DE102009001965A1 - Coating composition, process for producing a coating and coated article - Google Patents

Abstract

The present invention relates to a coating composition comprising at least one (meth) acrylic polymer and at least one reactive diluent, wherein the reactive diluent at least one octadienyl group and the (meth) acrylic polymer units derived from (meth) acrylic monomers which in Alkyl radical having at least one double bond and 8 to 40 carbon atoms, and units derived from Hydroyygruppen-containing monomers having. Furthermore, the present invention relates to a method for producing a coating. Further, the present invention describes a coated article comprising a coating obtainable by the process.

Description

The The present invention relates to a coating agent. About that In addition, the present invention is directed to a method for producing a coating using the coating agent is performed, and a coated article, which is obtainable by the method.

Coating agents, in particular paints, have been produced synthetically for a long time. An important group of these agents is based on aqueous dispersions which often comprise (meth) acrylate polymers. For example, the document describes DE-A-41 05 134 aqueous dispersions containing alkyl methacrylates as binders. Furthermore, such paints are made US 5,750,751 . EP-A-1 044 993 and WO 2006/013061 known. In addition, in particular from the document DE-A-27 32 693 Coating compositions based on solvents known that can be crosslinked by polyisocyanates.

In addition to aqueous dispersions, reactive coatings form another group of known coating compositions. Such paints are for example off EP-0 693 507 known. In addition, compositions are known which comprise so-called reactive diluents. For example, the document describes EP-A-546 417 Coating compositions, in particular comprising octadienyl ethers.

The previously described coating compositions already show a good property spectrum. However, there is a permanent need for this property spectrum to improve. To show coatings made from some of the previously are available, a for elevated demands inadequate resistance to Chemicals, in particular polar solvents.

In In view of the prior art, it is now the object of the present Invention to provide coating compositions with excellent properties. These properties include in particular a high chemical resistance the coatings obtainable from the coating compositions. This should be a high stability compared to many different solvents as well as opposite Bases and acids are achieved. In particular, a should very good resistance to methyl ethyl ketone Be given (MEK).

Of Further, the hardness of the coatings consisting of the Coating materials are available, via a wide range can be varied. In particular, should especially hard, scratch-resistant coatings from the coating compositions can be obtained. Furthermore, coatings, from the coating compositions of the invention are available, relative to the hardness, a relative have low brittleness.

Farther It was therefore an object of the present invention, a coating agent provide that a particularly long shelf life and durability. Another object is to be seen in coating compositions which lead to coatings with a high gloss. The coatings available from the coating compositions should have a high weather resistance, in particular have a high UV resistance.

Farther The coating agents should have good processibility over show a large temperature and humidity range. In relation to performance, the coating agents should show improved environmental compatibility. Especially should use as small amounts of organic solvents as possible be released into the environment through evaporation.

A Another object can be seen in providing coating compositions, the very cost-effective and large-scale received can be.

Solved These and other not explicitly mentioned tasks that are however, from the contexts discussed hereinbefore readily derivable or can be deduced by a Coating composition with all features of claim 1. Expedient Modifications of the coating composition of the invention are placed in subclaims under protection. Regarding a method for producing a coating and a coated Item 17 and 19 provide a solution of the underlying tasks.

The present invention accordingly provides a coating composition comprising at least one (meth) acrylic polymer and at least one reactive diluent, which is characterized in that the reactive diluent comprises at least one octadienyl group and the (meth) acrylic polymer units derived from (meth) acrylic Monomers are derived which have at least one double bond and 8 to 40 in the alkyl radical Having carbon atoms and units derived from hydroxy-containing monomers.

Furthermore, the measures according to the invention make it possible, inter alia, to achieve the following advantages:
The coatings available from the coating compositions of the present invention show high chemical resistance. In this case, a high stability compared to many different solvents and to bases and acids can be achieved. In particular, a very good resistance to methyl ethyl ketone (MEK) is often given. Likewise, a very good resistance to water can be achieved. Therefore, these coating agents can be used for the production of protective coatings.

Further can reduce the hardness of coatings made from the coating agents are available, varied over a wide range become. In particular, particularly hard, scratch-resistant Coatings are obtained.

Farther show coatings consisting of the inventive Coating agents are available, based on the hardness and the chemical resistance, a relatively low brittleness.

About that In addition, the coating compositions according to the invention a good processability over a large temperature and humidity range. In relation to the performance the coating compositions show improved environmental compatibility. So are very small amounts of organic solvents released into the environment through evaporation. Especially preferred Embodiments show no release of organic solvents into the atmosphere. In this case, the coating compositions can high solids content.

About that In addition, coating compositions according to the invention lead to coatings with a high gloss. The coating agents of the present invention show a particularly long shelf life and durability.

The coatings obtainable from the coating compositions show a high weather resistance, in particular a high UV resistance.

Further are the coating compositions of the invention particularly inexpensive and available on an industrial scale.

The Coating composition according to the invention comprises at least a reactive diluent containing at least one octadienyl group having. These compounds accordingly comprise at least a group of the formula -R, wherein R is a radical of exactly 8 carbon atoms represents, which has two carbon-carbon double bonds. Among the preferred radicals having exactly 8 carbon atoms and 2 double bonds include in particular octa-2,7-dienyl groups, octa-3,7-dienyl groups, Octa-4,7-dienyl groups, octa-5,7-dienyl groups, octa-2,4-dienyl groups, Octa-2,5-dienyl groups, octa-2,6-dienyl groups, octa-3,5-dienyl groups, Octa-3,6-dienyl groups and octa-4,6-dienyl groups.

The preferably as reactive diluents compounds to be used can have a molecular weight in the range of 140 g / mol to 2000 g / mol, preferably 140 g / mol to 1000 g / mol, and very particularly preferably 140 g / mol to 500 g / mol.

The dynamic viscosity of the reactive diluent can be in a wide range. Expediently, a dynamic viscosity in the range from 1 to 5000 mPas, preferably 10 to 1000 mPas and very particularly preferably 10 to 500 mPas, measured according to DIN EN ISO 2555 at 25 ° C (Brookfield).

From Of particular interest are therefore reactive diluents with a Boiling point of at least 180 ° C, preferably at least 250 ° C, more preferably at least 280 ° C at atmospheric pressure (1024 mbar). According to a preferred embodiment can the boiling point of the reactive diluent at atmospheric pressure in the range of 180 to 350 ° C, more preferably in the range from 250 to 300 ° C lie.

According to one particular aspect of the present invention is the at least an octadienyl reactive diluent Alcohol, an amine, an ether or an ester.

To the preferred alcohols include in particular octa-2,7-dienol, Octa-3,7-dienol, octa-4,7-dienol, octa-5,7-dienol, octa-2,4-dienol, Octa-2,5-dienol, octa-2,6-dienol, octa-3,5-dienol, octa-3,6-dienol and octa-4,6-dienol.

To The preferred ethers include in particular compounds with an ether group selected from monoalcohols having preferably 1 to 10 carbon atoms are derived. These mono alcohols can linear, cyclic or branched present. Furthermore can be unsaturated, saturated or aromatic alcohols are used to prepare the ethers. These include in particular the methyl, ethyl, propyl, Butyl, pentyl and hexyl ethers of the previously described Octadienole. Examples of these ethers are in particular methoxyocta-2,7-diene (methyl octa-2,7-dienyl ether), Ethoxyocta-2,7-diene and propoxyocta-2,7-diene. The molecular weight preferred ethers derived from monoalcohols preferably having 1 to 10 carbon atoms are derived, is preferably 140 to 300 g / mol, more preferably 140 to 250 g / mol.

