WO2012038197A1

WO2012038197A1 - Coating agent having (meth)acrylic polymers and coalescence additives

Info

Publication number: WO2012038197A1
Application number: PCT/EP2011/064785
Authority: WO
Inventors: Gerold Schmitt; Christine Maria BREINER; Thorben SCHÜTZ; Wolfgang Klesse; Matthias Urbanek
Original assignee: Evonik Röhm Gmbh
Priority date: 2010-09-23
Filing date: 2011-08-29
Publication date: 2012-03-29
Also published as: DE102010041272A1; TW201226480A

Abstract

The invention relates to an aqueous coating agent comprising at least one dispersion of a (meth)acrylic polymer and at least one coalescence additive, wherein the (meth)acrylic polymer comprises units derived from (meth)acrylic monomers, comprising at least one double bond in the alkyl radical and 8 to 40 carbon atoms, and the coalescence additive comprises at least one ethylenically unsaturated double bond and a molecular weight of less than 1000 g/mol.

Description

Coating agent with (meth) acrylic polymers and

coalescence

The present invention relates to an aqueous coating composition comprising a dispersion of a (meth) acrylic polymer and a coalescing aid.

Coating agents, in particular paints, have been produced synthetically for a long time. An important group of these funds is based on water

Dispersions that include multiple (meth) acrylate polymers. For example, the publication DE-A-41 05 134 describes aqueous dispersions which contain alkyl methacrylates as binders. Furthermore, such paints from US 5,750,751, EP-A-1 044 993, WO 2006/013061 and WO 2008/094503 are known. The coating agents described above already show a good

Spectrum of properties. However, there is a permanent need to improve this property spectrum.

In particular, it is disadvantageous that the coating agents described above in some cases show insufficient processability for elevated demands. Accordingly, those described in US 5,750,751

Coating agents should be added to organic solvents. These solvents are to be avoided for reasons of environmental protection. An improvement in this regard is made by the teaching of the document

Achieved EP-A-1 044 993. This document describes aqueous dispersions based on (meth) acrylates. The mixtures to be polymerized include (meth) acrylates which have been modified by unsaturated fatty acids. An essential aspect of this solution is the use of polymers having a particularly broad molecular weight distribution, wherein the number average molecular weight in the range of 300 to 3000 g / mol. However, a disadvantage of this system is that the films obtained are too soft for many applications.

Furthermore, document WO 2006/013061 describes dispersions which

Particles based on (meth) acrylates include. The for the production of

Particle monomer mixtures include (meth) acrylates modified by unsaturated fatty acids. A disadvantage of the in WO

2006/013061 described dispersions are in particular their complex preparation and the high proportion of residual monomers.

In addition to aqueous dispersions, reactive paints form another group of known coating agents. Such paints are for example off

EP-0 693 507 is known. In addition, compositions are known which comprise so-called reactive diluents. For example, this describes

Document EP-A-546 417 Coating compositions, which

especially octadienyl ethers. Coating agents with reactive solvents are disclosed, inter alia, in US 2009 / 151601A1, wherein said publications do not disclose polymers with (meth) acrylates which have been modified by unsaturated fatty acids.

The coating media described above already show a good

Spectrum of properties. However, there is a permanent need to improve this property spectrum. Thus, coatings obtainable from some of the coating agents set out above exhibit insufficient mechanical resistance, in particular scratch resistance, for high demands. Other coating agents show very high levels

Minimum film forming temperatures, so that must be added to their processing solvent. In view of the prior art, it is an object of the present invention to provide coating compositions which

have excellent property profile. To these properties In particular, features included by coating agents and

Coatings that are available from the coating materials, be apparent. In particular, the coating agent should be very environmentally friendly. This includes that they should have a very low residual monomer content and should release only small amounts of organic compounds into the environment during processing. Furthermore, it was therefore an object of the present invention

To provide coating agent, which has a particularly long shelf life and durability. Furthermore, the hardness of the coatings obtainable from the coating compositions should be able to be varied over a wide range. In particular, should be particularly hard, scratch-resistant

Coatings can be obtained.

The coatings obtainable from the aqueous dispersions should have a high weather resistance, in particular a high UV resistance. In addition, the films obtainable from the aqueous dispersions should have a low tackiness after a short time.

Furthermore, the coatings obtainable from the coating compositions should show a high chemical resistance. Here, a high stability compared to many different solvents and to bases and acids should be achieved. In particular, a very good resistance to methyl isobutyl ketone (MIBK) should be given.

The coating compositions should continue to show a good processability, which is particularly clear by a low minimum film-forming temperature, without thereby affecting the mechanical properties or the

Chemical resistance of the available from the coating agents

Coatings is adversely affected. A further object can be seen in providing coating compositions which 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 solved by an aqueous dispersion having all the features of patent claim 1. Appropriate modifications of the

Dispersion are provided in subclaims under protection. The present invention accordingly provides an aqueous coating composition comprising at least one dispersion of a (meth) acrylic polymer and at least one auxiliary coalescence aid, which is characterized in that the (meth) acrylic polymer comprises units which are protected by (meth) acrylic Monomers are derived which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical, and

Coalescence auxiliary has at least one ethylenically unsaturated double bond and a molecular weight of less than 1000 g / mol.

The coating compositions of the invention have an excellent property profile. In particular, the invention

Coating agent very environmentally friendly, which have a very low content of residual monomers and release only small amounts of organic compounds into the environment during processing. The hardness of the coatings consisting of inventive

Coating may be available, which in turn are based on the polymers or compositions can be varied over a wide range. Surprisingly, in particular mechanically stable coatings can be obtained, which are characterized by a high elongation at break and / or a high tensile strength. Furthermore, coatings which consist of the inventive

Coating may be available, based on the hardness and the

Chemical resistance, a relatively low brittleness. According to a preferred modification, in particular particularly hard, scratch-resistant coatings can be obtained according to the invention. The coatings obtainable from the dispersions of the present invention show a surprisingly high solvent resistance, which is particularly evident in experiments with methyl isobutyl ketone (MIBK), ammonia solutions or ethanol. Thus, the coatings obtained, in particular in tests according to the furniture test DIN 68861 -1 an excellent classification.

The coating compositions of the present invention show, in particular, good processability, which becomes apparent in particular through a low minimum film-forming temperature, without adversely affecting the mechanical properties or the chemical resistance of the coatings obtainable from the coating compositions. At comparable

Chemical resistance or comparable pendulum hardness from the

Therefore, the coating compositions of the present invention exhibit a particularly low minimum film-forming temperature. At comparable

Minimum film-forming temperature of the dispersions show the coatings obtainable from these improved chemical resistance and increased pendulum hardness.

In addition, the dispersions of the invention show a high

Storage stability, high durability and a very good

Storability. In particular, hardly any aggregate formation occurs. In relation to the performance, the dispersions show improved environmental compatibility. Preferred embodiments hardly show one

Release of organic compounds, in particular solvents in the atmosphere. Furthermore, the coating compositions have an extremely low residual monomer content.

Those obtainable from the coating compositions of the invention

Coatings show a high weather resistance, in particular a high UV resistance. Furthermore, the films obtainable from the dispersions have a low tackiness after a short time.

The coating compositions according to the invention can be produced inexpensively on a large scale. The coating compositions according to the invention are environmentally friendly and can be processed and produced safely and without great effort. Here, the coating compositions of the invention show a very high shear stability. The coating compositions according to the invention are aqueous dispersions.

Accordingly, they include an aqueous phase in the

Polymer particles dispersed. The term "dispersion" is in the

Known in the art. The aqueous coating compositions comprise at least one

Coalescence aid. The term "coalescence aid" is known in the art, by which are meant additives that the

Minimum film forming temperatures of those contained in the dispersions

Reduce polymers. The presently used coalescence aids have a molecular weight of at most 1000 g / mol, preferably at most 800 g / mol. Preferably, the molecular weight of the

Coalescence aid in the range from 120 to 600 g / mol, more preferably in the range from 140 to 500 g / mol. According to a particular embodiment of the present invention, the coalescing aid comprises at most 30, preferably at most 20, in particular at most 15 and more preferably at most 8

Carbon atoms.

