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
  • C09D5/032—Powdery paints characterised by a special effect of the produced film, e.g. wrinkle, pearlescence, matt finish
• • 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
  • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
  • C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/03—Powdery paints
  • C09D5/031—Powdery paints characterised by particle size or shape

Definitions

• the present invention relates to new powdered coating materials pigmented with effect pigments.
• the present invention relates to a new process for the production of powdered coating materials pigmented with effect pigments.
• the present invention relates to the use of the new, powdery coating materials pigmented with effect pigments for the production of coloring and / or effect coatings.
• optical properties such as brilliance, brightness and color flop
• optical properties depend on the degree of parallel alignment of the flake-like effect pigments in the hardened coating to their surface.
• Liquid coating materials are formulated in such a way that the leaf-like effect pigments can align themselves parallel to the surface of the resulting coating during drying and curing.
• powdery coating materials do not pass through a stage which is as low in viscosity as the liquid coating materials during curing, in particular thermal curing.
• coating materials or powder coatings consist of approximately spherical, dimensionally stable particles or resin particles which melt together during curing, in particular during thermal curing, but do not flow completely into one another.
• effect-imparting powder coatings in particular metallic effect-imparting
• the flake-form effect pigments are applied to the surface of the dimensionally stable particles or Resin particles fixed evenly. Therefore, the flake-like effect pigments are statistically aligned in all directions after the application of the powder coatings. This statistical directional distribution is then also present in the coating produced from this. Therefore, if at all, there is only a very small degree of alignment of the flake-like effect pigments parallel to the surface of the coating. For this reason, the coatings which have been produced from powder coatings pigmented with effect pigments do not have the brilliance, the brightness and the color flop as the coatings which have been produced from liquid coating materials pigmented with the corresponding effect pigments.
• Powdery coating materials or powder coatings have the decisive advantage over liquid coating materials, in particular those containing organic solvents, that they do not release any volatile organic compounds or only very small amounts thereof during application and curing.
• the powdery overspray that arises during powder painting can be easily collected and reused.
• German patent application DE 100 27 294 A 1 suggests incorporation and alignment through the use of To improve lamellar aluminum effect pigments with a particularly wide particle size distribution.
• German patent application DE 100 27 270 A 1 the alignment parallel to the surface can be improved by using leafing aluminum effect pigments, which are known to float in low-viscosity, liquid layers of coating materials.
• German patent application DE 100 27 267 A1 proposes incorporating and aligning sheet-like effect pigments by embedding them in oligomers or polymers which have a melting point or melting range of at least 10 ° C. below the melting point or melting range of the binders of the powder coatings , to improve. It is not clear from DE 100 27267 A1 whether the particles resulting from the embedding are platelet-shaped and whether they contain the platelet-shaped effect pigments in a completely or almost completely parallel orientation to their surface.
• Coating materials or powder coatings need to be improved further.
• the object of the present invention is to find new, pigmented, powdery coating materials, in particular powder coatings, with effect pigments, in particular flake-form effect pigments, which no longer have the disadvantages of the prior art, but can be produced easily and very reproducibly and coatings with excellent optical properties, in particular with high brilliance, high brightness and particularly strong color flop, in which the effect pigments, in particular the flake-form effect pigments, have a particularly high degree of alignment parallel to the surface of the coatings. Accordingly, the new powder coating materials consisting of
• (A) lamellar particles with a ratio of laminar diameter D to the layer thickness d of D: d 100: 1 to 10: 1, containing at least one lamellar effect pigment in completely or almost completely parallel alignment to the surface of the lamellar particles, and
• coating materials according to the invention.
• the object on which the present invention was based could be achieved with the aid of the coating materials according to the invention and the method according to the invention.
• the coating materials according to the invention can be produced particularly easily and very reproducibly, and coatings according to the invention with excellent optical properties, in particular with high brilliance, high brightness and particularly strong color flop, in which the effect pigments, in particular the flake-form effect pigments, had a particularly high degree of alignment parallel to the surface of the coatings according to the invention.
• the coatings according to the invention were of automotive quality and were therefore suitable for painting automobiles, in particular luxury automobiles.
• the coating materials of the invention consist of the two components (A) and (B).
