WO2010127910A1 - Coating agent, method for producing a coating agent and coated object - Google Patents

Abstract

The present invention relates to a coating agent, comprising at least one amino group-containing (meth)acrylate polymer, which comprises 0.1 to 15% by weight units derived from monomers having oxazolidine groups, and 20 to 99.9% by weight units derived from alkyl(meth)acrylates having 1 to 12 carbon atoms, and at least one functional polymer having carboxylic acid or carboxylic acid anhydride groups. Furthermore, the present invention describes a method for producing a coating. Further, the present invention describes a coated object, which comprises a coating which can be obtained by the method.

Description

 Coating composition, process for producing a coating and coated article

The present invention relates to a coating agent, a process for producing a coating and a coated article.

Coating agents, in particular paints, have been produced synthetically for a long time. Based on their economic importance, considerable efforts have been made to adapt the properties of these coating compositions to different needs. For this purpose, additives are often used or the binder modified as such. However, an optimization of a certain property often leads to disadvantages with respect to other features of these coating compositions.

For example, prior art coating compositions comprising compounds having oxazolidine groups are known. The prior art includes documents DE-A 26 10 406, EP-A 0 409 459, EP-A-0 728 822, US 5,672,379, US 3,037,006 and EP-A-0 302 373.

The document DE-A 26 10 406 relates to compositions containing at least one oxazolidine and at least one polyanhydride and to harden in the presence of water, harden chemically resistant polymer materials. In this document, a variety of different oxazolidines and polyanhydrides are enumerated, wherein the proportion of oxazolidine groups or anhydride groups in these compounds is not specified. In the examples, in particular polyanhydrides are used which by reaction of maleic anhydride with wood oil. A coating agent comprising copolymers with acid anhydride groups and copolymers with oxazolidine groups is not explicitly stated. Furthermore, only polymers which have been prepared in solvents are described.

The document EP-A 0 409 459 describes aqueous dispersions comprising a polyfunctional amine polymer and an anionically stabilized emulsion polymer. In the examples, homopolymers obtained by polymerization of oxazolidine ethyl methacrylate (OXEMA) in particular are used in combination with copolymers comprising acid groups. Polymers with a low content of oxazolidine groups are not explicitly listed in this publication, wherein the proportion of comonomers is limited to 80 wt .-%.

EP-A-0 728 822 discloses coating compositions comprising at least one film-forming polymer having anionic properties and at least one water-soluble or water-dispersible polymer having amino groups. The amino group-containing polymer comprises at least 20% by weight of units derived from monomers having an amino group. In the examples, in particular, mixtures of acid group-containing polymers and homopolymers obtained by polymerization of oxazolidine ethyl methacrylate (OXEMA) are set forth.

The patent US 5,672,379 describes aqueous dispersions, which can serve in particular for the production of road markings. Among other things, these aqueous dispersions may include polymers with acid groups and polymers with amino groups. According to the disclosure of this document, the polymers containing amino groups contain at least 20%, preferably min. at least 50% units derived from amino group-containing monomers. In the examples, only homopolymers of oxazolidine ethyl methacrylate are used.

The patent US 3,037,006 describes the preparation and the polymerization of various oxazolidinalkyl (meth) acrylates. Mixtures of polymers with oxazolidine groups and polymers with carboxylic acid or carboxylic anhydride groups are not disclosed.

The published patent application EP-A-0 302 373 describes moisture-curing binder compositions of polymers with maleic anhydride units and oxazolanes. The oxazolanes have a molecular weight in the range of 87 to 10,000. Polymers with a low content of oxazolidine groups are not listed in this document. The compositions presented include larger amounts of organic solvents.

The coating compositions described above already show a good property spectrum. However, there is a permanent need to improve this property spectrum. For example, coatings obtainable from previously disclosed coating compositions exhibit relatively high swelling to organic solvents or water. Although the inclusion of solvents or water can be improved by an additional crosslinking, for example with polyisocyanates. However, this other properties of the coating materials, in particular the processability, durability and, depending on the type of crosslinking agents used, the environmental impact reduced. In view of the prior art, it is an object of the present invention to provide coating compositions having excellent properties. These properties include, in particular, a very good resistance to chemicals of the coatings obtainable from the coating compositions, in which case the coating compositions should show good processability and durability. In particular, the coatings obtainable from the coating compositions should become dust-dry and tack-free after a very short time. Furthermore, the coating compositions should show a long pot life, based on the dust drying time, so that the coating composition can be processed for a relatively long time after opening the container.

With regard to the high resistance to chemicals, it is to be stated that the coatings obtainable from the coating compositions should achieve high stability against many different solvents as well as with respect to water, bases and acids. In particular, a very good resistance to methyl isobutyl ketone (MIBK) should be given.

Furthermore, the hardness of the coatings obtainable from the coating compositions should be able to be varied over a wide range. In particular, particularly hard, scratch-resistant coatings should be able to be obtained from the coating compositions. Furthermore, coatings obtainable from the coating compositions of the invention should have a relatively low brittleness in terms of hardness.

Furthermore, it was therefore an object of the present invention to provide a coating composition which has a particularly long shelf life and durability. Another object is to provide coating compositions which are useful in coatings lead to a high gloss. The coatings obtainable from the coating compositions should have a high weather resistance, in particular a high UV resistance.

In relation to performance, the coating compositions should show improved environmental compatibility. In particular, the smallest possible amounts of organic solvents should be released into the environment by evaporation. Furthermore, the coating compositions should have a low residual monomer content.

Another object can be seen to provide coating compositions that can be obtained very inexpensively and on an industrial scale.

These and other objects which are not explicitly mentioned, but which can be readily deduced or deduced from the contexts discussed hereinbelow, are achieved by a coating composition having all the features of patent claim 1. Advantageous modifications of the coating compositions according to the invention are protected in subclaims. With regard to a method for producing a coating and a coated article, claims 16 and 18 provide a solution to the underlying problems.

The present invention accordingly provides a coating composition which is characterized in that the coating composition comprises at least one amino group-containing (meth) acrylate polymer comprising 0.1 to 15% by weight of units derived from monomers containing oxazolidine groups and 20 to 99.9 wt.% of units derived from alkyl (meth) acrylates having 1 to 12 carbon atoms, and has at least one functional polymer with carboxylic acid or carboxylic anhydride groups.

This surprisingly makes it possible to provide a coating composition with which coatings can be obtained which have a particularly favorable profile of properties. These coatings show in particular a high chemical resistance.

Furthermore, the following advantages can be achieved by the measures according to the invention, inter alia:

The coating compositions of the invention show excellent processability. Thus, films formed from the coating compositions of the present invention become dust-dry and tack-free after a relatively short time. Relative to the dust-drying time, the coating compositions according to the invention have a long pot life, so that the coating compositions can be stored for a long time even after opening the storage container.

The coatings available from the coating compositions of the present invention show high chemical resistance. In this case, a high stability to water and many different organic solvents as well as to bases and acids can be achieved. In particular, a very good resistance to methyl isobutyl ketone (MIBK) is often given. Thus, preferred coatings, in particular in tests according to the furniture test DIN 68861 -1, have an excellent classification. Furthermore, the hardness of the coatings obtainable from the coating compositions can be varied over a wide range. In particular, particularly hard, scratch-resistant coatings can be obtained.

Furthermore, coatings which are obtainable from the coating compositions according to the invention, based on the hardness and the chemical resistance, a relatively low brittleness.

In relation to performance, the coating materials show improved environmental compatibility. Thus, extremely small amounts of organic solvents are released into the environment through evaporation. Particularly preferred embodiments show no release of organic solvents into the atmosphere. Furthermore, preferred coating compositions have a low residual monomer content. In this case, the coating agents may comprise a high solids content.

In addition, coating compositions according to the invention lead to coatings with a high gloss. The coating compositions of the present invention exhibit particularly long shelf life and durability. The coatings obtainable from the coating compositions show a high weather resistance, in particular a high UV resistance. Furthermore, the novel coating compositions are particularly cost-effective and commercially available.

A coating composition according to the invention comprises at least one amino-containing (meth) acrylate polymer which comprises from 0.1 to 15% by weight of units derived from monomers containing oxazolidine groups, and 20 to 99.9 wt .-% of units derived from alkyl (meth) acrylates having 1 to 12 carbon atoms.

Monomers are ethylenically unsaturated compounds which can be free-radically polymerized. Accordingly, monomers containing oxazolidine groups represent ethylenically unsaturated compounds having at least one oxazolidine group.

By "monomers having oxazolidine groups" is meant herein ethylenically unsaturated compounds having both five-membered oxazolidine rings and six-membered tetrahydraoxazines and also compounds containing two or more oxazolidine rings. Compounds containing more than one oxazolidine ring are generally referred to as polyfunctional oxazolidines.

In particular, it is possible to use, in particular, monomers with oxazolidine groups of the general formula (I)

wherein R ^{1 is} hydrogen or methyl, A is a linking group, m is 2 or 3, R ² and R ^{3 are} independently hydrogen or an alkyl radical having 1 to 4 carbon atoms, or R ² and R ³ together with the carbon atom to which they are attached saturated five or six-membered carbon ring form. Of particular interest to the polymers of the invention are monomers of formula (I) wherein R ^{1 is} methyl.

Preferably, the group A in formula (I) represents a group having 1 to 200 carbon atoms, preferably 1 to 100 carbon atoms, and more preferably 1 to 50 carbon atoms.

More preferably, A represents an ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene group, with the ethylene group being particularly preferred.

The preferred compound groups A furthermore include groups of the formula (II)

wherein ^<M) 'R ⁴ , R ⁵ , R ⁶ , independently of one another, are hydrogen or methyl, n is an integer from 0 to 100, preferably 1 to 50, o and p independently of one another are an integer from 0 to 2.

Preferred examples of monomers having oxazolidine groups include (meth) acrylates having at least one oxazolidine group. The spelling

(Meth) acrylate stands for esters of methacrylic acid and esters of acrylic acid and mixtures of these esters.

These include, in particular, oxazolidinylethyl (meth) acrylates, oxazolidinylpropyl (meth) acrylates, oxazolidinylbutyl (meth) acrylates, 3- (β-

Methacryloxyethyl) -2,2-pentamethylene-oxazolidine and 3- (β-methacryloxyethyl) - 2-methyl-2-propyl-oxazolidin. Particular preference is given here in particular 3- (ß-methacryloxyethyl) - oxazolidine, which is the CAS no. 46235-93-2 owns.

Monomers having oxazolidine groups are described, for example, in DE-A 26 10 406 filed on 12.03.1976 with the German Patent Office with the application number P 2610406.3; EP-A 0 409 459 filed on 09.07.1990 with the European Patent Office with the application number EP 90307464.9; EP-A-0 728 822, filed on 28.08.1996 at the European Patent Office with the application number EP 96300938.6; U.S. 5,672,379, filed Jul. 26, 1996, in the United States Patent Office (USPTO), Serial No. 687,851; and US 3,037,006 filed on Jul. 5, 1996 with the United States Patent Office (USPTO), application number 40,562; in which reference is made to these documents for the purpose of disclosure and the monomers comprising oxazolidine groups set out therein and their preparation are incorporated into the present application.

The monomers with oxazolidine groups set forth above can be obtained, for example, by transesterification of hydroxyl-containing oxazolidines with (meth) acrylates. Hydroxy-containing oxazolidines can be obtained, for example, by reacting amines with carbonyl compounds. Such reactions are described in the prior art set forth above, in particular in DE-A 26 10 406 and US 3,037,006.

The amino group-containing (meth) acrylate polymer comprises from 0.1 to 15% by weight, preferably from 1 to 8, and most preferably from 2 to 5% by weight of units derived from monomers having oxazolidine groups, based on Weight of the amino group-containing (meth) acrylate polymer. The (meth) acrylate polymers can preferably be obtained by free-radical polymerization. Accordingly, the proportion by weight of the respective units comprising these polymers results from the proportions by weight of corresponding monomers used to prepare the polymers, since the proportion by weight of groups derived from initiators or molecular weight regulators can usually be neglected.

