NO172852B - PROCEDURE FOR THE PREPARATION OF A WATER-DILINABLE AIR-DRY PAINTING AGENT - Google Patents

Description

The invention relates to a method for producing water-thinnable air-drying lacquer binders based on vinyl- or (meth)acrylic-modified alkyd resin emulsions and their use in oxidative, at temperatures up to 100°C, air-drying, water-thinnable lacquers.

Due to the growing ecological problems, the need for a drastic reduction of solvent emissions is also becoming increasingly stronger in the area of varnish and paint. While in the area of industrially used burn-in varnishes with special methods such as electro-dip varnishing or the use of "high-solid" systems or powder coating, a significant reduction of the solvent emission has already been achieved, there is for air-drying varnishes, as they are processed as so-called paint varnishes in large quantities, both industrially and in a "do-it-yourself" system, no satisfactory solution. Likewise, the known water-dilutable binders for air-drying industrial varnishes are only suitable to a limited extent.

Physically drying water-based systems, such as polymer dispersions, are significantly inferior to the solvent-based alkyl resin varnishes with regard to spreadability, smoothness, gloss and fullness. In addition, due to their thermoplasticity when exposed to sunlight, they tend to pick up dirt and "block", that is to say, stick lacquered surfaces together. When used in single-layer varnish for coating iron surfaces, the polymer dispersion fails as corrosion protection. In order to obtain a sufficient protective effect, a two-time application of a layer thickness of more than 80 µm is usually necessary.

With water-soluble alkyd resins or alkyd resin emulsions, the requirements as they are set for paint varnish, respectively air-drying industrial varnish, in terms of processing technology and with regard to the film properties, can already be strongly met. Their use has so far been limited by the lack of storage stability of the products and the too strong yellowing of the films during ageing.

Attempts to overcome the disadvantages of the individual components by mixing the two binder groups usually end up being incompatible.

Similar problems also arise for wood glazes, in that in the case of polymer dispersions the lack of penetration ability, in the case of water-dilutable alkyl resins, the lack of storage stability is decisive for their unsuitability.

Attempts have already been made to prepare the polymer dispersion in the presence of water-dilutable alkyd resins. By suitable selection of components and reaction conditions, it is easier in this case to achieve the desired compatibility.

Thus, US-PS 4,116,903 describes copolymer dispersions, where water-soluble alkyd resins based on isophthalic acid and trimellitic acid are used as emulsifier components.

With the help of these acids, a better hydrolysis stability of the alkyd resins is usually achieved than with the otherwise common orthophthalic anhydride (see E.T. Turpin, "Hydrolysis of Water-dispersible Resins", "Journ. of Paint Technl.", 47, 602, 40-46, March 1975 or J.J. Engel, "Problems of Airdrying Waserborne Alkyds", "Waterborn + Higher Solids Coating Symposium", New Orleans Feb. 1983).

In practice, however, the stability of the dispersions produced in this way is not sufficient in this case either. The progressive hydrolysis of the alkyd resin components leads, on the one hand, by splitting off end-positioned carboxyl groups, to a loss of emulsifying or dispersing effect for the polymer part and the pigments, on the other hand, by breaking down the alkyd resin molecules, to a decrease in the drying speed and film quality.

As maleic acid adducts on unsaturated oils or fatty acids exhibit carboxyl groups that cannot be split off as half-esters by hydrolysis, attempts have been made to use these products as a basis for polymerisation.

As appears from US-PS 2 941 968, according to which vinyl monomers are grafted onto maleic acid adducts of drying oils, or in GB-PS 1 534 432 where maleic acid adducts of fatty acid esters of styrene allyl alcohol copolymers are used as a basis for a copolymerization of (meth)acrylic acid esters , resulting in emulsions with good stability.

In the production of varnish, however, it turns out that the maleic anhydride adducts have a poor compatibility with siccatives and pigments, and it is not possible to produce shiny decorative varnishes.