According to one another embodiment of the present invention Ethers of alcohols are used which are two, three or more Having hydroxy groups. These polyhydric alcohols are preferred 2 to 10 carbon atoms, these alcohols being linear, branched, cyclic, saturated, unsaturated or aromatic could be. These include in particular the ethers of ethylene glycol, propylene glycol, glycerol, trimethylolpropane, Pentaerythritol, di-pentaerythritol, mannitol, sorbitol, sucrose or Mixtures of such alcohols. The ethers of polyhydric alcohols with Octadienole set forth above, one, two, three or more octadienyl groups. Among the preferred compounds include in particular monoocta-4,6-dienoxyethanol, 1,2-diocta-4,6-dienoxyethane, Monoocta-4,6-dienoxy-propanediol, diocta-4,6-dienoxy-propanol, triocta-2,7-dienoxypropane, Monoocta-2,7-dienoxyethanol, 1,2-diocta-2,7-dienoxyethane, monoocta-2,7-dienoxy-propanediol, Diocta-2,7-dienoxy-propanol and triocta-2,7-dienoxypropane. These Ethers may be alone or as a mixture of two or more be used. The molecular weight of preferred ethers derived from polyhydric alcohols having preferably 2 to 10 carbon atoms are preferably 170 to 800 g / mol, particularly preferably 170 to 600 g / mol.

Next The ethers and alcohols can also be used amines. Here. can compounds with one, two or more amine groups be used. Preferred amines comprise 8 to 20 carbon atoms. The preferred amines include in particular octa-2,7-dienylamine, Octa-3,7-dienylamine, octa-4,7-dienylamine, octa-5,7-dienylamine, octa-2,4-dienylamine, Octa-2,5-dienylamine, octa-2,6-dienylamine, octa-3,5-dienylamine, octa-3,6-dienylamine, Octa-4,6-dienylamine, (methyl (octa-2,7-dienyl) amino) ethanol, (ethyl (octa-2,7-dienyl) amino) ethanol, 2-octa-2,7-dienyloxyethanol and (methyl (octa-2,7-dienyl) amino) ethylamine. The molecular weight of preferred amines is preferably 140 to 800 g / mol, more preferably 170 to 600 g / mol.

About that In addition, esters having one or more octadienyl groups are included to the preferred reactive diluents to be used. suitable Carboxylic acids from which the esters are derived can linear, branched, cyclic, saturated or unsaturated be. In addition to aliphatic acids can also aromatic Acids are used. These include in particular Esters of the previously described octadienols, those of monocarboxylic acids are derived. Preferred monocarboxylic acids have 1 to 20, preferably 1 to 10 and more preferably 1 to 4 carbon atoms on. Among the preferred monocarboxylic acids include in particular formic acid, acetic acid, propionic acid, Butanoic acid, acrylic acid and methacrylic acid. These reactive diluents preferably have exactly one octadienyl group on. The molecular weight of preferred esters, those of monocarboxylic acids are derived with preferably 1 to 20 carbon atoms, is preferably 150 to 500 g / mol, more preferably 150 to 300 g / mol.

Further may also be esters of carboxylic acids with two, three or more carboxylic acid groups are used, such as Example the esters of oxalic acid, citric acid, terephthalic acid, fumaric acid, maleic acid or adipic acid. Preferred polycarboxylic acids have 1 to 20, preferably 1 to 10 and particularly preferably 1 to 6 carbon atoms. Of particular interest here are in particular Esters of polycarboxylic acids containing one, two or more octadienyl groups exhibit. The molecular weight of preferred esters, that of polycarboxylic acids are derived with preferably 1 to 20 carbon atoms, is preferably 200 to 1000 g / mol, more preferably 300 to 600 g / mol.

The alcohols, amines, ethers or esters set forth above can be obtained, inter alia, by known methods of telomerizing 1,3-butadiene. Here, the term "telomerization" means the reaction of compounds with conjugated double bonds in the presence of nucleophiles. The in the pamphlets WO 2004/002931 submitted on 17.06.2003 to the European Patent Office with the application number PCT / EP2003 / 006356 . WO 03/031379 submitted on 01.10.2002 with the registration number PCT / EP2002 / 10971 and WO 02/100803 submitted on 04.05.2002 with the application number PCT / EP2002 / 04909 The methods set forth, in particular the catalysts used for the reaction and the reaction conditions, such as pressure and temperature, are incorporated into the present application for purposes of disclosure.

Prefers may be the telomerization of 1,3-butadiene using metal compounds, the metals of the 8th to 10th group of the Periodic Table of the Elements include, take place as a catalyst, wherein palladium compounds, in particular Palladiumcarbenkomplexe, in the previously set forth Documents are set forth in detail, particularly preferred can be used.

In particular, water, ammonia, monoalcohols, polyhydric alcohols, especially dialcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol; Diamines such as ethylenediamine, N-methylethylenediamine, N, N'-dimethylethylenediamine or hexamethylenediamine; Aminoalkanols, such as aminoethanol, N-methylaminoethanol, N-ethylaminoethanol, aminopropanol, N-methylaminopropanol or N-ethylaminopropanol, or carboxylic acids, in particular the mono- and polycarboxylic acids set forth in detail be used. The in the pamphlets WO 2004/002931 submitted on 17.06.2003 to the European Patent Office with the application number PCT / EP2003 / 006356 . WO 03/031379 submitted on 01.10.2002 with the registration number PCT / EP2002 / 10971 and WO 02/100803 submitted on 04.05.2002 with the application number PCT / EP2002 / 04909 The nucleophiles set forth are included in the present application for purposes of disclosure.

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

The Preparation of isomers from compounds containing 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 are.

Particularly according to the invention suitable reactive diluents are obtained if octadienyl ether-containing alcohols with mono- or polycarboxylic acids or with polycarboxylic anhydrides in the sense of an ester formation reaction implements. For these reactions are particularly suitable telomeres, as a basis for at least trihydric alcohols or on statistical average at least trifunctional alcohol mixtures and, on average, at least one molecule per molecule having free hydroxyl group. For the esterification reaction The telomerization products of glycerol are particularly suitable and butadiene having a hydroxyl group content of 5.5 to 17% by weight and / or the telomerization products of trimethylolpropane and butadiene having a hydroxyl group content of 4.9 to 14.0 wt%.

Furthermore, preferred reactive diluents with octadienyl groups in the document EP-A-0 546 417 , filed on 30.11.1992 at the European Patent Office with the application number EP 92120433.5 wherein the reactive diluents and methods of preparation described therein for purposes of disclosure are incorporated herein by reference.

Surprising Advantages can be achieved in particular with coating agents which are preferably 0 to 50 wt .-%, particularly preferably 5 to 30 wt .-% and most preferably 15 to 25 wt .-% reactive diluents based on the total weight of the coating agent.

Next The reactive diluent described above has an inventive Coating composition at least one (meth) acrylic polymer with units which are derived from (meth) acrylic monomers which are in the alkyl radical have at least one double bond and 8 to 40 carbon atoms.

(Meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl group are esters or amides of (meth) acrylic acid whose alkyl group has at least one carbon-carbon double bond 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 group may have one, two, three or more carbon-carbon double bonds. The polymerization conditions in which the (meth) acrylic polymer is prepared, are preferably chosen so that a possible large proportion of the double bonds of the alkyl group 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 used for the preparation of (meth) acrylic polymers (Meth) acrylic monomers which have at least one double bond in the alkyl radical and having 8 to 40 carbon atoms, is preferably at least 50, more preferably at least 100, and most preferably at least 125 g of iodine / 100 g of (meth) acrylic monomer.

worin der Rest R Wasserstoff oder Methyl darstellt, X unabhängig Sauerstoff oder eine Gruppe der Formel NR', worin R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen ist, und R¹ einen linearen oder verzweigten Rest mit 8 bis 40, vorzugsweise 10 bis 30 und besonders bevorzugt 12 bis 20 Kohlenstoffatomen bedeutet, der mindestens eine C-C-Doppelbindung aufweist.Such (meth) acrylic monomers generally correspond to the formula (I)

wherein the radical R 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 ^{1 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 transesterification of (meth) acrylates with alcohols which are at least have a double bond and 8 to 40 carbon atoms. Accordingly, (meth) acrylamides can be obtained by reaction with an amine. These reactions are for example in Ullmann's Encyclopaedia 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). explained.

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 partly commercially available or can be obtained from fatty acids, this reaction being carried out, for example, in US Pat F.-B. Chen, G. Bufkin, Journal of Applied Polymer Science, Vol. 30, 4571-4582 (1985) is set forth.

To the preferred (meth) acrylates obtainable by this method especially include octadiene-yl (meth) acrylate, Octadeca-diene-yl (meth) acrylate, octadecanetrienyl (meth) acrylate, Hexadecenyl (meth) acrylate, octadecenyl (meth) acrylate and hexadecadienyl (meth) acrylate.

About that In addition, (meth) acrylates which in the alkyl radical at least have a double bond and 8 to 40 carbon atoms, too by reaction of unsaturated fatty acids with (Meth) acrylates which are reactive in the alkyl radical, in particular alcohol radical Groups are obtained. To the reactive groups belong 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 as starting materials for the preparation the aforementioned (meth) acrylates are used.

suitable Fatty acids for reaction with the abovementioned (meth) acrylates are often commercially available and are made of natural Received 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.

To the preferred (meth) acrylates obtainable by this method In particular, (meth) acryloyloxy-2-hydroxypropyl-linoleic acid esters, (Meth) acryloyloxy-2-hydroxypropyl-linolenic acid ester and (Meth) acryloyloxy-2-hydroxypropyl-ölsäureester.

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 US Pat DE-A-41 05 134 . DE-A-25 13 516 . DE-A-26 38 544 and US 5,750,751 explained.

worin R Wasserstoff oder eine Methylgruppe, X¹ und X² unabhängig Sauerstoff oder eine Gruppe der Formel NR', worin R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen ist, mit der Maßgabe, dass mindestens einer der Gruppen X¹ und X² eine Gruppe der Formel NR' bedeutet, worin R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen darstellt, Z eine Verbindungsgruppe, und R² ein ungesättigter Rest mit 9 bis 25 Kohlenstoffatomen ist, eingesetzt werden.According to a preferred embodiment, (meth) acrylic monomers of the general formula (II),

wherein R 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 a group of the formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, and R ^{2 is} an unsaturated radical having 9 to 25 carbon atoms, are used.

worin R Wasserstoff oder eine Methylgruppe, X¹ Sauerstoff oder eine Gruppe der Formel NR', worin R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen, Z eine Verbindungsgruppe, R Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen und R² ein ungesättigter Rest mit 9 bis 25 Kohlenstoffatomen ist, erzielen.Surprising advantages can furthermore be achieved by the use of a (meth) acrylic monomer of the general formula (III)

wherein R is hydrogen or a methyl group, X ^{1 is} oxygen or a group of formula NR ', wherein R' is hydrogen or a radical having 1 to 6 carbon atoms, Z is a linking group, R is hydrogen or a radical having 1 to 6 carbon atoms and R ^{2 is} an unsaturated Rest with 9 to 25 carbon atoms, achieve.

Of the Term "radical having 1 to 6 carbon atoms" stands for a group having 1 to 6 carbon atoms. It includes aromatic and heteroaromatic groups as well as alkyl, Cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl groups as well as heteroalipatic groups. The mentioned Groups are branched or unbranched. Furthermore you can these groups are substituents, especially halogen atoms or hydroxy groups exhibit.

Preferably the radicals R 'are alkyl groups. Among the preferred Alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl group.

The Group Z preferably stands for a connection group, 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 ² in formula (II) 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, heneicosenyl, , Docosenyl, octadiene-yl, nonanediazyl, decadiene-yl, undecanediazyl, dodecadienyl, tridecadienyl, tetradecadienyl , Pentadeca-diene-yl, hexadeca-dien-yl, heptadeca-dien-yl, octadeca-dien-yl, nonadeca-dien-yl, eicosa-dien-yl, heneicosa-diene-yl , Docosa-dien-yl, tricosa-dien-yl and / or heptadeca-triene-yl group.

The preferred (meth) acrylic monomers of the formula (II) or (III) include heptadecenyloyloxy-2-ethyl (meth) acrylamide, heptadecadienyloxy-2-ethyl (meth) acrylamide, heptadeca- trienyloxy-2-ethyl (meth) acrylamide, heptadecenyloxy-2-ethyl (meth) acrylamide, (meth) acryloyloxy-2-ethyl-palmitoleic acid amide, (meth) acryloyloxy-2-ethyl-oleic acid amide, (meth) acryloyloxy 2-ethyl-icosenoic acid amide, (meth) acryloyloxy-2-ethyl-cetolenic acid amide, (meth) acryloyloxy-2-ethyl-eruca acid amide, (meth) acryloyloxy-2-ethyl-linoleic acid amide, (meth) acryloyloxy-2-ethyl-linolenic acid amide, (meth) acryloyloxy-2-propyl-palmitoleic acid amide, (meth) acryloyloxy-2-propyl-oleic acid amide, (meth) acryloyloxy 2-propyl-icosenoic 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-propyl-linolenic acid amide ,

The Notation (meth) acrylic stands for acrylic and methacrylic radicals, where methacrylic radicals are preferred. Particularly preferred monomers of formula (II) or (III) 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 (II) or (III) 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 (II) or (III). 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, reacted with one of the aforementioned amines 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 of formula (II) or (III). Transesterification of alcohols with (meth) acrylates or the preparation of (meth) acrylamides are inter alia in CN 1355161 . DE 21 29 425 filed on 14.06.71 with the German Patent Office with the application number P 2129425.7, DE 34 23 443 filed on 26.06.84 with the German Patent Office with the application number P 3423443.8 or EP-A-0 534 666 submitted on 16.09.92 to the European Patent Office with the application number EP 92308426.3 with the reaction conditions described in these references as well as the catalysts set forth therein, etc. being included in this application for purposes of disclosure. Furthermore, these reactions are in "Synthesis of Acrylic Esters by Transesterification", J. Haken, 1967 described.

in this connection can be obtained intermediates, for example carboxamides, have the hydroxy groups in the alkyl radical to be purified. According to a particular embodiment of the present Invention can obtained intermediates without consuming Purification to the (meth) acrylic monomers according to the formula (II) or (III).

worin R Wasserstoff oder eine Methylgruppe, X Sauerstoff oder eine Gruppe der Formel NR', worin R' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen ist, R³ eine Alkylengruppe mit 1 bis 22 Kohlenstoffatomen, Y Sauerstoff, Schwefel oder eine Gruppe der Formel NR'' bedeutet, worin R'' Wasserstoff oder ein Rest mit 1 bis 6 Kohlenstoffatomen darstellt, und R⁴ ein ungesättigter Rest mit mindestens 8 Kohlenstoffatomen und mindestens zwei Doppelbindungen ist.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 in particular include monomers of the general formula (IV)

wherein R 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 ^{3 is} an alkylene group having 1 to 22 carbon atoms, Y is oxygen, sulfur or a group of the formula NR '', wherein R '' is hydrogen or a radical having 1 to 6 carbon atoms, and R ^{4 is} an unsaturated radical having at least 8 carbon atoms and at least two double bonds.

