DE10027294A1 - Powder paint dispersions, useful for the production of effect forming multi-layer coatings are prepared by the addition of an effect pigment made into a paste using a neotenside. - Google Patents

Abstract

Effect forming powder paints or powder paint dispersions (slurry) (I) are prepared by the addition of at least one effect pigment to the powder paint, slurry and/or at least one precursor to the paint or slurry whereby the effect pigment is made into a paste with a neotenside.

Description

The present invention relates to a novel process for the preparation of effect powder coatings and powder coating dispersions (powder slurries). Furthermore The present invention relates to the use of the resulting powder coatings and Powder slurries for the production of effect-based basecoats or Combination effect layers in effect multicoat paint systems.

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

For example, one after the other an electrically deposited electrocoating (ETL) as a primer, a primer coat or antiscratch primer, a Basecoat and a clearcoat applied to a substrate. This serves the ETL in particular the corrosion protection of the sheet. It is frequently used by experts also referred to as a primer. The primer coat is used to cover Unevenness of the ground and grant due to their elasticity the Chip resistance. If necessary, the surfacer coat can still be used for reinforcement the hiding power and to deepen the color of the paint. The Basecoating adds color and / or visual effects. The clearcoat It enhances the visual effects and protects the paintwork mechanical and chemical damage. Basecoat and clearcoat often referred to collectively as topcoat. In addition, it will still open Rompp Lexikon 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, the amount of in the Significantly reduce the amount of organic solvents released if not zero. Corresponding lacquers, such as ETL, aqueous fillers or aqueous clearcoats, powder coatings or powder slurry clearcoats are available. However, the disadvantage is still that for the basecoat still non-aqueous, d. H. Conventional, basecoats or aqueous basecoats with a comparatively high  Proportion of organic solvents must be used to make the pigments stable to disperse and to ensure a good course of the applied layers.

In addition, in the joint application of the paints, in particular the Basecoats and clearcoats, as part of the production of a color and / or effect Paint their properties are very finely tuned to each other For example, a collapse of the uncured layers in the application of Wet-on-wet process to avoid and / or cracking, the formation of cookers and / or to prevent the delamination of layers.

It would therefore be desirable to use the customary and known basecoats and Water-based paints by solvent-free powder coatings and powder slurries, the effect pigments (see Rompp Lexikon Lacke and printing inks, Georg Thieme Verlag, 1998, pages 176, "Effect pigments" and pages 380 and 381 "Metal oxide mica pigments" to "Metal pigments") included to replace. Initial approaches to this are already in place.

Coatings' partner, The magazine of BASF, for example, is using powder coatings Special, 1/2000, pages 4 to 6, or the company brochure of BASF Coatings AG "Powder coatings, powder coatings for industrial applications", January 2000, pigmented Powder coatings forth, which are also suitable as basecoats.

Furthermore, Japanese Patent Application JP 53 109 540 A1 (Derwent Unit 78800A / 44) a paint with a 10 to 45 microns thick base coat; prepared from an unspecified pigmented powder slurry and a 30 to 70 μm thick clearcoat.

German laid-open specification DE 27 10 421 A1 discloses a metallic effect pigment containing powder slurry based on amineutralized acrylate copolymers and Melamine resins or known from polyesters and epoxy resins. The well-known powder slurry provides smooth, shiny, metallic coatings.

From the Japanese patent application JP 02 014 776 A2 is a multi-layer coating from basecoat and clearcoat known, 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 are known Powder slurries based on, for example, hydroxyl-containing Acrylate copolymers and blocked polyisocyanates or glycidylgruppenhaltigen Acrylate copolymers and dodecanedioic known. Comparable effect pigments containing powder coatings and powder slurries are known from US Pat. No. 4,268,542 A1, known.

The effect pigments are usually dry in the finished powder coatings or Powder slurries and / or incorporated in their precursors. The disadvantage here is that the strong dry effect pigments. dust, resulting in contamination of the equipment, procedural and safety problems and occupational hygiene Problems leads.

Although the dust could be due to the addition of aqueous media to the Effect pigments are effectively suppressed, but this would be the desire for water- and solvent-free powder coatings and also this had a disadvantageous effect the storage stability, in particular of the metallic effect pigments.

The suppression of dust by the addition of organic solvents on the other hand contradicts the declared goal, only solvent-free powder coatings and powder slurries to use.

The object of the present invention is to provide a novel process for the preparation effect powder coatings and powder coating dispersions (powder slurries) to find the Process step of adding at least one effect pigment to a powder coating, a Powder slurry and / or at least one precursor of the powder coating or the powder slurry and that no longer has the disadvantages of the known methods, but The dust-free incorporation of effect pigments in powder clearcoats and powder slurries and / or their precursors allowed.  

Accordingly, the new process for producing effect powder coatings and Powder paint dispersions (powder slurries) found that the addition step at least one effect pigment to form a powder coating, a powder slurry and / or comprising at least one precursor of the powder coating or the powder slurry, wherein the Effect pigment or the effect pigments pasted with at least one nonionic surfactant used.

The following is the new process for producing effect powder coatings and Powder coating dispersions (powder slurries) referred to as "inventive method".

Other inventive objects will be apparent from the description.

In view of the prior art, it was surprising and not for the expert predictable that the inventive method without dust powder slurries and powder coatings that are excellent for producing effect Multicoat paint systems are suitable which meet even the most demanding market requirements suffice. Above all, the particularly even distribution of the Effect pigments in the matrix of the paint.

Even more surprising was that prepared in accordance with the method of the invention Powder slurries allow the production of so-called combination effect layers, which in effecting multichannel coatings both the function of surfacer and Stone impact protection primers as well as basecoats. This is about more surprising than on the one hand the powder slurries always for the production of Lacquer layers are proposed with essentially only one function and for others the usual and well-known surfacer and basecoats from Coating materials are produced, which are very different and very different are specially adapted to their intended use.

In the context of the present invention, the term "effect-giving Multi-layer coating "both achromatic (see Rompp Lexikon Lacke and printing inks, Georg Thieme Verlag, 1998, page 590, "Unbuntpunkt") as well as colorful, d. H. colored Coating systems.  

The inventive method is based on pasting the effect pigments in Nonionic surfactants.

In the context of the present invention is under "pasting", the mixing of the To understand effect pigments with the nonionic surfactants in an amount that the Dusting effectively suppressed. It is a significant advantage of the present Invention that this amount must not be so high that the resulting mixture has liquid consistency, but that it is sufficient to add so much to nonionic surfactants, that it is still of substantial powdery consistency. The latter means that the effect pigment particles wetted only with the nonionic surfactants and not dispersed therein are so that the mixture is a sort of "powder-free". It is another significant advantage of the present invention that this "powder-free" better doses as the original dry effect pigment. An additional essential The advantage is that the use of the pasted Effektpigments or the "powder circuit" to a particularly good distribution of the effect pigments in the powder coatings and the Powder slurries and in the coatings produced therefrom leads.