From AT-PS 365 215 or AT-PS 369 774, alkyd resin emulsions are known, where the alkyd resins acting as emulsifiers are structured so that the carboxyl groups effective for salt formation are introduced by copolymerizing methacrylic acid with part of the fatty acids used for alkyd resin formation. Lacquers on this basis are well suited for many purposes, where the required storage capacity amounts to approx. 1 year. However, after storage times of more than 1 year, the same disadvantages as known for isophthalic acid or trimellitic acid curing resins appear. Since for the so-called paint varnishes, but also for car repair varnishes and wood glazes, storage resistances of 2 to 3 years are required, no successful result could be achieved with these types of binder either.

In continuation of these works, a significant improvement could surprisingly be achieved, both with regard to storage resistance, as well as with regard to varnish properties, for example yellowing, when using alkyd resins, urethane alkyd resins or epoxy resin esters, where, in the case of the products according to AT- PS 365 215 and AT-PS 369 774 the carboxyl groups were incorporated into fatty acid-methacrylic acid copolymers as emulsifier resins for the polymerisation of vinyl and/or (meth)acrylic monomers in an aqueous medium.

According to this, the present invention relates to a method for the production of a water-dilutable, air-drying lacquer binder based on vinyl and/or (meth)acrylic-modified alkyd resin emulsions, and this method is characterized by the fact that 20 to 70 wt.-# of a mixture of vinyl - and/or (meth)-acrylic monomers which essentially do not carry any functional groups in addition to the C-C double bond, are polymerized in the presence of an aqueous solution or emulsion which, if desired, can contain smaller amounts of auxiliary solutions, of 30 to 80 wt-# of an alkyd resin and/or urethane alkyd resin and/or epoxy resin ester, which is water-soluble after at least partial neutralization and which has a total content of 40 to 70 wt-% fatty acids of which 10 to 40 wt-#, calculated on the emulsifier resin, is grafted with methacrylic acid and additional monomers, in which at least 80$ of the free carboxyl groups, corresponding to an acid number from 35 to 70 mg KOH/g, originates from the methacrylic acid names which, together with other vinyl and/or (meth)acrylic monomers which do not carry additional functional groups in addition to the C-C double bond, are grafted onto a part of the unsaturated fatty acids, before the resin formation, and

up to 20 wt-# of a water-insoluble alkyd resin and/or urethane alkyd resin and/or epoxy resin ester and/or a

optionally pre-polymerized drying oil, which is emulsified in the water-soluble resin,

at 60 to 80°C in the presence of a free radical initiator up to a polymerization conversion of at least 95$, the sum of the percentage figures for the composition always being 100$.

Due to the high non-saponifiable polymer part, these products show a significantly improved storage stability, without the thermoplasticity, which is otherwise common with polymers, appearing when dried well. As expected, the products show a slight yellowing of the aged films. Surprisingly, the products also show good pigment wetting and good gloss without the co-use of polyethylene glycols in the alkyd resin formulation. Of course, the use of these components is not excluded. In special cases, the lacquer formulation can thereby be made easier, for example by using "difficult" pigments.

A further advantage is evident from the fact that, in contrast to the products from the state of the art, the products retain the good pigment wetting and gloss properties also when using ammonia or also with alkali hydroxides in

instead of the ecologically undesirable organic amines, for salt formation.

The alkyd resins, urethane alkyd resins or epoxy resin esters used as emulsifier resins in the process according to the invention are, due to at least partial salt formation with ammonia or organic amines, water-soluble due to their carboxyl groups. It should be noted that this water solubility does not necessarily lead to clear solutions. As is known to those skilled in the art, the products in these solutions are present as larger resin micelles, so that the solution can also have an opaque or even cloudy appearance. The emulsifier resins have as a common feature a content of free acid groups corresponding to an acid number of 35 to 70 mg KOH/g, in which at least 80% of these acid groups originate from methacrylic acid esters which, in a separate reaction step, were grafted onto at least part of the used unsaturated fatty acids. Otherwise, the alkyd resins, the urethane alkyd resin and the epoxy resin esters show the structure known from the literature.

The content of these resins of drying and/or semi-drying fatty acids is between 40 and 70% by weight. Of these fatty acids, a portion of 10 to 40% by weight, calculated on the resin weight, is introduced in the form of fatty acid-methacrylic acid copolymer.

