EP2870208A1

EP2870208A1 - Use of aqueous hybrid binders and alkyd systems for coating agents

Info

Publication number: EP2870208A1
Application number: EP13732874.6A
Authority: EP
Inventors: Sebastian Roller; Harm Wiese; Roelof Balk
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2012-07-06
Filing date: 2013-06-21
Publication date: 2015-05-13
Also published as: AU2013286181A1; US20150126639A1; WO2014005862A1; ZA201500804B; US9567484B2; CN104428378A; RU2015103810A; BR112015000169A2; AU2013286181B2; JP2015522678A

Abstract

The invention concerns aqueous hybrid binders containing an aqueous polymer dispersion (PD) and 0.01-5 wt. % of a photoinitiator and aqueous alkyd systems containing a water-soluble alkyd resin or an aqueous alkyd or polyurethane emulsion or dispersion, and 0.01-5 wt.% of a photoinitiator, the use thereof in coating agents, in particular paints.

Description

Use of aqueous hybrid binders and alkyd systems for coating compositions

The present invention relates to aqueous hybrid binders comprising an aqueous polymer dispersion (PD), and 0.01 to 5 wt .-% of a photoinitiator and aqueous alkyd systems containing a water-soluble alkyd resin or an aqueous alkyd or Polyurethanalkyd- emulsion or dispersion, and 0 , 01-5 wt .-% of a photoinitiator, their use in coating compositions, in particular in paints.

Water-based alkyds and corresponding alkyd / acrylate hybrids show in paint (in particular high-gloss paints) under standard conditions a non-optimal hardness development, i. Corresponding lacquers often remain soft and sticky for too long after being applied to a substrate. The necessary hardness development results from an oxidative cross-linking of the alkyds or the alkyd moiety and takes place under the influence of atmospheric oxygen. In the case of water-based systems, however, this type of crosslinking is rather slow compared to solvent-based paints. In particular, in the hybrid systems, it is even more problematic because the proportion of crosslinking groups is lower. In order to accelerate this networking siccatives can be used. If the oxidative drying has to be fast, which is often desirable, larger quantities of these siccatives or drying agents must be used. A serious disadvantage of these substances, however, is that they are based on heavy metals and, depending on the type of metal used, reduce the environmental compatibility of the paint (see also U.Poth, Polyester and Alkyd Resins, ISBN 3-87870-792-4). If larger amounts of siccatives are used, an additional disadvantage is that the pot life and durability of the paint is reduced: as soon as contact with atmospheric oxygen takes place, the paint begins to crosslink in its container.

US 2008/0287581 describes an aqueous polymer dispersion containing a zinc-modified polymer and its use in paints. Here the zinc-containing component takes over the function of the siccative.

EP 2009072 describes an acetoacetoxyethyl (meth) acrylate (AAEM) aqueous decorative and protective polymeric polymer composition containing 8-35% of an autoxidisable material (e.g., an alkyd) by caustic blending or by addition during formulation. Nothing is disclosed about the development of hardness and its extent.

EP 874 875 discloses a waterborne hybrid binder composition and its use as a component in a paint or varnish mixture, wherein the

Hybrid binder composition has a dry content content of 60 to 95 wt .-%. In WO 2010/040844 hybrid binders are described prepared by means of a mini-emulsion polymerization process. Conventional siccatives have been added to the formulated paint systems so that an acceptable hardness development of the coatings can take place. WO 2010/1 12474 describes methacrylate polymers prepared by emulsion polymerization containing (meth) acrylate monomers with oxidatively crosslinkable side groups. Through the preferred use of co-polymerizable photoinitiators, a good hardness development of the coating after UV irradiation could be achieved.

Coating agents containing reactive groups and cured by UV radiation are known from WO 98/033855. Disadvantage of such systems is that they must be cured in the absence of atmospheric oxygen by UV irradiation with very high irradiation energies. Without these high light energies or in the presence of oxygen, the quality of the corresponding coatings is not sufficient.

The compositions of the prior art have the disadvantage that they exhibit a non-optimal hardness development in paints under standard conditions and corresponding coatings remain soft and sticky for too long if no siccatives based on heavy metals are used or no UV curing takes place.

The object of the invention was therefore the development of a binder, which is characterized by improved early hardness development.

The object has been achieved according to the invention by an aqueous hybrid binder comprising an aqueous polymer dispersion (PD) and 0.01-5% by weight of a photoinitiator and by aqueous alkyd systems comprising a water-soluble alkyd resin or an aqueous alkyd or polyurethane alkyd emulsion or .Dispersion, and 0.01 to 5 wt .-% of a photoinitiator. For hardening the films containing the hybrid binders according to the invention or the aqueous alkyd systems, no additional irradiation is required.

The aqueous polymer dispersion (PD) is obtainable by free-radical emulsion polymerization of

(a) at least one α, β-ethylenically unsaturated monomer (M)

(b) and optionally at least one further monomer (M1) to give a polymer (P)

(c) optionally subsequent chemical deodorization and

(d) adding at least one water-soluble alkyd resin having a weight-average molecular weight of between 5,000 and 40,000 Da or at least one aqueous alkyd or polyurethane alkyd emulsion,

characterized in that the addition of the alkyd resin, the alkyd or polyurethane alkyd emulsion or dispersion either

i. following the polymerization of M and M1 and optionally the chemical deodorization at room temperature, ii. following the polymerization of M and M1 with a stirring time of 0-2 h or

iii. following the chemical deodorization with a stirring time of 0-2 h,

wherein the temperature in the addition of (ii) or (iii) 60 to 99 ° C, preferably 70 to

95 ° C and in particular 80 to 90 ° C.

A further subject of the invention are also coating agents, in particular paints containing the hybrid binders according to the invention or the aqueous alkyd systems as well as their preparation and use.

The invention further provides coating compositions in the form of an aqueous composition, comprising: at least one hybrid binder according to the invention or an aqueous alkyd system, as defined below,

optionally at least one inorganic filler and / or inorganic pigment,

usual aids, and

- Water to 100 wt .-%.

The hybrid binder according to the invention contains the polymer dispersion (PD) according to the invention and 0.01-5% by weight of a photoinitiator. The aqueous alkyd system according to the invention comprises at least one water-soluble alkyd resin or an aqueous alkyd or polyurethane alkyd emulsion or dispersion, and 0.01-5% by weight of a photoinitiator.

The addition of the water-soluble alkyd resin or the aqueous alkyd or polyurethane alkyd emulsion or dispersion to the polymer dispersion (PD) is preferably carried out after the emulsion polymerization for the preparation of the polymer (P). The addition of the water-soluble alkyd resin or the aqueous alkyd or polyurethane-alkyd emulsion to the polymer dispersion (PD) can take place directly after the polymerization, ie directly after the initiator feed has ended. The addition preferably takes place after the end of the polymerization and the subsequent stirring time as defined above. Particularly preferably, the addition takes place after the chemical deodorization. Most preferably, the addition takes place after the chemical deodorization including the previously defined stirring time. The stirring time is 0 to 2 h, preferably less than 1 h, particularly preferably 30 min. The addition of the photoinitiator for producing the hybrid binder according to the invention is preferably carried out in the cooled to room temperature (23 ° C) polymer dispersion (PD), but can also take place during the polymerization. To prepare the aqueous alkyd system, the photoinitiator is added to the water-soluble alkyd resin or the aqueous alkyd or polyurethane alkyd emulsion or dispersion at room temperature.

The photoinitiator according to the invention is used in amounts of 0.01-5% by weight, preferably 0.1-4% by weight, in each case based on the solids content of the hybrid binder or of the aqueous alkyd system.

The term "early hardness development" refers to the increase in hardness in the film within the first time after drawing (up to 3 days). It is measured by the pendulum hardness. It can be accelerated by siccativation.