Accordingly, the amount of nonionic surfactant used can vary widely. Preferably lies at 0.1 to 20, preferably 0.2 to 19, particularly preferably 0.3 to 18, very particularly preferably 0.4 to 17 and in particular 0.5 to 16 wt .-%, each based on the amount from nonionic surfactant and effect pigment.

According to the invention come as nonionic surfactants or nonionic surfactants (see Römpp Lexikon Lacke and printing inks, Georg Thieme publishing house, 1998, page 410, "Niotenside") Surfactants whose hydrophilicity by polyether chains, hydroxyl groups, Carbonsäureamidgruppen and / or ester groups, but especially polyether chains, is set. Examples of well-suited nonionic surfactants are adducts of ethylene oxide and / or propylene oxide with fatty alcohols, alkylphenols, fatty acids, lower alcohols or Glycols (polyalkylene glycols), of which the polyalkylene glycols are particularly advantageous and are therefore preferably used according to the invention.

Examples of suitable polyalkylene glycols are polyethylene glycols, Polypropylene glycols, block copolymers of ethylene oxide and propylene oxide (Pluronics®) or polytetramethylene glycols (polytetrahydrofurans) (see Römpp Lexikon  Paints and printing inks, Georg Thieme Verlag, 1998, page 457, "Polyalkylene glycols"), of which the polypropylene glycols are particularly advantageous and therefore according to the invention particularly preferably used.

Particularly suitable polypropylene glycols have a number average Molecular weight of 350 to 1,000, preferably 400 to 950, particularly preferably 450 to 900, very particularly preferably 500 to 850 and in particular 550 to 800 daltons.

The polypropylene glycols are commercial products and are used, for example, by the BASF Aktiengesellschaft under the brand name Pluriol® 400, 600 or 900, where the trailing numbers are the molecular weight or its order of magnitude specify.

As effect pigments, all effect pigments are suitable, as described for example in Römpp Encyclopedia paints and printing inks, Georg Thieme Verlag, 1998, pages 176, "Effect pigments", and pages 380 and 381 "Metal oxide mica pigments" to "Metal pigments" are described. As effect pigments come accordingly Metal flake pigments such as commercial aluminum bronzes, according to DE-A 36 36 183 chromated aluminum bronzes, commercial stainless steel bronzes and metal-containing and non-metallic effect pigments, such as, for example, pearlescent or interference pigments, into consideration. Especially preferred are metallic effect pigments, in particular Aluminum effect pigments, used.

The effect pigments may also be leafing pigments (see Rompp Lexikon Paints and printing inks, Georg Thieme Verlag, 1998, page 351, "Leafing pigments").

They may also be coated with polymers and / or oligomers. Under Oligomers are understood as meaning resins having at least 2 to 15 monomer units in their Contain molecule. By polymers are meant resins which are at least 10 Contain monomer units in their molecule. In addition to these terms Rompp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Oligomers", page 425.  

In addition, the effect pigments can be comparatively narrow Have particle size distribution. Here, the mean particle size is - as below defined - preferably at 5 to 20 and especially at 10 to 11 microns, wherein the maximum particle size in general 30 and in particular 25 microns does not exceed

However, the effect pigments can also have a comparatively broad particle size distribution respectively. D. h., That the effect pigment concerned a comparatively large amount Fine grain, d. H. Pigment particles of a particle size in the range of 1 to 10 microns, and a comparatively large amount of coarse grain having a grain size in the range of 70 to 90 microns having. This results in a particularly flat slope of the cumulative Grading curve. Preferably, the minimum grain size is 1.0, preferably at 3.0, more preferably 5.0, most preferably 8.0 and especially at 10 μm. The maximum grain size is preferably 90, preferably 80, especially preferably at 70, most preferably at 60 and especially at 50 microns. The average particle size, as defined below, is preferably from 20 to 60, preferably at 22 to 58, more preferably at 24 to 56, most preferably at 26 to 54 and especially at 28 to 52 microns.

From a methodological point of view, the pasting or production of the "powdery rice" has no Special features on, but takes place according to the usual and well-known methods of Preparing Pigments in Common and Known Devices Using the Do not damage effect pigments, such as stirred tanks or mills.

According to the invention the pasted effect pigments in the powder coatings or Powder slurries after their preparation or in at least one precursor of the powder coatings and powder slurries incorporated. According to the invention, it is advantageous to place them in the powder coatings or powder slurries, because they have no procedural measures be exposed to chemicals which may cause chemical and / or mechanical damage could.

The incorporation preferably takes place with the aid of suitable mixing units and methods for mixing liquid and / or solid substances such as stirred tanks, high-speed stirrers, Ultraturrax, Microfluidizer or fluidized bed systems.  

If the pasted effect pigments are incorporated into the precursors, the finely divided dimensionally stable constituents of the powder clearcoats and powder slurries the Total amount of pasted effect pigments used.

In this case, however, the finely divided dimensionally stable components of the Powder coatings and powder slurries a part of the applied pasted effect pigments whereas the other part is present as a separate solid phase. This can happen at the proportion present in the finely divided, dimensionally stable constituents around the Main quantity, d. H. more than 50% of the pasted effect pigments used. However, less than 50% of the finely divided, dimensionally stable materials can be used Components are located.

If the pasted effect pigments, however, in the powder coatings or the powder slurries incorporated, contain the finely divided dimensionally stable components of Powder clearcoats and powder slurries no pasted effect pigments; d. Hall pasted effect pigments are present as a separate solid phase.

The content of powder clearcoats and powder slurries on the pasted effect pigments as such, d. h., calculated without nonionic surfactant, can vary very widely and depends on the Requirements of the individual case, in particular according to the optical effect to be set and / or the hiding power of the respective coated effect pigments used. The content of added effect pigments is preferably 0.1 to 20, preferably 0.3 to 18, more preferably 0.5 to 16, most preferably 0.7 to 14 and in particular 0.9 to 12 wt .-%, each based on the powder coating or on the Solid body of the powder slurry.

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

The finely divided dimensionally stable constituent or powder coating can be solid and / or be highly viscous. In the context of the present invention, "highly viscous" means that the particles under the usual and known conditions of manufacture, the  Storage and use of powder slurries or powder coatings essentially like Behave solid particles. Preferably, the powder coating is solid.

The individual particles of the finely divided component or the 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 the Application of powder slurries and powder coatings, if at all, only slightly agglomerate and / or disintegrate into smaller particles, but also under the influence essentially preserve their original shape from shear forces.

Preferably, the solids content of the powder slurry is 10 to 80, preferably 15 to 75, more preferably 20 to 70, most preferably 25 to 70 and in particular 30 to 65 wt .-%, each based on the powder slurry.

