WO2020099151A1

WO2020099151A1 - Multi-layer effect paint structure

Info

Publication number: WO2020099151A1
Application number: PCT/EP2019/079964
Authority: WO
Inventors: Marco CAPIZZI; Christoph Martin Schumacher
Original assignee: Karl Bubenhofer Ag
Priority date: 2018-11-16
Filing date: 2019-11-01
Publication date: 2020-05-22

Abstract

The invention relates to a multi-layer paint structure having, at least indirectly on a substrate (5), an effect paint layer (10) and, on the side thereof facing away from the substrate (5), a cover layer (14, 16, 17), the effect paint layer consisting of the following components: (AE) 50-99.9 wt.% of oligomeric binder selected from the group consisting of: acrylate, polyester, polyurethane or a combination of these systems with a hardener; (BE) 0.1-4 wt.% metal flakes-based effect pigment; (CE) 0-5 wt.% UV and/or HALS stabilization; (DE) 0-30 wt.% inorganic particulate fillers; (EE) 0-10 wt.% additives, wherein the components (AE)-(EE) add up to 100 weight percent of the formulation of the effect paint layer; and wherein the cover layer consists of the following components: (AD) 90-99.5 wt.% oligomeric binder selected from the group consisting of: acrylate, polyester, polyurethane or a combination of these systems with a hardener; (CD) 0.5-5 wt.% UV and/or HALS stabilization; (DD) 0-5 wt.% inorganic particulate fillers; (ED) 0-10 wt.% additives wherein the components (AD)-(ED) add up to 100 weight percent of the formulation of the cover layer.

Description

TITLE

MULTI-LAYER EFFECT LACQUER COMPOSITION

TECHNICAL AREA

The present invention relates to a multi-layer lacquer structure and lacquers for such structures and methods for producing such structures. Stable, inexpensive effect surfaces are provided, which have a mirror-like look similar to polished metal surfaces or electroplated parts. The proposed paint structure provides very weather-stable surfaces that meet the requirements of various automotive standards and various quality labels from the architectural field.

STATE OF THE ART

Metallically reflecting components of all kinds are mainly produced by means of chrome plating or by polishing metallic or rivet-coated materials. In the case of dimensionally complex parts (with places that are difficult to reach), the generation of uniform reflective properties is difficult, cost-intensive and under certain circumstances not possible at all (by polishing).

Very similar to seemingly similar surfaces can be created by applying special varnishes. Such paints are formulated with effect pigments, mainly metallic and platelet-like in nature. If the varnish is applied, the effect pigment floats to the surface in the course of the further drying or curing process and aligns itself planar there (stratification). With the best possible degree of coverage of the surface, suitable reflection properties and a sufficiently small particle size of these effect pigments, it is possible to create reflective surfaces that are very close or even equivalent to polished metal surfaces and especially chrome-plated parts of all types.

On the other hand, there is a high sensitivity of the effect pigment types, especially the aluminum, to weather influences (base character). Corrosion of the pigment leads to rapid fading and graying of the surface.

From GB2303139 a multi-layer coating is known, which comprises a base coating and a top coating, and is formed on an object such as a chemically treated steel plate by the object with a A basecoat composition is coated which contains (a) a crosslinking agent which does not interfere with the hydrosilylation of a topcoat composition, and (b) a functional resin reactive with the crosslinking agent and then a topcoat composition which (c) (i) a mixture of a hydrosilyl group-containing compound and an alkenyl group-containing compound and / or (ii) a self-crosslinkable resin and (d) a catalytic amount of a hydrosilylation catalyst, followed by separate or simultaneous heat curing. The top layer composition can contain functional groups (phosphorus and / or alkoxysilyl groups) or a compound containing functional groups. The proportion of effect pigment in this document is always at least 12 percent by weight.

US2015284585 describes a coating composition containing a carboxy-containing compound (A), a polyepoxide (B) and a specific polyol (C) having a number average molecular weight of 300 to 1,500, and a method for forming a multilayer coating film using the coating composition as a clear coating composition, the method comprising sequentially applying an aqueous first colored coating composition, an aqueous second colored coating composition and the clear coating composition to a substrate and simultaneously thermosetting the resulting coating films form the multilayer coating film.

W003033172 describes a two-part powder coating system in which the first part contains at least one film-forming polymer, at least one chromatic pigment and at least one metallic effect pigment and the second part is essentially free of chromatic pigment. When the first portion is applied to at least one surface of a substrate to form a base powder coating and cured in the absence of the second portion, it can reflect incident white light in a color that is substantially independent of the color of the chromatic pigment. When applied to the top of the base coat to form a clear coat and cured, the second portion can reflect incident white light in a color that is a function of the combined colors of the chromatic pigment and the metallic effect pigment. PRESENTATION OF THE INVENTION

It is an object of the present invention to provide an improved multilayer paint structure with a metallic reflective surface appearance. It is also an object to provide paint systems for such multilayer structures and methods for producing such multilayer paint structures. The object is achieved in that an at least one effect layer with effect pigment and a preferably directly adjacent and adhering to the effect layer cover layer having a multilayer structure is provided, the effect layer and the cover layer having a special composition according to claim 1.

In order to achieve a weather-resistant, metallic, reflective coating, at least a two-layer structure comprising the paint containing the effect agent and a protective top coat / protective coating is required. The primary purpose of this is to avoid corrosion of the effect pigment, which lies essentially on the surface of the effect lacquer without protection, and secondly also to protect the lacquer matrix of this layer, which itself is sensitive or more sensitive to weather influences. In addition, the use of top coats allows a great diversification in terms of color (combination with the mirror effect).

Definition of effect pigment: Effect pigments are based on metal platelets, preferably aluminum platelets, preferably in the order of magnitude (length) of 200 nm, 300 nm or 400 nm to approximately 5 micrometers, which have a form factor between 5: 1 and 1000: 1 (diameter: thickness). These particles are usually produced by special grinding processes (ball mills), which process the starting material (aluminum grit) into very fine particles with a plate-like geometry. The effect particles can be surface-modified with a material which causes or at least promotes the surface leafing effects from the paint during the drying or hardening process. Long-chain, aliphatic carboxylic acids such as stearic acid are often used. The polar carboxylic acid group binds to the metal surface (aluminum surface) while the hydrophobic aliphatic residue ensures that the compatibility with the rest of the lacquer matrix is lost and the pigment floats out. If an almost perfect floating behavior is achieved without too much overlap of neighboring effect particles, high-quality reflective surfaces (ie with high DOI values =>) result with a suitable choice of effect agents distinctiveness of image) as described. If too much effect pigment is used, the quality of the surface decreases and the polished impression disappears. Effect agents based on aluminum are primarily, but not exclusively, suitable. Comparably good results are difficult to achieve with other effect agents. A great advantage of this technology is the high cost efficiency, since the reflective / polished layer is very thin and therefore only small amounts of pigment are necessary. The coating can be done relatively quickly. In addition, toxic substances such as chromium (VI) acid (galvanic chrome plating) are eliminated and time-consuming post-treatment steps (such as polishing) are completely eliminated. For this reason, almost all aluminum effect pigments used in the paint and varnish industry have been surface-modified in order to achieve inerting. This can be achieved by applying special oxide layers or inertizing organic components. In the present case, however, such a treatment would not allow nearly as brilliant, polish-like mirror properties. Only very thin

Coatings such as stearic acid, which are on a molecular scale, allow the described brilliance of the coating results. Formulations of effect paints with floating pigments to create reflective surfaces:

The basis of an effect varnish is formed by oligomeric binder units (BM) based on acrylates, polyesters, polyurethanes or combinations thereof.