Coalescence aids are therefore of particular interest with a

Boiling point of at least 140 ° C, preferably at least 180 ° C, more preferably at least 190 ° C at atmospheric pressure (1013 mbar). According to a preferred embodiment, the boiling point of the coalescing aid at normal pressure in the range of 140 to 350 ° C, more preferably in the range of 180 to 300 ° C.

According to the invention, the coalescing aid has at least one,

preferably at least two ethylenically unsaturated double bonds. In this case, preferred coalescing aids have a ratio of

Carbon atoms to ethylenically unsaturated double bonds in the range of 3: 1 to 8: 1, more preferably 4: 1 to 6: 1 on.

Preferably, the coalescing aid may have an HLB value in the range of 3 to 19, more preferably in the range of 9 to 16, calculated according to the method of Griffin (a) Griffin, W.C., J. Soc. Cosmetic Chem, 1, 31 1 (1949), b) ICI Bulletin, HLB System, 8, (1984).

According to a particular aspect of the present invention, the coalescence aid to be used according to the invention is an alcohol, an amine, an ether or an ester, particularly preferably an ester or an alcohol.

Preferably, the coalescing aid comprises at least two ethylenically unsaturated double bonds. Accordingly, preference is given to compounds which have dienyl groups and / or are derived from polybasic compounds, for example dihydric or higher-valued alcohols and / or acids, in particular carboxylic acids.

According to a particular aspect of the present invention are

in particular coalescence aids which at least one Have octadienyl group. Preferably, the coalescing aid may be an alcohol, an amine, an ether or an ester. These compounds accordingly comprise at least one group of the formula -R, wherein R represents a residue of exactly 8 carbon atoms, which has two carbon-carbon double bonds. The preferred residues with exactly 8

In particular, carbon atoms and 2 double bonds include 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 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.

In addition, esters with one or more octadienyl groups are among the coalescence aids which are preferably used. Suitable carboxylic acids from which the esters are derived may be linear, branched, cyclic, saturated or unsaturated. In addition to aliphatic acids and aromatic acids can be used. These include, in particular, esters of the above-described octadienols which are derived from monocarboxylic acids.

Preferred monocarboxylic acids have 1 to 20, preferably 1 to 10 and particularly preferably 1 to 4 carbon atoms. Among the preferred

Monocarboxylic acids include in particular formic acid, acetic acid,

Propanoic acid, butanoic acid, acrylic acid and methacrylic acid. These

Coalescence aids preferably have exactly one octadienyl group. The molecular weight of preferred esters derived from monocarboxylic acids

preferably 1 to 20 carbon atoms are derived, is preferably 150 to 500 g / mol, particularly preferably 150 to 300 g / mol.

Furthermore, esters of carboxylic acids with two, three or more

Carboxylic acid groups are used, such as the esters of Oxalic acid, citric acid, terephthalic acid, fumaric acid, maleic acid or adipic acid. Preferred polycarboxylic acids have 2 to 20, preferably 2 to 10 and particularly preferably 2 to 6 carbon atoms. Of particular interest here are in particular esters of

Polycarboxylic acids having one, two or more octadienyl groups. The molecular weight of preferred esters derived from polycarboxylic acids

preferably 1 to 20 carbon atoms are derived, is preferably 200 to 1000 g / mol, more preferably 300 to 600 g / mol. The ethers include, in particular, compounds having an ether group derived from monoalcohols having preferably 1 to 10 carbon atoms. These monoalcohols may be linear, cyclic or branched. In addition, unsaturated, saturated or aromatic alcohols can be used to prepare the ethers. These include, in particular, the methyl, ethyl, propyl, butyl, pentyl and hexyl ethers of the octadienols set forth above. Examples of these ethers are in particular methoxyocta-2,7-diene (methyl octa-2,7-dienyl ether), ethoxy octa-2,7-diene and propoxy octa-2,7-diene. The molecular weight of preferred ethers derived from monoalcohols with

preferably 1 to 10 carbon atoms are derived, is preferably 140 to 300 g / mol, more preferably 140 to 250 g / mol. Particularly preferred ethers are compounds derived from oligo- or polyalkylenes which, in addition to at least one octadienyl group, comprise alkylene oxide units, where, for example, ethers having 2 to 40, more preferably 3 to 10, ethylene oxide units and / or propylene oxide units are particularly preferred. These include, for example, diethylene glycol octa-2,7-dienyl ether, triethylene glycol octa-2,7-dienyl ether, tetraethylene glycol octa-2,7-dienyl ether, pentaethylene glycol octa-2,7-dienyl ether, hexaethylene glycol octa-2, 7-dienyl ether, dipropylene glycol octa-2,7-dienyl ether, tripropylene glycol octa-2,7-dienyl ether, tetrapropylene glycol octa-2,7-dienyl ether, pentapropylene glycol octa-2,7-dienyl ether and hexapropylene glycol octa-2, 7-dienyl ethers. According to another embodiment of the present invention, ethers of alcohols may be used which are two, three or more

Having hydroxy groups. These polyhydric alcohols preferably have 2 to 10 carbon atoms, which alcohols may be linear, branched, cyclic, saturated, unsaturated or aromatic. 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 the polyhydric alcohols with octadienols set forth above may in this case have one, two, three or more octadienyl groups. 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 used singly or as a mixture of two or more. The molecular weight of preferred ethers derived from polyhydric alcohols having preferably 2 to 10 carbon atoms is preferably 170 to 800 g / mol, more preferably 170 to 600 g / mol.

Besides ethers and alcohols, amines can also be used.

Here, compounds with one, two or more amine groups can 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. Among the classes of compounds mentioned, particular preference is given to alcohols and ethers having two or more alkylene oxide units, with alcohols being particularly preferred. The alcohols, amines, ethers or esters set out 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

Nucleophilic. The processes set forth in the publications WO 2004/002931, WO 03/031379 and WO 02/100803, in particular the catalysts used for the reaction and the reaction conditions, such as, for example, pressure and temperature, are incorporated into the present application for the purpose of disclosure. 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, in the previously set forth

References are set forth in more detail, can be used with particular preference.

In particular, water, ammonia, monoalcohols, polyhydric alcohols, in particular dialcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol; Diamines, such as ethylenediamine, N-methylethylenediamine, Ν, Ν'-dimethylethylenediamine or hexamethylenediamine;

Aminoalkanols, such as aminoethanol, N-methylaminoethanol, N-ethylaminoethanol, aminopropanol, N-methylaminopropanol or N-ethylaminopropanol, or carboxylic acids, in particular the previously detailed mono- and polycarboxylic acids are used. The publications WO 2004/002931, WO 03/031379 and WO 02/100803

The nucleophiles set forth are disclosed for purposes of disclosure in U.S. Pat

present application inserted. 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 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.

Coalescing aids which are particularly suitable according to the invention are obtained when alcohols having octadienyl ether groups are reacted with monocarboxylic or polycarboxylic acids or with polycarboxylic anhydrides in the sense of a

Reacting esterification reaction. For these reactions are particularly suitable telomeres, which are based on at least trihydric alcohols or randomly at least trifunctional alcohol mixtures, and which have on average per molecule at least one free hydroxyl group. Particularly suitable for the esterification reaction are the telomerization of glycerol and butadiene with a

Hydroxylgruppengehalt of 5.5 to 17 wt .-% and / or the

Telomerization of trimethylolpropane and butadiene with a

Hydroxyl group content of 4.9 to 14.0 wt .-%.

Furthermore, preferred coalescence aids with octadienyl groups are set forth in the document EP-A-0 546 417, with those described therein

Reactive diluents and methods of making them for purposes of disclosure are incorporated herein by reference.

According to a further preferred aspect of the present invention, esters of carboxylic acids with two, three or more can also be used in particular

Carboxylic acid groups are used as coalescing aids, such as the esters of oxalic acid, malonic acid, citric acid, the Terephthalic acid, fumaric acid, maleic acid or adipic acid having at least one, preferably at least two ethylenically unsaturated double bonds. Preferred polycarboxylic acids have 2 to 20, preferably 2 to 10 and particularly preferably 2 to 6 carbon atoms. In this case, esters of ethylenically unsaturated alcohols which have 2 to 6, preferably 2 to 4, carbon atoms are particularly preferred.

These include in particular allyl alcohol and vinyl alcohol. Accordingly, in particular, diallyl malonate, divinyl malonate and tnallyl citrate are preferred, with diallyl malonate being particularly preferred.

