EP1419204A1 - Peinture pulverulente thermoplastique, procede permettant de la produire et systeme de melange pour peintures pulverulentes - Google Patents

Peinture pulverulente thermoplastique, procede permettant de la produire et systeme de melange pour peintures pulverulentes

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Publication number
EP1419204A1
EP1419204A1 EP02735291A EP02735291A EP1419204A1 EP 1419204 A1 EP1419204 A1 EP 1419204A1 EP 02735291 A EP02735291 A EP 02735291A EP 02735291 A EP02735291 A EP 02735291A EP 1419204 A1 EP1419204 A1 EP 1419204A1
Authority
EP
European Patent Office
Prior art keywords
thermoplastic
powder coating
particles
powder
dimensionally stable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02735291A
Other languages
German (de)
English (en)
Inventor
Christopher Hilger
Susanne Piontek
Michael Mauss
Günter ETZRODT
Robert Bayer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
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 BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP1419204A1 publication Critical patent/EP1419204A1/fr
Withdrawn legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/03—Powdery paints
    • C09D5/031—Powdery paints characterised by particle size or shape

Definitions

  • Thermoplastic powder coatings process for their preparation and mixing system for powder coatings
  • the present invention relates to new, in particular coloring and / or effect, thermoplastic powder coatings.
  • the present invention relates to a new method for the production and / or the subsequent adjustment of the material composition and / or the application properties profile of thermoplastic powder coatings, in particular of coloring and / or effect thermoplastic powder coatings.
  • the present invention relates to a new mixing system for the production and subsequent adjustment of the material composition and / or the application properties profile of thermoplastic powder coatings.
  • the present invention relates to the use of the new thermoplastic powder coatings for the automotive OEM coating, the coating of buildings indoors and outdoors, the coating of doors, windows and furniture, the industrial coating, including coil coating, container coating and the impregnation and / / or coating of electrical components, as well as the painting of white goods, including household appliances, boilers and radiators.
  • Thermoplastic powder coatings and processes for their production are known. They consist essentially of thermoplastic polymers such as polyethylene, polyvinyl chloride, polyamide, epoxy resins or Ethyle ⁇ / inylacetate copolymers. They are used, for example, to produce coatings on pipes (pipelines), all kinds of wire goods, flanges and fittings for indoor and outdoor use, wall wardrobes and bed frames, fence posts, garden furniture, guardrails, laboratory equipment, wire grids, inserts for dishwashers, shopping baskets, machine parts, Electric machines, rotors, stators, current coils, insulation boxes, boilers, brake cylinders, chemical plants or street signs.
  • thermoplastic polymers such as polyethylene, polyvinyl chloride, polyamide, epoxy resins or Ethyle ⁇ / inylacetate copolymers. They are used, for example, to produce coatings on pipes (pipelines), all kinds of wire goods, flanges and fittings for indoor and outdoor use, wall wardrobes and bed frames, fence posts, garden furniture
  • the preheated workpieces are "immersed" for a few seconds in a coating basin which is filled with powder coating fluidized by air flow. After dipping, the sintered powder melts to a closed film within a few seconds. A relatively uniform powder surface sintered from all sides now surrounds the workpiece.
  • the layer thicknesses can be 250 to 700 ⁇ m.
  • the vortex sinter powders have a grain size between 50 and 300 ⁇ m. They are therefore coarser than electrostatic powder, whose grain size is generally between 1 and 200 ⁇ m. In principle, however, each vortex sinter powder can also be adjusted by finer grinding so that it becomes accessible to electrostatic powder coating.
  • thermoplastic powder coatings show the two basic advantages of powder coatings, namely the complete or extensive freedom from organic solvents and the easy return of the powder coating overspray to the coating process.
  • thermoplastic powder coatings are produced either in the dry blend process with subsequent sieving or by melt homogenization of the starting materials with subsequent grinding and sieving. Both processes involve many process steps and are therefore comparatively complex.
  • the thermoplastics must first be roughly ground.
  • additives such as pigments or additives typical of powder solids are mixed together and extruded on special extruders.
  • the extrudate is carried out and cooled, for example, on a cooling belt.
  • the extrudate pieces are pre-broken, finely ground and sieved (with the oversize particles being fed back into the fine mill), after which the resulting thermoplastic powder coating is weighed and packaged.
  • the composition of the thermoplastic powder coatings produced by this process depends solely on the original weight; a subsequent correction of the composition is not possible.
  • thermoplastic powder clearcoats or pigmented thermoplastic powder coatings are produced in one and the same color, but pigmented thermoplastic powder coatings in alternating colors.
  • all units such as pre-mixers, extruders, cooling belts, crushers, fine grinders, screening machines and packaging machines have to be completely disassembled and cleaned, because, for example, a single blue powder coating granule in a yellow coating can be seen straight away. This cleaning can take several days and is therefore very expensive.
  • the manufacturing process also has another major disadvantage. Color adjustment and / or correction via mixing or tinting steps is not possible, but the color is determined solely by the original weight. Whether the finished coloring and / or effect thermoplastic powder coating or the coating produced from it ultimately also has the desired color and / or optical effect depends on numerous different process parameters and on the particular implementation of the process, so that it becomes extremely difficult to determine the cause of faulty batches. Furthermore, a number of problems can arise in the production of color and / or effect thermoplastic powder coatings, which can be attributed to the inadequate incorporation and incomplete dispersion of the color and / or effect pigments. This is particularly the case with transparent pigments and effect pigments. Overall, this leads to increased pigment consumption and quality problems.
