MXPA01006014A - Coating agent - Google Patents

Abstract

The invention relates to a coating agent, containing at least one conversion product (A) and at least one suitable additive (C), (A) being produced according to a method comprising the following step (i):(iv) reacting a reaction mixture comprising at least one radically convertible monomer in radical conditions, (a) in the presence of at least one radical initiator and a compound (I) of formula (II) wherein R1to R4 each represent, independently of each other, hydrogen, an unsubstituted or substituted alkyl radical, cycloalkyl radical or aralkyl radical or an unsubstituted or a substituted aromatic hydrocarbon radical, on the condition that at least two of R1 to R4 represent an unsubstituted or a substituted aromatic hydrocarbon radical, in an aqueous phase.

Description

"COATING AGENT" The present invention relates to a coating composition comprising at least one reaction product (A) prepared by a process uqe comprises reacting, under free radical conditions, at least one radically reactable monomer (a) free in the presence of at least one free radical initiator, and of a compound (I) as will be defined below in the aqueous phase, coating compositions comprising at least one polymer (B) as defined herein, and with compositions of coating comprising, if desired, (A) and / or (B) as a dispersion. Patent Number WO 98/01478 describes a process for preparing polymers wherein the monomer to be reacted, which is selected in particular from vinyl monomers and acid derivatives having unsaturated groups, such as anhydrides, esters and acid imides (meth) acrylic, for example, is reacted in the presence of a free radical initiator and a thiocarbonylthio compound, as a chain transfer agent. Patent Number WO 92/13903 describes a process for preparing polymers having a low molecular weight, - - by chain polymerization of free radical of one or more monomers in the presence of a group transfer agent, as defined herein, having a double bond C-S. As shown in that document, the compounds described herein, having a double CS link, act not only as chain transfer agents but also as growth regulators, so that according to the document, it is only possible to prepare polymers of molecular weight in the presence of this compound. A process for chain polymerization of free radical of unsaturated monomers in an aqueous medium and in the presence of a macromonomer having a terminal group -CH2-C (X) = C__2 is defined in Patent Number WO 93/22351, which also defines X. As proof of the examples of that request, several reactions are (meth) acrylates or (meth) acrylic acid and, if desired, monomers such as styrene, in each case, under emulsion or suspension polymerization conditions. Patent Number WO 93/22355 relates to a process for preparing crosslinkable polymers using a macromonomer as described in Patent Number WO 93/22351. Patent Number WO 96/15157 also describes a process for preparing polymers having a comparatively limited molecular weight distribution, wherein a vinyl monomer, as defined therein, is reacted with a macromonomer likewise terminated with vinyl in the presence of a free radical initiator. In addition, Patent Number WO 98/37104 relates to the preparation of controlled molecular weight polymers, including acrylate-based polymers, by free radical polymerization of the corresponding monomers, using a chain transfer agent that is more narrowly defined in it and having a double CC bond and the radicals that activate that double bond in terms of the reaction of the free radical addition of the monomers. A free radical polymerization or chain copolymerization with an oligo (methyl methacrylate) - unsaturated with ethyl acrylate, styrene and methyl methacrylate, acrylonitrile and vinyl acetate as comonomers is described in a scientific article - in J. Macromol, Sci. -Chem., A 23 (7), 839-852 (1986). These documents do not mention the use of product compositions described therein as coating ingredients. The polymer structures described above are of great interest for the coating compositions, since these polymers allow the properties of the coating compositions to be established in accordance with the present invention. a specific way. An object of the present invention is to provide constituents of the coating composition comprising chemically structured polymers which can be prepared by simple polymerization techniques. The polymers of the invention in particular must exhibit great variability in terms of chemical composition and molecular weight. We have found that these and other objects are surprisingly achieved by the coating composition of the invention comprising at least one reaction product (A), obtainable by a process comprising the