DE10027270A1 - Coating powders and powder slurries containing leafing pigments, used for production of basecoats or combination-effect coats in multi-coat paint systems, e.g. for painting cars, - Google Patents

Abstract

Coating powders and coating powder dispersions (powder slurries) (I) containing leafing pigment(s). Independent claims are also included for: (a) effect-giving multilayer paint systems with a combination effect layer, obtained by applying a powder slurry as above to a substrate coated with electrophoretic primer (cathodically deposited and optionally thermally hardened) and then hardening the powder slurry (or both layers) physically, thermally and/or with actinic radiation; (b) effect-giving multi-layer paint systems with a basecoat, obtained by applying a filler coat to an electrophoretic primer layer (see above), hardening the filler (or both layers) as above to form a filler coat or stone chip-proof primer coat, applying (I) and drying it without complete hardening (or completely hardening it as above) to form a basecoat, applying at least one clearcoat and hardening it (and any other unhardened layers).

Description

The present invention relates to new powder coatings and powder coating dispersions (Powder slurries), which contain effect pigments. Furthermore, the present concerns Invention the use of the new powder coatings and powder slurries in the Automotive painting, painting of buildings indoors and outdoors, the Painting of furniture, doors and windows and industrial painting, inclusive Coil coating and container coating.

Color and / or effect coatings of motor vehicle bodies, in particular Car bodies today consist preferably of several layers of paint that are applied one above the other and have different properties.

For example, an electrically deposited electrodeposition coating is applied in succession (ETL) as a primer, a filler paint or stone chip protection primer, a Base coat and clear coat applied to a substrate. Here serves the ETL especially the corrosion protection of the sheet. It is used frequently by experts also called primer. The filler coating serves to cover Bumps in the surface and, due to their elasticity, allow Stone chip resistance. If necessary, the filler paint can also be used for reinforcement the hiding power and to deepen the color of the paint. The Basecoat contributes the colors and / or the optical effects. The clear coat serves to enhance the optical effects and protect the paintwork from mechanical and chemical damage. Basecoat and clearcoat will be often referred to collectively as top coat. In addition, is still on Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 49 and 51, "automotive coatings" referenced.

It is therefore an important goal of modern automotive painting to control the amount of Significantly reduce the amount of organic solvent released if not to bring it to zero. Corresponding paints, such as ETL, aqueous fillers or  aqueous clear lacquers, powder lacquers or powder slurry clear lacquers are available. However, it is still disadvantageous that non-aqueous, d. H. conventional, basecoats or waterborne basecoats with a comparatively high Proportion of organic solvents must be used to keep the pigments stable disperse and ensure a good flow of the applied layers.

In addition, when using the varnishes together, especially the Basecoats and clearcoats, as part of the production of a color and / or effect Painting their properties can be matched very finely to one another for example, a break in of the uncured layers when using Avoid wet-on-wet procedures and / or cracking, the formation of stoves and / or to prevent delamination of layers.

It would therefore be desirable to use the customary and known basecoats and Waterborne basecoats through solvent-free powder coatings and powder slurries, the effect pigments (see Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 176, »Effect Pigments« and pages 380 and 381 »Metal Oxide Mica Pigments« to "Metal pigments") to replace. The first approaches to this are already in place.

For example, Coatings Partner, The magazine of BASF, Powder Coatings Special, 1/2000, pages 4 to 6, or the company lettering from BASF Coatings AG "Powder coatings, powder coatings for industrial applications", January 2000, pigmented Powder coatings, which can also be considered as basecoats.

Furthermore, Japanese patent application JP 53 109 540 A1 (Derwent- Unit 78800A / 44) a coating with a 10 to 45 µm thick base coating, produced from an unspecified pigmented powder slurry and a 30 bis 70 µm thick clear coat.

A metal effect pigment is known from German published patent application DE 27 10 421 A1 Containing powder slurry based on amine neutralized acrylate copolymers and  Melamine resins or known from polyesters and epoxy resins. The manufacture of the pigmented powder slurries, however, require the neutralization of the water-soluble ones amine neutralized starting products with hydrochloric acid. This allows the Metallic effect pigments are sustainably damaged. The well-known powder slurry delivers smooth, shiny, metallic coatings. It is not known if they are for the Production of multi-layer paints that provide effects.

Japanese patent application JP 02 014 776 A2 describes a multi-layer coating known from basecoat and clearcoat, the basecoat from a pigmented powder slurry based on hydroxy group-containing acrylate copolymers and blocked polyisocyanates.

From US Pat. No. 5,379,947 A1, cosolvent-free pigmented ones and unpigmented powder slurries based on, for example hydroxyl-containing acrylate copolymers and blocked polyisocyanates or known acrylate copolymers containing glycidyl groups and dodecanedioic acid.

Furthermore, from US Pat. No. 4,268,542 A1, comparable, Powder coatings and powder slurries containing effect pigments are known.

The well-known pigmented powder coatings and powder slurries, however, have metallic effects and / or optical effects that meet the high demands of Automobile series painting, especially in the luxury class, not yet fair can, which is why the powder coatings and powder slurries are not yet Have basecoats enforced.

The object of the present invention is to provide novel powder coatings containing effect pigments and powder slurries that no longer have the disadvantages of the prior art have, but the effect in their use as basecoats Multilayer coatings with metallic effects and / or dichroic effects deliver that  also the high demands of automobile manufacturers and customers in the segment of Upper class are enough.

Accordingly, the new powder coatings and powder coating dispersions (powder slurries), containing at least one leafing pigment, found in the following as "Powder coatings and powder slurries according to the invention" are referred to.

Further objects according to the invention are evident from the description.

In view of the prior art, it was surprising and not for the person skilled in the art predictable that the powder slurries and powder coatings according to the invention the production effect multi-layer coatings that meet the high demands of Market are enough.

It was even more surprising that the powder slurries according to the invention were used to manufacture them so-called combination effect layers that allow in effect Multi-layer painting both the function of filler painting and Stone chip protection primers as well as basecoats. This is the case more surprising than the powder slurries for the production of Lacquer layers with essentially only one function are proposed and others the usual and known filler coatings and basecoats Coating materials are produced that are very different and very different in material are specially adapted to their respective purpose.

In the context of the present invention, the term “effect-giving” Multi-layer painting "both achromatic (cf. cf. Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, 1998, page 590, "Unbuntpunkt") as well as colored, d. H. colored multi-layer paintwork.  

The powder slurry according to the invention contains at least one finely divided dimensionally stable component, d. H. a powder coating according to the invention, as a disperse Phase and an aqueous medium as a continuous phase.

The finely divided dimensionally stable component or the powder coating according to the invention can be solid and / or highly viscous. In the context of the present invention means "highly viscous" that the particles under the usual and known conditions of Production, storage and application of powder slurries or powder coatings in behave essentially like solid particles. The powder coating is preferably solid.

The individual particles of the finely divided ingredient or powder coating are also dimensionally stable. In the context of the present invention, "dimensionally stable" means that the particles under the usual and known conditions of storage and Use of powder slurries and powder coatings only slightly, if at all agglomerate and / or disintegrate into smaller particles, but also under the influence essentially retain their original shape from shear forces.

The solids content of the powder slurry according to the invention is preferably from 10 to 80, preferably 15 to 75, particularly preferably 20 to 70, very particularly preferably 25 to 70 and in particular 30 to 65 wt .-%, each based on the invention Powder slurry.

In the powder coating according to the invention, the solids content is naturally 100% by weight.

The average particle size of the finely divided dimensionally stable is preferably Constituents of the powder slurry according to the invention at 0.8 to 40 μm, preferably 0.8 to 20 μm, and particularly preferably 2 to 6 µm. The average particle size becomes the Understand the 50% median determined by the laser diffraction method, d. i.e. 50% of the particles have a particle diameter ≦ the median and 50% of the particles have one Particle diameter ≧ the median. Generally the particle size is the  finely distributed dimensionally stable components their upper limit when the Due to their size, particles can no longer run completely when stoved and that the film run is negatively influenced. The upper limit is 40 µm for considered reasonable, since from this particle size with a clogging of the rinsing channels highly sensitive application equipment can be expected.

Pigmented powder slurries with such average particle sizes have a better one Application behavior and show at the applied film thicknesses of <30 microns as they currently practiced in the automotive industry for the first painting of automobiles are, surprisingly, a significantly lower tendency to cookers and "mudcracking" as conventional combinations of filler, basecoat and clearcoat.