  • Pigmented thermoplastic powder coatings appear as transparent if the pigment particles are ⁇ 15 nm. However, these small primary pigment particles tend to agglomerate. The agglomerates can only be comminuted in special mills with great effort. When they are incorporated into the thermoplastic powder coatings, even when using special extruders, it is generally not possible to produce transparent stains with hard-to-disperse pigments, such as wet-chemical-produced, transparent iron oxide pigments, pigment blacks or perylene pigments.
  • thermoplastic powder coatings are then less attractive in terms of color than the lacquers based on wet lacquers produced with these effect pigments and lack the brilliance and the typical silky sheen from the depths.
  • Aluminum effect pigments turn gray, and no optical effects can be observed with mica effect pigments.
  • European patent application EP 0 687 714 B1 discloses a thermoplastic powder coating whose particles have a composite structure made up of first and second particles.
  • the first particles contain part of the film-forming thermoplastic polymer.
  • the second particles are arranged on the surface of the first particles and contain the remaining part of the film-forming thermoplastic polymer and have a glass transition temperature in the range from 50 to 150 ° C.
  • the powder coating is produced by dry mixing two powder coatings of different particle sizes which are produced in a manner known per se. The resulting powder coating has high blocking resistance and stability during transport.
  • Pigment concentrates in which solutions of binders in organic solvents are mixed with pigments dispersed in organic solvents.
  • the resulting dispersions are dried, after which the resulting solids have to be broken and ground in a customary and known manner.
  • Binder dispersions mixed together after which the resulting mixtures are spray dried.
  • the pigment concentrate is incorporated, for example, in polyethylene, after which the mixture is injection-molded into a plate.
  • thermoplastic powder coatings naturally also arise when other functional components are incorporated, e.g. fluorescent electrically conductive and / or magnetically shielding pigments, metal powder, scratch-resistant pigments, organic dyes, organic and inorganic, transparent or opaque fillers and / or nanoparticles and / or auxiliaries and / or additives such as UV absorbers, light stabilizers, radical scavengers, deaerators, slip additives , Adhesion promoter, flow control agent,
  • thermoplastic powder coatings which differ in their composition and their application-related property profile, in particular with regard to the color tones and / or the optical effects, from the specified specifications, cannot provide coatings that meet the specification.
  • processes for the production of pigment preparations in granular form which contain a pigment and at least one thermoplastic polymer. They are obtainable by dispersing the pigment in a solution of the polymer in an organic solvent in the presence or absence of a dispersing agent and subsequent granulation with removal of the solvent.
  • the granulation can take place, for example, by applying the dispersion of the pigment in the solution of the polymer in a fluidized bed dryer to powder from the thermoplastic polymer and evaporating the solvent. This results in granules of predominantly spherical shape with particle sizes up to 200 ⁇ m.
  • the pigment preparations are used to color plastic molding compounds and composite layer films. Their use as thermoplastic powder coatings is not described in the two patents.
  • the object of the present invention is to find new thermoplastic powder coatings, in particular coloring and / or effect-giving thermoplastic powder coatings, which no longer have the disadvantages of the prior art, but rather their composition and technical property profile, in particular what the colors and / or concerns the optical effects, correspond to the given specifications.
  • the potential of the functional constituents, in particular the coloring and / or effect-giving potential of the pigments is to be fully utilized in the coatings produced from the new thermoplastic powder coatings.
  • the new thermoplastic powder coatings should be easy to produce.
  • the present invention was based on the object of finding a new process for the production of thermoplastic powder coatings which no longer has the disadvantages of the prior art, but which allows thermoplastic powder coatings without complex cleaning of the systems used in the production of powder coatings different material
  • the aim of the new process is to ensure that the powder coatings produced with it always fully meet the specified specifications with regard to the composition and the technical property profile, in particular with regard to the color tones and / or the optical effects.
  • the new method should make it possible to subsequently adjust thermoplastic powder coatings which have already been produced and which deviate from the specified specifications, so that little or no defective batches occur.
  • thermoplastic powder coatings which not only the production of thermoplastic powder coatings, but also the subsequent adjustment of their material composition and their application properties profile, in particular what their colors and / or their optical effects and the recyclability, in particular that of thermoplastic powder coatings with effect pigments, allowed.
  • the new thermoplastic powder coating was found which has an average particle size of 200 to 500 ⁇ m, with a maximum of 20% of the particles having particle sizes> 500 ⁇ m and which can be produced by at least one dispersion (I) and / or at least one solution ( II) containing (A) at least one functional component of a thermoplastic powder coating,
  • thermoplastic particles (II) dimensionally stable thermoplastic particles
  • the new powder coating is referred to below as "powder coating according to the invention”.
  • thermoplastic powder coatings for the production of thermoplastic powder coatings and / or for the subsequent adjustment of the material composition and / or the application properties profile of thermoplastic powder coatings was found, comprising
  • thermoplastic powder coating At least one functional component of a thermoplastic powder coating
  • thermoplastic powder coatings at least one solid module, comprising dimensionally stable thermoplastic particles.