following step (i): (i) reacting under free radical conditions, a reaction mixture comprising at least one reactable, radically free monomer (a), in the presence of at least one a free radical initiator and a compound (I) of the formula ^ 3 Rl \ / c = c / \ R4 R2 where R] _ to R4 each independently of the other are hydrogen, an alkyl radical - substituted or unsubstituted, a cycloalkyl radical or an aralkyl radical, or an unsubstituted or a substituted aromatic hydrocarbon radical, with the proviso that at least two of R] _ to R4 are an unsubstituted aromatic hydrocarbon radical or one substituted, in the aqueous phase, and at least one additive (C). In order to prepare the aforementioned reaction product it is possible to use all the radically free reactable monomers as the monomer (a). As the monomer (a) it is preferred to use those compounds as radically free copolymerizable or copolymerizable compounds that include a hydrophilic group, such as, for example, a carbonyl group. With additional preference, the monomers (a) comprise free-radical monomers that are homopolymerizable or copolymerizable, that is, monomers whose solubility in water is greater than that of styrene. It is also possible, of course, that mixtures of different hydrophilic monomers, and mixtures of at least one hydrophilic monomer and at least one hydrophobic monomer, are present in the reaction mixture of step (i). The specific representatives of the monomers (a) are: methyl methacrylate, ethyl methacrylate, propyl methacrylate (all isomers), methacrylate of - butyl (all isomers), 2-ethylhexyl methacrylate, isobornyl methacrylate, methacrylic acid, benzyl methacrylate, phenyl methacrylate, methacrylonitrile, alpha-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate (all isomers) , butyl acrylate (all isomers), 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid, benzyl acrylate, phenyl acrylate, acrylonitrile, styrene, functionalized methacrylates; acrylic acids and styrenes, selected from glycidyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutyl methacrylate (all isomers), diethylaminoethyl methacrylate, triethylene glycol methacrylate, itaconic anhydride, itaconic acid, acrylate glycidyl, 2-hydroxyethyl acrylate, hydroxypropyl acrylate (all isomers), hydroxybutyl acrylate (all isomers), diethylaminoethyl acrylate, triethylene glycol acrylate, methacrylamide, N-tert-butyl methacrylamide, N-butyl methacrylamide, N-methylolmethacrylamide, N-ethylolmethacrylamide, N-tert-butylacrylamide, N-butylacrylamide, N-methylolacrylamide, N-ethyl olacrylamide, vinylbenzoic acid (all isomers), diethylaminostyrene (all isomers), alpha-methylvinylbenzoic acid (all isomers), diethylamino-alpha - - methylstyrene (all isomers), paramethylstyrene, p-vinilbencensulfónico methacrylate, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate tributoxisililpropilo methacrylate, diethoxymethylsilylpropyl methacrylate dibutoximetilsililpropilo methacrylate diisopropoximetilsililpropilo methacrylate, dimethoxysilylpropyl methacrylate, diethoxysilylpropyl methacrylate, dibutoxysilylpropyl methacrylate, diisopropoxysilylpropyl acrylate, trimethoxysilylpropyl acrylate, triethoxysilylpropyl acrylate, tributoxisililpropilo acrylate dimetoximetilsililpropilo acrylate, diethoxymethylsilylpropyl acrylate, dibutoximetilsililpropilo acrylate diisopropoximetilsilil-propyl acrylate, dimethoxysilylpropyl acrylate, diethoxysilylpropyl acrylate, dibutoxysilylpropyl acrylate, diisopropoxysilylpropyl, vinyl acetate and vinyl butyrate, vinyl chloride, vinyl fluoride, vinyl bromide, and mixtures of the monomers mentioned above. It is preferably used as a first monomer (a ") an acrylic or ethacrylic acid, an alkyl of 1 to 4 carbon atoms, or a hydroxyalkyl acrylate or methacrylate of 1 to 4 carbon atoms, vinyl acetate, a pyrrolidone of vinyl substituted or unsubstituted a mixture of two or more thereof, or a mixture of the first monomer (a ') with at least one additional monomer (a) radically free homopolymerizable or copolymerizable.It is also used in connection with the preparation of the reaction product (A) a compound (I) of the formula R3 Rl C R4 R2 wherein Ri to R4 each independently of the other are hydrogen, a substituted or unsubstituted alkyl radical, a cycloalkyl radical or an aralkyl radical, or an unsubstituted or substituted aromatic hydrocarbon radical, the invention requiring at least two from Ri to R4 as being an unsubstituted or substituted aromatic hydrocarbon radical. Here again it is possible in principle to use all the compounds of the aforementioned formula according to the invention. Preference is given as compound (I) to the use of diphenylethylene, dinaphthalethylene, 4, 4-vinylidenebis (N, T -dimethylaniline), 4, 