• the number and type of effect pigments depend on the optical effect that is to be set. This can be a metallic effect, a pearlescent effect or a very strong color flop, for example from red to blue or from green to gold.
• the optical effects can also be combined.
• the flake-form effect pigments from the group consisting of aluminum pigments, gold bronzes, fire-colored bronzes, iron oxide-aluminum pigments, fish silver, basic lead carbonate, bismuth oxide chloride, metal oxide-mica pigments, interference pigments, which show a strong color flop, are preferred (OVP), micronized titanium dioxide, platelet-shaped graphite, platelet-shaped iron oxide and liquid-crystalline pigments.
• the particle size of the flaky effect pigments can also vary very widely. They preferably contain no or only a very small proportion of fine dust, i. H. Particles with a particle size ⁇ 5 ⁇ m. They preferably contain at most 10% of particles with a particle size> 100 ⁇ m. In particular, their average particle size is 5 to 50 ⁇ m.
• the mean particle size is understood to mean the 50% median determined by the laser diffraction method, i.e. 50% of the particles have a particle diameter ⁇ the median and 50% of the particles have a particle diameter> the median.
• the particle size of the laminar particles (A) is preferably 50 to 300 ⁇ m laminar, preferably 60 to 250 ⁇ m and in particular 80 to 200 ⁇ m.
• the leaf-shaped particles (A) are preferably 1 to 50 ⁇ m, in particular 1 to 20 ⁇ m thick.
• the content of the leaf-like particles (A) in the leaf-like effect pigments can vary very widely and depends in particular on the dispersibility and hiding power of the effect pigments and the intensity of the optical effects which are to be set.
• the content is 0.1 to 60% by weight, preferably 1 to 50% by weight and in particular 1 to 40% by weight, in each case based on (A).
• the leaf-shaped particles (A) contain at least one, in particular one, transparent, in particular clear, oligomeric and / or polymeric binder.
• the binders are preferably selected from the group consisting of physically, thermally, with actinic radiation or thermally and with actinic radiation, thermoplastic, homopolymeric polyaddition resins and polycondensation resins; physically, thermally, with actinic radiation or thermally and with actinic radiation curable, thermoplastic, random, alternating and / or block-like, linear, branched and / or comb-like, copolymeric polyaddition resins and polycondensation resins, physically, thermally, with actinic radiation or thermally and thermoplastic homopolymers of ethylenically unsaturated monomers curable with actinic radiation and physically, thermally, with actinic radiation or thermally and with actinic radiation, random, alternating and / or block-shaped, linear, branched and / or comb-like copolymers of ethylenically unsaturated monomers, selected.
• actinic radiation includes electromagnetic radiation, such as near infrared (NIR), visible light, UV radiation, X-rays or gamma radiation, in particular UV radiation, and corpuscular radiation, such as electron beams, beta radiation, proton radiation, neutron radiation or
• Alpha radiation especially electron radiation, understood.
• Suitable binders which are curable thermally and / or with actinic radiation are customary and known and are described, for example, in German patent application DE 100 27 270 A1, page 5, paragraph [0067], to page 10, paragraph [0100].
• Suitable physically curable binders are also customary and known and are described, for example, in German patent application DE 101 20 770 A1, column 11, paragraph [0082] to column 13, paragraph [0095].
• binders are always selected which do not enter into any undesired interactions, in particular no decomposition reactions, with the sheet-like effect pigments used in each case.
• the binders are compatible with the binders of the particles (B) described below. It is also advantageous if the binders have a refractive index like the binders of the particles (B). Furthermore, it is advantageous if the binders have a melting point or a melting range which is at least 10 ° C. below the melting point or the Melting range of the binder of the particles (B) is (cf. the German patent application DE 100 27 267 A1, page 4, paragraphs [0034] to [0036], [0040] and [0041]).
• the minimum film-forming temperature of the binders is at least 0 ° C., preferably at least 10, particularly preferably at least 15, very particularly preferably at least 20 and in particular at least 25 ° C.
• the minimum film-forming temperature can be determined by drawing an aqueous dispersion of the binder onto a glass plate using a doctor blade or applying a finely divided binder powder to a glass plate and heating it in a gradient oven. The temperature at which the powdery layer films is called the minimum film-forming temperature.
• Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998 “Minimum film forming temperature”, page 391.
• the flaky particles (A) can also contain at least one additive in customary and known amounts.
• the additives are preferably selected from the group consisting of customary and known constituents of powder coatings. Examples of suitable additives of this type are crosslinking agents, additives and coloring pigments, fillers and dyes, as described in German patent application DE 100 27 270 A1, page 4, paragraphs [0046] to [0050], page 5, paragraph [0053] and Page 11, paragraph [0103] to page 12, paragraph [0107].
• the sheet-like particles (A) can also comprise at least one, in particular one, transparent, in particular optically clear layer that can be produced by a directional application process.
• directional application processes are casting, knife coating, rolling or extrusion coating processes.
• the transparent layer is preferably 1 to 30 ⁇ m, in particular 1 to 20 ⁇ m, thick.
• the thickness of the transparent layer and the thickness of the layer of the leaf-like particles (A) containing the leaf-like effect pigments are preferably selected such that a total layer thickness of 50 ⁇ m, in particular 20 ⁇ m, is not exceeded.
• the transparent layer contains or consists of at least one of the above-described oligomeric and / or polymeric binders. It can also contain the additives described above, with the exception of opaque pigments. Seen in itself, it can be hardened physically, thermally, with actinic radiation and thermally and with actinic radiation, in particular physically.
• the flaky particles (A) or the matrices, in which the flaky effect pigments are embedded can be physically, thermally, with actinic radiation or thermally and with actinic radiation. They are preferably physically hardened.
• the coating materials of the invention also consist of component (B).
• Constituent (B) is a transparent, in particular optically clear, dimensionally stable, non-platelet-shaped particle that is free of leaf-like effect pigments, or platelet-shaped particles with a ratio of laminar diameter D to layer thickness d of D: d ⁇ 10: 1, in particular ⁇ 5: 1.
• Dispossionally stable means that the transparent, dimensionally stable particles under the usual and known conditions of storage using powder coating materials, in particular If at all, powder coatings only agglomerate slightly and / or disintegrate into smaller particles and also essentially retain their original shape under the influence of shear forces.
• the transparent, dimensionally stable particles (B) are preferably essentially spherical or spherical.
• Essentially spherical means that the transparent, dimensionally stable particles (B) in question approximately have a more or less regular spherical shape and are, for example, cuboid, egg-shaped or cylindrical. They can have an irregular surface.
• Transparent, dimensionally stable particles (B) of this type arise primarily when comminuting coarse granules in grinding units, as is usually done in the manufacture of powder clearcoats.
• Spherical means that the relevant transparent, dimensionally stable particles (B) have a spherical shape with an essentially smooth surface.
• Transparent, dimensionally stable particles (B) of this type are produced above all during the production of the particles (B) with the aid of dispersion processes (see, for example, the European patent EP 0 960 152 B1).
• the particle size of the dimensionally stable particles (B) can vary very widely and depends in particular on the intended use of the coating materials according to the invention.
• the mean particle size, as defined above, is preferably 20 to 500 ⁇ m, preferably 20 to 250 ⁇ m, and in particular 20 to 100 ⁇ m.
• Narrow particle size distributions are particularly preferably set, as described, for example, in European patents EP 0666 779 B1 or EP 0 960 152 B1.
• the transparent, dimensionally stable particles (B) can be curable physically, thermally, with actinic radiation or thermally and with actinic radiation (see also German patent application DE 100 27 270 A1, page 5, paragraphs [0060] to [0063] ). They are preferably physically or thermally curable.
• the mixing ratio of lamellar particles (A) to transparent, in particular optically clear, dimensionally stable, particles (B) can vary very widely and depends in particular on the content of lamellar effect pigments which the coatings according to the invention produced from the coating materials according to the invention should have.
• the mixing ratio is preferably 1: 1 to 1:10, in particular 1: 1.5 to 1: 5.
• the coating materials of the invention can be produced using a wide variety of processes. They are preferably produced using the method according to the invention.
• At least one of the sheet-like effect pigments described above is dispersed in the aqueous and / or organic solution of at least one of the polymer and / or oligomeric binders described above.