The polymer dispersion (PD) used according to the invention preferably contains 5-60% by weight (solid), more preferably 10-50% by weight (solid), based on the total weight of the hybrid binder, at least one water-soluble alkyd resin or an aqueous alkyd - or polyurethane AI kyd emulsion.

The use according to the invention of the water-soluble alkyd resins or of the aqueous alkyd or polyurethane-alkyd emulsions or dispersions has the following advantage:

Increasing the gloss of coating compositions (paints), especially of acrylate-based gloss paints, while at the same time (in comparison with other hybridization processes) a reduced amount of acrylate ester monomers.

In the context of the present invention, the term alkyl includes straight-chain and branched alkyl groups. Suitable short-chain alkyl groups are, for. B. straight-chain or branched Ci-C7-alkyl, preferably Ci-C6-alkyl and particularly preferably Ci-C4-alkyl groups. These include in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl , 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,

1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,3-dimethylbutyl, 1, 1-dimethylbutyl, 2,2-dimethylbutyl,

3.3-dimethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2- Ethylpentyl, 1-propylbutyl etc. Suitable longer-chain Cs-Cso-alkyl groups are straight-chain and branched alkyl groups. These are preferably predominantly linear alkyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols. These include z. N-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, etc The term alkyl includes unsubstituted and substituted alkyl radicals.

The above comments on alkyl also apply to the alkyl moieties in arylalkyl. Preferred arylalkyl radicals are benzyl and phenylethyl.

C 8 -C 32 -alkenyl in the context of the present invention represents straight-chain and branched alkenyl groups which may be mono-, di- or polyunsaturated. Preferably, it is Cio-C2o-alkenyl. The term alkenyl includes unsubstituted and substituted alkenyl radicals. Specifically, these are predominantly linear alkenyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols. These include, in particular, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, linolyl, linolenyl, eleostearyl and oleyl (9-octadecenyl). The term alkylene in the context of the present invention stands for straight-chain

or branched alkanediyl groups having 1 to 7 carbon atoms, e.g. As methylene, 1, 2-ethylene, 1, 3-propylene, etc.

Cycloalkyl is preferably C4-C8-cycloalkyl, such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

The term aryl in the context of the present invention comprises mononuclear or polynuclear aromatic hydrocarbon radicals which may be unsubstituted or substituted. The term aryl is preferably phenyl, tolyl, xylyl, mesityl, duryl, fluorenyl, anthracenyl, phenanthrenyl or naphthyl, particularly preferably phenyl or naphthyl, these aryl groups in the case of a substitution generally 1, 2, 3 , 4 or 5, preferably 1, 2 or 3 substituents.

To prepare the polymer dispersion (PD) at least one α, β-ethylenically unsaturated monomer (M) is used which is preferably selected from esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C 1 -C 20 -alkanols, vinylaromatics, esters of vinylal alcohol with C 1 -C 8 -monocarboxylic acids, ethylenically unsaturated nitriles, vinyl halides, vinylidene halides, monoethylenically unsaturated carboxylic and sulfonic acids, phosphorus-containing monomers, esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 30 -alkanediols, amides α, ß-ethylenically unsaturated mono- and dicarboxylic acids with C2-C30-

Aminoalcohols having a primary or secondary amino group, primary amides of α, β-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives, N-vinyllactams, open-chain N-vinylamide compounds, esters of allyl alcohol with C1-C30 monocarboxylic acids, esters of α, ß-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, amides α, ß-ethylenically unsaturated mono- and dicarboxylic acids with diamines, which at least have a primary or secondary amino group,

Ν, Ν-diallylamines, N, N-diallyl-N-alkylamines, vinyl- and allyl-substituted nitrogen heterocycles, vinyl ethers, C 2 -C 8 -monoolefins, nonaromatic hydrocarbons having at least two conjugated double bonds, polyether (meth) acrylates, urea-containing monomers and mixtures thereof. Suitable esters of α, ß-ethylenically unsaturated mono- and dicarboxylic acids with

C 1 -C 20 -alkanols are methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate,

Ethyl ethacrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl methacrylate, n-hexyl ( meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, tridecyl (meth) acrylate,

Myristyl (meth) acrylate, pentadecyl (meth) acrylate, palmityl (meth) acrylate,

Heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, arachinyl (meth) acrylate,

Behenyl (meth) acrylate, lignoceryl (meth) acrylate, cerotinyl (meth) acrylate,

Melissinyl (meth) acrylate, palmitoleinyl (meth) acrylate, oleyl (meth) acrylate,

Linolyl (meth) acrylate, linolenyl (meth) acrylate, stearyl (meth) acrylate,

Lauryl (meth) acrylate and mixtures thereof.

Preferred vinyl aromatic compounds are styrene, 2-methylstyrene, 4-methylstyrene, 2- (n-butyl) styrene, 4- (n-butyl) styrene, 4- (n-decyl) styrene and particularly preferably styrene.

Suitable esters of vinyl alcohol with Ci-Cso monocarboxylic acids are, for. Vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl propionate, versatic acid vinyl ester and mixtures thereof.

Suitable ethylenically unsaturated nitriles are acrylonitrile, methacrylonitrile and mixtures thereof.

Suitable vinyl halides and vinylidene halides are vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.

Suitable ethylenically unsaturated carboxylic acids, sulfonic acids or derivatives thereof are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, the monoesters of monoethylenically unsaturated dicarboxylic acids having 4 to 10 , preferably 4 to 6 C atoms, for. Example, maleic acid monomethyl ester, vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acids and 2-acrylamido-2-methylpropanesulfonic acid. Suitable styrenesulfonic acids and derivatives thereof are styrene-4-sulfonic acid and styrene-3-sulfonic acid and the alkaline earth or alkali metal salts thereof, e.g. For example, sodium styrene-3-sulfonate and sodium styrene-4-sulfonate. Particularly preferred are acrylic acid, methacrylic acid and mixtures thereof.

Examples of phosphorus-containing monomers are, for. For example, vinylphosphonic acid and Allylphosphonsäu- re. Also suitable are the mono- and diesters of phosphonic acid and phosphoric acid with hydroxyalkyl (meth) acrylates, especially the monoesters. Also suitable are diesters of phosphonic acid and phosphoric acid, which are simply reacted with a hydroxyalkyl (meth) acrylate and, in addition, simply with a different alcohol, eg. As an alkanol, are esterified. Suitable hydroxyalkyl (meth) acrylates for these esters are those mentioned below as separate monomers, in particular 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,

4-hydroxybutyl (meth) acrylate, etc. Corresponding dihydrogen phosphate ester monomers include phosphoalkyl (meth) acrylates, such as 2-phosphoethyl (meth) acrylate,

2- phosphopropyl (meth) acrylate, 3-phosphopropyl (meth) acrylate, phosphobutyl (meth) acrylate and

3-phospho-2-hydroxypropyl (meth) acrylate. Also suitable are the esters of phosphonic acid and phosphoric acid with alkoxylated hydroxyalkyl (meth) acrylates, eg. B. the ethylene oxide condensates of (meth) acrylates, such as H ₂ C = C (CH 3) COO (CH ₂ CH ₂ 0) nP (OH) 2 and

H ₂ C = C (CH 3) COO (CH ₂ CH ₂ O) n P (= O) (OH) 2 where n is 1 to 50. Also suitable are phosphoalkyl crotonates, phosphoalkyl maleates, phosphoalkyl fumarates, phosphodialkyl (meth) acrylates, phosphodialkyl crotonates and allyl phosphates. Other suitable phosphorus group-containing monomers are described in WO 99/25780 and US 4,733,005, which is incorporated herein by reference.

Suitable esters of α, ß-ethylenically unsaturated mono- and dicarboxylic acids with

C ₂ -C 30 -alkanediols are e.g. 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,

2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate,

3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate,

3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate,

6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate,

3-hydroxy-2-ethylhexyl acrylate, 3-hydroxy-2-ethylhexyl methacrylate, etc.

