EP1200203B1 - Coloring and/or effect-creating multilayer enamel coating, method for the production thereof and its use - Google Patents

Abstract

The invention relates to a coloring and/or effect-creating multilayer enamel coating ML which is provided for a primed or non-primed substrate and which contains, in an overlapping manner: (1) a filler coat FL which absorbs mechanical energy, and (2) a coloring and/or effect-creating finishing enamel coating DL; or (1) a filler coat FL which absorbs mechanical energy, (2) a coloring and/or effect-creating base enamel coating BL, and (3) a clear enamel coating KL; or (1) a coloring and/or effect-creating base enamel coating BL, and (2) a clear enamel coating KL. At least one coat, preferably at least two coats and especially all coats of the multilayer enamel coating ML is/are made of a coating material that contains at least one constituent (A) which can be produced in an aqueous medium by radically polymerizing: a) olefinically unsaturated monomers and; b) olefinically unsaturated monomers which are different from the olefinically unsaturated monomers cited in a) and which are of formula (I) R?1R2C=CR3R4¿, wherein the radicals R?1, R2, R3 and R4¿, independent of one another, represent hydrogen atoms or radicals of alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl, whereby at least two are radicals of aryl, arylalkyl or arylcycloalkyl.

Description

The present invention relates to a novel multicoat color and / or effect coating for a primed or unprimed substrate. Furthermore, the present invention relates to a novel process for producing a multicoat color and / or effect coating on a primed or unprimed substrate. Last but not least, the present invention relates to the use of the new color and / or effect multi-layer coating and the new process for their preparation in the automotive original and - repair, the industrial coating, including container coating and coil coating, and the furniture coating.

Color and / or effect multi-layer coatings for primed or unprimed substrates are known. They usually contain a mechanical energy-absorbing filler layer and a color and / or effect solid-color topcoat. In another variant, they contain a filler layer, a color and / or effect basecoat and a clearcoat. For the coating of plastics, a multi-layer coating is often used which contains a color and / or effect basecoat and a clearcoat. Frequently, such multicoat paint systems are produced by the wet-on-wet process, in which, in particular, the basecoat film is merely dried but not cured before the application of the clearcoat film, and the basecoat film and the clearcoat film are cured together.

In the coating materials, which serve to produce known multicoat color and / or effect paint systems, constituents which are prepared by free-radical polymerization of olefinically unsaturated monomers are frequently used. These ingredients are also called binders designated. In the majority of cases, the binders of the type mentioned are acrylate copolymers.

Acrylate copolymers and coating materials containing them are described, for example, in the patents EP-B-0 447 428 . EP-B-0 593 454 . EP-B-0 052 776 or the DE-A-42 04 518 described.

The preparation of acrylate copolymers can be carried out by generally well-known polymerization processes in bulk, solution or emulsion. Polymerization processes for the preparation of acrylate copolymers, in particular polyacrylate resins, are generally known and have been described many times (cf., for example: Houben Weyl, Methods of Organic Chemistry, 4th Edition, Volume 14/1, pages 24 to 255 (1961 )).

Further examples of suitable copolymerization processes for the preparation of acrylate copolymers are disclosed in the patents DE-A-197 09 465 . DE-C-197 09 476 . DE-A-28 48 906 . DE-A-195 24 182 . EP-A-0 554 783 . EP-B-0 650 979 WO 95/27742 . DE-A-38 41 540 or WO 82/02387 described.

Suitable reactors for the copolymerization are the conventional and known stirred tank, stirred tank cascades, tubular reactors, loop reactors or Taylor reactors, as described for example in the patents DE-B-1 071 241 or EP-A-0 498 583 or in the article of K. Kataoka in Chemical Engineering Science, Vol. 50, No. 9, 1995, pages 1409 to 1416 , to be described.

The radical polymerization used to prepare the acrylate copolymers is often very exothermic and difficult to control. For the reaction, this means that high concentrations of monomers and / or the so-called batch procedure, in which the entire amount of the monomers initially charged in an aqueous medium, emulsified and then polymerized, must be avoided. The targeted setting of defined molecular weights, molecular weight distributions and other properties often presents difficulties. However, the targeted adjustment of a certain property profile of the acrylate copolymers is of great importance for their use as binders in coating materials, as this can directly influence the performance profile of the coating materials.

There has therefore been no lack of attempts to specifically regulate the radical copolymerization of olefinically unsaturated monomers.

This is how the international patent application describes WO 98/01478 a method in which the copolymerization is reacted in the presence of a radical initiator and a thiocarbonylthio compound as a chain transfer agent.

The international patent application WO 92/13903 describes a process for preparing low molecular weight copolymers by free radical polymerization in the presence of a group transfer agent having a carbon-sulfur double bond. These compounds not only act as chain transfer agents but also as growth regulators to result in only low molecular weight copolymers.

From the international patent application WO 96/15157 discloses a process for the preparation of copolymers having a comparatively narrow molecular weight distribution, in which a monomer is reacted with a vinyl-terminated macromonomer in the presence of a radical initiator.

It also comes from the international patent application WO 98/37104 the preparation of acrylate copolymers having defined molecular weights by radical polymerization in the presence of a chain transfer agent having a CC double bond and with radicals which activate this double bond with respect to the radical addition of monomers.

Despite significant progress in this field, there is still a lack of a universally applicable method for controlled free radical polymerization, which provides in a simple manner chemically structured polymers, in particular acrylate, and with its help, the property profile of the polymers with respect to their application in coating materials, the Production of multicoat color and / or effect paint systems can be targeted.

Therefore, it is still necessary, by others, for. T. more complex, measures to match the property profiles and material compositions of the filler, basecoats and clearcoats so to each other; that the multicoat color and / or effect paint systems have the high optical quality and intercoat adhesion demanded by the market and no longer pose problems such as lack of condensation resistance of the surfacer layers, cracking (mud cracking) in the basecoats or flow defects or surface structures in the clearcoats.

The object of the present invention is to provide novel multicoat color and / or effect paint systems and novel processes for their preparation, in which at least one layer of the multicoat color and / or effect paint is produced from a coating material which in a simple manner is suitable for its respective use Filler, basecoat and / or Clear coat can be adjusted. This should be accomplished in a simple manner that the property profile of the coating materials is specifically adjusted in particular by the use of chemically structured polymers which are obtainable by free-radical polymerization. The resulting new multicoat color and / or effect coating systems should no longer exhibit the disadvantages of the prior art but have excellent optical quality, intercoat adhesion and condensation resistance and show no cracking (mudcracking), flow defects or surface structures. These chemically structured polymers should also be useful as a friction resins, which allow advantageously to provide particularly well mixable pigment pastes for the filler, basecoats and clearcoats used for the preparation of the new color and / or effect multi-layer coatings.

1. (1) eine mechanische Energie absorbierende Füllerschicht FL und
2. (2) eine farb- und/oder effektgebende Decklackierung DL

oder

1. (1) eine mechanische Energie absorbierende Füllerschicht FL,
2. (2) eine farb- und/oder effektgebende Basislackierung BL und
3. (3) eine Klarlackierung KL

oder

1. (1) eine farb- und/oder effektgebende Basislackierung BL und
2. (2) eine Klarlackierung KL,

übereinanderliegend enthält, wobei mindestens eine Schicht FL und/oder DL oder BL und/oder KL oder FL, BL und/oder KL, vorzugsweise mindestens zwei Schichten FL, BL und/oder KL oder alle Schichten FL und DL oder BL und KL oder FL, BL und KL der Mehrschichtlackierung ML aus einem Beschichtungsstoff hergestellt worden ist oder sind, welcher mindestens einen Bestandteil (A) enthält, der durch radikalische Polymerisation von

1. a) mindestens einem olefinisch ungesättigten Monomer und
2. b) mindestens einem vom olefinisch ungesättigten Monomer (a) verschiedenen olefinisch ungesättigten Monomer der allgemeinen Formel I
   
           R¹R²C=CR³R⁴      (I),
   
   worin die Reste R¹; R², R³ und R⁴ jeweils unabhängig voneinander für Wasserstoffatome oder substituierte oder unsubstituierte Alkyl-, Cycloalkyl-, Alkylcycloalkyl-, Cycloalkylalkyl-, Aryl-, Alkylaryl-, Cycloalkylaryl-Arylalkyl- oder Arylcycloalkylreste stehen, mit der Maßgabe, daß mindestens zwei der Variablen R¹, R², R³ und R⁴ für substituierte oder unsubstituierte Aryl-, Arylalkyl- oder Arylcycloalkylreste, insbesondere substituierte oder unsubstituierte Arylreste, stehen;
   in einem wäßrigen Medium herstellbar ist.

Im folgenden wird die neue farb- und/oder effektgebende Mehrschichtlackierung ML für ein grundiertes oder ungrundiertes Substrat als "erfindungsgemäße Mehrschichtlackierung ML" bezeichnet.
Außerdem wurde das neue Verfahren zur Herstellung einer farb-und/oder effektgebenden Mehrschichtlackierung ML auf einem grundierten oder ungrundierten Substrat durch

1. (I) Herstellen einer Füllerlackschicht durch Applikation eines Füllers auf das Substrat,
2. (II) Härtung der Füllerlackschicht, wodurch die Füllerschicht FL resultiert,
3. (III) Herstellen einer Unidecklackschicht durch Applikation eines Unidecklacks auf die Füllerschicht FL und
4. (IV) Härtung der Unidecklackschicht DL, wodurch die Unidecklackierung DL resultiert,

oder

1. (I) Herstellen einer Basislackschicht durch Applikation eines Basislacks auf das Substrat,
2. (II) Trocknen der Basislackschicht,
3. (III) Herstellen einer Klarlackschicht durch Applikation eines Klarlacks auf die Basislackschicht und
4. (IV) gemeinsame Härtung der Basislackschicht und der Klarlackschicht, wodurch die Basislackierung BL und die Klarlackierung KL resultieren,

oder

1. (I) Herstellen einer Füllerlackschicht durch Applikation eines Füllers auf das Substrat,
2. (II) Härtung der Füllerlackschicht, wodurch die Füllerschicht FL resultiert,
3. (III) Herstellen einer Basislackschicht durch Applikation eines Basislacks auf die Füllerschicht FL,
4. (IV) Trocknen der Basislackschicht,
5. (V) Herstellen einer Klarlackschicht durch Applikation eines Klarlacks auf die Basislackschicht und
6. (VI) gemeinsame Härtung der Basislackschicht und der Klarlackschicht, wodurch die Basislackierung BL und die Klarlackierung KL resultieren,

gefunden, bei dem mindestens einer der jeweils angewandten Beschichtungsstoffe mindestens einen Bestandteil (A) enthält, der durch radikalische Polymerisation von

1. a) mindestens einem olefinisch ungesättigten Monomer und
2. b) mindestens einem vom olefinisch ungesättigten Monomer (a) verschiedenen olefinisch ungesättigten Monomer der allgemeinen Formel I
   
           R¹R²C=CR³R⁴      (I),
   
   worin die Reste R¹, R², R³ und R⁴ jeweils unabhängig voneinander für Wasserstoffatome oder substituierte oder unsubstituierte Alkyl-, Cycloalkyl-, Alkylcycloalkyl-, Cycloalkylalkyl-, Aryl-, Alkylaryl-, Cycloalkylaryl-Arylalkyl- oder Arylcycloakylreste stehen, mit der Maßgabe, daß mindestens zwei der Variablen R¹, R², R³ und R⁴ für substituierte oder unsubstituierte Aryl-, Arylalkyl- oder Arylcycloalkylreste, insbesondere substituierte oder unsubstituierte Arylreste, stehen;

in einem wäßrigen Medium herstellbar ist.Accordingly, the new multicoat color and / or effect coating ML was found for a primed or unprimed substrate, in the order given

1. (1) a mechanical energy absorbing filler layer FL and
2. (2) a color and / or effect topcoat DL

or

1. (1) a mechanical energy absorbing filler layer FL,
2. (2) a color and / or effect basecoat BL and
3. (3) a clearcoat KL

or

1. (1) a color and / or effect basecoat BL and
2. (2) a clearcoat KL,

containing at least one layer FL and / or DL or BL and / or KL or FL, BL and / or KL, preferably at least two layers FL, BL and / or KL or all layers FL and DL or BL and KL or FL , BL and KL of the multi-layer coating ML has been prepared from a coating material which contains at least one component (A) obtained by radical polymerization of

1. a) at least one olefinically unsaturated monomer and
2. b) at least one olefinically unsaturated monomer of the general formula I which is different from the olefinically unsaturated monomer (a)
   
   R ¹ R ² C = CR ³ R ⁴ (I),
   
   wherein the radicals R ¹ ; R ² , R ³ and R ^{4 are} each independently hydrogen or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals, with the proviso that at least two the variables R ¹ , R ² , R ³ and R ^{4 are} substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals;
   can be produced in an aqueous medium.

