DE3432482A1 - Process for the preparation of emulsions of oxidatively drying alkyd resins - Google Patents

Abstract

The invention relates to a process for the preparation of aqueous emulsions of oxidatively drying polyethylene glycol-modified alkyd resins, which is characterised in that a copolymer of unsaturated fatty acids, methacrylic acid and vinyl or vinylidene compounds is reacted with polyethylene glycol and polyols, mono- and dicarboxylic acids to give an acrylic-modified alkyd resin. This component is partially esterified by means of an alkyd resin containing drying fatty acids, and the alkyd resin combination is emulsified in water with neutralisation of the acid groups. The emulsions have particularly good properties with respect to stability, dryability and gloss.

Description

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Process for the production of emulsions of oxidatively drying alkyd resins

VIANOVA KUNSTHARZ AKTIENGESELLSCHAFT A-8402 Werndorf, Styria

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Process for the production of emulsions of oxidatively drying alkyd resins .

The invention relates to a process for the production of aqueous alkyd resin emulsions with improved drying properties.

In AT-PS 372.097 a process for the preparation of aqueous emulsions of polyethylene glycol-modified

TO claimed oxidatively drying alkyd resins, which are suitable for the formulation of oxidatively drying paints. This process is characterized in that 70-85% by weight of a low-molecular alkyd resin precursor containing 15-5% by weight of drying fatty acids and having an intrinsic viscosity between 4.5 and 8.5 ml / g (measured in chloroform at 20 ° C), an acid number below 10, preferably below 5 mg KOH / g, a hydroxyl number from 80 to 200 mg KOH / g and a content of polyethylene glycol (PEG) incorporated by esterification ^of ^ to 8 wt .- ^, optionally in the form of mixtures of PEG-containing and PEG-free alkyd resin precursors with 15-30 wt .- ^ of a polymer obtained by copolymerization of 10-25 wt .- ^ methacrylic acid with 30-55 wt .- ^ unsaturated fatty acid and 30 - 6o wt .- ^ vinyl and / or vinylidene compounds, which have no other functional groups besides the double bond, were prepared, reacted with esterification until an acid number of 10-25 mg KOH / g and a limiting viscosity number of 8 to 15 ml / g , measured in chloroform at 20 ° C, is achieved, and the modified alkyd resin thus obtained, which has a PEG content between 3. k and 6 wt .- $, with neutralization of the acid groups with ammonia or organic amines and with the addition of a maximum of 20 wt .- $ of organic auxiliary solvents in Water emulsified.

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In practice, the products manufactured in accordance with AT-PS 372.097 have proven to be particularly quick drying Varnishes have proven their worth, a use which is also cited as preferred in the patent mentioned (page

5 ' k, lines kl ff)'.

25 could ⁰ C, the comparison with respective alkyd resins, solvent-based or polymer dispersions withstand, without causing drawbacks - in the field of aqueous alkyd resin emulsions, however, is still present in front no material loading ■ züglich drying at normal temperature, ie about 15 other properties, such as emulsion stability or film properties, have to be accepted.

It has now been found that, proceeding from the basic concept AT-PS 372.097, by changing the molecular structure of the binder, is able to produce emulsions produce which no longer have the disadvantages of the products of the prior art.

In the course of investigations into the molecular structure of the alkyd resins according to AT-PS 372.097 it has been shown that ' each of the basic properties of an emulsion, namely the Emulsion stability, pigment wetting and drying ability, a pronounced dependence on mean molecular weight M, expressed by the intrinsic viscosity [?? J »has. The optimal However, ranges for the individual properties do not coincide in the products of the prior art. While optimal gloss and good paint stability (as a function of pigment wetting) in a U ^ / 20 ° Range of less than 10 ml / g are to be achieved, the favorable ranges for drying speed are and emulsion stability at different -

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Values above 10 ml / g, with an optimum between 12 and ~ \ k .ml / g. As a result of this shift, the result is that in the range of less than 10 ml / g useful for the paint stability, the drying capacity of the alkyd resin can only be used up to about 50 $.

The object of the present invention was therefore to match the optima of the various criteria as far as possible approximate.

Surprisingly, it was found that a change the process of AT-PS 372.097 and the associated change in the molecular structure, this task can be achieved can without losing the excellent basic properties of the prior art emulsions are lost.

