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
  • C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
  • B05D5/065—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects having colour interferences or colour shifts or opalescent looking, flip-flop, two tones
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/52—Two layers
  • B05D7/53—Base coat plus clear coat type
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/52—Two layers
  • B05D7/53—Base coat plus clear coat type
  • B05D7/536—Base coat plus clear coat type each layer being cured, at least partially, separately
• • 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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
  • C08L33/12—Homopolymers or copolymers of methyl methacrylate
• • 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
• • 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
  • C09D5/002—Priming paints
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/66—Additives characterised by particle size
  • C09D7/69—Particle size larger than 1000 nm
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
  • B05D1/286—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers using a temporary backing to which the coating has been applied
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2601/00—Inorganic fillers
  • B05D2601/02—Inorganic fillers used for pigmentation effect, e.g. metallic effect
  • B05D2601/08—Aluminium flakes or platelets
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2601/00—Inorganic fillers
  • B05D2601/20—Inorganic fillers used for non-pigmentation effect
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/56—Three layers or more
  • B05D7/57—Three layers or more the last layer being a clear coat
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0812—Aluminium

Definitions

• the invention described below relates to a multi-layer, color and / or effect coating comprising a clearcoat and a basecoat and a method for forming the basecoat.
• Color and / or effect coatings usually comprise several layers of paint, which are applied over each other and have different properties.
• a primer layer (primer) and / or a surfacer coat a basecoat film and a clearcoat film are frequently applied in succession.
• the primer layer can be deposited, for example, electrically, in particular by means of electrocoating. It is often used to improve the adhesion of the paint on the substrate. In metallic substrates such as the aforementioned motor vehicle body, it also continues to serve corrosion protection.
• the filler layer serves to cover unevennesses of the substrate surface to be painted and, because of its elasticity, can improve a coating with regard to its resistance to chipping.
• the filler layer can serve to enhance the opacity and to deepen the color of the paint.
• the basecoat layer carries colors and / or angle-dependent optical effects of the finish. Both the brightness and the color of the reflected light can vary as a function of the viewing angle, which is also referred to as brightness and / or color flop.
• the clearcoat film serves to enhance the optical effects and protect the paint from mechanical and chemical damage.
• the color and the flop behavior of the basecoat film can depend very much on the conditions under which the basecoat film is applied to a substrate. This is particularly relevant if platelet-shaped dye and / or effect pigments are incorporated in the basecoat film. Their orientation within the basecoat layer can strongly influence the optical properties of the coating. If a basecoat layer is formed approximately by means of a coating method such as rolling or doctoring, the platelet-shaped pigments within the basecoat layer are oriented predominantly in a preferred direction, namely in the direction of the application. Basically, one speaks in the coating in all application processes in which the pigments are arranged without further action in a preferred direction of directed application process, in contrast to non-directionalMapver drive, in which the pigments are not arranged in a preferred direction.
• the basecoat layer resulting from the directional application then has pigments in an anisotropic arrangement. This means that the optical properties of the basecoat film and therewith the paint are dependent on the viewing angle. In practice, this may necessitate expensive measures for color matching of painted components, which, for example, directly abut each other as parts of a motor vehicle body (color matching).
• EP 1 423 299 B1 discloses a procedure which makes it possible to produce coatings with basecoat films which contain platelet-shaped dye and / or effect pigments, but whose optical properties are nevertheless independent of the viewing angle.
• a comparatively thick first basecoat partial layer is first applied to a substrate with the aid of a directed application method.
• This is covered in a subsequent step with a comparatively thin second basecoat partial layer, wherein the formation of the second base partial paint layer by means of a non-directional application method, for example by means of spraying. It has surprisingly been found that the overall optical effect of the multilayer basecoat layer produced in this way is dominated exclusively by the second basecoat film.
• a comparatively thin base coat partial layer with pigments in an isotropic arrangement on a comparatively thick base coat partial layer with pigments in an anisotropic arrangement causes the same optical impression as a single-coat base coat layer which has exclusively pigments in an isotropic arrangement.
• a disadvantage of this procedure is that the application of the basecoat film in several stages makes the coating process more expensive and the use of the non-directional coating method can lead to an uneven surface of the basecoat film.
• the present invention has for its object, basecoat films containing pigments and / or effect pigments, and to provide coatings with such basecoat films, without being confronted with the problems of the prior art.
• the invention proposes the coating with the features of claim 1 and the method with the features of claim 6. Further developments of the invention are the subject of dependent claims.