The alkyd resins used according to the invention are further particularly characterized in that they have a content of 10 to 25 wt-# of polyalcohols with 2 to 6 hydroxyl groups, 10 to 15 wt-# of aromatic and/or aliphatic dicarboxylic acids, 0 to 10 wt-# cyclic and/or polycyclic monocarboxylic acids and 0 to 10 wt% of a polyethylene glycol. The products have a limit viscosity number between 7 and 14 ml/g, measured in chloroform at 20°C.

The urethane alkyd resin contains 10 to 25% by weight of polyalcohols with 2 to 6 hydroxyl groups, 0 to 10% by weight of aromatic and/or aliphatic dicarboxylic acids, 5 to 15% by weight of aromatic and/or aliphatic and/or cycloaliphatic diisocyanates, 0 to 10% by weight of cyclic and/or polycyclic monocarboxylic acids and 0 to 10% by weight of a polyethylene glycol. Their limit viscosity number is between 8 and 14 ml/g (CHC13/20°C).

In addition to the fatty acids and fatty acid methacrylic acid copolymers, the epoxy resin esters contain 15 to 35% by weight of epoxy resins, preferably the commercially available bisphenol A di-epoxide resins, with an epoxy equivalent weight of between approx. 180 and approx. 500, as well as 0 to 10% by weight of a polyethylene glycol. The limiting viscosity number is 8 to 14 ml/g (CHCl3/20<0>C). For the purification of the grafted fatty acids, unsaturated fatty acids with an iodine number above 135 (preferably 160-200) and with predominantly isolated positions for the double bonds are used. Suitable are, among other things, linseed oil fatty acid, safflower oil fatty acid and the fatty acids of hemp, lallemantia, perilla and stillingia oil, possibly in a mixture with 1 to 25$ of dehydrated castor fatty acid or a comparable conjuen fatty acid produced by isomerization.

The fatty acid copolymers consist of 30 to 50 wt-# of the above-mentioned fatty acids, 10 to 25 wt-# of methacrylic acid and 30 to 55 wt-# of other monomers, which besides the C-C double bond have no further functional groups, in the sum of the percentages must give 100. As monomers, which are used next to methacrylic acid, preferably (meth)acrylic compounds and aromatic vinyl compounds serve, especially those which form benzine-soluble polymers with a glass transition point (Tg) of 20 to 60°C.

Suitable are, among other things, esters of methacrylic acid and acrylic acid with n-butanol, isobutanol, tert-butanol or 2-ethylhexanol. To set the copolymer's optimum Tg range or the resulting film hardness, vinyltoluene is used. In small amounts (up to $20), monomers can also be used, which form petrol-insoluble polymers such as methyl methacrylate or styrene.

The graft copolymerization is carried out in such a way that the main amount of the fatty acids, possibly in the presence of smaller amounts of inert solvents, is heated to 110-150°C, and the mixture of the monomers with a suitable initiator and the remaining fatty acid is added over the course of a few hours. The reaction mixture is then kept at the reaction temperature until a residual determination occurs, giving a polymerization conversion of over 95%. Examples of initiators include di-tert-butyl peroxide, tert-butyl perbenzoate and cumene hydroperoxide.

The thus produced fatty acid-methacrylic acid graft copolymers are processed together with further fatty acids into water-soluble alkyd resins, urethane alkyd resins or epoxy resin esters. As fatty acids, vegetable or animal fatty acids can be used in this step, with an iodine value above 120, preferably in which part of the double bonds must be in the conjugated position. Soy, linseed oil, safflower oil, tall oil and castor fatty acids are suitable.

As polyols and dicarboxylic acids, all products that are also used for the production of normal alkyd resins are taken into consideration for the production of the alkyd resin. Trimethylolethane, trimethylolpropane, pentaerythritol and sorbitol are preferably used as polyols and ortho- or isophthalic acid, as well as adipic acid as dicarboxylic acid. Cyclic or polycyclic monocarboxylic acids such as resin acid or benzoic acid can also be used to regulate the film hardness.

To improve the dispersing and emulsifying effect, parts of 1 to 10 wt-# of the polyethylene glycol with a molecular weight of 1,000 to 3,000 can also be incorporated.