The present invention accordingly relates to a process for the production of aqueous emulsions by oxidation drying polyethylene glycol-modified alkyd resins, which is characterized in that (i) 25 to 50, preferably 30 to 45 wt .- ^ one

Copolymer from

30 - 55 wt .- ^ unsaturated fatty acids, 10-25 wt .- ^ methacrylic acid and 30-60 wt .- ^ vinyl or vinylidene ver.

bonds which apart from the double bond no other have functional groups with

5 to 15 »preferably 8 to 12 wt .- ^ polyethylene

glycol (PEG) with a molecular weight between 1000 and 3000 and

35-70, preferably 40 to 65 wt .- ^ of for the . "".

Production of alkyd resins, customary polyols,

Monocarboxylic acids and dicarboxylic acids

to an acrylic-modified alkyd resin with an acid number of hO to 70 mg KOH / g, a limiting viscosity number CVl # -. tr / -n of 5 to 8 ml / g, the

* CHC 1 "

Percentages relate to the proportions contained in the reaction product and add up to 100, and

(II) 30 to 50 wt .- ^ of this component with 50 to 70 wt .- ^ of an alkyd resin with a

Desiccant fatty acid content from $ 15 to $ 50, an acid number less than 5 mg KOH / g, a hydroxyl number of 50 to 150 mg KOH / g and a limiting viscosity

ity numberGW] from 8 to 13 ml / g

^CHCl 3.2O °

partially esterified at 160 to 200 ^° C., preferably using an azeotropic entrainer, until an acid number of 10 to 25 mg KOH / g and a limiting viscosity _{number CHC1 2QO} of 10 to 16 ml / g is reached, and

(Hl) the alkyd resin combination thus obtained, which has a PEG content of $ 3 to $ 6, below Neutralization of the acid groups with inorganic or organic bases, preferably ammonia, or organic amines and with the addition of a maximum of 20 wt .- ^ of organic auxiliary solvents, in Water emulsified.

The binders produced according to the invention show compared to the products of the prior art a significantly improved drying, which both in the The shortened drying time as well as the improved through-drying is expressed. Another advantage of the alkyd resins prepared according to the invention is in

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an improved reproducibility of the results, which is due to the greater achievable with this method Uniformity of the quality of the individual batches is given.

The acrylic-modified alkyd resins prepared in step (i) have a PEG content of 5 to 15, preferably 8 to 12 $, the polyethylene glycols used having a molecular weight of 1000 to 3000.

The PEG can be incorporated in various ways, for example by direct esterification or by etherification with epoxy fatty acid esters and subsequent transesterification, as described in AT-PS 3 ^ 5.215. Another method is described in AT-PS 365.216, the PEG being incorporated by means of phenol resols.

To introduce the carboxyl groups necessary to stabilize the emulsions, according to the invention, polymers are used which are obtained by radical polymerization of 10-25 wt .- ^ methacrylic acid, 30-55 wt .- ^ o of a drying oleic fatty acid with an iodine number of at least 125 ^and "d 30-60% by weight of one or more vinyl and / or vinylidene compounds, in particular acrylic compounds, which apart from the double bond contain no reactive groups.

The drying fatty acids used are those with conjugated double bonds - such as dehydrated castor oil fatty acids or isomerized fatty acids - or those with isolated double bonds - such as tecbn. Soy, safflower or linseed oil fatty acid - used. Since isolated unsaturated fatty acids have a lower reactivity, must they are used in larger excess. If the fatty acid is not completely removed during the polymerization

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a "yaws, the remainder is converted into the alkyd resin during the esterification built-in.

As vinyl or Nylon compounds can be styrene, vinyl toluene, vinyl esters of acetic acid, propionic acid or versatic acid can be used. Preferred are the commercial alkyl esters of acrylic and methacrylic acid are used. The selection depends on, among other things the compatibility with the alkyd resin precursor. As a rule, the polymers have the best compatibility also the best emulsifier effect.

The polymerization is carried out at 80 to 160 ° C. All radical formers which decompose in this temperature range can be used as initiators. The usual polymerization regulators, such as tert-dodecyl mercaptan, can be used to limit the molecular weight. To prepare the copolymers, the majority of the fatty acids, if appropriate as a mixture with inert solvents, are initially taken in the reaction vessel. After the reaction temperature has been reached, the remaining fatty acids, the monomers and the peroxide, and optionally the regulator, are added uniformly as a mixture over the course of 3 to 10 hours, depending on the reactivity of the fatty acids. The end point of the polymerization is assumed to be the steady state of the dry residue, ie the extensive disappearance of the volatile monomers from the reaction mixture. The intrinsic viscosity of the polymers or of the mixture of the polymers with unreacted fatty acids is between h and 9 ^m l / g "measured in dimethylformamide at 20 ⁰ C. Under the above conditions are side reactions such as the Fettsäuredimerisierung, largely suppressed. The fatty acids that have not been polymerized in therefore remain unchanged and remain after incorporation

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in the alkyd resin their ability to oxidatively crosslink.