• suitable organic solvents are from D. Stoye and W. Freitag (Editors), "Paints, Coatings and Solvents", Second, Completely Revised Edition, Wiley-VCH, Weinheim, New York, 1998, “14.9. Solvent Groups «, pages 327 to 373.
• Organic solvents are preferably used which do not have any interfering interactions with the constituents of the resulting dispersions (I), in particular do not damage the effect pigments, and have a high solubility for the binders and for any further constituents of the dispersions (I), such as those described above, for example Additives, for example customary and known crosslinking agents for thermally curable binders, have and also evaporate easily under practical drying conditions.
• suitable organic solvents on the basis of their known dissolving power and their reactivity. Examples of particularly suitable organic solvents are described in German patent application DE 100 57 165 A1, page 6, paragraph [0056].
• the solids content of the dispersions (I) can vary very widely and depends primarily on the solubility of the binders in water and / or organic solvents and the dispersibility of the effect pigments used in each case.
• the effect pigment / binder ratio can also vary very widely and depends primarily on the dispersibility of the binders for the effect pigments used in each case.
• the solids content of the dispersions (I) is preferably 10 to 60% by weight, in particular 10 to 40% by weight, in each case based on the dispersion (I).
• the pigment / binder ratio is preferably 1: 100 to 1: 1, in particular 1:50 to 1: 2.
• the content of the dispersions (I) is preferably present Effect pigments at 1 to 30% by weight, in particular 1 to 20% by weight, in each case based on the dispersion (I).
• the dispersion (I) is applied to a temporary carrier in process step (II) in a first alternative (11.1) with the aid of a directional application process by means of which the effect pigments are oriented in a particular preferred direction. Suitable directed application methods are described above.
• the dispersion (I) is applied to a transparent, in particular optically clear, one on the temporary support using an undirected application process, by means of which no orientation of the effect pigments in a particular preferred direction is produced directional application method applied layer applied.
• the temporary supports are preferably constructed from plastic, metal or glass. They preferably have a smooth surface with non-stick properties.
• the transparent layers applied by a directional application process can have a wide variety of material compositions.
• they can consist of the oligomeric and polymeric binders described above.
• they can also have the compositions of powder coatings, as described, for example, in German patent application DE 100 27270 A1, page 5, paragraph [0064], to page 12, Paragraph [0107], only that they do not contain opaque pigments.
• They can be curable physically, thermally, with actinic radiation or thermally and with actinic radiation. They are preferably 1 to 30 ⁇ m thick.
• the layers (11.1) are preferably applied in a wet layer thickness that after drying or drying and hardening, preferably with the aid of the hardening methods described above, in particular by drying and physical hardening Layers (11.1) in process step (III) results in a dry layer thickness of 1 to 50 ⁇ m, in particular 1 to 20 ⁇ m.
• the layers (II.2) are preferably applied in a wet layer thickness that after drying or drying and curing, preferably with the aid of the curing methods described above, in particular by drying and physical hardening, the layers (II.2) in process step (III) result in a dry layer thickness of 1 to 49 ⁇ m, in particular 1 to 20 ⁇ m.
• the dry layer thickness of the layers (II.2) is preferably selected such that, together with the transparent layer, a total layer thickness of 2 to 50 ⁇ m, in particular 2 to 20 ⁇ m, results.
• process step (IV) of the process according to the invention the layers (IM) resulting in process step (III) are isolated on their own [alternative (11.1)] or i. V. m. the transparent, in particular optically clear, coating [alternative (II.2)] is detached from the temporary support. This is preferably done by ultrasound or by mechanical action, in particular by the action of a sharp liquid jet, care being taken that the ones used Liquids do not dissolve the layers (III) again. When the layers (III) are detached from the temporary supports, the sheet-like parts (IV) result.
• the leaf-shaped parts (IV) are crushed and classified according to the particle size.
• the grinding units and classifying devices which are customary and known in the field of powdered coating materials can be used for this purpose.
• the resulting sheet-like particles (A) generally have a particle size which is larger than that of the sheet-like effect pigment contained therein.
• the leaf-like effect pigments contained in the leaf-shaped particles (A) are aligned completely or almost completely parallel to the surface of the particles (A).