  • mixing system for the production of thermoplastic powder coatings and / or for the subsequent adjustment of the material composition and / or the application-related property profile of thermoplastic powder coatings is referred to as "mixing system according to the invention”.
  • thermoplastic powder coatings and / or for the subsequent adjustment of the material composition and / or the application properties profile of thermoplastic powder coatings by mixing at least one thermoplastic polymer with at least one functional component was found in which
  • thermoplastic powder coatings and / or for subsequent adjustment the material composition and / or the application-related property profile of thermoplastic powder coatings by mixing at least one thermoplastic polymer with at least one functional component is referred to as the “process according to the invention”.
  • thermoplastic powder coatings which comprise the pigments, in particular the effect pigments and / or the fluorescent, electrically conductive and / or magnetic shielding pigments, and optionally auxiliaries and / or additives completely dispersed.
  • the pigment content of the powder coating materials according to the invention can be significantly reduced compared to that of conventional thermoplastic powder coating materials, without the opacity being reduced in the process.
  • recyclable powder coatings according to the invention can be produced without great effort.
  • the powder coatings according to the invention provide coatings of particularly high quality.
  • the starting product essential for the production of the powder coating according to the invention and for carrying out the method according to the invention and the component of the mixing system according to the invention which is essential according to the invention is at least one dispersion (I) and / or at least one solution (I) which comprises at least one functional component of a powder coating ( A) and at least one Contains solvent (B).
  • the dipsersion or solution (I) can contain at least one thermoplastic polymer (C).
  • the functional component (A) can be easily soluble in the solvent (B), so that a molecularly disperse solution is present.
  • the functional component (A) can be comparatively sparingly soluble, so that, depending on its concentration, it is partly dissolved and partly dispersed.
  • the functional component (A) can also be very sparingly soluble or completely insoluble, so that essentially a dispersion is present. Mixtures of soluble and insoluble functional constituents (A) can also be used.
  • Functional components (A) are all components typical of powder coating, with the exception of the substances mentioned under (C).
  • suitable constituents typical of powder coating (A) are color and / or effect, fluorescent, electrically conductive and / or magnetically shielding pigments, metal powder, soluble organic dyes, organic and inorganic, transparent or opaque fillers and / or nanoparticles.
  • the components (A) can be used individually or as mixtures.
  • actinic radiation is understood to mean electromagnetic radiation such as near infrared, visible light, UV radiation or X-rays, in particular UV radiation, or corpuscular radiation such as electron beams.
  • suitable effect pigments are metal plate pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE 36 36 183 A1, and commercially available stainless steel bronzes and non-metallic effect pigments, such as pearlescent or Interference pigments, platelet-shaped effect pigments based on iron oxide, which have a color from pink to brown-red, or liquid-crystalline effect pigments.
  • metal plate pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE 36 36 183 A1
  • non-metallic effect pigments such as pearlescent or Interference pigments, platelet-shaped effect pigments based on iron oxide, which have a color from pink to brown-red, or liquid-crystalline effect pigments.
  • Suitable inorganic color pigments are white pigments such as titanium dioxide, zinc white, zinc sulfide or lithopone; Black pigments such as carbon black, iron-manganese black or spinel black; Colored pigments such as chromium oxide, chromium oxide hydrate green, cobalt green or ultramarine green, cobalt blue, ultramarine blue or manganese blue, ultramarine violet or cobalt and manganese violet, iron oxide red, cadmium sulfoselenide, molybdenum red or ultramarine red; Iron oxide brown, mixed brown, spinel and corundum phases or chrome orange; or iron oxide yellow, nickel titanium yellow, chrome titanium yellow, cadmium sulfide, cadmium zinc sulfide, chrome yellow or bismuth vanadate.
  • white pigments such as titanium dioxide, zinc white, zinc sulfide or lithopone
  • Black pigments such as carbon black, iron-manganese black or spinel black
  • organic coloring pigments examples include monoazo pigments, bisazo pigments, anthraquinone pigments, benzimidazole pigments, quinacridone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, indanthrone pigments, azomethane pigment, iso-pigment pigments
  • Thioindigo pigments metal complex pigments, perinone pigments, and
  • fluorescent pigments are bis (azomethine) pigments.
  • Suitable electrically conductive pigments are titanium dioxide / tin oxide pigments.
  • magnétiqueally shielding pigments examples include pigments based on iron oxides or chromium dioxide.
  • suitable metal powders are powders made from metals and metal alloys aluminum, zinc, copper, bronze or brass.
  • Suitable soluble organic dyes are lightfast organic dyes with little or no tendency to migrate from the powder coating according to the invention and the coatings produced therefrom.
  • the person skilled in the art can estimate the tendency to migrate on the basis of his general specialist knowledge and / or determine it with the aid of simple preliminary tests, for example in the context of sound tests.
  • organic and inorganic fillers are chalk, calcium sulfates, barium sulfate, silicates such as talc, mica or Kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as plastic powder, in particular made of polylamide or polyacrylonitrile.
  • silicas oxides such as aluminum hydroxide or magnesium hydroxide
  • organic fillers such as plastic powder, in particular made of polylamide or polyacrylonitrile.