In addition to the units derived from monomers containing oxazolidine groups, the amino group-containing (meth) acrylate polymer comprises from 20 to 99.9% by weight, preferably from 30 to 98% by weight and most preferably from 60 to 96% by weight. % of units derived from alkyl (meth) acrylates having 1 to 12 carbon atoms, based on the weight of the amino group-containing (meth) acrylate polymer.

Alkyl (meth) acrylates having 1 to 12 carbon atoms are esters of methacryric acid or acrylic acid having 1 to 12 carbon atoms in the alkyl radical which have no double bonds or heteroatoms in the alkyl radical. Here, alkyl (meth) acrylates having 1 to 10 carbon atoms in the alkyl radical are preferred.

The alkyl (meth) acrylates having 1 to 12 carbon atoms in the alkyl radical which have no double bonds or heteroatoms in the alkyl radical include (meth) acrylates having a linear or branched alkyl radical, such as, for example, methyl (meth) acrylate, ethyl (meth acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate and pentyl (meth) acrylate, Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 3-isopropyl-propyl (meth) acrylate, nonyl (meth) acrylate, Decyl (meth) acrylate, undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate,

Dodecyl (meth) acrylate; and

Cycloalkyl (meth) acrylates, such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylates having at least one substituent on the ring, such as tert-butylcyclohexyl (meth) acrylate and trimethylcyclohexyl (meth) acrylate, Norbornyl (meth) acrylate, methylnorbornyl (meth) acrylate and

Dimethyl norbornyl (meth) acrylate, bornyl (meth) acrylate, 1 -

Adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, menthyl (meth) acrylate and isobornyl (meth) acrylate. The above-mentioned alkyl (meth) acrylates having 1 to 12 carbon atoms in the alkyl group may be used singly or as a mixture.

In addition to the units set out above, an amino group-containing

(Meth) acrylate polymer include units derived from comonomers. These include, inter alia, (meth) acrylates having a hydroxy group in the

Alkyl radical, in particular

2-hydroxyethyl (meth) acrylate, preferably 2-hydroxyethyl methacrylate

(HEMA),

Hydroxypropyl (meth) acrylate, for example, 2-hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate, preferably hydroxypropyl methacrylate

(HPMA)

Hydroxybutyl (meth) acrylate, preferably hydroxybutyl methacrylate (HBMA),

3,4-dihydroxybutyl (meth) acrylate,

2,5-dimethyl-1,6-hexanediol mono (meth) acrylate 1, 10-decanediol mono (meth) acrylate and

Glycerol mono (meth) acrylate. Another group of preferred monomers has an acid group. Acid group-containing monomers are compounds which can preferably be radically copolymerized with the (meth) acrylic monomers set forth above. These include, for example, monomers having a sulfonic acid group, such as, for example, vinylsulfonic acid; Monomers having a phosphonic acid group, such as vinylphosphonic acid and unsaturated carboxylic acids, such as methacrylic acid, acrylic acid, fumaric acid and maleic acid. Particularly preferred are methacrylic acid and acrylic acid. The acid group-containing monomers can be used individually or as a mixture of two, three or more acid group-containing monomers.

Of particular interest are, in particular, amino-containing (meth) acrylate polymers which have from 0 to 10% by weight, preferably from 0.5 to 8% by weight and more preferably from 1 to 5% by weight, of units derived from Derived acid group-containing monomers, based on the total weight of the polymer.

Another class of comonomers are (meth) acrylates having at least 13 carbon atoms in the alkyl radical, which are derived from saturated alcohols, such as 2-methyldodecyl (meth) acrylate, tridecyl (meth) acrylate, 5-methyltridecyl (meth) acrylate, tetradecyl ( meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, 2-methylhexadecyl (meth) acrylate, heptadecyl (meth) acrylate, 5-iso-propylheptadecyl (meth) acrylate, 4-tert-butyloctadecyl (meth) acrylate , 5-Ethyloctadecyl (meth) acrylate, 3-iso-propyloctadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, cetyleicosyl (meth) acrylate, stearyleicosyl (meth) acrylate, docosyl (meth) acrylate and / or eicosyltetratriacontyl (meth) acrylate; Cycloalkyl (meth) acrylates such as 2,4,5-tri-t-butyl-3-vinylcyclohexyl (neth) acrylate, 2,3,4,5-tetra-t-butylcyclohexyl (neth) acrylate; heterocyclic (meth) acrylates such as 2- (1-imidazolyl) ethyl (meth) acrylate, 2- (4-morpholinyl) ethyl (meth) acrylate, 1- (2-methacryloyloxyethyl) -2-pyrrolidone; Nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates, such as N- (methacryloyloxyethyl) diisobutylketimine, N-

(Methacryloyloxyethyl) dihexadecylketimine, methacryloylamidoacetonitrile, 2-methacryloyloxyethylmethylcyanamide, cyanomethylmethacrylate; Aryl (meth) acrylates, such as benzyl (meth) acrylate or phenyl (meth) acrylate, wherein the aryl radicals may each be unsubstituted or substituted up to four times; polyalkoxylated derivatives of (meth) acrylic acid, in particular polypropylene glycol mono (meth) acrylate with 2 to 10, preferably 3 to 6 propylene oxide units, preferably polypropylene glycol monomethacrylate with about 5 propylene oxide units (PPM5), polyethylene glycol mono (meth) acrylate with 2 to 10, preferably 3 to 6 ethylene oxide units, preferably

Polyethylene glycol monomethacrylate with approx. 5 ethylene oxide units (PEM5),

Polybutylene glycol mono (meth) acrylate, polyethylene glycol polypropyleneglycol mono (meth) acrylate;

(Meth) acrylamides, in particular N-methylol (meth) acrylamide, N ₁ N- dimethylaminopropyl (meth) acrylamide, tert-butylaminoethyl methacrylate, methacrylamide and acrylamide; and

(Meth) acrylates derived from saturated fatty acids or fatty acid amides, such as (meth) acryloyloxy-2-hydroxypropyl-palmitic acid ester, (meth) acryloyloxy-2-hydroxypropyl-stearic acid ester and (meth) acryloyloxy-2-hydroxypropyl-laurin ester, pentadecyloyloxy- 2-ethyl (meth) acrylamide, heptadecyloyloxy-2-ethyl (meth) acrylamide, (meth) acryloyloxy-2-ethyl-lauric acid amide, (meth) acryloyloxy-2-ethyl-myristic acid amide, (Meth) acryloyloxy-2-ethyl-palmitic acid anide, (meth) acryloyloxy-2-ethylstearic acid anide, (meth) acryloyloxy-2-propyl-lauric acid anide, (meth) acryloyloxy-2-propyl-myristic acid anide, (meth) acryloyloxy-2 propyl palmitic acid anide and (meth) acryloyloxy-2-propyl stearic acid anide.

In addition, (meth) acrylic monomers which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical can be used as comonomers. These monomers are esters or amides of (meth) acrylic acid whose alkyl group has at least one carbon-carbon double bond which is not part of an aromatic system and 8 to 40 carbon atoms. The notation (meth) acrylic acid means methacrylic acid and acrylic acid and mixtures thereof. The alkyl or alcohol or amide radical may preferably have 10 to 30 and more preferably 12 to 20 carbon atoms, this radical may include heteroatoms, in particular oxygen, nitrogen or sulfur atoms. The alkyl radical may have one, two, three or more carbon-carbon double bonds. The polymerization conditions in which a polymer to be used according to the invention is prepared are preferably selected such that the largest possible proportion of the double bonds of the alkyl radical is retained during the polymerization. This can be done for example by steric hindrance of the double bonds contained in the alcohol radical. Furthermore, at least a part, preferably all of the double bonds contained in the alkyl radical of the (meth) acrylic monomer, has a lower reactivity in a free-radical polymerization than a (meth) acrylic group, so that preferably no further (meth) acrylic groups in the alkyl radical are included. The iodine number of the (meth) acrylic monomers which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical is preferably at least 50, more preferably at least 100 and most preferably at least 125 g iodine / 100 g (meth) acrylic monomer, without this being a limitation.

Such (meth) acrylic monomers generally correspond to the formula (III)

wherein the radical R ^{1 is} hydrogen or methyl, X is independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, and R ^{8 is} a linear or branched radical having 8 to 40, preferably 10 to 30 and more preferably 12 to 20 carbon atoms, which has at least one CC double bond.

(Meth) acrylic monomers which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical can be obtained, for example, by esterification of (meth) acrylic acid, reaction of (meth) acryloyl halides or (meth) acrylic acid anhydride or transesterification of (meth) acrylates Alcohols are obtained which have at least one double bond and 8 to 40 carbon atoms. Accordingly, (meth) acrylamides can be obtained by reaction with an amine. These reactions are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry 5th Edition on CD-ROM or F.-B. Chen, G. Bufkin, "Crosslinkable Emulsion Polymers by Autooxidation I", Journal of Applied Polymer Science, Vol. 30, 4571-4582 (1985). Suitable alcohols include octenol, nonenol, decenol, undecenol, dodecenol, tridecenol, tetradecenol, pentadecenol, hexadecenol, heptadecenol, octadecenol, nonadecenol, ikosenol, docosenol, octadiene-ol, nonanoedia-ol, deca- dien-ol, undecadiene-ol, dodecadiene-ol, trideca-dien-ol, tetradeca-dien-ol, pentadeca-dien-ol, hexadeca-dien-ol, heptadeca-dien-ol, octadeca-diene ol, Nonadeca-dien-ol, Ikosa-dien-ol and / or Docosa-dien-ol. These so-called fatty alcohols are sometimes commercially available or can be obtained from fatty acids, this reaction being carried out, for example, in F.-B. Chen, G. Bufkin, Journal of Applied Polymer Science, Vol. 30, 4571-4582 (1985).

The preferred (meth) acrylates obtainable by this process include, in particular, octadiene-yl (meth) acrylate, octadeca-diene-yl (meth) acrylate, octadecanetrienyl (meth) acrylate, Hexadecenyl (meth) acrylate, octadecenyl (meth) acrylate and hexadecadienyl (meth) acrylate.

In addition, (meth) acrylates which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical can also be obtained by

Reaction of unsaturated fatty acids with (meth) acrylates which have reactive groups in the alkyl radical, in particular alcohol radical. The reactive groups include in particular hydroxy groups and epoxy groups. Accordingly, for example, hydroxyalkyl (meth) acrylates such as 3-hydroxypropyl (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,5-dimethyl -1, 6-hexanediol (meth) acrylate, 1, 10-decanediol (meth) acrylate; or epoxy group-containing (meth) acrylates, For example, glycidyl (meth) acrylate can be used as starting materials for the preparation of the abovementioned (meth) acrylates.

Suitable fatty acids for reaction with the abovementioned (meth) acrylates are often commercially available and are obtained from natural sources. These include undecylenic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, icosenoic acid, cetoleic acid, erucic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, clupanodonic acid and / or cervonic acid.

The preferred (meth) acrylates obtainable by this process include, in particular, (meth) acryloyloxy-2-hydroxypropyl linoleic acid ester, (meth) acryloyloxy-2-hydroxypropyl linolenic acid ester and (meth) acryloyloxy-2-hydroxypropyl oleic acid ester.

The reaction of the unsaturated fatty acids with (meth) acrylates which have reactive groups in the alkyl radical, in particular alcohol radical, is known per se and is described, for example, in DE-A-41 05 134, DE-A-25 13 516, DE-A-26 38 544 and US 5,750,751.

According to a preferred embodiment, (meth) acrylic monomers of the general formula (IV)

(IV),

wherein R ^{1 is} hydrogen or a methyl group, X ¹ and X ^{2 are} independently oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, with the proviso that at least one of the groups X ¹ and X ^{2 represents} a group of the formula NR 'in which R' represents hydrogen or a radical having 1 to 6 carbon atoms, Z ^{1 represents} a linking group and R ^{9 is} an unsaturated radical having 9 to 25 carbon atoms.