The grain size distribution of the powder coating materials of the invention can be comparatively broad vary and depends on the respective purpose. Preferably, the Grain size distribution comparatively narrow with a very low proportion of coarse grain (Grain sizes above 95 µm) and fine grain (grain sizes below 5.0 µm). Especially powder coatings are preferred with those in European patent application EP 0 666 779 A1 described grain size distribution applied.

Surprisingly, the powder coatings according to the invention essentially show the same advantages as listed above for the powder slurries according to the invention become.

The powder slurry according to the invention and the powder coating according to the invention are preferably free of organic solvents (cosolvents). As part of the present The present invention means that it has a residual volatile solvent content of <2.0% by weight, preferably <1.5% by weight and particularly preferably <1.0% by weight. According to the invention, it is particularly advantageous if the residual content is below the gas chromatographic detection limit.  

The essential component of the powder coatings according to the invention and Powder slurries is at least one leafing pigment.

Leafing pigments are pigments that are in layers of pigmented coating materials swim up. According to DIN 55 945 (12/1988), this denotes the enrichment of Pigments on the surface of a coating material.

Their average particle size - as defined above - is preferably 5 to 20 and in particular at 10 to 11 μm, the maximum particle size generally being 30 and in particular should not exceed 25 microns to block the nozzles and / or Rinsing channels in the application devices and / or the protruding leafing Pigments from the basecoats and combination effect layers according to the invention to prevent

Leafing effect pigments are preferably used according to the invention. To that The term effect pigments is used on Römpp Lexikon Lacke and printing inks, Georg Thieme Verlag, 1998, pages 176, »Effect Pigments«, and pages 380 and 381 »Metalloxid- Mica pigments «to» metal pigments «. Leafing are preferred Metallic effect pigments, in particular leafing aluminum pigments, are used.

The leafing aluminum pigments to be used according to the invention are around aluminum pigments that are not completely covered by surface tension the binders described below are wetted and therefore in the Float on wet layer.

The powder coatings and powder slurries according to the invention are notable for comparatively low content of at least one saturated fatty acid or one Polysiloxane, but especially a saturated fatty acid. These can be as Additive can be introduced. Preferably the saturated fatty acids or Polysiloxanes entered via the leafing pigments, which are obtained by grinding pigments, preferably effect pigments, preferably metallic effect pigments, in particular  Aluminum pigments, in the presence of at least one saturated fatty acid or one Polysiloxane, especially a saturated fatty acid, can be produced as grinding aids (see Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 351, "Leafing pigments").

Saturated fatty acids with 8 to 30 carbon atoms in the molecule are preferred used. Examples of suitable fatty acids of this type are n-octanoic acid, n- Nonanoic acid, n-decanoic acid, n-undecanoic acid, n-dodecanoic acid (lauric acid), n- Tridecanoic acid, myristic acid, n-pentadecanoic acid, palmitic acid, n-heptadecanoic acid Margaric acid), stearic acid, n-nonadecanoic acid, n-eiconsanoic acid or n-hexacosanoic acid. Of these, stearic acid has particular advantages, which is why it is so special is preferably used.

Suitable leafing aluminum pigments are known and are, for example, from Eckart under the type designation or brand CHROMAL X or PC 100 expelled.

In a first embodiment, which is preferred according to the invention, contain the finely divided dimensionally stable constituents of the powder clearcoats and Powder slurries the total amount of leafing pigments used.

In a second embodiment, which is preferred according to the invention, contain the finely divided dimensionally stable constituents of the powder clearcoats and Powder slurries no leafing pigments; d. H. all leafing pigments used are as separate solid phase before. The foregoing applies analogously to their particle size.

In a third embodiment, which is preferred according to the invention, contain the finely divided dimensionally stable constituents of the powder clearcoats and Powder slurries use part of the leafing pigments used, whereas the other part as separate solid phase is present. This can be the case in the finely divided Dimensionally stable constituents by the main amount, d. H. to ... more  act as 50% of the leafing pigments used. However, less can than 50% in the finely divided dimensionally stable components. With regard to the Particle sizes apply here as well.

Which variant of the powder clearcoats and powder slurries according to the invention is preferred given depends in particular on the nature of the leafing pigments and / or by the method by which the powder clearcoats used in each case according to the invention and powder slurries. In the many cases, the first one is preferred Embodiment special advantages, which is why it is particularly preferred according to the invention is.

The content of the powder clearcoats and powder slurries according to the invention Leafing pigments to be used according to the invention can vary and vary very widely depending on the requirements of the individual case, especially the one to be set optical effect and / or the hiding power of the leafing used in each case Effect pigments. The content of leafing pigments is preferably 0.1 to 20, preferably 0.3 to 18, particularly preferably 0.5 to 16, very particularly preferably 0.7 to 14 and in particular 0.9 to 12 wt .-%, each based on the invention Powder coating or on the solids content of the powder slurry according to the invention.

In addition to the leafing pigments to be used according to the invention, the Powder clearcoats and powder slurries according to the invention, further customary and known color and / or contain effect pigments.

These pigments can consist of inorganic or organic compounds. The Powder coatings and powder slurries according to the invention therefore ensure this Many suitable pigments have a universal range of applications and enable that Realization of a multitude of particularly beautiful colors and optical effects.

Metal pigments such as commercially available can be used as effect pigments Aluminum bronze, aluminum bronze chromated according to DE-A-36 36 183,  commercially available stainless steel bronzes and metal-containing and non-metallic effect pigments, such as pearlescent or interference pigments can be used. Complementary on Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 176, »Effect Pigments« and pages 380 and 381 »Metal Oxide Mica Pigments« to "Metal pigments," referenced.

Examples of suitable inorganic color pigments are titanium dioxide and iron oxides and soot. Examples of suitable organic coloring pigments are Thioindigo pigments, indanthrene blue, irgalite blue, heliogen blue, irgazin blue, palomar Blue, Cromophthal Red, Hostaperm Pink, Irgazin Orange, Sicotrans Yellow, Sicotan Yellow, Hostaperm yellow, paliotan yellow, and heliogen green.

In addition, Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, Pages 180 and 181, "Iron Blue Pigments" to "Iron Oxide Black", Pages 451 to 453, »Pigments« to »Pigment Volume Concentration«, page 563, »Thioindigo Pigments« and Page 567, “Titanium dioxide pigments”.

The pigments can, as described above for the leafing pigments, within and outside the finely divided dimensionally stable components of the invention Powder coatings and powder slurries are available. This applies to particle sizes what has been said above also applies here.

The powder coatings and powder slurries according to the invention can also be organic and contain inorganic fillers that like the pigments inside and outside the finely divided dimensionally stable components may be present; that with the pigments What has been said applies here analogously.

Examples of suitable organic and inorganic fillers are chalk, calcium sulfates, Barium sulfate, silicates such as talc or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as textile fibers, cellulose fibers, Polyethylene fibers, polyacrylonitrile powder, polyamide powder or wood flour. Complementary  on Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, 1998, pages 250 ff., "Fillers," referenced. Further examples of suitable fillers are from the German Patent application DE 196 06 706 A1, column 8, lines 30 to 64, known. Preferably they are used in the quantities specified there.

The pigments and fillers can also be in ultra-fine, non-opaque form.

The proportion of pigments, fillers and leafing to be used according to the invention Pigments on the powder coatings and powder slurries according to the invention can be very broad vary and depends on the requirements of the individual case, in particular the Optical effect to be set and / or the opacity of the used Pigments. The content of pigments, fillers and leafing Pigments at 1.0 to 80, preferably 2.0 to 75, particularly preferably 3.0 to 70, whole particularly preferably 4.0 to 65 and in particular 5.0 to 60% by weight, in each case based on on the powder coating according to the invention or on the solids content of the Powder slurry according to the invention.

The powder coatings and powder slurries according to the invention can in addition to pigments and / or fillers described above or instead of these contain molecularly dispersed organic dyes.

These molecularly dispersed dyes are in the finely divided Dimensionally stable components of the powder coatings according to the invention.

In the powder slurries according to the invention, they can either be in the dispersed finely divided dimensionally stable components or in the continuous phase of Powder slurries according to the invention may be present.

However, they can also be found in the dispersed, finely divided, dimensionally stable constituents and be in the continuous phase. This can be the case in the finely divided dimensionally stable constituents by the main amount,  d. H. deal with more than 50% of the organic dyes used. It can however, less than 50% are located here. The distribution of organic dyes between the phases can correspond to the thermodynamic equilibrium that consists of the solubility of the organic dyes in the phases results. The distribution can but are also far from the thermodynamic equilibrium.