In addition to the PEG and the copolymer, the acrylic-modified alkyd resins prepared in stage (i) contain the usual raw materials. Preferred polyols are pentaerythritol, as well as trimethylolpropane, glycerol, sorbitol, and, if appropriate, a proportion of diols used. The used Fatty acids have iodine numbers of over 125. In addition to the usual dicarboxylic acids, such as the various Phthalic acids, monocarboxylic acids such as benzoic acid or p-tert-butylbenzoic acid can also be used.

The modified alkyd resins produced in stage (l) have a fatty acid content of 20 to 60 % . The esterification of the components is quq- under the usual conditions until an acid number of kO to 70 mg KOH / g and a GrenzviskositätszahlLhJ, ₂ ° ^from o ^ led ^to 8 ml / g. · ³

in stage (il) 30 to 50 wt .- ^ of the acrylic or PEG-modified alkyd resin with 50 to 70 wt .- ^ one partially esterified in a conventional manner prepared alkyd resin. The PEG-free alkyd resins used have the following key figures:

Unsaturated fatty acid content: $ 15-50 (iodine number over 125)
Acid number: below 5 mg KOH / g

Hydroxyl number: (preferably below 3 mg KOH, Limiting viscosity number L1
< 50-150 mg KOH / g 30th _20O : 8 to 13 ml / g 35 7 ^J CHCl ₃

ΛΛ ²³⁷ °

-JT-

The two components are combined in stage (II) in proportions such that the PEG content is from 3 to 6%. The acid number of the product results from the methacrylic acid content, which in the end product is 1.5 to $ 5.5. The two components are partially esterified at 16O to 200 ⁰ C, the water of reaction is removed by an azeotropic entrainer. Before the end values are reached, the entrainer is removed by applying a vacuum. The partial esterification is carried out up to an acid number of 10 to 25 mg KOH / g and a limiting viscosity number ^{of 1} ^ ^> is ¹ ^ ml / g. Ranges from 12 to 20 mg KOH / g for the acid number and 12 to 15 ml / g for the limiting viscosity number are preferred.

The resins are dissolved in stage (tu) with a maximum of 20 wt .- ^, preferably 5 to 15 wt .- ^ organic auxiliary solvents and in "water, which for 50 to 100% neutralization of the acid groups of the resin, the appropriate amount of ammonia , organic amines or alkali metal hydroxides, emulsified at temperatures between k0 and 80 ° C. Particularly suitable auxiliary solvents are alcohols or ethereal alcohols, such as n-butanol or ethylene glycol monobutyl ether.

Those produced by the process of the invention After appropriate desiccation, products serve as the basis for oxidatively drying, water-thinnable paints, which can be applied by all customary methods, both at normal and at elevated temperature dry and are especially suitable for industrial use.

When using alkyd resins with a fatty acid content of hO $ o or more, those prepared according to the invention can be used

Emulsions also for the production of water-dilutable .Wood glazes are used. In addition, due to their compatibility, they are also suitable for the production of Paints based on combinations with acrylate polymer dispersions.

The customary water-thinnable drying agents are used in the amounts known to the person skilled in the art for the siccative treatment.
10

The following examples explain the process according to the invention. All parts given are parts by weight. The Grenzviskositatepsablsi given were, unless otherwise indicated, determined in chloroform at 20 ⁰ C.

(i) Production of the copolymers

Copolymer P 1 : In a suitable reaction vessel equipped with a reflux condenser and adding device, 40 parts of xylene, kO parts of isopropanol, 60 parts of linseed oil fatty acid, 11 parts of isobutyl methacrylate, 1 part of ethylhexyl acrylate, 2 parts of vinyl toluene, 6 parts of methacrylic acid and 3 parts of dibenzoyl peroxide and 0, 2 parts of dodecyl mercaptan heated to reflux temperature (approx. 95 ° C) and at the same time a mixture of kk parts of isobutyl methacrylate, 4 parts of ethylhexyl acrylate, 8 parts of vinyl toluene, 24 parts of methacrylic acid and 0.8 parts of dodecyl mercaptan and a mixture of 10 parts of xylene, 10 parts of methyl ethyl ketone, 40 parts of linseed oil fatty acid and 11 parts of dibenzoyl peroxide. added evenly within 5 hours. Polymerization is then carried out at the reflux temperature until the conversion is practically complete (determination of the solids content). If necessary, a quarter of the specified amount of peroxide can be added during this time.