In formula (IV), the radical R ^{3 is} an alkylene group having 1 to 22 carbon atoms, preferably 1 to 10, more preferably 2 to 6 carbon atoms. The radical R ³ , according to a particular embodiment of the present invention, represents 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, iso-propylene, n-butylene, iso-butylene, t-butylene or cyclohexylene group, with the ethylene group being particularly preferred.

The radical R ⁴ comprises at least two CC double bonds which are not part of an aromatic system. Preferably, the radical R ^{4 represents} a group with exactly 8 carbon atoms, which has exactly two double bonds. The radical R ⁴ preferably represents a linear hydrocarbon radical which is not ne heteroatoms. According to a particular embodiment of the present invention, the radical R ⁴ in formula (IV) may comprise a terminal double bond. In a further variant of the present invention, the radical R ⁴ in formula (IV) can not comprise a terminal double bond. The double bonds contained in the radical R ⁴ may preferably be conjugated. According to a further preferred embodiment of the present invention, the double bonds contained in the radical R ⁴ are not conjugated. Preferred R ⁴ radicals having at least two double bonds include, but are not limited to, the 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.

To the (meth) acrylic monomers of the general formula (IV) count 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-methylprop-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] acrylic acid amide ethyl (meth) acrylate, 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] acrylamide ethyl (meth) 2 - [(octa-2,4-dienyl) methylamino] acrylic acid amide ethyl (meth) acrylate, 2 - [(octa-3,5-dienyl) methylamino] acrylic acid amide ethyl (meth) acrylate, 2 - [((2-E) octa-2,7-dienyl) ethylamino] ethyl-2-methylprop-2-enoate, 2 - [((2-Z) octa-2,7-dienyl) mthylamino] 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) methylamino] ethyl-prop-2-enoate, 2 - [((3-E) octa-3,7-dienyl) methylamino] ethyl-propanol 2-enoate, 2 - [((4-Z) octa-4,7-dienyl) methylamino] ethyl-prop-2-enoate, 2 - [(octa-2,6-dienyl) methylamino] ethyl-prop-2-enoate, 2 - [(octa-2,4-dienyl) methylamino] ethyl-prop-2-enoate, 2 - [(octa-3,5-dienyl) methylamino] 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-methylprop-2-enoate, 2 - ((4-Z) octa-4,7-dienyloxy) ethyl-2-methylprop-2-yl 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 previously set forth (meth) acrylic monomers according to formula (IV) can be obtained in particular by methods in which (Meth) acrylic acid or a (meth) acrylate, in particular methyl (meth) acrylate or ethyl (meth) acrylate reacted with an alcohol and / or an amine becomes. 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 (V), HXR ³ -YR ⁴ (V), 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 ^{3 is} an alkylene group having 1 to 22 carbon atoms, Y is oxygen, sulfur or a group of the formula NR ", wherein R '' is hydrogen or a radical having 1 to 6 carbon atoms, and R ^{4 is} an at least double unsaturated radical having at least 8 carbon atoms.

With regard to the meaning of preferred radicals R ', R ", R ³ , Y and R ⁴ , reference is made to the description of the formula (IV).

The preferred starting materials according to formula (V) 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-die nyl) 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) ethylamine, (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) ethylamine, (methyl (octa-3,5-dienyl) amino) ethanol, (ethyl (octa-3,5-diene) 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 the formula (V) can be used individually or as a mixture.

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

Prefers may be the telomerization of 1,3-butadiene using metal compounds, the metals of the 8th to 10th group of the Periodic Table of the Elements include, take place as a catalyst, wherein palladium compounds, in particular Palladiumcarbenkomplexe, in the previously set forth Documents are set forth in detail, particularly preferred can be used.

When Nucleophile may in particular be dialcohols, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol; Diamines, such as ethylenediamine, N-methyl-ethylenediamine, N, N'-dimethylethylenediamine or hexamethylenediamine; or aminoalkanols, such as aminoethanol, N-methylaminoethanol, N-ethylaminoethanol, aminopropanol, N-methylaminopropanol or N-ethylaminopropanol can be used.

at Use of (meth) acrylic acid as a nucleophile can For example, octadienyl (meth) acrylates are obtained, in particular suitable as (meth) acrylic monomers having 8 to 40 carbon atoms are.

preferred Pressure and temperature values at which carried out the telomerization have been set out above, so that reference is made to this becomes.

The Preparation of isomers from compounds containing 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 are.

The (meth) acrylic polymer to be used according to the invention preferably comprises 0.5 to 60% by weight, preferably 1 to 30% by weight, more preferably 1.5 to 20 wt .-% and most preferably 2 to 15% by weight of units derived from (meth) acrylic monomers are those in the alkyl radical at least one double bond and 8 to 40 Have carbon atoms, based on the weight of the (meth) acrylic polymer.

The (Meth) acrylic polymers can preferably by free radical Polymerization can be obtained. Accordingly, the results Proportion by weight of the respective units which comprise these polymers, from the weight fractions used to prepare the polymers to corresponding monomers, since the weight fraction of groups, which are derived from initiators or molecular weight regulators, usual can be neglected.

The previously set forth (meth) acrylic monomers which in the alkyl radical at least have a double bond and 8 to 40 carbon atoms used singly or as a mixture of two or more monomers become.

Of Furthermore, according to the invention, this comprises in the coating agent to be used (meth) acrylic polymer units containing hydroxy-containing Monomers are derived.

Hydroxyl-containing monomers are compounds which, in addition to a carbon-carbon-dop Have pelbindung at least one hydroxyl group. These compounds preferably have 3 to 30, more preferably 4 to 20 and most preferably 5 to 10 carbon atoms. The carbon group of these compounds may be linear, branched or cyclic. Furthermore, these compounds may have aromatic or heteroaromatic groups. In addition to olefinic alcohols, such as allyl alcohol, these compounds include in particular unsaturated esters and ethers having a hydroxy group.

These preferably include (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.

According to one particular aspect of the present invention, the (meth) acrylic polymer 1 to 70 wt .-%, particularly preferably 5 to 60 wt .-% and very particularly preferably 10 to 40 wt .-% units which contain hydroxyl-containing Monomers are derived, based on the weight of the (meth) acrylic polymer.

Next the above-described (meth) acrylic monomers which in the alkyl radical at least have a double bond and 8 to 40 carbon atoms, and The hydroxyl-containing monomers can be used according to the invention (Meth) acrylic polymers have units that are of other monomers are derived. These comonomers include, among others Derived (meth) acrylates having 1 to 12 carbon atoms in the alkyl radical are those which have no double bonds or heteroatoms in the alkyl radical. Here are (meth) acrylates having 1 to 10 carbon atoms in the alkyl radical, which have no double bonds or heteroatoms in the alkyl radical, prefers.