In addition to the coalescing aid set out above, a

Coating composition according to the invention at least one aqueous dispersion comprising at least one (meth) acrylic polymer with units derived from

(Meth) acrylic monomers are derived, which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical.

The term polymer means that the dispersion contains compounds which can be obtained by reaction of (meth) acrylic monomers which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical with each other or with other monomers, this reaction being carried out in one step or in stages.

The dispersion may contain one or more polymers which

Repeating units derived from (meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl radical. These polymers may be, for example, in the proportion of (meth) acrylic monomers which in the alkyl radical at least one

Have double bond and 8 to 40 carbon atoms, or in the

Chain length, solubility or other properties

differ. The polymer may preferably be obtained by radical polymerization. Accordingly, the term repeat unit results from the monomers used to prepare the polymer. (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 radical 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 the largest possible proportion of the double bonds of the alkyl radical in the

Polymerization is maintained. This can be done, for example, by steric

Prevent the double bonds contained in the alcohol residue. 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 to be used in the alkyl radical having 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 of iodine / 100 g of (meth) acrylic monomer. 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 having at least one C-C double bond.

The notation (meth) acrylic stands for acrylic and methacrylic radicals, where

Methacryl radicals are preferred.

(Meth) acrylic monomers which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical can be synthesized, for example, by esterification of (meth) acrylic acid, reaction of (meth) acryloyl halides and / or (meth) acrylic anhydride or transesterification of (meth) acrylates be obtained with alcohols containing at least one double bond and 8 to 40

Have carbon atoms. Accordingly, (meth) acrylamides can be obtained by reaction with an amine. These reactions are

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 partly 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 in the alkyl radical at least one

Have double bond and 8 to 40 carbon atoms, also 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 as well

Epoxy groups. Accordingly, for example, too

Hydroxylalkyl (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-containing (meth) acrylates, for example glycidyl (meth) acrylate can be used as starting materials for the preparation of the aforementioned (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 (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. 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 radical having 9 to 25

Carbon atoms, achieve.

The term "radical having 1 to 6 carbon atoms" means a group having 1 to 6 carbon atoms

heteroaromatic groups and also alkyl, cycloalkyl, alkoxy, cycloalkoxy, alkenyl, alkanoyl, alkoxycarbonyl groups and heteroalipatic groups. The groups mentioned can be branched or unbranched. Furthermore, these groups may have substituents, in particular halogen atoms or hydroxyl groups.

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

The group Z 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 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 the nonenyl,

Decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl,

Heneicosenyl, docosenyl, octadiene-yl, nonanediazyl, decadiene-yl, undecadienyl, dodeca-diene-yl, trideca-diene-yl, tetradeca- diene -yl, pentadeca-diene 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-trien-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- trienoyloxy-2-ethyl (meth) acrylamide, heptadecenyloyloxy-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-erucic 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-propyllinolenic acid amide. The notation (meth) acryl stands for acrylic and methacrylic radicals, with methacrylic radicals being preferred. Particularly preferred monomers of the 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 formula (II) or (III) can be

obtained in particular by multistage processes. In a first stage, for example, one or more unsaturated fatty acids or

Fatty acid esters with an amine, for example, ethylenediamine, ethanolamine, propylenediamine or propanolamine, to be reacted to 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 give the To obtain monomers of the formula (II) or (III). For production 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, may correspondingly first be an alkyl (meth) acrylate, for example

Methyl (meth) acrylate, with one of the aforementioned amines to a

(Meth) acrylamide are reacted with 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) acrylic acid amides are described inter alia in CN 1355161, DE 21 29 425, DE 34 23 443 or

EP-A-0 534 666, wherein the reaction conditions described in these references as well as the catalysts set forth therein, etc. are included for the purposes of disclosure in this application. 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 (II) or (III).

Furthermore belong to the (meth) acrylic monomers with 8 to 40, preferably 10 to 30 and particularly prefers 12 to 20 carbon atoms and

at least one double bond in the alkyl radical, in particular 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 ", where 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 with 1 to 10, particularly preferably with 2 to 6 carbon atoms. The radical R ³ represents according to a special

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, 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 has no 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. Among the preferred radicals R ⁴ , the at least two

The double bonds include, among others, 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. The (meth) acrylic monomers of the general formula (IV) 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-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] acrylic acid amide ethyl (meth) acrylate,

2 - [((2-Z) octa-2,7-dienyl) methylamino] acrylic acid amide ethyl (meth) acrylate,

2 - acrylamide [((3-E) octa-3,7-dienyl) methylamino] ethyl (meth) acrylate,

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) methylamino] ethyl-propanol 2-enoate, 2 - [((3-E) octa-3,7-dienyl) methylamino] ethyl-prop-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-methylpropyl 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 (V),

HX-R-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.

As regards the meaning of preferred radicals R ', R ", R ^3, Y and R ⁴ to the description of the formula (IV) is referenced.

The preferred starting materials of the 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) ethyl amine, (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) ethyl amine,

(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) ethyl amine,

(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) ethyl amine,

(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) ethyl amine,

(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) ethyl amine,

(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) ethyl amine,

(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) ethyl amine. The educts of the formula (V) can be used individually or as a mixture. The educts of formula (V) can be, inter alia, by known

Process of telomerization of 1, 3-butadiene obtained. Here, the term "telomerization" means the reaction of compounds with conjugated double bonds in the presence of nucleophiles The processes set forth in the publications WO 2004/002931, WO 03/031379 and WO 02/100803, in particular the catalysts used for the reaction and the

Reaction conditions, such as pressure and temperature, are included in the present application for purposes of disclosure.

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, in the previously set forth References are set forth in more detail, 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, Ν, Ν'-dimethylethylenediamine 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. Preferred pressure and temperature values at which the telomerization can be carried out have been set forth above, so that reference is hereby made.

The (meth) acrylic polymer to be used according to the invention comprises

preferably from 0.5 to 60% by weight, preferably from 1 to 40% by weight, particularly preferably from 1.5 to 25% by weight and very particularly preferably from 2 to 20% by weight of units derived from (meth) derived from acrylic monomers having in the alkyl radical at least one double bond and 8 to 40 carbon atoms, based on the weight of the (meth) acrylic polymer. The (meth) acrylic polymers can preferably be obtained by free-radical polymerization. Accordingly, the proportion by weight of the respective units which comprise these polymers results from that for the production % of the monomers used in the corresponding monomers, since the proportion by weight of groups derived from initiators or

Molecular weight regulators are derived, usually negligible. 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.

In addition to repeating units derived from at least one of the above-described (meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl group, preferred polymers contained in the dispersions of the present invention may include recurring units derived from more

Monomers are derived.

These copolymerizable monomers include, but are not limited to, monomers having an acid group, monomers A comprising ester groups

Styrene monomers. Acid group-containing monomers are compounds which are preferably free-radical with the photoinitiator monomers set forth above

copolymerize. These include, for example, monomers having a sulfonic acid group, such as 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. The preferred ester groups comprising monomers A include in particular (meth) acrylates which differ from the monomers described above, fumarates, maleates and / or vinyl acetate. The expression (Meth) acrylates include methacrylates and acrylates as well as mixtures of both. These monomers are well known.

The comonomers mentioned include, inter alia, (meth) acrylates having 1 to 10 carbon atoms in the alkyl radical, which are not

Have double bonds or heteroatoms in the alkyl radical.

The (meth) acrylates having 1 to 10 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, iso-propyl (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; and

Cycloalkyl (meth) acrylates, such as cyclopentyl (meth) acrylate,

Cyclohexyl (meth) acrylate, bornyl (meth) acrylate, norbornyl (meth) acrylate and isobornyl (meth) acrylate. The above-described (meth) acrylates having 1 to 10 carbon atoms in the alkyl group may be used singly or as a mixture.

According to a particular aspect of the present invention are

in particular (meth) acrylic polymers which comprise a high proportion of (meth) acrylates having 1 to 6, preferably 1 to 4 and particularly preferably 1 or 2, carbon atoms in the alkyl radical, these monomers having no double bonds or heteroatoms in the alkyl radical. Accordingly, particularly preferred are (meth) acrylic polymers which are at least 20,

preferably at least 40, more preferably at least 50 and most preferably at least 55% by weight of methyl (meth) acrylate,

preferably have methyl methacrylate. The weight ratio of methyl (meth) acrylate to (meth) acrylates having 2 to 10 carbon atoms in the

Alkyl radical which has no double bonds or heteroatoms in the alkyl radical, According to a particular embodiment of the present invention, it can be at least 0.5: 1, more preferably at least 2: 1, this weight ratio preferably being in the range from 10: 1 to 1: 2, more preferably 6: 1 to 1: 1, and very particularly preferably 4: 1 to 3: 2.

