede de preparation de revetements presentant des proprietes de surface specifiques
EP2214917A1 (fr) 2007-11-30 2010-08-11 E. I. du Pont de Nemours and Company Processus de décoration de substrats munis d'un revêtement en poudre

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2610372A1 (de) 1976-03-12 1977-09-15 Pfersee Chem Fab Verfahren zum behandeln von textilien mit polymerisaten von acrylsaeure- und methacrylsaeureestern
US4929666A (en) 1987-05-14 1990-05-29 The Dow Chemical Company Fluorocarbon containing, reactive polymeric surfactants and coating compositions therefrom
US5426151A (en) 1992-11-28 1995-06-20 Herberts Gesellschaft Mit Beschrankter Haftung Polysiloxane-containing binders, manufacture thereof, coating agents containing them, and use thereof
EP0772514A1 (fr) 1994-07-29 1997-05-14 Wilhelm Barthlott Surfaces autonettoyantes d'objets et leur procede de production
US6187863B1 (en) * 1997-08-01 2001-02-13 Ppg Industries Ohio, Inc. Curable compositions based on functional polysiloxanes
WO2002064266A2 (fr) 2001-02-10 2002-08-22 Ferro Gmbh Revetement autonettoyant sous forme de peinture et procede et agent permettant de fabriquer ladite peinture
DE102004058069A1 (de) * 2004-12-01 2006-06-08 Basf Ag Kratzfeste strahlungshärtbare Beschichtungen
WO2007059133A2 (fr) 2005-11-14 2007-05-24 E.I. Du Pont De Nemours And Company Procede de preparation de revetements presentant des proprietes de surface specifiques
US20070112164A1 (en) * 2005-11-17 2007-05-17 Bayer Materialscience Llc Low surface energy, ethylenically unsaturated polyisocyanate addition compounds and their use in coating compositions
EP2214917A1 (fr) 2007-11-30 2010-08-11 E. I. du Pont de Nemours and Company Processus de décoration de substrats munis d'un revêtement en poudre

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111057203A (zh) * 2019-12-31 2020-04-24 北京松井工程技术研究院有限公司 硅氟聚氨酯丙烯酸树脂及其制备方法与应用
WO2022062402A1 (fr) * 2020-09-24 2022-03-31 浙江华彩新材料有限公司 Revêtement en poudre facile à nettoyer, de haute dureté, et procédé de préparation associé
CN114163907A (zh) * 2021-11-04 2022-03-11 广东省科学院化工研究所 一种自清洁涂料及其制备方法和应用

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