Suitable primary amides of α, ß-ethylenically unsaturated monocarboxylic acids and their N-alkyl and Ν, Ν-dialkyl derivatives are acrylic acid amide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide , N- (n-butyl) (meth) acrylamide, N- (tert-butyl) (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (1,1,3,3-)

Tetramethylbutyl) (meth) acrylamide, N-ethylhexyl (meth) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide, N- (n-undecyl) (meth) acrylamide , N-tridecyl (meth) acrylamide, N-myristyl (meth) acrylamide, N-pentadecyl (meth) acrylamide, N-palmityl (meth) acrylamide,

N-heptadecyl (meth) acrylamide, N-nonadecyl (meth) acrylamide, N-arachinyl (meth) acrylamide, N-behenyl (meth) acrylamide, N-lignoceryl (meth) acrylamide, N-cerotinyl (meth) acrylamide, N- Melissinyl (meth) acrylamide,

N-palmitoleinyl (meth) acrylamide, N-oleyl (meth) acrylamide, N-linolyl (meth) acrylamide,

N-linolenyl (meth) acrylamide, N-stearyl (meth) acrylamide, N-lauryl (meth) acrylamide,

N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide,

Morpholinyl (meth) acrylamide.

Suitable N-vinyl lactams and derivatives thereof are, for. N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, etc.

Suitable open-chain N-vinyl amide compounds are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide and N-vinylbutyramide.

Suitable esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols are N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminopropyl (cf. meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and N, N-dimethylaminocyclohexyl (meth) acrylate.

Suitable amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group are N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide,

N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide,

N- [2- (diethylamino) ethyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] acrylamide,

N- [4- (dimethylamino) cyclohexyl] methacrylamide etc.

Suitable monomers (M) are furthermore Ν, Ν-diallylamines and N, N-diallyl-N-alkylamines and their acid addition salts and quaternization products. Alkyl is preferably Ci-C24-alkyl. Preference is given to N, N-diallyl-N-methylamine and N, N-diallyl-N, N-dimethylammonium compounds, such as. As the chlorides and bromides.

Suitable monomers (M) are also vinyl- and allyl-substituted nitrogen heterocycles, such as N-vinylimidazole, N-vinyl-2-methylimidazole, vinyl- and allyl-substituted heteroaromatic compounds, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the Salts thereof.

Suitable C 2 -C 8 monoolefins and nonaromatic hydrocarbons having at least two conjugated double bonds are e.g. For example, ethylene, propylene, isobutylene, isoprene, butadiene, etc.

Suitable urea group-containing monomers are, for. N-vinyl or N-allyl urea or derivatives of imidazolidin-2-one. These include N-vinyl and N-allylimidazolidin-2-one, N- Vinyloxyethylimidazolidin-2-one, N- (2- (meth) acrylamidoethyl) imidazolidin-2-one,

N- (2- (meth) acryloxyethyl) imidazolidin-2-one (= 2-ureido (meth) acrylate), N- [2 - ((meth) acryloxyacetamido) ethyl] imidazolidin-2-one, etc. Preferred urea groups having monomers are N- (2-acryloxyethyl) imidazolidin-2-one and N- (2-methacryloxyethyl) imidazolidin-2-one. Particularly preferred is N- (2-methacryloxyethyl) imidazolidin-2-one (2-ureidomethacrylate, UMA).

The aforementioned monomers (M) can be used individually, in the form of mixtures within a monomer class or in the form of mixtures of different monomer classes.

At least 40% by weight, particularly preferably at least 60% by weight, in particular at least 80% by weight, based on the total weight of the monomers (M), of at least one monomer (M1) which is selected are preferably used for the emulsion polymerization is among esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C 1 -C 20 -alkanols, vinylaromatics, esters of vinyl alcohol with C 1 -C 50 -monocarboxylic acids, ethylenically unsaturated nitriles, vinyl halides, vinylidene halides and mixtures thereof (main monomers). Preferably, the monomers (M1) are used in an amount of up to 95 wt .-%, based on the total weight of the monomers (M), for the emulsion polymerization.

The main monomers (M1) are preferably selected from

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, styrene, 2-methylstyrene, vinyl acetate, acrylonitrile, methacrylonitrile and

Mixtures thereof.

In addition to at least one main monomer (M1), at least one further monomer (M2) which is generally present to a lesser degree (secondary monomers) can be used in the free radical emulsion polymerization for the preparation of (PD). Preferably up to 60% by weight, more preferably up to 40% by weight, in particular up to 20% by weight, based on the total weight of the monomers (M), of at least one monomer (M2) is used for the emulsion polymerization is selected from ethylenically unsaturated mono- and dicarboxylic acids and the anhydrides and half esters of ethylenically unsaturated dicarboxylic acids, (meth) acrylamides, Ci-Cio-hydroxyalkyl (meth) acrylates, C1-C10 hydroxyalkyl (meth) acrylamides and mixtures thereof. Preferably, the monomers (M2), if present, in an amount of at least 0.1 wt .-%, particularly preferably at least 0.5 wt .-%, in particular at least 1 wt .-%, based on the total weight of the monomers ( M), used for emulsion polymerization. It is particularly preferred to use 0.1 to 60% by weight, preferably 0.5 to 40% by weight, in particular 1 to 20% by weight of at least one monomer (M2) for the emulsion polymerization. The monomers (M2) are especially selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, acrylic acid amide, methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethylacrylamide, 2-

Hydroxyethylmethacrylamide, acetoacetoxyethyl methacrylate (AAEM), allyl methacrylate, methacrylate Vinylme-, hydroxybutenyl methacrylate, the allyl or diallyl ester of maleic acid, poly (allyl glycidyl ether), and mixtures thereof, in the form of various products in the name Bisomer ^® from Laporte Performance Chemicals, UK. This includes z. B. bisomer ^® MPEG 350 MA, a methoxy polyethylene glycol monomethacrylate or UMA. AAEM is particularly preferably used in amounts of from 0.1 to 20, preferably from 0.1 to 4.9,% by weight.

Particularly suitable combinations of main monomers (M1) for the process according to the invention are, for example: n-butyl acrylate, methyl methacrylate;

n-butyl acrylate, methyl methacrylate, styrene;

n-butyl acrylate, styrene, butyl (meth) acrylate;

n-butyl acrylate, ethylhexyl acrylate, styrene.

n-butyl acrylate, styrene

n-butyl acrylate, n-butyl (meth) acrylate, methyl methacrylate

The above is particularly suitable combinations of main monomers (M1) to (M2) are combined with particularly suitable monomers are preferably selected from acrylic acid, methacrylic acid, acrylamide, methacrylamide, AAEM, UMA or Bisomer ^® and mixtures thereof.

By an alkyd resin is meant a polyester esterified with a drying oil, a fatty acid or the like (U. Poth, Polyester and Alkyd resins, Vincentz Network 2005).

An aqueous alkyd resin is understood to mean, in particular, an alkyd resin solution based on an alkyd resin having a sufficiently high acid number of preferably 20-80 mg KOH / g alkyd resin, optionally after neutralization, and a weight-average molecular weight of> 5000 and <40 000 Da, preferably > 8000 and <35000 Da and more preferably> 10000 and <35000 Da.

The molecular weights are determined by size exclusion chromatography (SEC). Acid number means the amount of potassium hydroxide, expressed in mg, which is necessary to neutralize 1 g of the sample. The oil or fatty acid used is the property-determining component. It allows a subdivision according to the fatty acid triacylglycerol content (oil content, oil length) in short-oil alkyd resins with <40%, medium oil alkyd resins with 40-60% and long-oil alkyd resins with> 60% triacylglycerol, based on solvent-free alkyd resin (fatty acid content possibly in tri - convert acylglycerol, factor approx. 1, 045) (oil content).