Another class of comonomers are (meth) acrylates having at least 1 1 carbon atoms in the alkyl radical, which are derived from saturated alcohols and have no heteroatoms in the alkyl radical, such as

Undecyl (meth) acrylate, 5-methylundecyl (meth) acrylate, dodecyl (meth) acrylate, 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- (meth) acryloyloxyethyl) -2-pyrrolidone, 2- (3-oxazolidinyl) ethyl methacrylate, N- (2- (meth) acryloyloxyethyl) ethylene urea, N- (2- (meth) acrylamidoethyl) ethylene urea);

Carbonyl group-containing (meth) acrylates such as acetoacetyloxyethyl methacrylate (AAEMA);

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, benzophenone methacrylate (BPMA) or phenyl (meth) acrylate, where the aryl radicals are each unsubstituted or up to may be substituted four times;

(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 (meth) acrylate,

1, 10-decanediol (meth) acrylate,

Glycerol mono (meth) acrylate and

polyalkoxylated derivatives of (meth) acrylic acid, in particular

Polypropylene glycol mono (meth) acrylate having 2 to 10, preferably 3 to 6 propylene oxide, preferably polypropylene glycol monomethacrylate with about 5 propylene oxide units (PPM5), polyethylene glycol mono (meth) acrylate having 2 to 10, preferably 3 to 6 ethylene oxide units, preferably

Polyethylene glycol monomethacrylate having 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,

Diacetone acrylamide (DAAM), methacrylamide and acrylamide;

Glycerincarbonatmethacrylat;

2-carbamoyloxyethyl methacrylate and

(Meth) acrylates derived from saturated fatty acids, such as

(Meth) acryloyloxy-2-hydroxypropyl palmitic acid ester, (meth) acryloyloxy-2-hydroxypropyl stearic acid ester and (meth) acryloyloxy-2-hydroxypropyl laurin ester.

Another class of comonomers are crosslinking monomers. These monomers have at least two double bonds with similar reactivity in a free-radical polymerization. These include, in particular, (meth) acrylates derived from diols or higher alcohols such as glycol di (meth) acrylates, such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetra- and polyethylene glycol di (meth) acrylate, 1,3-butanediol (meth) acrylate,

1, 4-butanediol (meth) acrylate, 1,6-hexanediol di (meth) acrylate,

Glycerol di (meth) acrylate, dimethacrylates of ethoxylated bisphenol A and diurethane dimethacrylate; (Meth) acrylates having three or more double bonds, e.g. Glycerol tri (meth) acrylate, trimethylol propane tri (meth) acrylate,

Pentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) acrylate. 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,

methyl maleic anhydride; and fumaric acid derivatives, such as

Dimethyl fumarate.

Another group of comonomers are styrenic monomers, such as

Example styrene, substituted styrenes having an alkyl substituent in the

Side chain, such. For example, α-methylstyrene and α-ethylstyrene, substituted styrenes having an alkyl substituent on the ring, such as vinyltoluene 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.

Surprising advantages in particular (meth) acrylic polymers, preferably 1 wt .-% to 99 wt .-%, preferably 20 wt .-% to 95 wt .-% and most preferably 40 wt .-% to 90 wt. -% of units derived from (meth) acrylates having 1 to 10 carbon atoms in the alkyl radical, which have no double bonds or heteroatoms in the alkyl radical, based on the weight of the (meth) acrylic polymer.

Of particular interest are, in particular, (meth) acrylic polymers which contain 0 to 10% by weight, preferably 0.5 to 8% by weight and more preferably 1 to 5% by weight, of units derived from acid groups Monomers are derived, based on the weight of the (meth) acrylic polymer.

According to a particular modification of the present invention, the (meth) acrylic polymer according to the invention may comprise 0 to 60% by weight, more preferably 5 to 50% by weight and most preferably 10 to 40% by weight of units derived from Styrene monomers, in particular of styrene, substituted styrenes having an alkyl substituent in the side chain, substituted styrenes with an alkyl substituent on the ring and / or halogenated styrenes are derived, based on the weight of the (meth) acrylic polymer.

In addition, preferred are (meth) acrylic polymers which have a very small proportion of (meth) acrylates having two or more carbon-carbon double bonds having a reactivity identical to a (meth) acrylate group. According to a special

Modification of the present invention is the proportion of compounds having two or more (meth) acrylate groups preferably at most 5 wt .-%, in particular at most 2 wt .-%, particularly preferably at most 1 wt .-%, particularly preferably at most 0 5 wt .-% and especially preferably at most 0, 1 wt .-% limited, based on the weight of the (meth) acrylic polymer.

Preferred polymers to be used according to the invention comprise

0.5 to 60 wt .-%, preferably 1 to 40 wt .-% and particularly preferably 2 to 20 wt .-% of units derived from (meth) acrylic monomers having in the alkyl radical at least one double bond and 8 bis Have 40 carbon atoms;

0 to 99% by weight, preferably 30 to 95% by weight and more preferably 40 to 90% by weight of units derived from monomers A comprising ester groups;

0 to 10% by weight, preferably 1 to 8% by weight of units derived from monomers having an acid group;

0 to 10 wt .-%, preferably 1 to 5 wt .-% of one or more monomers selected from N- (2- (meth) acryloyloxyethyl) ethylene urea, N- (2-

(Meth) acrylamidoethyl) ethylene urea, acetoacetyloxyethyl methacrylate, diacetonacylamide, benzophenone methacrylate.

0 to 50% by weight of units derived from styrenic monomers; and 0 to 50% by weight of units derived from other comonomers; the data in each case relate to the total weight of the polymer.

According to a further preferred modification, polymers to be used according to the invention comprise polymers

0.5 to 60 wt .-%, preferably 1 to 30 wt .-% and particularly preferably 4 to 20 wt .-% of units derived from (meth) acrylic monomers having in the alkyl radical at least one double bond and 8 bis Have 40 carbon atoms;

0 to 99 wt .-%, preferably 30 to 95 wt .-% and particularly preferably 40 to 90 wt .-% of units derived from (meth) acrylates having 1 to 6 carbon atoms in the alkyl radical;

0 to 10% by weight, preferably 1 to 8% by weight of units derived from monomers having an acid group; 0 to 50 wt .-% of units derived from styrene monomers and

0 to 50 wt .-% units derived from other comoners, wherein the data in each case relate to the total weight of the polymer. Furthermore, core-shell polymers can be used as (meth) acrylic polymer, wherein the outermost shell of the core-shell polymer preferably has a (meth) acrylate segment, the

From 1 to 30% by weight, preferably from 15 to 25% by weight, of units derived from

(Meth) acrylic monomers are derived which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical,

0, 1 to 10 wt .-% of units derived from acid group-containing monomers, and

50 to 98.9 wt .-% units of (meth) acrylates having 1 to 6

Carbon atoms are derived in the alkyl radical, each based on the

Weight of the (meth) acrylate segment.

The iodine number of the polymers to be used according to the invention is 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 iodine number can in particular also be measured by means of a dispersion according to the invention.

Suitably, the polymer to be used according to the invention can be a

Acid number in the range of 0 to 40 mg KOH / g, preferably 1 to 20 mg KOH / g and most preferably in the range of 2 to 20 mg KOH / g. The acid number can also be determined according to DIN EN ISO 21 14 by means of a dispersion.

The hydroxyl number of the polymer to be used according to the invention may preferably be in the range from 0 to 200 mg KOH / g, more preferably 1 to 100 mg KOH / g and most preferably in the range from 3 to 50 mg KOH / g lie. The hydroxyl number can also be determined by dispersion according to DIN EN ISO 4629.