  • Mica and talc are preferably used if the scratch resistance of the coatings produced from the powder coatings according to the invention is to be improved. ⁇ o.
  • platelet-shaped inorganic fillers such as talc or mica
  • non-platelet-shaped inorganic fillers such as chalk, dolomite, calcium sulfate, or barium sulfate
  • suitable transparent fillers are those based on silicon dioxide, aluminum oxide or zirconium oxide, but in particular nanoparticles based on this. 0
  • Auxiliaries and / or additives such as UV absorbers, light stabilizers, radical scavengers, deaerating agents, slip additives, adhesion promoters, film-forming aids, flame retardants, corrosion inhibitors, pouring aids, waxes and / or matting agents, 5 which are used individually or as mixtures, are also used as constituents (A) can be considered.
  • antioxidants examples include hydrazines and phosphorus compounds.
  • suitable light stabilizers are HALS compounds, benzotriazoles or oxalanilides.
  • suitable radical scavengers are organic phosphites or 2,6 di-tert-butylphenol derivatives.
  • Suitable deaerating agents are diazadicycloundecane or benzoin;
  • Coloring and / or effect pigments are preferably used.
  • solvents (B) are suitable as solvents (B).
  • Solvents are preferably used in which the constituents (C) described below are soluble and / or dispersible.
  • suitable inorganic solvents are water, supercritical carbon dioxide or liquid nitrogen.
  • Suitable organic solvents (B) are aliphatic and alicyclic ketones, ethers, alcohols, aliphatic carboxylic acid esters, lactones and aromatic hydrocarbons and their halogenated derivatives such as acetone, hexafluoroacetone, isobutanol, hexafluoro-2-propanol, ethyl acetate, N-methylpyrrolidyl or toluene , Of these solvents (B), the low-boiling, preferably those boiling below 100 ° C., are advantageous and are therefore used with preference in accordance with the invention. Acetone is particularly advantageous.
  • the solution or dispersion (I) may additionally contain at least one thermoplastic polymer (C).
  • thermoplastic polymer (C) is preferably compatible with the thermoplastic polymer or the thermoplastic polymers of the dimensionally stable thermoplastic particles (II) described below.
  • the polymer (C) is preferably identical to the polymer of the dimensionally stable thermoplastic particles (II).
  • thermoplastic polymer envelops the functional components, especially the pigment particles (A) and prevents agglomeration of even the finest pigment particles. It "passivates" finely divided metal pigments, such as aluminum flakes, and thus makes them accessible for coloring plastics, which up to now was not possible due to their dust explosion hazard or fire hazard due to their content of flammable organic solvents. Finally, it also protects the mechanically non-stressable pigments.
  • a dispersant (D) is present in the preparation of the solutions or dispersions (I). This is the case, for example, when pigments such as carbon black are particularly difficult to disperse.
  • a further, unexpected, advantageous effect is that the viscosity of the solutions or dispersions (I) is significantly reduced in the presence of a dispersant (D) and thus the dispersing work is also reduced.
  • Particularly suitable dispersants (D) are polymeric compounds which, by reacting (co) polymers of CrC 25 alkyl esters, ⁇ -unsaturated carboxylic acids which have a terminal hydroxyl group, with polyvalent isocyanates and further reacting the products obtained with ammonia or polyfunctional amines are available.
  • the (co) polymers are preferably polyalkyl (meth) acrylates, poly-C 8 -C 8 -alkyl (meth) acrylates being particularly preferred and polymethyl methacrylate and polybutyl methacrylate, especially copolymers of methyl and butyl methacrylate, being very particularly preferred ,
  • the molecular weight of these (co) polymers is generally 200 to 50,000, preferably 1000 to 10,000 g / mol.
  • the (co) polymers can be initiated with initiators which give a hydroxyl radical upon decomposition, e.g. Hydroperoxides such as tetrahydrofuran hydroperoxide or regulators containing a hydroxyl function, e.g. Thio alcohols such as 2-hydroxyethanethiol, are implemented.
  • initiators which give a hydroxyl radical upon decomposition
  • Hydroperoxides such as tetrahydrofuran hydroperoxide or regulators containing a hydroxyl function, e.g. Thio alcohols such as 2-hydroxyethanethiol
  • Mixtures of aliphatic polyisocyanates with an average functionality of 3 to 6, preferably 3.5 to 5, isocyanate groups per mol are preferably used as polyvalent isocyanates.
  • the amount of isocyanate is preferably chosen so that 1, 2 to 3, in particular 1, 5 to 2.5, isocyanate groups per hydroxyl group of the (co) polymer react, the remaining isocyanate groups are converted into urea groups by reaction with amines.
  • isocyanate mixtures are mixtures of 0.1 to 10% by weight, especially 0.3 to 8% by weight of a diisocyanate (for example hexamethylene diisocyanate), 30 to 80% by weight, especially 42 to 79 %
  • a triisocyanate e.g. trifunctional biuret of hexamethylene diisocyanate
  • 20 to 60% by weight, especially 22 to 50% by weight of an isocyanate with a functionality of 4 to 10 (e.g. a corresponding higher functional biuret of hexamethylene diisocyanate ) called.