The powder content of the powder coating is naturally 100% by weight.

Preferably, the mean particle size of the finely divided dimensionally stable Ingredients of the powder slurry at 0.8 to 40 microns, preferably 0.8 to 20 microns, and especially preferably at 2 to 6 microns. Under average particle size is the after the Laser diffraction method determined 50% median understood, d. h., 50% of the particles have a particle diameter ≦ the median value and 50% of the particles one Particle diameter ≧ the median value. Generally, the particle size of the the dimensionally stable components then distributed their upper limit when the Due to their size, particles can no longer run completely when burned in and thus the film history is negatively affected. The upper limit is 40 microns for makes sense.

Powder slurries with such average particle sizes have a better Application behavior and show at the applied film thicknesses of <30 microns, such as she is currently practicing in the automotive industry in the initial painting of automobiles be surprisingly a much lower propensity to cookers and the "mudcracking" as conventional combinations of filler, basecoat and clearcoat on.  

The particle size distribution of the powder coatings, when used as such, can vary widely and depends on the intended use. Preferably, the particle size distribution is comparatively narrow with a very small one Percentage of coarse grain (particle sizes above 95 μm) and fine grain (particle sizes below 5.0 μm). Particularly preferred are powder coatings with those in the European Applied Patent Application EP 0 666 779 A1 described grain size distribution.

The powder slurry and the powder coating are preferably free of organic solvents (Cosolvents). In the context of the present invention, this means that they have a Residual content of volatile solvents of <2.0 wt .-%, preferably <1.5 wt .-% and particularly preferably <1.0 wt .-% have. It is very special according to the invention Advantage, if the residual content is below the gas chromatographic detection limit.

In addition to the angetigten effect pigments to be used according to the invention, the en Powder coatings and powder slurries more common and well-known color and / or effect Contain pigments.

These pigments may consist of inorganic or organic compounds. The Powder coatings and powder slurries therefore ensure due to this variety of suitable Pigments a universal scope and allows the realization of a variety of especially beautiful shades and optical effects.

Examples of suitable effect pigments are the non-attached effect pigments.

Examples of suitable inorganic color pigments are titanium dioxide, iron oxides and soot. Examples of suitable organic coloring pigments are Thioindigo pigments, indanthrene blue, irgalith blue, heliogen blue, irgazine 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", referenced.  

The pigments can, as described above for the pasted effect pigments, inside and outside the finely divided dimensionally stable constituents of the powder coatings and powder slurries are present. With regard to the particle sizes, the above applies here, too.

The powder coatings and powder slurries can also organic and inorganic Contain fillers that are like the pigments inside and outside the finely divided dimensionally stable constituents may be present; what has been said about the pigments applies here analogous.

Examples of suitable organic and inorganic fillers are chalk, calcium sulphates, 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. In addition will on Rompp Lexikon Lacke and printing inks, 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 indicated there.

The pigments and fillers may also be in ultrafine, non-hiding form.

The proportion of pigments, fillers and pasted effect pigments to be used The powder coatings and powder slurries can vary very widely and depends on the Requirements of the individual case, in particular according to the optical effect to be set and / or the hiding power of the pigments used in each case. Preferably, the Content of pigments, fillers and effect pigments at 1.0 to 80, preferably 2.0 to 75, particularly preferably 3.0 to 70, very particularly preferably 4.0 to 65 and in particular 5.0 to 60 wt .-%, each based on the powder coating or on the solid Powder slurry.

The powder coatings and powder slurries may be in addition to those described above Pigments and / or fillers or instead of these molecular disperse distributed contain organic dyes.  

These molecularly dispersed dyes are in the finely divided dimensionally stable constituents of the powder coatings.

In the powder slurries they can either be dispersed in the dispersed dimensionally stable constituents or in the continuous phase of the powder slurries to be available.

You can, however, also in the dispersed finely divided dimensionally stable components and in the continuous phase. This may be in the in the finely divided dimensionally stable constituents present proportion around the main amount, d. H. account for more than 50% of the organic dyes used. It can be however, less than 50% are also present. The distribution of organic dyes between the phases can correspond to the thermodynamic equilibrium that is out the solubility of the organic dyes in the phases results. The distribution can but also far from the thermodynamic equilibrium.

Suitable are all organic dyes used in the powder coatings and powder slurries in as described above are soluble. Well suited are lightfast organic Dyes. Particularly suitable are lightfast organic dyes with a low or lack of migration. The migration tendency can be the To estimate the expert on the basis of his general knowledge and / or with the help of simple preliminary experiments, for example in the context of Tönversuchen determine.

The content of the powder coatings and powder slurries distributed to the molecular disperse Organic dyes can vary widely and are primarily intended according to the color and the hue to be adjusted, as well as the amount of optionally present pigments and / or fillers.

The powder coatings and powder slurries may be physical or thermal and / or with be curable actinic radiation. The thermally curable powder coatings and powder slurries in turn, may be self-crosslinking or externally crosslinking.  

In the context of the present invention, the term "physical curing" means Curing a layer of a coating material by filming Solvent delivery from the coating material, the link within the Coating via looping of the polymer molecules of the binder (to the Term cf. Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Binders," pages 73 and 74). Or the filming takes place via the coalescence of binder particles (see Rompp Lexikon Lacke and Printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening", pages 274 and 275). Usually, no crosslinking agents are necessary for this purpose. Possibly can be the 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 engage in self-crosslinking reactions. The prerequisite for this is that in the binders already both types of complementary reactive functional groups containing, which are suitable for crosslinking necessary. On the other hand, such coating materials as externally crosslinking are Adhesives and sealants referred to, in which one type of complementary reactive functional groups in the binder, and the other kind in a hardener or crosslinking agent. Complementing this is on Römpp Lexikon Lacke and Printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening", pages 274 to 276, in particular page 275, below, referenced.

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

Are the thermal and the curing with actinic light in a powder coating applied jointly; one also speaks of "dual cure" and "dual-cure powder coating" or "dual-cure powder slurry".

The powder coatings and powder slurries contain at least one binder.  

The binders are oligomeric and polymeric resins.

According to the invention, it is advantageous if the minimum film-forming temperature of the binder at least 0 ° C, preferably at least 10, more preferably at least 15, completely particularly preferably at least 20 and in particular at least 25 ° C. The Minimum film forming temperature can be determined by using an aqueous dispersion of Binder mounted by means of a doctor blade 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 powdered layer melts is called Minimum film-forming temperature. In addition, on Römpp Lexikon Lacke and Printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Minimum Film-forming Temperature", page 391, referenced.

Examples of suitable binders are random, alternating and / or block-like constructed linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated monomers, or polyaddition resins and / or Polycondensation. 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)", and pages 463 and 464, "Polycondensates", "polycondensation" and "polycondensation resins", as well as pages 73 and 74, "Binders".