All organic dyes are suitable, which are in the powder coatings and Powder slurries are soluble in the sense described above. Lightfast are well suited organic dyes. Lightfast organic dyes are particularly suitable little or no tendency to migrate. The tendency to migrate the expert can estimate on the basis of his general specialist knowledge and / or with the help simple preliminary tests, for example in the context of tinting tests determine.

The molecular disperse content of the powder coatings and powder slurries according to the invention distributed organic dyes can vary extremely widely and depends on primarily according to the color and hue to be adjusted, as well as the Amount of any pigments and / or fillers present

The powder coatings and powder slurries according to the invention can be physical or be curable thermally and / or with actinic radiation. The thermally curable Powder coatings and powder slurries, in turn, can be self-crosslinking or externally crosslinking his.

In the context of the present invention, the term "physical hardening" means the Hardening a layer of a coating material by filming Solvent release from the coating material, the link within the Coating via loop formation of the polymer molecules of the binders (to which Term cf. Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Binders", pages 73 and 74). Or the film adaptation takes place via the coalescence of binder particles (cf. Römpp Lexikon Lacke and  Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening", pages 274 and 275). No crosslinking agents are usually necessary for this. If necessary physical hardening by atmospheric oxygen, heat or by irradiation with actinic radiation are supported.

In the context of the present invention, the term “self-crosslinking” denotes the Property of a binder to undergo crosslinking reactions with itself. The prerequisite for this is that both types of complementary reactive functional groups are required for crosslinking are necessary. On the other hand, such coating materials Adhesives and sealants referred to, which is a type of complementary reactive functional groups in the binder, and the other type in a hardener or crosslinking agents are present. In addition, Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening", pages 274 to 276, especially page 275, below.

In the context of the present invention, electromagnetic radiation is actinic Radiation, such as near infrared (NIR), visible light, UV radiation or X-rays, especially UV radiation, and corpuscular radiation such as To understand electron radiation.

Pasture thermal and actinic light curing on a powder coating used together, one speaks of "dual cure" and "dual cure powder coating" or "dual-cure powder slurry".

The powder coatings and powder slurries according to the invention contain at least one Binder.

The binders are oligomeric and polymeric resins. Resins are among oligomers understood that contain at least 2 to 15 monomer units in their molecule. in the In the context of the present invention, polymers are understood to be resins which  contain at least 10 recurring monomer units in their molecule. Complementary becomes these terms on Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, »Oligomere«, page 425.

According to the invention, it is advantageous if the minimum film-forming temperature of the binders at least 0 ° C, preferably at least 10, particularly preferably at least 15, entirely is particularly preferably at least 20 and in particular at least 25 ° C. The Minimum film forming temperature can be determined by an aqueous dispersion of the Binder by means of a squeegee on a glass plate or a finely divided Binder powder applied to a glass plate and heated on a gradient oven becomes. The temperature at which the powdery layer films is called Designated minimum film forming temperature. In addition, varnish and varnish are used on Römpp Printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, »Minimum film formation temperature«, page 391.

Examples of suitable binders are statistical, alternating and / or block-like linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated monomers, or polyaddition resins and / or Polycondensation resins. These terms are supplemented by Römpp Lexikon Lacke and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "Polyaddition" and "Polyaddition Resins (Polyadducts)", as well as pages 463 and 464, »Polycondensates«, »Polycondensation« and »Polycondensation Resins«, as well as pages 73 and 74, "Binder".

Examples of suitable (co) polymers are (meth) acrylate (co) polymers or partially saponified polyvinyl esters, especially (meth) acrylate copolymers.

Examples of suitable polyaddition resins and / or polycondensation resins are polyesters, Alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, Polyureas, polyamides, polyimides, polyester-polyurethanes, polyether-polyurethanes or polyester-polyether-polyurethanes, in particular polyester-polyurethanes.  

Of these binders, the (meth) acrylate (co) polymers have particular advantages and are therefore used with particular preference.

The self-crosslinking binders of the thermally curable powder coatings and powder slurries and the dual-cure powder coatings and powder slurries according to the invention contain reactive functional groups with groups of their kind or with complementary reactive functional groups can undergo crosslinking reactions. The externally networking Binders contain reactive functional groups that are reactive with complementary ones functional groups present in crosslinking agents, crosslinking reactions can enter into. Examples of suitable complementary ones to be used according to the invention reactive functional groups are summarized in the following overview. In the In the overview, the variable R stands for an acyclic or cyclic aliphatic, one aromatic and / or an aromatic-aliphatic (araliphatic) radical; the Variables R 'and R "stand for or are the same or different aliphatic radicals linked together to form an aliphatic or heteroaliphatic ring.

Overview

Examples of complementary functional groups

The selection of the respective complementary groups depends on the one hand on the fact that in the manufacture, storage, application and melting of the powder coatings and powder slurries according to the invention no undesirable reactions, in particular no premature crosslinking, and / or possibly hardening not interfere with actinic radiation or inhibit, and secondly afterwards in which temperature range the crosslinking should take place.

Preferred in the powder coatings and powder slurries according to the invention Crosslinking temperatures of 60 to 180 ° C applied. It will therefore be preferred Thio, hydroxyl, N-methylolamino, N-alkoxymethylamino, imino, carbamate, Allophanate and / or carboxyl groups, preferably hydroxyl or carboxyl groups, on the one hand and preferably crosslinking agents with anhydride, carboxyl, epoxy, blocked isocyanate, urethane, methylol, methylol ether, siloxane, carbonate, amino, Hydroxy and / or beta-hydroxyalkylamide groups, preferably epoxy, beta Hydroxyalkylamide, blocked isocyanate, urethane or alkoxymethylamino groups, on the other hand applied.

In the case of self-crosslinking powder coatings and powder slurries according to the invention the binders in particular methylol, methylol ether and / or N Alkoxymethylamino groups.

Complementary reactive functional groups that are particularly well suited for use in the powder coatings and powder slurries according to the invention

• Carboxyl groups on the one hand and epoxy groups and / or beta Hydroxyalkylamide groups on the other hand as well  
• - Hydroxyl groups on the one hand and blocked isocyanate, urethane or Alkoxymethylamino groups, on the other hand.

The functionality of the binders with respect to the reactive described above functional groups can vary very widely and depends in particular on the Networking density that you want to achieve and / or according to the functionality of each applied crosslinking agent. For example, in the case of carboxyl groups Binder the acid number preferably at 10 to 100, preferably 15 to 80, particularly preferably 20 to 75, very particularly preferably 25 to 70 and in particular 30 to 65 mg KOH / g. Or in the case of binders containing hydroxyl groups, the OH number is preferably 15 to 300, preferably 20 to 250, particularly preferably 25 to 200, entirely particularly preferably 30 to 150 and in particular 35 to 120 mg KOH / g. Or in the case epoxy group-containing binders, the epoxy equivalent weight is preferably included 400 to 2,500, preferably 420 to 2,200, particularly preferably 430 to 2,100, very particularly preferably 440 to 2,000 and in particular 440 to 1,900.

The complementary functional groups described above can be according to the usual and known methods of polymer chemistry built into the binder become. This can be done, for example, by the incorporation of monomers which corresponding reactive functional groups, and / or with the help polymer-analogous reactions happen.

Examples of suitable olefinically unsaturated monomers with reactive functional groups are

• 1. Monomers which carry at least one hydroxyl, amino, alkoxymethylamino, carbamate, allophanate or imino group per molecule, such as
  • - Hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-olefinically unsaturated carboxylic acid derived from an alkylene glycol esterified with the acid, or by reacting the alpha, beta-olefinically unsaturated carboxylic acid with an alkylene oxide such as ethylene oxide or propylene oxide are available, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl , 4-Hydroxybutyl acrylate, methacrylate, ethacrylate, crotonate, maleate, fumarate or itaconate; or hydroxycycloalkyl esters such as 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-inden dimethanol or methyl propanediol monoacrylate, monomethacrylate, monoethacrylate, monocrotonate, monomaleinate, monofumarate or monoitaconate; Reaction products from cyclic esters, such as. B. epsilon caprolactone and these hydroxyalkyl or cycloalkyl esters;
  • - olefinically unsaturated alcohols such as allyl alcohol;
  • - Polyols such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether;
  • - Reaction products from acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid with 5 to 18 carbon atoms per molecule branched in the alpha position, in particular one Versatic® acid, or an equivalent amount of acrylic and / or methacrylic acid instead of the reaction product then during or after the polymerization reaction with the glycidyl ester of a monocarboxylic acid branched in the alpha position with 5 to 18 C atoms per molecule, in particular a Versatic® acid, is reacted;
  • - aminoethyl acrylate, aminoethyl methacrylate, allylamine or N-methyliminoethyl acrylate;
  • - N, N-di (methoxymethyl) aminoethyl acrylate or methacrylate or N, N-di (butoxymethyl) aminopropyl acrylate or methacrylate;
  • - (Meth) acrylic acid amides such as (meth) acrylic acid amide, N-methyl, N-methylol, N, N-dimethylol, N-methoxymethyl, N, N-di (methoxymethyl) -, N-ethoxymethyl and / or N, N-Di (ethoxyethyl) - (meth) acrylic acid amide;
  • - Acryloyloxy or methacryloyloxyethyl, propyl or butyl carbamate or allophanate; further examples of suitable monomers which contain carbamate groups are described in the patents US 3,479,328, US 3,674,838, US 4,126,747, US 4,279,833 or US 4,340,497;
• 2. Monomers which carry at least one acid group per molecule, such as
  • - Acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid;
  • - Olefinically unsaturated sulfonic or phosphonic acids or their partial esters;
  • - Maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester or phthalic acid mono (meth) acryloyloxyethyl ester; or
  • - Vinylbenzoic acid (all isomers), alpha-methylvinylbenzoic acid (all isomers) or vinylbenzenesulfonic acid (all isomers).
• 3. monomers containing epoxy groups, such as the glycidyl ester of acrylic acid, Methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or Itaconic acid or allyl glycidyl ether.