The solids content characterizes the "active substance content" of the dispersion according to general practice. The dispersion is usually dried at a temperature between 100 and 140 ° C to constant weight (see ISO standard 1625). The solids content indicates the dry matter compared to the total mass (in%).

The dry matter comprises the polymer, emulsifiers and inorganic salts (from initiator decomposition and neutralization). Volatiles include water and monomers that were not reacted during the polymerization.

The oil content of the alkyd resins used is 25-55%, the solids content in the form of delivery: 30-80%, in the form of use (after dilution with NH3 or NaOH / water) 35- 50%.

Preferred alkyd resins are for example the products WorleeSol ^® 61 A, 61 WorleeSol ^® E, WorleeSol ^® 65A, Worlee, and Synthalat ^® W46 or W48 Synthalat ^®, the company synchronous thopol.

An aqueous alkyd resin emulsion or dispersion or, for short, alkyd emulsion is understood as meaning alkyd resins which, if appropriate, are mixed with emulsifiers and dispersed in water. In comparison to water-soluble or dilutable alkyd resins, alkyds having higher average molecular weights are also suitable for this purpose [U. Poth, polyester and alkyd resins, Vincentz Network 2005, p 183 f].

An aqueous polyurethane-alkyd resin emulsion is understood as meaning a polyurethane-modified alkyd resin which has been dispersed in water. A urethane modification can be carried out in the alkyd synthesis, for example, by replacing part of the usual phthalic anhydride with a diisocyanate [U. Poth, Polyester and Alkyd resins, Vincentz Network 2005, p. 205 f]. A urethane modification can furthermore be carried out by a reaction of an alkyd with an at least difunctional polyisocyanate [DE102006054237].

Preferred alkyd resin emulsions are characterized by an oil content of 25-55% and an acid number of 20-60 mg KOH / g.

Preferred alkyd resin emulsions or polyurethane-modified alkyd resin emulsions are WorleeSol® E 150 W, WorleeSol® E 280 W, WorleeSol® E 530 W or WorleeSol® E 927 W.

For the preparation of the polymer dispersion (PD) it is preferred to use aqueous alkyd or polyurethane alkyd emulsions. In the preparation of the polymer dispersions of the invention, at least one crosslinker may be used in addition to the aforementioned monomers (M). Monomers having a crosslinking function are compounds having at least two polymerizable, ethylenically unsaturated, non-conjugated double bonds in the molecule. A networking can also z. B. by photochemical activation. For this purpose, at least one monomer with photoactivatable groups can additionally be used for the preparation of (PD). Photoinitiators can also be added separately. A networking can also z. Example, by functional groups which can enter into a chemical crosslinking reaction with complementary functional groups. In this case, the complementary groups may both be bonded to the emulsion polymer or for crosslinking it is possible to use a crosslinker which is capable of undergoing a chemical crosslinking reaction with functional groups of the emulsion polymer.

Suitable crosslinkers are z. As acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols. The OH groups of the underlying alcohols may be completely or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups.

Examples of the underlying alcohols are dihydric alcohols such as 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 2,3-butanediol, 1, 4-butanediol , But-2-ene-1, 4-diol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 10-decanediol, 1, 2-dodecanediol, 1 , 12-Dodecanediol, neopentyl glycol, 3-methylpentane-1, 5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol, 1 , 4-cyclohexanediol,

1,4-bis (hydroxymethyl) cyclohexane, hydroxypivalic acid neopentyl glycol monoester, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxypropyl) phenyl] propane, diethylene glycol, triethylglycol, Tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thiapentane-1, 5-diol, and polyethylene glycols, polypropylene glycols and polytetrahydrofurans having molecular weights of 200 to 10,000. In addition to the homopolymers of ethylene oxide or propylene oxide and block copolymers of ethylene oxide or propylene - oxide or copolymers containing incorporated incorporated ethylene oxide and propylene oxide groups. Examples of underlying alcohols having more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1, 2,5-pentanetriol, 1, 2,6-hexanetriol, cyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose. Of course, the polyhydric alcohols can also be used after reaction with ethylene oxide or propylene oxide as the corresponding ethoxylates or propoxylates. The polyhydric alcohols can also be first converted by reaction with epichlorohydrin in the corresponding glycidyl ether.

Further suitable crosslinkers are the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically unsaturated C3-C6-carboxylic acids, for example

Acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Examples of such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopene tenyl alcohol, 10-undecene-1-ol, cinnamyl alcohol, citronellol,

Crotyl alcohol or cis-9-octadecene-1-ol. However, it is also possible to esterify the monohydric, unsaturated alcohols with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.

Further suitable crosslinkers are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid. Also suitable as crosslinking agents are straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which may not be conjugated in aliphatic hydrocarbons, eg. B. divinylbenzene, divinyltoluene, 1, 7-octadiene, 1, 9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes having molecular weights of 200 to 20,000.

Other suitable crosslinking agents are the acrylic acid amides, methacrylic acid amides and N-allylamines of at least divalent amines. Such amines are for. B. 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, 1, 12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine. Also suitable are the amides of allylamine and unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids, as described above.

Further, triallylamine and Triallylmonoalkylammoniumsalze, z. As triallylmethylammonium chloride or methyl sulfate, suitable as a crosslinker.

Also suitable are N-vinyl compounds of urea derivatives, at least divalent amides, cyanurates or urethanes, for example of urea, ethyleneurea, propylene urea or tartaramide, for. B. Ν, Ν'-Divinylethylenharnstoff or Ν, Ν'- Divinylpropylenharnstoff.

Further suitable crosslinkers are divinyldioxane, tetraallylsilane or tetravinylsilane. Of course, it is also possible to use mixtures of the abovementioned compounds. Preferably, water-soluble crosslinkers are used. Furthermore, the crosslinking monomers include those which in addition to an ethylenically unsaturated double bond, a reactive functional group, eg. Example, an aldehyde group, a keto group or an oxirane group, which can react with an added crosslinker. Preferably, the functional groups are keto or aldehyde groups. The keto or aldehyde groups are preferably bound to the polymer by copolymerization of copolymerizable, ethylenically unsaturated compounds with keto or aldehyde groups. Suitable such compounds are acrolein, methacrolein, vinyl alkyl ketones having 1 to 20, preferably 1 to 10, carbon atoms in the alkyl radical, formylstyrene, (Meth) acrylic acid alkyl ester having one or two keto or aldehyde, or an aldehyde and a keto group in the alkyl radical, wherein the alkyl radical preferably comprises a total of 3 to 10 carbon atoms, for. B. (meth) acryloxyalkylpropanale, as described in DE-A-2722097. Furthermore, N-oxoalkyl (meth) acrylamides as described, for. From US-A-4226007, DE-A-2061213 or DE-A-2207209 are known. Particularly preferred are acetoacetyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate and especially diacetone acrylamide. The crosslinkers are preferably a compound having at least two functional groups, especially two to five functional groups, which can undergo a crosslinking reaction with the functional groups of the polymer, especially the keto or aldehyde groups. These include z. As hydrazide, hydroxylamine or oxime ether or amino groups as functional groups for the crosslinking of the keto or aldehyde groups. Suitable compounds with hydrazide groups are, for. B. Polycarbonsäurehydrazide having a molecular weight of up to 500 g / mol. Particularly preferred hydrazide compounds are dicarboxylic acid dihydrazides having preferably 2 to 10 C atoms. These include z. For example, oxalic acid dihydrazide, malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, sebacic dihydrazide, maleic dihydrazide, fumaric dihydrazide, itaconic dihydrazide and / or isophthalic dihydrazide. Of particular interest are adipic dihydrazide, sebacic dihydrazide and isophthalic dihydrazide. Suitable compounds with hydroxylamine or oxime ether groups are, for. As mentioned in WO 93/25588.