These binders are made crosslinkable by adding a hardener (HA), which can itself be in the form of oligomeric binder units. Systems such as 1, 12-dodecanedicarboxylic acid, (methylated) imino-melamine hardeners, isocyanate hardeners such as uretdione-blocked isocyanate hardeners, e-caprolactam-blocked isocyanate hardeners, epoxides such as bis (2,3-epoxypropyl) terephthalate,

Tris (oxiranylmethyl) benzene-l, 2,4-tricarboxylate, 1,3,5-tris (oxiran-2-ylmethyl) -l, 3,5-triazinane-2,4,6-trione, bisphenol-A based, or combinations thereof.

The crosslinked (baked) lacquers have a polymer content (binder crosslinked with hardener) between 50 and 99% by weight. This basic formulation principle can be used for powder coatings as well as liquid coatings.

Effect pigments are also added. In the case of powder coatings, on which the following examples are based, the addition takes place only after the extrusion by the Effect pigments are bound to the powder coating grains under a slight temperature influence (bonding process). The direct extrusion of effect pigments would destroy them due to the strong shear forces. The proportion of the effect pigments, based on the coating formulation, is between 0.1 and 4% by weight. Particularly preferably between 0.5 and 1.2%.

The coating system can contain UV absorbers and / or HALS (hindering amine light stabilizer) to stabilize it against light and weather influences. The addition amounts for HALS and / or UV absorbers, preferably in combination, range between 0.5 and 5% by weight, preferably 1-4% by weight. The ratio of UV to HALS is in the range from 1: 10-5: 1, preferably in the range from 1: 3-l: l.

As a rule, curing takes place at higher temperatures from 120 ° C (so-called baking). In order to produce a perfectly running surface, surface-active substances, which are usually based on liquid acrylates, can be added to the system as additives (AD). These allow a uniform surface tension which makes the surface appear flawless (no craters and other wetting problems). Pigments or fillers (other than effect pigments) can also be added to the lacquer as further additives. Dark pigments in the coating system may increase the brilliance of floating effect pigments (similar to a primer on a mirror). In the present case, however, this is not absolutely necessary. Micronized waxes can be used as additional additives to improve the surface properties of the lacquer. Among other things, these make the paint less sensitive to the effects of scratching.

Formulations of weather-resistant protective top coats:

The composition of a protective topcoat essentially consists of oligomeric binder units based on acrylates, polyesters, polyurethanes or combinations thereof.

These binders are made crosslinkable by adding a hardener, which can also be in the form of oligomeric binder units. Systems such as 1,12-dodecanedicarboxylic acid, (methylated) imino-melamine hardeners, isocyanate hardeners such as uretdione-blocked isocyanate hardeners, e-caprolactam-blocked isocyanate hardeners, epoxides such as bis (2,3-epoxypropyl) terephthalate, tris (oxiranylmethyl) benzene can be used as hardeners. l, 2,4-tricarboxylate, l, 3,5-tris (oxiran-2-ylmethyl) -l, 3,5-triazinan-2,4,6-trione, bisphenol-A based, or combinations thereof . As a rule, curing takes place at higher temperatures from 120 ° C (so-called baking).

The crosslinked (burned-in) topcoats usually have a polymer content (binder crosslinked with hardener) of between 95 and 99%. This basic formulation can be used for powder coatings as well as liquid coatings.

To stabilize it against light and weather influences, the coating system is protected by UV absorbers and HALS (hindered amine light stabilizer). The sensible additions for HALS and UV absorbers range between 0.5% and 6% by weight, preferably between 1 and 5% by weight. This addition protects both the topcoat itself and the underlying paint layers from harmful light effects. The way it works is like sunglasses, which is placed over this lacquer. Harmful UV radiation is absorbed by the UV absorber. The HALS absorber, on the other hand, can only work in the paint itself, since it can neutralize the radicals that come into contact with it. The ratio of UV to HALS is in the range from 1: 10-5: 1, preferably in the range from 1: 3-1: 1.

In order to produce a perfectly running surface, surface-active substances, which are usually based on acrylates, can be added to the system as additives. These enable a uniform surface tension which leads to a perfect surface (no craters and other wetting problems). Furthermore, certain pigments or dyes can be added to the paint in a deeply concentrated amount, these give the paint structure a color nuance. Micronized waxes can also be used as additives to improve the surface of the lacquer. Among other things, these make the paint less sensitive to the effects of scratching.

Formulation of a primer:

The task of a primer essentially includes the appropriate preparation of a substrate for the subsequent painting steps. The primer often has better adhesive properties on the metal workpiece, for example, smoothes its surface and also compensates for imperfections (unevenness, protruding metal pimples, etc.). The primer should offer good adhesion conditions for layers of paint applied to it. In addition, the primer often protects the metal workpiece, for example, against corrosion. The following is described a possible powder coating primer.

As a rule, primers have a polymer component (hardened paint film, i.e. the binder cross-linked with hardener) between 50 and 80%.

As a rule, oligomeric bisphenol A-based resins with glass transition temperatures of 40 to 75 ° C. are used. These can have epoxy equivalent weights between 500 g / eq and 1400 g / eq.

The lacquer is typically cured using cyanamides such as dicyandiamide, guanidines such as l - (o-tolyl) biguanide or, more rarely, phenolic hardeners. A crosslinking of the epoxy resin with itself is also conceivable, often not practical in practice due to the longer curing times. The curing reaction can be accelerated if necessary using catalysts, for example from the group of imidazoles.

In order to improve the corrosion protection effect and to reduce stresses in the paint better, and for other purposes, additives or fillers can be added to the formulation, e.g. Pigments, fillers such as chalk, barium sulfate or aluminum hydroxide. In order not to jeopardize good adhesion to the next layer of paint, the primer should not contain excessive amounts of polyolefin waxes (<0.5%). These are added to the system for resistance to scratching and to improve extrusion performance. Epoxy primers as described above offer excellent adhesion conditions for subsequent layers of paint. The protective effect of the effect varnish works particularly well under the following conditions:

Topcoat and effect paint should work well together. Good interlayer adhesion is important. Experience has shown that this is particularly good when an epoxy-polyester hardener / binder combination (base of the effect lacquer) meets a polyester-containing acrylate topcoat that is cross-linked with an imino-melamine hardener. Acrylates per se have very good light and weather stability and can be significantly improved again by adding UV and HALS absorbers. It is primarily about preventing the light-related and weather-related degradation of the top coat, because this leads to a massive increase in the water permeability of the paint. Water vapor is very aggressive towards the effect pigment and can lead to graying and delamination of the layers of paint. The topcoat should therefore be applied in a sufficient layer thickness in the range of 0.01-0.2 mm, preferably 0.02-0.1 mm, in order to keep the diffusion barrier high and on the other hand, to enhance the effect of the UV absorber. The more layer there is, the higher the extinction of the UV light up to the effect lacquer layer. Since the top coat layer thickness is limited, this requires a sufficient amount of UV absorber in the top coat (at least 0.5%). Another basic requirement is the overall high diffusion barrier of the top coat against water vapor. This can be increased by a comparatively high cross-linking density. However, the physical properties of the binder are decisive here.