Examples of suitable (co) polymers are (meth) acrylate (co) polymers or partially saponified polyvinyl esters, in particular (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, especially polyester-polyurethanes.

Of these binders, the (meth) acrylate (co) polymers have advantages and are therefore used more often.  

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

Overview

Examples of complementary functional groups

The selection of the respective complementary groups depends firstly on the fact that in the manufacture, storage, application and melting of the Powder coatings and powder slurries no undesirable reactions, especially none premature crosslinking, received and / or optionally curing with actinic  Radiation should not disturb or inhibit, and secondly afterwards, in which Temperature range networking should take place.

Preferably, in the powder coatings and powder slurries crosslinking temperatures applied from 60 to 180 ° C. It is therefore preferable 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 agent 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, the binders contain in particular methylol, methylol ether and / or N-alkoxymethylamino groups.

Complementary reactive functional groups particularly suitable for use in the powder coatings and powder slurries are

• - carboxyl groups on the one hand and epoxide 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 ones described above Functional groups can vary very widely and is especially aimed at the Crosslinking density that you want to achieve, and / or according to the functionality of each applied crosslinking agents. For example, in the case of carboxyl groups Binder the acid number preferably at 10 to 100, preferably 15 to 80, especially preferably 20 to 75, very particularly preferably 25 to 70 and in particular 30 to 65 mg KOH / g. Or in the case of hydroxyl-containing binder is the OH number preferably from 15 to 300, preferably from 20 to 250, more preferably from 25 to 200, completely particularly preferably 30 to 150 and in particular 35 to 120 mg KOH / g. Or in case epoxy-containing binder, the epoxide equivalent weight is preferably included  400 to 2,500, preferably 420 to 2,200, particularly preferably 430 to 2,100, completely most preferably 440 to 2,000 and especially 440 to 1,900.

The complementary functional groups described above may be used according to customary and known methods of polymer chemistry incorporated into the binder become. This can be achieved, for example, by the incorporation of monomers containing the wear appropriate reactive functional groups, and / or with the help polymer-analogous reactions happen.

Examples of suitable olefinically unsaturated monomers having reactive functional groups are

• 1. Monomers which carry at least one hydroxyl, amino, alkoxymethylamino, carbamate, allophanate or imino group per molecule
  • 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 especially 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, methacrylate, crotonate, maleate, fumarate or itaconate; or hydroxycycloalkyl esters such as 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-in the dimethanol or methylpropanediol monoacrylate, monomethacrylate, monoethacrylate, monocrotonate, monomalate, monofumarate or monoitaconate; Reaction products of cyclic esters, such as. 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 of acrylic acid and / or methacrylic acid with the glycidyl ester of an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms per molecule, in particular a Versatic® acid, or instead of the reaction product an equivalent amount of acrylic and / or methacrylic acid, the then reacted during or after the polymerization reaction with the glycidyl ester of an alpha-branched ver monocarboxylic acid having 5 to 18 carbon atoms per molecule, in particular a Versatic® acid;
  • 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) acrylamide, N-methyl, N-methylol, N, N-dimethylol, N-methoxymethyl, N, N-di (methoxymethyl) -N-ethoxymethyl and / or N , N-di (ethoxyethyl) - (meth) acrylamide;
  • Acryloyloxy or methacryloyloxyethyl, propyl or butyl carbamate or allophanate; other examples of suitable monomers containing carbamate groups are described in US-A-3,479,328, US 3,674,838 A1, US 4,126,747 A1, US 4,279,833 A1 or US 4,340,497 A1;
• 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 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 epoxide 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 preparation of (meth) acrylate copolymers, in particular of glycidyl containing.

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

Examples of suitable monomer units for introducing reactive functional groups in Polyester or polyester-polyurethanes are 2,2-dimethylolethyl- or -propylamine, the blocked with a ketone, the resulting ketoxime group after incorporation is hydrolyzed again; or compounds having two hydroxyl groups or two pri and / or secondary amino groups and at least one acid group, in particular at least one carboxyl group and / or at least one Sulfonic acid group, such as dihydroxypropionic acid, dihydroxysuccinic acid, Dihydroxybenzoic acid, 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2- Dimethylol butyric acid, 2,2-dimethylol pentanoic acid, α, δ-diaminovaleric acid, 3,4- Diaminobenzoic acid, 2,4-diaminotoluenesulfonic acid or 2,4-diamino diphenylethersulfonsäure.  

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

The binders of the dual-cure powder coatings and powder slurries further include in statistical means at least one, preferably at least two, group (s) with at least one activatable with actinic radiation bond (s) per molecule.

In the context of the present invention is under a with actinic radiation activable bond understood a bond that upon irradiation with actinic Radiation becomes reactive and with other activated bonds of its kind Polymerization reactions and / or crosslinking reactions, which after radical and / or ionic mechanisms. 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 therefore very particularly preferably used according to the invention. For the sake of brevity they will be in hereinafter referred to as "double bonds".

Accordingly, the preferred group according to the invention contains one double bond or two, three or four double bonds. If more than one double bond is used, then the double bonds be conjugated. According to the invention, however, it is advantageous if the Isolated double bonds, in particular each terminally, in the here in question standing group. According to the invention, it is particularly advantageous two, in particular to use a double bond.

The dual-cure binder contains on average at least one of the above described activatable with actinic radiation groups. This means that the Functionality of the binder in this regard integer, d. h., for example, the same  is two, three, four, five or more, or not integer, d. h., for example equal to 2.1 to 10.5 or more. Which functionality one chooses, depends on the Requirements that are placed on the respective pigmented dual-cure powder slurry.

Become on statistical average more than one activatable with actinic radiation group applied per molecule, the groups are structurally different from each other or from same structure.

If they are structurally different from each other, this means within the scope of the present invention Invention, that two, three, four or more, but especially two, with actinischer Radiation activatable groups can be used ranging from two, three, four or more, but especially two, derive 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.

Preferably, the groups are via urethane, urea, allophanate, ester, ether and / or amide groups, but in particular via ester groups, to the respective Basic structures of the binder bound. This is usually done by conventional and known polymer-analogous reactions such as the reaction of pendant ones Glycidyl groups with the above-described olefinically unsaturated monomers, which contain an acid group of pendant hydroxyl groups with the Halides of these monomers, of hydroxyl groups containing 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 Isocanatgruppen with the hydroxyl-containing monomers described above.

In the dual-cure powder coatings, however, mixtures of purely thermal hardenable and purely actinic radiation curable binders are applied.  

The pure with actinic radiation curable powder coatings and powder slurries contain preferably purely actinic radiation curable binders, preferably only the contain activatable with actinic radiation groups described above.