Also by a corresponding addition of the aqueous polymer dispersion (PD), a surface crosslinking can be additionally produced. This includes z. B. addition of a photoinitiator or siccative. Suitable photoinitiators are those which are excited by sunlight, for example benzophenone or benzophenone derivatives. Sikkativierung are the recommended for aqueous alkyd resins metal compounds, for example based on Co or Mn (review in U. Poth, polyester and alkyd resins, Vincentz Network 2005, p 183 f).

The crosslinking component is preferably used in an amount of from 0.0005 to 5% by weight, preferably from 0.001 to 2.5% by weight, in particular from 0.01 to 1.5% by weight, based on the total weight of the used for the polymerization of monomers (including the crosslinker) used.

A special embodiment are polymer dispersions (PD) which contain no crosslinker polymerized.

The radical polymerization of the monomer mixture (M) can be carried out in the presence of at least one regulator. Regulators are preferably used in an amount of 0.0005 to 5 wt .-%, particularly preferably from 0.001 to 2.5 wt .-% and in particular from 0.01 to 1, 5 wt .-%, based on the total weight of the Polymerization used monomers used. Regulators (polymerization regulators) are generally compounds with high transfer constants. Regulators accelerate chain transfer reactions and thus cause a reduction in the degree of polymerization of the resulting polymers without affecting the gross reaction rate. In the case of the regulators, one can distinguish between mono-, bi- or polyfunctional regulators, depending on the number of functional groups in the molecule which can lead to one or more chain transfer reactions. For example, suitable regulators are described in detail by KC Berger and G. Brandrup in J. Brandrup, EH Immergut, Polymer Handbook, 3rd ed., John Wiley & Sons, New York, 1989, pp. 11-81-11 / 141.

Suitable regulators are, for example, aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde.

It is also possible to use as regulators: formic acid, its salts or esters, such as ammonium formate, 2,5-diphenyl-1-hexene, hydroxylammonium sulfate, and hydroxylammonium phosphate.

Other suitable regulators are halogen compounds, for. As alkyl halides such as carbon tetrachloride, chloroform, bromotrichloromethane, bromoform, allyl bromide and benzyl compounds such as benzyl chloride or benzyl bromide.

Other suitable regulators are allyl compounds, such as. As allyl alcohol, functionalized allyl ethers such as allyl ethoxylates, alkyl allyl ethers or glycerol monoallyl ether. Preference is given to using compounds which contain sulfur in bound form as regulators.

Compounds of this type are, for example, inorganic hydrogen sulfites, disulfites and dithionites or organic sulfides, disulfides, polysulfides, sulfoxides and sulfones. These include di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-t-butyl trisulfide, dimethyl sulfoxide, Dialkyl sulfide, dialkyl disulfide and / or diaryl sulfide.

Also suitable as polymerization regulators are thiols (compounds which contain sulfur in the form of SH groups, also referred to as mercaptans). Preferred regulators are mono-, bi- and polyfunctional mercaptans, mercaptoalcohols and / or mercaptocarboxylic acids. Examples of these compounds are allyl thioglycolates,

Ethyl thioglycolate, cysteine, 2-mercaptoethanol, 1, 3-mercaptopropanol, 3-mercaptopropan-1, 2-diol, 1, 4-mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglycerol, thioacetic acid, thiourea and alkylmercaptans, such as Butylmercaptan, n-hexylmercaptan or n-dodecylmercaptan. Examples of bifunctional regulators containing two sulfur atoms in bonded form are bifunctional thiols such as. As dimercaptopropanesulfonic acid (sodium salt), dimercaptosuccinic acid, dimercapto-1-propanol, dimercaptoethane, dimercaptopropane, dimercaptobutane, dimercaptopentane, dimercaptohexane, ethylene glycol bis-thioglycolate and butanediol bis-thioglycolate. Examples of polyfunctional regulators are compounds containing more than two sulfur atoms in bonded form. Examples of these are trifunctional and / or tetrafunctional mercaptans.

All mentioned controllers can be used individually or in combination with each other. A specific embodiment relates to polymer dispersions PD which are prepared by free-radical emulsion polymerization without addition of a regulator.

To prepare the polymers, the monomers can be polymerized by means of free-radical initiators.

As initiators for the radical polymerization, the peroxo and / or azo compounds customary for this purpose can be used, for example alkali or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl permaleinate, cumene hydroperoxide,

Diisopropyl peroxydicarbamate, bis (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide, azo-bis-isobutyronitrile, 2,2'-azo bis (2-amidinopropane) dihydrochloride or 2- 2'-azobis (2-methylbutyronitrile). Also suitable are mixtures of these initiators.

As initiators it is also possible to use reduction / oxidation (= red-ox) initiator systems. The redox initiator systems consist of at least one mostly inorganic reducing agent and one inorganic or organic oxidizing agent. The oxidation component is z. B. to the above-mentioned initiators for emulsion polymerization. The reduction component is z. B. to alkali metal salts of sulfurous acid, such as. For example, sodium sulfite, sodium hydrogen sulfite, alkali metal salts of the desulfurous acid such as sodium disulfite, bisulfite addition compounds aliphatic aldehydes and ketones, such as acetone bisulfite or reducing agents such as hydroxymethanesulfinic acid and salts thereof, or ascorbic acid. The red-ox initiator systems can be used with the concomitant use of soluble metal compounds whose metallic component can occur in multiple valence states. Usual Red Ox initiator systems are z. As ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / Na-hydroxymethanesulfinic acid. The individual components, eg. As the reduction component, mixtures may also be z. B. a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite. The amount of initiators is generally 0.1 to 10 wt .-%, preferably 0.1 to 5% by weight, based on all monomers to be polymerized. It is also possible to use a plurality of different initiators in the emulsion polymerization. The preparation of the polymer dispersion (PD) is usually carried out in the presence of at least one surface-active compound. A detailed description of suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, p. 41 1 to 420. Suitable emulsifiers are also found in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208.

Suitable emulsifiers are both anionic, cationic and nonionic emulsifiers. Emulsifiers whose relative molecular weights are usually below those of protective colloids are preferably used as surface-active substances.

Useful nonionic emulsifiers are araliphatic or aliphatic nonionic emulsifiers, for example ethoxylated mono-, di- and trialkylphenols (EO degree: 3 to 50, alkyl radical: C4-C10), ethoxylates of long-chain alcohols (EO degree: 3 to 100, alkyl radical: C) ₈ -C ₃ 6) and polyethylene oxide / polypropylene oxide homo- and copolymers. These may comprise the alkylene oxide units randomly distributed or in copolymerized form in the form of blocks. Well suited z. B. EO / PO block copolymers. Preferred are ethoxylates of long-chain alkanols (alkyl radical C 1 -C 30, average degree of ethoxylation 5 to 100) and, with particular preference, those having a linear C 12 -C 20 -alkyl radical and a mean degree of ethoxylation of from 10 to 50 and also ethoxylated monoalkylphenols.

Suitable anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C8-C22), of sulfuric acid or phosphoric monoesters of ethoxylated alkanols (EO degree: 2 to 50, alkyl radical: C12-C18) and ethoxylated alkylphenols (EO degree : 3 to 50, alkyl radical: C4-C9), of alkylsulfonic acids (alkyl radical: C12-C18) and of alkylarylsulfonic acids (alkyl radical: Cg-Cis). Further suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208). Also suitable as anionic emulsifiers are bis (phenylsulfonic acid) ethers or their alkali metal or ammonium salts which carry a C ₄ -C 24 -alkyl group on one or both aromatic rings. These compounds are well known, for. From US-A-4,269,749, and commercially available, for example as Dowfax® 2A1 (Dow Chemical Company).