They are preferably used for the production of (meth) acrylate copolymers, in particular of glycidyl group-containing used.

Higher functional monomers of the type described above are generally described in minor quantities used. In the context of the present invention are under minor amounts of higher functional monomers to understand such amounts which are not for crosslinking or gelling of the copolymers, in particular the (Meth) acrylate copolymers, unless you specifically want cross-linked polymers Make microparticles.

Examples of suitable monomer units for the introduction of reactive functional groups in Polyesters or polyester polyurethanes are 2,2-dimethylolethyl or propylamine, which with a ketone are blocked, the resulting ketoxime group after incorporation is hydrolyzed again; or compounds containing two hydroxyl groups or two pri mary and / or secondary amino groups and at least one acid group, in particular contain at least one carboxyl group and / or at least one sulfonic acid group, such as dihydroxypropionic acid, dihydroxysuccinic acid, dihydroxybenzoic acid, 2,2-di methylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2- Dimenthylolpentanoic acid, α, δ-diaminovaleric acid, 3,4-diaminobenzoic acid, 2,4- Diaminotoluenesulfonic acid or 2,4-diamino-diphenyl ether sulfonic acid.

An example of the introduction of reactive functional groups via polymer analogues Reactions is the reaction of hydroxyl-containing resins with phosgene, whereby Resins containing chloroformate groups result, and the polymer-analogous reaction the resins containing chloroformate groups with ammonia and / or primary and / or secondary amines to resins containing carbamate groups. Further examples Suitable methods of this type are known from the patents US 4,758,632 A1, US 4,301,257 A1 or US 2,979,514 A1 known.

The binders of the dual-cure powder coatings and powder slurries according to the invention also contain on average at least one, preferably at least  two, group (s) with at least one bond (s) which can be activated with actinic radiation per molecule.

In the context of the present invention, one with actinic radiation activatable bond understood a bond that when irradiated with actinic Radiation becomes reactive and with other activated bonds of its kind Polymerization reactions and / or crosslinking reactions, which are radical and / or ionic mechanisms take place. Examples of suitable bonds are Carbon-hydrogen single bonds or carbon-carbon, carbon Oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon Single bonds or double bonds. Of these, the carbon-carbon Double bonds are particularly advantageous and are therefore entirely according to the invention used particularly preferably. For the sake of brevity, they are referred to below as "Double bonds" called.

Accordingly, the group preferred according to the invention contains one double bond or two, three or four double bonds. More than one double bond can be used the double bonds are conjugated. According to the invention, however, it is advantageous if the Double bonds isolated, in particular each one individually, in the here in question standing group. According to the invention, it is particularly advantageous two especially one to use double bond.

On a statistical average, the dual-cure binder contains at least one of the above described groups which can be activated with actinic radiation. This means that the Functionality of the binder in this regard is an integer, i. i.e., for example is two, three, four, five or more or not an integer, d. i.e., equal to 2.1 to 10.5 or more. Which functionality you choose depends on the Requirements that are placed on the pigmented dual-cure powder slurry.  

On average, more than one group can be activated with actinic radiation applied per molecule, the groups are structurally different from each other or from same structure.

If they are structurally different from one another, this means within the scope of the present one Invention that two, three, four or more, but especially two, with actinic Radiation-activatable groups can be used, which differ from two, three, four or more, but in particular derive two monomer classes.

Examples of suitable groups are (meth) acrylate, ethacrylate, crotonate, cinnamate, Vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, Allyl or butenyl groups; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, Allyl or butenyl ether groups or dicyclopentadienyl, norbornenyl, isoprenyl, Isopropenyl, allyl or butenyl ester groups, but especially acrylate groups.

The groups are preferably via urethane, urea, allophanate, ester, ether and / or amide groups, but in particular via ester groups, to the respective Basic structures of the binders bound. This is usually done by usual and known polymer-analogous reactions such as the reaction of pendant Glycidyl groups with the olefinically unsaturated monomers described above, which contain an acid group, from pendant hydroxyl groups with the Halides of these monomers, containing hydroxyl groups with double bonds Isocyanates such as vinyl isocyanate, methacryloyl isocyanate and / or 1- (1-isocyanato-1- methylethyl) -3- (1-methylethenyl) benzene (TMI® from CYTEC) or from Isocanate groups with the hydroxyl-containing monomers described above.

However, mixtures of purely thermal can also be used in the dual-cure powder coatings curable binders which are curable purely with actinic radiation.

The powder coatings according to the invention which are curable purely with actinic radiation and Powder slurries preferably contain binders curable purely with actinic radiation,  preferably only those described above, with actinic radiation activatable groups included.

The material composition of the binders does not have any special features, but it does come

• - All those in US Pat. No. 4,268,542 A1 or US 5,379,947 A1 and the Patent applications DE 27 10 421 A1, DE 195 40 977 A1, DE 195 18 392 A1, DE 196 17 086 A1, DE 196 13 547 A1, DE 196 18 657 A1, DE 196 52 813 A1, DE 196 17 086 A1, DE 198 14 471 A1, DE 198 35 206 A1, DE 198 41 842 A1 or DE 198 41 408 A1, the not previously published German Patent applications DE 199 08 018.6 or DE 199 08 013.5 or the European one Patent EP 0 652 264 A1 described for use in thermal and / or powder clearcoat slurries curable with actinic radiation Binder,
• - All those in the patent applications DE 198 35 296 A1, DE 197 36 083 A1 or DE 198 41 842 A1 described for use in dual-cure clearcoats provided binder or
• - All those in the German patent application DE 42 22 194 A1, the product Information from the company BASF Lacke + Farben AG, "Pulverlacke", 1990, or the BASF Coatings AG "Powder coatings, powder coatings for industrial Applications ", January, 2000, for use in thermal binder provided for hardenable powder clearcoats

into consideration.

Here, the curable thermally or thermally and with actinic radiation Powder coatings and powder slurries mainly used (meth) acrylate copolymers.  

Examples of suitable (meth) acrylate copolymers are the epoxy group-containing (meth) acrylate copolymers with an epoxy equivalent weight, preferably at 400 to 2,500, preferably 420 to 2,200, particularly preferably 430 to 2,100, very particularly preferably 440 to 2,000 and in particular 440 to 1,900, a number average molecular weight (gel permeation chromatography) determined using a polystyrene standard) of preferably 2,000 to 20,000 and in particular 3,000 to 10,000, and a glass transition temperature (T _G ) of preferably 30 to 80, preferably 40 to 70 and in particular 40 to 60 ° C (measured with the aid of differential scanning calometry ( DSC), as they come into consideration in particular for use in thermally curable powder clearcoat slurries (see above) and as they are also described in the patents and patent applications EP 0 299 420 A1, DE 22 14 650 B1, DE 27 49 576 B1, US 4,091,048 A1 or US 3,781,379 A1.