The material composition of the binder has basically no special features, but it come

• - All those in US Patent US 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 18 657 A1, DE 196 52 813 A1, DE 196 17 086 A1, DE 198 14 471 A1, DE 196 13 547 A1, DE 198 41 842 A1 or DE 198 41 408 A1, the unpublished German Patent applications DE 199 08 018.6 or DE 199 08 013.5 or the European Patent EP 0 652 264 A1, for use in thermal and / or provided with actinic radiation curable powder clearcoat slurries Binder,
• - All the 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 intended binder or
• - all those in the German patent application DE 42 22 194 A1, the product Information of the company BASF Lacke + colors AG, "powder coatings", 1990, or the Company brochure of BASF Coatings AG "Powder coatings, powder coatings for industrial Applications ", January 2000, for use in thermal curable powder clearcoats provided binder

into consideration.

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

Examples of suitable (meth) acrylate copolymers are the epoxide group-containing (meth) acrylate copolymers having an epoxide 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 by means of differential scanning calometry ( DSC), as they come in particular for use in thermally curable powder clearcoat slurries into consideration (see above) and as they also 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 additional binders for the dual-cure powder coatings and powder slurries or as the sole binder for the purely actinic radiation curable powder coatings and Powder slurries are disclosed in 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 0 650 985 A1, EP 0 540 884 A1, EP 0 568 967 A1, EP 0 054 505 A1 or EP 0 002 866 A1, the 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, the international patent applications WO 97/46549 or WO 99/14254 or the US Pat. Nos. 5,824,373 A1, 4,675,234 A1, 4,634,602 A1, US Pat. 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 Powder clearcoat provided binder.

The preparation of the binders has no special features, but takes place with the aid of the customary and known methods of polymer chemistry, such as For example, they are described in detail in the patents listed above become.

Further examples of suitable preparation processes for (meth) acrylate copolymers are disclosed in the European patent applications or EP 0 767 185 A1, the German patents DE 22 14 650 B1 or DE 27 49 576 B1 and US Pat. Nos. 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  Chemistry, 4th Edition, Volume 14/1, pages 24 to 255, 1961 described. As reactors for the copolymerization come the customary and known stirred tank, Stirred tank cascades, tubular reactors, loop reactors or Taylor reactors, as they are for example in the patent specifications and patent applications DE 1 071 241 B1, EP 0 498 583 A1 or DE 198 28 742 A1 or in the article by K. Kataoka in Chemical Engineering Science, Vol. 50, No. 9, 1995, pages 1409 to 1416, in Consideration.

The production of polyesters and alkyd resins, for example, still in the Standard work Ullmanns Encyklopadie der technischen Chemie, 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-Polyester" by J. Bourry, Paris, published by Dunod, 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 preparation of polyurethanes and / or acrylated polyurethanes, for example nor 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 coatings or the disperse phase of the powder slurries on binders can vary very widely and depends mainly on whether they are physically curable or thermally and / or self-crosslinking curable with actinic Stralung. In these cases It may preferably be 20 to 99.9, preferably 25 to 99.7, particularly preferably 30 to 99.5 most preferably 35 to 99.3 and in particular 40 to 99.1 wt .-%, respectively based on the solids content of the pigmented powder slurry amount. In the others Cases (thermally and / or hardenable with actinic radiation curable) is the Binder content preferably at 10 to 80, preferably 15 to 75, particularly preferred 20 to 70, most preferably 25 to 65 and especially 30 to 60 wt .-%, respectively based on the powder coating or the solid of the powder slurry.

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

Examples of suitable crosslinking agents are

• Aminoplast resins, as described, for example, in Rompp Lexikon Lacke and Printing inks, Georg Thieme Verlag, 1998, page 29, "Aminoharze", the textbook "Paint Additives" 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 Pat. No. 4,710,542 A1 or EP 0 245 700 A1 as well as in the article by B. Singh and coworkers "Carbamylmethylated Melamine, Novel Crosslinker for the Coatings Industry ", in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193 to 207, to be discribed,
• - Carboxyl-containing compounds or resins, such as those in the patent DE 196 52 813 A1 or 198 41 408 A1 are described, especially dodecanedioic acid,
• - Epoxy-containing compounds or resins, such as those in the patents 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, US Pat. DE 196 17 086 A1, DE 196 31 269 A1, EP 0 004 571 A1 or US Pat EP 0 582 051 A1,
• - 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 the patents US 4,939,213 A 1, 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 on the crosslinking agents may also be vary widely and depends on the requirements of the case, in particular by the number of reactive functional groups present. Preferably, it lies at 1.0 to 40, preferably 2.0 to 35, particularly preferably 3.0 to 30, very particularly preferably 4.0 to 27 and especially 5.0 to 25 wt .-%, each based on the Powder coating or the solid of the en powder slurry.

In addition to the above-described pasted effect pigments and binders and optionally the above-described pigments, fillers, dyes and / or crosslinking agents, the powder coatings and powder slurries at least contain an additive. This may vary according to its physicochemical Properties and / or its function essentially in the solid finely divided Constituents of the powder coatings and powder slurries or in the case of powder slurries in essentially in the continuous phase.

Examples of suitable additives are

• Thermally curable reactive diluents such as positionally isomeric diethyloctanediols or Hydroxyl-containing hyperbranched compounds or dendrimers such they are described in the German patent application DE 198 50 243 A1;
• - reactive diluents curable with actinic radiation, such as those in Römpp Lexikon Paints and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, on Page 491 described under the heading "reactive diluents";
• Catalysts for crosslinking such as dibutyltin dilaurate, lithium decanoate or Zinc octoate, amine-blocked organic sulfonic acids, quaternary Ammonium compounds, amines, imidazole and imidazole derivatives such as Styrylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole and 2- Butyl imidazole as described in Belgian Patent No. 756,693, or phosphonium catalysts such as ethyltriphenylphosphonium iodide, Ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium thiocyanate, Ethyltriphenylphosphonium acetate-acetic acid complex,  Tetrabutylphosphonium iodide, tetrabutylphosphonium bromide and tetrabutyl phosphonium acetate-acetic acid complex, as described, for example, in US Pat. US Pat. Nos. 3,477,990 A1 or 3,341,580 A1;
• - thermolabile radical initiators such as organic peroxides, organic Azo compounds or C-C-cleaving initiators such as dialkyl peroxides, Peroxycarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides, Ketone peroxides, azodinitriles or benzpinacol silyl ethers;
• - Photoinitiators, as in Römpp Chemie Lexikon, 9th extended and revised edition, Georg Thieme Verlag Stuttgart, Vol. 4, 1991, or in Römpp Lexikon 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 benztriphenol;
• - Sunscreens such as HALS compounds, benzotriazoles or oxalanilides;
• - flow control agents;
• Radical scavengers and polymerization inhibitors such as organic phosphites or 2,6 Di-tert-butyl phenol derivatives;
• - slip additives;
• - defoamers;
• - Emulsifiers, in particular nonionic emulsifiers such as alkoxylated alkanols and polyols, phenols and alkylphenols, anionic emulsifiers such as alkali salts or ammonium salts of alkanecarboxylic acids, alkanesulfonic acids and sulfonic acids alkoxylated alkanols and polyols, phenols and alkylphenols;  
• Wetting agents such as siloxanes, fluorine-containing compounds, carboxylic acid monoesters, Phosphoric acid esters, polyacrylic acids and their copolymers or polyurethanes, such as For example, in detail in the patent application DE 198 35 296 A1 described in particular in connection with the following described associative thickeners based on polyurethane;
• - adhesion promoters such as tricyclodecanedimethanol;
• - film-forming aids such as cellulose derivatives;
• - Flame retardants;
• - deaerating agents such as diazadicycloundecane or benzoin;
• - water retention agents;
• - anti-caking agents
• Rheology-controlling additives (thickeners), such as those described in patents 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 phyllosilicates such as aluminum-magnesium silicates, Sodium-magnesium and sodium-magnesium-fluorine-lithium-phyllosilicates of 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 described in Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Thickener", pages 599 to 600, and in the textbook "Paint Additives" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pp. 51-59 and 65; in particular combinations of ionic and nonionic thickeners, such as in the patent application DE 198 41 842 A1 for setting a  pseudoplastic behavior, or the combination of associative thickeners based on polyurethane and wetting agents Polyurethane base, as described in the German patent application DE 198 35 296 A1 will be described in detail;