In particular, the present invention thus relates to a multilayer paint structure, at least indirectly on a substrate (ie directly on the substrate or indirectly, ie with one or more layers, for example primer layers, between the substrate and the effect lacquer layer), at least one effect lacquer layer and on top of that Side facing away from the substrate at least one cover layer,

in which

the effect lacquer layer consists of the following components:

(AE) 50-99.9% by weight of oligomeric binder selected from the group consisting of:

Acrylate, polyester, polyurethane or a combination of these systems with a hardener;

(BE) 0.1-4 wt .-% effect pigment based on metal flakes, which are not inert, and in particular without an oxide layer;

(CE) 0-5% by weight UV and / or HALS stabilization;

(DE) 0-30% by weight of inorganic particulate fillers;

(EE) 0-10% by weight of additives

where the components (AE) - (EE) add up to 100 percent by weight of the formulation of the effect lacquer layer;

and wherein the cover layer (14, 16, 17) consists of the following components:

(AD) 90-99.5% by weight of oligomeric binder selected from the group consisting of:

(CD) 0.5-5% by weight UV and / or HALS stabilization;

(DD) 0-5% by weight of inorganic particulate fillers;

(ED) 0-10% by weight of additives

where the components (AD) - (ED) add up to 100 percent by weight of the formulation of the top layer. The following systems or combinations thereof are possible as component (AE) of the effect lacquer layer: acrylate resins containing glycidyl groups (e.g.

Methacrylate-based), hydroxylated acrylate resins, carboxylated polyester resins, hydroxylated polyester resins.

The systems of component (AE) typically have a glass transition temperature of less than 75 ° C, preferably in the range of 40-70 ° C.

The systems of component (AE) further preferably have an OH value in the range of 20-40 mg KOH / g when they are hydroxylated and an acid number in the range of 10-180 mgKOH / g when they are carboxylated.

The following systems or combinations thereof are possible as component (AD) of the cover layer: glycidyl group-containing acrylate resins (e.g. methacrylate-based), hydroxylated acrylate resins, carboxylated polyester resins, hydroxylated polyester resins, polyester-containing acrylate resins.

The systems of component (AD) typically have a glass transition temperature of less than 75 ° C, preferably in the range of 40-70 ° C.

The systems of component (AD) further preferably have an OH value in the range of 20-200 mg KOH / g when they are hydroxylated or in the form of polyester-containing acrylate resin, and when they are carboxylated an acid number in the range of 10-180 mgKOH / G.

A first preferred embodiment of such a lacquer structure is characterized in that component (AE) of the effect lacquer layer contains polyester as the oligomeric binder or is formed exclusively from polyester, and contains an epoxy resin based in particular on bisphenol-A, preferably as the only hardener, as hardener,

and that component (AD) of the top layer contains polyester-containing acrylate as the oligomeric binder or is formed exclusively from polyester-containing acrylate, and contains a preferably methylated imino-melamine hardener, preferably as the only hardener, as the hardener.

The effect lacquer layer and the top layer can be arranged directly adjacent to one another, and the top layer can form the exposed surface.

A primer layer can be arranged between the substrate and the effect lacquer layer.

Another preferred embodiment is characterized in that the preferably single effect lacquer layer has a thickness in the range of 0.01-0.3 mm, preferably in the range of 0.05-0.2 mm.

A further preferred embodiment is characterized in that the preferably single cover layer has a thickness in the range from 0.01 to 0.2 mm, preferably in the range from 0.02 to 0.1 mm.

A further preferred embodiment is characterized in that an optionally present primer layer has a thickness in the range from 0.03 to 0.3 mm, preferably in the range from 0.06 to 0.2 mm.

The hardener within component (AE) of the effect lacquer layer and / or within component (AD) of the top layer can be selected from the following group: 1,12-dodecanedicarboxylic acid, (methylated) imino-melamine hardener, isocyanate hardener such as uretdione-blocked isocyanate hardener, e -Caprolactam-blocked isocyanate hardener, epoxides such as bis (2,3-epoxypropyl) terephthalate, tris (oxiranylmethyl) benzene-l, 2,4-tricarboxylate, l, 3,5-tris (oxiran-2-ylmethyl) -l, 3 , 5-triazinan-2,4,6-trione, bisphenol-A based, or combinations thereof.

The inorganic fillers within component (DE) of the effect lacquer layer and / or within component (DD) of the top layer can be selected from the group consisting of: fillers, in surface-treated or untreated form, selected from the group consisting of: talc, mica , Silicate, such as in particular iron aluminum silicate and / or sodium aluminum silicate particles, aluminum hydroxide, quartz, quartz powder, titanium dioxide, wollastonite, kaolin, silicas, in particular amorphous silicas, ground or precipitated calcium carbonate, magnesium carbonate, magnesium hydroxide, chalk, lime, feldspar, mica, ground or precipitated barium sulfate, barium titanate, zinc sulfide, glass spheres, in particular solid or hollow glass spheres, ground glass, in particular ground glass fibers, glass flakes, glass flakes, permanently magnetic or magnetizable metal compounds and / or alloys, inorganic pigments, such as in particular iron oxide, iron manganese oxide, metal powder he, in particular iron powder, copper powder, aluminum powder, metal flakes, in particular aluminum flakes, iron flakes, metal-coated fillers, metal oxides, hard or soft magnetic metals or alloys or ceramics, hollow spherical silicate fillers, aluminum oxide, boron nitride, boron carbide, aluminum nitride, calcium fluoride, and mixtures of the elements this group.

The additives within the component (EE) of the effect lacquer layer and / or within the Component (ED) of the cover layer can be selected from the following group: surface-active substances, in particular based on acrylates; Waxes, in particular micronized waxes, pigments other than effect pigments, antistatic agents or combinations thereof.

The stabilizer of component (CE) of the effect lacquer layer and / or within component (CD) of the top layer as HALS can be selected from the following group: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( 1,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, bis (2,2,6,6-tetramethyl) -4-piperidyl) sebacate, or combinations thereof, and / or selected as a UV stabilizer from the following group: 2-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) -

4-methylphenol, 2,2 '- (6-anilino- [1,3,5] triazine-2,4-diyl) bisphenol, 3- (2H-benzotriazolyl) -

5- (1, 1-di-methylethyl) -4-hydroxybenzenepropanoic acid octyl ester, or combinations thereof.

The stabilizer of component (CE) of the effect lacquer layer and / or within component (CD) of the top layer can be formed as a mixture of an HALS and a UV stabilizer, the ratio of UV to HALS stabilizer preferably being in the range of 1:10. 5: 1, preferably in the range of 1: 3-l: 1.

The effect pigment of component (BE) can consist of aluminum flakes free of oxide layer, optionally coated with a saturated fatty acid, preferably stearic acid, these having an average order of magnitude of 200 nm, 300 nm or 400 nm to about 5 micrometers, and preferably a form factor between 5: 1 and 1000: 1 (diameter: thickness).

The proportion of component (CD) in the cover layer can be in the range of 1-4.5% by weight, preferably in the range of 2-4.5% by weight.

The proportion of component (CE) in the effect lacquer layer can be in the range from 0.5-4.5% by weight, preferably in the range from 1-4.5% by weight.

The top layer and / or the effect lacquer layer can have been produced on the basis of a powder lacquer.

The present invention further relates to a component with a lacquer structure as described above, preferably a metallic component, particularly preferably from the automotive sector, including body components, rims, moldings, switches, transitions, holders, handles, closures, covers, mirrors and combinations of such components . In addition, the present invention relates to a kit-of-parts of an effect lacquer and an effect lacquer for producing a lacquer structure as described above, particularly preferably as a liquid lacquer or powder lacquer.

Last but not least, the present invention relates to a method for producing a lacquer structure as described above, which is characterized in that the effect lacquer is applied and cured in a first step, if appropriate after previously producing a primer layer, and in a second step the top layer is applied and cured, the curing, in the case of powder coating, particularly preferably at a temperature of more than 100 ° C. and over a period of at least 10 minutes.