• the sheet-like particles (A) are mixed in process step (VI) of the process according to the invention with the transparent, in particular optically clear, dimensionally stable, powdery particles (B) described above.
• the mixing ratios described above are preferably used.
• the mixing of (A) and (B) offers no special features, but rather the usual and known methods and devices for dry mixing of powdery substances are used.
• the process according to the invention provides the coating materials according to the invention in a particularly simple and extremely reproducible manner.
• the coating materials of the invention can be prepared using the customary and known application methods for powder coatings, as described, for example, in the product information from BASF Lacke + Wegner Coating«, 1990, or the company name of BASF Coatings AG, »Powder Coating, Powder Coating for Industrial Applications «, January 2000, is excellent for further processing. After their application, they can be cured in a simple manner physically, thermally, with actinic radiation or thermally and with actinic radiation, in particular physically or thermally, as described, for example, in German patent application DE 100 27 270 A1, page 15, paragraphs [0140 ] to [0148].
• the coating materials according to the invention are outstandingly suitable for the production of color and / or effect coatings on substrates, in particular single-layer or multi-layer coatings.
• the coating materials according to the invention are used in particular for the coating of substrates, such as bodies of means of transportation, including aircraft, watercraft, vehicles powered by muscle power and motor vehicles, as well as parts thereof, indoor and outdoor structures and parts thereof, Furniture, windows, doors, small industrial parts, coils, containers, packaging, white goods, foils, optical components, electrotechnical components, mechanical components or glass hollow bodies.
• substrates such as bodies of means of transportation, including aircraft, watercraft, vehicles powered by muscle power and motor vehicles, as well as parts thereof, indoor and outdoor structures and parts thereof, Furniture, windows, doors, small industrial parts, coils, containers, packaging, white goods, foils, optical components, electrotechnical components, mechanical components or glass hollow bodies.
• the coatings according to the invention have outstanding optical properties, in particular with regard to the brilliance, the brightness and the color flop.
• the coatings according to the invention are of automotive quality and can therefore also be used for painting top-class automobiles. Examples and comparative tests
• a leaf-shaped aluminum effect pigment (Alphate ® 7670 NS from Toyal; calculated on the solids content) were crystal clear in a solution of 80 parts by weight of polymethyl methacrylate called Plexiglas ® molding compound 8N (company Röhm GmbH & Co. KG) and 320 parts by weight of acetone Dissolver gently dispersed for ten minutes.
• the resulting dispersion was applied to a substrate made of polyethylene terephthalate in a precision coating system with a knife caster.
• the substrate / casting ruler gap was set to 60 ⁇ m.
• the applied layer was dried in the plant at 80 ° C. At a coating speed of 30 m / minute, a layer with a thickness d of 5 + 0.2 ⁇ m was obtained.
• the sheet-like aluminum effect pigments were arranged completely parallel to the surface in the layer.
• the layer was decoated using a sharp water jet in a continuously running system.
• the resulting mixture of water and sheet-like parts was filtered off with suction and dried at 80 ° C. for twelve hours.
• the leaf-shaped parts were then ground in a cutting mill and the leaf-shaped particles (A) with a laminar diameter D of 90 to 180 ⁇ m were separated off for further use.
• Example 2 The production of a coating material from the components (A) and (B)
• the coating material of example 2 was used for example 3.
• the coating materials each contained the same amount of aluminum effect pigment. They were applied electrostatically to test sheets and baked, so that the same layer thickness resulted.
• the brightness L * was measured with the Byk ® Colorview measuring device using light types D65 / TL and 84 / A and evaluated according to CIELAB.
• the coating of example 3 resulted in a brightness L * of 71.5, which was significantly higher than the brightness L * of 57 of the coating of comparative test V 1.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Paints Or Removers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)

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• 2003
  • 2003-09-19 DE DE10343393A patent/DE10343393A1/de not_active Withdrawn
• 2004
  • 2004-09-08 JP JP2006526646A patent/JP2007505962A/ja active Pending
  • 2004-09-08 EP EP04787209A patent/EP1664212A1/de not_active Withdrawn
  • 2004-09-08 WO PCT/EP2004/052307 patent/WO2005028573A1/de active Application Filing
  • 2004-09-08 US US10/595,105 patent/US20070186814A1/en not_active Abandoned

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