The (meth) acrylates having 1 to 12 carbon atoms in the alkyl radical which have no double bonds or heteroatoms in the alkyl radical include inter alia
(Meth) acrylates having a linear or branched alkyl radical, such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate and pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 3 -iso-propylheptyl (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 dimethylnorbornyl (meth) acrylate, bornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, menthyl (meth) acrylate and isobornyl (meth) acrylate. The (meth) acrylates having 1 to 12 carbon atoms in the alkyl radical set forth above can be used singly or as a mixture.

Surprising Advantages in particular (meth) acrylic polymers, preferably 5 wt .-% to 95 wt .-%, preferably 10 wt .-% to 70 wt .-% and completely more preferably from 20% to 60% by weight of units derived from (meth) acrylates are derived with 1 to 12 carbon atoms in the alkyl radical, the have no double bonds or heteroatoms in the alkyl radical, based on the weight of the (meth) acrylic polymer.

According to one particular aspect of the present invention, the previously set forth (meth) acrylates having 1 to 12 carbon atoms in the alkyl radical which does not contain double bonds or heteroatoms in the alkyl radical should be selected such that a (meth) acrylic polymer consisting of these (meth) acrylates having 1 to 12 carbon atoms in the alkyl radical, a glass transition temperature of at least 40 ° C, preferably at least 50 ° C and especially preferably at least 60 ° C.

wobei x_n für den Massebruch (Gew.-%/100) des Monomeren n steht und Tg_n die Glasübergangstemperatur in Kelvin des Homopolymeren des Monomeren n bezeichnet. Weitere hilfreiche Hinweise kann der Fachmann dem Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975) entnehmen, welche Tg-Werte für die geläufigsten Homopolymerisate angibt. Gemäß diesem Handbuch weist beispielsweise Poly(methylmethacrylat) eine Glasübergangstemperatur von 378 K, Poly(butylmethacrylat) von 297 K, Poly(isobornylmethacrylat) von 383 K, Poly(isobornylacrylat) von 367 K und Poly(cyclohexylmethacrylat) von 356 K auf. Zur Bestimmung der Glasübergangstemperatur kann das Polymer, welches aus (Meth)acrylaten mit 1 bis 12 Kohlenstoffatomen im Alkylrest, die keine Doppelbindungen oder Heteroatome im Alkylrest aufweisen, besteht, ein Gewichtsmittel des Molekulargewichts von mindestens 100000 g/mol und ein Zahlenmittel des Molekulargewichts von mindestens 80000 g/mol aufweisen.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 be determined. 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 ° C per minute be. Furthermore, the glass transition temperature Tg can also be calculated approximately in advance by means of the Fox equation. To Fox TG, Bull. Physics Soc. 1, 3, page 123 (1956) applies:

where x _n is the mass fraction (wt .-% / 100) of monomer n and Tg _{n is} the glass transition temperature in Kelvin of the homopolymer of the monomer n denotes. Further helpful hints can the specialist the Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975) which indicates 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. For determining the glass transition temperature, the polymer consisting of (meth) acrylates having 1 to 12 carbon atoms in the alkyl group having no double bonds or heteroatoms in the alkyl group, a weight average molecular weight of at least 100,000 g / mol and a number average molecular weight of at least 80000 g / mol.

The choice of the type and amount of the previously set forth (meth) acrylates having 1 to 12 carbon atoms in the alkyl radical, which have no double bonds or heteroatoms in the alkyl radical, can via the previously set forth formula of Fox et al. respectively.

A another group of preferred monomers have an acid group on. Acid group-containing monomers are compounds which preferably free-radically with the (meth) acrylic monomers set forth above copolymerize. These include, for example Monomers having a sulfonic acid group, such as vinylsulfonic; Monomers with a phosphonic acid group, such as vinylphosphonic and unsaturated Carboxylic acids, such as methacrylic acid, Acrylic acid, fumaric acid and maleic acid. Especially 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 can be used.

From Of particular interest are (meth) acrylic polymers which 0 to 10 wt .-%, preferably 0.5 to 8 wt .-% and particularly preferably 1 to 5 wt .-% of units which contain acid groups Monomers are derived, based on the total weight of the (meth) acrylic 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 (meth) acrylate, 2,3,4,5-tetra-t-butylcyclohexyl (meth) 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 about 5 ethylene oxide units (PEM5), polybutylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate;
(Meth) acrylamides, especially N-methylol (meth) acrylamide, N, 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-laurinester, 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 amide, (meth) acryloyloxy-2-ethyl-stearic acid amide, (Meth) acryloyloxy-2-propyl-lauric acid amide, (meth) acryloyloxy-2-propyl-myristic acid amide, (meth) acryloyloxy-2-propyl palmitic acid amide and (meth) acryloyloxy-2-propyl-stearic acid amide.

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, for example, maleic anhydride, esters of maleic acid, for example dimethyl maleate, methylmaleic anhydride; and
Fumaric acid derivatives, such as dimethyl fumarate.

A another group of comonomers are styrene monomers, such as Styrene, substituted styrenes having an alkyl substituent in the Side chain, such. B. α-methylstyrene and α-ethylstyrene, substituted styrenes with an alkyl substituent on the ring, such as Vinyltuluol and p-methylstyrene, 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.

According to one particular variant of the present invention, the (meth) acrylic polymer 0 to 60 wt .-%, particularly preferably 5 to 50 wt .-% and very particularly preferably from 10 to 40% by weight of units derived from styrene monomers, in particular styrene, substituted styrenes having an alkyl substituent in the side chain, substituted styrenes with an alkyl substituent derived from ring and / or halogenated styrenes on the total weight of the (meth) acrylic polymer.

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

The Molecular weight to be used according to the invention (Meth) acrylic polymers can be in a wide range. In general the weight average molecular weight is usual at least 1000 g / mol, preferably at least 2000 g / mol and completely more preferably at least 5000 g / mol. According to one For example, first aspect of the present invention may be (Meth) acrylic polymers are used which have a relatively high molecular weight exhibit. These (meth) acrylic polymers can in particular by Emulsion polymerization can be obtained, these (meth) acrylic polymers for example, a weight average molecular weight, for example in the range of 100,000 to 10,000,000 g / mol, more preferably in Range may be from 200,000 to 500,000 g / mol. According to one Another aspect of the present invention may also be (Meth) acrylic polymers with a low molecular weight used become. These (meth) acrylic polymers may be, for example a weight average molecular weight in the range of 1000 to 150000 g / mol, in particular 4000 to 100000 g / mol, particularly preferred in the range of 5,000 to 50,000 g / mol.

The number average molecular weight of preferred (meth) acrylic polymers is in the range of 1,000 to 10,000 g / mol, more preferably in the range of 1,500 to 5,000 g / mol. Also of particular interest are (meth) acrylic 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.

According to one particular aspect of the present invention, the (meth) acrylic polymer have a molecular weight distribution with at least 2 maxima, measured according to gel permeation chromatography.

The glass transition temperature of the (meth) acrylic polymer is preferably in the range of 20 ° C to 90 ° C, more preferably in the range of 25 to 80 ° C, and most preferably in the range of 30 to 80 ° C. The glass transition temperature can be influenced by the type and proportion of monomers used to prepare the (meth) acrylic polymer. In this case, the glass transition temperature Tg of the (meth) acrylic polymer in a known manner by means of differential scanning calorimetry (DSC), in particular according to DIN EN ISO 11357 be determined. 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 ° C per minute. Furthermore, the glass transition temperature Tg can also be calculated approximately in advance by means of the previously described Fox equation.