4-vinylidenebis (aminobenzene), cis and trans-stilbene or a mixture of two or more of them, giving additional preference to the use of diphenylethylene. It is also possible to use substituted diphenylethylenes, which are substituted on one or both of the aromatic hydrocarbon radicals with electron withdrawing substituents or electron donors, such as, for example, tertiary butyl, benzyl or CN groups, or an alkoxydiphenyl-ethylene , such as, for example, methoxy-, ethoxy-, or tert-butoxydiphenylethylene, or analogous thio or amine compounds. In addition, the reaction product (A) is prepared by reaction in the presence of at least one free radical initiator, with preference being given to the free radical initiators oxidants. The initiator preferably must be soluble in water. In general, however, it is possible to use all the azo and / or peroxo compounds that are conventionally used in the free radical chain polymerization. Suitable initiators are described in U.S. Patent No. WO 98/01478 on page 10, lines 17-34, which in this respect is incorporated in its entirety in the present specification. Preference is given to the use of free radical initiators oxidants, such as potassium, sodium and ammonium peroxodisulfates, for example, or a combination of - a conventional initiator - that is, non-oxidizing, with H202- In a preferred embodiment for the preparation of the reaction product, a comparatively large amount of the free radical initiator, free radical initiator is added as a proportion of the reaction mixture being preferably 0.5 to 50 percent by weight. percent by weight, more preferably from 1 percent to 20 percent by weight, based in each case on the total amount of monomer (a) and initiator. The ratio of the initiator of the compound (I) is preferably from 3: 1 to 1: 3, more preferably from 2: 1 to 1: 2, and in particular from 1.5: 1 to 1: 1.5. The reaction described above according to step (i) is carried out in the aqueous phase, in which case preference is given here to water or mixtures of water with water miscible solvents, such as THF and ethanol, for example. However, it is also possible to carry out the reaction in the presence of a mixture of water and a water-immiscible solvent, such as, for example, an aromatic solvent, such as toluene, for example. In a further embodiment, the aforesaid reaction according to step (i) is carried out in the presence of at least one base. In this context, all the bases of low molecular mass - - they can be used in principle, with preference being given to NaOH, KOH, ammonia, diethanolamine, triethanolamine, mono-, di- and triethylamine, dimethylethanolamine or a mixture of two or more thereof and particularly preferably to ammonia and di- and tri- Ethanolamine The temperature during the reaction according to step (i) is generally above the ambient temperature and below the decomposition temperature of the monomers, a temperature scale of 50 ° C to 150 ° being preferably selected. C, more preferably from 70 ° C to 120 ° C, and in particular, from 80 ° C to 110 ° C. Although there are no restrictions with respect to the molecular weight distribution, it is possible in the reaction according to (i) to obtain a reaction product having a molecular weight distribution Mw / Mn, as measured by gel permeation chromatography using polystyrene as a norm, by <; 4, preferably < 3, more preferred < 2, in particular from < 1.5 and, in certain cases, < 1.3. The molecular weights of the reaction product (A) can be controlled within wide limits by selecting the ratio of monomers (a) to compounds (I) to the free radical initiator. In this context, the molecular weight is determined in particular by the amount of the compound (I), - - specifically in such a way that the higher the proportion of the compound (I), the lower the resulting molecular weight. The reaction according to step (i) can also be carried out in the presence of a surfactant. The product of the reaction in accordance with (i), which is usually obtained in the form of an aqueous mixture, can be further processed directly as a dispersion or preferably, can be used as a macroinitiator for the subsequent reaction in accordance with step (ii), as defined later then. It is also possible to isolate the reaction product from step (i) as a solid and then react it further. In the reaction according to step (ii) it is possible to react at least one freely selectable, radically free homopolymerizable or copolymerizable monomer (b). This monomer (b) can be identical to or different from the monomer (a) used in step (i). The selection of the monomer (b) is made in principle in accordance with the desired structure of the polymer prepared in step (ii) and therefore depending on the proposed use of this polymer.