The new color and / or effect multi-layer coating ML for a primed or unprimed substrate is referred to below as "multilayer coating ML according to the invention".
In addition, the new process for producing a multicoat color and / or effect coating ML on a primed or unprimed substrate was carried out

1. (I) producing a surfacer paint layer by applying a filler to the substrate,
2. (II) curing the surfacer coating layer, resulting in the surfacer layer FL,
3. (III) producing a solid-color topcoat by applying a solid-color topcoat to the filler layer FL and
4. (IV) curing of the solid-color topcoat DL, resulting in the solid-color finish DL,

or

1. (I) producing a basecoat film by applying a basecoat to the substrate,
2. (II) drying the basecoat film,
3. (III) producing a clearcoat by application of a clearcoat to the basecoat film and
4. (IV) co-curing of the basecoat film and the clearcoat film, resulting in the basecoat BL and the clearcoat KL,

or

1. (I) producing a surfacer paint layer by applying a filler to the substrate,
2. (II) curing the surfacer coating layer, resulting in the surfacer layer FL,
3. (III) producing a basecoat film by applying a basecoat to the filler coat FL,
4. (IV) drying the basecoat film,
5. (V) producing a clearcoat layer by applying a clearcoat to the basecoat film and
6. (VI) joint hardening of the basecoat film and the clearcoat film, resulting in the basecoat BL and the clearcoat KL,

found, in which at least one of the coating materials used in each case at least one component (A) containing by free radical polymerization of

1. a) at least one olefinically unsaturated monomer and
2. b) at least one olefinically unsaturated monomer of the general formula I which is different from the olefinically unsaturated monomer (a)
   
   R ¹ R ² C = CR ³ R ⁴ (I),
   
   wherein the radicals R ¹ , R ² , R ³ and R ^{4 are} each independently hydrogen or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl-arylalkyl or arylcycloalkyl radicals with the proviso that at least two of the variables R ¹ , R ² , R ³ and R ^{4 are} substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals;

can be produced in an aqueous medium.

The new process for producing a multicoat color and / or effect coating ML on a primed or unprimed substrate is referred to below as "process according to the invention".

In view of the prior art, it was surprising that the complex object on which the present invention was based could be achieved with the aid of the method according to the invention and the multicoat systems ML according to the invention. In particular, it was surprising that the multicoat paint systems ML according to the invention have an outstanding optical quality, intercoat adhesion and condensation resistance and no longer exhibit cracking (mud cracking), flow defects or surface structures. Even more surprising was that the use of thixotropic agents or rheology aids in basecoats, the production of pearlescent effects and / or dichroic effects, largely or possibly can be completely dispensed with.

According to the invention, at least one layer of the multicoat system ML according to the invention is produced from a coating material which contains a constituent (A). According to the invention, it is advantageous if at least two layers, in particular all layers, of the multi-layer coating ML according to the invention are produced from such coating materials.

According to the invention, the component (A) is prepared by controlled radical polymerization of at least one olefinically unsaturated monomer (a) and at least one olefinically unsaturated monomer (b) which is different from the monomer (a).

• a1) im wesentlichen säuregruppenfreien (Meth)acrylsäureester wie (Meth)Acrylsäurealkyl- oder -cycloalkylester mit bis zu 20 Kohlenstoffatomen im Alkylrest, insbesondere Methyl-, Ethyl-, Propyl-, n-Butyl-, sec.-Butyl-, tert.-Butyl-, Hexyl-, Ethylhexyl-, Stearyl- und Laurylacrylat oder -methacrylat; cycloaliphatische (Meth)acrylsäureester, insbesondere Cyclohexyl-, Isobornyl-, Dicyclopentadienyl-, Octahydro-4,7-methano- 1H-inden-niethanol- oder tert.-Butylcyclohexyl(meth)acrylat; (Meth)Acrylsäureoxaalkylester oder -oxacycloalkylester wie Ethyltriglykol(meth)acrylat und Methoxyoligoglykol(meth)acrylat mit einem Molekulargewicht Mn von vorzugsweise 550 oder andere ethoxylierte und/oder propoxylierte hydroxylgruppenfreie (Meth)acrylsäurederivate. Diese können in untergeordneten Mengen höherfunktionelle (Meth)Acrylsäurealkyl- oder -cycloalkylester wie Ethylengylkol-, Propylenglykol-, Diethylenglykol-, Dipropylenglykol-, Butylenglykol-, Pentan-1,5-diol-, Hexan-1,6-diol-, Octahydro-4,7-methano-1H-inden-dimethanol- oder Cyclohexan-1,2-, -1,3- oder -1,4-diol-di(meth)acrylat; Trimethylolpropan-di- oder - tri(meth)acrylat; oder Pentaerythrit-di-, -tri- oder -tetra(meth)acrylat enthalten. Im Rahmen der vorliegenden Erfindung sind hierbei unter untergeordneten Mengen an höherfunktionellen Monomeren solche Mengen zu verstehen, welche nicht zur Vernetzung oder Gelierung der Copolymerisate (A) führen.
• a2) Monomere, welche mindestens eine Hydroxylgruppe, Aminogruppe, Alkoxymethylaminogruppe oder Iminogruppe pro Molekül tragen und im wesentlichen säuregruppenfrei sind, wie Hydroxyalkylester der Acrylsäure, Methacrylsäure oder einer anderen alpha,beta-olefinisch ungesättigten Carbonsäure, die sich von einem Alkylenglykol ableiten, das mit der Säure verestert ist, oder die durch Umsetzung der alpha,beta-olefinsich ungesättigten Carbonsäure mit einem Alkylenoxid erhältlich sind, insbesondere Hydroxyalkylester der Acrylsäure, Methacrylsäure, Ethacrylsäure; Crotonsäure, Maleinsäure, Fumarsäure oder Itaconsäure, in denen die Hydroxyalkylgruppe bis zu 20 Kohlenstoffatome enthält, wie 2-Hydroxyethyl-, 2-Hydroxypropyl-, 3-Hydroxypropyl-, 3-Hydroxybutyl-, 4-Hydroxybutylacrylat, -methacrylat, -ethacrylat, -crotonat, -maleinat, -fumarat oder -itaconat; oder Hydroxycycloalkylester wie 1,4-Bis(hydrbxymethyl)cyclohexan-, Octahydro-4,7-methano-1H-inden-dimethanol- oder Methylpropandiolmonoacrylat, -monomethacrylat, - monoethacrylat, -monocrotonat, -monomaleinat, -monofumarat oder - monoitaconat; oder Umsetzungsprodukte aus cyclischen Estern, wie z.B. epsilon-Caprolacton und diesen Hydroxyalkyl- oder -cycloalkylestern; oder olefinisch ungesättigte Alkohole wie Allylalkohol oder Polyole wie Trimethylolpropanmono- oder diallylether oder Pentaerythritmono-, -di- oder -triallylether (hinsichtlich dieser höherfunktionellen Monomeren (a2) gilt das für die höherfunktionellen Monomeren (a1) Gesagte sinngemäß); N,N-Dimethylaminoethylacrylat, N,N-Diethylamiioethylmethacrylat, Allylamin oder N-Methyliminoethylacrylat oder N,N-Di(methoxymethyl)aminoethylacrylat und -methacrylat oder N,N-Di(butoxymethyl)aminopropylacrylat und -methacrylat; Monomere dieser Art werden bevorzugt für die Herstellung von selbst vernetzenden Bestandteilen (A) verwendet.
• a3) Monomere, welche mindestens eine Säuregruppe, die in die entsprechende Säureaniongruppe überführbar ist, pro Molekül tragen, wie Acrylsäure, Methacrylsäure, Ethacrylsäure, Crotonsäure, Maleinsäure, Fumarsäure oder Itaconsäure; olefinisch ungesättigte Sulfon- oder Phosphonsäuren oder deren Teilester; oder Maleinsäuremono(meth)acryloyloxyethylester, Bernsteinsäuremono(meth)acryloyloxyethylester oder Phthalsäuremono(meth)acryloyloxyethylester.
• a4) Vinylester von in alpha-Stellung verzweigten Monocarbonsäuren mit 5 bis 18 Kohlenstoffatomen im Molekül. Die verzweigten Monocarbonsäuren können erhalten werden durch Umsetzung von Ameisensäure oder Kohlenmonoxid und Wasser mit Olefinen in Anwesenheit eines flüssigen, stark sauren Katalysators; die Olefine können Crack-Produkte, von paraffinischen Kohlenwasserstoffen, wie Mineralölfraktionen, sein und können sowohl verzweigte wie geradkettige acyclische und/oder cycloaliphatische Olefine enthalten. Bei der Umsetzung solcher Olefine mit Ameisensäure bzw. mit Kohlenmonoxid und Wasser entsteht ein Gemisch aus Carbonsäuren, bei denen die Carboxylgruppen vorwiegend an einem quaternären Kohlenstoffatom sitzen. Andere olefinische Ausgangsstoffe sind z.B. Propylentrimer, Propylentetramer und Diisobutylen. Die Vinylester (a4) können aber auch auf an sich bekannte Weise aus den Säuren hergestellt werden, z.B. indem man die Säure mit Acetylen reagieren läßt. Besonders bevorzugt werden - wegen der guten Verfügbarkeit - Vinylester von gesättigten aliphatischen Monocarbonsäuren mit 9. bis 11 C-Atomen, die am alpha-C-Atom verzweigt sind, insbesondere aber Versatic®-Säuren, eingesetzt.
• a5) Umsetzungsprodukte aus Acrylsäure und/oder Methacrylsäure mit dem Glycidylester einer in alpha-Stellung verzweigten Monocarbonsäure mit 5 bis 18 C-Atomen je Molekül, insbesondere einer Versatic®-Säure, oder anstelle des Umsetzungsproduktes eine äquivalenten Menge Acryl- und/oder Methacrylsäure, die dann während oder nach der Polymerisationsreaktion mit dem Glycidylester einer in alpha-Stellung verzweigten Monocarbonsäure mit 5 bis 18 C-Atomen je Molekül, insbesondere einer Versatic®-Säure, umgesetzt wird.
• a6) Cyclische und/oder acyclische Olefine wie Ethylen, Propylen, But-1-en, Pent-1-en, Hex-1-en, Cyclohexen, Cyclopenten, Norbonen, Butadien, Isopren, Cylopentadien und/oder Dicyclopentadien.
• a7) (Meth)Acrylsäureamide wie (Meth)Acrylsäureamid, N-Methyl-, N,N-Dimethyl-, N-Ethyl-, N,N-Diethyl-, N-Propyl-, N,N-Dipropyl-, N-Butyl-, N,N-Dibutyl-, N-Cyclohexyl-, N,N-Cyclohexyl-methyl- und/oder N-Methylol-, N,N-Dimethylol-, N-Methoxymethyl-, N,N-Di(methoxymethyl)-, N-Ethoxymethyl- und/oder N,N-Di(ethoxyethyl)-(meth)acrylsäureamid: Monomere der letztgenannten Art werden vor allem für die Herstellung von selbstvernetzenden Bestandteilen (A) verwendet.
• a8) Epoxidgruppen enthaltende Monomere wie der Glycidylester der Acrylsäure, Methacrylsäure, Ethacrylsäure, Crotonsäure, Maleinsäure, Fumarsäure und/oder Itaconsäure.
• a9) Vinylaromatische Kohlenwasserstoffe wie Styrol, alpha-Alkylstyrole, insbesondere alpha-Methylstyrol, und/oder Vinyltoluol; Vinylbenzoesäure (alle Isomere), N,N-Diethylaminostyrol (alle Isomere), alpha-Methylvinylbenzoesäure (alle Isomere), N,N-Diethylamino-alpha-methylstyrol (alle Isomere) und/oder p-Vinylbenzsolsulfonsäure.
• a10) Nitrile wie Acrylnitril und/oder Methacrylnitril.
• a11) Vinylverbindungen, insbesondere Vinyl- und/oder Vinylidendihalogenide wie Vinylchlorid, Vinylfluorid, Vinylidendichlorid oder Vinylidendifluorid; N-Vinylamide wie Vinyl-N-methylformamid, N-Vinylcaprolactam, 1-Vinylimidazol oder N-Vinylpyrrolidon; Vinylether wie Ethylvinylether, n-Propylvinylether, Isopropylvinylether, n-Butylvinylether, Isobutylvinylether und/oder Vinylcyclohexylether; und/oder Vinylester wie Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinylpivalat und/oder der Vinylester der 2-Methyl-2-ethylheptansäure.
• a12) Allylverbindungen, insbesondere Allylether und -ester wie Allylmethyl-, - ethyl-, -propyl- oder -butylether oder Allylacetat, -propionat oder -butyrat.
• a13) Polysiloxanmakromonomere, die ein zahlenmittleres Molekulargewicht Mn von 1.000 bis 40.000 und im Mittel 0,5 bis 2,5 ethylenisch ungesättigte Doppelbindungen pro Molekül aufweisen; insbesondere Polysiloxanmakromonomere, die ein zahlenmittleres Molekulargewicht Mn von 2.000 bis 20.000, besonders bevorzugt 2.500 bis 10.000 und insbesondere 3.000 bis 7.000 und im Mittel 0,5 bis 2,5, bevorzugt 0,5 bis 1,5, ethylenisch ungesättigte Doppelbindungen pro Molekül aufweisen, wie sie in der DE-A-38 07 571 auf den Seiten 5 bis 7, der DE-A 37 06 095 in den Spalten 3 bis 7, der EP-B-0 358 153 auf den Seiten 3 bis 6, in der US-A 4,754,014 in den Spalten 5 bis 9, in der DE-A 44 21 823 oder in der internationalen Patentanmeldung WO 92/22615 auf Seite 12, Zeile 18, bis Seite 18, Zeile 10, beschrieben sind.
  und/oder
• a14) Acryloxysilan-enthaltende Vinylmonomere, herstellbar durch Umsetzung hydroxyfunktioneller Silane mit Epichlorhydrin und anschließender Umsetzung des Reaktionsproduktes mit (Meth)acrylsäure und/oder Hydroxyalkyl- und/oder -cycloalkylestern der (Meth)Acrylsäure (vgl. Monomere a2).