Surprising advantages can furthermore be achieved by the use of a (meth) acrylic monomer of the general formula (V)

wherein R ^{1 is} hydrogen or a methyl group, X ^{1 is} oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z ^{1 is} a linking group, R is hydrogen or a radical having 1 to 6 carbon atoms and R ⁹ is an unsaturated group having 9 to 25 carbon atoms.

The term "radical having 1 to 6 carbon atoms" means a group having 1 to 6 carbon atoms and includes aromatic and heteroaromatic groups as well as alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl groups The heteroaliphatic groups may be branched or unbranched, furthermore these groups may have substituents, in particular halogen atoms or hydroxyl groups. The radicals R 'are preferably alkyl groups. Preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl group.

The group Z ¹ in formulas (IV) and (V) preferably represents a linking group comprising 1 to 10, preferably 1 to 5 and most preferably 2 to 3 carbon atoms. These include in particular linear or branched, aliphatic or cycloaliphatic radicals, such as a methylene, ethylene, propylene, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene group, wherein the Ethylene group is particularly preferred.

The group R ⁹ in formula (IV) and (V) represents an unsaturated radical having 9 to 25 carbon atoms. These groups include in particular alkenyl, cycloalkenyl, alkenoxy, cycloalkenoxy, alkenoyl and heteroalipatic groups. Furthermore, these groups may have substituents, in particular halogen atoms or hydroxyl groups. The preferred groups include in particular alkenyl groups, such as, for example, the nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl , Heneosylsyl, docosenyl, octadiene-yl, nonanediazyl, decadiene-yl, undecanediazyl, dodeca-diene-yl, trideca-diene-yl , Tetradeca-dien-yl, pentadeca-dien-yl, hexadeca-dien-yl, heptadeca-dien-yl, octadeca-dien-yl, nonadeca-dien-yl, eicosa-dien-yl, Heneicosa-dien-yl, docosa-dien-yl, tricosa-dien-yl and / or heptadeca-triene-yl group.

The preferred (meth) acrylic monomers of the formula (IV) or (V) include, but are not limited to, heptadecenyloyloxy-2-ethyl (meth) acrylamide, hepta decadiene-yloyloxy-2-ethyl (meth) acrylamide, heptadeca-triene-yloyloxy-2-ethyl- (meth) acrylic acid anide, heptadecenyloyloxy-2-ethyl- (meth) acrylic acid anide, (meth) acryloyloxy-2-ethyl- palmitoleic acid anhydride, (meth) acryloyloxy-2-ethyl-oleic acid amide, (meth) acryloyloxy-2-ethyl-icosenoic acid amide, (meth) acryloyloxy-2-ethyl-cetoleic acid amide, (meth) acryloyloxy-2-ethyl-erucic acid amide, (meth) acryloyloxy 2-ethyl-linoleic acid amide, (meth) acryloyloxy-2-ethyl-linolenic acid amide, (meth) acryloyloxy-2-propyl-palmitoleic acid anhydride, (meth) acryloyloxy-2-propyl-oleic acid amide, (meth) acryloyloxy-2-propyl-icosenic acid amide , (Meth) acryloyloxy-2-propyl cetoleic acid amide, (meth) acryloyloxy-2-propyl-erucic acid amide,

(Meth) acryloyloxy-2-propyl-linoleic acid amide and (meth) acryloyloxy-2-propyllinolenic acid amide.

Particularly preferred monomers according to formula (IV) or (V) are methacryloyloxy-2-ethyl-oleic acid amide, methacryloyloxy-2-ethyl-linolenic acid amide and / or methacryloyloxy-2-ethyl-linolenic acid amide.

The (meth) acrylic monomers of the formula (IV) or (V) can be obtained in particular by multistage processes. In a first step, for example, one or more unsaturated fatty acids or fatty acid esters can be reacted with an amine, for example, ethylenediamine, ethanolamine, propylenediamine or propanolamine, to form an amide. In a second step, the hydroxy group or the amine group of the amide is reacted with a (meth) acrylate, for example methyl (meth) acrylate, to obtain the monomers of the formula (IV) or (V). For the preparation of monomers in which X ^{1 is} a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, and X ^{2 is} oxygen, correspondingly first an alkyl (meth) acrylate, for example methyl (meth ) acrylate, with one of the above amines mentioned are reacted to a (meth) acrylamide having a hydroxy group in the alkyl radical, which is then reacted with an unsaturated fatty acid to a (meth) acrylic monomer according to formula (IV) or (V). Transesterification of alcohols with (meth) acrylates or the preparation of (meth) acrylic acid amides are inter alia in CN 1355161, DE 21 29 425 filed on 14.06.71 at the German Patent Office with the application number P 2129425.7, DE 34 23 443 filed on 26.06.84 at the German Patent Office with the application number P 3423443.8 or EP-AO 534 666 filed on 16.09.92 the European Patent Office with the application number EP 92308426.3 set forth, wherein the reaction conditions described in these publications and the catalysts set forth therein, etc. for purposes of disclosure in this application be inserted. Furthermore, these reactions are described in "Synthesis of Acrylic Esters by Transesterification", J. Haken, 1967.

In this case, intermediates obtained, for example carboxamides which have hydroxyl groups in the alkyl radical, can be purified. According to a particular embodiment of the present invention, intermediates obtained can be reacted without expensive purification to the (meth) acrylic monomers of formula (IV) or (V).

Furthermore, the (meth) acrylic monomers having 8 to 40, preferably 10 to 30 and particularly preferably 12 to 20 carbon atoms and at least one double bond in the alkyl radical include in particular monomers of the general formula (VI)

wherein R ^{1 is} hydrogen or a methyl group, X is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, R ^{10 is} an alkylene group having 1 to 22 carbon atoms, Y is oxygen, sulfur or a group of Formula NR ", wherein R" is hydrogen or a radical having 1 to 6 carbon atoms, and R ^{11 is} an unsaturated radical having at least 8 carbon atoms and at least two CC double bonds.

In formula (VI), the radical R ^{10 is} an alkylene group having 1 to 22 carbon atoms, preferably 1 to 10, particularly preferably 2 to 6 carbon atoms. The radical R ¹⁰ represents, according to a particular embodiment of the present invention, an alkylene group having 2 to 4, more preferably 2 carbon atoms. The alkylene groups having 1 to 22 carbon atoms include in particular the methylene, ethylene, propylene, isopropylene, n-butylene, iso-butylene, t-butylene or cyclohexylene group, with the ethylene group being particularly preferred.

The radical R ¹¹ comprises at least two CC double bonds which are not part of an aromatic system. Preferably, the radical R ^{11 represents} a group with exactly 8 carbon atoms, which has exactly two carbon-carbon double bonds. The radical R ¹¹ preferably represents a linear hydrocarbon radical which has no heteroatoms. According to a particular embodiment of the present invention, the radical R ¹¹ in formula (VI) may comprise a terminal double bond. In a further discussion In the context of the present invention, the radical R ¹¹ in formula (VI) can not comprise a terminal carbon-carbon double bond. The double bonds contained in the radical R ¹¹ may preferably be conjugated. According to another preferred embodiment of the present invention, the double bonds contained in the radical R ¹¹ are not conjugated. Preferred R ¹¹ radicals having at least two double bonds include, among others, octa-2,7-dienyl group, octa-3,7-dienyl group, octa-4,7-dienyl group, octa-5,7-dienyl group, octa 2,4-dienyl group, octa-2,5-dienyl group, octa-2,6-dienyl group, octa-3,5-dienyl group, octa-3,6-dienyl group and octa-4,6-dienyl group.

The (meth) acrylic monomers of the general formula (VI) include, inter alia, 2 - [((2-E) octa-2,7-dienyl) methylamino] ethyl 2-methylprop-2-enoate, 2 - [( (2-Z) octa-2,7-dienyl) methylamino] ethyl 2-methylprop-2-enoate, 2 - [((3-E) octa-3,7-dienyl) methylamino] ethyl-2-methylpropyl 2-enoate,

2 - [((4-Z) octa-4,7-dienyl) methylamino] ethyl 2-methylprop-2-enoate, 2 - [(octa-2,6-dienyl) methylamino] ethyl-2-methylprop-2 -enoate, 2 - [(octa-2,4-dienyl) methylamino] ethyl-2-methylprop-2-enoate, 2 - [(octa-3,5-dienyl) methylamino] ethyl-2-methylprop-2-enoate , 2 - [((2-E) octa-2,7-dienyl) methylamino] ethyl (meth) acrylamide, 2 - [((2-Z) octa-2,7-dienyl) methylamino] ethyl (meth ) Acrylic acid amide, 2 - [((3-E) octa-3,7-dienyl) methylamino] ethyl (meth) acrylamide, 2 - [((4-Z) octa-4,7-dienyl) methylamino] ethyl (meth) acrylamide, 2 - [(octa-2,6-dienyl) methylamino] ethyl (meth) acrylamide, 2 - [(octa-2,4-dienyl) methylamino] ethyl (meth) acrylamide, 2- [ (Octa-3,5-dienyl) methylamino] ethyl (meth) acrylamide,

2 - [((2-E) octa-2,7-dienyl) ethylamino] ethyl 2-methylprop-2-enoate, 2 - [((2-Z) octa-2,7-dienyl) ethylamino] ethyl 2-methylprop-2-enoate, 2 - [((3-E) octa-3,7- dienyl) ethylamino] ethyl 2-methylprop-2-enoate, 2 - [((4-Z) octa-4,7-dienyl) ethylamino] ethyl 2-methylprop-2-enoate, 2 - [(octa-2 , 6-dienyl) ethylamino] ethyl 2-methylprop-2-enoate, 2 - [(octa-2,4-dienyl) ethylamino] ethyl 2-methylprop-2-enoate, 2 - [(octa-3,5 - dienyl) ethylamino] ethyl-2-methylprop-2-enoate,

2 - [((2-E) octa-2,7-dienyl) methylamino] ethyl-prop-2-enoate, 2 - [((2-Z) octa-2,7-dienyl) -methylannino] ethyl-propanol 2-enoate, 2 - [((3-E) octa-3,7-dienyl) -methylannino] ethyl-prop-2-enoate, 2 - [((4-Z) octa-4,7-dienyl) -methylamino] ethyl-prop-2-enoate, 2 - [(octa-2,6-dienyl) -methylannino] ethyl-prop-2-enoate, 2 - [(octa-2,4-dienyl) -methylannino] -ethyl-prop-2- enoate, 2 - [(octa-3,5-dienyl) methylannino] ethyl-prop-2-enoate,

2 - ((2-E) octa-2,7-dienyloxy) ethyl 2-methylprop-2-enoate, 2 - ((2-Z) octa-2,7-dienyloxy) ethyl-2-methylprop-2-yl enoate, 2 - ((3-E) octa-3,7-dienyloxy) ethyl-2-methyl-prop-2-enoate, 2 - ((4-Z) octa-4,7-dienyloxy) ethyl-2-methylprop -2-enoate, 2- (octa-2,6-dienyloxy) ethyl-2-methylprop-2-enoate, 2- (octa-2,4-dienyloxy) ethyl-2-methylprop-2-enoate, 2- (Octa-3,5-dienyloxy) ethyl 2-methylprop-2-enoate, 2 - ((2-E) octa-2,7-dienyloxy) ethyl-prop-2-enoate, 2 - ((2-Z ) Octa-2,7-dienyloxy) ethyl-prop-2-enoate, 2 - ((3-E) octa-3,7-dienyloxy) ethyl-prop-2-enoate, 2 - ((4-Z) octa -4,7-dienyloxy) ethyl-prop-2-enoate, 2- (octa-2,6-dienyloxy) ethyl-prop-2-enoate, 2- (octa-2,4-dienyloxy) ethyl-prop-2 enoate and 2- (octa-3,5-dienyloxy) ethyl-prop-2-enoate.