Further embodiments are specified in the dependent claims.

BRIEF DESCRIPTION OF THE DRAWINGS

Preferred embodiments of the invention are described below with reference to the drawings, which are used only for explanation and are not to be interpreted restrictively. The drawings show:

Fig. 1 is a schematic representation of the generation of a paint surface the

Gives the impression of a polished metal surface. Powder coating (top left), which is mixed with a special effect pigment, or a liquid coating (top right) with the same effect pigment is applied to a substrate and melts / hardens or dries / hardens thereon; with a suitable amount of effect pigment, a metal-polished surface is formed (bottom left), while the polish effect is not properly pronounced with the wrong amount of effect pigment (bottom right);

2 shows a schematic representation of a paint structure with a primer, which may or may not necessarily be present, the effect paint layer with the floating effect pigment and a protective cover layer;

3 shows a powder coating compound which has been bonded to special effect pigment particles (aluminum-based) by a so-called bonding process;

4 shows a powder-coated surface in the hardened state; The floating effect pigment particles are well distributed and without overlaps, which gives a high brilliance of the macroscopic, metallic allows polished impression;

Fig. 5 three differently equipped with UV and HALS absorbers

Top coats (examples 5 - 7 from left to right, absorber quantity varies) on the same effect lacquer after 3000 hours of rapid weathering test in accordance with DIN EN ISO 16474-2; there are massive differences in the protective effect against the pigment and also clear differences in the degree of gloss of the topcoat;

Fig. 6 Results of three different varnishes in a cross-cut test with subsequent tape tear according to DIN EN ISO 2409 after 1000 hours of rapid weathering according to DIN EN ISO 16474-2; the oxidation of the effect pigment leads, in addition to visual losses, to strong detoxification phenomena; and

7 shows a lacquer structure which is particularly important for multi-colored metal rims; priming can, but does not necessarily have to be done; a further protective clear coat, transparent or colored, is applied to the effect paint with floating or non-floating pigments; this is in turn covered with a colored or opaque lacquer layer; For design reasons, this can be removed in places (by twisting, laser etching or other processes); at the end the painting is done with a protective top coat, transparent or colored.

DESCRIPTION OF PREFERRED EMBODIMENTS

FIG. 1 shows schematically how a multilayer structure comprising an effect lacquer layer and a top layer arranged above it can be formed on a substrate 5. The left branch shows at the top how a raw powder coating 1, which has particles 2 with effect coating particles 3 arranged on the surface, is applied to the substrate 5. The raw powder coating layer 4 on the substrate is shown below. If this layer is exposed to a suitable elevated temperature for a suitable time period t. H. If heat is supplied, the hardening process 9 shown in the middle begins. As a rule, the flake-like effect paint particles migrate to the surface of the corresponding layer.

If the appropriate amount and the appropriate type of effect paint particles are used, then a high-gloss layer forms, as shown at the bottom left. The particles 3 are oriented on the surface and form an effect lacquer layer 10 with a metallic polished effect, because the particles are arranged next to one another parallel to the surface plane.

E.g. If oxidizable metal particles are used as the effect lacquer layer particles, there is a risk if no further layer is arranged on them that the particles arranged on the surface oxidize and the gloss effect is gradually lost.

A situation is schematically shown at the bottom right, in which too much effect paint pigment was contained in the formulation. The particles then also migrate to the surface, but prevent each other from adopting a plane-parallel position, so that a sufficient gloss effect cannot occur.

The right branch of FIG. 1 shows above how a liquid lacquer 6 is applied to a substrate 5, so that a raw liquid lacquer layer 8 is formed. Here too, as shown in the middle, the layer is hardened either by drying or by drying and applying heat.

According to the invention, a further cover layer is applied to such a layer.

Another possible multilayer structure is shown schematically in FIG. A primer layer 12 is initially arranged on the substrate 5. The effect lacquer layer 10 is then arranged on this primer layer 12. The primer layer 12 is particularly advantageous if the substrate consists of metal and the adhesion between the effect lacquer layer and the substrate is to be improved.

A top layer 14 is now additionally arranged on the effect lacquer layer 10, on the surface of which the effect lacquer particles are to a certain extent concentrated and aligned in a layer 13. The cover layer then exposes the exposed surface 15 of the final component.

Figure 7 shows an alternative layer structure. There are several top layers here, a primer 12 is initially provided on the substrate 5, followed by the effect lacquer layer 10, in which this time the pigments are not concentrated and oriented to the same extent on the surface, but nevertheless have a metallic surface. Appearance is guaranteed. This is followed by a first top layer in the form of a clear lacquer layer 16, another top layer in the form of an opaque lacquer layer 17, which can be pigmented, for example, and then at the end is the final covering layer 14. The pigmented lacquer layer 17 can have cutouts 18 in order to provide certain optical effects.

Formulation of a primer:

560g epoxy resin BM (bisphenol-A based, glass transition temperature TG approx. 55 ° C, epoxy equivalent weight EEW approx. 775g / eq, Dow Chemicals) and 70g epoxy resin leveling agent masterbatch AD (contains an acrylate-based, surface-active additive, epoxide equivalent weight approx. 800g / eq, Jana ) were mixed with a stoichiometric amount of epoxy hardener HA (l- (o-tolyl) biguanide, AlzChem). For this purpose, 3g micronized polyolefin wax AD (dropping point approx. 110 ° C, Clariant), 15g iron oxide black pigment PI (Lanxess), 2g iron oxide yellow pigment PI (Lanxess), 110g titanium dioxide pigment PI (Huntsman), 100g barium sulfate FU (average grain size approx. 5mih, Sachtleben) given. The mixture was weighed with the addition of chalk FU (average grain size approx. 5 pm, Omya) to a total weight of 1000 g.

The homogeneously mixed mixture was extruded at about 110 ° C. using a single-screw extruder (PLK-46, Buss). The extrudate was then ground with an impact mill with sifter (Hosokawa Alpine) to form an applicable powder coating.

By means of the baking process after application, smooth-running coatings with a silky gloss to glossy surface are obtained (70 to 95 gloss units in a 60 ° measuring angle according to DIN EN ISO 2813).

Formulations of examples of effect paints with floating pigments to create reflective surfaces:

1.780g glycidyl group-containing acrylic resin BM (methacrylate-based, TG approx.

50 ° C, EEW approx. 500 g / eq, DIC) was mixed with a stoichiometric amount of 1,12-dodecanedicarboxylic acid HA (BASF). There were also 10 g of acrylate-based leveling agent AD (on silicate support, Altana), 10 g of bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate HALS (BASF), 5 g of 2-tert-butyl-6- (5-chloro -2H-benzotriazol-2-yl) -4-methylphenol UV (BASF) and 3 g micronized

Polyolefin wax mixed in AD (dropping point approx. 110 ° C, Clariant). In total, this resulted in a mass of 1000 g.

The homogeneously mixed mixture was extruded with a single-shaft extruder (PLK-46, Buss) at approx. 120 ° C and then with an impact mill with classifier (Hosokawa Alpine) ground to powder. This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of <5pm, Sun Chemical) under the influence of light heat (just above the glass transition temperature of the powder), which leads to the effect pigment particles sticking to the powder grains (so-called bonding process, see 3) to prevent subsequent separation of the effect pigment, the proportion of the amount of the effect pigment based on the 1000 g specified above being 0.666% by weight. The result was an applicable powder coating that forms mirror-like surfaces during the stoving process.