- - The following specific monomers preferred to be used as the monomers (b) may be mentioned: The monomers (b) are preferably selected from the monocarboxylic acids of 3 to 10 carbon atoms monoethylenically unsaturated, their alkali metal salts and / or their salts of ammonium, the examples being acrylic acid, methacrylic acid, dimethylacrylate acid, ethylacrylic acid, allylacetic acid and vinylacetic acid, and also the monocarbonyly unsaturated monocarbonylic acids of 4 to 8 carbon atoms, their monoesters, anhydrides, alkali metal salts and / or ammonium salts, examples being maleic acid, fumaric acid, itaconic acid, mesaconic acid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconic anhydride, and methylmalonic anhydride; and also monoethylenically unsaturated monomers containing sulfonic acid groups, examples being allylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-propanesulfonic acid, methallylsulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate and 3-sulfopropyl methacrylate. , and also monoethylenically unsaturated monomers containing phosphonic acid groups, examples being vinylphosphonic acid, allylphosphonic acid and acrylamidoethylpropane phosphonic acid, alkyl esters of 1 to 20 carbon atoms and of - hydroxyalkyl monocarboxylic acids of 3 to 10 carbon atoms monoethylenically unsaturated or dicarboxylic acids of 4 to 8 carbon atoms, examples being methyl acrylate, ethyl acrylate, n-butyl acrylate, stearyl acrylate, maleate diethyl, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate, and also the (meth) acrylic esters of the alcohols of 1 to 18 alkoxylated carbon atoms which have been reacted with 2 to 50 moles of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, and also the N-substituted amides and amides of the mono-carboxylic acids of 3 to 10 carbon atoms, monoethylenically unsaturated or acid dicarboxylics of 4 to 8 carbon atoms, the examples being acrylamide, N-alkyl acrylamides and N, N-dialkyl acrylamides having in each case from 1 to 18 carbon atoms in the alkyl group, such as N-methylacrylamide, N, N-di-methylacrylamide, N-tert-butylacrylamide and N-octadecylacrylamide, N-methylhexylmaleamide, N-decylmaleamide, diethylaminopropylmethacrylamide and acrylamidoglycolic acid, and also the ) -alkylamidoalkyl acrylates, the examples being di-ethylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, and dimethylaminopropyl methacrylate; and also vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate, which may also be in hydrolyzed form after polymerization; and also the N-vinyl compounds, examples being N-vinylpyrrolidone, N-vinylcaprolactoma, N-vinylformamide, N-vinyl-N-methylformamide, 1-vinylimidazole and l-vinyl-2-methylimidazole; and also the vinyl esters of the alcohols of 1 to 18 carbon atoms, vinyl ethers of the alcohols of 1 to 18 alkoxylated carbon atoms and vinyl ethers of the polyalkylene oxides such as polyethylene oxides, polypropylene oxide or polybutylene oxide, styrene and its derivatives such as alpha-methylstyrene, indene and dicyclopentadiene; monomers containing amino or imino groups such as, for example, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminopropyl-methacrylamide and allylamine monomers, which carry quaternary ammonium groups in the form, for example, of salts, as obtained by react the functions of the basic amino with acids such as hydrochloric acid, sulfuric acid, nitric acid, formic acid or acetic acid, or in quaternized form (being the - examples of suitable quaternizing agents in dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and benzyl chloride), such as, for example, dimethylaminoethyl acrylate hydrochloride, diallyldimethylammonium chloride, dimethylaminoethyl acrylate methyl chloride , dimethylaminoethylaminopropyl ethacrylamide methosulfate, vinylpyridinium salts and 1-vinylimidazolium salts; and monomers wherein amino groups and / or ammonium groups are released only after polymerization and subsequent hydrolysis, such as, for example, N-vinylformamide and N-vinylacetamide. The present invention accordingly also provides a coating composition comprising in addition to at least one suitable additive (C), a polymer (B) obtainable by a process comprising: (ii) reacting the reaction product (A) obtained in step (i) under free radical conditions, in the presence of at least one monomer free radically homopolymerizable or copolymerizable (b). The reaction according to step (ii) is carried out in principle in accordance with the customary conditions for the free radical polymerization, it being possible for the appropriate solvents to be present.