The (meth) acrylic monomers of the formula (IV) set out above can be obtained in particular by processes in which (meth) acrylic acid or a (meth) acrylate, in particular methyl (meth) acrylate or ethyl (meth) acrylate with an alcohol and / or an amine is reacted. These reactions have been previously stated. The starting material to be reacted with the (meth) acrylic acid or the (meth) acrylate may advantageously correspond to the formula (VII),

10 11

H-X-R-Y-R (VII),

wherein X is oxygen or a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, R ^{10 is} an alkylene group having 1 to 22 carbon atoms, Y is oxygen, sulfur or a group of the formula NR ", where R "Represents hydrogen or a radical having 1 to 6 carbon atoms, and R ^{11 is} an at least double unsaturated radical having at least 8 carbon atoms.

With regard to the meaning of preferred radicals R ', R ", R ¹⁰ , Y and R ¹¹ , reference is made to the description of the formula (VI).

The preferred starting materials of the formula (VII) include (methyl (octa-2,7-dienyl) amino) ethanol, (ethyl (octa-2,7-dienyl) amino) ethanol, 2-octa-2,7-dienyloxyethanol, (methyl octa-2,7-dienyl) amino () ethylamine,

(Methyl (octa-3,7-dienyl) amino) ethanol, (ethyl (octa-3,7-dienyl) amino) ethanol, 2-octa-3,7-dienyloxyethanol, (methyl (octa-3,7-dienyl ) amino) ethylamine, (methyl (octa-4,7-dienyl) amino) ethanol, (ethyl (octa-4,7-dienyl) amino) ethanol, 2-octa-4,7-dienyloxyethanol, (methyl (octa 4,7-dienyl) amino) ethylamine, (methyl (octa-5,7-dienyl) amino) ethanol, (ethyl (octa-5,7-dienyl) amino) ethanol, 2-octa-5,7-dienyloxyethanol, (Methyl (octa-5,7-dienyl) amino) ethylamine, (methyl (octa-2,6-dienyl) amino) ethanol, (ethyl (octa-2,6-dienyl) amino) ethanol, 2-octa-2 , 6-dienyloxyethanol, (methyl (octa-2,6-dienyl) amino) ethylamine, (methyl (octa-2,5-dienyl) amino) ethanol, (ethyl (octa-2,5-dienyl) amino) ethanol, 2-octa-2,5-dienyloxyethanol, (methyl (octa-2,5-dienyl) amino) ethylamine,

(Methyl (octa-2,4-dienyl) amino) ethanol, (ethyl (octa-2,4-dienyl) amino) ethanol, 2-octa-2,4-dienyloxyethanol, (methyl (octa-2,4-dienyl ) amino) ethyl amine, (Methyl (octa-3,6-dienyl) amino) ethanol, (ethyl (octa-3,6-dienyl) amino) ethanol, 2-octa-3,6-dienyloxyethanol, (methyl (octa-3,6-dienyl ) amino) ethylannin, (methyl (octa-3,5-dienyl) amino) ethanol, (ethyl (octa-3,5-dienyl) amino) ethanol, 2-octa-3,5-dienyloxyethanol, (methyl (octa 3,5-dienyl) amino) ethylamine, (methyl (octa-4,6-dienyl) amino) ethanol, (ethyl (octa-4,6-dienyl) amino) ethanol, 2-octa-4,6-dienyloxyethanol and (methyl (octa-4,6-dienyl) amino) ethylamine. The educts of formula (VII) can be used individually or as a mixture.

The educts according to formula (VII) can be obtained inter alia by known methods of telomerizing 1,3-butadiene. Herein, the term "telomerization" means the reaction of compounds with conjugated double bonds in the presence of nucleophiles, filed in the documents WO 2004/002931 filed on 17.06.2003 with the European Patent Office with the application number PCT / EP2003 / 006356, WO 03/031379 01.10.2002 with the application number PCT / EP2002 / 10971 and WO 02/100803 filed on 04.05.2002 with the application number PCT / EP2002 / 04909, especially the catalysts used for the reaction and the reaction conditions, such as pressure and temperature for the purposes of disclosure in the present application.

Preferably, the telomerization of 1, 3-butadiene using metal compounds comprising metals of the 8th to 10th group of the Periodic Table of the Elements can be carried out as a catalyst, wherein palladium compounds, in particular Palladiumcarbenkomplexe, which are set forth in more detail in the above-mentioned documents, can be used with particular preference. As nucleophile, especially dialcohols such as ethylene glycol, 1, 2-propanediol, 1, 3-propanediol; Diamines such as ethylenediamine, N-methylethylenediamine, N, N'-dimethylethylenediannine or hexamethylenediamine; or aminoalkanols, such as aminoethanol, N-methylaminoethanol, N-ethylaminoethanol, aminopropanol, N-methylaminopropanol or N-ethylaminopropanol.

When using (meth) acrylic acid as nucleophile, for example, octadienyl (meth) acrylates can be obtained, which are particularly suitable as (meth) acrylic monomers having 8 to 40 carbon atoms.

The temperature at which the telomerization reaction is carried out is between 10 and 180 ⁰ C, preferably between 30 and 120 ⁰ C, particularly preferably between 40 and 100 ⁰ C. The reaction pressure is 1 to 300 bar, preferably from 1 to 120 bar , more preferably 1 to 64 bar and most preferably 1 to 20 bar.

The preparation of isomers from compounds having an octa-2,7-dienyl group can be carried out by isomerization of the double bonds contained in the compounds having an octa-2,7-dienyl group.

The above-mentioned (meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl group may be used singly or as a mixture of two or more monomers.

The comonomers also include vinyl esters such as vinyl acetate, vinyl chloride, vinyl versatate, ethylene vinyl acetate, ethylene vinyl chloride; Maleic acid derivatives, such as maleic anhydride, esters of Maleic acid, for example dimethyl maleate, methylninitic anhydride; and fumaric acid derivatives such as dimethyl fumarate.

Another group of comonomers are styrene monomeric, such as styrene, substituted styrenes having an alkyl substituent in the side chain, such. For example, α-methyl styrene and α-ethyl styrene, substituted styrenes having an alkyl substituent on the ring, such as vinyl toluene and p-methyl styrene, halogenated styrenes, such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes.

Heterocyclic vinyl compounds, such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles; Maleimide, methylmaleimide;

Vinyl and isoprenyl ethers; and

Vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride are further examples of comonomers.

Furthermore, a coating composition according to the invention comprises at least one functional polymer with carboxylic acid or carboxylic anhydride groups. Polymers having carboxylic acid or carboxylic anhydride groups are polymeric compounds obtained by reacting monomer mixtures containing monomers having at least one carboxylic acid group or monomers having at least one carboxylic acid anhydride group. The term "functional polymer" means in the context of the present

Invention that this polymer, preferably via the carboxylic acid or the carboxylic anhydride groups with the above-described amino group-containing (meth) acrylate polymer can react, the term "reacting" is to be understood so that a reaction under certain circumstances only at higher temperatures occurs.

Preferably, the functional polymer comprises from 0.1 to 15% by weight, more preferably from 1 to 10, and most preferably from 2 to 5% by weight of units derived from monomers having at least one carboxylic acid group or monomers having at least one carboxylic acid anhydride group, and 20 to 99.9% by weight, preferably 30 to 98, and more preferably 60 to 97% by weight of units derived from alkyl (meth) acrylates having 1 to 12 carbon atoms.

The functional polymers can preferably be obtained by free-radical polymerization. Accordingly, the proportion by weight of the respective units comprising these polymers results from the proportions by weight of corresponding monomers used to prepare the polymers, since the proportion by weight of groups derived from initiators or molecular weight regulators can usually be neglected.

Among the carboxylic acid monomers include acrylic acid, methacrylic acid, fumaric acid, monoesters of fumaric acid, maleic acid and Monoesters of maleic acid, with acrylic acid and methacrylic acid being particularly preferred.

Examples of monomers having at least one carboxylic anhydride group are maleic anhydride, derivatives of maleic anhydride, such as methylmaleic anhydride, dimethylmaleic anhydride or phenylmaleic anhydride, and itaconic anhydride. Here, maleic anhydride is particularly preferred.

In this case, it is also possible to use monomer mixtures which comprise monomers having at least one carboxylic acid group and monomers having at least one carboxylic acid anhydride group. In a particular aspect of the present invention, particularly preferred are functional polymers comprising a higher proportion of units derived from monomers having at least one carboxylic acid group than units derived from monomers having at least one carboxylic anhydride group. Preferably, the molar ratio of carboxylic acid groups to carboxylic anhydride groups in the functional polymer is greater than 1.5, more preferably greater than 2, and most preferably greater than 5.

Alkyl (meth) acrylates having 1 to 12 carbon atoms have been previously set forth, so reference is hereby made.

In addition to the monomers set forth above, a functional polymer having carboxylic acid or carboxylic anhydride groups may comprise units derived from comonomers. These include, in particular, the monomers with oxazolidine groups set out above, where the functional polymer 0.1 to 15% by weight of units derived from these monomers. These monomers have been previously stated.

Of particular interest are coating agents in which the amino group-containing (meth) acrylate polymer has a higher proportion of units derived from monomers containing oxazolidine groups than the functional polymer. Preferably, the amino group-containing (meth) acrylate polymer has at least 5% more, more preferably at least 10%, more units derived from monomers having oxazolidine groups than the functional polymer, based on the weight fraction of these units in the particular one Polymer.

According to a further aspect of the present invention, it is possible with preference to use coating compositions which are distinguished by the fact that the functional polymer has a higher proportion of carboxylic acid groups or carboxylic anhydride groups than the amino group-containing (meth) acrylate polymer. Preferably, the functional polymer has at least 5% more, more preferably at least 10%, more units derived from monomers having at least one carboxylic acid group or at least one carboxylic anhydride group than the amino group-containing (meth) acrylate polymer based on weight fraction at these units in the respective polymer.

Other comonomers, in particular (meth) acrylic monomers having in the alkyl radical at least one double bond and 8 to 40 carbon atoms, acid group-containing monomers, (meth) acrylates having at least 13 carbon atoms in the alkyl radical derived from saturated alcohols and have no heteroatoms in the alkyl radical; heterocyclic (meth) acrylates; Nitriles of (meth) acrylic acid and other nitrogen-containing methacrylates; Aryl (meth) acrylates; (Meth) acrylates having a hydroxy group in the alkyl radical; polyalkoxylated derivatives of (meth) acrylic acid; Glycerincarbonatmethacrylat; 2-Carbamoyloxyethylmethacrylat; (Meth) acrylates derived from saturated fatty acids or fatty acid amides; Vinylester; styrene; heterocyclic vinyl compounds; Maleimide, methylmaleimide; Vinyl and isoprenyl ethers; and vinyl halides have been set forth above, so that reference is hereby made.

With particular advantage, the amino group-containing (meth) acrylate polymer and / or the functional polymer may comprise units derived from methyl methacrylate and / or butyl (meth) acrylate.

An amino-containing (meth) acrylate polymer and / or a functional polymer to be used according to the invention may preferably be from 0 to 60% by weight, preferably from 0.5 to 30% by weight, more preferably from 1 to 20% by weight and completely most preferably comprise from 2 to 15% by weight of units derived from (meth) acrylic monomers having in the alkyl radical at least one double bond and from 8 to 40 carbon atoms, based on the weight of the respective polymer.

According to a particular modification of the present invention, the amino group-containing (meth) acrylate polymer and / or the functional polymer 0 to 60 wt .-%, particularly preferably 5 to 50 wt .-% and most preferably 10 to 40 wt. have% of units of styrene monomers, in particular of styrene, substituted styrenes with a Alkyl substituents in the side chain, substituted styrenes with an alkyl substituent on the ring and / or halogenated styrenes are derived, based on the total weight of the (meth) acrylic polymer or of the functional polymer.

In addition, for the preparation of the amino group-containing (meth) acrylate polymer or the functional polymer monomer mixtures are preferred which have a very low proportion of (meth) acrylates having two or more carbon-carbon double bonds, one with a (Meth) acrylic group have identical reactivity. According to a particular modification of the present invention, the proportion of compounds having two or more (meth) acrylic groups is preferably at most 5 wt .-%, in particular at most 2 wt .-%, particularly preferably at most 1 wt .-%, particularly preferred not more than 0.5% by weight and very particularly preferably not more than 0.1% by weight, based on the total weight of the monomers.