As an additional binder for the dual-cure powder coatings and powder slurries or as that sole binder for the powder coatings and curable purely with actinic radiation Powder slurries are used in the European patent applications EP 0 928 800 A1, EP 0 636 669 A1, EP 0 410 242 A1, EP 0 783 534 A1, EP 0 650 978 A1, EP 0 650 979 A1, EP 0 650 985 A1, EP 0 540 884 A1, EP 0 568 967 A1, EP 0 054 505 A1 or EP 0 002 866 A1, German patent applications DE 197 09 467 A1, DE 42 03 278 A1, DE 33 16 593 A1, DE 38 36 370 A1, DE 24 36 186 A1 or DE 20 03 579 B1 international patent applications WO 97/46549 or WO 99/14254 or den American patents US 5,824,373 A1, US 4,675,234 A1, US 4,634,602 A1, 4,424,252 A1, US 4,208,313 A1, US 4,163,810 A1, US 4,129,488 A1, US 4,064,161 A1 or US 3,974,303 A1, for use in UV-curable clearcoats and Binder provided for powder clearcoats.

The production of the binders also has no special methodological features, but is done using the usual and known methods of polymer chemistry, such as they are described in detail, for example, in the patents listed above become.  

Further examples of suitable production processes for (meth) acrylate copolymers are described in European patent applications or EP 0 767 185 A1, German patents DE 22 14 650 B1 or DE 27 49 576 B1 and the American patents US 4,091,048 A1, US 3,781,379 A1, US 5,480,493 A1, US 5,475,073 A1 or US 5,534,598 A1 or in the standard work Houben-Weyl, Methods of Organic Chemie, 4th edition, volume 14/1, pages 24 to 255, 1961. As reactors for the copolymerization comes the usual and well-known stirred kettles, Stirred tank cascades, tubular reactors, loop reactors or Taylor reactors, such as them for example in the patent specifications and patent applications DE 10 71 241 B1, EP 0 498 583 A1 or DE 198 28 742 A1 or in the article by K. Kataoka in Chemical Engineering Science, Volume 50, No. 9, 1995, pages 1409 to 1416, in Consideration.

The production of polyesters and alkyd resins, for example, is still in the Standard Work Ullmann's Encyclopedia of Technical Chemistry, 3rd Edition, Volume 14, Urban & Schwarzenberg, Munich, Berlin, 1963, pages 80 to 89 and pages 99 to 105, as well as in the books: "Résines Alkydes-Polyesters" by J. Bourry, Paris, Dunod Verlag, 1952, "Alkyd Resins" by C. R. Martens, Reinhold Publishing Corporation, New York, 1961, and "Alkyd Resin Technology" by T. C. Patton, Intersience Publishers, 1962, described.

The production of polyurethanes and / or acrylated polyurethanes is used, for example still in the patent applications EP 0 708 788 A1, DE 44 01 544 A1 or DE 195 34 361 A1 described.

The content of the powder coating materials according to the invention or the disperse phase of the Powder slurries according to the invention on binders can vary and vary very widely depends primarily on whether they are physical or thermal and / or actinic Radiation can be hardened in a self-crosslinking manner. In these cases it can preferably be 20 to 99.9 preferably 25 to 99.7, particularly preferably 30 to 99.5, very particularly preferably 35 to 99.3 and in particular 40 to 99.1% by weight, in each case based on the solids content of the  pigmented powder slurry. In the other cases (thermal and / or with actinic radiation, cross-linkable curable) the binder content is preferably at 10 to 80, preferably 15 to 75, particularly preferably 20 to 70, very particularly preferably 25 to 65 and in particular 30 to 60% by weight, in each case based on the powder coating according to the invention or the solids content of the invention Powder slurry.

The externally cross-linking curable thermally or thermally and with actinic radiation Powder coatings and powder slurries according to the invention contain at least one Crosslinking agent, which is the reactive functional groups of the binder contains complementary reactive functional groups. The expert can therefore suitable for a given powder coating or powder slurry Select crosslinking agent easily.

Examples of suitable crosslinking agents are

• - Aminoplast resins, such as those found in Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, 1998, page 29, »Aminoharze«, the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, Pages 242 ff., The book "Paints, Coatings and Solvents", second completely revised edition, Edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 ff., The patents US 4,710,542 A1 or EP 0 245 700 A1 as well as in the article by B. Singh and co-workers "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry ", in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193 to 207, to be discribed,
• - Compounds or resins containing carboxyl groups, as described, for example, in the patent specification DE 196 52 813 A1 or 198 41 408 A1 are described, especially dodecanedioic acid,  
• - Epoxy group-containing compounds or resins, such as those in the Patent specifications EP 0 299 420 A1, DE 22 14 650 B1, DE 27 49 576 B1, US 4,091,048 A1 or US 3,781,379 A1,
• Blocked polyisocyanates, as described, for example, in US Pat. No. 4,444,954 A1, DE 196 17 086 A1, DE 196 31 269 A1, EP 0 004 571 A1 or EP 0 582 051 A1 to be discribed,
• - Beta-hydroxyalkylamides such as N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide or N, N, N ', N'-tetrakis (2-hydroxypropyl) adipamide and / or
• Tris (alkoxycarbonylamino) triazines, as described in US Pat. No. 4,939,213 A1, US 5,084,541 A1, US 5,288,865 A1 or EP 0 604 922 A1 become.

The content of the powder coatings and powder slurries according to the invention Crosslinking agents can also vary very widely and depend on the Requirements of the individual case, especially according to the number of available reactive functional groups. It is preferably 1.0 to 40, preferably 2.0 to 35, particularly preferably 3.0 to 30, very particularly preferably 4.0 to 27 and in particular 5.0 up to 25 wt .-%, each based on the powder coating according to the invention or Solids content of the powder slurry according to the invention.

In addition to the leafing pigments and binders described above, as well optionally the pigments, fillers, dyes and / or described above The powder coatings and powder slurries according to the invention can also crosslink contain at least one additive. Depending on its physical nature chemical properties and / or its function essentially in the solid finely divided constituents of the powder coatings and powder slurries according to the invention or in In the case of the powder slurries according to the invention essentially in the continuous phase available.  

Examples of suitable additives are

• - Thermally curable reactive diluents such as positionally isomeric diethyloctanediols or Hyperbranched compounds containing hydroxyl groups or dendrimers such as they are described in German patent application DE 198 50 243 A1;
• - reactive diluents curable with actinic radiation, such as those in Römpp Lexikon Varnishes and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998 Page 491 under the keyword »reactive thinners«;
• - Crosslinking catalysts such as dibutyltin dilaurate, lithium decanoate or Zinc octoate, quaternary organic sulfonic acids blocked with amines Ammonium compounds, amines, imidazole and imidazole derivatives such as 2- Styrylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole and 2- Butylimidazole, as described in Belgian Patent No. 756,693, or phosphonium catalysts such as ethyltriphenylphosphonium iodide, Ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium thiocyanate, Ethyl triphenylphosphonium acetate-acetic acid complex, Tetrabutylphosphonium iodide, tetrabutylphosphonium bromide and tetrabutyl phosphonium acetate-acetic acid complex, as used, for example, in the US Patents US 3,477,990 A1 or US 3,341,580 A1 are described;
• - Thermolabile free radical initiators such as organic peroxides, organic Azo compounds or C-C-cleaving initiators such as dialkyl peroxides, Peroxocarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides, Ketone peroxides, azodinitriles or benzpinacol silyl ether;
• - Photoinitiators, as extended and expanded in Römpp Chemie Lexikon, 9th revised edition, Georg Thieme Verlag Stuttgart, Vol. 4, 1991, or in  Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag Stuttgart, 1998, Pages 444 to 446;
• - Antioxidants such as hydrazines and phosphorus compounds;
• - UV absorbers such as triazines and benzotriphenol;
• - Light stabilizers such as HALS compounds, benzotriazoles or oxalanilides;
• - leveling agent;
• - radical scavengers and polymerization inhibitors such as organic phosphites or 2,6 Di-tert-butylphenol derivatives;
• - slip additives;
• - defoamer;
• - Emulsifiers, especially non-ionic emulsifiers such as alkoxylated alkanols and polyols, phenols and alkylphenols, anionic emulsifiers such as alkali salts or ammonium salts of alkane carboxylic acids, alkane sulfonic acids and sulfonic acids of alkoxylated alkanols and polyols, phenols and alkylphenols;
• Wetting agents such as siloxanes, fluorine-containing compounds, carboxylic acid semiesters, Phosphoric acid esters, polyacrylic acids and their copolymers or polyurethanes, such as see for example in detail in patent application DE 198 35 296 A1 be described, particularly in connection with the following associative polyurethane-based thickeners described;
• - adhesion promoters such as tricyclodecane dimethanol;  
• - film-forming aids such as cellulose derivatives;
• - flame retardants;
• - venting agents such as diazadicycloundecane or benzoin;
• - water retention agent;
• - flow aids
• Rheology-controlling additives (thickeners), such as those from the patent specifications WO 94/22968, EP 0 276 501 A1, EP 0 249 201 A1 or WO 97/12945; crosslinked polymeric microparticles, as described, for example, in EP 0 008 127 A1 are disclosed; inorganic layered silicates such as aluminum-magnesium silicates, Sodium-magnesium and sodium-magnesium-fluorine-lithium layered silicates of the Montmorillonite type; Silicas such as aerosils; or synthetic polymers with ionic and / or associative groups such as polyvinyl alcohol, Poly (meth) acrylamide, poly (meth) acrylic acid, polyvinylpyrrolidone, Styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives or polyacrylates; or associative thickeners Polyurethane base, as used in Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Thickener", pages 599 to 600, and in the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 51 to 59 and 65; especially combinations of ionic and non-ionic thickeners, such as them in patent application DE 198 41 842 A1 for setting a pseudoplastic Behavior, or the combination of associative thickeners based on polyurethane and wetting agents based on polyurethane, as in the German patent application DE 198 35 296 A1 is described in detail.