The particle radius of the polymers to be used according to the invention can be within a wide range. Thus, in particular emulsion polymers having a particle radius in the range of 1 to 500 nm, preferably 10 to 100 nm, preferably 10 to 59 nm can be used. According to another aspect of the present invention, the radius of the particles is preferably in the range of 60 nm to 500 nm, more preferably 70 to 150 nm, and all

more preferably 75 to 100 nm. The radius of the particles can be determined by PCS (Photon Correlation Spectroscopy), wherein the

refer to the d50 value (50% of the particles are smaller, 50% are larger). For example, a Beckman Coulter N5

Submicron Particle Size Analyzer can be used.

The glass transition temperature of the polymer is preferably in the range of 0 ° C to 70 ° C, more preferably in the range of 5 to 60 ° C and most preferably in the range of 10 to 50 ° C. The

Glass transition temperature can be influenced by the type and proportion of monomers used to make the polymer. It can the

Glass transition temperature Tg of the polymer in a known manner by means

Differential scanning calorimetry (DSC), in particular according to DIN EN ISO

1 1357 can be determined. Preferably, the glass transition temperature as

Center of the glass stage of the second heating curve can be determined with 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 Fox equation.

After Fox TG, Bull. Am. 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 expert the polymer Handbook 2 Edition, J. Wiley & Sons, New York (1975), which gives Tg values for the most common homopolymers. In this case, the polymer may have one or more different glass transition temperatures. This information is therefore valid for a segment that is covered by

Polymerization of a monomer mixture according to the invention is available.

Preferably, the dispersions of the (meth) acrylic polymers to be used according to the invention with units derived from (meth) acrylic monomers which in the alkyl radical have at least one double bond and 8 to 40

Have carbon atoms, a minimum film formation temperature of at least 10 ° C, more preferably at least 25 ° C and most preferably at least 40 ° C, which can be measured according to DIN ISO 21 15. These values refer to a dispersion that is not

Coalescence aid contains.

The architecture of the polymer is not critical to many applications and properties. Accordingly, the polymers, in particular the emulsion polymers, can be random copolymers, gradient copolymers,

Block copolymers and / or graft copolymers. Block copolymers or gradient copolymers can be obtained, for example, by reacting the monomer composition during chain growth

changed discontinuously. According to a preferred aspect of the present invention, the emulsion polymer is a random copolymer in which the monomer composition is substantially constant throughout the polymerization. However, because the monomers are different

Copolymerization parameters may have the exact

Varying composition over the polymer chain of the polymer.

The polymer, preferably the emulsion polymer, may be a homogeneous polymer which, for example in an aqueous dispersion, forms particles having a uniform composition. In this case, for example, the emulsion polymer may consist of one or more segments exist, which are obtainable by polymerization of the monomers or monomer mixtures set forth above.

In another embodiment, the polymer may comprise multiple segments. For example, an emulsion polymer having a core-shell structure which may have one, two, three or more shells may be employed. Here, the segment which is obtainable by polymerization of the monomer mixture shown above, preferably forms the outermost shell of the core-shell polymer. The shell may be connected to the core or inner shells via covalent bonds. Furthermore, the shell can be polymerized without grafting on the core or an inner shell. In this embodiment, the segment, which by

Polymerization of the previously set forth monomers or monomer mixtures is available, often separated by suitable solvents from the core and isolated.

Preferably, the weight ratio of segment obtained by polymerizing a monomer mixture with (meth) acrylic monomers obtainable in the alkyl radical having at least one double bond and 8 to 40 carbon atoms to core in the range of 10: 1 to 1: 6 is particularly preferred 5: 1 to 1: 3 lie.

The core may preferably be formed from polymers comprising from 50 to 100% by weight, preferably from 60 to 90% by weight, of units derived from

(Meth) acrylates are derived. Preference is given here to esters of

(Meth) acrylic acid whose alcohol radical preferably comprises 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and most preferably 1 to 10 carbon atoms. These include in particular

(Meth) acrylates derived from saturated alcohols, such as

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate,

iso-propyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate and pentyl (meth) acrylate, hexyl (meth) acrylate. According to a particular embodiment of the present invention, a mixture comprising methacrylates and acrylates can be used to produce the core. Thus, in particular mixtures of methyl methacrylate and acrylates having 2 to 6 carbons, such as ethyl acrylate, butyl acrylate and hexyl acrylate can be used.

In addition, the polymers of the core may be those set forth above

Comonomers include. According to a preferred modification, the core may be crosslinked. This crosslinking can be achieved by the use of monomers having two, three or more free-radically polymerizable double bonds. Allyl methacrylate is the preferred polyunsaturated monomer when shell grafting onto the core is desired.

The shell of preferred emulsion polymers to be used may preferably comprise from 15 to 50% by weight of units derived from (meth) acrylic monomers having at least one double bond and from 8 to 40 carbon atoms in the alkyl radical.

According to a particular aspect, the core may preferably be a

Glass transition temperature in the range of -30 to 200 ° C, more preferably in the range of -20 to 150 ° C. The shell may preferably have a glass transition temperature in the range of -30 ° C to 70 ° C, more preferably in the range of -0 to 50 ° C and most preferably in the range of 10 to 40 ° C. According to a particular aspect of the present invention, the glass transition temperature of the core may be greater than the glass transition temperature of the shell. Appropriately, the

Glass transition temperature of the core at least 10 ° C, preferably at least 20 ° C above the glass transition temperature of the shell. Comprising the (meth) acrylic polymers set forth above

Repeating units derived from (meth) acrylic monomers having in the alkyl group at least one double bond and 8 to 40 carbon atoms can be prepared in a known manner, for example by solution, bulk or emulsion, wherein also variants of these polymerization processes, such as ATRP (= Atom Transfer Radical Polymerization), NMP process (Nitroxide Mediated

Polymerization) or RAFT (= Reversible Addition Fragmentation Chain

Transfer) can be used. Preferably, the polymerization is carried out as emulsion polymerization.

Methods of emulsion polymerization are set forth, inter alia, in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition. In general, an aqueous phase is prepared for this purpose, which is customary in addition to water

Additives, in particular emulsifiers and protective colloids for stabilizing the emulsion may include. Monomers are then added to this aqueous phase and polymerized in the aqueous phase. The addition of the monomers may be continuous or batchwise as a mixture or emulsion in water over a period of time. The emulsion polymerization can be carried out, for example, as a mini or as

Microemulsion be carried out. The more detailed 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 pm. 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 thereby be obtained. 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 the preparation of homogeneous emulsion polymers can

preferably a monomer mixture are used, which preferably comprises 0.5 to 60 wt .-%, more preferably 1 to 40 wt .-% of (meth) acrylic monomers having in the alkyl radical at least one double bond and 8 to 40 carbon atoms.

In the preparation of core-shell polymers, the composition of the monomer mixture can be changed stepwise, wherein before changing the composition, the polymerization is preferably up to a conversion of at least 80 wt .-%, particularly preferably at least 95 wt .-%, each based on the Total weight of the monomer mixture used is polymerized. 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 mixture for producing the core preferably comprises from 50 to 100% by weight of (meth) acrylates, with a mixture of acrylates and methacrylates being particularly preferably used. After the core has been prepared, it is preferably possible to graft or polymerize onto the core a monomer mixture which comprises from 1 to 60% by weight, preferably from 15 to 25% by weight, of (meth) acrylic monomers which have at least one double bond in the alkyl radical and 8 to 40 carbon atoms.

The emulsion polymerization is preferably carried out at a temperature in the range of 0 to 120 ° C, particularly preferably in the range of 30 to 100 ° C. In this case, polymerization temperatures in the range of greater than 60 to less than 90 ° C, suitably in the range of greater than 70 to less than 85 ° C, preferably in the range of greater than 75 to less than 85 ° C, proved to be particularly favorable.

The initiation of the polymerization is carried out with the for

Emulsion polymerization common 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, especially ammonium, sodium and

Potassium. 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,

especially sodium and potassium peroxodisulfate. Further details may be found in the specialist literature, in particular H. Rauch-Puntigam, Th. Völker, "Acrylic and

Methacrylic compounds ", Springer, Heidelberg, 1967 or Kirk-Othmer,

Encyclopedia 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

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

Sulfonates, preferably alkylsulfonates having 8 to 18 carbon atoms in the alkyl radical, alkylarylsulfonates 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 can also be from 1 to 40

Be ethoxylated 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

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.