The esterification can take place by joint heating of all components. When using high-melting raw materials such as pentaerythritol and isophthalic acid, it is, however, advisable in the first place to esterify fatty acids, polyols and dicarboxylic acids alone until a clear melt is obtained, and only then to add fatty acid-methacrylic acid copolymer. The esterification is then carried out until the final value of the acid number corresponds to approx. 90$ of the concentration of the carboxyl groups of the methacrylic acid. As these acid groups in the copolymer chains have a tertiary position and are thus sterically hindered, it can be assumed that they esterify significantly more slowly than the other carboxyl groups, and after the end of the reaction give the bulk of the free acid groups that cause the resin's water solubility.

As these acid groups are connected to the alkylene chain of the fatty acids by means of C-C bonds and the preferred grafting sites of the isolated unsaturated plant fatty acids are on the activated CH2 groups of and C14, there is a long hydrophobic molecular segment that blocks attack by water between the acid groups and the next ester bond. The alkyd resin components according to the invention are therefore superior to the previously known water-dilutable alkyd resins based on o-phthalic acid, isophthalic acid or trimellitic acid in terms of hydrolysis resistance.

In the production of the urethane alkyd resins, the unmodified fatty acids, possibly the dicarboxylic acid and the fatty acid-methacrylic acid copolymer, are first esterified in the same way as in the production of the alkyd resins with the polyols. The oligoester formed is then reacted in the presence of inert solvents with the isocyanates until the NCO content has fallen below 0.1% and the desired limit viscosity number has been reached.

In the production of the epoxy resin esters, the unmodified fatty acids, as well as the preferably used amine or alkali hydroxide catalyst, are introduced into the reactor. At approx. At 150°C, the epoxy resin is added in portions, and the mixture is heated to 180°C. The fatty acid copolymer is then added and the esterification is carried out at 170 to 200°C until the desired acid number or limit viscosity number is achieved.

The water-dilutable alkyd resins, urethane alkyd resins and epoxy resins thus produced serve as emulsifier resins for the production of the copolymer emulsion. Thereby, they are freed from inert solvents under vacuum, and pre-diluted with a portion of the water-compatible Co-solvents required for the emulsion production. Ammonia, organic amines or alkali hydroxides are then added, in the amount required to achieve impeccable water dilutability, and the total water, and by stirring at 60 to 80°C, an aqueous solution or emulsion is produced. The mixture of the monomers selected for the emulsion polymerization is then dosed again with the remaining water-compatible Co-solvent and the initiator over the course of a few hours. The reaction temperature is maintained until a polymerization conversion of more than 95% appears when determining the residue.

In a particular embodiment, part of the emulsifier resin is added slowly together with the monomer mixture.

Optionally, water-soluble alkyd resins, urethane alkyd resins, epoxy resin esters or possibly pre-polymerized drying oils and the like can also be emulsified together with the emulsifier resin up to 20%, calculated on the binder solids, and added during the emulsion polymerization.

As monomers for the emulsion polymerization, vinyl and/or (meth)acrylic compounds are essentially used which, next to the C-C double bond, have no further reactive group. Examples of such monomers are the acrylic acid alkanol esters, preferably of butanol or their isomers, or higher homologues, the methacrylic acid ester of methanol, ethanol, of propanols and butanols, as well as aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene and the like. To a lesser extent, monomers containing functional groups may also be used. For example, up to 10$, calculated on total binder, of OH-functional monomers, such as 2-hydroxyethyl methacrylate and also up to 2% of acidic monomers such as methacrylic acid, can also be co-used.

Azo compounds are best suited as initiators, for example azo-isobutyrodinitrile or azo-isovalerodinitrile. In principle, however, organic and inorganic peroxides such as dibenzoyl peroxide or potassium peroxydisulphate can also be used.

As organic, water-compatible co-solvents, methyl, ethyl and butyl ethers of ethylene glycol, diethylene glycol, 1,2-propylene glycol and dipropylene glycol are particularly suitable. Proportion-wise, only limited water-compatible solvents such as n- and iso-butanol can also be used. The total content of organic solvents in the finished emulsion must not exceed 1056.

In addition to ammonia, triethylamine, dimethylethanolamine, KOH, NaOH and LiOH are preferred for neutralization of the acid groups.

The binders produced according to the invention can be used in the usual way, in pigmented or non-pigmented form, possibly after the addition of common lacquer auxiliaries, by ironing, pouring, spraying or dipping. The coats are dried at room temperature or by forced air drying at temperatures up to 100°C. With a similar build-up of the binder and co-use of cross-linking agents, the binder can also be used for burn-in lacquers.