Further examples of suitable additives are given in the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998. You will be in the usual and known amounts applied.

The production of the powder coatings according to the invention has no methodological Special features, but takes place, as in the product information from BASF Lacke + Farben AG, "Pulverlacke", 1990, or the company name of BASF Coatings AG "Powder coatings, powder coatings for industrial applications", January 2000 Homogenize and disperse, for example using an extruder or Screw kneader, and grinding the components described above. To The powder coatings according to the invention are produced by further grinding and if necessary by sifting and sieving for application or for dispersion to Prepared for the production of the powder slurries according to the invention.

The production of the powder slurries according to the invention also has no methodological features Peculiarities, but takes place according to customary and known methods.

In a first preferred variant, the production of the invention takes place Powder slurries from the ingredients described above essentially as in the Patent applications DE 195 40 977 A1, DE 195 18 392 A1, DE 196 17 086 A1, DE-A-196 13 547, DE 196 18 657 A1, DE 196 52 813 A1, DE 196 17 086 A1, DE-A-198 14 471 A1, DE 198 41 842 A1 or DE 198 41 408 A1 described in detail, only that in Leafing pigments can also be processed within the scope of the present invention. Here, the powder coating according to the invention is by wet grinding or by Stir dry ground powder coating in water or an aqueous medium transferred the powder slurry according to the invention. The is particularly preferred Wet grinding.

In a further preferred variant of the production of the invention Powder slurries are the ingredients described above in an organic Solvent emulsifies, resulting in an oil-in-water type emulsion, hereafter  the organic solvent is removed, causing the emulsified droplets solidify and the powder slurry according to the invention results. Possibly. can she still be wet milled to improve filterability.

In a third preferred variant of the production of the powder slurries according to the invention a liquid melt of the components described above together with the preferably not melted leafing pigments into an emulsifying device given with the addition of water and stabilizers, the resulting emulsion cooled and filtered, resulting in the powder slurry of the invention. To ensure a high level of mixing achieve, it is essential to carry out the mixture solvent-free in the melt. Accordingly, the polymeric components are melted into the viscous resin Dispersing units fed.

The powder coatings and powder slurries according to the invention are used to produce the basecoats of the inventive effect paint Multi-layer coatings on a substrate.

The multi-layer paint effect according to the invention is mainly in the Automotive painting, painting of buildings indoors and outdoors, the Painting of furniture, doors and windows and industrial painting, inclusive Coil coating and container coating are used, all based on these technical Fields of common and known substrates made of metal, plastic, glass, wood, textile, Leather, natural and artificial stone, concrete, cement or composites of these materials in Consider, the electrically conductive substrates are preferred.

The effect-giving multilayer coating according to the invention can preferably be produced by placing on a substrate

• 1. a filler on a cathodically deposited and thermally hardened Electrocoating or wet-on-wet on a cathodically deposited, not or only partially hardened electrocoat layer applied, after which  
• 2. the resulting filler layer alone thermally or thermally and with actinic radiation or thermal together with the electrocoat or cures thermally and with actinic radiation, causing the filler paint or stone chip protection primer results,
• 3. the powder coating according to the invention or the powder slurry according to the invention on the Filler paint or stone chip protection primer applied, whereby a Powder coating layer or powder slurry layer results,
• 4. the powder coating layer or powder slurry layer without completely crosslinking it, flashes off or dries, or - alternatively - physically or thermally and / or cures with actinic radiation, which results in the basecoat,
• 5. at least one clear coat on the powder coating layer or powder slurry layer or - alternatively - applied to the basecoat, after which
• 6. the powder coating layer or powder slurry layer and the clear coating layer (s) cures together thermally and / or with actinic radiation, or - alternatively - the clearcoat layer by itself thermally and / or with actinic radiation hardens resulting in the basecoat and clearcoat.

Examples of suitable cathodic electrocoating materials and, if appropriate, wet-on-wet processes are disclosed in Japanese Patent Application 1975-142501 (Japanese Patent Laid-Open JP 52-065534 A2, Chemical Abstracts Unit No. 87: 137427) or the patents US 4,375,498 A1, US 4,537,926 A1, US 4,761,212 A1, EP 0 529 335 A1, DE 41 25 459 A1, EP 0 595 186 A1, EP 0 074 634 A1, EP 0 505 445 A1, DE 42 35 778 A1, EP 0 646 420 A1, EP 0 639 660 A1, EP 0 817 648 A1, DE 195 12 017 C1, EP 0 192 113 A2, DE 41 26 476 A1 or WO 98/07794.  

Examples of suitable fillers, especially aqueous fillers, which are also known as Stone chip protection primers or functional layers are described in the patents US 4,537,926 A1, EP 0 529 335 A1, EP 0 595 186 A1, EP 0 639 660 A1, DE 44 38 504 A1, DE 43 37 961 A1, WO 89/10387, US 4,450,200 A1, US 4,614,683 A1 or WO 490/26827.

All customary and known clearcoats come into consideration as clearcoats.

Examples of suitable clear coats are:

• - thermally curable one-component (1K) -, two-component (2K) - or Multi-component (3K, 4K) clearcoat materials, as described in German patent application DE 42 04 518 A1, European patent applications EP 0 594 068 A1, EP 0 594 071 A1, EP 0 594 142 A1, EP 0 604 992 A1 or EP 0 596 460 A1 den international patent applications WO 94/10211, WO 94/10212, WO 94/10213, WO 94/22969 or WO 92/22615 or the American patents US 5,474,811 A1, US 5,356,669 A1 or US 5,605,965 A1;
• - Thermally curable powder clearcoats, such as those from the German Patent application DE 42 22 194 A1 or the product information from BASF Lacke + Farben AG, "Powder coatings", 1990 are known;
• - Powder slurry clear coats curable thermally and / or with actinic radiation, such as for example in US Pat. No. 4,268,542 A1 or US 5,379,947 A1 and the patent applications DE 27 10 421 A1, DE 195 40 977 A1, DE 19 51 8 392 A1, DE 196 17 086 A1, DE 196 13 547 A1, DE 196 18 657 A1, DE 196 18 657 A1, DE 196 52 813 A1, DE 196 17 086 A1, DE 198 14 471 A1, DE 198 41 842 A1 or DE 198 41 408 A1 or the unpublished German patent applications DE 199 08 018.6 or DE 199 08 013.5 can be described; or  
• - UV-curable clear coats and powder clear coats, such as those from the European patent applications EP 0 928 800 A1, EP 0 636 669 A1, EP 0 410 242 A1, EP 0 783 534 A1, EP 0 650 978 A1, EP 0 650 979 A1, EP 0 650 985 A1, EP 0 540 884 A1, EP 0 568 967 A1, EP 0 054 505 A1 or EP 0 002 866 A1, German patent applications DE 197 09 467 A1, DE 42 03 278 A1, 33 16 593 A1, DE 38 36 370 A1, DE 24 36 186 A1 or DE 20 03 579 B1 international patent applications WO 97/46549 or WO 99/14254 or den American patents US 5,824,373 A1, US 4,675,234 A1, US 4,634,602 A1, 4,424,252 A1, US 4,208,313 A1, US 4,163,810 A1, US 4,129,488 A1, US 4,064,161 A1 or US 3,974,303 A1 emerge. Furthermore are Powder coatings known that are crosslinked thermally and with actinic radiation can (see European patent application EP 0 844 286 A1).

The resulting clear coats can still have a scratch-resistant coating an organically modified ceramic material, such as that available under the brand ORMOCER® is commercially available.