The molecular weight of the amino group-containing (meth) acrylate polymers and the functional polymers can be in a wide range. In general, the weight-average molecular weight is usually at least 1000 g / mol, preferably at least 2000 g / mol and very particularly preferably at least 5000 g / mol. According to a first aspect of the present invention, for example, polymers having a relatively high molecular weight can be used. These amino-containing (meth) acrylate polymers or functional polymers can be obtained in particular by emulsion polymerization, the weight-average molecular weight of these polymers being, for example, in the range from 100,000 to 10,000,000 g / mol, particularly preferably in the range from 200,000 to 500,000 g / mol can lie. Emulsion polymers are notable in particular for their high environmental compatibility, since they often require no organic solvents and can have a particularly low residual monomer content.

In a further aspect, low molecular weight polymers to be used according to the invention may also be used. These amino group-containing (meth) acrylate polymers or functional polymers may, for example, have a weight average molecular weight in the range from 1000 to 150000 g / mol, in particular 4000 to 100000 g / mol, particularly preferably in the range from 5000 to 50 000 g / mol. Low molecular weight polymers are widely used in organic solvent coating compositions. Coating compositions comprising organic solvents show good processability over a wide range of temperature and humidity.

Improvements that were unforeseeable for the skilled worker can be achieved in particular by a very similar molecular weight of the polymers to be used according to the invention. According to this preferred embodiment, the ratio of the weight average molecular weight of the amino group-containing (meth) acrylate polymer to the weight average molecular weight of the functional polymer can be in the range of 5: 1 to 1: 5, more preferably in the range of 2: 1 to 1: 2 lie.

Also of interest are, in particular, amino-containing (meth) acrylate polymers or functional polymers which have a polydispersity index M _w / M _n in the range from 1 to 5, particularly preferably in the range from 2 to 3. The molecular weight can be determined by gel permeation chromatography (GPC) against a PMMA standard. The glass transition temperature of the polymers to be used according to the invention, namely the amino group-containing (meth) acrylate polymers and the functional polymers, is preferably in the range from -60 ⁰ C to 100 ⁰ C, in particular -30 ° C to 70 ⁰ C particularly preferred in the range of -20 to 40 ° C, and most preferably in the range of 0 to 25 ° C. The glass transition temperature can be influenced by the type and proportion of monomers used to make the polymer. The glass transition temperature Tg of the polymer can be determined in a known manner by means of differential scanning calorimetry (DSC), in particular according to DIN EN ISO 11357. Preferably, the glass transition temperature can be determined as the center of the glass stage of the second heating curve at a heating rate of 10 ⁰ C per minute. Furthermore, the glass transition temperature Tg can also be calculated approximately in advance by means of the Fox equation. After Fox TG, Bull. Am. Physics Soc. 1, 3, page 123 (1956) applies:

- = - ^J - + -2- + ... + - - Tg Tg ₁ Tg ₂ Tg _n where X _{n is} the mass fraction (wt .-% / 100) of the monomer n and Tg _{n is} the glass transition temperature in Kelvin of the homopolymer of the monomer n. Further helpful information can be found in the Polymer Handbook 2 ^nd Edition, J. Wiley & Sons, New York (1975), which gives Tg values for the most common homopolymers. For example, according to this handbook, poly (methyl methacrylate) has a glass transition temperature of 378K, poly (butyl methacrylate) of 297K, poly (isobornyl methacrylate) of 383K, poly (isobornyl acrylate) of 367K, and poly (cyclohexyl methacrylate) of 356K. In this case, the polymer may have one or more different glass transition temperatures. This information therefore applies to at least one segment which satisfies the characteristics of the amino group described above. pen-containing (meth) acrylate polymer or the functional polymer.

Among other things, surprising advantages can be achieved in that the difference between the glass transition temperature of the amino group-containing (meth) acrylate polymer and the glass transition temperature of the functional polymer is at most ± 20 ° C., more preferably at most ± 10 ° C., and most preferably at most ± 5 ° C.

The architecture of the polymers to be used according to the invention is not critical for many applications and properties. Accordingly, the polymers, in particular the emulsion polymers, can represent random copolymers, gradient copolymers, block copolymers and / or graft copolymers. Block copolymers or gradient copolymers can be obtained, for example, by discontinuously changing the monomer composition during chain growth. According to a preferred aspect of the present invention, the emulsion polymer, in particular the amino group-containing (meth) acrylate polymer and / or the functional polymer is a random copolymer in which the monomer composition is substantially constant via the polymerization. However, since the monomers may have different copolymerization parameters, the exact composition may vary across the polymer chain of the polymer.

The polymers to be used according to the invention can be homogeneous polymers which, for example, form particles with a constant composition in an aqueous dispersion. In this case, the amino group-containing (meth) acrylate polymer and the functional polymer, which are preferably an emulsion polymer, may be one or more Segments exist, each of which is obtainable by polymerization of a monomer mixture.

According to a further embodiment, the polymers to be used according to the invention can be a core-shell polymer which can have one, two, three or more shells. The shell may be connected to the core or inner shells via covalent bonds. Furthermore, the shell can also be polymerized on the core or an inner shell.

The iodine number of polymers to be used according to the invention can preferably be in the range from 0 to 300 g of iodine per 100 g of polymer, preferably in the range from 2 to 250 g of iodine per 100 g of polymer, more preferably 5 to 100 g of iodine per 100 g of polymer and most preferably 10 to 50 g of iodine per 100 g of polymer, measured in accordance with DIN 53241-1.

Suitably, the (meth) acrylate polymer containing amino groups may have an acid number in the range of 0 to 40 mg KOH / g, preferably 0.1 to 20 mg KOH / g and most preferably in the range of 2 to 10 mg KOH / g , The acid number can also be determined by dispersion according to DIN EN ISO 2114. The acid number of the functional polymer is preferably above that of the amino group-containing (meth) acrylate polymer, wherein values in the range of preferably 0.1 to 40 mg KOH / g, preferably 1 to 20 mg KOH / g, and most preferably in the range from 2 to 10 mg KOH / g.

It is preferable to use coating compositions in which the functional polymer differs from the amino group-containing (meth) acrylate polymer. can become. According to this embodiment, coating agents are preferred in which the difference between the acid number of the functional polymer and the acid number of the amino group-containing (meth) acrylate polymer is at least 0.1 mg KOH / g and more preferably at least 1 mg KOH / g.

The hydroxyl number of the polymers to be used according to the invention may preferably be in the range from 0 to 150 mg KOH / g, more preferably 20 to 120 mg KOH / g and most preferably in the range from 40 to 100 mg KOH / g. The hydroxyl number can be determined according to DIN EN ISO 4629.

The polymers to be used according to the invention can be obtained, in particular, by solution polymerizations, bulk polymerizations or emulsion polymerizations, it being possible to achieve surprising advantages by means of a radical-elastic emulsion polymerization. These are set forth in LJII-Mann's Encyclopaedia of Industrial Chemistry, Sixth Edition.

In addition to methods of classical radical polymerization and related methods of controlled radical polymerization, such as ATRP (= Atom Transfer Radical Polymerization), NMP (Nitroxide-mediated polymerization) or RAFT (= Reversible Addition Fragmentation Chain Transfer) can be used to prepare the polymers.

Methods of emulsion polymerization are set forth, inter alia, in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition. In general, for this purpose, an aqueous phase is prepared, the usual addition to water additives, especially emulsifiers and protective colloids for stabilizing the emulsion.

Monomers are then added to this aqueous phase and polymerized in the aqueous phase. In the preparation of homogeneous polymer particles in this case a monomer mixture over a period of time can be added continuously or batchwise.

The emulsion polymerization can be carried out, for example, as a miniemulsion or as a microemulsion, described in detail in Chemistry and Technology of Emulsion Polymerization, A.M. van Herk (editor), Blackwell Publishing, Oxford 2005 and J. O'Donnell, E.W. Kaier, Macromolecular Rapid Communications 2007, 28 (14), 1445-1454. A miniemulsion is customary characterized by the use of costabilizers or swelling agents, many of which use long-chain alkanes or alkanols. The droplet size in miniemulsions is preferably in the range of 0.05 to 20 microns. The droplet size in the case of microemulsions is preferably in the range below 1 μm, whereby particles below a size of 50 nm can be obtained in this way. Microemulsions often use additional surfactants, for example hexanol or similar compounds.

The dispersing of the monomer-containing phase in the aqueous phase can be carried out by known means. These include, in particular, mechanical methods and the use of ultrasound.

In addition to homogeneous emulsion polymers, core-shell polymers can also be prepared. For this purpose, the composition of the monomer mixture can be changed stepwise, wherein before changing the composition Polymerization is preferably up to a conversion of at least 80 wt .-%, more preferably at least 95 wt .-%, in each case based on the total weight of the monomer mixture used, polymehsiert. Core-shell polymer here stands for a polymer which has been prepared by a two-stage or multistage emulsion polymerization, without the core-shell structure having been demonstrated, for example, by electron microscopy. The tracking of the progress of the polymerization in each step may be carried out in a known manner, for example gravimetrically or by gas chromatography.

The monomer composition for producing the core preferably comprises from 50 to 100% by weight of (meth) acrylates, with a mixture of acrylates and methacrylates being used with particular preference. According to a particular aspect of the present invention, the weight ratio of acrylates to methacrylates in the core may be greater than or equal to 1, more preferably greater than or equal to 2. After the core has been produced, a monomer mixture may preferably be grafted onto it or polymerized onto the core, which contains 0.5 to 20% by weight, particularly preferably 2 to 15% by weight, in particular 5 to 10% by weight. Monomer with oxazolidine groups.

The emulsion polymerization is preferably carried out at a temperature in the range from 0 to 120 ^° C., more preferably in the range from 30 to 100 ^° C. Here, polymerization temperatures in the range from greater than 60 to less than 90 ^° C., expediently in the range from greater than 70 to less than 85 ^° C., preferably in the range from greater than 75 to less than 85 ^° C., have proven to be particularly favorable. The initiation of the polymerization takes place with the customary for the emulsion polymerization initiators. Suitable organic initiators are, for example, hydroperoxides, such as tert-butyl hydroperoxide or cumene hydroperoxide. Suitable inorganic initiators are hydrogen peroxide and the alkali metal and ammonium salts of peroxodisulfuric acid, in particular ammonium, sodium and potassium peroxodisulfate. Suitable redox initiator systems are, for example, combinations of tertiary amines with peroxides or sodium disulfite and alkali metal and the ammonium salts of peroxodisulfuric acid, in particular sodium and potassium peroxodisulfate. Further details can be found in the specialist literature, in particular H. Rauch-Puntigam, Th. Völker, "Acrylic and Methacrylic Compounds", Springer, Heidelberg, 1967 or Kirk-Othmer, Encyclopaedia of Chemical Technology, Vol. 1, p. 386ff, J. Wiley, New York, 1978. In the context of the present invention, the use of organic and / or inorganic initiators is particularly preferred.

The initiators mentioned can be used both individually and in mixtures. They are preferably used in an amount of 0.05 to 3.0 wt .-%, based on the total weight of the monomers of each stage. It is also preferable to carry out the polymerization with a mixture of different polymerization initiators having a different half-life, in order to keep the radical stream constant during the polymerization and at different polymerization temperatures.

The stabilization of the approach is preferably carried out by means of emulsifiers and / or protective colloids. Preferably, the emulsion is stabilized by emulsifiers to obtain a low dispersion viscosity. The total amount of emulsifier is preferably 0.1 to 15 wt .-%, in particular 1 to 10 Wt .-% and particularly preferably 2 to 5 wt .-%, based on the total weight of the monomers used. According to a particular aspect of the present invention, a part of the emulsifiers may be added during the polymerization.