Examples of suitable monomers (a) are

• a1) substantially acid group-free (meth) acrylic esters such as (meth) alkyl or alkyl cycloalkyl esters having up to 20 carbon atoms in the alkyl radical, in particular methyl, ethyl, propyl, n-butyl, sec-butyl, tert. Butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate or methacrylate; cycloaliphatic (meth) acrylic esters, in particular cyclohexyl, isobornyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indene-niethanol- or tert-butylcyclohexyl (meth) acrylate; (Meth) acrylic acid oxaalkyl esters or oxacycloalkyl esters such as ethyltriglycol (meth) acrylate and methoxyoligoglycol (meth) acrylate having a molecular weight Mn of preferably 550 or other ethoxylated and / or propoxylated hydroxyl-free (meth) acrylic acid derivatives. These may contain minor amounts of higher-functional (meth) alkyl or cycloalkyl alkyl esters, such as ethylene glycol, propylene glycol, diethylene glycol, Dipropylene glycol, butylene glycol, pentane-1,5-diol, hexane-1,6-diol, octahydro-4,7-methano-1H-indenedimethanol or cyclohexane-1,2-, 1,3 or -1,4-diol di (meth) acrylate; Trimethylolpropane di- or tri (meth) acrylate; or pentaerythritol di-, tri- or tetra (meth) acrylate. In the context of the present invention, minor amounts of higher-functional monomers are quantities which do not lead to crosslinking or gelling of the copolymers (A).
• a2) monomers which carry at least one hydroxyl group, amino group, alkoxymethylamino or imino group per molecule and are substantially free of acid groups, such as hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-olefinically unsaturated carboxylic acid derived from an alkylene glycol which reacts with the Acid is esterified, or which are obtainable by reacting the alpha, beta-olefin-unsaturated carboxylic acid with an alkylene oxide, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid, ethacrylic acid; Crotonic acid, maleic acid, fumaric acid or itaconic acid in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl acrylate, methacrylate, methacrylate, crotonate, maleate, fumarate or itaconate; or hydroxycycloalkyl esters such as 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indenedimethanol or methylpropanediol monoacrylate, monomethacrylate, monoethacrylate, monocrotonate, monomalate, monofumarate or monoitaconate; or reaction products of cyclic esters, such as epsilon-caprolactone and these hydroxyalkyl or cycloalkyl esters; or olefinically unsaturated alcohols such as allyl alcohol or polyols such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether (with regard to these higher-functional monomers (a2), what has been said for the higher-functional monomers (a1) applies mutatis mutandis); N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, allylamine or N-methyliminoethyl acrylate or N, N-di (methoxymethyl) aminoethyl acrylate and methacrylate or N, N-di (butoxymethyl) aminopropyl acrylate and methacrylate; Monomers of this type are preferably used for the preparation of self-crosslinking components (A).
• a3) monomers which carry at least one acid group which can be converted into the corresponding acid anion 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; or maleic mono (meth) acryloyloxyethyl ester, succinic mono (meth) acryloyloxyethyl ester or phthalic mono (meth) acryloyloxyethyl ester.
• a4) Vinyl esters of alpha-branched monocarboxylic acids having 5 to 18 carbon atoms in the molecule. The branched monocarboxylic acids can be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins may be cracking products of paraffinic hydrocarbons, such as mineral oil fractions, and may contain both branched and straight-chain acyclic and / or cycloaliphatic olefins. The reaction of such olefins with formic acid or with carbon monoxide and water produces a mixture of carboxylic acids in which the carboxyl groups are predominantly on a quaternary carbon atom. Other olefinic starting materials are, for example, propylene trimer, propylene tetramer and diisobutylene. The vinyl esters (a4) but can also on in known manner be prepared from the acids, for example by allowing the acid to react with acetylene. Particularly preferred are - because of the good availability - vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms, which are branched at the alpha-C atom, but especially Versatic® acids used.
• a5) 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, which is then reacted during or after the polymerization reaction with the glycidyl ester of an alpha-branched monocarboxylic acid having 5 to 18 carbon atoms per molecule, in particular a Versatic® acid.
• a6) Cyclic and / or acyclic olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene.
• a7) (meth) acrylic acid amides such as (meth) acrylamide, N-methyl, N, N-dimethyl, N-ethyl, N, N-diethyl, N-propyl, N, N-dipropyl, N- Butyl, N, N-dibutyl, N-cyclohexyl, N, N-cyclohexyl-methyl and / or N-methylol, N, N-dimethylol, N-methoxymethyl, N, N-di (methoxymethyl ) -, N-ethoxymethyl and / or N, N-di (ethoxyethyl) - (meth) acrylamide: Monomers of the latter type are mainly used for the preparation of self-crosslinking components (A).
• a8) monomers containing epoxide groups, such as the glycidyl esters of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and / or itaconic acid.
• a9) vinylaromatic hydrocarbons, such as styrene, alpha-alkylstyrenes, in particular alpha-methylstyrene, and / or vinyltoluene; Vinylbenzoic acid (all isomers), N, N-diethylaminostyrene (all isomers), alpha-methylvinylbenzoic acid (all isomers), N, N-diethylamino-alpha-methylstyrene (all isomers) and / or p-vinylbenzenesulfonic acid.
• a10) Nitriles such as acrylonitrile and / or methacrylonitrile.
• a11) vinyl compounds, especially vinyl and / or vinylidene dihalides such as vinyl chloride, vinyl fluoride, vinylidene dichloride or vinylidene difluoride; N-vinylamides such as vinyl-N-methylformamide, N-vinylcaprolactam, 1-vinylimidazole or N-vinylpyrrolidone; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and / or vinyl cyclohexyl ether; and / or vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and / or the vinyl ester of 2-methyl-2-ethylheptanoic acid.
• a12) allyl compounds, in particular allyl ethers and esters, such as allylmethyl, - ethyl, -propyl or -butylether or allyl acetate, propionate or butyrate.
• a13) polysiloxane macromonomers having a number average molecular weight Mn of from 1,000 to 40,000 and an average of from 0.5 to 2.5 ethylenically unsaturated double bonds per molecule; in particular Polysiloxanmakromonomere having a number average molecular weight Mn of 2,000 to 20,000, more preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0.5 to 1.5, ethylenically unsaturated double bonds per molecule, as described in the DE-A-38 07 571 on pages 5 to 7, the DE-A 37 06 095 in columns 3 to 7, the EP-B-0 358 153 on pages 3 to 6, in the US-A 4,754,014 in columns 5 to 9, in the DE-A 44 21 823 or in the international patent application WO 92/22615 on page 12, line 18, to page 18, line 10, are described.
  and or
• a14) Acryloxysilane-containing vinyl monomers, preparable by reaction of hydroxy-functional silanes with epichlorohydrin and subsequent reaction of the reaction product with (meth) acrylic acid and / or hydroxyalkyl and / or cycloalkyl esters of (meth) acrylic acid (compare monomers a2).

Each of the above-mentioned monomers (a1) to (a14) may be polymerized alone with the monomer (b). According to the invention, however, it is advantageous to use at least two monomers (a), because in this way the profile of properties of the resulting constituents (A), ie the copolymers (A), varies very widely in a particularly advantageous manner and is very specifically adapted to the particular intended use of the coating material can be. In particular, functional groups can be incorporated into the copolymers (A) in this manner, by means of which the copolymers (A) become hydrophilic, so that they can be dispersed or dissolved in aqueous media. In addition, functional groups (afg) can be incorporated which can undergo thermal crosslinking reactions with the below-described complementary functional groups (bfg) of the crosslinking agents (B). In addition, functional groups incorporating the component (A) self-crosslinking properties such as N-methylol or N-alkoxymethyl groups.

According to the invention, very particular advantages result if the monomers (a) used are the monomers (a1) and (a2) and optionally (a3).

According to the invention, the monomers (b) used are compounds of the general formula I.

In the general formula I, the radicals R ¹ , R ² , R ³ and R ^{4 are} each independently of one another hydrogen or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl-arylalkyl or Arylcycloallcylreste, with the proviso that at least two of the variables R ¹ , R ² , R ³ and R ^{4 are} substituted or unsubstituted aryl, arylalkyl or Arylcycloalkylreste, in particular substituted or unsubstituted aryl radicals.

Examples of suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, hexyl or 2-ethylhexyl.

Examples of suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl.

Examples of suitable alkylcycloalkyl radicals are methylenecyclohexane, ethylene cyclohexane or propane-1,3-diylcyclohexane.

Examples of suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl, -ethyl, -propyl or -butylcyclohex-1-yl.

Examples of suitable aryl radicals are phenyl, naphthyl or biphenylyl, preferably phenyl and naphthyl and in particular phenyl.

Examples of suitable alkylaryl radicals are benzyl or ethylene or propane-1,3-diylbenzene.

Examples of suitable cycloalkylaryl radicals are 2-, 3- or 4-phenylcyclohex-1-yl.

Examples of suitable arylalkyl radicals are 2-, 3- or 4-methyl, -ethyl, -propyl or -butylphen-1-yl.

Examples of suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1-yl:

The above-described radicals R ¹ , R ² , R ³ and R ⁴ may be substituted. Electron-withdrawing or electron-donating atoms or organic radicals can be used for this purpose.

Examples of suitable substituents are halogen atoms, in particular chlorine and fluorine, nitrile groups, nitro groups, partially or completely halogenated, in particular chlorinated and / or fluorinated, alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and Arylcycloalkyl radicals, including those mentioned above by way of example, in particular tert-butyl; Aryloxy, alkyloxy and cycloalkyloxy, especially phenoxy, naphthoxy, methoxy, ethoxy, propoxy, butyloxy or cyclohexyloxy; Arylthio, alkylthio and cycloalkylthio radicals, in particular phenylthio, naphthylthio, methylthio, ethylthio, propylthio, butylthio or cyclohexylthio; hydroxyl groups; and / or primary, secondary and / or tertiary amino groups, in particular amino, N-methylamino, N-ethylamino, N-propylamino, N-phenylamino, N-cyclohexylamino, N, N-dimethylamino, N, N-diethylamino, N, N -Dipropylamirio, N, N-diphenylamino, N, N-dicyclohexylamino, N-cyclohexyl-N-methylamino or N-ethyl-N-methylamino.

Examples of monomers (b) used particularly preferably according to the invention are diphenylethylene, dinaphthaleneethylene, cis-trans-stilbene, vinylidene bis (4-N, N-dimethylaminobenzene), vinylidene bis (4-aminobenzene) or vinylidene bis (4-nitrobenzene ).

According to the invention, the monomers (b) can be used individually or as a mixture of at least two monomers (b).

With regard to the reaction procedure and the properties of the resulting copolymers (A), in particular the acrylate copolymer (A), diphenylethylene is of very particular advantage and is therefore used with very particular preference according to the invention.

The monomers (a) and (b) to be used according to the invention are reacted with one another in the presence of at least one free-radical initiator to give the copolymer (A). Examples of suitable initiators are: dialkyl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide; Hydroperoxides, such as cumene hydroperoxide or tert-butyl hydroperoxide; Peresters, such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per 3,5,5-trimethylhexanoate or tert-butylper-2-ethylhexanoate; Potassium, sodium or ammonium peroxodisulfate; Azodinitriles such as azobisisobutyronitrile; C-C-cleaving initiators such as benzpinacol silyl ether; or a combination of a non-oxidizing initiator with hydrogen peroxide.

Preferably, comparatively large amounts of free-radical initiator are added, the proportion of initiator in the reaction mixture being based in each case to the total amount of the monomers (a) and the initiator, more preferably 0.5 to 50 wt .-%, most preferably 1 to 20 wt .-% and in particular 2 to 15 wt .-% is.

The weight ratio of initiator to monomers (b) is preferably 4: 1 to 1: 4, particularly preferably 3: 1 to 1: 3 and in particular 2: 1 to 1: 2. Further advantages result if the initiator is within the stated limits in the Excess is used.

Preferably, the free-radical copolymerization in the aforementioned devices, in particular stirred tanks or Taylor reactors carried out, wherein the Taylor reactors are designed so that over the entire reactor length. Conditions of Taylor flow are satisfied, even if the kinematic viscosity of the reaction medium due to the copolymerization greatly changes, in particular increases.

According to the invention, the copolymerization is carried out in an aqueous medium.