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

The production of powder coatings in the context of the method according to the invention has no special features on, but takes place, as in the product information the company BASF Lacke + colors AG, "powder coatings", 1990, or the company publication of BASF Coatings AG "Powder Coatings, Powder Coatings for Industrial Applications", January 2000, by homogenizing and dispersing, for example by means of a Extruder or screw kneader, and grinding the above described Ingredients. After preparation of the powder coatings, these are ground by further grinding and optionally by sifting and sieving for the incorporation of the invention to pasting effect pigments used, the application or for dispersion prepared for the purpose of producing the powder slurries.

Also the production of the powder slurries in the context of the method according to the invention has no special features, but follows the usual and known methods.

In a first preferred variant, the preparation of the powder slurries from the components described above substantially, 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, except that in the context of Present invention nor the pasted effect pigments are mitverarbeitet can. Here, the powder coating by wet grinding or by stirring dry powdered powder coating in water or an aqueous medium in the powder slurry overruns. Particular preference is given to wet grinding.  

In a further preferred variant of the production of the powder slurries, the emulsified above components in an organic solvent, thereby resulting in an oil-in-water type emulsion, hereinafter the organic Solvent removed, which solidify the emulsified droplets and the Powder slurry results. Possibly. it can still be wet-milled to filterability improve.

In a third preferred variant of the preparation of the powder slurries is a liquid Melting of the above-described components together with the not melted effect pigments in an emulsifying preferably under Added addition of water and stabilizers, the emulsion obtained cooled and filtered, resulting in the powder slurry results. To achieve a high mixing quality, it is essential to perform the mixture solvent-free in the melt. Accordingly, The polymeric components are as viscous resin melts in the dispersing fed.

The powder coatings and powder slurries prepared in accordance with the method of the invention serve for the production of basecoats in effecting multicoat paint systems on a substrate.

The effect of multi-coat painting is mainly in automotive painting, the Painting of buildings in the interior and exterior, the painting of furniture, Doors and windows and industrial painting, including coil coating and Container Coating used, with all common in these technical fields and known substrates of metal, plastic, glass, wood, textile, leather, natural and Artificial stone, concrete, cement or composites of these materials may be considered, wherein the electrically conductive substrates are preferred.

Preferably, the effective multicoat paint system can be prepared by applying to a substrate

• 1. a filler on a cathodically deposited and thermally cured Electrodeposition or wet-on-wet on a cathodic deposited, not or only partially cured electrodeposition coating applied, after which one  
• 2. The resulting filler layer by itself thermally or thermally and with actinic radiation or thermally together with the electrodeposition coating layer or thermally and with actinic radiation cures, whereby the surfacer coat or antistonechip primer results,
• 3. the powder coating prepared in accordance with the method of the invention or in According to the method of the invention prepared powder slurry on the Füllerlackierung or Steinschlagschutzprimierurig applied, creating a Powder coating layer or powder slurry layer results,
• 4. the powder coating layer or powder slurry layer without completely crosslinking it, deaerates or dries or, alternatively, physically or thermally and / or cured 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 base coat, after which one
• 6. the powder coating layer or powder slurry layer and the clearcoat layer (s) thermally and / or with actinic radiation cures together, or - alternatively - the clearcoat layer by itself thermally and / or with actinic radiation hardens resulting in the basecoat and the clearcoat.

Examples of suitable cathodic electrodeposition paints and optionally wet-on-wet processes become in Japanese Patent Application 1975-142501 Japanese Patent Application 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, in particular aqueous filler, which are also known as Rockfall protection primers or functional layers are called, in US Pat. Nos. 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 Pat. No. 4,450,200 A1, US Pat. No. 4,614,683 A1 or WO 490/26827.

Suitable clearcoats are all customary and known clearcoats.

Examples of suitable clearcoats 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 international patent applications WO 94/10211, WO 94/10212, WO 94/10213, WO 94/22969 or WO 92/22615 or US Pat. Nos. 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 of the company BASF Lacke + Farben AG, "Powder Coatings", 1990 are known;
• - Thermally and / or actinic radiation curable powder slurry clearcoats, such as for example, in US Pat. No. 4,268,542 A1 or US Pat. No. 5,379,947 1 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 13547 A1, DE 196 13 547 A1, DE 196 18 657 A1, DE 19 65 2 813 A1, DE 196 17 086 A1, DE 198 14 471 A1, DE 198 41 842 A1 or DE 198 41 408 A1 or the not previously published German patent applications DE 199 08 018.6 or DE 199 08 013.5 are described; or
• - UV-curable clearcoats and powder clearcoats, as for example 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 A 1, EP 0 540 884 A1, EP 0 568 967 A1, EP 0 054 505 A1 or EP 0 002 866 A1, the 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, the international patent applications WO 97/46549 or WO 99/14254 or the  US Pat. Nos. 5,824,373 A1, 4,675,234 A1, 4,634,602 A1, US Pat. US 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. Of Further, powder coatings are known, which thermally and with actinic radiation can be crosslinked (see European Patent Application EP 0 844 286 A1).

The resulting clearcoats can still with a scratch-resistant coating an organically modified ceramic material such as, for example, under the trademark ORMOCER® is commercially available to be coated.