The particularly preferred anionic emulsifiers include, in particular, fatty alcohol ether sulfates, diisooctyl sulfosuccinate, lauryl sulfate, C15 paraffin sulfonate, these compounds generally being usable as the alkali metal salt, in particular as the sodium salt. These compounds may in particular be sold under the trade names Disponil® FES 32, Aerosol® OT 75, Texapon® K1296 and Statexan® K1 are commercially available from 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. In this case, mixtures containing a sulfate, in particular a fatty alcohol ether sulfate, a lauryl sulfate, or a sulfonate, in particular a Diisooctylsulfosuccinat or a paraffin sulfonate as an anionic emulsifier and a

Alkylphenol ethoxylate or a fatty alcohol polyethylene glycol ethers, which in each case preferably have 8 to 20 carbon atoms in the alkyl radical and 8 to 40 ethylene oxide units, have proven particularly useful as nonionic emulsifier.

Optionally, the emulsifiers can also be used in admixture with protective colloids. Suitable protective colloids include u. a. partially hydrolyzed polyvinyl acetates, polyvinylpyrrolidones, carboxymethyl, methyl, hydroxyethyl, hydroxypropyl cellulose, starches, proteins, poly (meth) acrylic acid,

Poly (meth) acrylamide, polyvinylsulfonic, Melaminformaldehydsulfonate, Naphthalinformaldehydsulfonate, styrene-maleic acid and

Vinyl ether 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 submitted or added. Furthermore, it is also possible to submit a portion of the initiator and to meter in the remainder.

Preferably, the polymerization by heating the batch on the

Polymerization temperature and metered addition of the initiator, preferably in aqueous solution started. The dosages of emulsifier and monomers can be carried out separately or as a mixture, in particular as an emulsion in water. In the metered addition of mixtures of emulsifier and monomer, the procedure is such that emulsifier and monomer are premixed in a mixer upstream of the polymerization reactor or emulsified in water. Preferably, a portion of the monomers, e.g. 1 - 10%, presented in the reactor and the polymerization started by addition of initiator. With the dosage of the remaining monomers is preferably after the initiation of the polymerization, e.g. Started 5 to 15 minutes after the start of the polymerization.

Preferred emulsion polymers having a high content of insoluble polymers can be obtained in the manner set forth above, the reaction parameters for obtaining a high molecular weight being known. Thus, in particular, the use of

Molecular weight regulators are dispensed with. If a small proportion of insoluble polymers is desired, the use of

Be helpful to molecular weight regulators. 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.

The dispersion is preferably adjusted to a pH of 7 to 10 after the preparation or during the preparation of a coating formulation by the addition of alkali. For the preparation of the aqueous dispersions according to the invention, an emulsion polymer set forth above with one or more

Coalescence aid be mixed. The mixing of emulsion polymer with at least one

Coalescence aid may preferably be carried out at a temperature in the range from -10 to 50 ° C, more preferably in the range from 0 to 40 ° C. This can be done after the polymerization or only during the formulation into a coating medium.

The proportions by weight of coalescing aid and (meth) acrylic polymer comprising repeating units derived from (meth) acrylic monomers having in the alkyl radical at least one double bond and 8 to 40

Carbon atoms can be in a wide range, which can be generally adapted to the desired property profile. Preferably, the weight ratio of

Coalescence aid to (meth) acrylic polymer comprising

Repeating units derived from (meth) acrylic monomers having in the alkyl group at least one double bond and 8 to 40 carbon atoms in the range of 1: 1 to 1: 100, more preferably 1: 5 to 1: 50, and most preferably 1: 10 to 1: 30.

The aqueous dispersions can be used as Beschichtungsm ittel. 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.

For the preparation of a coating composition according to the invention

preferably a polymer dispersion are used, which has a dynamic viscosity in the range of 0, 1 to 10,000 mPas, preferably 1 to 1000 mPas and most preferably 10 to 500 mPas, measured according to DIN EN ISO 2555 at 25 ° C (Brookfield) , In addition to water, coalescing aids and the above-described (meth) acrylic polymers comprising repeating units derived from (meth) acrylic monomers which have at least one double bond and 8 to 40 carbon atoms in the alkyl radical, the novel coating compositions or the aqueous compositions to be used according to the invention Dispersions contain additives or other components to the

Properties of the coating to adapt to specific requirements. These additives include in particular

Drying aids, so-called siccatives, flow improvers, pigments and dyes.

The coating compositions of the invention do not require siccatives, but these may be included as an optional ingredient in the compositions. Desiccatives can be particularly preferred for the aqueous

Dispersions are added. These include in particular

organometallic compounds, for example metal soaps of

Transition metals such as cobalt, manganese, lead, zirconium; Alkali or alkaline earth metals such as lithium, potassium and calcium.

As an 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 coating compositions according to the invention preferably have a

Minimum film formation temperature of at most 50 ° C, more preferably at most 30 ° C and most preferably at most 20 ° C, which can be measured according to DIN ISO 21 15.

The aqueous dispersions with the abovementioned coalescence aids of the present invention can be used in particular as a coating agent or as an additive. These include in particular paints,

Impregnating agents, adhesives and / or primers. Especially preferred For example, the aqueous dispersions for the production of paints or

Impregnating agents for applications on wood and / or metal serve.

Available from the coating compositions of the invention

Coatings show a high solvent resistance, in particular, only small proportions are dissolved by solvent from the coating. Preferred coatings show a high resistance in particular to methyl isobutyl ketone (MIBK). So is the

Weight loss after treatment with MIBK preferably at most 50 wt .-%, preferably at most 35 wt .-%. The uptake of MIBK is preferably at most 500% by weight, particularly preferably at most 300% by weight, based on the weight of the coating used. These values are measured at a temperature of approx. 25 ° C and a contact time of

measured at least 4 hours, with a completely dried

Coating is measured. In this case, the drying takes place in the presence of oxygen, for example air, in order to allow crosslinking.

The coatings obtained from the coating compositions of the invention show a high mechanical resistance. The pendulum hardness is preferably at least 25 s, preferably at least 35 s, particularly preferably at least 50 s, measured in accordance with 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 100%, particularly preferably at least 200%, measured in accordance with DIN EN ISO 527 Part 3.

In addition, coatings are still preferred, the one

Tensile strength, measured according to DIN EN ISO 527 Part 3, of at least 0.5 MPa, more preferably at least 2 MPa show. Furthermore, the present invention surprisingly provides coatings which have a tensile strength of at least 1 MPa, particularly preferably at least 2 MPa, an elongation at break of at least 100%, particularly preferably at least 200%.

Furthermore, preferred coatings are distinguished from the

coating compositions according to the invention are available, 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 by way of examples and

Comparative examples are explained in more detail, without thereby a

Restriction is to take place.

Production Example 1

Preparation of the methacryloyloxy-2-ethyl-fatty acid amide mixture used In a four-necked round-bottomed flask equipped with a saber stirrer with stirring sleeve and stirring motor, nitrogen inlet, sump thermometer and a

Distillation bridge was equipped, 206.3 g (0.70 mol)

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 saturated C12 to C16 fatty acid methyl ester, 2.5% by weight saturated C17 to C20 fatty acid methyl ester, 52% by weight monounsaturated C18

Fatty acid methyl ester, 1, 5 wt .-% 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 2 h, 19.5 ml of methanol were distilled off. The resulting reaction product contained 86.5% fatty acid ethanolamides. The resulting reaction mixture was without

Processing further processed.

After cooling, 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 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 ° C. After completion of the reaction, the reaction mixture was cooled to about 70 ° C and filtered.

Excess methyl methacrylate was separated on a rotary evaporator. 370 g of product (MUMA II) were obtained.

Preparation of the dispersion (MMA-co-BA-MUMA II - MAS 64-20-15-1)

First, 280 g of butyl acrylate (BA), 896 g of methyl methacrylate (MMA), 210 g of methacryloyloxy-2-ethyl-fatty acid amide mixture, 14 g of methacrylic acid (MAS), 4.2 g of ammonium peroxodisulfate (APS) were used in a 2 l PE beaker. , 42.0 g of Disponil FES 32 (30%) and 1202 g of water emulsified by Ultra-Turrax for 3 minutes at 4000 rpm.

In a 2 l glass reactor, which could be tempered with a water bath and was equipped with a paddle stirrer, 830 g of water and 1:05 g of Disponil FES 32 (30%) were initially charged, heated to 80 ° C and with 1, 05 g

Ammonium peroxodisulfate (APS) dissolved in 10 g of water. 5 minutes after the APS addition, the previously prepared emulsion was within 240 Minutes (interval: 3 minutes inflow, 4 minutes pause, 237 minutes remaining inflow).