The aqueous medium contains essentially water: In this case, the aqueous medium in minor amounts, the crosslinking agent (B) described below in detail, reactive diluents (F), coating additives (G) and / or organic solvents (H) and / or other dissolved solid, liquid or gaseous organic and / or inorganic, low and / or high molecular weight substances, in particular surface-active substances, if they do not affect the copolymerization in a negative way or even inhibit. In the context of the present invention, the term "minor amount" means an amount which does not abolish the aqueous character of the aqueous medium.

However, the aqueous medium may also be pure water.

Preferably, the copolymerization is carried out in the presence of at least one base. Particularly preferred are low molecular weight bases such as sodium hydroxide, potassium hydroxide, ammonia, diethanolamine, triethanolamine, mono-, di- and triethylamine, and / or dimethylethanolamine, in particular ammonia and / or di- and / or triethanolamine.

The copolymerization is advantageously carried out at temperatures above room temperature and below the lowest decomposition temperature of the monomers used in each case, preference being given to a temperature range from 10 to 150 ° C., very particularly preferably from 70 to 120 ° C. and in particular from 80 to 110 ° C.

If particularly readily volatile monomers (a) and / or (b) are used, the copolymerization can also be carried out under pressure, preferably below 1.5 to 3,000 bar, especially 5 to 1,500 and in particular 10 to 1,000 bar.

With regard to the molecular weight distribution, the component (A) is not limited. Advantageously, however, the copolymerization is conducted so that a molecular weight distribution Mw / Mn measured by gel permeation chromatography using polystyrene as a standard of ≤ 4, preferably more preferably <2 and in particular ≤ 1.5 and in some cases also ≤ 1.3 results. The molecular weights of components (A) are controllable by the choice of the ratio of monomer (a) to monomer (b) to radical initiator within wide limits. In particular, the content of monomer (b) determines the molecular weight in such a way that the larger the proportion of monomer (b), the lower the molecular weight obtained.

The component (A) resulting from the copolymerization is generally obtained as a mixture with the aqueous medium in the form of a dispersion. It can be further processed directly in this form or used as macroinitiator for further reaction with at least one further monomer (a) in a second stage (ii). However, the component (A) resulting in the first stage (i) can also be isolated as a solid and then reacted further.

The further reaction according to step (ii) is preferably carried out under the usual conditions for a free radical polymerization, wherein suitable solvents (H) and / or reactive diluents (F) may be present. The stages (i) and (ii) can be carried out both spatially and temporally separated from each other in the context of the method according to the invention. In addition, however, the steps (i) and (ii) can also be carried out in succession in a reactor. For this purpose, the monomer (b) is first reacted with at least one monomer (a) completely or partially depending on the desired application and the desired properties, after which at least one further monomer (a) is added and free-radically polymerized. In a further embodiment, at least two monomers (a) are used from the beginning, the monomer (b) first reacting with one of the at least two monomers (a) and subsequently the resulting reaction product (A) above a certain molecular weight also with the other monomer (a) reacts.

Depending on the reaction procedure, it is possible according to the invention to produce functionalized polymers, block or multiblock and gradient (co) polymers, star-shaped polymers, graft copolymers and branched (co) polymers as constituents (A).

Component (A) may contain at least one, preferably at least two, functional groups (afg) which may undergo thermal crosslinking reactions with complementary functional groups (bfg) of the optional crosslinking agent (B) described below. The functional groups (afg) can be introduced via the monomers (a) into the component (A) or introduced after its synthesis by polymer-analogous reactions.

Examples of suitable complementary reactive functional groups (afg) and (bfg) to be used according to the invention, which undergo crosslinking reactions, are listed in the following overview. In the overview, the variable R ^{5 is} substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals; the variables R ⁶ and R ⁷ are identical or different alkyl, cycloalkyl, alkylcycloalkyl or cycloalkylalkyl radicals or are linked together to form an aliphatic or heteroaliphatic ring. Examples of suitable radicals of this type are those listed above for the radicals R ¹ , R ² , R ³ and R ⁴ .

Overview: Examples of complementary functional groups (afg) and (bfg) in the Ingredient, (A) and Crosslinking Agent (B) or Crosslinking Agent (B) and Component (A)

SH -C (O) -OH -NH ₂ -C (O) -O-C (O) - -OH NCO -O- (CO) -NH- (CO) -NH ₂ -NH-C (O) -OR ⁵ -O- (CO) -NH ₂ -CH ₂ -OH -CH ₂ -O-CH ₃ -NH-C (O) -CH (-C (O) OR ⁵ ) ₂ -NH-C (O) -CH (-C (O) OR ⁵ ) (- C (O) -R ⁵ ) -NH-C (O) -NR ⁶ R ⁷ = Si (OR ⁵ ) ₂

-C (O) -OH

-OC (O) -CR ⁵ = CH ₂ -OH -O-CR = CH ₂ -NH ₂ -C (O) -CH ₂ -C (O) -R ⁵ -CH = CH ₂

On the one hand, the selection of the respective complementary groups (afg) and (bfg) depends on the fact that they do not undergo undesired reactions during storage and / or may not disturb or inhibit curing with actinic radiation, and secondly, in which Temperature range, the thermal curing is to take place.

In this case, it is advantageous according to the invention, in particular with regard to thermally sensitive substrates such as plastics, to select a temperature range which does not exceed 100 ° C., in particular 80 ° C. In view of these basic conditions, hydroxyl groups and isocyanate groups or carboxyl groups and epoxy groups have proved to be advantageous as complementary functional groups, for which reason they are preferably used according to the invention in the coating materials according to the invention which are present as two-component or multicomponent systems. Particular advantages result when the hydroxyl groups are used as functional groups (afg) and the isocyanate groups as functional groups (bfg).

If higher crosslinking temperatures, for example from 100.degree. C. to 180.degree. C., are used, suitable coating materials are also one-component systems in which the functional groups (afg) are preferably thio-, amino-, hydroxyl-, carbamate-, allophanate-, carboxy- and / or (meth) acrylate groups, but especially hydroxyl groups and the functional groups (bfg) preferably anhydride, carboxy, epoxy, blocked isocyanate, urethane, Methylol, methylol ether, siloxane, amino, hydroxy and / or beta-hydroxyalkylamide groups.

The component (A) or the coating material produced therewith, however, can also be film-free without a crosslinking agent (B) and form an excellent finish. In this case, the component (A) is physically curing. In the context of the present invention, the physical curing and the curing via the complementary groups (afg) and (bfg) described above are summarized under the generic term "thermal curing".

The proportion of the component (A) to be used according to the invention on the coating material can vary very widely and depends in particular on whether the coating material for the mechanical energy absorbing filler layer FL, the color and / or effect topcoat DL, the color and / or effect-imparting basecoat BL or the clearcoats KL should be used. Advantageously, the proportion is 1 to 90, preferably 2 to 80, particularly preferably 3 to 75 and in particular 4 to 70 wt.%, In each case based on the total solids content of the coating material.

The coating material may further comprise at least one component (A ') which is a common and known binder (A') having at least one functional group (afg). Examples of suitable binders (A ') are linear and / or branched and / or block-like, comb-like and / or random poly (meth) acrylates or acrylate copolymers, polyesters, alkyds, aminoplast resins, polyurethanes, acrylated polyurethanes, acrylated polyesters, polylactones, polycarbonates, Polyethers, epoxy resin-amine adducts, (meth) acrylate diols, partially saponified polyvinyl esters or polyureas containing said functional groups (afg). If used, they are preferably present in the coating material in an amount of 1 to 50, preferably 2 to 40, particularly preferably from 3 to 30 and in particular from 4 to 25% by weight, based in each case on the total solids content of the coating material.

The coating material may further contain at least one crosslinking agent (B) containing at least two, in particular three, of the complementary functional groups (bfg) described in detail above.

If the coating material is a two-component or multi-component system, polyisocyanates and / or polyepoxides, but in particular polyisocyanates, are used as crosslinking agent (B).

Examples of suitable polyisocyanates (B) are organic polyisocyanates, in particular so-called lacquer polyisocyanates, having aliphatically, cycloaliphatically, araliphatically and / or aromatically bound, free isocyanate groups. Preference is given to using polyisocyanates having from 2 to 5 isocyanate groups per molecule and having viscosities of from 100 to 10,000, preferably from 100 to 5,000 and in particular from 100 to 2,000 mPas (at 23 ° C.). Optionally, the polyisocyanates still small amounts of organic solvent (H); preferably 1 to 25 wt .-%, based on pure polyisocyanate, are added, so as to improve the incorporation of the isocyanate and optionally to lower the viscosity of the polyisocyanate to a value within the above ranges. Examples of suitable solvents for the polyisocyanates are ethoxyethyl propionate, amyl methyl ketone or butyl acetate. In addition, the polyisocyanates (B) may be hydrophilic or hydrophobic modified in a conventional manner.

Examples of suitable polyisocyanates (B) are, for example, in " Methods of Organic Chemistry ", Houben-Weyl, Volume 14/2, 4th Edition, Georg Thieme Verlag, Stuttgart 1963, pages 61 to 70 , and from W. Siefken, Liebigs Annalen der Chemie, Volume 562, pages 75 to 136 , described.

Further examples of suitable polyisocyanates (B) are isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea and / or uretdione polyisocyanates. For example, urethane group-containing polyisocyanates are prepared by reacting a portion of the isocyanate groups with polyols, e.g. Trimethylolpropane and glycerin. Preferably, aliphatic or cycloaliphatic polyisocyanates, in particular hexamethylene diisocyanate, dimerized and trimerized hexamethylene diisocyanate, isophorone diisocyanate, 2-Isocyanatopropylcyclohexylisocyanat, dicyclohexylmethane-2,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate or 1,3-bis (isocyanatomethyl) cyclohexane (BIC ), Diisocyanates derived from dimer fatty acids, such as those sold under the trade name DDI 1410 by Henkel, 1,8-diisocyanato-4-isocyanatomethyl-octane, 1,7-diisocyanato-4-isocyanatomethyl-heptane or 1-isocyanato 2- (3-isocyanatopropyl) cyclohexane or mixtures of these polyisocyanates used.

Examples of suitable polyepoxides (B) are all known aliphatic and / or cycloaliphatic and / or aromatic polyepoxides, for example based on bisphenol-A or bisphenol-F. Also suitable as polyepoxides are, for example, the polyepoxides commercially available under the names Epikote® from Shell, Denacol® from Nagase Chemicals Ltd., Japan, such as Denacol EX-411 (pentaerythritol polyglycidyl ether), Denacol EX-321 (trimethylolpropane polyglycidyl ether), Denacol EX-512 (polyglycerol polyglycidyl ether) and Denacol EX-521 (polyglycerol polyglycidyl ether).

In the case of the one-component systems, crosslinking agents (B) are used which react at higher temperatures with the functional groups of the binders to build up a three-dimensional network. Of course, such crosslinking agents (B) may be used in minor amounts in the multicomponent systems. In the context of the present invention, "minor amount" means a proportion which does not disturb or even completely prevent the main crosslinking reaction.

Examples of suitable crosslinking agents (B) of this type are blocked polyisocyanates. Examples of suitable polyisocyanates for the preparation of the blocked polyisocyanates are those described above.

• i) Phenole wie Phenol, Cresol, Xylenol, Nitrophenol, Chlorophenol, Ethylphenol, t-Butylphenol, Hydroxybenzoesäure, Ester dieser Säure oder 2,5- di-tert.-Butyl-4-hydroxytoluol;
• ii) Lactame, wie ε-Caprolactam, δ-Valerolactam, γ-Butyrolactam , oder β-Propiolactam;
• iii) aktive methylenische Verbindungen, wie Diethylmalonat, Dimethylmalonat, Acetessigsäureethyl- oder -methylester oder Acetylaceton;
• iv) Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, Isobutanol, t-Butanol, n-Amylalkohol, t-Amylalkohol, Laurylalkohol, Ethylenglykolmonomethylether, Ethylenglykolmonoethylether, Ethylenglykolmonobutylether, Diethylenglykolmonomethylether, Diethylenglykolmonoethylether, Propylenglykolmonomethylether, Methoxymethanol, Glykolsäure, Glykolsäureester, Milchsäure, Milchsäureester, Methylolharnstoff, Methylolmelamin, Diacetonalkohol, Ethylenchlorohydrin, Ethylenbromhydrin, 1,3-Dichloro-2-propanol, 1,4-Cyclohexyldimethanol oder Acetocyanhydrin;
• v) Mercaptane wie Butylmercaptan, Hexylmercaptan, t-Butylmercaptan, t-Dodecylmercaptan, 2-Mercaptobenzothiazol, Thiophenol, Methylthiophenol oder Ethylthiophenol;
• vi) Säureamide wie Acetoanilid, Acetoanisidinamid, Acrylamid, Methacrylamid, Essigsäureamid, Stearinsäureamid oder Benzamid;
• vii) Imide wie Succinimid, Phthalimid oder Maleimid;
• viii) Amine wie Diphenylamin, Phenylnaphthylamin, Xylidin, N-Phenylxylidin, Carbazol, Anilin, Naphthylamin, Butylamin, Dibutylamin oder Butylphenylamin;
• ix) Imidazole wie Imidazol oder 2-Ethylimidazol;
• x) Harnstoffe wie Harnstoff, Thioharnstoff, Ethylenharnstoff, Ethylenthioharnstoff oder 1,3-Diphenylharnstoff;
• xi) Carbamate wie N-Phenylcarbamidsäurephenylester oder 2-Oxazolidon;
• xii) Imine wie Ethylenimin;
• xiii) Oxime wie Acetonoxim, Formaldoxim, Acetaldoxim, Acetoxim, Methylethylketoxim, Diisobutylketoxim, Diacetylmonoxim, Benzophenonoxim oder Chlorohexanonoxime;
• xiv) Salze der schwefeligen Säure wie Natriumbisulfit oder Kaliumbisulfit;
• xv) Hydroxamsäureester wie Benzylmethacrylohydroxamat (BMH) oder Allylmethacrylohydroxamat; oder
• xvi) substituierte Pyrazole, Imidazole oder Triazole; sowie