The invention will be explained in more detail with the help of some examples. All indications in parts or percentages are, unless otherwise stated, units of weight. The given limit viscosity numbers were determined in chloroform or dimethylformamide (DMF) at 20°C and are given in ml/g.

(I) Production of fatty acid-methacrylic acid copolymers

Copolymer C 1: 30 parts of linseed oil fatty acid and 5 parts of xylene are heated to 135 to 140° C. At this temperature, a mixture of 32 parts of isobutyl methacrylate, 6 parts of vinyl toluene and 21 parts of methacrylic acid is added evenly over the course of 6 to 8 hours. and a mixture of a further 11 parts of linseed oil fatty acid, 3 parts of tert-butyl perbenzoate, 1 part of dibenzoyl peroxide (50 #-ig) and 5 parts of xylene. After the end of the addition, the reaction temperature is maintained until a residue determination gives at least 95% polymerization conversion. If the reaction progress is too slow, mix the mixture with 1 part tert-butyl benzoate. The copolymer has an acid number of 209 mg KOH/g, and a limiting viscosity number (DMF) of 5.5.

Copolymer C 2: A copolymer of 41 parts linseed oil fatty acid, 22 parts isobutyl methacrylate, 10 parts n-butyl methacrylate, 10 parts vinyltoluene and 17 parts methacrylic acid in the presence of 10 parts xylene is prepared in the same way. The copolymer has an acid number of 185 mg KOH/g and a limiting viscosity number (DMF) of 5.1.

Copolymerizate C 3: 36 parts of linseed oil fatty acid are heated with 5 parts of xylene to 135 to 140°C. Then, over the course of 6 to 8 hours, a mixture of 31 parts of n-butyl methacrylate, 7 parts of styrene, 21 parts of methacrylic acid and 0 .5 parts dodecyl mercaptan, as well as a mixture of 5 parts dehydrated castor oil fatty acid, 5 parts xylene, 5 parts tert-butyl perbenzoate, 1 part dibenzoyl peroxide. After completion of the polymerization, the product has an acid number of 211 mg KOE/g and a limiting viscosity number (DMF) of 4.9.

(II) Preparation of the emulsifier resin

(a) Alkyd resins; According to the composition given in table 1, alkyd resins are produced in the following way: in a suitable reaction vessel, the components of part 1 are esterified at 230° C until a clear melt is formed. After a further hour, add • part 2, which reacts at 200°C until the specified final values are reached. (b) Urethane alkyd resins: Parts 1 and 2 are esterified as discussed under point (a), the acid number corresponds to approx. 95$ of the methacrylic acid carboxyl groups. The oligoesters formed are dissolved in so much toluene that the reaction product with the diisocyanate has a solids content of 60%. After heating at 60°C, the isocyanate is added and after completion of the addition, the temperature is increased to 100°C. The reaction is then continued until an NCO value of 0 is achieved and the desired limit viscosity number is reached. (c) Epoxy resin esters: The fatty acids specified in part 1 of the table and the catalyst are heated in a suitable reaction vessel under inert gas to 150°C. During 60 minutes, the epoxy resin is added in portions and then the fatty acid-methacrylic acid copolymer (part 2) is added at 180°C. The mixture is esterified at 200°C to obtain the final values.

Examples 1 to 11 according to the invention

The mixtures, as well as the solids contents and the pH value of the binder emulsion are listed in table 2.

When producing the emulsions, the emulsifier resins A1-A5, U1-U3 respectively E1 and E2 are freed from the solvent present by vacuum distillation. The mixture is then mixed with 10% by weight of ethylene glycol monobutyl ether

(BUGGLE).

About. 75% of this resin solution is mixed with the deionized water and the ammonia solution and heated with stirring to 70°C. To this milky to transparent resin solution is added evenly, at a constant temperature, the mixture of remaining alkyd resin, the monomers, remaining BUGL and the initiator, over the course of 4 hours. The temperature is maintained until the solids content specified in the table is reached. If necessary, adjust the pH value to approx. 9 with ammonia solution after cooling.