  • Suitable polyfunctional amines are, for example, polyvalent alkyl and alkylene amines such as propylamine, butylamine, ethylene diamine, diethylene triamine, triethylene tetramine and higher polyethylene amines and polyethylene imines, and preferably also N, N ' - bis (aminopropyl) ethylene diamine.
  • Polyurethane urea (meth) acrylates usually have an average molecular weight M w of 1000 to 15000 g / mol, preferably 8000 to 14000 g / mol.
  • the weight ratios of the components (A), (B) and optionally (C) and optionally (D) on a dispersion or a solution (I) can vary very widely and depends on the requirements of the individual case and in particular on parameters such as Solubility of components (A) and (C) in (B) or the viscosity of (C).
  • the solution or the dispersion (I) preferably consists, in each case based on the total amount of the solution or the dispersion (I),
  • the preparation of the dispersions or solutions (I) has no special features, but is carried out in a customary and known manner by mixing the above-described components (A) and (B) and, if appropriate, (C) in suitable mixing units such as stirred kettles, dissolvers, agitator mills or extruder.
  • the solutions and / or dispersions (I) described above are applied to the surface of dimensionally stable particles (II) in the procedure according to the invention with complete or essentially complete evaporation of the solvent or solvents (B).
  • the solvents (B) are used at temperatures below the glass transition temperature Tg or the minimum film-forming temperature of the thermoplastic polymers (C) (cf.Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 391 , "Minimum film forming temperature (MFT)" of the dimensionally stable particles (II) evaporates.
  • Tg glass transition temperature
  • MFT Minimum film forming temperature
  • the average particle size and the particle size distribution of the dimensionally stable thermoplastic particles (II) do not change or only change slightly by the application of the solutions and / or dispersions (I), unless such a change is intended. This can be the case, for example, if one starts from dimensionally stable thermoplastic particles (II) of a comparatively small average particle size and wants to build up a powder coating of the invention having a larger average particle size. This also results in new possibilities for controlling and optimizing the production and the composition of the powder coatings according to the invention.
  • thermoplastic particles (II) agglomerate only slightly, if at all, and / or disintegrate into smaller particles under the customary and known conditions of storage and use of powder coatings, but also under the influence essentially retain their original shape from shear forces.
  • the grain size distribution of the dimensionally stable thermoplastic particles (II) can vary comparatively broadly and depends on the particular intended use of the powder coating materials of the invention.
  • the average particle size of the dimensionally stable particles (II) is preferably 200 to 500, preferably 200 to 350 and in particular 200 to 300 ⁇ m. It is advantageous if only a maximum of 20% of the particles (II) have a particle size> 500 ⁇ m. The maximum particle size should preferably not exceed 1000 ⁇ m.
  • the mean particle size is understood to mean the 50% median value determined by the laser diffraction method, ie 50% of the particles have a particle diameter ⁇ the median value and 50% of the particles have a particle diameter> the median value.
  • the powder coating materials of the invention are largely free of organic solvents, so that they can be poured and applied. They preferably have a residual volatile solvent content of ⁇ 15% by weight, preferably ⁇ 10% by weight and particularly preferably ⁇ 5% by weight.
  • the powder coatings have an average particle size of 200 to 500, preferably 200 to 350 and in particular 200 to 300 ⁇ m. A maximum of 20% of the particles have particle sizes> 500 ⁇ m. The particle size preferably does not exceed 1000 ⁇ m.
  • the composition of the dimensionally stable thermoplastic particles (II) can vary widely. They preferably contain at least one thermoplastic polymer selected from the group consisting of (meth) acrylate (co) polymers, styrene (co) polymers, polyethylene, polypropylene, polycarbonates, polyamides, polyesters, thermoplastic polyurethanes, polyether sulfones, polysulfones and vinyl (co ) polymers. Of these, the (meth) acrylate polymers, the styrene (co) polymers and the thermoplastic polyurethanes are used with particular preference.
  • Suitable (meth) acrylate (co) polymers are the polyalkyl and / or aryl esters of (meth) acrylic acid, poly (meth) acrylamides and poly (meth) acrylonitrile.
  • Preferred acrylic resins are polyalkyl methacrylates, also in impact-modified form, polymethyl methacrylate (PMMA) and impact-modified polymethyl methacrylate (HI (high impact) -PMMA) being particularly preferred.
  • the PMMA preferably contains a proportion of generally not more than 20% by weight of (meth) acrylate comonomers such as n-butyl (meth) acrylate or methyl acrylate.
  • HI-PMMA is impact-resistant with suitable additives.
  • Impact modifiers include, for example, EPDM rubbers, polybutyl acrylates, polybutadiene, polysiloxanes or methacrylate / butadiene / styrene (MBS) - and
  • Methacrylate / acrylonitrile / butadiene / styrene copolymers in question are described, for example, by M. Stickler, T. Rhein in Ulimann 's Encyclopedia of Industrial Chemistry Vol. A21, pages 473-486, VCH Publishers Weinheim, 1992, and H.Domininghaus, Die Kunststoffe and their properties, VDI -Verlag, Düsseldorf, 1992.
  • Suitable polymethyl methacrylates are otherwise known to the person skilled in the art and are available, for example, under the trademarks Guest-l R (BASF AG) and Plexiglas R (Röhm GmbH).