820 g of hydroxylated acrylate resin BM (TG approx. 54 ° C, OH value 30 mg KOH / g, DIC) was mixed with a stoichiometric amount of uretdione-blocked isocyanate hardener HA (TG approx. 48 ° C, NCO content approx. 13.5%, Covestro ) mixed. There were also 10 g of acrylate-based leveling agent (on silicate support, Altana), 10 g of bis (1,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] methyl] butylmalonate HALS (BASF), 5g 2,2 '- (6-anilino- [1,3,5] triazine-2,4-diyl) -bis-phenol UV (Clariant) and 3g micronized polyolefin wax mixed in AD ( Dropping point approx. 110 ° C, Clariant). In total, this resulted in a mass of 1000 g.

The homogeneously mixed mixture was extruded at approx. 130 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine). This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of <5 pm, Sun Chemical) under the action of light heat, the proportion of the amount of the effect pigment based on the above-mentioned 1000 g being 0.6% by weight. The result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.

(without stabilization) 900g carboxylated polyester resin BM (TG approx. 65 ° C,

Acid number 34 mg KOH / g, Allnex) was mixed with a stoichiometric amount of a reaction mass consisting of bis (2,3-epoxypropyl) terephthalate and

Tris (oxiranylmethyl) benzene-1, 2,4-tricarboxylate HA (Huntsman) mixed. Furthermore, 10 g of acrylate-based leveling agent AD (on silicate carrier, Altana), 3 g of micronized polyolefin wax AD (dropping point approx. 110 ° C., Clariant) and 7 g of pearl black PI (Orion Engineered Carbons) are added. In total, this resulted in a mass of 1000 g.

The homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine). This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of <5 pm, Sun Chemical) under the action of light heat, the proportion of the amount of the effect pigment based on the above-mentioned 1000 g being 0.6% by weight. The result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.

915g carboxylated polyester resin BM (TG approx. 68 ° C, acid number 26mg KOEl / g,

DSM) was mixed with a stoichiometric amount of a reaction mass composed of bis (2,3-epoxypropyl) terephthalate and tris (oxiranylmethyl) benzene-1,2,4-tricarboxylate HA (Huntsman). 10 g of acrylate-based leveling agent AD (on silicate carrier, Altana), 10 g of bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate HALS (BASF), 5 g of 2-tert-butyl-6- (5- chloro-2H-benzotriazol-2-yl) -4-methylphenol UV (BASF) and 3 g micronized

Polyolefin wax AD (dropping point approx. 1 10 ° C, Clariant) added. In total, this resulted in a mass of 1000 g.

The homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine). This was mixed together with the effect pigment (surface-modified aluminum flakes with an average diameter of <5 pm, Sun Chemical) under the action of light heat, the proportion of the effect pigment based on the 1000 g stated above being 0.5% by weight. The result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.

(without stabilization) 933g carboxylated polyester resin BM (TG approx. 68 ° C, acid number 26mg KOH / g, DSM) was mixed with a stoichiometric amount of 1,3,5-tris (oxiran-2-ylmethyl) -l, 3,5- triazinan-2,4,6-trione HA (Huntsman) mixed. 10 g of acrylate-based leveling agent AD (on silicate carrier, Altana), 3 g of micronized polyolefin wax AD (dropping point approx. 110 ° C., Clariant) and 7 g of pearl black PI (Orion Engineered Carbons) were also added. Summed up in total a mass of 1000 g.

The homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine). This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of <5 pm, Sun Chemical) under the action of light heat, the proportion of the effect pigment based on the 1000 g stated above being 0.8% by weight. The result was an applicable powder coating that forms mirror-like surfaces during the stoving process.

6. 790 g of hydroxylated polyester resin BM (TG approx. 53 ° C, OH value 43 mg KOH / g, DSM) was mixed with a stoichiometric amount of e-caprolactam-blocked isocyanate hardener HA (TG approx. 52 ° C, NCO content approx 15%, Covestro) mixed. In addition, 10 g of acrylate-based leveling agent AD (on silicate carrier, Altana), 10 g of bis (1, 2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4- hydroxyphenyl] methyl] butylmalonate HALS (BASF), 5g 2,2 '- (6-anilino- [1,3,5] triazine-2,4-diyl) -bis-phenol UV (Clariant) and 3g micronized polyolefin wax mixed in AD (Drop point approx. 110 ° C, Clariant). In total, this resulted in a mass of 1000 g.

The homogeneously mixed mixture was extruded at approx. 130 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine). This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of <5 pm, Sun Chemical) under the action of light heat, the proportion of the effect pigment based on the above-mentioned 1000 g being 0.7% by weight. The result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.

7. 650 g of hydroxylated polyester resin BM (TG approx. 51 ° C, OH value 85 mg KOH / g, DSM) was mixed with a stoichiometric amount of uretdione-blocked isocyanate hardener HA (TG approx. 48 ° C, NCO content approx. 13.5% , Covestro) mixed. There were also 10 g of acrylate-based leveling agent (on silicate carrier, Altana), 10 g of bis (1,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] methyl] butylmalonate HALS (BASF), 5g 2,2 '- (6-anilino- [1,3,5] triazine-2,4-diyl) -bis-phenol UV (Clariant) and 3g micronized Polyolefin wax mixed in AD (dropping point approx. 110 ° C, Clariant). In total, this resulted in a mass of 1000 g.

The homogeneously mixed mixture was extruded with a single-screw extruder (PLK-46, Buss) at approx. 130 ° C and then ground to powder with an impact mill with sifter (Hosokawa Alpine). This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of <5 m 2, Sun Chemical) under the action of light heat, the proportion of the effect pigment based on the 1000 g given above being 0.6% by weight. The result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.

718g carboxylated polyester resin BM (TG approx. 61 ° C, acid number 26mg KOH / g,

DSM) was based on 239g epoxy resin HA (bisphenol-A,

Glass transition temperature TG approx. 55 ° C, epoxy equivalent weight EEW approx. 775g / eq, Dow Chemicals) mixed. 10 g of acrylate-based leveling agent AD (on silicate carrier, Altana), 10 g of bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate HALS (BASF), 5 g of 2-tert-butyl-6- (5- chloro-2H-benzotriazol-2-yl) -4-methylphenol UV (BASF), 5g 3,9-bis (2,4-di-tert-butylphenoxy) -2,4,8,10-tetraoxa-3,9 -diphosphaspiro [5.5] undecan AN (BASF) and 3g micronized polyolefin wax AD (dropping point approx. 1 10 ° C, Clariant) mixed. In total, this resulted in a mass of 1000 g.

The homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine). This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of <5 m 2, Sun Chemical) under the action of light heat, the proportion of the effect pigment based on the 1000 g given above being 0.7% by weight. The result was an application-like powder coating that forms mirror-like surfaces during the stoving process.

(without stabilization) 686g carboxylated polyester resin BM (TG approx. 60 ° C, acid number 33mg KOH / g, DSM) was mixed with 294g epoxy resin HA (bisphenol-A based, glass transition temperature TG approx. 55 ° C, epoxy equivalent weight EEW approx. 775g / eq , Dow Chemicals).

Furthermore, 10 g of acrylate-based leveling agent AD (on Silicate carrier, Altana), 7g pearl black (Orion Engineered Carbons) and 3g micronized polyolefin wax AD (dropping point approx. 110 ° C, Clariant). In total, this resulted in a mass of 1000 g.

The homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine). This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of <5 pm, Sun Chemical) under the action of light heat, the proportion of the effect pigment being 0.5% by weight based on the abovementioned 1000 g. The result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.