In general, the coating materials to be used according to the invention are in one Applied wet film thickness that after their curing, coatings with the for their Functions necessary and advantageous layer thicknesses result. In case of Electrodeposition, they are 5 to 40, preferably 10 to 35, particularly preferably 12 to 30 and in particular 15 to 25 μm, in the case of filler coating, Stone chip protection primer or functional layer, they are 10 to 60, preferably 12 to 55, particularly preferably 15 to 50 and in particular 18 to 45 μm, in the case of Basecoat they are 5 to 50, preferably 5 to 40, particularly preferably 5 to 30 and in particular 10 to 25 microns, and in the case of a clear coat they are 10 to 100, preferably 15 to 80, particularly preferably 20 to 75 and in particular 25 to 70 μm. However, the functional layer can only in the multi-layer coating according to the invention a layer thickness of 20 to 50% of the total layer thickness of the functional layer and Have basecoat.  

In addition, the powder slurries according to the invention are also used for production the combination effect layers according to the invention.

In the context of the present invention, this should be understood to mean coatings which are in an effect-giving multi-layer coating fulfills at least two functions. Functions of this type are in particular protection against corrosion, the provision of adhesion, the absorption of mechanical energy and the effect. According to the invention Combination effect layer especially the absorption of mechanical energy as well as the Effects at the same time; it therefore fulfills the functions of a filler paint or Stone chip protection primer and a base coat. Preferably, the Combination effect layer also corrosion protection effect and / or adhesion promoting effect.

The thickness of the combination effect layer is within a given effect multilayer coating according to the invention preferably constant. In In some cases, however, it may be advisable to adjust the thickness in the areas of the substrate, less exposed to mechanical action and / or less or not at all are not visible to make thinner to save material.

Of course, the thickness of the combination effect layer of the invention multi-layer effect paint to effect paint according to the invention Vary the multi-layer paint very widely. This is aimed at the respective In some cases, optimal thickness, especially according to the opacity of the used Pigments (see Römpp Lexicon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 124, "Opacity"), the ability to apply mechanical energy absorb or dissipate; the ability to remove the unevenness of the substrate surface to compensate, and / or the other constituents of the powder slurry used in each case. The person skilled in the art can therefore determine the optimum thickness based on his general specialist knowledge, if necessary. with the help of simple preliminary tests. Preferably, the Thickness of the combination effect layer at 10 to 100, preferably 15 to 90, particularly  preferably 20 to 80, very particularly preferably 25 to 70 and in particular 30 to 60 μm, each based on the shift.

To produce the combination effect layer essential to the invention, according to inventive methods the inventive described above Powder slurries on the primed and unprimed substrates described above applied.

The powder slurries according to the invention also come for use outside automotive painting, but its main technical Intended use in the area mentioned, because here their special advantages entirely be particularly open. The substrates are therefore Motor vehicle bodies, in particular car bodies, and parts thereof, such as For example doors, bonnets, fenders, trunk lids, spoilers, sills or Wind deflector.

These consist in particular of steel or aluminum. The metal surfaces can have primers. For example, in the case of aluminum act an oxide layer generated by anodic oxidation (Eloxal® process). in the In the case of steel, it is usually a cathodically deposited and thermally hardened electrocoating. But it can also be a cathodic deposited electrocoat that is not thermally hardened, but only dried or partially hardened.

The electrocoating or electrocoating is then carried out with the Powder slurry according to the invention overlays, either alone or is cured together with the electrocoat layer (wet-on-wet process).

The resulting combination effect layer according to the invention can be combined with at least one additional paint can be coated. These are preferably at least one of the clearcoats described above. This will result  particularly advantageous multi-layer coatings with effect according to the invention an excellent overall visual impression and a particularly high one Scratch resistance.

When coating the combination effect layer with a clear lacquer, the cured combination effect layer with at least one clear lacquer layer are overlaid, after which it is hardened on its own.

In a second variant, which is preferred according to the invention, it cannot or only partially cured pigmented powder slurry layer directly with at least one Clear coat are overcoated, after which the clear coat (s) together with the pigmented powder slurry layer and, if necessary, the electrocoat layer cured is (wet-on-wet method).

The powder slurries according to the invention can be used with those from liquid coating technology apply known methods. In particular, they can be sprayed be applied. They are preferably coated by electrostatic painting Exterior parts of the body, followed by pneumatic spraying (compressed air spraying) Body parts applied.

The electrostatic painting can be done using an electrostatic spray gap, an electrostatic spray bell or an electrostatic spray disc.

Furthermore, the electrostatic painting can be supported by electrostatics mechanical atomization. This is preferably done using electrostatic high-speed rotating discs or high-speed rotating bells.

Pneumatic spraying or compressed air painting also shows no methodological Peculiarities, but can be done by hand or with the help of usual and known Painting machines or robots:  

In addition to this, Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 186: »Electrostatic painting«, page 187: »Electrostatic spray guns«, »Electrostatic spraying«, and page 165: "Pneumatic spraying," referenced.

Application when illuminated with visible light of one wavelength is preferred of over 550 microns or in the dark when the pigmented Powder slurries are curable thermally and with actinic radiation. This will create a material change or damage to be used according to the invention Avoid coating material and overspray.

Of course, these application methods can also apply additional layers of varnish, preferably clear varnish layers, may be used, provided that are not powder coatings, in particular powder clearcoats and / or Powder coatings according to the invention, which is preferably according to the in. Product- Information from the company BASF Lacke + Farben AG, "Pulverlacke", 1990 or the BASF Coatings AG "Powder coatings, powder coatings for industrial Applications ", January 2000, processes described.

The hardening of the applied electrocoat layers, filler layers, Basecoat layers, combination effect layers and clear lacquer layers have none methodological peculiarities, but carried out with the help of the usual and known Methods and devices.

When it comes to physical hardening, no special measures are required be taken; however, physical hardening can be caused by atmospheric oxygen, heat or supported by exposure to actinic radiation.

Thermal curing can take place after a certain rest period or flash-off time. she can last from 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to Have 45 min. The rest period is used, for example, for the course and for degassing the  Layers and for evaporation of volatile constituents such as, if necessary existing solvent and / or water. The ventilation can be increased by an Temperature that is not yet sufficient for hardening and / or through a reduced one Humidity can be accelerated.

Thermal curing takes place, for example, by heating in a forced air oven or Irradiate with IR and / or NIR lamps. As with curing with actinic radiation thermal curing can also be carried out in stages. This is advantageously carried out thermal curing at temperatures from 100 to 180 ° C.

When curing with actinic radiation, a dose of 1,000 to 3,000, preferably 1,100 to 2,900, particularly preferably 1,200 to 2,800, very particularly preferably 1,300 to 2,700 and in particular 1,400 to 2,600 mJ / cm ^{2 is} preferably used. If necessary, this hardening can be supplemented with actinic radiation from other radiation sources. In the case of electron beams, work is preferably carried out under an inert gas atmosphere. This can be ensured, for example, by supplying carbon dioxide and / or nitrogen directly to the surface of the powder slurry layer. In the case of curing with UV radiation, too, it is possible to work under inert gas in order to avoid the formation of ozone.

For curing with actinic radiation, the usual and well-known Radiation sources and optical auxiliary measures applied. Examples of more suitable Radiation sources are flash lamps from VISIT, high-pressure mercury or low-pressure vapor lamps, which are optionally doped with lead, around a Open beam window up to 405 nm, or electron beam sources. Their arrangement is known in principle and can the conditions of the workpiece and the Process parameters are adjusted. In the case of workpieces of complex shape, such as that Are intended for automotive bodies, which can not direct radiation accessible areas (shadow areas) such as cavities, folds and others design-related undercuts with point, small area or  All-round spotlights connected to an automatic movement device for the Irradiation of cavities or edges, (partially) cured.

The facilities and conditions of these hardening methods are described, for example, in R. Holmes, U. V. and E. B. Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kindom 1984.

The curing can take place in stages, i. H. by multiple exposure or Irradiation with actinic radiation. This can also take place alternately, i. that is alternately cured with UV radiation and electron radiation.

With Dual Cure, thermal curing and curing with actinic radiation can be used simultaneously or in succession. Will the two hardening methods used sequentially, for example, thermal curing can begin and end with curing with actinic radiation. In other cases, it can prove advantageous to start with actinic radiation and hereby to end.

Overall, the methods according to the invention offer for the production of the inventive ones effect-giving multi-layer coatings that are particularly ecological and economical advantageous and significant possibility not only paint on a purely aqueous basis without emitting volatile organic substances, but also with one reduced number of layers. If the appropriate solvent-free clear coats applied, this also applies to the effect donors according to the invention Multicoat paint systems that contain at least one clear coat.