  • Stryrene (co) polymers are all (co) polymers which are composed entirely or in part of vinyl aromatic compounds. Suitable vinyl aromatic compounds are, for example, styrene and styrene derivatives such as mono- or polysubstituted alkyl and / or halogen-substituted styrene and corresponding naphthyl compounds. Styrene copolymers are preferably used.
  • graft copolymers of acrylonitrile and styrene on butadiene rubbers also known as ABS polymers (for example the commercial product Terluran R from BASF AG), graft copolymers of styrene and acrylonitrile on polyalkylacrylate rubbers, also as ASA polymers known (for example, the commercial product Luran R S from BASF AG), or styrene-acrylonitrile copolymers, also called SAN copolymers (for example, the commercial product Luran R from BASF AG).
  • ABS polymers for example the commercial product Terluran R from BASF AG
  • ASA polymers for example, the commercial product Luran R S from BASF AG
  • SAN copolymers for example, the commercial product Luran R from BASF AG.
  • ASA polymers are particularly preferred styrene polymers.
  • Suitable polycarbonates are known per se. Polycarbonates also include copolycarbonates.
  • the (co) polycarbonates preferably have a molecular weight (weight average M w determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standard) in the range from 10,000 to 200,000 g / mol. M w is preferably in the range from 15,000 to 100,000 g / mol. This corresponds to relative solution viscosities in the range from 1.1 to 1.5, measured in 0.5% by weight solution in dichloromethane at 25 ° C., preferably from 1.15 to
  • Polycarbonates are e.g. obtainable in accordance with the processes of DE 300 266 C1 by interfacial polycondensation or in accordance with the process of DE 14 95 730 A1 by reacting diphenyl carbonate with bisphenols.
  • Preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, commonly referred to as bisphenol A.
  • bisphenol A may also be other aromatic dihydroxy compounds are used, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, 4,4 '-Dihydroxydiphenylether, 4,4'-
  • Dihydroxydiphenylcycloalkanes preferably dihydroxydiphenylcyclohexanes or dihydroxycyclopentanes, in particular 1, 1-bis (4-hydroxyphenyl) -3,3,5- trimethylcyclohexane, as well as mixtures of the aforementioned dihydroxy compounds.
  • Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 80 mol% of the aromatic dihydroxy compounds mentioned above.
  • Copolycarbonates according to US Pat. No. 3,737,409 A can also be used.
  • copolycarbonates based on bisphenol A and bis (3,5-dimethyl-4-hydroxyphenyl) sulfone and / or 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane which are characterized by high heat resistance.
  • the polycarbonates Makrolon R (Bayer) and Lexan R (GE Plastics) are commercially available, for example.
  • Suitable polyamides can be polycondensation products of diamines and dicarboxylic acids, for example adipic acid and hexamethylenediamine, or of amino acids, for example aminoundecanoic acid, or can be prepared by ring-opening polymerization of lactams, for example caprolactam or laurolactam.
  • Examples include Ultramid R (BASF AG), Zytel R and Minlon R (Du Pont), Sniamid R , Technyl R and Amodel R (Nyltech), Durethan R (Bayer), Akulon R and Stanyl R (DSM), Grilon R , Grilamid R and Grivory R (EMS), Orgamid R and Rilsan R (Atochem) and Nivionplast R (Enichem).
  • polyesters The higher to high molecular esterification products of dihydric acids, in particular terephthalic acid, with dihydric alcohols, especially ethylene glycol, are suitable as polyesters.
  • dihydric acids in particular terephthalic acid
  • dihydric alcohols especially ethylene glycol
  • PET polyethylene terephthalate
  • Arnite R Arnite R
  • Grilpet R EMS-Chemie
  • Valox R GEP
  • TPU thermoplastic polyurethanes
  • TPU thermoplastic polyurethanes
  • polyurethane foams Compared to polyisocyanates (containing at least three isocyanate groups) and polyhydric alcohols (containing at least three hydroxyl groups), especially polyether and polyester polyols, polyurethane foams have no or only slight crosslinking and accordingly have a linear structure.
  • Thermoplastic polyurethanes are well known to the person skilled in the art and can be found, for example, in the plastics handbook, volume 7, polyurethanes, ed. G. Oertel, 2nd edition, Carl Hanser Verlag, Kunststoff, 1983, in particular on pages 428-473. Elastolan R (Elastogran) may be mentioned here as a commercially available product.
  • polyethersulfones and polysulfones are commercially available to the company and are known under the trade names Ultrason R E and Ultrason R S
  • polyvinyl chloride may be mentioned as a suitable vinyl polymer.
  • thermoplastic particles (II) has no special features in terms of method, but instead takes place with the aid of the methods and devices for producing powder coatings from the components (C) and, if appropriate, (A) described in the prior art mentioned at the beginning.
  • the particles (II) can be the preliminary stage of a powder coating which is to be completed with at least one functional component (A).
  • a powder coating which is to be completed with at least one functional component (A).
  • the clear, transparent precursor of a coloring and / or thermoplastic effect powder coating can be used a dispersion (I) can be coated, which contains at least one coloring and / or effect pigment as a functional component (A).