Examples of suitable blocking agents are those of US Pat US-A-4,444,954 known blocking agents such as

• i) phenols, such as phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, t-butylphenol, hydroxybenzoic acid, esters of this acid or 2,5-di-tert-butyl-4-hydroxytoluene;
• ii) lactams, such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, or β-propiolactam;
• iii) active methylenic compounds, such as diethyl malonate, dimethyl malonate, ethyl or methyl acetoacetate or acetylacetone;
• iv) alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, methoxymethanol, glycolic acid, glycolic acid ester, lactic acid, lactic acid ester, methylolurea, methylolmelamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1,3-dichloro-2-propanol, 1,4-cyclohexyldimethanol or acetocyanohydrin;
• v) mercaptans such as butylmercaptan, hexylmercaptan, t-butylmercaptan, t-dodecylmercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol or ethylthiophenol;
• vi) acid amides such as acetoanilide, acetoanisidine amide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide or benzamide;
• vii) imides such as succinimide, phthalimide or maleimide;
• viii) amines such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine;
• ix) imidazoles such as imidazole or 2-ethylimidazole;
• x) ureas such as urea, thiourea, ethyleneurea, ethylene thiourea or 1,3-diphenylurea;
• xi) carbamates such as N-phenylcarbamic acid phenyl ester or 2-oxazolidone;
• xii) imines such as ethyleneimine;
• xiii) oximes such as acetone oxime, formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime, benzophenone oxime or chlorohexanone oximes;
• xiv) salts of sulfurous acid such as sodium bisulfite or potassium bisulfite;
• xv) hydroxamic acid esters such as benzyl methacrylohydroxamate (BMH) or allyl methacrylohydroxamate; or
• xvi) substituted pyrazoles, imidazoles or triazoles; such as

Mixtures of these blocking agents, in particular dimethylpyrazole and triazoles, malonic esters and acetoacetic acid esters or dimethylpyrazole and succinimide.

eingesetzt werden.As crosslinking agent (B) can also tris (alkoxycarbonylamino) triazines (TACT) of the general formula

be used.

Examples of suitable tris (alkoxycarbonylamino) triazines (B) are disclosed in the patents US-A-4,939,213 . US-A-5,084,541 or EP-A-0 624 577 described. In particular, the tris (methoxy, tris (butoxy and / or tris (2-ethylhexoxycarbonylamino) triazines are used.

Advantageous are the methyl-butyl mixed esters, the butyl 2-ethylhexyl mixed esters and the butyl esters. These have the advantage over the pure methyl ester the advantage of better solubility in polymer melts and also less prone to crystallization.

In particular, aminoplast resins, for example, melamine resins, guanamine resins or urea resins, are usable as the crosslinking agent (B). Any aminoplast resin suitable for transparent topcoats or clearcoats or a mixture of such aminoplast resins may be used here. In addition, it will open Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, 1998, page 29 , "Amino resins," and the textbook " Lackadditive "by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 ff ., or on the book " Paints, Coatings and Solvents ", secondly revised edition, Edit D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pp. 80 et seq ., directed. Furthermore, the usual and known amino resins are suitable, the methylol and / or methoxymethyl z. T. are defunctionalized by means of carbamate or allophanate. Crosslinking agents of this type are described in the patents US-A-4,710,542 and EP-B-0 245 700 as well as in the article of B. Singh and coworkers "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry" in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193 to 207 , described.

Further examples of suitable crosslinking agents (B) are beta-hydroxyalkylamides such as N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide or N, N, N', N-tetrakis (2-hydroxypropyl) adipamide.

Further examples of suitable crosslinking agents (B) are siloxanes, in particular siloxanes having at least one trialkoxy or dialkoxysilane group.

Further examples of suitable crosslinking agents (B) are polyanhydrides, in particular polysuccinic anhydride.

Further examples of suitable crosslinking agents (B) are compounds having on average at least two groups capable of transesterification, for example of malonic diesters and polyisocyanates or reaction products of monoisocyanates with esters and partial esters of malonic acid with polyhydric alcohols, as described in European Pat EP-A-0 596 460 to be discribed;

The amount of crosslinking agent (B) in the coating material, if used, can vary widely and depends, in particular, on the functionality of the crosslinking agents (B) and on the number of crosslinking functional groups (afg) present in the binder (A). as well as the network density that you want to achieve. The person skilled in the art can therefore determine the amount of crosslinking agent (B) on the basis of his general knowledge, if appropriate with the aid of simple orienting experiments. Advantageously, the crosslinking agent (B) in the coating material according to the invention in an amount of 1 to 60 wt .-%, particularly preferably 2 to 50 wt .-% and in particular 3 to 45 wt .-%, each based on the total solids content of the coating material, contain. In this case, it is further recommended to choose the amounts of crosslinking agent (B) and binder (A) so that in the Coating material the ratio of functional groups (bfg) in the crosslinking agent (B) and functional groups (afg) in the binder (A) between 2: 1 to 1: 2, preferably 1.5: 1 to 1: 1.5, particularly preferably 1 , 2: 1 to 1: 1.2, and more preferably 1.1: 1 to 1: 1, 1.

If the coating material is to be curable not only thermally but also with actinic radiation, in particular UV radiation and / or electron radiation (dual cure), it contains at least one component (C) which is curable with actinic radiation. However, if the coating material is to be curable predominantly (dual cure) or exclusively with actinic radiation, which is suitable in the context of the process according to the invention, in particular for the clearcoats, it must contain a constituent (C).

Suitable constituents (C) are in principle all actinic radiation, in particular UV radiation and / or electron radiation, curable oligomeric and polymeric compounds, such as are conventionally used in the field of UV curable or electron beam curable coating materials.

Advantageously, radiation-curable binders are used as constituents (C). Examples of suitable radiation-curable binders (C) are (meth) acryl-functional (meth) acrylic copolymers, polyether acrylates, polyester acrylates, unsaturated polyesters, epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates, silicone acrylates, isocyanato acrylates and the corresponding methacrylates. Preference is given to using binders (C) which are free of aromatic structural units. Preference is therefore given to using urethane (meth) acrylates and / or polyester (meth) acrylates, more preferably aliphatic urethane acrylates.

If components (C) are used, they are present in the coating material in an amount of preferably from 1 to 80, preferably from 1.5 to 70, particularly preferably from 2 to 65 and in particular from 2.5 to 60,% by weight, in each case on the total solids content of the coating material.

The coating material may further contain at least one photoinitiator (D). If the coating material or the layers produced therefrom in the process according to the invention additionally or should be crosslinked (dual cure) or exclusively with UV radiation, the use of a photoinitiator (D) is generally necessary. If it is used with, it is in the coating material according to the invention preferably in proportions of 0.01 to 10 wt .-%, preferably 0.1 to 8 wt .-% and in particular 0.5 to 6 wt .-%, each based on the total solids content of the coating material according to the invention.

Examples of suitable photoinitiators (D) are those of the Norrish II type whose mechanism of action is based on an intramolecular variant of the hydrogen abstraction reactions, as they occur in a variety of ways in photochemical reactions (by way of example here Römpp Chemie Lexikon, 9th extended and revised edition, Georg Thieme Verlag Stuttgart, Vol 4, 1991 , referenced) or cationic photoinitiators (for example, see Römpp Lexikon »Paints and Printing Inks« Georg Thieme Verlag Stuttgart, 1998, pages 444 to 446 , referenced), in particular benzophenones, benzoins or benzoin ethers or phosphine oxides. It is also possible, for example, to use the products commercially available under the names Irgacure® 184, Irgacure® 1800 and Irgacure® 500 from Ciba Geigy, Grenocure® MBF from Rahn and Lucirin® TPO from BASF AG.

Besides the photoinitiators (D), conventional sensitizers (D) such as anthracene can be used in effective amounts.

Furthermore, the coating material may contain at least one thermal crosslinking initiator (E). These form from 80 to 120 ° C radicals that start the crosslinking reaction. Examples of thermolabile free-radical initiators are 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. C-C-cleaving initiators are particularly preferred, since during their thermal decomposition no gaseous decomposition products are formed which could lead to disruptions in the lacquer layer. If used with, their amounts are generally between 0.01 to 10 wt .-%, preferably 0.05 to 8 wt .-% and in particular 0.1 to 5 wt .-%, each based on the total solids content of coating material of the invention.

In addition, the coating material may contain at least one actinic radiation and / or thermally curable reactive diluent (F).

Examples of suitable thermally crosslinkable reactive diluents (F) are branched, cyclic and / or acyclic C ₉ -C ₁₆ -alkanes which are functionalized with at least two hydroxyl groups, preferably dialkyloctanediols, in particular the positionally isomeric diethyloctanediols.

Further examples of suitable thermally crosslinkable reactive diluents (F) are oligomeric polyols which are obtainable from oligomeric intermediates obtained by metathesis reactions of acyclic monoolefins and cyclic monoolefins by hydroformylation and subsequent hydrogenation; Examples of suitable cyclic monoolefins are cyclobutene, cyclopentene, Cyclohexene, cyclooctene, cycloheptene, norbornene or 7-oxanorbonen; Examples of suitable acyclic monoolefins are contained in hydrocarbon mixtures which are obtained in petroleum processing by cracking (C _{5 cut} ); Examples of suitable oligomeric polyols to be used according to the invention have a hydroxyl number (OHN) of 200 to 450, a number-average molecular weight Mn of 400 to 1,000 and a weight-average molecular weight Mw of 600 to 1,100.

Further examples of suitable thermally crosslinkable reactive diluents (F) are hyperbranched compounds having a tetrafunctional central group derived from ditrimethylolpropane, diglycerol, ditrimethylolethane, pentaerythritol, tetrakis (2-hydroxyethyl) methane, tetrakis (3-hydroxypropyl) methane or 2,2-bishydroxymethyl-butanediol - (1,4) (homopentaerythritol). The preparation of these reactive diluents can be carried out by the customary and known methods of preparing hyperbranched and dendrimeric compounds. Suitable synthesis methods are described for example in the patents WO 93/17060 or WO 96/12754 or in the book of GR Newkome, CN Moorefield and F. Vögtle, "Dendritic Molecules, Concepts, Syntheses, Perspectives", VCH, Weinheim, New York, 1996 , described.

Further examples of suitable reactive diluents (F) are polycarbonate diols, polyester polyols, poly (meth) acrylate diols or hydroxyl-containing polyaddition products.

Examples of suitable reactive solvents which can be used as reactive diluents (F) are butylglycol, 2-methoxypropanol, n-butanol, methoxybutanol, n-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, Diethylenglykolmonobutylether, trimethylolpropane, 2-Hydroxypropionsäureethylester or 3-methyl-3-methoxybutanol and derivatives based on propylene glycol, for example, isopropoxypropanol called.

Suitable reactive diluents (F) which can be crosslinked with actinic radiation are, for example, polysiloxane macromonomers, (meth) acrylic acid and its other esters, maleic acid and its esters or monoesters, vinyl acetate, vinyl ethers, vinyl ureas and the like. used. Examples which may be mentioned are alkylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate , Trimethylolpropane di (meth) acrylate, tripropylene glycol diacrylate, styrene, vinyltoluene, divinylbenzene, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipropylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, ethoxyethoxyethyl acrylate, N-vinylpyrrolidone, phenoxyethyl acrylate, dimethylaminoethyl acrylate , Hydroxyethyl (meth) acrylate, butoxyethyl acrylate, isobornyl (meth) acrylate, dimethylacrylamide and dicyclopentyl acrylate, and those described in the EP-A-0 250 631 described, long-chain linear diacrylates having a molecular weight of 400 to 4,000, preferably from 600 to 2,500 called. For example, the acrylate groups may also be separated by a polyoxybutylene structure. It is also possible to use 1,12-dodecyldiacrylate and the reaction product of 2 moles of acrylic acid with one mole of a dimer fatty alcohol, which generally has 36 C atoms. Also suitable are mixtures of the monomers mentioned.

As reactive diluents (F) it is preferred to use mono- and / or diacrylates, for example isobornyl acrylate, hexanediol diacrylate, tripropylene glycol diacrylate, Laromer® 8887 from BASF AG and Actilane® 423 from Akcros Chemicals Ltd., GB. Particular preference is given to using isobornyl acrylate, hexanediol diacrylate and tripropylene glycol diacrylate.