Other emulsifiers are the esters, ie the mono- and diesters, the phosphoric acid with optionally up to 20-fold alkoxylated Cs-Cso-alkanols, especially the monoesters. Often the mono- and diesters are provided side by side as a mixture. Further suitable emulsifiers are also the diesters of phosphoric acid, which are easily reacted with an optionally up to 20-times alkoxylated Cs-Cso-alkanol and additionally simply with a different Ci-C3o-alkanol, preferably with a

Ci-C7-alkanol, esterified.

Preferred emulsifiers are compounds of the general formula C _s H 2 S + 10 (CH 2 CH 2 O) t -P (= O) (OH) ₂ , where s is from 6 to 30 and t is from 0 to 20.

Preferred as emulsifiers are e.g.

Maphos 24 T (CioH ₂ iO (CH ₂ CH ₂ O) 4-P (= 0) (OH) 2) and

Maphos 10T ((2-ethylhexyl) phosphate), both from BASF BTC.

Further suitable emulsifiers are (ethoxylate fatty alcohols, organophosphate, polymer), the Lutensit ^® types, BASF SE, such as Lutensit ^® A-EP (fatty alcohol alkoxylate, organophosphate) or Lutensit ^® HC9812.

The polymer dispersions (PD) according to the invention generally contain up to 20% by weight, preferably up to 10% by weight, particularly preferably up to 5% by weight of at least one emulsifier, based on the total weight of the mono-emulsion polymerization - mere. The polymer dispersions (PD) according to the invention generally contain at least 0.05% by weight, preferably at least 0.1% by weight, of at least one emulsifier, based on the total weight of the monomers used for the emulsion polymerization.

Suitable cationic emulsifiers are preferably quaternary ammonium halides, e.g. B. trimethylcetylammonium chloride, methyltrioctylammonium chloride, benzyl triethylammonium chloride or quaternary compounds of N-C6-C2o-alkylpyridines,

-morpholines or -imidazoles, e.g. B. N-Laurylpyridinium chloride.

The amount of emulsifier is generally about 0.01 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on the amount of monomers to be polymerized.

The polymer dispersions (PD) can also be added to customary auxiliaries and additives. These include, for example, the pH-adjusting substances, reducing and bleaching agents, such as. For example, the alkali metal salts of hydroxymethanesulfinic acid (eg Rongalit® C from BASF SE), complexing agents, deodorants, flavorings, perfumes and viscosity modifiers, such as alcohols, eg. As glycerol, methanol, ethanol, tert-butanol, glycol, etc. These auxiliaries and additives can be added to the polymer dispersions in the template, one of the feeds or after completion of the polymerization. The polymerization is generally carried out at temperatures in a range from 0 to 150 ° C, preferably 20 to 100 ° C, particularly preferably 30 to 95 ° C. The polymerization is preferably carried out at normal pressure, but is also possible a polymerization under elevated pressure, for example, the autogenous pressure of the components used for the polymerization. In a suitable embodiment, the polymerization takes place in the presence of at least one inert gas, such as. As nitrogen or argon. The polymerization medium may consist of water only, as well as of mixtures of water and thus miscible liquids such as methanol. Preferably, only water is used. The emulsion polymerization can be carried out both as a batch process and in the form of a feed process, including a stepwise or gradient procedure. Preferably, the feed process, in which one submits a portion of the polymerization or a polymer seed, heated to the polymerization, polymerized and then the remainder of the polymerization, usually over several spatially separate feeds, of which one or more of the monomers in pure or in emulsified Form, continuously, stepwise or with the addition of a concentration gradient while maintaining the polymerization of the polymerization zone supplies.

The manner in which the initiator is added to the polymerization vessel in the course of the free radical aqueous emulsion polymerization is known to one of ordinary skill in the art. It can be introduced either completely into the polymerization vessel or used continuously or in stages according to its consumption in the course of the free-radical aqueous emulsion polymerization. Specifically, this depends in a manner known per se to those of ordinary skill in the art both on the chemical nature of the initiator system and on the polymerization temperature. Preferably, a part is initially charged and the remainder supplied according to the consumption of the polymerization. The dispersions formed during the polymerization can be subjected to a physical or chemical aftertreatment (chemical desorption) after the polymerization process. Such methods are, for example, the known methods for residual monomer reduction, such as. Example, the post-treatment by addition of polymerization initiators or mixtures of polymerization initiators at suitable temperatures, aftertreatment of the polymer solution by means of steam or ammonia vapor, or stripping with inert gas or treating the reaction mixture with oxidizing or reducing reagents, adsorption processes such as the adsorption of impurities on selected media such , As activated carbon or ultrafiltration. The aqueous acrylate-alkyd polymer dispersion (PD) usually has a solids content of from 20 to 70% by weight, preferably from 40 to 65% by weight, based on the polymer dispersion including the water-soluble alkyd resin or aqueous alkyd resin emulsion or polyurethane alkyd emulsion used.

The solids content in a specific embodiment is 30-55% by weight, preferably 35 to 50% by weight, particularly preferably 40 to 50% by weight, based on the aqueous acrylate-alkyd polymer dispersion including water-soluble alkyd resin or aqueous alkyd resin emulsion used or polyurethane alkyd resin emulsion. The theoretical glass transition temperature T _g of the acrylate portion of the acrylate-alkyd polymer dispersion is preferably less than 50 ° C but greater than 20 ° C, more preferably less than 40 ° C but greater than 20 ° C, in particular less than 30 ° C but greater than 20 ° C.

The glass transition temperature T _g is understood here to mean the "mid-point temperature" determined by differential thermal analysis (DSC) in accordance with ASTM D 3418-82 (compare Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A 21, VCH Weinheim 1992 169 and Zosel, paint and varnish 82 (1976), pp. 125-134, see also DIN 53765).

According to Fox (see Ullmann's Enzyklopadie der technischen Chemie, 4th Edition, Volume 19, Weinheim (1980), p. 17, 18), the glass transition temperature TG can be estimated. It applies to the glass transition temperature of weak or uncrosslinked Mischpoly-merisaten for large molar masses in a good approximation:

Tg where X ¹ , X ² , X ^{n are} the mass fractions 1, 2, n and T _g ¹ , T _g ² , T _g ⁿ the Glasübergangstempe- temperatures of each of only one of the monomers 1, 2, n constructed polymers in degrees Kelvin , The latter are z. From Ullmann's Encyclopedia of Industrial Chemistry, VCH, 5.ed. Weinheim, Vol. A 21 (1992) p 169 or from J. Brand-rup, EH Immergut, Polymer Handbook, 3 ^rd ed, J. Wiley, New York known 1989th The hybrid binder according to the invention or the aqueous alkyd system can be used as such or mixed with further, generally film-forming, polymers as a binder composition in aqueous coating compositions, such as dye or lacquer mixtures. Of course, the hybrid binder according to the invention can also be used as a component in the production of adhesives, sealants, plastic cleaning, paper coating slips, fiber webs, and coating compositions for organic substrates and for the modification of mineral binders.

The photoinitiator used in the hybrid binder according to the invention or in the aqueous alkyd system is understood as meaning, for example, benzophenone or acetophenone or one or more non-monoethylenically unsaturated acetophenone or benzophenone derivatives or a mixture of these active compounds, such as benzophenone / 4-methylbenzophenone or 2,4 , 6-trimethylbenzophenone. Other suitable photoinitiators are described in EP 417 568, page 3, line 39 to page 7, line 51 and this disclosure is explicitly referenced. Photoinitiators known to those skilled in the art may be used as further photoinitiators, for example those in Advances in Polymer Science, Volume 14, Springer Berlin 1974 or in KK Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, PKT Oldring (Eds), SITA Technology Ltd, London.