In general, the coating materials are applied to the in a wet layer thickness, that after curing coatings with the necessary for their functions and advantageous layer thicknesses result. In the case of electrocoating, they are included 5 to 40, preferably 10 to 35, more preferably 12 to 30 and especially 15 to 25 μm, in the case of the surfacer coat, antistonechip primer or functional layer they are 10 to 60, preferably 12 to 55, particularly preferably 15 to 50 and in particular from 18 to 45 μm, in the case of the basecoat they are from 5 to 50, preferably 5 to 40, particularly preferably 5 to 30 and in particular 10 to 25 μm, and in the case of a clearcoat, they are 10 to 100, preferably 15 to 80, especially preferably 20 to 75 and in particular 25 to 70 microns. However, in the Multicoat paint the functional layer only a layer thickness of 20 to 50% of Total layer thickness of functional layer and base coat have.

In addition, the powder slurries also serve the production of Combination effect coats.

In the context of the present invention, these are to be understood as coatings which are described in US Pat an effect-imparting multicoat paint system fulfills at least two functions. Functions of this kind are in particular the protection against corrosion, the adhesion mediation, the absorption of mechanical energy and the effects. According to the invention serves the Combination effect layer especially the absorption of mechanical energy and the Effects at the same time; So it fulfills the functions of a filler coat or Rockfall protection primer and a base coat. Preferably, the  Combination effect layer also still anti-corrosion effect and / or adhesion-promoting effect.

The thickness of the combination effect layer is within a given effect Multilayer coating preferably constant. In some cases, it may be recommend the thickness in the areas of the substrate, the mechanical action less exposed and / or less or not visible, thinner too to save material.

Of course, the thickness of the combination effect layer of effect Multicoat paint to effect multicoat paint vary very widely. In this case, the optimum thickness for the respective individual case depends in particular the opacity of the pigments used (see Rompp Lexikon Lacke and Printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, page 124, "Hiding power"), the ability to absorb or dissipate mechanical energy, the ability to compensate for the unevenness of the substrate surface, and / or the in each case applied other ingredients of the powder slurry. The expert can therefore the optimum thickness based on his general knowledge, possibly with the help determine easier-orientated preliminary tests. Preferably, the thickness of the Combination effect layer at 10 to 100, preferably 15 to 90, particularly preferably 20 to 80, most preferably 25 to 70 and in particular 30 to 60 microns, each based on the layer.

For the preparation of the combination effect layer, those described above Powder slurries on the primed and ungrounded substrates described above applied.

Although the powder slurries come for the application outside of the Automobackackierung into consideration, however, is their main technical Use in the said area, because here are their particular advantages completely to be particularly open-minded. The substrates are thus Motor vehicle bodies, in particular car bodies, and parts thereof, such as For example, doors, hoods, fenders, boot lid spoiler, sills or Wind deflector.  

These consist in particular of steel or aluminum. The metal surfaces can have primers. In the case of aluminum, for example an oxide layer produced by anodic oxidation (Eloxal® method). in the Fall of steel is usually a cathodic deposited and thermally cured electrodeposition coating. But it can also be a cathodic deposited electrocoat film which does not cure thermally, but only dried or partially cured.

The electrocoating or electrodeposition coating is then combined with the Overlaid with powder slurry, either alone or together with the Electrocoating is cured (wet-in-wet process).

The resulting combination effect layer may be provided with at least one additional Paint coating. Preferably, these are at least one the clearcoats described above. This results especially advantageous effect multicoat systems with an excellent optical Overall impression and a particularly high scratch resistance.

When coating the combination effect layer with a clearcoat, the cured combination effect layer with at least one clearcoat be covered, after which it is cured by itself.

In a second variant, which is preferred according to the invention, which can not or only partially cured powder slurry layer directly with at least one clearcoat are overlaid, after which the clear coat (s) together with the Pulverlurryschicht and optionally the electrodeposition coating layer is cured (wet-in-wet Method).

The powder slurries can be achieved with the methods known from liquid paint technology muster. In particular, they can be applied by means of spraying. Preferably, they are made by electrostatic painting the body exterior parts, followed by pneumatic spraying (compressed air spraying) of the interior body parts applied.  

In this case, the electrostatic coating by means of an electrostatic spray gap, an electrostatic spray bell or an electrostatic spray disc.

Furthermore, the electrostatic coating can be assisted by electrostatics mechanical atomization done. Preferably, this is done with the help of electrostatic high rotation disks or high rotation bells performed.

Even the pneumatic spraying or air pressure painting has no methodical Special features on but can be done by hand or with the help of usual and familiar Vending machines or robots are performed.

Complementing this is on Römpp Lexikon Lacke and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, page 186: "Electrostatic coating", page 187: "Electrostatic spray guns", "Electrostatic spraying", and page 165: "Compressed air spraying", referenced.

The application is preferably when illuminated with visible light of a wavelength of over 550 microns or under exclusion of light when the pigmented Powder slurries (also) are curable with actinic radiation. This will be a Substantial change or damage to be used according to the invention Coating material and overspray avoided.

Of course, these application methods also in the application additional lacquer layers, preferably clear lacquer layers, are used, provided that it not powder coatings, in particular powder clearcoats and / or the powder coatings, is preferably after the in the product information of BASF Lacke + Farben AG, "Powder Coatings", 1990 or the company publication of BASF Coatings AG "Powder Coatings, Powder Coatings for Industrial Applications", January 2000 Procedures are processed.

The curing of the applied electrocoating layers, filler layers, Basecoat films, combination effect coatings and clearcoat films have none  methodical features, but erfogt with the help of the usual and well-known Methods and devices.

Physical hardening does not require any special measures be taken; However, the physical hardening by through atmospheric oxygen, heat or by irradiation with actinic radiation.

The thermal curing can take place after a certain rest period or ventilation time. you may have a duration of 30 seconds to 2 hours, preferably 1 minute to 1 hour and especially 1 minute to 45 min. The rest period is used, for example, for the course and the degassing of Layers and to the evaporation of volatile components such as possibly existing solvent and / or water. The ventilation can be increased by a Temperature that is not sufficient for curing, and / or by a reduced Humidity can be accelerated.

The thermal curing is carried out for example by heating in a convection oven or Irradiation with IR and / or NIR lamps. As with curing with actinic radiation The thermal curing can also be carried out gradually. Advantageously, the thermal curing at temperatures of 100 to 180 ° C.

When curing with actinic radiation, preferably 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} used. Optionally, this cure can be supplemented with actinic radiation from other sources. In the case of electron beams, it is preferable to operate 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. Even in the case of curing with UV radiation, to avoid the formation of ozone, under inert gas can be used.

For curing with actinic radiation, the usual and known Radiation sources and optical aids applied. Examples of suitable Radiation sources are flash lamps from the company VISIT, mercury high- or low-pressure vapor lamps, which are optionally doped with lead to a  Beam windows open up to 405 nm, or electron beam sources. Their arrangement is, in principle known and can the conditions of the workpiece and the Process parameters are adjusted. For complicated shaped workpieces like them are intended for automotive bodies, the non-direct radiation accessible areas (shadow areas) such as cavities, folds and others Design-related undercuts with point, small area or Rundumstrahlern, associated with an automatic movement device for the Irradiation of cavities or edges, (partially) cured.