After the end of the feed was stirred at 80 ° C for 1 hr. It was then cooled to room temperature and the dispersion was filtered through VA mesh with 0.09 mm mesh size.

The prepared dispersion had a solids content of 39.5%, a pH of 5.9, a viscosity of 1 1 m Pas, an r _N 5 value of 91 nm and a minimum film-forming temperature of 52 ° C.

Preparation Example 2 (MMA-co-BA-MUMA II - MAS 59-25-15-1)

Preparation Example 1 was substantially repeated but using a monomer mixture comprising 350 g of butyl acrylate (BA), 826 g of methyl methacrylate (MMA), 210 g of methacryloyloxy-2-ethyl-fatty acid amide mixture, 14 g of methacrylic acid (MAS).

The dispersion produced had a solids content of 39.7%, a pH of 5.8, a viscosity of 12.5 mPas, an r _N 5 value of 73 nm and a minimum film-forming temperature of 36.5 ° C.

Preparation Example 3 (MMA-co-BA-MUMA I - MAS 64-20-15-1)

First, 280 g of butyl acrylate (BA), 896 g of methyl methacrylate (MMA), 210 g of methacryloyloxy-2-hydroxypropyl linoleic acid ester, 14 g of methacrylic acid (MAS), 4.2 g of ammonium peroxodisulfate (APS), 42 were used in a 2 l PE beaker , 0 g Disponil FES 32 (30%) and 1202 g of water are emulsified by Ultra-Turrax for 3 minutes at 4000 rpm. The methacryloyloxy-2-hydroxypropyl linoleic acid ester was obtained by reaction of linoleic acid with glycidyl methacrylate. In a 2 l glass reactor, which could be tempered with a water bath and equipped with a paddle stirrer, 835 g of water and 1.05 g of Disponil FES 32 (30% strength) were introduced, heated to 80 ° C and with 1, 05 g

Ammonium peroxodisulfate (APS) dissolved in 10 g of water. 5 minutes after the addition of APS, the previously prepared emulsion was metered in within 240 minutes (interval: 3 minutes feed, 4 minutes break, 237 minutes residual feed).

The prepared dispersion had a solids content of 39.8%, a pH of 2.5, a viscosity of 14 mPas. a r _N 5 value of 71 nm and a minimum film formation temperature of 44.0 ° C.

Preparation Example 4 (MMA-co-BA-MUMA I - MAS 59-25-15-1)

Preparation Example 3 was substantially repeated but using a monomer mixture comprising 350 g of butyl acrylate (BA), 826 g of methyl methacrylate (MMA), 210 g of methacryloyloxy-2-hydroxypropyl linoleic acid ester, 14 g of methacrylic acid (MAS).

The dispersion produced had a solids content of 39.8%, a pH of 2.3, a viscosity of 13.5 mPas, an r _N 5 value of 74 nm and a minimum film-forming temperature of 34.5 ° C.

Preparation Example 5 (MMA-co-BA-MUMA I - MAS 64-20-15-1) First, in a 2 l PE beaker, 80 g of butyl acrylate (BA), 273.9 g of methyl methacrylate (MMA), 70.9 g Methacryloyloxy-2-hydroxypropyl linoleic acid ester, 4.28 g methacrylic acid (MAS), 1, 2 g ammonium peroxodisulfate (APS), 12.0 g of Disponil FES 32 (30%) and 375.5 g of water were emulsified by Ultra-Turrax at 4000 rpm for 3 minutes. The Methacryloyloxy-2-hydroxypropyl linolsäureester was by reaction of linoleic acid with

Glycidyl methacrylate obtained.

In a 2 l glass reactor, which could be tempered with a water bath and was equipped with a paddle stirrer, 230 g of water and 0.3 g of Disponil FES 32 (30% strength) were introduced, heated to 80 ° C and 0.3 g

The dispersion produced had a solids content of 38.5%, a pH of 2.5, a viscosity of 14 m Pas, an r _N 5 value of 59 nm and a minimum film-forming temperature of 41 ° C.

From the dispersions set out above were inventive

Coating medium prepared by addition of coalescence aids. In particular, 2,7-octadienol and 2,7-octadienol ^* 5 PO (molar mass 416 g / mol) were used for this purpose. In particular, the humiliation of the

Minimum film-forming temperature, the chemical resistance and the mechanical properties of the coating compositions obtained examined. Examples 1 to 14

Lowering the minimum film-forming temperature by adding 2,7-octadienol.

The dispersions set forth in Preparation Examples 1 and 3 were mixed with varying amounts of 2,7-octadiene-1-ol, the

Lowering the minimum film forming temperature (MFT) was measured. The data obtained and the amounts of 2,7-octadienol used are set forth in Tables 1 and 2. The data relate to the weight of the respective components, wherein the data of the dispersion refer to the solids content.

Table 1 :

2,7-octadienol dispersion according to MFT [%] Preparation Example 1 [% [° C] based on

Solids content]

0 100 52

Example 1 2 98 46.5

Example 2 4 96 34.5

Example 3 6 94 25.5

Example 4 8 92 17

Example 5 12 88 <0

Example 6 16 84 <0

Example 7 20 80 <0 Table 2:

Examples 15 to 19

Lowering the minimum film-forming temperature by adding 2,7-octadienol ^* 5 PO

The dispersion set forth in Preparation Example 3 was mixed with different amounts of 2,7-octadienol ^* 5 PO, the lowering of the

Minimum film forming temperature (MFT) was measured. The data obtained and the amounts of 2,7-octadienol ^* 5 PO used are set forth in Table 3. The information refers to the weight of the respective

Components, wherein the information of the dispersion refer to the solids content. Table 3:

Examples 20 to 22

Lowering the minimum film formation temperature by adding

diallyl malonate

The dispersion set forth in Preparation Example 5 was mixed with different amounts of diallyl malonate, the lowering of the

Minimum film forming temperature (MFT) was measured. The data obtained and the amounts of diallylmalonate used are set forth in Table 4. The data relate to the weight of the respective components, wherein the data of the dispersion refer to the solids content.

Table 4:

Examples 23 to 25

Lowering the minimum film-forming temperature by adding triallyl citrate

The dispersion set forth in Preparation Example 5 was admixed with varying amounts of triallyl citrate, the lowering of the

Minimum film forming temperature (MFT) was measured. The data obtained and the amounts of triallyl citrate used are set forth in Table 5. The data relate to the weight of the respective components, wherein the data of the dispersion refer to the solids content. Table 5:

Triallyl citrate [%] dispersion according to MFT

Production Example 5 [% [° C] based on

Solids content]

0 100 41

Example 23 2 98 27

Example 24 4 96 19

Example 25 5 95 15 Examples 26 to 28

Lowering the minimum film formation temperature by adding

Trimethylolpropane tri (meth) acrylate (TMPTMA)

The dispersion set forth in Preparation Example 5 was treated with varying amounts of trimethylolpropane tri (meth) acrylate (TMPTMA), with the lowering of the minimum film forming temperature (MFT) being measured. The data obtained and the amounts of TMPTMA used are set forth in Table 6. The information refers to the weight of the respective

Components, wherein the information of the dispersion refer to the solids content.

Table 6:

property investigations

The properties of the coating composition thus obtained were examined by various methods. For this purpose, tests on solvent resistance, water absorption and hardness were carried out on dried films. Solvent resistance was determined using methyl isobutyl ketone (MIBK), swelling a sample with MIBK at room temperature for 4 hours. Subsequently, the sample was removed from the

Solvent removed and excess solvent removed.

Subsequently, the sample was dried for 1 hour at about 140 ° C. The values set forth in Table 7 refer to the weight of the coating after treatment with MIBK, also referred to herein as "true swelling." The hardness of the coating, which is usually a measure of scratch resistance, was measured using the Pendulum Test according to König (DIN ISO 1522).

Examples 29 to 34 The dispersion described in Preparation Example 2 was washed with

different amounts of 2,7-octadienol ^* 5-PO (OCP) and siccatives (co-naphthenate (Fluka)). The information set out in Table 7 in

Weight percent refers to the solids content of the dispersion. Before testing the solvent resistance, the paints were dried for 10 days. The pendulum hardnesses were measured after different drying times.