  • thermoplastic powder coating which is finished per se and whose material composition and / or its application properties have to be adjusted subsequently. Subsequent adjustment may be necessary, for example, if the finished powder coating is an incorrect batch. However, it can also be used to adapt finished powder coatings, which correspond to older specifications, to new specifications without the need for a new production.
  • the production of the powder coating materials according to the invention or the method according to the invention can be used to color or pigment powder coatings and / or to tone them, for example if the pigmentation or coloring in the first step did not meet specifications.
  • the application of the solutions and dispersions described above on the dimensionally stable particles or the coating of their surface with the functional constituents (A) and the constituents (C) can be carried out with the aid of customary and known methods and devices which serve to coat solid particles ,
  • the dispersions and / or solutions are preferably sprayed into a fluidized bed containing the dimensionally stable particles.
  • Fluidized bed dryers are preferably used.
  • the dimensionally stable thermoplastic particles are fed continuously or discontinuously to the fluidized bed, in which they are coated with at least one dispersion and / or at least one solution. If different dispersions and / or solutions are used, they are preferably sprayed in at different points. If only one solution or dispersion is used, it can also be sprayed on at various points in order to optimize its distribution in the fluidized bed.
  • coated dimensionally stable thermoplastic particles (II) or the powder coating materials of the invention are discharged.
  • the coated dimensionally stable thermoplastic particles (II) or the powder coating materials of the invention are discharged.
  • the coated dimensionally stable thermoplastic particles (II) or the powder coating materials of the invention are discharged.
  • Particles (II) can be returned to the fluidized bed (Circular mode), in which they are coated with the same or different dispersions and / or solutions. For this purpose, they can also be fed to at least one further fluidized bed dryer.
  • the powder coating materials of the invention can be ground and / or classified in order to set the desired particle size distribution.
  • the process according to the invention can be controlled so that thermally sensitive, catalytically active and / or highly reactive functional constituents (A) can be incorporated into the powder coatings according to the invention, in which there is a risk under the conditions of the customary and known processes for producing powder coatings that they decompose.
  • the essential advantage of the powder coatings according to the invention described above and the method according to the invention is that they allow the mixing system according to the invention to be provided.
  • the mixing system according to the invention is used to produce thermoplastic powder coatings and / or to subsequently adjust the material composition and / or the application properties profile of thermoplastic powder coatings.
  • it serves for the subsequent adjustment of the color tone and / or the optical effect of coloring and / or effect-giving thermoplastic Powder coatings of different colors and / or intensity of the optical effects.
  • the mixing system according to the invention comprises at least two setting modules (I) and at least one solid module (II).
  • module denotes a standardized, ready-to-use commercial product whose application-related property profile is precisely adapted to the property profiles and supplements these so that the modules as a whole can be combined to form a mixing system.
  • a setting module (I) each comprises a dispersion or solution containing the components (A) and (B) described above and, if appropriate, (C) and / or (D).
  • the functional constituents (A) can be at least one of the additives described above for typical powder coatings, with the aid of which a wide variety of technical properties, such as, for example, the corrosion protection effect, weather resistance or color, can be adjusted.
  • the functional component (A) of an adjustment module (I) is at least one coloring and / or effect pigment.
  • the setting modules (I) can contain different coloring and / or effect pigments, so that a series of basic color modules (I) results, from which a color mixing system can be built, with the help of a few basic colors a practically unlimited number of different colors and / or optical effects for the coatings produced from the powder coatings according to the invention can be realized.
  • the material compositions of the color and / or effect powder coatings according to the invention of different chromaticity and / or intensity of the optical effects are preferably determined with the aid of a color mixing formula system based on the basic color modules (I).
  • the mixing system according to the invention further comprises at least one solid module (II) which contains at least one type, in particular one type, of the dimensionally stable thermoplastic particles (II) described above. Which type of particles (II) is selected depends on the intended use of the powder coatings and coatings according to the invention produced therefrom.
  • the mixing system comprises at least one mixing unit for mixing the contents of at least one setting module (I) and the contents of at least one solid module (II) under defined proportions and temperatures.
  • the mixing unit is preferably a fluidized bed dryer.
  • the mixing system according to the invention offers the essential advantage for the manufacturer and for the user of powder coatings that they no longer have to produce or buy a finished powder coating in large quantities for special purposes, but that they, according to the needs of the user, have a small amount of one Powder coating, which is precisely adapted to the respective intended use, can be produced or adjusted in a targeted manner. This eliminates the expensive disposal of excess powder coating. All this makes the production of small amounts of powder coating with the aid of the mixing system according to the invention also economically attractive.
  • the powder coatings according to the invention are outstandingly suitable as whirl sinter powders, which can be applied to a wide variety of substrates or workpieces using the whirl sintering process (cf.
  • Stone chip protection primers the painting of buildings indoors and outdoors, the painting of doors, windows and furniture, the industrial painting, including coil coating, container coating, the coating of pipes (pipelines) and the impregnation and / or coating of electrical components Paint of white goods, including household appliances, boilers and radiators, as well as painting of flanges, fittings, wall wardrobes, bed frames, insulation boxes, fence posts, garden furniture, guardrails, street signs, shopping baskets, inserts for dishwashers, brake cylinders, laboratory equipment and chemical plants.