• the coating according to the invention is a multi-layered, applied to a substrate, color and / or effect paint. It is always characterized by a combination of the following features:
• the coating comprises a clearcoat film having a dry film thickness in the range from 10 ⁇ m to 50 ⁇ m, in particular from 25 ⁇ m to 40 ⁇ m, and
• the coating comprises a basecoat film having a dry film thickness in the range from 6 pm to 35 pm, in particular from 10 pm to 20 pm, into which colorants and / or effect pigments are incorporated whose orientation within the basecoat film influences the optical properties of the paint.
• the coating is characterized in that the base coat layer for controlling the Ori ent mich of the color and / or effect pigments contains so-called control particles, which control particles in turn by a dlO value of at least 50%, preferably of at least 60%, especially preferably at least 70%, the rock layer thickness of the basecoat layer and
• a d50 value in the range of 80% to 120% of the dry layer thickness of the basecoat layer, in particular in the range of 80% to 100% of the dry layer thickness of the basecoat layer, and
• dl00 value of not more than 200%, preferably of not more than 150%, in particular not more than 120%, of the rocking layer thickness of the basecoat film.
• the stated numerical values relate to the totality of all control particles contained in the basecoat film.
• the d50 value of the control particles (which subdivides the control particles contained in the basecoat into two equal partial fractions) is at least 80% and at most 120% of the dry layer thickness, at most 10% of the total control particles contained in the layer Having diameters less than 0.5 times, preferably 0.6 times, more preferably 0.7 times, the dry film thickness of the basecoat film, and the basecoat film is free of control particles having a diameter, which exceeds the dry layer thickness of the basecoat by more than 100%, preferably by more than 50%, especially before more than 20%.
• the diameters of the control particles are usually in the double-digit pm range.
• dlO, d50 and d100 values can be determined very reliably, in particular according to ISO 13320_2009 in conjunction with DIN ISO 9276-l_2004 (presentation of the results of particle size analyzes - Part 1: Graphical representation) and ISO 9276-2_2014 (Presentation of the results of particle size analyzes - Part 2: Calculation of mean particle sizes / diameters and moments from particle size distributions). Numerical data on the diameter of control particles are values determined using these standards.
• control particles defined in this way means that even when the basecoat film is applied by means of a directed application process, an isotropic arrangement of the dye and / or effect pigments can be achieved.
• the essential part of the control particles has a diameter which corresponds approximately to the T rocken Anlagendicke the base lacquer layer. This forces some of the color and / or effect pigments to be tangent to the surface of the control particles and thus at an angle, for example perpendicular, to the direction of the job.
• the control particle used can control the visual appearance of the basecoat film.
• the control particles exclusively control the angular dependence of the hue and no optical effects, such as color. the gloss of the paint.
• the dry layer thickness of the clearcoat layer and the basecoat layer in each case means the thickness of these layers after drying, ie if no solvent is contained in the layers. Dry layer thicknesses can be determined in particular according to DIN EN ISO 2808. In this case, numerical data for dry layer thicknesses are values determined by this standard. Particularly preferably, the clearcoat layer and the basecoat layer each have a substantially uniform T rocken harshdicke on. This is to be understood in particular that the average deviation of the dry layer thickness is preferably less than 10% of the value determined, for example, according to DIN EN ISO 2808.
• clearcoat film and the basecoat film of a erfindungsge MAESSEN paint although by definition are dried, but in no case must be cured already zwin quietly.
• the substrate can basically be any object, for example the motor vehicle body mentioned at the beginning or a piece of furniture.
• the substrate is particularly preferably a film, in particular a plastic film.
• a laminate of the carrier film and the coating layer (s) to be transferred is generally provided, in particular as a web material, for example with a web width of 600 mm and a web length of 700 m.
• the laminate is pressed with the paint layer or layers ahead on the workpiece to be painted.
• an adhesion-promoting layer can be applied beforehand to the lacquer side of the laminate and / or the workpiece to be lacquered.
• the carrier film is peeled off, with the lacquer layer or the lacquer layers remaining on the workpiece.
• Such procedures are known for example from DE 10 2007 040376 Al.
• the coating according to the invention is particularly preferably part of such a transfer-lacquer film and, for this purpose, applied to a corresponding carrier film which serves as a substrate. If this is the case, the transfer-coated film preferably has the sequence carrier film / clearcoat / basecoat.
• a basecoat and / or clearcoat it may be advantageous to dry a basecoat and / or clearcoat, but not to cure it.