10. 580g carboxylated polyester resin BM (TG approx. 51 ° C, acid number 52mg KOH / g, Megara Resins) was mixed with 387g epoxy resin HA (bisphenol-A based, glass transition temperature TG approx. 55 ° C, epoxy equivalent weight EEW approx. 775g / eq, Dow Chemicals) mixed. 10 g of acrylate-based leveling agent AD (on silicate carrier, Altana), 10 g of bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate HALS (BASF), 5 g of 2-tert-butyl-6- (5- chloro-2H-benzotriazol-2-yl) -4-methylphenol UV (BASF), 5g 3,9-bis (2,4-di-tert-butylphenoxy) -2,4,8,10-tetraoxa-3,9 -diphosphaspiro [5.5] undecan AN (BASF) and 3g micronized polyolefin wax AD (dropping point approx. 1 10 ° C, Clariant) mixed. In total, this resulted in a mass of 1000 g.

The homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine). This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of <5 ml, Sun Chemical) under the influence of light heat, the proportion of the effect pigment based on the 1000 g stated above being 0.6% by weight. The result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.

1 1. 483g carboxylated polyester resin BM (TG approx. 54 ° C, acid number 70mg KOH / g,

Allnex) was based on 483g epoxy resin HA (bisphenol-A,

Glass transition temperature TG approx. 55 ° C, epoxy equivalent weight EEW approx. 775g / eq, Dow Chemicals) mixed. There were also 10g acrylate-based leveling agent AD (on silicate carrier, Altana), 10g bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate HALS (BASF), 5g 2-tert-butyl-6- (5-chloro-2FI-benzotriazole -2-yl) -4-methylphenol UV (BASF), 5g 3,9-bis (2,4-di-tert-butylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecan AN (BASF) and 3g micronized polyolefin wax AD (dropping point approx. 110 ° C, Clariant) mixed. In total, this resulted in a mass of 1000 g.

12. 387g carboxylated polyester resin BM (TG approx. 58 ° C, acid number 74mg KOH / g,

DSM) was based on 580g epoxy resin HA (bisphenol-A,

Glass transition temperature TG approx. 60 ° C, epoxy equivalent weight EEW approx. 915g / eq, Dow Chemicals) mixed. 10 g of acrylate-based leveling agent AD (on silicate carrier, Altana), 10 g of bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate HALS (BASF), 5 g of 2-tert-butyl-6- (5- chloro-2H-benzotriazol-2-yl) -4-methylphenol UV (BASF), 5g 3,9-bis (2,4-di-tert-butylphenoxy) -2,4,8,10-tetraoxa-3,9 -diphosphaspiro [5.5] undecan AN (BASF) and 3g micronized polyolefin wax AD (dropping point approx. 1 10 ° C, Clariant) mixed. In total, this resulted in a mass of 1000 g.

The homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine). This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of <5 pm, Sun Chemical) under the action of light heat, the proportion of the effect pigment based on the 1000 g stated above being 0.666% by weight. The result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.

13. (not according to the invention) 745g epoxy resin BM (bisphenol-A based, Glass transition temperature TG approx. 55 ° C, epoxy equivalent weight EEW approx. 775g / eq, Dow Chemicals) and 70g epoxy resin leveling agent masterbatch AD (contains an acrylate-based, surface-active additive, epoxy equivalent weight approx. 800g / eq, Jana) were mixed with a stoichiometric amount of epoxy hardener HA (l- (o-tolyl) biguanide, AlzChem) mixed. 15 g of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate HALS (BASF), 8 g of 2-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) - 4-methylphenol UV (BASF), 10g 3,9-bis (2,4-di-tert-butylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecan AN (BASF) and 3g micronized polyolefin wax AD (dropping point approx. 110 ° C, Clariant) added. In addition, 200g of precipitated barium sulfate FU (average grain size approx. 0.7pm, Sachtleben). The homogeneously mixed mixture was extruded at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with classifier (Hosokawa Alpine). In total, this resulted in a mass of 1000 g.

This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of <5 pm, Sun Chemical) under the action of light heat, the proportion of the effect pigment based on the 1000 g stated above being 0.777% by weight. The result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.

(not according to the invention) 742g epoxy resin BM (bisphenol-A based, glass transition temperature TG approx. 53 ° C, epoxy equivalent weight EEW approx. 650g / eq, Dow Chemicals) and 70g epoxy resin leveling agent masterbatch AD (contains an acrylate-based, surface-active additive, epoxy equivalent weight approx 800g / eq, Jana) were mixed with a stoichiometric amount of epoxy hardener HA (l- (o-tolyl) biguanide, AlzChem). 15 g of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate HALS (BASF), 8 g of 2-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) - 4-methylphenol UV (BASF), 10g 3,9-bis (2,4-di-tert-butylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecan AN (BASF) and 3g micronized polyolefin wax AD (dropping point approx. 1 10 ° C, Clariant) mixed. In addition, 200g of precipitated barium sulfate FU (average grain size approx. 0.7mhi, Sachtleben). The homogeneously mixed mixture was extruded with a single-screw extruder (PLK-46, Buss) at approx. 120 ° C. and then ground to powder with an impact mill with sifter (Hosokawa Alpine). In total, this resulted in a mass of 1000 g.

This was mixed together with the effect pigment EF (surface-modified aluminum flakes with an average diameter of <5 pm, Sun Chemical) under the action of light heat, the proportion of the amount of the effect pigment based on the above-mentioned 1000 g being 0.6% by weight. The result was an application-capable powder coating that forms mirror-like surfaces during the stoving process.

Formulations of examples of weather-resistant protective top coats:

1. 495 g of hydroxylated polyester resin BM (TG approx. 58 ° C, OH value 100 mg KOH / g,

Allnex) and 70g polyester resin leveling agent masterbatch AD (contains an acrylate-based, surface-active additive, OH value 45 mg KOH / g, Allnex) with a stoichiometric amount of e-caprolactam-blocked isocyanate hardener HA (TG approx. 49 ° C, NCO content approx. 10.5%, Evonik) mixed. 20 g of bis (1, 2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1, dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate HALS (BASF), 10 g 2 , 2 '- (6-anilino-

[1,3,5] triazine-2,4-diyl) -bis-phenol UV (Clariant) and 3 g micronized polyolefin wax AD (dropping point approx. 110 ° C., Clariant). In total, this resulted in a mass of 1000 g.

The homogeneously mixed mixture was extruded twice at approx. 130 ° C. using a single-screw extruder (PLK-46, Buss) and was then ground to powder using an impact mill with classifier (Hosokawa Alpine). The baking process after application gives smooth-running coatings with high transparency, good weather resistance, a glossy surface (> 95 gloss units in a 60 ° measuring angle according to DIN EN ISO 2813) and very good UV-absorbing properties.

2. 785 g of carboxylated polyester resin BM (TG approx. 65 ° C., acid number 34 mg KOH / g, Allnex) was mixed with a stoichiometric amount of a reaction mass consisting of bis (2,3-epoxypropyl) terephthalate and tris (oxiranylmethyl) benzene-1,2. 4-tricarboxylate HA (Huntsman) mixed. In addition, 100 g of polyester resin adhesive masterbatch AD (contains an acrylate-based, surface-active additive, acid number 35 mg KOH / g, Allnex), 20 g bis (2,2,6,6- tetramethyl-4-piperidyl) sebacate HALS (BASF), 10g 2-tert-butyl-6- (5-chloro-2H-benzotriazol-2-yl) -4-methylphenol UV (BASF), 3g micronized polyolefin wax AD (dropping point approx . 1 10 ° C, Clariant) and 0.02g pearl black PI (Orion Engineered Carbons) mixed. In total, this resulted in a mass of 1000 g.