Particularly suitable emulsifiers are anionic or nonionic emulsifiers or mixtures thereof, in particular

Alkyl sulfates, preferably those having 8 to 18 carbon atoms in the alkyl radical, alkyl and alkylaryl ether sulfates having 8 to 18 carbon atoms in the alkyl radical and 1 to 50 ethylene oxide units;

Sulfonates, preferably alkyl sulfonates having 8 to 18 carbon atoms in the alkyl radical, alkylaryl sulfonates having 8 to 18 carbon atoms in the alkyl radical, esters and half-esters of sulfosuccinic acid with monohydric alcohols or alkylphenols having 4 to 15 carbon atoms in the alkyl radical; optionally, these alcohols or alkylphenols may also be ethoxylated with 1 to 40 ethylene oxide units;

Partial phosphoric acid esters and their alkali metal and ammonium salts, preferably alkyl and alkylaryl phosphates having 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 1 to 5 ethylene oxide units; - Alkylpolyglykolether, preferably having 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units;

Alkylarylpolyglykolether, preferably having 8 to 20 carbon atoms in the alkyl or alkylaryl radical and 8 to 40 ethylene oxide units; Ethylene oxide / propylene oxide copolymers, preferably block copolymers, desirably with 8 to 40 ethylene oxide or propylene oxide units, respectively.

Particularly preferred anionic emulsifiers include in particular fatty alcohol ether sulfates, diisooctyl sulfosuccinate, lauryl sulfate, C15- Paraffin sulfonate, which compounds can generally be used as the alkali metal salt, in particular as the sodium salt. These compounds can in particular be obtained commercially under the trade names Disponil® FES 32, Aerosol® OT 75, Texapon® K1296 and Statexan® K1 from the companies Cognis GmbH, Cytec Industries, Inc. and Bayer AG.

Useful nonionic emulsifiers include tert-octylphenol ethoxylate with 30 ethylene oxide units and fatty alcohol polyethylene glycol ethers which preferably have 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units. These emulsifiers are commercially available under the trade names Triton® X 305 (Fluka), Tergitol® 15-S-7 (Sigma-Aldrich Co.), Marlipal® 1618/25 (Sasol Germany) and Marlipal® O 13/400 (Sasol Germany) available.

Preference is given to using mixtures of anionic emulsifier and nonionic emulsifier. Suitably, the weight ratio of anionic emulsifier to nonionic emulsifier in the range of 20: 1 to 1: 20, preferably 2: 1 to 1: 10 and more preferably 1: 1 to 1: 5 are. Mixtures comprising a sulfate, in particular a fatty alcohol ether sulfate, a lauryl sulfate, or a sulfonate, in particular a diisooctyl sulfosuccinate or a paraffin sulfonate as anionic emulsifier and an alkylphenol ethoxylate or a fatty alcohol polyethylene glycol ether, each preferably 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units have proven particularly useful as a nonionic emulsifier. Optionally, the emulsifiers can also be used in admixture with protective colloids. Suitable protective colloids include, among others, partially hydrolyzed polyvinyl acetates, polyvinylpyrrolidones, carboxymethyl, methyl, hydroxyethyl, hydroxypropyl cellulose, starches, proteins, poly (meth) acrylic acid, poly (meth) acrylamide, polyvinylsulfonic acids, melamine-formaldehyde sulfonates,

Naphthalene formaldehyde sulfonates, styrene-maleic acid and vinyl ether maleic copolymers. If protective colloids are used, this is preferably carried out in an amount of 0.01 to 1, 0 wt .-%, based on the total amount of the monomers. The protective colloids can be initially charged or added before the start of the polymerization. The initiator can be initially charged or added. Furthermore, it is also possible to submit a portion of the initiator and to meter in the remainder.

The polymerization is preferably started by heating the batch to the polymerization temperature and initially and / or adding the initiator, preferably in aqueous solution. In this case, a part of the monomers can be initially charged in the reactor and the remainder added over a certain period of time. As a rule, it is advantageous to polymerize the part of the monomers initially introduced in the reactor and only then to start the feed. Alternatively, for the presentation of a defined amount of monomer, the feed may be interrupted for a few minutes after e.g. 1-5% of the monomers are added. The dosages of emulsifier and monomers can be carried out separately or preferably as a mixture, in particular as an emulsion in water.

The emulsion polymerization can be carried out in a wide pH range. It is preferably between 2 and 9. In a particular embodiment, the polymerization is carried out at pH values between 4 and 8, in particular between 6 and 8. Likewise, the dispersion after the polymerization can be adjusted to a preferred pH range for the application. For pigmented coating systems, the range is generally 8 - 9 or above.

The molecular weight of the polymers is initially uncritical within wide limits.

If particularly hard and solvent-resistant coating compositions with good mechanical properties are desired, the highest possible molecular weight can be helpful. Preferred emulsion polymers having a high content of polymers which are insoluble in THF may be obtained in the manner set forth above. The reaction parameters to obtain a high molecular weight are known. Thus, in particular, the use of molecular weight regulators can be dispensed with.

Coating compositions that are particularly easy and easy to process may also have lower molecular weight polymers, with the solvent resistance and hardness of these coatings reaching a relatively high level. Preferably, these polymers having a particularly good processability, a molecular weight below 1 000 000 g / mol, preferably below 500 000 g / mol and more preferably below 250 000 g / mol. The molecular weight can be determined by gel permeation chromatography (GPC) against a PMMA standard.

Low molecular weight polymers, especially emulsion polymers, can be obtained by the addition of molecular weight regulators to the reaction mixture before or during polymerization. For this Sulfur-free molecular weight regulators and / or sulfur-containing molecular weight regulators may be used.

The sulfur-free molecular weight regulators include, but are not limited to, dimeric α-methylstyrene (2,4-diphenyl-4-methyl-1-pentene), enol ethers of aliphatic and / or cycloaliphatic aldehydes, terpenes, β-terpinene, Terpinolene, 1,4-cyclohexadiene, 1,4-dihydronaphthalene, 1, 4,5,8-tetrahydronaphthalene, 2,5-dihydrofuran, 2,5-dimethylfuran and / or 3,6-dihydro-2H-pyran, is preferred dimeric α-methylstyrene.

The sulfur-containing molecular weight regulators used may preferably be mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides. The following polymerization regulators are given by way of example: di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-n-butyl sulfide. t-butyl sulfide and dimethyl sulfoxide. Preferred compounds used as molecular weight regulators are mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides. Examples of these compounds are ethyl thioglycolate, 2-ethylhexyl thioglycolate, cysteine, 2-

Mercaptoethanol, 1, 3-mercaptopropanol, 3-mercaptopropane-1,2-diol, 1,4-mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglycerol, thioacetic acid, thiourea and alkyl mercaptans such as n-butylmercaptan, n- Hexylmercaptan or n-dodecylmercaptan. Particularly preferred polymerization regulators are mercaptoalcohols and mercaptocarboxylic acids. The molecular weight regulators are preferably used in amounts of 0.05 to 10, more preferably 0.1 to 5 wt .-%, based on the monomers used in the polymerization. Of course, mixtures of polymerization regulators can also be used in the polymerization.

In addition, polymerizations using molecular weight regulators can be used to reduce the minimum film-forming temperature (MFT) of the polymers obtainable thereby. According to this preferred embodiment, the proportion of molecular weight regulators can be dimensioned such that the polymers or the coating compositions of the invention have a minimum film-forming temperature (MFT) of at most 60 ^° C., more preferably at most 50 ^° C., and very particularly preferably at most 40 ° C, which can be measured according to DIN ISO 2115. The higher the proportion of molecular weight regulators, the lower the minimum film-forming temperature.

The adjustment of the particle radii can be influenced inter alia by the proportion of emulsifiers. The higher this proportion, especially at the beginning of the polymerization, the smaller the particles are obtained.

Preferably, the emulsion polymer, in particular the amino group-containing (meth) acrylate polymer or the functional polymer is uncrosslinked or crosslinked so low that the soluble in tetrahydrofuran (THF) at 20 ⁰ C content above 60 wt .-% based on the weight of Emulsion polymers is. In a further preferred embodiment, the emulsion polymer may contain from 2 to 60% by weight, more preferably from 10 to 50% by weight, and most preferably 20 to 40 wt .-%, based on the weight of the emulsion polymer which is soluble in THF at 20 ⁰ C.

For the determination of the soluble portion of a dried sample of polymethyl risats is stored in a 200-fold amount of solvent, based on the weight of the sample, at 20 ⁰ C for 4 h. Here, the drying is carried out so that no possible self-crosslinking occurs. This can be done for example by freeze-drying. Subsequently, the solution is separated from the insoluble fraction, for example by filtration. After evaporation of the solvent, the weight of the residue is determined. For example, a 0.5 g sample of a vacuum-dried emulsion polymer can be stored in 150 ml of THF for 4 hours.

Of particular interest here are coating compositions with amino group-containing (meth) acrylate polymers and functional polymers which have a very similar solubility behavior in THF. Thus, the difference between the solubility of the amino group-containing (meth) acrylate polymer and the solubility of the functional polymer in tetrahydrofuran (THF) at 20 ° C. in preferred coating compositions is preferably at most ± 20%, more preferably at most ± 10%, and most especially preferably at most ± 5%.

The particle radius of the emulsion polymers, namely the amino group-containing (meth) acrylate polymers and the functional polymers, can be in a wide range. Thus, in particular emulsion polymers having a particle radius in the range of 10 to 500 nm, preferably 10 to 100 nm, particularly preferably 20 to 60 nm can be used. In particular, particle radii below 50 nm can be advantageous for the film formation and the coating properties. The radius of the particles can be determined by PCS (Photon Correla- tion spectroscopy), the data given refer to the r50 value (50% of the particles are smaller, 50% are larger). For example, a Beckman Coulter N5 Submicron Particle Size Analyzer can be used for this purpose.

Surprising advantages in particular show coating compositions with amino-containing (meth) acrylate polymers and functional polymers which have a very similar particle radius. Thus, the difference between the particle radius of the amino group-containing (meth) acrylate polymer and the particle radius of the functional polymer in preferred coating compositions is preferably at most ± 30 nm, more preferably at most ± 20 nm, and most preferably at most ± 10 nm.

Of particular interest are, in particular, coating compositions which preferably contain from 40 to 80% by weight, particularly preferably from 50 to 75% by weight, of polymers to be used according to the invention.

Coating agents in which the weight ratio of amino group-containing (meth) acrylate polymer to functional polymer is in the range from 10: 1 to 1:10, preferably from 5: 1 to 1: 5 and particularly preferably in the range from 2: 1 to 1: 2 is located.

Surprisingly, the present coating compositions show the tendency of self-crosslinking. The term "self-crosslinking" in this context refers to a possible reaction of the oxazolidine groups or the amino groups derived therefrom with the carboxylic acid or carboxylic anhydride groups of the functional polymer be accelerated in particular by heat treatment of the films at temperatures above 60 ⁰ C, more preferably above 100 ⁰ C.

The time over which the films are crosslinked at temperatures above room temperature is, for example, the pH of the film and the nature and amount of the oxazolidine group-bearing or carboxylic acid or carboxylic anhydride group-comprising repeat units and the desired one mechanical strength of the coating or chemical resistance dependent. Of particular interest are, in particular, processes in which the self-crosslinking is carried out over a period in the range from 60 seconds to 60 minutes, more preferably in the range from 5 minutes to 30 minutes. This self-crosslinking can preferably be carried out to tack-free according to DIN 53150 or beyond, wherein according to another embodiment, the self-crosslinking to exactly the freedom from gluten according to DIN 53150 takes place. Crosslinked films are often characterized by high solvent resistance and excellent mechanical properties.

Coatings which have been subjected to a heat treatment have clear advantages in terms of chemical resistance and mechanical properties, in particular tensile strength and pendulum hardness. Thus, chemical resistance and mechanical properties can be improved to an unexpected degree by annealing.

The coating compositions according to the invention can be crosslinked in particular by crosslinking agents which can react with the amino groups of the (meth) acrylate polymer to be used according to the invention and / or the acid or acid anhydride groups of the functional polymer. The preferred crosslinking agents include in particular polyisocyanates or compounds which release polyisocyanates. Polyisocyanates are compounds having at least 2 isocyanate groups.