• the coating can be converted into a non-sticky state by drying the clearcoat layer, yet still have a high mechanical flexibility due to curing that has not yet occurred.
• Suitable films which can be used as substrate are known, for example, from DE 10 2007 040 376 A1.
• Particularly suitable films consist of polymers such as fluoropolymers (eg ethylene-tetrafluoroethylene (ETFE)), polyethylene terephthalate, polyolefin, polycarbonate, acrylonitrile-butadiene-styrene (ABS), acrylic-styrene-acrylonitrile (ASA), acrylonitrile-butadiene-styrene / polycarbonate ( ABS / PC), acrylic styrene-acrylonitrile / polycarbonate (ASA / PC), polyacrylate, polystyrene, polycarbonate / polybutylene terephthalate (PC / PBT) and / or polymethyl methacrylate.
• fluoropolymers eg ethylene-tetrafluoroethylene (ETFE)
• ETS acrylonitrile-butadiene-styrene
• ASA acrylic-styrene-acrylonitrile
• ABS / PC acrylic styrene
• the coating according to the invention may comprise, in addition to the clearcoat layer and the basecoat layer, further lacquer layers, for example the filler layer mentioned at the outset.
• a transfer lacquer film with the lacquer coating according to the invention may have the sequence carrier foil / clear lacquer layer / base lacquer layer / surfacer coat.
• Suitable clearcoats for the production of the clearcoat film are, in addition to all customary and known one-component (1K), two-component (2K) or multi-component (3K, 4K) clearcoat materials, clear powder coatings.
• Suitable 1K, 2K, 3K or 4K clearcoats are known, for example, from the patent applications DE 4204518 A1, EP 0594068 A1, or EP 0596460 A1.
• 1K clearcoats contain known hydroxyl-containing binders and crosslinking agents such as blocked polyisocyanates, tris (alkoxycarbonylamino) triazines and / or aminoplast resins.
• crosslinking agents such as blocked polyisocyanates, tris (alkoxycarbonylamino) triazines and / or aminoplast resins.
• they contain as binders polymers with pendant carbamate and / or allophanate groups and carbamate- and / or allophanate-modified aminoplast resins as cross-linking agents (see American patents US 5474811 A or US 5605965 A or European patent applications EP 0594068 A1 or EP 0594 142 A1.
• 2K, 3K or 4K clearcoats contain, as essential constituents, hydroxylgrup pen inconvenience binders and polyisocyanates as crosslinking agents, which are stored separately until their use.
• Suitable powder clearcoats are known, for example, from German patent application DE 4222194 A1.
• the paints described in WO 2009/024310 A2 comprising a double bond-containing, OH-functional component A, a double bond-containing, NCO-functional component B and optionally a component C containing double bonds are particularly suitable.
• component A is preferably a polyol and in the case of components B and C are preferably urethane acrylates.
• the setting of the solids content of the clearcoats influences the wet film thickness in which the clearcoat is applied as well as the dry film thickness that sets after the clearcoat has dried taken.
• basecoats for the preparation of the basecoat are basically all known letteatorihal term and aqueous basecoats in question. Suitable examples can be found in US 5114789 A (column 7, line 41 to column 8, line 33, column 11, lines 24-50, and column 13, lines 30-40), EP 0 352 298 B1 (page 9, Line 19, to page 12, line 38), EP 0 089 497 A1, EP 0 256 540 A1, EP 0 260 447 A1, EP 0 297 576 A1, WO 96/12747, EP 0 523 610 Al, EP 0 228 003 A1, EP 0 397 806 A1, EP 0 574417 A1, EP 0 531 510 A1, EP 0 581 211 A1, EP 0 708 788 A1, EP 0 593 454 A1, DE 4328092 A1, EP 0 299 148 A1, EP 0 394 737 A1, EP 0 590 484 A1, EP 0 234 362 A1, EP 0 234 3
• the clearcoat and / or the basecoat are cured thermally and / or by radiation after their application and, where appropriate, after a drying step. If appropriate, the clearcoat and basecoat can be cured in one step, ie simultaneously.
• color and / or effect pigments is intended here to encompass all pigments which can impart an angle-dependent hue and / or an angle-dependent optical effect to a lacquer layer applied by means of a conventional directional application method in which they are embedded.
• the color and / or effect pigments are particularly preferably platelet-shaped.
• the ratio of the extent of the platelet-shaped color and / or effect pigments in a main dimension to the thickness of the platelet-shaped dye and / or effect pigments is preferably more than 3 and in particular more than 5.