Suitable examples are phosphine oxides, α-hydroxy-alkyl-aryl ketones, thioxanthones, anthraquinones, benzoins and benzoin ethers, ketals, imidazoles or phenylglyoxylic acids or those as described in WO 2006/005491 A1, page 21, line 18 to page 22, line 2 (corresponding to US 2006/0009589 A1, paragraph [0150]), which is hereby incorporated by reference into the present disclosure.

A further subject of the invention is a coating composition in the form of an aqueous composition containing the aqueous hybrid binder according to the invention, or the aqueous alkyd system as defined above.

The hybrid binder according to the invention or the aqueous alkyd system is preferably used in aqueous paints. These paints are for example in the form of an unpigmented system (clearcoat) or a pigmented system. The proportion of pigments can be described by the pigment volume concentration (PVK). The PVK describes the ratio of the volume of pigments (VP) and fillers (VF) to the total volume, consisting of the volumes of binder (VB), pigments and fillers of a dried coating film in percent: PVK = (VP + VF) x 100 / ( VP + VF + VB). For example, paints can be classified using the PVK as follows: Highly filled interior paint, washable, white / matt PVK = approx. 85

Interior paint, scrub resistant, white / matt PVK = approx. 80 exterior façade, white PVC = approx. 45-55

Semi-gloss color, semi-gloss PVK = approx. 35

Semi-gloss color, silky gloss PVK = approx. 25

High gloss PVK = approx. 15-25

Clearcoat PVK = <5

These dispersions are preferably used in formulations having a PVK <50, more preferably PVK <40.

Suitable fillers in clearcoat systems are z. As matting agents, which greatly affect the desired gloss. Matting agents are usually transparent and can be both organic and inorganic. Inorganic fillers based on silica are the most suitable and are widely available commercially. Examples are the Syloid® brands from WR Grace & Company and the Acematt® brands from Evonik GmbH. Organic matting agents are available, for example, from the BYK-Chemie GmbH under the Ceraflour® and the Ceramat® grades, from Deuteron GmbH, under the Deuteron MK® brand. Other suitable fillers for emulsion paints are aluminosilicates such as feldspars, silicates such as kaolin, talc, mica, magnesite, alkaline earth carbonates such as calcium carbonate, for example in the form of calcite or chalk, magnesium carbonate, dolomite, alkaline earth sulfates such as calcium sulfate, silica, etc. In paints Naturally finely divided fillers are preferred. The fillers can be used as individual components. In practice, however, filler mixtures have proven particularly useful, for. Calcium carbonate / kaolin, calcium carbonate / talc. Glossy paints generally have only small amounts of very finely divided fillers or contain no fillers.

Finely divided fillers can also be used to increase the hiding power and / or to save on white pigments. To adjust the hiding power of the hue and the depth of shade, blends of color pigments and fillers are preferably used. Suitable pigments are, for example, inorganic white pigments, such as titanium dioxide, preferably in rutile form, barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, lithopones (zinc sulfide + barium sulfate) or colored pigments, for example iron oxides, carbon black, graphite, zinc yellow, zinc green, ultramarine, Manganese black, antimony black, manganese violet, Paris blue or Schweinfurter green. In addition to the inorganic pigments, the dispersion paints according to the invention may also contain organic color pigments, eg. B. Sepia, Cambogia,

Kasseler Braun, Toluidine Red, Para red, Hansa Yellow, Indigo, azo dyes, anthraquinoid and indigo dyes as well as dioxazine, quinacridone, phthalocyanine, isoindolinone and metal complex pigments. Also suitable are synthetic white pigments with air inclusions to increase light scattering, such as the Ropaque® and AQACell® dispersions. Also suitable are the Luconyl® grades from BASF SE, such as e.g. Lyconyl® Yellow, Luconyl® Brown and Luconyl® Red, especially the transparent variants.

In addition to the hybrid binder or aqueous alkyd system according to the invention, the coating composition (aqueous coating material) according to the invention may optionally contain additional film-forming polymers, pigment and other auxiliaries.

The usual auxiliaries include wetting or dispersing agents, such as sodium, potassium or ammonium polyphosphates, alkali metal and ammonium salts of acrylic or maleic anhydride copolymers, polyphosphonates, such as 1-hydroxyethane-1, 1-diphosphonsauresodium and Naphthalinsulfonsäuresalze, in particular their sodium salts ,

More important are the film-forming aids, thickeners and defoamers. Examples of suitable film-forming aids are Texanol.RTM. From Eastman Chemicals and the glycol ethers and esters, for example commercially available from BASF SE, under the names Solvenon.RTM. And Lusolvan.RTM., And from Dow under the trade names Dowanol.RTM. The amount is preferably <10 wt .-% and particularly preferably <5 wt .-% of the total formulation. It is also possible to formulate completely without solvents. Further suitable auxiliaries are leveling agents, defoamers, biocides and thickeners. Suitable thickeners are z. B. Associative thickener, such as polyurethane thickener. The amount of thickener is preferably less than 2.5 wt .-%, more preferably less than 1, 5 wt .-% thickener, based on solids content of the paint. Further formulations for wood coatings are described in detail in "water-based acrylates for decorative coatings" by the authors M. Schwartz and R. Baumstark, ISBN 3-87870-726-6.

The preparation of the paint according to the invention is carried out in a known manner by mixing the components in mixing devices customary for this purpose. It has proven useful to prepare an aqueous paste or dispersion from the pigments, water and optionally the adjuvants, and then first the polymeric binder, d. H. as a rule, to mix the aqueous dispersion of the polymer with the pigment paste or pigment dispersion.

The paint according to the invention can be applied to substrates in the usual way, for. B. by brushing, spraying, dipping, rolling, knife coating.

The paints of the invention are characterized by easy handling, good processing properties and high early hardness. The paints are low in emissions. They have good performance properties, eg. B. a good water resistance, good wet adhesion, especially on alkyd paints, good blocking resistance, a good recoatability and they show a good course when applied. The tool used can be easily cleaned with water.

The invention will be further illustrated by the following non-limiting examples.

Examples

Determination of the solids content The solids content (FG) was generally determined by drying a defined amount of the aqueous binder (about 1 g) in an aluminum crucible with an inner diameter of about 5 cm at 140 ° C. in a drying oven to constant weight. Two separate measurements were made. The values given in the examples represent the mean value of the respective two measurement results.

Examples 1 - 3

The water-dilutable alkyd resin WorleeSol® 61 E was previously adjusted to a solids content of 40% and a pH of about 8 with a 25% strength by weight aqueous ammonia solution and demineralized water.

The aqueous alkyds WorleeSol® E 150 W and E 280 W were used as received from the suppliers. Example 4

The following were placed in a polymerization vessel equipped with dosing devices and temperature control:

Template: 1 16 g of water

19.2 g of a polystyrene seed dispersion having a solids content of 33% and

a mean particle size of 30 nm

1.5 g of a 15% solution of sodium lauryl sulfate and heated to 85 ° C. with stirring. Then, while maintaining this temperature, 10% of feed 3 was added and stirred for 5 min. Then, feed 1 was added in 180 minutes and, in parallel, the residual amount of feed 3 in 195 min.

Feed 1: 79.5 g of water

51.2 g of a 15% solution of sodium lauryl sulfate

1 17 g of n-butyl acrylate

97.1 g of methyl methacrylate

65.5 g of styrene

13.5 g of acetoacetoxyethyl methacrylate

Feed 2: 393 g of a 40% aqueous solution of WorleeSol 61 E, which

previously neutralized with 25% aqueous ammonia solution

has been

Feed 3: 72.2 g of a 2.5% aqueous solution of sodium peroxodisulfate

When Feed 3 was ended, 22.6 g of rinse water were metered in, followed by postpolymerization for 30 minutes. Feed 2 was metered in over 1 h and then neutralized with 1.81 g of a 25% aqueous solution of ammonia.