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The copolymer has a fatty acid content (based on 100% resin) of 50 ft>, a methacrylic acid content of 15 $, a solids content of 65.5 $ and an intrinsic viscosity [?)} 20 ⁰ C ^of ^ ^ral / s.

Copolymer P 2 : 50 parts of dehydrated linseed oil fatty acid are heated to i45 ° C. and a mixture of 55 parts of isobutyl methacrylate, 35 parts of methacrylic acid and 10 parts of vinyl toluene, and at the same time a mixture of 20 parts of dehydrated linseed oil fatty acid and 6 parts of tert. Butyl perbenzoate added evenly. To complete the polymerization, the batch is kept at 1445 ° C. for a further 8 hours, a mixture of 5 parts each of xylene and 0.5 part of tert-butyl perbenzoate being added three times at intervals of 2 hours.

The copolymer has a fatty acid content of 4i.2%, a methacrylic acid content of 20.6%, a solids content of 90.3 $ and a limiting viscosity number L ^ J of _DMF h, 7 ml / g. (DMF = dimethylformamide.)

(il) Production of the acrylic- modified alkyd resins Modified alkyd resin PA 1 ; 100 parts p.-tert. Butylbenzoic acid, 20 parts of benzoic acid, i60 parts of linseed oil fatty acid and 141 parts of pentaerythritol are heated to 250 ⁰ C and held for 90 minutes at this temperature. Conjugated linoleic fatty acid, 120 parts of technical, 100 parts of PEG 1500, 6k parts of phthalic anhydride, tetrahydrophthalic anhydride and 376 parts JO parts are then of the polymer P2 / 90.3 $ ig, added at 220 ⁰ C. The batch is esterified in the presence of xylene as an entrainer at 180 ° C. until an acid number of 5 ^ mg kOH / g and a limiting viscosity number U) J * ooon of 6.8 ml / g is reached. The resin has a

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Pest body content of 92 #, a PEG content of 9.8 ^ and, a polymer content of $ 33.

Modified alkyd resin PA 2 : 200 parts of linseed oil, 130 parts of p.-tert. Butylbenzoic acid, 91 parts of pentaerythritol and 20 parts of trimethylolpropane are ^{heated to 250 °} C. and kept at this temperature for 2 hours. 715 parts of polymer Pi / 65% are added at 140.degree. C. and the temperature is increased again to 180.degree. The solvent present is removed as completely as possible under vacuum. Then, 100 parts of PEG 1500 and 92 parts Pthtalsäureanhydrid added and the reaction in the presence of xylene as an entrainer to an acid number of 52 mg KOH / g and an intrinsic viscosity zahluhj _CHC1 20 ⁰ C. ^of ^ ^{'1 ml} / ^e esterified. The solids content of the resin is 92 #, the PEG content 9.5 # and the polymer content is hk $.

(ill) Alkyd resins with a low acid number The raw materials given in the table are esterified in a known manner at 240 ° C. in the presence of xylene as an entrainer. In A3 the linseed oil with the pentaerythritol and p-tert-butylbenzoic is transesterified for 90 minutes at 250 ⁰ C first. After addition of the dicarboxylic acid at about 200 ⁰ C, the esterification is carried out at 240 ° C. All resins are diluted to $ 80 solids with xylene.

- Alkyd resin 1 1 e A 2 A 3 2370
3432482 a 5: 1 T a b e Pent aery thrift
p-tert-butybenzoic acid A 1 1 10
120 93
120 110
130 linseed oil 110
14O 1 10 A 4 - 5 Wood oil - __ - 110
90 110 Linseed oil fatty acid - 6o - - - Tall oil fatty acid 40 __ - - 105 10 dehydrated
Castor oil fatty acid - 45 - - 100 technical conjugate
Linoleic fatty acid 45 __ - Phthalic anhydride - - 6o 62 __ 100 15th Tetrahydrophthalic acid
anhydride 90 42 45 5 © - Fatty acid content, % 20th 25.9 25.9 110 4o, o Acid number (mg KOH / g) 20.6 1.9 ■ 2.9 - 1.4 20th Hydroxyl number (mh KOH / g) 1.5 115 90 35.0 85 95 10.3 11.5 1.4 11.2 - 10.8 95 25th 10.6 30th 35