The homogeneously mixed mixture was extruded twice at approx. 120 ° C. using a single-screw extruder (PLK-46, Buss) and was then ground to powder using an impact mill with classifier (Hosokawa Alpine). By means of the baking process after application, slightly dark tinted, smooth-running coatings with good weather resistance, a glossy surface (> 95 gloss units in a 60 ° measuring angle according to DIN EN ISO 2813) and very good UV-absorbing properties are obtained.

775g glycidyl group-containing acrylic resin BM (methacrylate-based, TG approx.

50 ° C, EEW approx. 500 g / eq, DIC) was mixed with a stoichiometric amount of 1,12-dodecanedicarboxylic acid HA (BASF). There were also 10 g of acrylate-based leveling agent AD (on silicate carrier, Altana), 20 g of bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate HALS (BASF), 10 g of 2-tert-butyl-6- (5-chloro -2H- benzotriazol-2-yl) -4-methylphenol UV (BASF) and 3g micronized polyolefin wax AD (dropping point approx. 10 ° C, Clariant). In total, this resulted in a mass of 1000 g.

The homogeneously mixed mixture was extruded twice at about 120 ° C. using a single-screw extruder (PLK-46, Buss) and then ground to powder using an impact mill with sifter (Hosokawa Alpine). The baking process after application gives smooth-running coatings with high transparency, very good weather resistance, a glossy surface (> 95 gloss units at a 60 ° measuring angle according to DIN EN ISO 2813) and very good UV-absorbing properties.

788 g of hydroxylated acrylate resin BM (TG approx. 54 ° C, OH value 30 mg KOH / g, DIC) was mixed with a stoichiometric amount of e-caprolactam-blocked isocyanate hardener HA (TG approx. 49 ° C, NCO content approx. 10.5% , Evonik) mixed. 10 g of acrylate-based leveling agent AD (on silicate carrier, Altana)), 20 g of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate HALS (BASF), 10 g of 2-tert-butyl-6- (5- chloro-2H-benzotriazol-2-yl) -4-methylphenol UV (BASF) and 3g micronized polyolefin wax AD (dropping point approx. 110 ° C, Clariant). In total, this resulted in a mass of 1000 g.

600g polyester-containing acrylate resin in butyl acetate BM (77%, OH value 150mg KOH / g, Synthopol) was mixed with 180g methylated imino-melamine hardener in isobutanol HA (80%, Allnex), 50g 2-butoxyethyl acetate LM (Brenntag) and 155g White Spirit LM (Exxon Mobil) mixed using a dissolver. 3.75 g of a mixture of bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate HALS and 1- (methyl) -8- (1,2,2,6,6-pentamethyl- 4-piperidinyl) sebacate HALS (Clariant), 1.25g 3- (2H-benzotriazolyl) -5- (1,1-di-methylethyl) -4-hydroxybenzenepropanoic acid octyl ester UV (BASF), 5g of a polyether-modified polydimethylsiloxane leveling agent in xylene / isobutanol AD (Altana) and 5g of a silicone-free defoamer AD (Altana) and mixed using a dissolver. In total, this resulted in a mass of 1000 g.

By means of the baking process after application, smooth-running coatings with high transparency, very good weather resistance, a glossy surface (> 95 gloss units in a 60 ° measuring angle according to DIN EN ISO 2813) and very good UV-absorbing properties are obtained.

600g polyester-containing acrylate resin in butyl acetate BM (77%, OH value 150mg KOH / g, Synthopol) was mixed with 180g methylated imino-melamine hardener in isobutanol HA (80%, Allnex), 50g 2-butoxyethyl acetate LM (Brenntag) and 150g White Spirit LM (Exxon Mobil) mixed using a dissolver. 7.5 g of a mixture of bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate HALS and 1- (methyl) -8- (1,2,2,6,6-pentamethyl- 4-piperidinyl) sebacate HALS (Clariant), 2.5g 3- (2H-benzotriazolyl) -5- (1, 1-di-methylethyl) -4-hydroxybenzenepropanoic acid UV (BASF), 5g of a polyether-modified polydimethylsiloxane leveling agent in xylene / isobutanol AD (Altana) and 5 g of a silicone-free defoamer AD (Altana) and mixed using a dissolver. The total resulted a mass of 1000 g.

7. 600g polyester resin containing acrylate in butyl acetate BM (77%, OH value 150mg

KOH / g, Synthopol) was mixed with 180g methylated imino-melamine hardener in isobutanol HA (80%, Allnex), 50g 2-butoxyethyl acetate LM (Brenntag) and 120g White Spirit LM (Exxon Mobil) using a dissolver. 30 g of a mixture of bis (1,2,6,6-pentamethyl-4-piperidinyl) sebacate HALS and 1- (methyl) -8- (1,2,2,6,6-pentamethyl-4 -piperidinyl) -sebacate HALS (Clariant), 10g 3- (2H-benzotriazolyl) -5- (l, l-dimethylethyl) -4-hydroxybenzenepropanoic acid octyl ester UV (BASF), 5g of a polyether-modified polydimethylsiloxane leveling agent in xylene / isobutanol AD (Altana ) and 5g of a silicone-free defoamer AD (Altana) and mixed using a dissolver. In total, this resulted in a mass of 1000 g.

Paint build-up tests:

The resistance to weathering (degree of gloss, cloudiness of the top coat and integrity of the mirror effect) is checked using the accelerated process of the xenon arc lamp test (in accordance with DIN EN ISO 16474-2 or similar to various automotive standards). For this purpose, the entire paint structure is applied to sample panels or directly to coated components. The structure is then artificially weathered for a period to be defined. Alternatively, outdoor exposure can also be carried out. With a suitable choice and layer thickness of the topcoat, 3000 hours and more can be achieved in the xenon arc lamp test according to DIN EN ISO 16474-2 without loss of gloss and corrosion of the effect pigments (Fig. 5). The adhesion of the top coat to the effect paint is also important. This can be checked before and after weathering by means of a cross cut with adhesive tape tear off according to DIN EN ISO 2409. A suitable top coat in sufficient layer thickness shows good adhesion to the substrate even after advanced weathering (Fig. 6 right).

The layers were each applied to a metal substrate (aluminum) with the following layer thicknesses:

Primer: 0.1 mm;

Effect paint layer: 0.1 mm;

Top layer: 0.03 mm.

The lacquers were applied in the form of powder lacquers and in each case cured at a temperature of 180 ° C. over a period of 15 minutes. Liquid topcoats were cured at 120 ° C. for 10 minutes.