The systems and conditions of these curing 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.

Here, the curing can be done in stages, d. H. through multiple exposure or Irradiation with actinic radiation. This can also be done alternately, d. h., that is cured alternately with UV radiation and electron radiation.

At Dual Cure can be thermal curing and curing with actinic radiation be applied simultaneously or in succession. Be the two curing methods used sequentially, for example, can be started with the thermal curing and be terminated with the curing with actinic radiation. In other cases it can be prove to be advantageous to begin with the curing with actinic radiation and hereby to end.

Preferably, the powder slurry layers and the powder coating layers are in molten state cured by the methods described above.

Overall, the processes for producing the effect-giving provide Multicoat paint systems the ecologically and economically very particularly advantageous and significant possibility not only coatings on a purely aqueous basis without Emission of volatile organic substances, but also with a reduced number of layers. If the appropriate solvent-free clearcoats This also applies to the effect of multicoat paint systems contain at least one clearcoat.  

The effect-giving multi-layer coatings are characterized by a very good adhesion on the substrate, a very good interlayer adhesion, a superb Corrosion protection, a very good protection against stone chipping and others mechanical damage, a very good course and a very good optical Overall impression, especially what color depth, metallic effect, dichroic effect and D.O.I. (Distinctiveness of the reflected image).

The correspondingly coated bodies therefore give a particularly high aesthetic overall impression and have a particularly long service life.

Examples example 1 The production of an effect multicoat paint system using an in Powder slurry prepared according to the method of the invention

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

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

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

Table 1 The preparation of the powder slurry

component Parts by weight Example 1 AL = L <predispersed: Demineralised water ^a) 42 Disperse Aid W22 ^b) 1.03 Triton X100 ^c) 0.02 dimethylethanolamine 0.08 RM 8 ^d) 0.9 powder coating 28 AL = L <completion: Demineralised water ^a) 17.49 RM 8 ^d) 0.7 Byk 333 ^e) 0.05 Triton X100 ^c) 0.18 Effect pigment ^f) 5.0 a) demineralized water; @ b) polyurethane-based dispersant from Daniel Products; @ c) defoamer company Union Carbide; @ d) polyurethane-based thickener from Rohm &Haas; @ e) leveling agent of Byk Chemie; @ f) aluminum effect pigment from Eckhart, pasted by the dry-blend process with the polypropylene glycol Pluriol® 600 from BASF Aktiengesellschaft in a weight ratio aluminum effect pigment: Pluriol = 90: 10.

Steel panels (body panels), with a usual and well-known cathodic coated and baked electrodeposition coating were coated with the powder slurry manually coated using a conventional and known spray gun (Pressure: 5 bar, 2 spray holes, horizontal and vertical). The wet layer thickness was so chosen that after stoving a layer thickness of 40 microns resulted. The Powder slurry layer were flashed for 10 min at 50 ° C and with a commercial conventional two-component clearcoat from BASF Coatings AG overlayed. The resulting clearcoat was flashed off for 10 minutes, after which the powder slurry layer and the clearcoat are baked at 150 ° C. for 30 minutes were. The thickness of the clearcoat was 50 μm.

The resulting paint had excellent hiding power. you Metallic effect and flip-flop fully corresponded to those of a corresponding pigmented basecoat. The adhesion to the primer and the Intercoat adhesion as well as the stone impact protection effect were also after the Weathering in the Schwitzwasserkonstantklima (SKK) very good. Disturbances in the course, Cooker, cracking (mudcracking) or surface structures like orange peel skin were not observable.  

Example 2 The production of an effect multicoat paint system using an in powder coating prepared according to the method of the invention

For Example 2, the powder coating of Example 1 were prepared, except that subsequently 5.5 parts by weight of the coated aluminum effect pigment according to Table 1 were added.

For this purpose, the ingredients listed in Example 1 of the powder coating and the coated aliminium effect pigment weighed. The batch size was 5.0 kg. The Ingredients were dissolved in a Henschel fluid mixer for 2 minutes at 2,800 rpm homogenized. The resulting mixture was mixed after the premix a hopper fed to an extruder (BUSS PR 46). The extruder was each with 110 ° C jacket temperature started, and the speed was chosen so that the Jacket temperature kept at 60 ° C. The exiting extrudate was with a chill roll cooled to 20 ° C and crushed with a crusher to chips. The chips were pre-cut and ground in a pin mill. The resulting powder was washed with sieved over a tumble sieve over 125 microns, after which the pasted effect pigment in a Powder mixer was incorporated.

The application of the powder coating of Example 2 was carried out with the aid of a laboratory handgun with corona charging type Wagner ESB in a layer thickness of 40 to 50 μm Steel panels covered with a conventional and well-known cathodic and baked electrocoating and a conventional and well-known Rockfall protection primer were coated. The resulting powder coating layers were baked at 160-180 ° C for 10-25 minutes.

The basecoat thus obtained was mixed with a commercially available two-component Clearcoat overcoated, after which the resulting clearcoat cured at 60 ° C. has been.  

The effect of multicoat paint showed a very good course and optical Overall impression. Overall, the same benefits were obtained as in the effect multicoat of Example 1.

Claims (10)

1. A process for the preparation of effect powder coatings and powder coating dispersions (powder slurries), which comprises the process step of adding at least one effect pigment to a powder coating, a powder slurry and / or at least one precursor of the powder coating or the powder slurry, characterized in that the effect pigment or the effect pigments used with at least one nonionic surfactant. 2. The method according to claim 1, characterized thereby, that as nonionic surfactant at least one polyalkylene glycol used. 3. The method according to claim 2, characterized thereby, that as polyalkylene glycol used at least one polypropylene glycol. 4. The method according to claim 3, characterized thereby, that the number average Molecular weight of the polypropylene glycol at 350 to 1,000 daltons. 5. The method according to any one of claims 1 to 4, characterized in that the or the nonionic surfactant (s) in an amount of 0.1 to 20 wt .-%, based on the amount of Effect pigment and nonionic surfactant. 6. The method according to any one of claims 1 to 5, characterized in that the Effect pigment is a metallic effect pigment. 7. The method according to claim 6, characterized thereby that the metallic effect pigment an aluminum effect pigment. 8. Powder coatings and powder slurries, prepared by the method according to one of Claims 1 to 7.   9. Use of the powder coatings and powder slurries according to claim 8 for the Production of effect-based basecoats or Combination effect layers in effect multicoat paint systems. 10. Use according to claim 10, characterized in that the powder coatings and powder slurries in automotive painting, the painting of buildings in the Interior and exterior, the painting of furniture, doors and windows and the industrial coating, including coil coating and container coating.