If used with, the reactive diluents (F) in an amount of preferably 1 to 70 wt .-%, more preferably 2 to 65 wt .-% and in particular 3 to 50 wt .-%, each based on the total solids content of Inventive coating material applied.

The coating material may contain conventional lacquer additives (G) in effective amounts. The type and amount of the additives (G) are mainly determined by the intended use of the coating material of the invention. Advantageously, the additives (G) are not volatile under the processing and application conditions of the coating material according to the invention.

If the coating materials are used as fillers FL, Unidecklack DL and / or basecoat BL, it contains as coating additives (G) compulsorily at least one filler and / or a color and / or effect pigment (G) in customary and known, effective amounts.

Preferably, the coating material contains the fillers and / or pigments (G) in amounts of 1 to 95 wt .-%, particularly preferably 2 to 90 wt .-% and in particular 3 to 85 wt .-%, each based on the total solids content of the coating material.

The pigments (G) may consist of inorganic or organic compounds and may be effect and / or coloring. Because of this large number of suitable pigments (G), the coating material according to the invention therefore ensures a universal range of application of the coating materials and makes it possible to realize a large number of hues and optical effects.

As effect pigments (G), it is possible to use metal flake pigments, such as commercial aluminum bronzes, according to US Pat DE-A-36 36 183 chromated aluminum bronzes, and commercial stainless steel bronzes and non-metallic effect pigments, such as pearlescent or. Interference pigments are used. Examples of suitable inorganic color pigments (G) are titanium dioxide, iron oxides, sicotrans yellow and carbon black. Examples of suitable organic coloring pigments (G) are Indanthrenblau, Cromophthalrot, Irgazinorange and Heliogengrün.

Furthermore, the coating material, in particular the filler FL organic and inorganic fillers (G) in conventional and known, effective amounts. Examples of suitable fillers are chalk, calcium sulfate, 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 or wood flour. In addition, it will open Römpp Lexikon Lacke and printing inks, Georg Thieme publishing house, 1998, pages 250 ff ., "Fillers", referenced.

These additives (G) can also be incorporated into the coating materials via pigment pastes, suitable abrasion resins being, in particular, the constituents (A) described above and optionally the constituents (A ') described above.

These additives (G) are omitted if the coating materials are used as clearcoats KL in the context of the process according to the invention.

• UV-Absorber;
• Lichtschutzmittel wie HALS-Verbindungen, Benztriazole oder Oxalanilide;
• Radikalfänger;
• Katalysatoren für die Vernetzung wie Dibutylzinndilaurat oder Lithiumdecanoat;
• Slipadditive;
• Polymerisationsinhibitoren;
• Entschäumer;
• Neutralisationsmittel wie Ammoniak oder Dimethylethanolamin;
• Emulgatoren, insbesondere nicht ionische Emulgatoren wie alkoxylierte Alkanole und Polyole, Phenole und Alkylphenole oder anionische Emulgatoren wie Alkalisalze oder Ammoniumsalze von Alkancarbonsäuren, Alkansulfonsäuren, und Sulfosäuren von alkoxylierten Alkanolen und Polyolen, Phenolen und Alkylphenolen;
• Netzmittel wie Siloxane, fluorhaltige Verbindungen, Carbonsäurehalbester, Phosphorsäureester, Polyacrylsäuren und deren Copolymere oder Polyurethane;
• Haftvermittler wie Tricyclodecandimethanol;
• Verlaufmittel;
• filmbildende Hilfsmittel wie Cellulose-Derivate;
• transparente Füllstoffe auf der Basis von Siliziumdioxid, Aluminiumoxid oder Zirkoniumoxid; ergänzend wird noch auf das Römpp Lexikon »Lacke und Druckfarben« Georg Thieme Verlag, Stuttgart, 1998, Seiten 250 bis 252 , verwiesen;
• Sag control agents wie Harnstoffe, modifizierte Harnstoffe und/oder Kieselsäuren, wie sie beispielsweise in den Literaturstellen EP-A-192 304 , DE-A-23 59 923 , DE-A-18 05 693 , WO 94/22968 , DE-C-27 51 761 , WO 97/12945 oder "farbe + lack", 11/1992, Seiten 829 ff., beschrieben werden;
• rheologiesteuernde Additive wie die aus den Patentschriften WO 94/22968 , EP-A-0 276 501 , EP-A-0 249 201 oder WO 97/12945 bekannten; vernetzte polymere Mikroteilchen, wie sie beispielsweise in der EP-A-0 008 127 offenbart sind; anorganische Schichtsilikate wie Aluminium-Magnesium-Silikate, Natrium-Magnesium- und Natrium-Magnesium-Fluor-Lithium-Schichtsilikate des Montmorillonit-Typs; Kieselsäuren wie Aerosile; oder synthetische Polymere mit ionischen und/oder assoziativ wirkenden Gruppen wie Polyvinylalkohol, Poly(meth)acrylamid, Poly(meth)acrylsäure, Polyvinylpyrrolidon, Styrol-Maleinsäureanhydrid- oder Ethylen-Maleinsäureanhydrid-Copolymere und ihre Derivate oder hydrophob modifizierte ethoxylierte Urethane oder Polyacrylate;
• Flammschutzmittel und/oder
• Mattierungsmittel.

Examples of suitable additives (G) which may be present both in the clearcoats KL and in the fillers FL according to the invention, solid-color topcoats DL and basecoats BL

• UV absorbers;
• Light stabilizers such as HALS compounds, benzotriazoles or oxalanilides;
• Radical scavengers;
• Catalysts for crosslinking such as dibutyltin dilaurate or lithium decanoate;
• slip additives;
• polymerization inhibitors;
• defoamers;
• Neutralizing agents such as ammonia or dimethylethanolamine;
• Emulsifiers, in particular nonionic emulsifiers such as alkoxylated alkanols and polyols, phenols and alkylphenols or anionic emulsifiers such as alkali metal salts or ammonium salts of alkanecarboxylic acids, alkanesulfonic acids, and sulfonic acids of 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;
• Adhesion promoters such as tricyclodecanedimethanol;
• Leveling agents;
• film-forming aids such as cellulose derivatives;
• transparent fillers based on silica, alumina or zirconia; In addition, it is still on the Römpp Lexikon »Paints and Printing Inks« Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252 , directed;
• Sag control agents such as ureas, modified ureas and / or silicas, as described for example in the literature EP-A-192304 . DE-A-23 59 923 . DE-A-18 05 693 . WO 94/22968 . DE-C-27 51 761 . WO 97/12945 or "paint + varnish", 11/1992, pages 829 et seq .;
• Rheology-controlling additives such as those from the patents WO 94/22968 . EP-A-0 276 501 . EP-A-0 249 201 or WO 97/12945 known; crosslinked polymeric microparticles, as described for example in the EP-A-0 008 127 are disclosed; inorganic phyllosilicates such as aluminum-magnesium silicates, sodium magnesium and sodium magnesium fluorine lithium phyllosilicates of the montmorillonite type; Silicas such as aerosils; or synthetic polymers having 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 hydrophobically modified ethoxylated urethanes or polyacrylates;
• Flame retardants and / or
• Matting agent.

Further examples of suitable paint additives (G) of this type are described in US Pat Textbook »Paint Additives« by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998 , described.

It is essential that the paint additives (G) described above, which may be present in both the fillers, the solid-color topcoats and the basecoats, as well as in the clearcoats, do not adversely affect the transparency and clarity of the coating material when it is used as clearcoat KL.

Preferably, the coating material contains these coating additives (G), which may be present both in the fillers, the solid-color topcoats and the basecoats and in the clearcoats, in amounts of up to 40% by weight, particularly preferably up to 30% by weight and in particular up to 20 wt .-%, each based on the total solids content of the coating material.

Not least, the coating materials, especially in the case of non-aqueous coating materials, 1 to 70 wt .-%, preferably 2 to 60 wt .-%, (based on the application-ready coating material) water-miscible and water-immiscible organic solvent (H), such. aliphatic, aromatic and / or cycloaliphatic hydrocarbons such as toluene or methylcyclohexane or decalin, alkyl esters of acetic acid or propionic acid, alkanols such as ethanol, ketones such as methyl isobutyl ketone, glycol ethers glycol ether, and / or ethers such as tetrahydrofuran. In the context of the present invention, carbon dioxide can also be used as solvent (H).

The coating material can be in different forms.

Thus, with a suitable choice of its components (A) described above and optionally at least one of its constituents (A '), (B), (C), (D), (E), (F) and / or (G) as liquid coating material which is substantially free of organic solvents and / or water (100% system).

However, the coating material may be a solution or dispersion of the ingredients described above in organic solvents (H) and / or water. It is a further advantage of the coating material that solid contents of up to more than 80% by weight, based on the coating material, can be set.

Furthermore, the coating material may be a powder paint, with a suitable choice of its constituents described above. For this purpose, component (B) may be microencapsulated if it is a polyisocyanate. This powder coating can then optionally be dispersed in water, resulting in a powder slurry coating.

The coating material may be a two-component or multi-component system in which at least component (B) is stored separately from the other constituents and added to it just prior to use. In this case, the coating material of the invention may also be aqueous, wherein the component (B) is preferably present in a component containing a solvent (H).

Furthermore, the coating material may be part of a so-called mixing system or modular system, as described for example in the patents DE-A-41 10 520 . EP-A-0 608 773 . EP-A-0 614 951 or EP-A-0 471 972 to be discribed.

Preferably, the coating material according to the invention is present as an aqueous solution, dispersion and / or emulsion, in particular dispersion, because in this case the isolation of the component (A) to be used according to the invention can be omitted.

The preparation of the coating material from its components (A) and optionally at least one of its constituents (A '), (B), (C), (D), (E), (F), (G) and / or (H) has no special features, but is carried out in a conventional manner by mixing the components in suitable mixing units such as stirred tank, dissolver or extruder according to the methods suitable for the preparation of the respective coating materials.

The coating material according to the invention serves to prepare the multicoat paint systems ML according to the invention on primed or unprimed substrates.

Suitable substrates are all surfaces to be painted, which are not damaged by a curing of the coatings thereon using heat and optionally actinic radiation into consideration, these are, for. As metals, plastics, wood, ceramics, stone, textile, fiber composites, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials such as gypsum and cement boards or roof tiles, and composites of these materials. Accordingly, the multicoat system ML according to the invention is also suitable for applications outside of automotive finishing, in particular for the coating of furniture and industrial coating, including coil coating and container coating. In the context of industrial coatings, it is suitable for the coating of virtually all parts for private or industrial use such as radiators, household appliances, small metal parts, hubcaps or rims.

In the case of electrically conductive substrates primers can be used, which are prepared in a conventional manner from electrocoating (ETL). For this purpose, both anodic (ATL) and cathodic (KTL) Elektrotanchlacke, but especially KTL, into consideration.

With the multi-layer coating ML according to the invention in particular primed or unprimed plastics such. ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (abbreviated to DIN 7728T1). Of course, the plastics to be coated can also be polymer blends, modified plastics or fiber-reinforced plastics. It is also possible to use the plastics usually used in vehicle construction, in particular motor vehicle construction.

In the case of non-functionalized and / or non-polar substrate surfaces, they may be subjected to a pretreatment, such as with a plasma or with flames, or provided with a hydro-primer prior to coating in a known manner.

The multicoat paint systems ML according to the invention can be prepared in different ways by the process according to the invention.

• (I) Herstellen einer Füllerlackschicht durch Applikation eines Füllers auf das Substrat,
• (II) Härtung der Füllerlackschicht, wodurch die Füllerschicht FL resultiert,
• (III) Herstellen einer Unidecklackschicht durch Applikation eines Unidecklacks auf die Füllerschicht FL und
• (IV) Härtung der Unidecklackschicht DL, wodurch die Unidecklackierung DL resultiert.

In a first preferred variant, the process according to the invention comprises the following process steps:

• (I) producing a surfacer paint layer by applying a filler to the substrate,
• (II) curing the surfacer coating layer, resulting in the surfacer layer FL,
• (III) producing a solid-color topcoat by applying a solid-color topcoat to the filler layer FL and
• (IV) Curing the solid-color topcoat DL, resulting in the solid-color finish DL.

• (I) Herstellen einer Basislackschicht durch Applikation eines Basislacks auf das Substrat,
• (II) Trocknen der Basislackschicht,
• (III) Herstellen einer Klarlackschicht durch Applikation eines Klarlacks auf die Basislackschicht und
• (IV) gemeinsame Härtung der Basislackschicht und der Klarlackschicht, wodurch die Basislackierung BL und die Klarlackierung KL resultieren (Naß-in-naß-Verfahren).

A further preferred variant of the method according to the invention comprises the method steps:

• (I) producing a basecoat film by applying a basecoat to the substrate,
• (II) drying the basecoat film,
• (III) producing a clearcoat by application of a clearcoat to the basecoat film and
• (IV) co-curing of the basecoat film and the clearcoat film, resulting in the basecoat BL and the clearcoat KL (wet-in-wet process).