Subsequently, the dispersion was cooled and filtered through a 125 μηη filter. There was obtained 1, 04 kg of a 45% dispersion. Example 5

As Example 4, but as feed 2: 395 g WorleeSol® E 150 W

Example 6

As Example 4, but as feed 2: 416 g WorleeSol® E 280 W 2. Testing of the aqueous hybrid binder

pendulum hardness

The coating to be tested was knife-coated with an Erichsen film applicator (300 μηη wet) on a 38 × 7 cm glass plate. After drying at room temperature, three measured values were blotted on three places of the glass plate. The measurement was carried out according to König (DIN EN ISO 1522).

Examples

Formulation of the polymer dispersion (PD) with photoinitiator

100 g of the polymer dispersion (PD) were initially introduced at room temperature in a stirred vessel and then, with stirring, 1 or 2% by weight of Esacure® TZM (from Lehmann & Voss & Co., Germany), a mixture of benzophenone and 4- Methylbenzophenone, based on solids content of the respective polymer dispersion was added and stirred for 15 min.

Subsequently, a film was knife-dried and dried in the absence of light for 3 days. Then, the film was stored in a light position and the development of the pendulum hardness was followed by measuring each at 24, 72 and 168 hours. As a comparison, the hardness development of a film of the pure binder was used.

Example 1: WorleeSol 61 E (oxidatively drying, water-reducible alkyd from the company Worlee)

Example 2: WorleeSol E 150 W (oxidatively drying, water-based PU alkyd emulsion from Worlee)

Pendulum hardness [s] 24 h 72 h 168 h

without addition 15 22 34

with 1% by weight of Esa 21 28 35

cure®TZM (f / f)

with 2% by weight of Esa21 28 36

cure ®TZM (f / f) Example 3: WorleeSol E 280 W (non-oxidatively drying, water-based PU alkyd emulsion of

Fa. Worlee)

It is clear from the results of Examples 1 and 2 that the hardness development is accelerated when photoinitiator is present.

Example 4 Acrylate / Alkyd Hybrid Using WorleeSol 61 E as Alkyd Part (oxidatively drying, water-reducible alkyd from the company Worlee)

Example 5 Acrylate / Alkyd Hybrid Using WorleeSol E 150 W as Alkyd Part (oxidatively drying, water-based PU alkyd emulsion from Worlee)

Example 6 Acrylate / Alkyd Hybrid Using WorleeSol E 280 W as Alkyd Part (non-oxidatively drying, water-based PU alkyd emulsion from Worlee)

Pendulum hardness [s] 24 h 72 h 168 h

without addition 28 27 34

with 1% by weight of Esa28 29 39

cure ®TZM (f / f)

with 2% by weight of Esa20 35 50

cure ®TZM (f / f) Examples 4 - 6 also clearly show that the use of the photoinitiator has a significant influence on the hardness development.

Claims

Patent claims

Aqueous hybrid binder containing an aqueous polymer dispersion (PD), obtainable by radical emulsion polymerization of

(a) at least one α,β-ethylenically unsaturated monomer (M)

(b) and optionally at least one further monomer (M1) to form a polymer (P)

(c) optionally subsequent chemical deodorization and

(d) adding at least one water-soluble alkyd resin with a weight-average molecular weight between 5,000 and 40,000 Da or at least one aqueous alkyd or polyurethane alkyd emulsion or dispersion, characterized in that the addition of the alkyd resin, the alkyd or polyurethane alkyd emulsion or .-Dispersion either

i. directly following the polymerization of M and M1, and if necessary the chemical deodorization at room temperature ii. following the polymerization of M and M1 with a subsequent stirring time of 0-2 h or

iii. following the chemical deodorization with a subsequent stirring time of 0-2 hours,

wherein the temperature during the addition according to (ii) or (iii) is 60 to 99 ° C, preferably 70 to 95 ° C and in particular 80 to 90 ° C, as well as 0.01 -5% by weight of a photoinitiator.

Aqueous hybrid binder according to claim 1, characterized in that the photoinitiator is added to the polymer dispersion cooled to room temperature (23 ° C).

Aqueous hybrid binder according to claims 1 or 2, characterized in that the main monomers M1 are selected from the group

n-butyl acrylate, methyl methacrylate;

n-butyl acrylate, methyl methacrylate, styrene;

n-butyl acrylate, styrene, butyl (meth)acrylate;

n-butyl acrylate, ethylhexyl acrylate, styrene,

n-Butyl acrylate, styrene or

n-Butyl acrylate, n-Butyl (meth) acrylate, methyl methacrylate.

Aqueous hybrid binder according to one of claims 1 to 3, characterized in that acrylic acid, methacrylic acid, acrylamide, methacrylamide, AAEM, UMA or Bisomer ® or mixtures thereof are used as monomers M2 in combination with the monomers M1 according to claim 6.

5. Aqueous hybrid binder according to one of claims 1 to 4, characterized in that the polymer dispersion (PD) contains 5-60% by weight (solid), based on the total weight of the hybrid binder, of at least one water-soluble alkyd resin or an aqueous alkyd - or polyurethane alkyd emulsion.

6. Aqueous hybrid binder according to one of claims 1 to 5, characterized in that the glass transition temperature T _g of the acrylate part of the acrylate-alkyd polymer dispersion (PD) is less than 50 ° C but greater than 20 ° C.

7. Aqueous alkyd system containing at least one water-soluble alkyd resin or an aqueous alkyd or polyurethane alkyd emulsion or dispersion, and 0.01 - 5% by weight of a photoinitiator

8. Coating agent in the form of an aqueous composition containing:

at least one hybrid binder according to the invention according to one of claims 1 to 6,

optionally at least one inorganic filler and/or inorganic pigment,

common aids, and

Water to 100% by weight.

9. Coating agent in the form of an aqueous composition containing:

at least one aqueous alkyd system according to the invention according to claim 7,

optionally at least one inorganic filler and/or inorganic pigment,

common aids, and

Water to 100% by weight.

10. Coating agent according to claim 8 or 9, characterized in that the coating agent is a paint.

1 1 . Process for producing an aqueous hybrid binder, by producing an aqueous polymer dispersion (PD) by radical emulsion polymerization of at least one α,β-ethylenically unsaturated monomer (M)

and optionally at least one further monomer (M1).

Polymer (P)

optionally subsequent chemical deodorization and

Adding at least one water-soluble alkyd resin with a weight-average molecular weight between 5,000 and 40,000 Da or at least one aqueous alkyd or polyurethane alkyd emulsion,

characterized in that the addition of the alkyd resin, the alkyd or polyurethane alkyd emulsion or dispersion either i. directly following the polymerization of M and M1, and if necessary the chemical deodorization at room temperature

ii. following the polymerization of M and M1 with a subsequent stirring time of 0-2 h or

iii. following the chemical deodorization with a subsequent stirring time of 0-2 h, the temperature during the addition after (ii) or (iii) being 60 to 99 ° C, preferably 70 to 95 ° C and in particular 80 to 90 ° C is, as well as the addition of 0.01 -5 wt .-% of a photoinitiator.

12. Use of an aqueous hybrid binder according to one of claims 1 to as a binder in paints.

13. Use of an aqueous alkyd system according to claim 7 in paints.

14. Use of an aqueous hybrid binder or an aqueous alkyd system according to claim 12 or 13, characterized in that the paint is a clear varnish or a dispersion paint.

15. Use of an aqueous hybrid binder or an aqueous alkyd system according to claim 12 or 13, characterized in that the paint is a high-gloss clear varnish or a high-gloss emulsion paint.

16. A method for increasing the early hardness development of a coating based on an aqueous hybrid binder according to one of claims 1 to 6.

17. Process for increasing the early hardness development of a coating based on an aqueous alkyd system according to claim 7.