The dehydrated castor oil (DCO) used in example 5 is emulsified as an additional component with the first part of the alkyd resin with the water-ammonia mixture.

Comparative examples 1-4: To demonstrate the advantages of the products produced according to the invention in relation to the state of the art, emulsions were produced according to GB-PS 1 534 432, example 1 (= comparative example 1) and US-PS 4 116 903, example 1 (= comparison example 2).

Comparative example 3 corresponds to example 1 according to the invention, in that the emulsifier resin Al was replaced by the alkyd resin used in example li US-PS 4 116 903 (example

D).

To show the improvement of the properties compared to the products from AT-PS 369 774 and AT-PS 365 215, an emulsion according to example 1 from AT-PS 369 774 was prepared as comparative example 4.

Examination of the application technical properties

(A) Investigation of the storage stability

(Al) Varmel<g>rin<g>: The emulsions according to examples 1 and 11 and

comparative examples 1 to 4, were diluted with deionized water to a solids content of 30% and subjected to forced aging at 80°C. Any coagulation that occurred was assessed. The results of all investigations are listed in table 3. (M: The emulsion is still in very good condition after 200 hours of storage time).

(A2) Hydrolysis stability: A change of the acid number, of the pH value and the limiting viscosity number after a 96-hour

storage of the 30% emulsion at 70°C was investigated.

(B) Examination of clearcoats: The emulsions are mixed, calculated on solid resin with 2$ of a trade usual

water-compatible cobalt siccative solution and 1$ of a commercially available skin barrier agent based on oxime, is diluted so much with deionized water that a liquid clear coat is produced with a solids content of between approx. 35 and 40$. The varnishes are drawn onto glass strips after a maturation time of 24 hours, in a layer thickness that corresponds to a dry film thickness of 30 to 40 pm. The drying process is monitored with a corresponding device (for example Drying Recorder). (C) Examination of white lacquers: The emulsions were, as below (B), mixed with siccative and skin barrier agent and ground

up on a bead mill with titanium dioxide (rutile type) in a

pigment:binder ratio of 0.8:1. The examination of the varnish applied to the glass plate took place at a dry film thickness of 30 to 40 µm with regard to drying, hardness, gloss and water resistance. The drying examination took place as indicated at (B).

Examination of the hardness took place according to DIN 53 157 (KONIG). The specified values are seconds. The gloss measurement took place with the Gonioreflectometer GR-COMP, (Paar, Austria; Measuring angle 60°, indication in $ against the standard). The degree of yellowing is subjectively assessed on coats stored for 1 week at room temperature and then 24 hours at 80°C (1 = corresponding to a solvent-based soya alkyd resin used as a comparison standard, 63$ oil content; 5 = corresponding to a long-oiled 1in oil-wood oil-alkyd resin used as a comparison standard). Examination of the water resistance took place during 24 hours of storage in water at 20° C, of the films dried for a week at room temperature (E: Film softeners, regenerates after a few hours).

(D) Examination of colored equals. varnishes: A red machine varnish is produced using SICOMIN red L 3330

S (BASF AG) in a pigment:binder ratio of 0.5:1 and according to the specifications given under point (C), and examined.

(E) Investigation of corrosion. ion protection varnishes: Corresponding to the guidelines specified under (C), a

corrosion protection varnish which was produced in the above-mentioned manner according to the following recipe:

The varnish was applied 24 hours after production on glass plates or for the salt spray test (according to ASTM B-117-64) on degreased sheet steel.

Hardness and salt spray test are examined after 1 week of drying at 20° C (G/3 = little rusting, detachment at cross section maximum 3 mm).

(F) Discussion of the test results

The investigation of the storage stability at 80° C shows

clearly the superiority of the products according to the invention in relation to the products according to the state of the art. An exception thereby forms comparative example 1, however, it turns out that the formulation of decorative varnishes is completely impossible with products of this structure

(see (C), (D), gloss). In practice, it has been shown that with emulsions or lacquers according to comparative example 4, a storage time of 8 to 12 months is achieved. From the test results for the examples according to the invention, one can therefore assume a storage time of more than 2 years for these products. From the lacquer technical investigations, the superiority of the products according to the invention is immediately visible, with regard to the sum of the properties.