1. (I) Herstellen einer Füllerlackschicht durch Applikation eines Füllers auf das Substrat,
2. (II) Härtung der Füllerlackschicht, wodurch die Füllerschicht FL resultiert,
3. (III) Herstellen einer Basislackschicht durch Applikation eines Basislacks auf die Füllerschicht FL,
4. (IV) Trocknen der Basislackschicht,
5. (V) Herstellen einer Klarlackschicht durch Applikation eines Klarlacks auf die Basislackschicht und
6. (VI) gemeinsame Härtung der Basislackschicht und der Klarlackschicht, wodurch die Basislackierung BL und die Klarlackierung KL resultieren (Naß-in-naß- . Verfahren).

A third preferred variant of the method according to the invention comprises the method steps:

1. (I) producing a surfacer paint layer by applying a filler to the substrate,
2. (II) curing the surfacer coating layer, resulting in the surfacer layer FL,
3. (III) producing a basecoat film by applying a basecoat to the filler coat FL,
4. (IV) drying the basecoat film,
5. (V) producing a clearcoat layer by applying a clearcoat to the basecoat film and
6. (VI) joint hardening of the basecoat film and the clearcoat film, resulting in the basecoat BL and the clearcoat KL (wet-in-wet process).

Which preferred variant is chosen depends on the intended use of the multicoat systems ML according to the invention. For example, the third variant is particularly preferably used in automotive OEM finishing.

As a result, the multicoat systems ML according to the invention can have a different structure.

1. (1) eine mechanische Energie absorbierende Füllerschicht FL und
2. (2) eine farb- und/oder effektgebende Decklackierung DL

in der angegebenen Reihenfolge übereinander.In a first preferred variant of the multicoat system ML according to the invention

1. (1) a mechanical energy absorbing filler layer FL and
2. (2) a color and / or effect topcoat DL

in the order given above each other.

1. (1) eine mechanische Energie absorbierende Füllerschicht FL,
2. (2) eine farb- und/oder effektgebende Basislackierung BL und
3. (3) eine Klarlackierung KL

in der angegebenen Reihenfolge übereinander.In a second preferred variant of the multicoat system ML according to the invention

1. (1) a mechanical energy absorbing filler layer FL,
2. (2) a color and / or effect basecoat BL and
3. (3) a clearcoat KL

in the order given above each other.

1. (1) eine farb- und/oder effektgebende Basislackierung BL und
2. (2) eine Klarlackierung KL

in der angegebenen Reihenfolge übereinander. Die dritte bevorzugte Variante wird insbesondere bei der Kunststofflackierung angewandt. µmIn a third preferred variant of the multicoat system ML according to the invention

1. (1) a color and / or effect basecoat BL and
2. (2) a clearcoat KL

in the order given above each other. The third preferred variant is used in particular in the plastic coating. microns

The application of the coating material can be carried out in the context of the method according to the invention by all customary application methods, such as spraying, knife coating, brushing, pouring, dipping or rolling. Preferably, spray application methods are used, such as compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as hot air hot spraying. The applications can be carried out at temperatures of max. 70 to 80 ° C are performed, so that suitable application viscosities are achieved without a change or damage to the coating material and its optionally reprocessable overspray occurring during the brief thermal load. Thus, the hot spraying can be designed so that the coating material is heated only very briefly in or just before the spray nozzle.

The spray booth used for the application can be operated, for example, with an optionally temperature-controlled circulation, with a suitable absorption medium for overspray, z. B. the coating material itself, is operated.

If the coating material contains components (C) which can be crosslinked with actinic radiation, the application is carried out with illumination with visible light of a wavelength of more than 550 nm or with exclusion of light. As a result, a material change or damage to the coating material and the overspray are avoided.

The application methods described above can be used for the preparation of all layers FL, DL, BL and KL and optionally further lacquer layers.

In the process according to the invention, the surfacer coating layer, topcoat layer, basecoat layer and clearcoat layer are applied in a wet layer thickness such that layers FL, DL, BL and KL result with their layer thicknesses which are necessary and advantageous for their functions. In the case of the filler layer FL, this layer thickness is from 10 to 150, preferably from 15 to 120, particularly preferably from 20 to 100 and in particular from 25 to 90 μm, in the case of the topcoat DL it is from 5 to 90, preferably from 10 to 80, particularly preferably 15 to 60, and in particular 20 to 50 microns, in the case of the basecoat BL it is 5 to 50, preferably 10 to 40, particularly preferably 12 to 30 and in particular 15 to 25 microns, and in the case of the clearcoats KL it is 10 to 100, preferably 15 to 80, particularly preferably 20 to 70 and in particular 25 up to 60 μm.

According to the invention, the surfacer coating layer, topcoat layer, basecoat layer and clearcoat layer can be cured thermally or thermally and with actinic radiation, depending on their material composition. According to the invention, it is advantageous not to cure the basecoat film at all or only partially before applying the clearcoat film in order subsequently to cure it together with the clearcoat film (wet-in-wet process).

Curing can take place after a certain rest period. It may have a duration of 30 seconds to 2 hours, preferably 1 minute to 1 hour and especially 1 minute to 30 minutes. The rest period is used, for example, for the course and the degassing of. Coating layers or for evaporation of volatile components such as solvents, water or carbon dioxide, when the coating material has been applied with supercritical carbon dioxide as the solvent (H). The rest period can be supported and / or shortened by the use of elevated temperatures up to 80 ° C, provided that no damage or changes in the paint layers occur, such as premature complete crosslinking.

The thermal curing has no special features, but takes place according to the usual and known methods such as heating in a convection oven or irradiation with IR lamps. Here, the thermal curing can also be done gradually. Advantageously, the thermal curing is carried out at a temperature of 50 to 100 ° C, more preferably 80 to 100 ° C and in particular 90 to 100 ° C for a time of 1 min to 2 h, more preferably 2 min to 1 h and in particular 3 min to 30 min. Become substrates used, which are thermally highly resilient, the thermal crosslinking can also be carried out at temperatures above 100 ° C. In general, it is advisable to not exceed temperatures of 180 ° C, preferably 160 ° C and especially 140 ° C.

The thermal curing can be supplemented by curing with actinic radiation with appropriate material composition of the coating material, wherein UV radiation and / or electron beams can be used. Optionally, it may be carried out or 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 paint 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 are used. Examples of suitable radiation sources are high and low pressure mercury vapor lamps, optionally doped with lead, to open a beam window up to 405 nm, or electron beam sources. Their arrangement is known in principle and can be adapted to the conditions of the workpiece and the process parameters. In complicated shaped workpieces such as automobile bodies, the non-direct radiation accessible areas (shadow areas) such as cavities, folds and other constructional undercuts may be cured with spot, small area or omnidirectional radiators coupled with an automatic moving device for irradiating cavities or edges.

The facilities and conditions of these curing methods are used, for example, in R. Holmes, UV and EB Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kindom 1984 , described.

Here, the curing can be done in stages, d. H. by 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.

If thermal curing and curing are combined with actinic radiation (dual cure), these methods can be used simultaneously or alternately. If the two curing methods are used alternately, for example, the thermal curing can be started and the curing with actinic radiation can be ended. In other cases, it may be advantageous to begin and terminate curing with actinic radiation. The person skilled in the art can determine the curing method, which is particularly suitable for each individual case, on the basis of its general knowledge, if appropriate with the aid of simple preliminary tests.

The multicoat paint systems ML according to the invention have an outstanding property profile which is very well balanced in terms of mechanics, appearance, corrosion resistance and adhesion. Thus, the multicoat paint systems ML according to the invention have the high optical quality and intercoat adhesion demanded by the market and no longer pose problems such as lack of condensation resistance of the surfacer layers, cracking (mud cracking) in the basecoats or flow defects or surface structures in the clearcoats.

In particular, the multi-layer coating ML of the present invention has excellent excellent metallic effect, excellent DO1. (Distinctiveness of the Reflected Image) and excellent surface smoothness, on. It is weather-resistant, resistant to chemicals and bird droppings and scratch-resistant and shows a very good reflow behavior.

Another essential advantage is the very good recoatability of the multicoat system ML according to the invention, even without sanding. As a result, it can be easily coated with customary and known highly scratch-resistant coating materials based on organically modified ceramic materials.

Not least, it proves to be a very particular advantage that with the aid of the method according to the invention, a multi-layer coating can be realized which is based exclusively on aqueous coating materials.

Examples Production Example 1 The preparation of a dispersion of a copolymer (A)

In a steel reactor, as it is usually used for the preparation of dispersions, equipped with a stirrer, a reflux condenser and 3 feed vessels 52.563 parts by weight of deionized water were introduced and heated to 90 ° C. In the first feed vessel 10.182 parts by weight of acrylic acid, 18.345 parts by weight of methyl methacrylate and 1.493 parts by weight of diphenylethylene were submitted. In the second feed vessel, 9.914 parts by weight of 25 percent ammonia solution were initially charged. 5.25 parts by weight of deionized water and 2.253 parts by weight of ammonium peroxodisulfate were initially introduced into the third feed vessel. Under intensive stirring of the template in the steel reactor, the three feeds were simultaneously started. The first and second feed were added within one hour. The third feed was metered in over 1.25 hours. The resulting reaction mixture was held at 90 ° C for four hours and then cooled to below 40 ° C and filtered through a 100 micron GAF bag. The resulting dispersion had a solids content of 32 to 34% by weight (1 hour, 130 ° C.) and a content of free monomers of less than 0.2% by weight (determined by gas chromatography).

The dispersion (A) was used for the preparation of a block copolymer (A).

Production Example 2 The preparation of a dispersion of a block copolymer (A)

In a steel reactor, as is usually used for the preparation of dispersions, equipped with a stirrer, a reflux condenser and a feed vessel 51.6017 parts by weight of deionized water and 9.907 parts by weight of the dispersion according to Preparation Example 1 were introduced and heated with stirring to 90 ° C. After that, a mixture of 9.856 parts by weight of n-butyl methacrylate, 7.884 parts by weight of styrene, 12.661 parts by weight of hydroxyethyl methacrylate and 8.885 parts by weight of ethylhexyl methacrylate was added from the feed vessel within six hours. The resulting reaction mixture was stirred for 2 hours at 90 ° C. Subsequently, the resulting dispersion was cooled below 40 ° C and filtered through a 50 micron GAF bag. The dispersion (A) had a solids content of 41 to 42 wt .-% (1 hour, 130 ° C) and a content of free monomers of less than 0.2 wt .-% (determined by gas chromatography).

example 1 The preparation of a multi-layer coating ML according to the invention 1.1 The Preparation of a Filler Containing Component (A) 1.1.1 The preparation of the pigment paste

For the preparation of the filler, first a pigment paste of 3.8 parts by weight of flame black, 32.87 parts by weight of barium sulfate (Blanc Fixe® Super-F), 1.73 parts by weight of talc, 1.04 parts by weight of Additol® XW395 (commercial wetting agent) and 60, 56 parts by weight of the dispersion (A) prepared according to Preparation Example 2. The mixture was predispersed for ten minutes in a dissolver and then ground on a sand mill to a Hegmann fineness <15 microns. The viscosity of the paste was 160 mPas at a shear rate of 100 s ^-1 and 23 ° C.

1.1.2 The manufacture of the filler

The filler was prepared by mixing 57.8 parts by weight of the pigment paste according to Examples 1.1.1 and 30 parts by weight of the dispersion (A) according to Preparation Example 2. It had a viscosity of 122 mPas at a shear rate of 100 s ^-1 and 23 ° C. With water, the filler was adjusted to an injection viscosity of 55 mPas.

1.2 The Preparation of a Metallic Basecoat Containing Component (A) 1.2.1 The production of a color paste

For the preparation of the metallic basecoat was first a color paste of 50 parts by weight of the dispersion (A) according to Preparation Example 2, 2 parts by weight of Pluriol® P900 (BASF AG), 43 parts by weight of Sicopalgelb® L1100 (BASF AG), 0.4 parts by weight of Agitan® 281 (commercial defoamer, Münzing Chemie GmbH). The mixture was predispersed in a dissolver for ten minutes and then ground in a sand mill to a Hegmann fineness <5 microns. The viscosity of the resulting color paste was 424 mPas at a shear rate of 1,000 s ^-1 and 23 ° C.

For mixing with the metallic paste, 37.2 parts by weight of the color paste were mixed with 62.8 parts by weight of the dispersion (A) according to Preparation Example 2 and with 5 parts by weight of water.

1.2.2 The preparation of a thixotropic agent

For the preparation of the metallic basecoat, a thixotropic agent was further prepared from 94 parts by weight demineralized water, 3.0 parts by weight Laponite® RD (Solvay Alkali GmbH) and Pluriol® P900 (BASF AG).

1.2.3. The preparation of a polyester dispersion

For the preparation of the metallic basecoat, a polyester was further prepared in a conventional manner from 23.23 parts by weight dimer fatty acid (Pripol.RTM. 1009), 10.43 parts by weight 1,6-hexanediol, 6.28 parts by weight hexahydrophthalic anhydride, 9.9 parts by weight neopentyl glycol and 10.43 parts by weight of trimellitic anhydride. As entrainer, one part by weight of cyclohexane was used.

The resulting polyester was dispersed in with 17.48 parts by weight of deionized water, 18.9 parts by weight of butylglycol and 2.25 parts by weight of dimethylethanolamine.