The iodine number of (meth) acrylic polymers to be used preferably lies in the range from 1 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 according to DIN 53241-1 ,

The hydroxyl number of the polymer may preferably be in the range of 3 to 300 mg KOH / g, more preferably 20 to 200 mg KOH / g, and most preferably in the range of 40 to 150 mg KOH / g. The hydroxyl number can according to DIN EN ISO 4629 be determined.

The (meth) acrylic 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 free-radical solution polymerization. These are in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition explained.

Next Methods of classical radical polymerization can also related methods of controlled radical polymerization, such as ATRP (= atom transfer radical polymerization), NMP (nitroxide-mediated polymerization) or RAFT (= reversible Addition fragmentation chain transfer) for the preparation of the polymers be used.

The usual free-radical polymerization is, inter alia, in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition explained. In general, a polymerization initiator and optionally a molecular weight regulator are used for this purpose.

To The initiators that can be used include, among others azo initiators well known in the art, such as AIBN and 1,1-azobiscyclohexanecarbonitrile, and peroxy compounds, such as methyl ethyl ketone peroxide, acetylacetone peroxide, Dilauryl peroxide, tert-butyl per-2-ethylhexanoate, ketone peroxide, tert-butyl peroctoate, Methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane, tert-butyl peroxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, Dicumyl peroxide, 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane, Cumyl hydroperoxide, tert-butyl hydroperoxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, Mixtures of two or more of the aforementioned compounds with each other and mixtures of the aforementioned compounds with those not mentioned Compounds that can also form radicals.

The mentioned initiators can both individually and in Mixture be used. They are preferably in a crowd from 0.05 to 10.0 wt .-%, particularly preferably 5 to 8 wt .-%, based on the total weight of the monomers used.

you may also preferably the polymerization with a mixture of different Carry out polymerization of different half-life. For example, the sulfur-free molecular weight regulators include without this being a limitation is intended to be 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, preferred is dimeric α-methylstyrene.

Mercury compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides can preferably be used as the sulfur-containing molecular weight regulator. The following polymerization regulators are exemplified: di-n-butylsulfide, di-n-octylsulfide, diphenylsulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-t-butyl trisulfide and dimethyl sulfoxide. Preferred compounds used as molecular weight regulators are mercapto compounds, di alkyl 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 alkylmercaptans such as n-butylmercaptan, n-hexylmercaptan or n-dodecylmercaptan. Particularly preferably used polymerization regulators are mercapto alcohols and mercaptocarboxylic acids.

The Molecular weight regulators are preferably used in amounts of from 0.05 to 10, more preferably 0.1 to 5 wt .-% and most preferably in the range of 0.5 to 2, based on that in the polymerization used monomers. In the polymerization can Of course, mixtures of polymerization regulators be applied.

The Polymerization can be carried out at normal pressure, under- or overpressure be performed. Also the polymerization temperature is not critical. In general, however, it is in the range of -20 ° -200 ° C, preferably 50 ° -150 ° C and especially preferably 80 ° -130 ° C.

The Polymerization can be carried out with or without solvent become. The term of the solvent is hereby far to understand. Among 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, in particular isopropanol, n-butanol, isobutanol; Ethers, in particular glycol monomethyl ether, glycol monoethyl ether, glycol monobutyl ether; Aliphates, preferably pentane, hexane, cycloalkanes 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.

From Of particular interest are, in particular, coating compositions which preferably 40 to 80% by weight, particularly preferably 50 to 75% by weight at least one (meth) acrylic polymer having units derived from (meth) acrylic monomers are derived which in the alkyl radical at least one double bond and 8 to 40 carbon atoms.

According to one particular aspect of the present invention, the weight ratio from reactive diluent to (meth) acrylic polymer in the range from 10 to 90 to 90 to 10, more preferably in the range of 20 to 80 to 40 to 60 are.

The Coating compositions according to the invention can in particular by crosslinking agents that react with the hydroxy groups of the (meth) acrylic polymer to be used according to the invention can be networked.

For example For example, the present polymers having hydroxy groups can be used with Compounds that have two or more N-methylolamide groups such as polymers with repeating units, derived from N-methylolmethacrylamide. Common are used for crosslinking temperatures of at least 100 ° C, preferably at least applied.

Farther can the polymers of the invention with hydroxy groups with polyanhydrides, such as dianhydrides, in particular pyromellitic dianhydride, or polymers with two or more units derived from maleic anhydride be networked. Crosslinking with polyanhydrides may preferably at elevated temperature of, for example, at least 100 ° C, preferably at least 120 ° C.

A Another class of crosslinking agents are melamine or urea derivatives. The crosslinking with melamine or urea derivatives may preferably at elevated temperature of, for example, at least 100 ° C, preferably at least 120 ° C.

To the preferred crosslinking agents include in particular Polyisocyanates or compounds that release polyisocyanates. Polyisocyanates are compounds having at least 2 isocyanate groups.

The According to invention usable polyisocyanates can any aromatic, aliphatic, cycloaliphatic and / or (cyclo) aliphatic polyisocyanates.

Preferred aromatic polyisocyanates include 1,3- and 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, tolidine diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 4,4'-diphenylmethane diisocyanate , the Mi 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. In contrast, is meant by cycloaliphatic diisocyanates those which have only directly attached to the cycloaliphatic ring NCO groups, for. B. H ₁₂ MDI. Examples are cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane 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 and triisocyanate, undecanediol and triisocyanate, dodecandi- and triisocyanates.

Preference is given to isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), diisocyanatodicyclohexylmethane (H ₁₂ MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene 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) isocyanatomethyl-1-methylcyclohexyl isocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 2,4'-methylene-bis (cyclohexyl) diisocyanate, 1,4-diisocyanato-4-methyl-pentane.

Preferred aliphatic, cycloaliphatic and araliphatic, ie aryl-substituted aliphatic diisocyanates are, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume 14/2, pages 61-70 and in the article of W. Siefken, Justus Liebig's Annalen der Chemie 562, 75-136 described.

Of course It is also possible to use mixtures of the polyisocyanates.

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, to be obtained.

From Of particular interest are therefore coating agents which are preferably 0.5 to 10 wt .-%, particularly preferably 2 to 7 wt .-% crosslinking agent contain.

at Use of polyisocyanates as crosslinking agents can be the implementation the (meth) acrylic polymers with the organic polyisocyanates in this case, depending on the intended use of the reaction products, with 0.5 to 1.1 NCO group per hydroxyl group can be performed. The Reaction is preferably carried out so that the quantities of the organic polyisocyanate, based on the total hydroxy content the components present in the reaction mixture per hydroxyl group, in an amount of 0.7 to 1.0 isocyanate groups.

The need coating material according to the invention no siccative, but this is an optional ingredient in may be included in the compositions. These include in particular organometallic compounds, for example metal soaps of transition metals, such as cobalt, manganese, Lead, zirconium, iron, cerium; Alkali or alkaline earth metals, such as for example, lithium, potassium and calcium. For example, be exemplary Cobalt naphthalate and cobalt acetate mentioned. The siccative can be used singly or as a mixture, wherein in particular mixtures, the cobalt, zirconium and lithium salts contain, are particularly preferred.