  • industrial painting including coil coating, container coating, the coating of pipes (pipelines) and the impregnation and / or coating of electrical components Paint of white goods, including household appliances, boilers and radiators, as well as painting of flanges, fittings, wall wardrobes, bed frames, insulation boxes, fence posts, garden furniture, guardrails, street signs, shopping baskets, inserts for dishwashers, brake cylinders, laboratory equipment and chemical plants.
  • the pigment dispersion obtained was then in a fluidized bed dryer (diameter of the fluidized bed 150 mm, cylindrical height 500 mm) to 1.6 kg of the PMMA powder used to prepare the dispersion, which was fluidized at 70 m 3 / h at 60 ° C. heated air , sprayed on in 2 h (0.7 kg / h).
  • Example 2 The procedure was analogous to Example 1, but 100 g of a copper-colored, platelet-shaped ⁇ -iron (III) oxide pigment doped with aluminum and manganese (average particle size 18 ⁇ m; Paliocrom copper L3000, BASF) were used.
  • Example 3 The procedure was analogous to Example 1, but 100 g of an Fe 2 O 3 -coated aluminum pigment (average particle size 10 to 12 ⁇ m; Paliocrom Orange L 2800, BASF) were used.
  • Example 2 The procedure was analogous to Example 1, but 100 g of aluminum flakes (average particle size 10 to 12 ⁇ m, stacked
  • the total pigment dispersion obtained was then in a
  • Fluid bed dryer (diameter of the fluidized bed 800 mm, cylindrical height 2000 mm) to 80 kg of the for the preparation of the dispersion PMMA powder used, which was fluidized with 2700 m 3 / h of air heated to 60 ° C, sprayed in 3 h (25 kg / h).
  • the pigment dispersion obtained as a whole was then diluted by stirring into a solution of 180 g of the same PMMA powder in 0.6 l of acetone and then sprayed analogously to Example 1 to 1.6 g of the PMMA powder used to prepare the dispersion ,

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  • Life Sciences & Earth Sciences (AREA)
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  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

L'invention concerne une peinture pulvérulente thermoplastique de dimension particulaire moyenne de l'ordre de 200 à 500 mu m, 20 % au plus des particules présentant une dimension particulaire > 500 mu m. Cette peinture s'obtient par application sur la surface des particules thermoplastiques stables en dimensions, au moins une dispersion et/ou au moins une solution contenant (A) au moins un constituant fonctionnel d'une peinture pulvérulente thermoplastique ; (B) au moins un solvant et (C) éventuellement au moins un constituant oligomère et/ou polymère, par évaporation complète ou sensiblement complète du solvant ou des solvants (B). L'invention concerne un nouveau système de mélange et un nouveau procédé de production et/ou d'adaptation subséquente de la composition des substances et/ou du profil de caractéristiques technologiques des peintures pulvérulentes, selon lequel au moins une dispersion et/ou au moins une solution (A/B) ou (A/B/C) est/sont utilisée(s).
EP02735291A 2001-04-27 2002-04-24 Peinture pulverulente thermoplastique, procede permettant de la produire et systeme de melange pour peintures pulverulentes Withdrawn EP1419204A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10120770 2001-04-27
DE2001120770 DE10120770A1 (de) 2001-04-27 2001-04-27 Thermoplastische Pulverlacke, Verfahren zu ihrer Herstellung und Mischsystem für Pulverlacke
PCT/EP2002/004476 WO2002088261A1 (fr) 2001-04-27 2002-04-24 Peinture pulverulente thermoplastique, procede permettant de la produire et systeme de melange pour peintures pulverulentes

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EP1419204A1 true EP1419204A1 (fr) 2004-05-19

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DE10334308A1 (de) * 2003-07-28 2005-02-24 Basf Coatings Ag Feste Pigmentpräparationen und ihre Dispersionen in organischen Lösemitteln, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10343393A1 (de) * 2003-09-19 2005-04-14 Basf Coatings Ag Mit Effektpigmenten pigmentierte, pulverförmige Beschichtungsstoffe, Verfahren zu ihrer Herstellung und ihre Verwendung
CN106366805A (zh) * 2016-08-29 2017-02-01 芜湖众力部件有限公司 一种导电性聚甲基丙烯酸甲酯改性涂料及其制备方法

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WO2002042384A1 (fr) * 2000-11-27 2002-05-30 Basf Coatings Ag Peintures pulverulentes durcissables, procede permettant de les produire et systeme melangeur pour peintures pulverulentes

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GB1458188A (en) * 1972-11-29 1976-12-08 Kodak Ltd Method of powder coating
JPS52128927A (en) * 1976-04-22 1977-10-28 Kansai Paint Co Ltd Method of manufacturing powder paint for metallic finish
US5856378A (en) * 1988-12-02 1999-01-05 Courtaulds Coatings (Holdings) Limited Powder coating compositions
DE10057164A1 (de) * 2000-11-16 2002-05-23 Basf Ag Pigmentzubereitungen

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
WO2002042384A1 (fr) * 2000-11-27 2002-05-30 Basf Coatings Ag Peintures pulverulentes durcissables, procede permettant de les produire et systeme melangeur pour peintures pulverulentes

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Title
See also references of WO02088261A1 *

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DE10120770A1 (de) 2002-11-07

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