- Steps (i) and (ii) of the process of the invention can be carried out separately from each other spatially and temporally, in which case, of course, step (i) is carried out first and then the step ( ii). In addition, however, steps - (i) and (ii) can also be carried out in succession in a reactor, that is, first all the compound of formula (I) is reacted partially or totally, as a depending on the desired use and / or the desired properties, with at least one monomer (a) and then at least one monomer (b) is added and the free radical polymerization is carried out, or otherwise from the start a mixture of the monomer comprising at least one monomer (a) and at least one monomer (b) is used and reacted with the compound (I). In this context, it is assumed that the compound (I) is first reacted with at least one monomer (a) and then the reaction product (A) formed therefrom also reacts, above a certain molecular weight, with the monomer (b). Depending on the reaction regime, it is possible according to the invention in this case to prepare the functionalized polymers of the terminal group, the (co) pointers, block or multi-block and gradients, star polymers, graft copolymers and branched (co) polymers as components of the coating composition. In addition, the present invention also provides a coating composition comprising an aqueous mixture comprising the reaction product (A) or the polymer (B) or in combination of two or more thereof. The reaction product (A) and / or the polymer (B) or a mixture of two or more thereof can be used in accordance with the utility as a component of the coating composition in a form suitable for that purpose, especially as polymer dispersions. In accordance with its field of use, the coating compositions of the invention include appropriate additives (C) such as polymers, especially crosslinkers, crosslinking catalysts, initiators, especially pigments, colorants, fillers or fillers, fillers or fillers reinforcement, rheology auxiliaries, wetting and dispersing agents, defoamers, adhesion promoters, additives to improve substrate wetting, additives to improve surface smoothness, leveling agents, leveling agents, auxiliaries, film formers, drying agents anti-detachment, light stabilizers, corrosion inhibitors, biocides, flame retardants, polymerization inhibitors, especially photoinhibitors, or plasticizers, as they are well known and conventional, for example, in the plastic or coating sectors. The selection of the additives is guided by the desired profile of the properties of the coating composition and by its proposed use. The coating compositions of the invention can be applied using the known application methods of liquid phases, such as dipping, spraying, knife coating, brush application, roller coating or curtain coating. Examples of suitable substrates are films, thin sheets, fibers, rolled metal, woven fabrics or molding parts, especially automotive body components made of metal, glass, wood, paper, plastic, leather, mineral substrates, or composite materials. At the time of application, these substrates may be in a state of mobility rest, such as in the case of the roll coating technique, for example. Thus, the present invention also relates to a process for coating substrates, which comprises using a composition as defined herein.