Of the Proportion of siccatives in preferred coating compositions may preferably in the range of greater than 0 to 5 wt .-%, especially preferably in the range from greater than 0 to 3% by weight and most preferably in the range of larger 0 to 0.1 wt .-%, based on the weight of the polymer.

Next the (meth) acrylic polymers of the invention can the coating compositions of the invention solvents include. Examples of preferred solvents were previously associated with a radical polymerization so that reference is made to this. The proportion of solvent in preferred coating compositions, in particular in the field from 0 to 50, more preferably in the range of 1 to 20.

Further the coating compositions according to the invention can be customary Auxiliaries and additives such as rheology modifiers, defoamers, Water catcher (moisture-removing additives, orthoester), Deaerators, pigment wetting agents, dispersing additives, substrate wetting agents, Slip and leveling additives, which are preferably each in an amount from 0 wt .-% to 3 wt .-%, based on the total formulation included as well as water repellents, plasticizers, Thinner, in particular further reactive thinner, UV stabilizers and adhesion promoters, preferably each in an amount of from 0% to 20% by weight, based on the total formulation may be included.

Further the coating compositions according to the invention can be customary Fillers and pigments, such as. Talc, calcium carbonate, Titanium dioxide, carbon black, etc. in an amount up to 50 wt .-% of Total composition can be added.

The drawing coating composition according to the invention characterized by an excellent range of properties, which in particular excellent processability with excellent Quality of the coating obtained. preferred Coating agents can be processed in a wide temperature window be, preferably a width of at least 20 ° C, in particular at least 30 ° C, without compromising the quality the coating, which is characterized in particular by a high solvent and water resistance impaired becomes. Accordingly, a preferred coating agent in a temperature of 15 ° C, 20 °, 30 ° C or 40 ° C are processed without any significant Quality impairment is measurable.

The dynamic viscosity of the coating agent is dependent on the solids content and the nature of the reactive diluent and may include a wide range. So this can be more than 20,000 mPas at high polymer content. Expediently, a dynamic viscosity in the range from 10 to 10000 mPas, preferably 100 to 8000 mPas and very particularly preferably 1000 to 6000 mPas, measured according to DIN EN ISO 2555 at 25 ° C (Brookfield).

A surprising good processability moreover show coating compositions, their solids content preferably at least 50 wt .-% especially preferably at least 60 wt .-% is.

at given solids content, the inventive Coating agent over a much wider temperature range be processed as previously known coating agent. at comparable processing properties are the invention Coating agent by a surprisingly high solids content from, so that the coating compositions of the invention are particularly environmentally friendly.

Farther the present invention provides a method for producing a Coating ready, in which an inventive Coating agent applied to a substrate and cured becomes.

The Coating agent according to the invention can be prepared by conventional Application methods, such as dipping, rolling, flooding, casting, in particular by brushing, rolling, spraying (high pressure, Low pressure, airless or electrostatic (ESTA)) are applied. The curing of the coating agent is carried out by drying and by oxidative crosslinking by means of atmospheric oxygen. According to one special aspect of the present invention may be a crosslinking with a crosslinking agent, in particular a polyisocyanate become.

To the substrates, preferably with a novel Coating can be provided include in particular metals, in particular iron and steel, zinc and galvanized Steels, as well as plastics and concrete substrates.

About that In addition, the present invention provides coated articles available, which by an inventive Procedures are available. The coating of these objects is characterized by an excellent range of properties.

Preferred coatings obtained from the coating compositions of the invention exhibit high mechanical resistance. The pendulum hardness is preferably at least 30 s, preferably at least 50 s and very particularly preferably at least 100 s, measured according to DIN ISO 1522 ,

Furthermore, preferred coatings which are obtainable from the coating compositions of the invention have 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 0 according to the Standard DIN EN ISO 2409 be achieved.

The coatings obtainable from the coating compositions according to the invention generally exhibit high solvent resistance, with only small amounts in particular being dissolved out of the coating by solvents. Preferred coatings exhibit excellent resistance, in particular to polar solvents, in particular alcohols, for example 2-propanol, or ketones, for example methyl ethyl ketone (MEK), non-polar solvents, for example diesel fuel (alkanes). After an exposure of 15 minutes and subsequent drying (24 hours at room temperature), preferred coatings according to the present invention exhibit a pendulum hardness according to DIN ISO 1522 of at least 120 seconds, preferably at least 150 seconds. In addition, the coating compositions of the invention can be designed so that they show a high resistance to acids and bases.

In addition, preferred coatings show a surprisingly good cupping. According to particular modifications of the present invention, coatings have a depth of at least 4.5 mm, more preferably at least 5.0 mm, measured according to DIN 53156 (Erichsen).

following the present invention is based on examples and comparative examples be explained without this being a limitation should be done.

Preparation of a mixture of methacryloyloxy-2-ethyl-fatty acid amides (MUMA)

In a four-necked round bottom flask equipped with a saber stirrer with mixing sleeve and stirring motor, nitrogen inlet, Equipped with a sump thermometer and a distillation bridge 206.3 g (0.70 mol) of fatty acid methyl ester mixture, 42.8 g (0.70 mol) of ethanolamine and 0.27 g (0.26%) submitted LiOH. The fatty acid methyl ester mixture comprised 6% by weight of saturated C12 to C16 fatty acid methyl ester, 2.5% by weight saturated C17 to C20 fatty acid methyl ester, 52 wt .-% monounsaturated C18 fatty acid methyl ester, 1.5% by weight monounsaturated C20 to C24 fatty acid methyl ester, 36 wt .-% polyunsaturated C18 fatty acid methyl ester, 2 wt .-% polyunsaturated C20 to C24 fatty acid methyl ester.

The Reaction mixture was heated to 150 ° C. Within After 2 h, 19.5 ml of methanol were distilled off. The obtained reaction product contained 86.5% fatty acid ethanolamides. The resulting reaction mixture was further processed without purification.

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

Under The reaction apparatus was stirred for 10 minutes with nitrogen rinsed. Thereafter, the reaction mixture was heated to boiling. The methyl methacrylate / methanol azeotrope was separated and then the head temperature gradually increased to 100 ° C. To Upon completion of the reaction, the reaction mixture was at about 70 ° C cooled and filtered.

At the Rotary evaporator became excess methylmethacrylate separated. It could be obtained 370 g of product.

example 1

In a reaction vessel, 30.0 g of solvent (Solvesso 100) were introduced and heated to 140 ° C. Oxygen in the reaction vessel was removed by introducing nitrogen. Subsequently was a reaction mixture containing 17.37 g of di-tert-butyl peroxide (DTBP), 46.64 g of isobornyl methacrylate (IBOMA), 69.97 hydroxyethyl methacrylate (HEMA), 23.32 g of ethylhexyl methacrylate (EHMA), 23.32 g of methacryloyloxy 2-ethyl-fatty acid amide (MUMA), 69.97 g of styrene and 4.17 g of 2-mercaptoethanol were added over a period of 4 hours. Subsequently, the reaction was continued for 30 minutes with stirring. Thereafter, the mixture was cooled to 80 ° C. To complete the reaction, a mixture comprising 0.24 g of di-tert-butyl peroxide (DTBP) and 15 g of solvent (Solvesso 100) was added, followed by stirring for a further 2 hours at 80 ° C. The mixture was then further stirred for 30 minutes without heating.