The polyisocyanates which can be used according to the invention may comprise any desired aromatic, aliphatic, cycloaliphatic and / or (cyclo) aliphatic polyisocyanates.

The preferred aromatic polyisocyanates include 1, 3 and

1, 4-phenylene diisocyanate, 1, 5-naphthylene diisocyanate, tolidine diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 4,4'-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates (MDI) and oligomeric diphenylmethane diisocyanates (polymer-MDI), xylylene diisocyanate, tetramethylxylylene diisocyanate and triisocyanatotoluene.

Preferred aliphatic polyisocyanates have 3 to 16 carbon atoms, preferably 4 to 12 carbon atoms, in the linear or branched alkylene radical and suitable cycloaliphatic or (cyclo) aliphatic diisocyanates advantageously 4 to 18 carbon atoms, preferably 6 to 15 carbon atoms, in the cycloalkylene radical. Under (cyclo) aliphatic diisocyanates, the skilled worker understands at the same time cyclic and aliphatic bound NCO groups, as z. B. isophorone diisocyanate is the case. On the other hand, cycloaliphatic diisocyanates are understood to be those which have only NCO groups bonded directly to the cycloaliphatic ring, eg. B. H ₁₂ MDI. Examples are cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclo hexane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate, nonane diisocyanate, nonane triisocyanate, such as 4-isocyanatomethyl-1, 8-octane diisocyanate (TIN), decane diisocyanate and triisocyanate, undecanediisocyanate and triisocyanate, dodecane diisocyanates and triisocyanates ,

Preference is given to isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), diisocyanatodicyclohexylmethane (H ₁₂ MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-thmethylhexamethylene diisocyanate / 2,4,4-thymethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI) , Very particular preference is given to using IPDI, HDI, TMDI and H ₁₂ MDI, it also being possible to use the isocyanurates.

Also suitable are 4-methylcyclohexane-1, 3-diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 3 (4) -lsocyanatomethyl-1-methylcyclohexyl isocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 2,4'-methylenebis (cyclohexyl) diisocyanate, 1, 4-diisocyanato-4-methyl-pentane.

Preferred aliphatic, cycloaliphatic and araliphatic, d. H. Aryl-substituted aliphatic diisocyanates are described, for example, in Houben-Weyl, Methoden der organischen Chemie, Volume 14/2, pages 61-70 and in the article by W. Siefken, Justus Liebigs Annalen der Chemie 562, 75-136.

Of course, mixtures of the polyisocyanates can be used. Furthermore, preference is given to using oligoisocyanates or polyisocyanates which are prepared from the abovementioned diisocyanates or polyisocyanates or mixtures thereof by linking by means of urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine , Oxadiazinetrione or iminooxadiazinedione structures. This preferred class of polyisocyanates can be prepared by dimerization, trimerization, allophanatization, biuretization and / or urethanization of simple diisocyanates compounds having more than two isocyanate groups per molecule, for example, the reaction products of these simple diisocyanates, such as. B. IPDI, TMDI, HDI and / or H ₁₂ MDI with polyhydric alcohols (eg, glycerol, trimethylolpropane, pentaerythritol) or polyhydric polyamines, or the triisocyanurates, by trimerization of simple diisocyanates, such as IPDI, HDI and H ₁₂ MDI.

Coating agents which preferably contain from 0.5 to 10% by weight, particularly preferably from 2 to 7% by weight, of crosslinking agent are therefore of particular interest.

When polyisocyanates are used as crosslinking agents, the reaction of the (meth) acrylic polymers with the organic polyisocyanates may in this case be carried out with 0.5 to 1.1 NCO group per reactive group, depending on the intended use of the reaction products. The reaction is preferably carried out in such a way that the amounts of the organic polyisocyanate, based on the total hydroxy content of the components present in the reaction mixture per reactive group, are present in an amount of from 0.7 to 1.0 isocyanate groups. With regard to a reaction with isocyanate, the term "reactive group" means a group which is reacted with an isocyanate. can be set. These include in particular hydroxy groups and / or amino groups.

The coating compositions of the invention do not require siccatives, but these may be included as an optional ingredient in the compositions. These include in particular organometallic compounds, for example metal soaps of transition metals, such as cobalt, manganese, vanadium, lead, zirconium; Alkali or alkaline earth metals, such as lithium, potassium and calcium. By way of example, mention may be made of cobalt naphthalate and cobalt acetate. The siccatives can be used individually or as a mixture, with particular preference being given to mixtures containing cobalt, zirconium and lithium salts.

The proportion of siccatives in preferred coating compositions may preferably be in the range from greater than 0 to 5% by weight, more preferably in the range from 1 to 3% by weight, based on the polymer content.

According to a particular aspect of the present invention, the coating agents may comprise solvents. These coating agents can be processed over a particularly broad temperature and humidity range. The term of the solvent is to be understood here broadly. The preferred solvents include in particular aromatic hydrocarbons, such as toluene, xylene; Esters, in particular acetates, preferably butyl acetate, ethyl acetate, propyl acetate; Ketones, preferably ethyl methyl ketone, acetone, methyl isobutyl ketone or cyclohexanone; Alcohols, especially isopropanol, n-butanol, isobutanol; Ethers, in particular glycol monomethyl ether, glycol monoethyl ether, glycol monobutyl ether; Aliphatic, preferably pentane, hexane, cycloalkane and substituted cycloalkanes, for example cyclohexane; Mixtures of aliphatics and / or aromatics, preferably naphtha; Gasoline, biodiesel; but also plasticizers such as low molecular weight polypropylene glycols or phthalates. The proportion of solvent in preferred coating compositions may in particular be in the range from 0 to 50% by weight, more preferably in the range from 1 to 20% by weight.

In addition, coating compositions whose solids content is preferably at least 50% by weight, more preferably at least 60% by weight, exhibit surprisingly good processability. This information applies in particular to coating compositions comprising organic solvents.

According to a further embodiment, the coating compositions of the invention comprise a relatively high proportion of water, with aqueous dispersions being particularly preferred coating compositions. The aqueous dispersions preferably have a solids content in the range from 10 to 70% by weight, particularly preferably from 20 to 60% by weight. These coating compositions often comprise only a very small, preferably no fraction of organic solvents. Preferred aqueous dispersions contain at most 5% by weight, more preferably at most 2

% By weight volatile organic compounds (VOC), such as residual monomers or organic solvents. These coating compositions are therefore characterized by a particularly high environmental friendliness.

Furthermore, the coating compositions of the invention may contain conventional additives, in particular UV stabilizers, flow control agents and biocides. The dynamic viscosity of the coating agent is dependent on the solids content and may include a wide range. So this can be more than 10,000 mPas at high polymer content. A dynamic viscosity in the range from 10 to 4000 mPas, preferably from 10 to 1000 mPas and very particularly preferably from 10 to 500 mPas, measured according to DIN EN ISO 2555 at 25 ° C. (Brookfield), is usually expedient.

Furthermore, the present invention provides a method for producing a coating in which a coating composition of the invention is applied to a substrate and cured.

The coating composition according to the invention can be applied by conventional application methods, in particular by roller application or spraying. Furthermore, dipping methods are also suitable for applying the coating composition.

The present coating composition can be used in particular for the production of paints, varnishes, sealants, adhesives and printing inks.

The substrates which can preferably be provided with a coating composition according to the invention include in particular metals, in particular iron and steel, zinc and galvanized steels, wood, plastics and concrete substrates.

Moreover, the present invention provides coated articles obtainable by a method according to the invention. Thieves- The layering of these objects is characterized by an outstanding range of properties.

The coatings obtainable from the coating compositions according to the invention show a high resistance to solvents, with only small amounts in particular being dissolved out of the coating by solvents. Preferred coatings show a high resistance, in particular to methyl isobutyl ketone (MIBK). Thus, the weight loss after treatment with MIBK is preferably at most 50% by weight, preferably at most 35% by weight. The uptake of MIBK is preferably at most 1000 wt .-%, more preferably at most 600 wt .-%, based on the weight of the coating used. These values are measured at a temperature of about 25 ° C and an exposure time of at least 4 hours, whereby a completely dried coating is measured, which was preferably crosslinked.

The coatings obtained from the coating compositions of the invention show high mechanical resistance. The pendulum hardness is preferably at least 15 s, preferably at least 25 s, measured according to DIN ISO 1522.

Inventive coatings show surprisingly good mechanical properties. Of particular interest are, in particular, coatings which have a nominal elongation at break of preferably at least 200%, more preferably at least 300%, measured in accordance with DIN EN ISO 527 Part 3. In addition, coatings are furthermore preferred which have a tensile strength, measured in accordance with DIN EN ISO 527 Part 3, of at least 2 MPa, more preferably at least 4 MPa.

Furthermore, preferred coatings which are obtainable from the coating compositions according to the invention are distinguished by a surprisingly high adhesive strength, which can be determined in particular according to the cross-cut test. Thus, in particular a classification of 0-1, particularly preferably of 0 according to the standard DIN EN ISO 2409 can be achieved.

Hereinafter, the present invention will be explained with reference to examples and comparative examples, without thereby limiting it.

production methods

Preparation of a polymer with oxazolidine groups BA-MMA-OXEMA = 52.5-42.5-5

First, 124.39 g of butyl acrylate (BA), 100.69 g of methyl methacrylate (MMA), 11.85 g of oxazolidinylethyl methacrylate (OXEMA), 7.11 g of 4,4'-azobis (4) were placed in a 2 l PE beaker. cyanovaleric acid) sodium salt (10%), 21, 24 g of Disponil FES 32 (30%) and 192.24 g of water were emulsified by Ultra-Turrax for 4 minutes at 4000 rpm.

In a 1 I Rettberg reactor, which could be tempered with a water bath and equipped with a metal blade stirrer, 140.16 g of water and 0.54 g of Disponil FES 32 (30%) were initially charged, heated to 80 ⁰ C. and with 1.78 g of 4,4'-azobis (4-cyanovaleriansäure) sodium salt (10%). 5 minutes after the initiator addition, the previously prepared emulsion was metered in within 240 minutes (interval: 3 minutes feed, 4 minutes break, 237 minutes residual feed). The stirring speed was 120 rpm.

After the end of the feed was stirred at 80 ⁰ C for 1 hr. It was then cooled to 60 ⁰ C and treated with 13.71 g of Triton X 305 (Rohm & Haas). The resulting dispersion was cooled to room temperature with stirring and filtered through VA screen mesh with 0.09 mm mesh size.

The dispersion prepared had a solids content of 40 ± 1 wt .-%.

Preparation of a polymer with acid groups BA-MMA-GMAA = 50-49-1

The process previously described for the preparation of a polymer having oxazolidine groups was substantially repeated, but using a monomer mixture comprising 148.5 g of butyl acrylate (BA), 145.5 g of methyl methacrylate (MMA), 3.0 g methacrylic acid (GMAA), 7.1 g of 4,4'-azobis (4-cyanovaleric acid) sodium salt (10%), 7.1 g of Disponil FES 32 (30%) and 146.3 g of water.

The dispersion prepared had a solids content of 40 ± 1 wt .-%.

Preparation of Acid Anhydride Polymer BA-MMA-maleic anhydride = 52.5-42.5-5 The above-described process for producing a polymer having oxazolidine groups was substantially repeated, but using a monomer mixture comprising 124.4 g of butyl acrylate (BA), 100.7 g of methyl methacrylate (MMA), 11, 9 g of maleic anhydride, 7.1 g of 4,4'-azobis (4-cyanovaleric acid) sodium salt (10%), 7.1 g of Disponil FES 32 (30%) and 206.4 g of water.

The dispersion prepared had a solids content of 40 ± 1 wt .-%.