Claims (8)

1. Process for the production of a water-dilutable, air-drying lacquer binder based on vinyl and/or (meth)acrylic-modified alkyd resin emulsions, characterized in that 20 to 70% by weight of a mixture of vinyl and/or (meth)-acrylic monomers bearing essentially no functional groups in addition to the C-C double bond is polymerized in the presence of an aqueous solution or emulsion which, if desired, may contain smaller amounts of auxiliary solutions, of 30 to 80 wt-$ of an alkyd resin and/or urethane alkyd resin and/or epoxy resin ester, which is water-soluble after at least partial neutralization and which has a total content of 40 to 70 wt-$ fatty acids of which 10 to 40 wt-$, calculated on the emulsifier resin, is grafted with methacrylic acid and further monomers, in which at least 80$ of the free carboxyl groups, corresponding to an acid number from 35 to 70 mg KOE/g, originate from methacrylic acid units which, together with other vinyl and/or (meth)acrylic monomers which do not carries additional functional groups in addition to the C-C double bond, prior to resin formation, is grafted onto part of the unsaturated fatty acids, and up to 20% by weight of a water-insoluble alkyd resin and/or urethane alkyd resin and/or epoxy resin ester and/or an optionally pre-polymerized drying oil, which is emulsified in the water-soluble resin, at 60 to 80°C in the presence of a free radical initiator up to a polymerization conversion of at least 95$, the sum of the percentage figures for the composition always being 100$. 2. Process according to claim 1, characterized in that the fatty acid-methacrylic acid copolymer consists of 30 to 50 wt-$ of fatty acid with an iodine number of over 135, preferably of 160 to 200 and a predominant part of isolated multiple double bonds, 10 to 25 wt-# methacrylic acid and 30 to 55% by weight of other monomers, preferably (meth)acrylic compounds and/or aromatic vinyl compounds, especially those which form white-spirit soluble polymers with a glass transition point of 20 to 60°C. 3. Process according to claims 1 and 2, characterized in that the alkyd resins used as emulsifier resins, next to the fatty acid part and the grafted polymer part, consist of 10 to 25 weight-$ polyalcohols with 2 to 6 hydroxyl groups, 10 to 15 weight-$ aromatic and/or aliphatic dicarboxylic acids , up to 10 wt-$ of (poly)cyclic monocarboxylic acids and up to 10 wt-$ of a polyethylene glycol with a molecular weight between 1,000 and 3,000, and has an intrinsic viscosity of 7 to 14 ml/g measured in chloroform at 20°C. 4. Method according to claims 1 and 2, characterized in that the urethane alkyl resins used as emulsifier resins, next to the fatty acid part and the grafted polymer part, consist of 10 to 25 weight-$ polyalcohols with 2 to 6 hydroxyl groups, 5 to 15 weight-$ aromatic and/or aliphatic and /or cycloaliphatic diisocyanates, up to 10 wt-$ of aromatic and/or aliphatic dicarboxylic acids, up to 10 wt-# of (poly)cyclic monocarboxylic acids and up to 10 wt-$ of a polyethylene glycol with a molecular weight between 1,000 and 3,000 and having an intrinsic viscosity of 8 to 14 ml/g measured in chloroform at 20°C. 5 . Process according to claims 1 and 2, characterized in that the epoxy resin esters used as emulsifier resin, next to the fatty acid part and the grafted polymer part, consist of 15 to 35 wt-# of an epoxy resin, preferably a bisphenol-A diepoxide resin, with an epoxy equivalent weight of 180 to 500 , and up to 10% by weight of a polyethylene glycol with a molecular weight between 1,000 and 3,000 and having an intrinsic viscosity of 8 to 14 ml/g measured in chloroform at 20°C. 6. Method according to claims 1 to 5, characterized in that the fatty acids used next to the fatty acid methacrylic acid copolymer have an iodine number above 120. 7. Method according to claim 1, characterized in that as monomers for the emulsion polymerization, up to 10 wt.-$, calculated on total binder of hydroxy-functional monomers and/or up to 2 wt.-$, calculated on total binder of carboxyl-functional monomers are used. 8. Method according to claims 1 to 7, characterized in that part of the emulsifier resin is dosed together with the monomer mixture. to the polymerization mixture.