Tab. 1 Performance of various paint structures in the rapid weathering test

Rapid weathering (SB) according to DIN EN ISO 16474-2, adhesion tests according to DIN EN ISO 2409., ++ very good (no problems), + good (minor problems), o neutral (some problems), - bad (significant failures), - very bad (complete failure)

REFERENCE SIGN LIST

1 raw powder coating 12 primer coat

2 raw powder coating particles 13 on the surface of 10

3 effect paint particles concentrated and

4 raw powder paint layer aligned effect paint

5 substrate particles

6 liquid paint 14 top coat

7 liquid paint drops 15 free surface of 14

8 raw liquid lacquer layer 16 clear lacquer layer

9 Hardening process of 4 17 opaque paint layer

respectively 8 with migration 18 recess in 17 and alignment of the BM binders (binder effect paint particles can functional groups

10 metallic polished ones contain so that two different

Effect paint layer binder together

11 non-polished ones can harden)

Effect paint layer AD additive HA hardener EF effect pigment

UV UV absorber FU filler

HALS HALS absorber LM solvent

AN antioxidant

PI pigment

Claims

PATENT CLAIMS

1. having a multi-layer lacquer structure, at least indirectly on a substrate (5), at least one effect lacquer layer (10) and on the side thereof remote from the substrate (5) at least one cover layer (14, 16, 17),

in which

the effect lacquer layer (10) consists of the following components:

(AE) 50-99.9% by weight of oligomeric binder selected from the group consisting of: acrylate, polyester, polyurethane or a combination of these systems with a hardener;

(CE) 0-5% by weight UV and / or HALS stabilization;

(DE) 0-30% by weight of inorganic particulate fillers;

(EE) 0-10% by weight of additives

the components (AE) - (EE) to 100 percent by weight of

Complete the formulation of the effect lacquer layer;

and wherein the cover layer (14, 16, 17) consists of the following components:

(AD) 90-99.5% by weight of oligomeric binder selected from the group consisting of: acrylate, polyester, polyurethane or a combination of these systems with a hardener;

(CD) 0.5-5% by weight UV and / or HALS stabilization;

(DD) 0-5% by weight of inorganic particulate fillers;

(ED) 0-10% by weight of additives

the components (AD) - (ED) to 100 percent by weight of

Complete the formulation of the top layer.

2. Paint structure according to claim 1, characterized in that the component

(AE) the effect lacquer layer contains polyester as the oligomeric binder or is formed exclusively from polyester, and contains as the hardener an epoxy resin based in particular on bisphenol-A, preferably as the only hardener, and that the component (AD) of the top layer as an oligomeric binder contains polyester-containing acrylate contains or exclusively from polyester Acrylate is formed, and contains as a hardener a preferably methylated imino-melamine hardener, preferably as a single hardener.

3. Lacquer structure according to one of the preceding claims, characterized in that the effect lacquer layer and the top layer are arranged immediately adjacent to one another, and the top layer forms the exposed surface, and / or that between the substrate (5) and the effect lacquer layer (10) a primer layer (12) is arranged.

4. Lacquer structure according to one of the preceding claims, characterized in that the preferably single effect lacquer layer has a thickness in the range from 0.01 to 0.3 mm, preferably in the range from 0.05 to 0.2 mm,

and / or that the preferably single cover layer has a thickness in the range from 0.01 to 0.2 mm, preferably in the range from 0.02 to 0.1 mm,

and / or that an optionally present primer layer has a thickness in the range of 0.03-0.3 mm, preferably in the range of 0.06-0.2 mm.

5. Lacquer structure according to one of the preceding claims, characterized in that the hardener within component (AE) of the effect lacquer layer and / or within component (AD) of the top layer is selected from the following group: 1,12-dodecanedicarboxylic acid, (methylated) Imino

Melamine hardeners, isocyanate hardeners such as uretdione-blocked isocyanate hardeners, caprolactam-blocked isocyanate hardeners, epoxides such as bis (2,3-epoxypropyl) terephthalate, tris (oxiranylmethyl) benzene-l, 2,4-tricarboxylate, 1, 3,5-tris (oxirane -2-ylmethyl) -l, 3,5-triazinan-2,4,6-trione, bisphenol-A based, or combinations thereof.

6. Lacquer structure according to one of the preceding claims, characterized in that the inorganic fillers within component (DE) of the effect lacquer layer and / or within component (DD) of the top layer are selected from the group consisting of: fillers are in surface-treated or untreated Shape selected from the group consisting of: talc, mica, silicate, such as in particular iron aluminum silicate and / or sodium aluminum silicate particles, aluminum hydroxide, quartz, quartz powder, titanium dioxide, wollastonite, kaolin, silicas, in particular amorphous silicas, ground or precipitated calcium carbonate, magnesium carbonate, magnesium hydroxide, chalk, lime, Feldspar, mica, ground or precipitated barium sulfate, barium titanate, zinc sulfide, glass spheres, in particular solid or hollow glass spheres, ground glass, in particular ground glass fibers, glass flakes, glass flakes, permanently magnetic or magnetizable metal compounds and / or alloys, inorganic pigments, such as in particular Iron oxide, iron manganese oxide, metal powder, especially iron powder, copper powder, aluminum powder, metal flakes, especially aluminum flakes, iron flakes, metal-coated fillers, metal oxides, hard or soft magnetic metals or alloys or ceramics, hollow spherical silicate fillers, aluminum oxide, Bo nitride, boron carbide, aluminum nitride, calcium fluoride, and mixtures of the elements from this group.

7. Lacquer structure according to one of the preceding claims, characterized in that the additives within the component (EE) of the effect lacquer layer and / or within the component (ED) of the top layer are selected from the following group: surface-active substances, in particular based on acrylates; Waxes, in particular micronized waxes, pigments other than effect pigments, antistatic agents or combinations thereof.

8. Lacquer structure according to one of the preceding claims, characterized in that the stabilizer of component (CE) of the effect lacquer layer and / or within component (CD) of the top layer is selected as HALS from the following group: bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate , Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, or combinations thereof, and / or as a UV stabilizer is selected from the following group: 2-tert-butyl-6- (5-chloro- 2H-benzotriazol-2-yl) -4-methylphenol, 2,2 '- (6-anilino- [1, 3, 5] triazine-2,4-diyl) -bis-phenol, 3 - (2H- Benzotriazolyl) -5- (l, l-dimethylethyl) -4-hydroxybenzenepropanoic acid octyl ester, or combinations thereof,

and / or that the stabilizer of component (CE) of the effect lacquer layer and / or within component (CD) of the top layer is formed as a mixture of an HALS and a UV stabilizer, the ratio of UV to HALS stabilizer preferably being in the range from 1 : 10-5: 1, preferably in the range of 1: 3-1: 1.

9. Lacquer structure according to one of the preceding claims, characterized in that the effect pigment of component (BE) consists of oxide flake-free aluminum flakes, optionally coated with a saturated fatty acids, preferably stearic acid, these having an average order of magnitude of 200 nm, 300 nm or 400 nm to about 5 microns, and preferably a form factor between 5: 1 and 1000: 1 (diameter: thickness).

10. Lacquer structure according to one of the preceding claims, characterized in that the proportion of component (CD) in the cover layer is in the range of 1-4.5% by weight, preferably in the range of 2-4.5% by weight.

1 1. Lacquer structure according to one of the preceding claims, characterized in that the proportion of component (CE) in the effect lacquer layer is in the range of 0.5-4.5% by weight, preferably in the range of 1-4.5% by weight.

12. Lacquer structure according to one of the preceding claims, characterized in that the top layer and / or the effect lacquer layer were produced on the basis of a powder lacquer.

13. Component with a lacquer structure according to one of the preceding claims, preferably metallic component, particularly preferably from the automotive sector, including body components, rims, moldings, switches, transitions, holders, handles, closures, covers, mirrors and combinations of such components.

14. Kit-of-parts of an effect lacquer and an effect lacquer for creating a lacquer structure according to one of claims 1-11, particularly preferably as a liquid lacquer or powder lacquer.

15. A method for producing a lacquer structure according to any one of claims 1-12, characterized in that, if necessary after previously producing a primer layer on a substrate, the effect lacquer is applied and cured in a first step, and the top layer is applied in a second step and is cured, the curing, in the case of powder coating, particularly preferably at a temperature of more than 100 ° C. and over a period of at least 10 minutes.