1.2.4 The production of a metallic paste

For the preparation of the metallic basecoat, a metallic paste of 378.7 parts by weight of the thixotropic agent according to Example 1.2.2, 74 parts by weight of a commercially available polyester (Maprenal® VM 3924), 70 parts by weight of butylglycol, 334.5 parts by weight of the dispersion (A) prepared according to Preparation Example 2, 5 parts by weight of a commercial wetting agent (BYK® 346), 50.6 parts by weight of a commercially available aluminum paste (Stapa Hydrolux® 8154), 86 parts by weight of the polyester according to Example 1.2.3 and 33 parts by weight of deionized water.

The pH of the metallic paste was adjusted to 7.8 with 10% dimethylethanolamine solution. The viscosity of the metallic paste was adjusted to 80 mPas by further addition of water.

1.2.5 The preparation of the metallic basecoat

The metallic basecoat was prepared by mixing the color paste according to Example 1.2.1 and the metallic paste according to Example 1.2.4 in a weight ratio of 2: 10.

1.2.6 The Preparation of a Clearcoat Containing Component (A)

For the preparation of the multilayer coating ML of the invention, a clearcoat of 100 parts by weight of the dispersion (A) according to the preparation example was also used 2.5 parts by weight of a commercially available crosslinking agent based on tris (alkoxycarbonylamino) triazines (Cylink® 2000, CYTEC) and 0.4 parts by weight of Agitan® 281. The low viscosity mixture was homogenized with an Ultraturrax. Thereafter, the viscosity at 128 mPas was at a shear rate of 1.00 s ^-1 and 23 ° C.

1.2.7 The coating of a substrate with the multicoat system ML according to the invention

For the production of the multicoat system ML according to the invention, customary and known steel test panels were used, which were coated with a commercial electrodeposition paint.

The test panels were pneumatically coated with the filler according to Example 1.1. The resulting surfacer coat was predried at room temperature for ten minutes and at 80 ° C for ten minutes. After that, it was baked at 100 ° C for 20 minutes and at 130 ° C for 20 minutes. This resulted in a filler layer FL of a layer thickness of 35 μm.

On the filler layer FL, the metallic basecoat according to Example 1.2 was applied pneumatically. The resulting metallic basecoat layer was predried at room temperature for ten minutes and at 80 ° C for ten minutes.

The clearcoat according to Example 1.2.6 was applied to the predried metallic basecoat film, after which the resulting clearcoat film was flashed off for 15 minutes at room temperature. Thereafter, the metallic basecoat film and the clearcoat film were baked at 140 ° C. for 30 minutes (wet-in-wet process). This resulted in a metallic basecoat BL having a layer thickness of 15 .mu.m and a clearcoat KL having a layer thickness of 35 .mu.m.

The multilayer coating ML of the present invention prepared in this manner had an excellent overall appearance, in particular, an excellent metallic effect, excellent D.O.I. (Distinctiveness of the Reflected Image) and excellent surface smoothness, on. The clearcoat KL was weather-stable, resistant to chemicals and bird droppings and scratch-resistant and showed a very good reflow behavior.

Another significant advantage was the very good recoatability of the multicoat system ML according to the invention, even without grinding. As a result, the clearcoat KL could be easily coated with conventional and well-known highly scratch-resistant coatings based on organically modified ceramic materials.

Claims (14)

1. Multicoat color and/or effect coating system ML for a primed or unprimed substrate, comprising, lying above one another in the stated sequence,

   (1) a surfacer coat FL which absorbs mechanical energy, and

   (2) a color and/or effect topcoat DL

   or

   (1) a surfacer coat FL which absorbs mechanical energy,

   (2) a color and/or effect basecoat BL, and

   (3) a clearcoat KL

   or

   (1) a color and/or effect basecoat BL and

   (2) a clearcoat KL,

   characterized in that at least one coat FL and/or DL or BL and/or KL or FL, BL and/or KL, preferably at least two coats FL, BL and/or KL or all coats FL and DL or BL and KL or FL, BL and KL of the multicoat system ML has or have been produced from a coating material comprising at least one constituent (A) preparable by free-radical polymerization of

   a) at least one olefinically unsaturated monomer and

   b) at least one olefinically unsaturated monomer different than the olefinically unsaturated monomer (a) and of the general formula I
   
           R¹R²C=CR³R⁴      (I),
   
   in which the radicals R¹, R², R³ and R⁴ each independently of one another are hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals, with the proviso that at least two of the variables R¹, R², R³ and R⁴ are substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, especially substituted or unsubstituted aryl radicals;

   in an aqueous medium.
2. Process for producing a multicoat color and/or effect coating system ML on a primed or unprimed substrate by

   (I) preparing a surfacer film by applying a surfacer to the substrate,

   (II) curing the surfacer film to give the surfacer coat FL,

   (III) preparing a solid-color topcoat film by applying a solid-color coat material to the surfacer coat FL, and

   (IV) curing the solid-color topcoat film to give the solid-color topcoat DL,

   or

   (I) preparing a basecoat film by applying a basecoat material to the substrate,

   (II) drying the basecoat film,

   (III) preparing a clearcoat film by applying a clearcoat material to the basecoat film, and

   (IV) jointly curing the basecoat film and the clearcoat film to give the basecoat BL and the clearcoat KL,

   or

   (I) preparing a surfacer film by applying a surfacer to the substrate,

   (II) curing the surfacer film to give the surfacer coat FL,

   (III) preparing a basecoat film by applying a basecoat material to the surfacer coat FL,

   (IV) drying the basecoat film,

   (V) preparing a clearcoat film by application to the basecoat film, and

   (VI) jointly curing the basecoat film and the clearcoat film to give the basecoat BL and the clearcoat KL,

   characterized in that at least one, preferably at least two and in particular all of the coating materials employed in each case comprise(s) at least one constituent (A) preparable by free-radical polymerization of

   a) at least one olefinically unsaturated monomer,

   b) at least one olefinically unsaturated monomer different than the olefinically unsaturated monomer (a) and of the general formula I
   
           R¹R²C=CR³R⁴      (I),
   
   in which the radicals R¹, R², R³ and R⁴ each independently of one another are hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals, with the proviso that at least two of the variables R¹, R², R³ and R⁴ are substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, especially substituted or unsubstituted aryl radicals;

   in an aqueous medium.
3. The multicoat system ML according to Claim 1, characterized in that the constituent (A) of the coating material is obtainable by

   (i) subjecting at least one monomer (a) and at least one monomer (b) to free-radical polymerization in an aqueous medium, and then

   (ii) reacting the resultant reaction product with at least one further monomer (a) under free-radical conditions.
4. The multicoat system ML according to claim 1 or 3, characterized in that the aryl radicals R¹, R², R³ and/or R⁴ of the compound (b) comprise phenyl or naphthyl radicals, especially phenyl radicals.
5. The multicoat system ML according to any of Claims 1, 3 and 4, characterized in that the substituents in the radicals R¹, R², R³ and/or R⁴ of the compound (b) are electron-donating or electron-withdrawing atoms or organic radicals, especially halogen atoms, nitrile, nitro, partially or fully halogenated alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalkyl radicals; aryloxy, alkyloxy and cycloalkyloxy radicals; arylthio, alkylthio and cycloalkylthio radicals, hydroxyl groups; and/or primary, secondary and/or tertiary amino groups.
6. The multicoat system ML according to Claim 1 or any of Claims 3 to 5, characterized in that monomers (a) comprise

   a1) (meth)acrylic esters which are essentially free from acid groups;

   a2) monomers which carry per molecule at least one hydroxyl group, amino group, alkoxymethylamino group or imino group and are essentially free from acid groups;

   a3) monomers which carry per molecule at least one acid group which can be converted into the corresponding acid anion group;

   a4) vinyl esters of alpha-branched monocarboxylic acids having 5 to 18 carbon atoms in the molecule;

   a5) 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;

   a6) cyclic and/or acyclic olefins;

   a7) (meth)acrylamides;

   a8) monomers containing epoxide groups;

   a9) vinylaromatic hydrocarbons;

   a10) nitriles;

   a11) vinyl compounds, especially vinyl halides and/or vinylidene dihalides, N-vinylpyrrolidone, vinyl ethers and/or vinyl esters;

   a12) allyl compounds, especially allyl ethers and allyl esters;

   a13) polysiloxane macromonomers having a number-average molecular weight Mn of from 1000 to 40 000 and having on average from 0.5 to 2.5 ethylenically unsaturated double bonds per molecule; and/or

   a14) acryloxysilane-containing vinyl monomers, preparable by reacting hydroxyl-functional silanes with epichlorohydrin and then reacting the reaction product with (meth)acrylic acid and/or with hydroxyalkyl and/or cycloalkyl esters of (meth)acrylic acid (monomers a2).
7. The multicoat system ML according to Claim 1 or any of Claims 3 to 6, characterized in that the coating material further comprises at least one of the following constituents:

   A) at least one binder having at least one functional group (afg) which is able to undergo thermal crosslinking reactions with complementary functional groups (bfg) in the crosslinking agent (B);

   B) at least one crosslinking agent having at least two functional groups (bfg) which are able to undergo thermal crosslinking reactions with complementary functional groups (afg) in the constituent (A),

   C) at least one constituent which is crosslinkable with actinic radiation,

   D) at least one photoinitiator,

   E) at least one thermal crosslinking initiator,

   F) at least one reactive diluent curable thermally and/or with actinic radiation,

   G) at least one coatings additive, and/or

   H) at least one organic solvent.
8. Process according to Claim 2, characterized in that the constituent (A) of the coating material is obtainable by

   (i) subjecting at least one monomer (a) and at least one monomer (b) to free-radical polymerization in an aqueous medium, and then

   (ii) reacting the resultant reaction product with at least one further monomer (a) under free-radical conditions.
9. Process according to Claim 2 or 8, characterized in that the aryl radicals R¹, R², R³ and/or R⁴ of the compound (b) comprise phenyl or naphthyl radicals, especially phenyl radicals.
10. Process according to any of Claims 1, 8 or 9, characterized in that the substituents in the radicals R¹, R², R³ and R⁴ of the compound (b) are electron-donating or electron-withdrawing atoms or organic radicals, especially halogen atoms, nitrile, nitro, partially or fully halogenated alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalkyl radicals; aryloxy, alkyloxy and cycloalkyloxy radicals; arylthio, alkylthio and cycloalkylthio radicals, hydroxyl groups; and/or primary, secondary and/or tertiary amino groups.
11. Process according to Claim 2 or any of Claims 8 to 10, characterized in that monomers (a) comprise

    a1) (meth)acrylic esters which are essentially free from acid groups;

    a2) monomers which carry per molecule at least one hydroxyl group, amino group, alkoxymethylamino group or imino group and are essentially free from acid groups;

    a3) monomers which carry per molecule at least one acid group which can be converted into the corresponding acid anion group;

    a4) vinyl esters of alpha-branched monocarboxylic acids having 5 to 18 carbon atoms in the molecule;

    a5) 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;

    a6) cyclic and/or acyclic olefins;

    a7) (meth)acrylamides;

    a8) monomers containing epoxide groups;

    a9) vinylaromatic hydrocarbons;

    a10) nitriles;

    a11) vinyl compounds, especially vinyl halides and/or vinylidene dihalides, N-vinylpyrrolidone, vinyl ethers and/or vinyl esters;

    a12) allyl compounds, especially allyl ethers and allyl esters;

    a13) polysiloxane macromonomers having a number-average molecular weight Mn of from 1000 to 40 000 and having on average from 0.5 to 2.5 ethylenically unsaturated double bonds per molecule; and/or

    a14) acryloxysilane-containing vinyl monomers, preparable by reacting hydroxyl-functional silanes with epichlorohydrin and then reacting the reaction product with (meth)acrylic acid and/or with hydroxyalkyl and/or cycloalkyl esters of (meth)acrylic acid (monomers a2).
12. Process according to Claim 2 or any of Claims 8 to 11, characterized in that the coating material further comprises at least one of the following constituents:

    A) at least one binder having at least one functional group (afg) which is able to undergo thermal crosslinking reactions with complementary functional groups (bfg) in the crosslinking agent (B);

    B) at least one crosslinking agent having at least two functional groups (bfg) which are able to undergo thermal crosslinking reactions with complementary functional groups (afg) in the constituent (A);

    C) at least one constituent which is crosslinkable with actinic radiation,

    D) at least one photoinitiator,

    E) at least one thermal crosslinking initiator,

    F) at least one reactive diluent curable thermally and/or with actinic radiation,

    G) at least one coatings additive, and/or

    H) at least one organic solvent.
13. Use of the multicoat system ML according to Claim 1 or any of Claims 3 to 7 or of the multicoat system ML produced by the process according to Claim 2 or any of Claims 8 to 12 for automotive OEM finishing and refinishing, industrial coating, including coil coating and container coating, the coating of plastics, and furniture coating.
14. Primed or unprimed substrates comprising at least one multicoat system ML according to Claim 1 or any of Claims 3 to 7 or at least one multicoat system ML produced by the process according to Claim 2 or any of Claims 8 to 12.