Table 7 (solvent resistance)

Table 7 (pendulum hardness)

OCP siccative pendulum hardness after drying the

Sample from

[Wt%] [wt%] 7 days 13 days 36 days

[s] [s] [s]

Example 29 10 0 38 36 46

Example 30 10 0.75 43 45 55

Example 31 10 1, 5 43 43 57

Example 32 14 0 22 21 29

Example 33 14 0.75 32 32 48

Example 34 14 1, 5 32 34 45 Examples 35 to 37

The dispersion described in Preparation Example 2 was with

varying amounts of methoxyocta-2,7-diene (octa-2,7-dienylmethyl ether) (OCM) and siccatives (co-naphthenate (Fluka)). The percentages given in Table 8 are based on the solids content of the dispersion. Before the investigation of

Solvent resistance, the paints were dried for 10 days. The

Pendulum hardness was measured after different drying times.

Table 8 (solvent resistance)

Table 8 (pendulum hardness)

OCM siccative pendulum hardness after drying the

Sample from

[Wt%] [wt%] 7 days 13 days 30 days

[s] [s] [s]

Example 35 20 0 67 74 83

Example 36 20 0.75 83 78 73

Example 37 20 1, 5 57 63 63 Examples 38 to 40

The dispersion described in Preparation Example 2 was with

different amounts of octa-2,7-dienol (OCL) and siccatives (co-naphthenate (Fluka)). The information set out in Table 9 in

Table 9 (solvent resistance)

Table 9 (pendulum hardness)

OCL desiccant pendulum hardness after drying the

Sample from

[Wt%] [wt%] 7 days 16 days 23 days

[s] [s] [s]

Example 38 10 0 62 64 95

Example 39 10 0.75 59 94 109

Example 40 10 1, 5 59 90 101 Examples 41 to 43

The dispersion described in Preparation Example 4 was with

different amounts of 2,7-octadienol ^* 5-PO (OCP) and siccatives (co-naphthenate (Fluka)). The information given in Table 10 in

Weight percent refers to the solids content of the dispersion. Before testing the solvent resistance, the paints were dried for 10 days. Table 10

Examples 44 to 46 The dispersion described in Preparation Example 4 was washed with

varying amounts of methoxyocta-2,7-diene (octa-2,7-dienylmethyl ether) (OCM) and siccatives (co-naphthenate (Fluka)). The percentages given in Table 1 1 are based on the solids content of the dispersion. Before the investigation of

Solvent resistance, the paints were dried for 10 days. Table 1 1

Examples 47 to 49

The dispersion described in Preparation Example 2 was with

different amounts of octa-2,7-dienol (OCL) and siccatives (co-naphthenate (Fluka)). The percentages given in Table 12 in percent by weight refer to the solids content of the dispersion. Before testing the solvent resistance, the paints were dried for 10 days.

Table 12

OCL Desiccant True Solvents Mass

Swelling uptake [%] loss

[% By weight] [% by weight] [%] [%]

Example 8 0 858 573 30 47

Example 8 0.75 557 41 1 22 48

Example 8 1, 5 526 394 21 49 Examples 50 to 52

The dispersion described in Preparation Example 1 was with

different amounts of 2,7-octadienol ^* 5-PO (OCP) and siccatives (co-naphthenate (Fluka)). The percentages given in Table 13 are based on the solids content of the dispersion. The pendulum hardnesses were measured after different drying times of the lacquers. Table 13 (pendulum hardness)

Examples 53 to 55 The dispersion described in Preparation Example 1 was washed with

varying amounts of methoxyocta-2,7-diene (octa-2,7-dienylmethyl ether) (OCM) and siccatives (co-naphthenate (Fluka)). The percentages given in Table 14 are based on the solids content of the dispersion. The pendulum hardnesses were after

measured different drying times of the paints. Table 14 (pendulum hardness)

Examples 56 to 58

The dispersion described in Preparation Example 1 was with

different amounts of octa-2,7-dienol (OCL) and siccatives (co-naphthenate (Fluka)). The information set out in Table 15 in

Weight percent refers to the solids content of the dispersion. The pendulum hardnesses were measured after different drying times of the lacquers.

Table 15 (pendulum hardness)

OCL desiccant pendulum hardness after drying the

Sample from

[Wt%] [wt%] 4 days 14 days 23 days

[s] [s] [s]

Example 56 8 0 41 52 78

Example 57 8 0.75 38 73 90

Example 58 8 1, 5 42 73 90 Examples 59 to 61

The dispersion described in Preparation Example 5 was admixed with 5% by weight of the coalescing aid indicated in Table 16 and 1.5% by weight of siccative (Nuodex®), the percentages being based on the solids content of the dispersion. The pendulum hardnesses were measured after different drying times of the lacquers.

Table 16 (pendulum hardness)

Pendulum hardness after drying the sample of

1 days 7 days 21 days [s] [s] [s]

Example 59 Diallyl malonate 61, 6 71, 4 96.6

Example 60 Triallycitrate 42.0 46.2 47.6

Example 61 TMPTMA 61, 6 58.3 85.4

Claims

claims

Aqueous coating composition comprising at least one dispersion of a (meth) acrylic polymer and at least one coalescing aid, characterized in that the (meth) acrylic polymer comprises units derived from (meth) acrylic monomers having at least one double bond in the alkyl radical and Have from 8 to 40 carbon atoms,

and the coalescing aid has at least one ethylenically unsaturated double bond and a molecular weight of less than 1000 g / mol.

An aqueous coating composition according to claim 1, characterized

in that the coalescing aid comprises at least two ethylenically unsaturated double bonds.

Aqueous coating composition according to claim 1 or 2, characterized in that the coalescing aid is at most 15

Carbon atoms.

Aqueous coating composition according to at least one of

preceding claims, characterized in that the

Molecular weight of Koaleszenshilfsmittels 140 g / mol to 500 g / mol.

Aqueous coating composition according to at least one of

preceding claims, characterized in that the

Boiling point of the coalescing aid at least 180 ° C at

Normal pressure (1024 mbar) is. Aqueous coating composition according to at least one of the preceding claims, characterized in that the

Coalescing aid has a ratio of carbon atoms to ethylenically unsaturated double bonds in the range of 3: 1 to 8: 1.

Aqueous coating composition according to at least one of the preceding claims, characterized in that the

Coalescence auxiliary has an HLB value in the range of 3 to 19.

Coalescence aid is an alcohol.

Aqueous coating composition according to at least one of the preceding claims 1 to 7, characterized in that the coalescing aid is an ester.

An aqueous coating composition according to claim 9, characterized

in that the coalescence aid is a diallyl ester

Dicarboxylic acid is.

(Meth) acrylic polymer comprises 0.5 to 60% by weight of units derived from (meth) acrylic monomers having at least one double bond and 8 to 40 carbon atoms in the alkyl radical. Aqueous coating composition according to at least one of

preceding claims, characterized in that the

(Meth) acrylic polymer 1 to 30 wt .-% of units derived from (meth) acrylates having in the alkyl radical at least one double bond and 8 to 40 carbon atoms,

0, 1 to 10 wt .-% of units derived from acid group-containing monomers, and

50 to 98.9 wt .-% of units derived from (meth) acrylates having 1 to 6 carbon atoms in the alkyl radical, each based on the weight of the (meth) acrylic polymer comprises.

Aqueous coating composition according to at least one of

preceding claims, characterized in that the

(Meth) acrylic polymer is a core-shell polymer and the outermost shell comprises a (meth) acrylate segment, the

1 to 30 wt .-% of units derived from (meth) acrylates having in the alkyl radical at least one double bond and 8 to 40

Have carbon atoms,

0, 1 to 10 wt .-% of units derived from acid group-containing monomers, and

50 to 98.9 wt .-% of units derived from (meth) acrylates having 1 to 6 carbon atoms in the alkyl radical, each based on the weight of the (meth) acrylate segment comprises.

Aqueous coating composition according to at least one of

preceding claims, characterized in that the

Dispersion of the (meth) acrylic polymer containing no coalescing aid, a minimum film formation temperature (MFT) of at least 25 ° C.

15. Aqueous coating composition according to at least one of the preceding claims, characterized in that the coating agent has a minimum film-forming temperature (MFT) of at most 20 ° C.