Preparation of a polymer having groups derived from methacryloyloxy-2-ethyl fatty acid amides

First, a mixture of methacryloyloxy-2-ethyl-fatty acid amides was prepared. For this purpose, 206.3 g (0.70 mol) of fatty acid methyl ester mixture, 42.8 g (0.70 mol) of ethanolamine and in a four-necked round-bottomed flask equipped with a saber stirrer with stirrer sleeve and stirrer motor, nitrogen inlet, bottom thermometer and a distillation bridge 0.27 g (0.26%) LiOH submitted. The fatty acid methyl ester mixture comprised 6% by weight of saturated C12 to C16 fatty acid methyl ester, 2.5% by weight of saturated C17 to C20 fatty acid methyl ester, 52% by weight of monounsaturated C18 fatty acid methyl ester, 1.5% by weight of monounsaturated C20 to C24 fatty acid methyl esters , 36% by weight of polyunsaturated C18 fatty acid methyl ester, 2% by weight of polyunsaturated C20 to C24 fatty acid methyl esters.

The reaction mixture was heated to 150 ⁰ C. Within 2 h, 19.5 ml of methanol were distilled off. The resulting reaction product contained 86.5%. Fatty acid ethanol amides. The resulting reaction mixture was further processed without purification.

After cooling, 1919 g (19.2 mol) of methyl methacrylate, 3.1 g of LiOH and an inhibitor mixture consisting of 500 ppm hydroquinone monomethyl ether and 500 ppm phenothiazine were added.

While stirring, the reaction apparatus was purged with nitrogen for 10 minutes. Thereafter, the reaction mixture was heated to boiling. The methyl methacrylate / methanol azeotrope was separated and then the head temperature gradually increased to 100 ⁰ C. After completion of the reaction, the reaction mixture was cooled to about 70 ⁰ C and filtered.

Excess methyl methacrylate was separated on a rotary evaporator. It was possible to obtain 370 g of a mixture of methacryloyloxy-2-ethyl-fatty acid amides.

The above-described process for producing a polymer having oxazolidine groups was substantially repeated except that a monomer mixture containing 106.6 g of butyl acrylate (BA), 92.4 g of methyl methacrylate (MMA), 2.4 g of methacrylic acid was used (GMAA), 35.5 g of methacryloyloxy-2-ethyl-fatty acid amide mixture, 7.1 g of 4,4'-azobis (4-cyanovaleric acid) sodium salt (10%), 7.1 g of Disponil FES 32 (30 %) and 206.4 g of water.

The prepared dispersion had a solids content of 39 ± 1% by weight.

example 1 A mixture was prepared comprising the polymer set forth above with oxazolidine groups and the polymer set forth above with acid groups. For this purpose, the corresponding dispersions were mixed, wherein the OXEMA content was adjusted to 2.5 wt .-% (based on the solids content).

The swelling properties of the coating composition thus obtained were examined. For this purpose a 1000 .mu.m-thick film (wet) was applied to a silikonumran- finished glass plate and dried for seven days at room temperature or for 6 hours at 145 ⁰ C.

From the dimensions of the glass plate, the solids content of the dispersion and the required thickness of the dry film of 0.5 mm, the required mass of the dispersion was calculated.

From the polymer films produced, specimens measuring 0.5 × 10 × 20 mm were cut. These were weighed out on the analytical balance and destilled for 4 h in 100 ml. Water or 100 ml_ of isobutyl methyl ketone (MIBK) stored in wide-mouth bottles at 23 ⁰ C.

After expiry of the storage time, the specimens were removed, dabbed with pulp and weighed again. The solvent absorption was calculated from the resulting weight.

The data obtained by the swelling experiments are listed in Table 1. Furthermore, the pendulum hardness was determined according to DIN ISO 1522 using a 150 micron film (wet film), which was dried at 145 ⁰ C for 6 hours. This was 18 s.

Comparative Example 1

First, a homopolymer based on oxazolidinylethyl methacrylate (OXEMA) was prepared according to Example 9 of the publication US Pat. No. 3,037,006, whereby a 25% strength aqueous solution was obtained.

This aqueous solution was mixed with the polymer set forth above with acid groups, the OXEMA content was adjusted to 2.5 wt .-% (based on the solids content).

The properties of the coating composition thus obtained were partially investigated by the methods set forth in Example 1. The results obtained are shown in Table 1.

Table 1

A comparison of the data set out above shows that a polymer which has a relatively low OXEMA content can achieve very marked improvements in swelling in MIBK without having to accept significant water-swelling deterioration. Furthermore, the coating compositions according to the invention can also be dried at relatively high temperatures, without this resulting in a deterioration of properties.

Example 2

A blend was prepared comprising the previously described oxazolidine polymer and the acid anhydride group polymer set forth above. For this purpose, the corresponding dispersions were mixed, wherein the OXEMA content was adjusted to 2.5 wt .-% (based on the solids content).

The properties of the coating composition thus obtained were partially investigated by the methods set forth in Example 1. The results obtained are shown in Table 2. Comparative Example 2

First, a homopolymer based on oxazolidinylethyl methacrylate (OXEMA) was prepared according to Example 9 of the publication US Pat. No. 3,037,006, whereby a 25% strength aqueous solution was obtained.

This aqueous solution was mixed with the acid anhydride group polymer set forth above to adjust the OXEMA content to 2.5% by weight (based on the solid content).

The properties of the coating composition thus obtained were partially investigated by the methods set forth in Example 1. The results obtained are shown in Table 2.

Table 2

Example 3

First, 123.2 g of butyl acrylate (BA), 99.5 g of methyl methacrylate (MMA), 11.8 g of oxazolidinyl ethyl methacrylate (OXEMA), 2.4 g of methacrylic acid (GMAA), 7.1 g of 4 were in a 2 l PE beaker , 4'-Azobis (4-cyanovaleric acid) Nathumsalz (10%), 21, 24 g Disponil FES 32 (30%) and 192.2 g of water emulsified by Ultra-Turrax for 4 minutes at 4000 rpm.

In a 1 I Rettberg reactor, which could be tempered with a water bath and equipped with a metal blade stirrer, 140.16 g of water and 0.54 g of Disponil FES 32 (30%) were initially charged, heated to 80 ⁰ C. and with 1.78 g of 4,4'-azobis (4-cyanovalerianic acid) sodium salt (10%). 5 minutes after the initiator addition, the previously prepared emulsion was metered in within 240 minutes (interval: 3 minutes feed, 4 minutes break, 237 minutes residual feed). The stirring speed was 120 rpm.

After the end of the feed was stirred at 80 ⁰ C for 1 hr. It was then cooled to 60 ° C and treated with 13.71 g of Triton X 305 (Rohm & Haas). The resulting dispersion was cooled to room temperature with stirring and filtered through VA screen mesh with 0.09 mm mesh size.

The dispersion prepared had a solids content of 40 ± 1 wt .-%.

The properties of the coating composition thus obtained were investigated by the methods set forth in Example 1, with only one drying at 145 ° C for 6 hours. The true swelling in MIBK was 459%; the true swelling in water is 13.0% and the pendulum hardness is 6 s.

Surprisingly, coating compositions comprising a polymer having a high content of oxazolidine groups and a polymer having a lower content of oxazolidine groups accordingly exhibit higher pendulum hardness and less swelling in water than coating agents comprising only polymers having oxazolidine groups and acid groups. It should be noted here that the coating composition of Example 3, based on the solids content, comprised twice as many oxazolidine groups with 5% by weight as the coating composition of Example 1.

Example 4

The coating agent obtained in Example 1 was provided with a crosslinking agent. For this purpose, 40.0 g of the dispersion described in Example 1 were admixed with 1.0 g of a solution of hexamethylene diisocyanate (HDI) and n-butyl acetate (6/1).

The properties of the coating composition thus obtained were investigated by the methods set forth in Example 1, with only drying at 145 ° C for 6 hours. The true swelling in MIBK was 413%; the true swelling in water 7.0% and the pendulum hardness 21 s. Example 5

The coating agent obtained in Example 3 was provided with a crosslinking agent. For this purpose, 40.0 g of the dispersion described in Example 3 were admixed with 1.0 g of hexamethylene diisocyanate (HDI) and dibutyltin dilaurate (DBTL, 0.01% by weight, based on the polymer weight).

The properties of the coating composition thus obtained were investigated by the methods set forth in Example 1, with only drying at 145 ° C for 6 hours. The true swelling in MIBK was 341%; the true swelling in water 11, 4% and the pendulum hardness 9 s.

Example 6

A blend was prepared comprising the above-described oxazolidine group polymer and the polymer set forth above having groups derived from methacryloyloxy-2-ethyl-fatty acid amides. For this purpose, the corresponding dispersions were mixed, wherein the OXEMA content was adjusted to 2.5 wt .-% (based on the solids content).

The properties of the coating composition thus obtained were investigated by the methods set forth in Example 1, with only drying at 145 ° C for 6 hours. The true swelling in MIBK was 270% and the true swelling in water was 3%.

Claims

claims

1. Coating composition, characterized in that the coating agent comprises at least one amino group-containing (meth) acrylate polymer which comprises 0.1 to 15% by weight of units derived from monomers containing oxazolidine groups, and 20 to 99 , 9 wt .-% of units derived from alkyl (meth) acrylates having 1 to 12 carbon atoms, each based on the weight of the amino-containing (meth) acrylate polymer, and at least one functional polymer with carboxylic acid - Has or carboxylic anhydride groups.

2. A coating composition according to claim 1, characterized in that the functional polymer comprises 0.1 to 15 wt .-% of units derived from monomers having at least one carboxylic acid group or monomers having at least one carboxylic acid anhydride group, and 20 to 99.9 wt % of units derived from alkyl (meth) acrylates of 1 to 12 carbon atoms.

3. Coating composition according to claim 2, characterized in that the functional polymer has a higher proportion of carboxylic acid groups or carboxylic anhydride groups than the amino group-containing (meth) acrylate polymer.

4. Coating composition according to one of the preceding claims, characterized in that the amino group-containing (meth) acrylate polymer comprises a higher proportion of units derived from monomers with Oxazolidingruppen, as the functional polymer.

5. Coating composition according to claim 4, characterized in that the weight ratio of amino group-containing (meth) acrylate polymer to functional polymer in the range of 2: 1 to 1: 2.

6. Coating composition according to one of the preceding claims, characterized in that the amino group-containing (meth) acrylate polymer comprises 0.5 to 8 wt .-% of units derived from acid group-containing monomers.

7. Coating composition according to one of the preceding claims, characterized in that the amino group-containing (meth) acrylate polymer and / or the functional polymer comprise 0.5 to 30 wt .-% of units that of (meth) acrylic monomers are derived, which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical.

8. Coating composition according to one of the preceding claims, characterized in that the amino group-containing (meth) acrylate polymer and / or the functional polymer comprise units derived from

Methyl methacrylate and / or butyl (meth) acrylate are derived.

9. Coating composition according to one of the preceding claims, characterized in that the amino group-containing (meth) acrylate polymer and the functional polymer have a weight average molecular weight of at least 5000 g / mol.

A coating composition according to any one of the preceding claims, characterized in that the ratio of the weight average molecular weight of the amino group-containing (meth) acrylate polymer to the weight average molecular weight of the functional polymer is in the range of 5: 1 to 1: 5.

11. Coating composition according to one of the preceding claims, characterized in that the amino group-containing (meth) acrylate polymer and / or the functional polymer have a glass transition temperature in the range of -20 to 70 ⁰ C.

12. Coating composition according to claim 11, characterized in that the difference between the glass transition temperature of the amino group-containing (meth) acrylate polymer and the glass transition temperature of the functional polymer is at most ± 10 ° C.

13. Coating composition according to one of the preceding claims, characterized in that the coating agent is an aqueous dispersion.

14. Coating composition according to one of the preceding claims, characterized in that the coating agent comprises a crosslinking agent.

15. Coating composition according to one of the preceding claims, characterized in that the crosslinking agent comprises or releases a polyisocyanate.

16. A method for producing a coating, characterized in that a coating agent according to any one of claims 1 to 15 is applied to a substrate and cured.

17. The method according to claim 16, characterized in that the substrate is made of metal, wood, concrete or plastic.

18. A coated article obtainable by a process according to claim 16 or 17.