The effect donors according to the invention obtained in the procedure according to the invention Multi-layer coatings are characterized by very good adhesion to the substrate, a very good interlayer adhesion, an excellent corrosion protection effect, a very good protection against stone chips and other mechanical damage, one very good course and a very good overall visual impression, especially what  Color depth, metallic effect, dichroic effect and D.O.I. (Distinctiveness of the reflected image) concerns, from.

The correspondingly coated bodies according to the invention therefore convey one particularly high aesthetic overall impression and have a particularly long Service life.

Examples Examples 1 and 2 The production of multi-layer paints according to the invention with Powder slurries according to the invention

For Examples 1 to 2, as in German patent application DE 196 13 547 A1 described, first a powder coating of 77.4 parts by weight of a Methacrylate copolymer made from methyl methacrylate, glydidyl methacrylate, n-butyl acrylate and styrene, 19.4 parts by weight of dodecanedioic acid, 2 parts by weight of a commercially available UV absorber (Ciba® CGL 1545), 1 part by weight of the commercially available light stabilizer Tinuvin® 123 and 0.25 part by weight of the commercially available antioxidant Irgafos® PEPQ manufactured.

This powder coating was prepared in accordance with the German patent application DE 196 18 657 A1, Column 6, specified experimental procedure dispersed in water, so that a pigmented Powder slurry resulted.

Table 1 gives an overview of the type and amount of the used Components.

Table 1

The production of powder slurries according to the invention (Examples 1 to 2)

Steel panels (body panels), with a usual and known cathodic deposited and baked electrocoating were coated with the pigmented powder slurries with the help of a conventional and known spray gun manually coated (pressure: 5 bar; 2 spray passes, horizontal and vertical). The Wet layer thicknesses were chosen so that layer thicknesses of 40 µm resulted. The pigmented powder slurry layers were added during 10 min Flashed off 50 ° C and with a commercially available conventional Two-component clear coat from BASF Coatings AG overlaid. The resulting Clear lacquer layers were flashed off for 10 min, after which the pigmented Powder slurry layers and the clear lacquer layers baked at 150 ° C. for 30 minutes were. The thickness of the clearcoats was 50 µm.

The resulting coatings of Examples 1 and 2 were excellent Opacity. Their respective metallic effect and flip-flop corresponded in full Scope corresponding to those pigmented basecoats. Liability on the Primer and the interlayer adhesion as well as the stone chip protection effect were  very good even after weathering in a condensation constant climate (SKK). Disturbances in Course, cooker, crack formation (mud cracking) or surface structures such as No orange peel skin was observed.

Examples 3 and 4 The production of multi-layer paints according to the invention with With the help of powder coatings according to the invention

For examples 3 and 4, the powder coating was prepared according to examples 1 and 2, only 5.5 parts by weight of a leafing aluminum pigment was added. At Example 3 was CHROMAL X and in Example 4 PC 100 from Eckart was used.

For this purpose, the constituents of the powder coating listed in Examples 1 and 2 were used and the leafing aluminum pigments are weighed out. The batch size was 5.0 kg. The respective ingredients were in a Henschel fluid mixer for two minutes homogenized at 2,800 rpm. The resulting mixtures were after the Premixed into an extruder using a funnel (BUSS PR 46). The The extruder was started up with a jacket temperature of 110 ° C., and the speed was reduced chosen so that the jacket temperature was kept at 60 ° C. The emerging extrudate was cooled to 20 ° C with a chill roll and crushed into chips with a crusher. The Chips were pre-cut and ground in a pin mill. The resulting powder was sieved with a tumbler sieve over 125 µm.

The powder coatings of Examples 3 and 4 were each applied using a Laboratory handgun with corona charging type Wagner ESB in a layer thickness of 40 to 50 microns on steel plates, with a usual and known cathodic deposited and baked electrodeposition coating and a usual and known rockfall protection primer were coated. The resulting Powder coating layers were baked at 160-180 ° C for 10-25 minutes.  

The basecoats thus obtained were treated with a commercially available Two-component clearcoat overlaid, after which the resulting clearcoat layers were cured at 60 ° C.

The effect-giving multi-layer coatings showed a very good flow and overall optical impression. Overall, the same benefits were obtained as with the multi-layer coatings of Examples 1 and 2.

Claims (16)

1. Powder coatings and powder coating dispersions (powder slurries) containing at least one Leafing pigment. 2. Powder coatings and powder slurries according to claim 1, characterized in that they contain a leafing metallic effect pigment as the leafing pigment. 3. Powder coatings and powder slurries according to claim 2, characterized in that they contain a leafing aluminum pigment as the leafing metal effect pigment. 4. Powder coatings and powder slurries according to one of claims 1 to 3, characterized characterized in that they contain at least one saturated fatty acid or a polysiloxane contain. 5. Powder coatings and powder slurries according to one of claims 1 to 4, characterized characterized in that the leafing effect pigments by grinding Effect pigments in the presence of at least one saturated fatty acid or at least one polysiloxane, in particular a saturated fatty acid, can be prepared are. 6. powder coatings and powder slurries according to claim 4 or 5, characterized in that it is a saturated fatty acid with 8 to 30 carbon atoms in the Contain molecule. 7. Powder coatings and powder slurries according to one of claims 4 to 6, characterized characterized in that they are saturated fatty acids n-octanoic acid, n-nonanoic acid, n- Decanoic acid, n-undecanoic acid, n-dodecanoic acid (lauric acid), n-tridecanoic acid, Myristic acid, n-pentadecanoic acid, palmitic acid, n-heptadecanoic acid  Margaric acid), stearic acid, n-nonadecanoic acid, n-eiconsanoic acid or n- Contain hexacosanoic acid. 8. Powder coatings and powder slurries according to claim 8, characterized in that they contain stearic acid as fatty acid. 9. powder coatings and powder slurries according to any one of claims 1 to 8, characterized characterized in that they are physical, thermal or thermal and with actinic Radiation (dual cure) are curable. 10. Powder coatings and powder slurries according to one of claims 1 to 9, characterized characterized in that they are free from organic solvents. 11. Powder coatings and powder slurries according to one of claims 1 to 10, characterized characterized in that the total amount in the powder coatings and powder slurries the leafing effect pigments in the powder coating particles, as a separate solid phase or partly in the powder coating particles and partly as a separate solid phase. 12. Powder slurries according to one of claims 1 to 11, characterized in that they are structurally viscous. 13. Use of the powder coatings according to one of claims 1 to 11 and Powder slurries according to one of claims 1 to 12 for the production of Basecoats or combination effect layers in effect Multi-layer paintwork. 14. Effect-giving multi-layer coating with a combination effect layer, producible by adding a powder slurry according to any one of claims 1 to 12 a cathodically deposited and thermally hardened electrodeposition coating or wet-on-wet on a cathodically deposited, not or only partially hardened Applied electrocoat, after which the resulting powder slurry layer for  itself physically or thermally and / or with actinic radiation or together with the electrocoat layer thermally or thermally and with actinic radiation is cured, causing the combination effect layer results. 15. Effect-giving multi-layer coating according to claim 14, characterized in that either the powder slurry layer or the combination effect layer is covered with at least one clear lacquer, after which the resulting clear lacquer layer

• 1. for themselves thermally and / or with actinic radiation,
• 2. together with the powder slurry layer thermally and / or with actinic radiation or
• 3. together with the electrocoat layer and the powder slurry layer thermally or thermally and with actinic radiation

is hardened. 16. Effect multi-layer coating with a basecoat, can be produced by

• 1. a filler is applied to a cathodically deposited and thermally hardened electrodeposition coating or wet-on-wet to a cathodically deposited, not or only partially hardened electrodeposition coating, after which
• 2. the resulting filler layer hardens itself thermally or thermally and with actinic radiation or together with the electrocoat layer thermally or thermally and with actinic radiation, resulting in the filler coating or stone chip protection primer,
• 3. applied a powder coating or powder slurry to the filler coating or stone chip protection primer, resulting in a powder coating layer or powder slurry layer,
• 4. the powder coating layer or powder slurry layer, without completely crosslinking, flashes off or dries, or - alternatively - it hardens physically or thermally and / or with actinic radiation, resulting in the basecoat,
• 5. at least one clear coat on the powder coating layer or powder slurry layer or - alternatively - applied to the basecoat, after which
• 6. the powder coating layer or powder slurry layer and the clear coating layer (s) cure together thermally and / or with actinic radiation, or - alternatively - the clear coating layer cures itself thermally and / or with actinic radiation, resulting in the basecoat and the clearcoat,

characterized in that a powder coating according to one of claims 1 to 11 or a powder slurry according to one of claims 1 to 12 is used.