Of the Polymer content was reduced by the addition of 18.75 g of n-butyl acetate and 69.2 g 2,7-Octadienylmethylether adjusted to 65%.

The Properties of the coating agent thus obtained were examined. For this purpose, a film with a thickness of about 50 microns formed of an aluminum plate, wherein the polymer film by adding of polyisocyanate (hexamethylene diisocyanate, HDI 50/60 NCO / OH) and Dibutyltin dilaurate (DBTL, 0.01% by weight, based on polymer weight) was networked.

The Hardness or scratch resistance of the crosslinked polymer film was examined by determining pendulum hardness. The Resistance to chemicals was investigated by using the polymer film was treated with methyl ethyl ketone. Subsequently was measured the pendulum hardness of the film. As criterion serves in particular a softening of the film by the treatment with the solvent. The brittleness of the film was examined by deepening experiments according to Erichsen. Furthermore, the adhesive strength of the coating by a Crosshatch test determined.

The The results obtained are shown in Table 1.

Comparative Example 1

In To a reaction vessel was added 50.01 g of solvent (Solvesso 100) and heated to 140 ° C. Oxygen, which was in the reaction vessel was through Introducing nitrogen away. Subsequently, a Reaction mixture containing 15.33 g of di-tert-butyl peroxide (DTBP), 41.15 g isobornyl methacrylate (IBOMA), 61.73 hydroxyethyl methacrylate (HEMA), 20.58 g of ethylhexyl methacrylate (EHMA), 20.58 g of methacryloyloxy-2-ethyl-fatty acid amide (MUMA), 61.73 g of styrene and 3.69 g of 2-mercaptoethanol a period of 4 hours. Subsequently was the reaction continued for 30 minutes with stirring. After that the mixture was cooled to 80 ° C. To complete The reaction was a mixture comprising 0.21 g of di-tert-butyl peroxide (DTBP) and 15 g of solvent (Solvesso 100) added, then stirred at 80 ° C for a further 2 hours has been. The mixture was then further stirred for 30 minutes without heating.

Of the Polymer content was reduced to 65% by adding 46.16 g of n-butyl acetate. set.

Out the resulting coating composition was a film according to the prepared in Example 1. The properties The coatings obtained were compared with the investigation methods set out above determined, the results obtained in Table 1 set forth are.

Comparative Example 2

In a reaction vessel was 100.02 g of solvent (Solvesso 100) and heated to 140 ° C. Oxygen, which was in the reaction vessel was through Introducing nitrogen away. Subsequently, a Reaction mixture containing 30.66 g of di-tert-butyl peroxide (DTBP), 82.31 g isobornyl methacrylate (IBOMA), 123.46 hydroxyethyl methacrylate (HEMA), 82.31 g of ethylhexyl methacrylate (EHMA), 123.46 g of styrene and 7.38 g 2-mercaptoethanol over a period of 4 hours added. Subsequently, the reaction for Continued for 30 minutes with stirring. After that the mixture was cooled to 80 ° C. To complete The reaction was a mixture comprising 0.42 g of di-tert-butyl peroxide (DTBP) and 10 g of solvent (Solvesso 100) added, then stirred at 80 ° C for a further 2 hours has been.

Subsequently another 40 g of solvent (Solvesso 100) were added, while still stirring for 30 minutes without heating.

Of the Polymer content was reduced to 65% by adding 92.31 g of n-butyl acetate. set.

From the resulting coating composition, a film was prepared according to the procedure set forth in Example 1 produced. The properties of the coatings obtained were determined by the test methods set out above, the results of which are shown in Table 1. Table 1: Properties of the investigated coating compositions example 1 Comparative Example 1 Comparative Example 2 IBOMA [% by weight] 20 20 20 HEMA [% by weight] 30 30 30 EHMA [% by weight] 10 10 20 MUMA [% by weight] 10 10 - Styrene [% by weight] 30 30 30 Solids content [wt .-%] 65 65 65 Solvent [% by weight] 16.2 35 35 Reactive diluents [% by weight] 18.8 - - Pendulum hardness [s] 189 192 186 Resistance to MEK according to pendulum hardness [s] 176 112 84 Recess [mm] 5.1 5.4 5.3 Cross-hatch [Gt] 0 0 0

The Previous examples show that the coatings are continuous a very good pendulum hardness, good adhesion and have a relatively low brittleness (subsidence test).

Surprised For example, the (meth) acrylic polymers containing MUMA have a somewhat higher content higher pendulum hardness, although the number of carbon atoms significantly larger in the alkyl radical of the methacrylate is as in EHMA. Furthermore, the (meth) acrylic polymers with a MUMA content significantly increased solvent resistance against polar solvents. When using a reactive diluent This resistance can be surprising Measure be increased.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

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Claims (19)

Coating composition comprising at least one (meth) acrylic polymer and at least one reactive diluent, characterized in that the reactive diluent at least one octadienyl group and the (meth) acrylic polymer units which are derived from (meth) acrylic monomers which in the alkyl radical at least one Having double bond and 8 to 40 carbon atoms, and units derived from hydroxyl-containing monomers has. Coating composition according to claim 1, characterized in that the molecular weight of the reactive diluent 140 g / mol to 500 g / mol. Coating composition according to claim 1 or 2, characterized in that the boiling point of the reactive diluent at least 180 ° C at normal pressure. (1024 mbar) is. Coating composition according to at least one of the preceding claims, characterized the reactive diluent is an alcohol, amine, ester and / or Ether is. Coating composition according to at least one of the preceding claims, characterized the (meth) acrylic polymer has a weight average molecular weight of at least 2000 g / mol. Coating composition according to claim 5, characterized in that the (meth) acrylic polymer is a weight average of the molecular weight in the range of 4000 to 100000 g / mol. Coating composition according to at least one of the preceding claims, characterized the (meth) acrylic polymer has an iodine value in the range from 5 to 100 Iodine per 100 g of (meth) acrylic polymer. Coating composition according to at least one of the preceding claims, characterized the (meth) acrylic polymer has a hydroxyl number in the range from 3 to 300 mg KOH / g. Coating composition according to at least one of the preceding claims, characterized the (meth) acrylic polymer contains from 1 to 20% by weight of units derived from (Meth) acrylic monomers are derived which in the alkyl radical at least a double bond and having from 8 to 40 carbon atoms. Coating composition according to at least one of the preceding claims, characterized the (meth) acrylic polymer contains from 1 to 70% by weight of units derived from Hydroxy-containing monomers. Coating composition according to at least one of the preceding claims, characterized the (meth) acrylic polymer contains from 5 to 95% by weight of units derived from (Meth) acrylates having 1 to 12 carbon atoms derived in the alkyl radical are those which have no double bonds or heteroatoms in the alkyl radical comprises. Coating composition according to at least one of the preceding claims, characterized the coating agent comprises a crosslinking agent. Coating composition according to claim 12, characterized in that the crosslinking agent is a polyisocyanate includes or releases. Coating composition according to at least one of the preceding claims, characterized that the coating agent 5 to 30 wt .-% reactive diluent includes. Coating composition according to at least one of the preceding claims, characterized the coating composition comprises a siccative. Coating composition according to claim 15, characterized in that the coating agent 1 to 20 Wt .-% solvent. Process for producing a coating, characterized in that a coating agent according to any one of claims 1 to 16 applied to a substrate and cured. A method according to claim 17, characterized characterized in that the substrate is made of metal. Coated article, available through a method according to claim 17 or 18.