• the coloring and / or effect pigments are preferably selected from the group consisting of organic and inorganic, colored, optically effecting, electrically conductive, magnetically shielding or fluorescent pigments and metal powders.
• the dye and / or effect pigments particularly preferably have an aspect ratio, ie a ratio of average diameter to the mean thickness of the platelets, of> 1, more preferably in the range from 2 to 2000, in particular in the range from 3 to 1000, particularly preferably in Range of 3 to 100, more preferably in the range of 3 to 50, on.
• effect pigments which can be used according to the invention are platelet-shaped aluminum flakes having an aspect ratio in the range from 3 to 10.
• suitable effect pigments are metal flake pigments, such as commercially available aluminum bronzes, aluminum chromates chromated according to DE 3636183, commercial stainless steel bronzes, non-metallic effect pigments, such as pearlescent or interference pigments, platelet-shaped effect pigments based on iron oxide 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, molybdate red or ultra marin red; Iron oxide brown, mixed brown, spinel and corundum phases or chrome orange; or iron oxide yellow, nickel titanium yellow, chromium 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
• Colored pigments such
• suitable organic colored elements are monoazo pigments, disazo, anthraquinone nonpigmente, benzimidazole pigments, quinacridone pigments, quinophthalone pigments, Diketopyrro- lopyrrolpigmente, te dioxazine pigments, indanthrone pigments, isoindoline pigments, Isoindolinonpigmen, azomethine pigments, thioindigo pigments, metal complex pigments, perinone pigments, perylene pigments, phthalocyanine pigments or aniline black.
• Suitable electrically conductive pigments are carbon black and carbon nanotubes.
• suitable magnetically shielding pigments are pigments based on iron oxides or chromium dioxide.
• suitable metal powders are powders of aluminum, zinc, copper, bronze or brass.
• control particles which can be used in the context of the invention are preferably characterized by at least one of the following, particularly preferably by all three of the following properties:
• control particles are spherical or at least approximately spherical in shape: By approximately spherical it should be understood here that they have no corners and no edges and have a maximum and a minimum diameter, where at the ratio of maximum to minimum diameter not more than 1.5 , preferably not more than 1.2, more preferably not more than 1.1. By contrast, spherical means that they have only one diameter.
• control particles consist of a plastic, in particular a plastic resistant to organic solvents such as ethyl, methyl alcohol, xylene, butyl acetate, methoxypropyl acetate.
• the control particles consist of a plastic that is thermally stable up to 140 ° C.
• control particles The material nature of the control particles is basically not important for the invention tion. On the other hand, what is important is the above-defined relative size of the control particles in relation to the core layer thickness of the basecoat film.
• control particles may consist of an acrylate such as polymethylmethacrylate.
• control particles even the basecoat layer in which they are embedded can give neither an angle-dependent hue nor an angle-dependent optical effect.
• their presence merely controls the hues or optical effects caused by the dye and / or effect pigments.
• the mean diameters of the control particles are generally in the two-digit range pm.
• the use of coming color and / or effect pigments is preferably characterized by d.sub.50 and d.sub.50 values which amount to a maximum of 5 times, preferably 3 times, more preferably 2 times, the d.sub.50 and d.sub.10 values of the control particles ,
• the d50 and d100 values of the control particles used are 0.1-fold to 5-fold, in particular 0.1-fold to 3-fold.
• the coating according to the invention is preferably characterized by at least one of the following features, particularly preferably by a combination of the following two features:
• the basecoat film contains the control particles in a proportion of from 2% by weight to 15% by weight (based on the solids content of the basecoat from which the basecoat film is formed, based on the basecoat film in the dried state).
• the basecoat film contains the color and / or effect pigments in a proportion of 0.15% by weight to 15% by weight (based on the basecoat film in the dried state, ie based on the solids content of the basecoat from which the basecoat film is formed becomes).
• the process according to the invention is used for the production of a basecoat film, particularly preferably for the production of the basecoat film of the above-described multilayer coating. Accordingly, the components necessary for the preparation of the basecoat film (basecoat, color and / or effect pigments, control particles) are also selected from those described above.
• the procedure always includes the following three steps:
• the basecoat always contains the color and / or effect pigments whose orientation within the basecoat affects their optical properties
• control particles for controlling the orientation of the dye and / or effect pigments in the base coat layer to be delivered.
• the basecoat contains a solvent in addition to the components mentioned.
• the solids content of the basecoat and / or the thickness of the basecoat film are adjusted such that the basecoat film is obtained with a dry film thickness in the range from 6 .mu.m to 35 .mu.m.