In addition, the coating compositions of the invention can be used in powder form, especially in the case of powder coating. In particular, the coating compositions of the invention can be the constituents of multi-layer coating systems, as found, for example, in automotive OEM finishing, automotive refinishing, plastic coating, industrial coating, container coating. , the technique of roll coating, or the lining of furniture. The composition, especially when used in the process defined above, may further comprise crosslinkable constituents. The intention of the context presented below is to illustrate the present invention with reference to a number of examples.

Example 1 A reaction vessel was charged with 52.56 grams of deionized water and this initial charge was heated to 90 ° C. Subsequently, at a constant temperature of 90 ° C, three separate feed currents were supplied to a uniform regime in parallel. Feed stream 1 consisted of 10.18 grams of acid - - Acrylic, 18.35 grams of methyl methacrylate and 1.49 grams of diphenylethylene. As the feed stream 2, 9.9 grams of a 25 weight percent concentration of ammonia solution was added. The feed stream 3 consisted of a solution of 2.25 grams of ammonium peroxodisulfate in 5.25 grams of deionized water. The feed currents I and II were supplied in a regulated manner through the course of 1 hour, the feed stream III through the course of 1.25 hours. When the addition was completed, a post-polymerization phase of 4 hours followed, with cooling. This resulting micellar solution had a solids content of 33 weight percent.

Example 2 First, 9.1 grams of the product prepared in Example 1 was initially introduced into 51.62 grams of deionized water and this initial charge was heated to 90 ° C with stirring in a reactor. Subsequently, a feed stream consisting of 9.86 grams of n-butyl methacrylate, 7.88 grams of styrene, 12.66 grams of hydroxyethyl methacrylate and 8.88 grams of methyl methacrylate was fed through the course of 6 hours with complete stirring. . The - The resulting dispersion had a solids content of about 40 weight percent.

Example 3 First, 9.1 grams of the product prepared in Example 1 was initially introduced into 51.62 grams of deionized water and this initial charge was heated to 90 ° C with stirring in a reactor. Subsequently, a feed stream consisting of 9.86 grams of n-butyl methacrylate, 7.88 grams of styrene, 12.66 grams of hydroxyethyl methacrylate and 8.88 grams of ethylhexyl methacrylate was supplied in a regulated manner throughout the course of 6 hours with complete stirring. . The resulting dispersion had a solids content of about 40 weight percent.

Example 4 First, 9.1 grams of the product prepared in Example 1 was initially introduced into 51.62 grams of deionized water and this initial charge was heated to 90 ° C with stirring in a reactor. Subsequently, a feed stream consisting of 9.86 grams of n-butyl methacrylate, 7.88 - - was supplied in a regulated manner. grams of vinyl acetate, 12.66 grams of hydroxyethyl methacrylate and 8.88 grams of 2-ethylhexyl methacrylate through the course of 6 hours with complete agitation. The resulting dispersion had a solids content of about 40 weight percent.

Example 5 First, 9.1 grams of the product prepared in Example 1 was initially introduced into 51.62 grams of deionized water and this initial charge was heated to 90 ° C with stirring in a reactor. Subsequently, a feed stream consisting of 9.86 grams of n-butyl methacrylate, 7.88 grams of styrene, 3.94 grams of isobutoxymethyl methacrylate, 8.72 grams of hydroxyethyl methacrylate, and 8.88 grams of ethylhexyl methacrylate was supplied in a regulated manner. 6-hour course with complete agitation. The resulting dispersion had a solids content of about 40 weight percent.

Example 6 A steel reactor with a capacity of 5 kilograms was loaded with 528.7 grams of deionized water and this load - - initial temperature was heated to 90 ° C. Subsequently, at a constant temperature of 90 ° C, three separate feed currents were supplied in a regulated manner to a uniform regime in parallel through the course of 4 hours. The feed stream I consisted of 106.2 grams of MA-13, 378.1 grams of n-butyl methacrylate, 159.3 grams of styrene, 54.5 grams of acrylic acid, 332.4 grams of methyl methacrylate and 31.9 grams of diphenylethylene. Feed stream II was a solution of 42.5 grams of ammonium peroxodisulfate in 170 grams of deionized water. The feed stream III contained 51.61 grams of dimethylethanolamine. When the addition was to finish, it continued at 90 ° C. a post-polymerization phase of 2 hours. The cooling provided a white dispersion having a pH of 5.5, a solids content (60 minutes, 130 ° C) of 41 percent, an alcohol-determined acid number of 58 milligrams of KOH / gram of solids and a viscosity of 0.9 dPas (23 ° C, cone / plate). The molecular weight was determined by GPC against polystyrene as a standard and was Mn 4406 grams per mole, Molecular weight of 8603 grams per mole, polydispersity of 1.95.