• the control particles used are those which have a d10 value of at least 50% of the dry film thickness of the basecoat film and a d50 value in the range of 80% to 120% of the dry film thickness of the basecoat material layer, in particular in the range of 80% to 100% of the dry layer thickness of the basecoat layer, and
• dl00 value of not more than 200%, preferably of not more than 150%, in particular not more than 120%, of the rocking layer thickness of the basecoat film.
• control particles used by no means necessarily have to have a mono-modal distribution. Rather, it may even be advantageous to use two or more STEU particulate fractions, each having a different d50 value, optionally also a different dlO and / or dl00 value.
• the d50 value of the entirety of the control particles in the basecoat film would then be 90% of the T rocker layer thickness of the basecoat film.
• the substrate is preferably one of the above-mentioned substrates.
• the substrate is a film to which a clearcoat has already been applied. In general, however, it is preferred if initially the basecoat film is applied to the film and then the clearcoat film.
• the application of the basecoat takes place with the aid of a directed application method.
• a directed application method in particular an order by means of casting, knife coating, rolling or Extrusionsbe layers in question.
• customary and known devices such as casting devices, doctor blades, rolls, in particular counter-rotating rolls, or extruders, in particular Folienex trudern.
• FIG. 1 schematically shows, in cross section, a basecoat film 101 applied to a substrate 100.
• the basecoat film 101 was applied by means of knife coating, ie by means of a directed order procedure.
• Platelet-shaped metal flakes 102 are embedded in the basecoat film 101 as color and / or effect pigments. These are all arranged in a preferred direction, namely in the direction of the job (arrow), as a result of the directed application method. Incident light is reflected by all metal flakes 102 similarly.
• the color and optical appearance of the basecoat film 101 is therefore strongly dependent on the angle.
• FIG. 2 shows schematically in cross section a basecoat film 201 applied to a substrate 200.
• the basecoat film 201 was formed by means of spray application, ie by means of a non-directional application process.
• Platelet-shaped metal flakes 202 are embedded in the basecoat film 201 as color and / or effect pigments. These are substantially more disordered than the metal flakes according to FIG. 1 as a result of the non-registered application method.
• Incident light is not uniformly reflected by all metal flakes 202.
• the color and optical appearance of the basecoat layer 201 is therefore significantly less dependent on the angle than in the case of FIG. 1.
• FIG. 3 shows schematically in cross-section a basecoat film 301 applied to a substrate 300.
• the basecoat film 301 was formed by means of knife coating, that is to say by means of a directed application process.
• the base lacquer layer 301 In the base lacquer layer 301 are plate-shaped metal flakes 302 embedded as a color and / or effect pigments. Despite the directed order procedure, these are not all arranged in a preferred direction, namely in the direction of the order. This is prevented by the ku gelförmigen control particles 303, which are like the metal flakes 302 embedded in the base coat layer 301.
• the control particle 303 has a diameter which corresponds approximately to the thickness of the basecoat film 301.
• a portion of the metal flakes 302 is forced to be parallel to the surface of the control particles 303 and thus to be skewed or even perpendicular to the direction of the job (arrow).
• the color and optical appearance of the basecoat film 301 is therefore significantly less dependent on the angle than in the case of FIG. 1.
• FIG. 4 is a detail from a photomicrograph of a section through a basecoat film 401 formed on a substrate 400 according to the invention by means of a directed application process, which is covered by a clearcoat film 404.
• the base coat layer 401 as metal and / or effect pigments metal flakes 402 and the control particles 403 are embedded.
• the control particle 403 has a diameter which corresponds approximately to the thickness of the base coat layer 401. It will be appreciated that the metal flakes 402 are forced into an oblique orientation by the control particle.
• a base paint having a solid content of 25% was applied by means of a doctor blade in a wet film thickness of 60 ⁇ m.
• the basecoat included a polyurethane-based binder, an additive mixture, and water as a dispersant.
• the mean diameter (d50) of the aluminum flakes was 10 ⁇ m.
• the particles of the organic color pigment consistently had sizes below 1 ⁇ m.
• a base paint having a solid content of 35% by means of a doctor blade was also applied in a wet film thickness of 60 ⁇ m.
• the basecoat had an identical composition to the basecoat used under A, with one exception: in addition to the aluminum flakes, it contained spheres of polymethylmethacrylate having an average diameter (d50) of 15 pm in a proportion of 1% by weight Weight refers to the basecoat in total, that is, including the dispersing agent and / or solvent). These serve in the sense of the present application as control particles.

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• 2018
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