MA-13: methacrylic ester, 13.0 Rohm - Example 7 The dispersions obtained according to Examples 1 to 6 are applied in a dry film thickness of about 50 to 100 microns to glass plates using a coating rod and dried at a temperature between room temperature and 130 ° C. In all cases, clear, highly glossy transparent films are obtained. The films of Examples 2 to 5 also exhibit a high level of water resistance.

Claims (13)

- CLAIMS

1. A coating composition comprising at least one reaction product (A) and at least one appropriate additive (C), being obtainable (A) by a process comprising the following step (i): (i) reacting under Free radical conditions, a reaction mixture comprising at least one reactable, radically free monomer (a), in the presence of at least one free radical initiator and a compound (I) of the formula R3 Rl C c R4 R2 wherein R] _ to R4 each independently of the other are hydrogen, a substituted or unsubstituted alkyl radical, a cycloalkyl radical or aralkyl radical, or an unsubstituted or substituted aromatic hydrocarbon radical, with the proviso that at least two of Rx to R4 are an unsubstituted or substituted hydrocarbon radical in an aqueous phase.

2. A composition according to claim 1, wherein the reaction (i) is carried out in the presence of at least one base.

3. A composition according to claim 1 or 2, wherein the free radical initiator is an oxidant free radical initiator.

4. A composition according to any of claims 1 to 3, wherein the ratio of free radical initiator to at least one monomer (a) is 0.5 percent to 50 percent by weight, based on the total amount of the initiator and the monomer (a).

5. A composition according to any of claims 1 to 4, wherein the compound (I) is diphenylethylene, an alkoxydiphenylethylene, dinaphthaleethylene, 4,4-vinylidenebis (N, N-dimethylaniline), 4,4-vinylidenebis (1). -aminobenzene), cis- or trans-stilbene or a mixture of two or more thereof.

6. A composition according to any of claims 1 to 5, wherein the monomer (a) is a hydrophilic monomer, a mixture comprising at least two hydrophilic monomers or a mixture comprising at least one hydrophilic monomer and at least one hydrophobic monomer.

7. A composition according to any of claims 1 to 6, wherein the reaction mixture comprises as a first monomer (a) acrylic or methacrylic acid, an alkyl acrylate or methacrylate of 1 to 4 carbon atoms or hydroxyalkyl of 1 to 4 carbon atoms, vinyl acetate, a substituted or unsubstituted vinyl pyrrolidone, a mixture of two or more thereof, or a mixture of the first monomer (a) with at least one additional free radical homopolymerizable or copolymerizable monomer.

8. A composition according to any of claims 1 to 7, wherein the base of low molecular mass is NaOH, KOH, ammonia, diethanolamine, triethanolamine, mono-, di- or triethylamine, dimethylethanolamine or a mixture of two or more thereof.

9. A coating composition comprising a reaction product (A) as set forth in any of the preceding claims, at least one suitable additive (C) and at least one polymer (B) obtainable (ii) by reacting the reaction product (A) obtained in step (i) under free radical conditions in the presence of at least one monomer free radically homopolymerizable or copolymerizable (b). -

10. A composition according to any of claims 1 to 9, comprising the reaction product (A) and / or the polymer (B) as a dispersion.

11. A process for coating substrates, comprising using a composition according to any of claims 1 to 10.

12. A process according to claim 11, wherein the composition is a constituent of a multilayer system.

13. A process according to claim 11 or 12, wherein the composition comprises crosslinkable constituents.