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(iv) Examples according to the invention:

Example 1 : 68.75 parts A1 and 48.9 parts PAI (solid resin ratio 55.ί 45) are at 180 ° C in the presence of

Xylene as entraining agent to reach an intrinsic viscosity [^ Jj, of about 11 ml / g and an acid number of about 20 mg KOH / g is esterified. After the xylene has been removed in vacuo, the batch is further kept at 180.degree. When the key figures below are reached, a sample is taken and diluted with monoethylene glycol monobutyl ether (BUGL) to a solids content of $ 85. The solutions are mixed with triethylamine (TEA) according to their acid number and diluted with deionized water to a solids content of 40 $. In all cases, milky-opaque, structurally viscous emulsions are formed which have a pH of 9.2 to 9.2.

Pattern V 2 3

Acid number 17.8 17.5 17.3

[V] 12.7 13.8 15.3

To test the stability, the emulsions are left for 3 months stored at 40 ° C. After this exposure, the emulsions show, apart from a slight decrease in viscosity, no changes.

To test the paint properties, the emulsions are pigmented in a ratio of 1: 1 with TiOp (rutile), with a water-compatible siccative mixture (i, 2 $ cobalt, 7.2 $ barium, 3.2 % zinc), 1 $ an anti-skin agent and 0.5 * "£ a leveling agent added and diluted to application viscosity with deionized water.

343? 4 ⁷ §2

Paint properties M 1 M 2 M 3

Shelf life, 40? C practice jr η wocher 111 Il 50 Drying 105 dry to the touch (Minutes) 55 50 8th dust free (Minutes) 120 1 10 grabbed (Hours) . 8th 8th

König pendulum hardness (DIN 53157)

after 1 week 53 50 55

shine

Gonioreflectometer

VIANOVA GR - COMP, # 78 74 75

The example shows that there are no significant change in emulsion stability and paint properties depending on the limiting viscosity number, therefore also from the average molecular weight. The batch-wise quality is correspondingly low s fluctuations in production. The drying of the paints is the same as that of industrial paints based on in alkyd resins dissolved in organic solvents comparbc

Example 2 : In a manner analogous to Example 1, 75 parts of A 2 are reacted with 43.5 parts of PA 1 (pesticide ratio 60: 40). The result is a binder which has an acid number of 16.9 mg KOH / g and an L ^ J of 13.9 ml / g. The resin is as indicated in Example 1, emulsified in water. The emulsion stability at 40 ° C is more than 3 months.

Example '3 ; In a manner analogous to Example 1, 81.25 parts of A 3 are reacted with 38.0 parts of PA 1 (solids ratio 65:35). The binder has an acid number

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of 15.2 mg KOH / g and an LTy of 14.3 ml / g. As indicated in Example 1, the resin is emulsified in water. The emulsion stability at 40 ° C is more than three months.

The emulsions according to Examples 2 and 3 are tested in the form of a machine paint (pigment / binder 0.5 '· 1; molybdate red; siccative and auxiliaries as indicated in Example 1). The following results are obtained: 10

Example 2 3

The paint can be stored for more than k weeks (40 ° C)

Drying

touch dry (minutes) touch dry (minutes) touch dry (hours)

Pendulum hardness according to König, DIN 53157 42 48

shine

Gonioreflectometer

VIANOVA GR - COMP, # 73 68

Example 4 As indicated in Example 1, 81.25 parts A are partially up to an acid number of i4, 6 mg KOH / g and a \ jhj of I4.3 mL / g 5 esterified with 38.0 parts of PA 1. diluted and emulsified in water after neutralization. (Solids ratio 65:35) · The emulsion has a pH of 9.4. The emulsion stability at 40 ° C is more than 3 months.

The emulsion is tested in a rust protection primer. 100 parts of solid resin are mixed with 50 parts of red iron oxide,

65 55 135 120 9 8th

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50 parts of lead silica chromate, 70 parts of barium sulfate and 30. Divide the talc and grind after adding the siccative or the additives (as in Example 1) diluted to application viscosity. The tests result in the following values:

Paint stability low sedimentation,

(4 weeks / 40 ° C) can be easily stirred up

Drying: (Minutes) 40 dry to the touch (Minutes) 65 touch dry (Hours) 6th grabbed

Salt spray test after 1 week / 22 ° C

(ASTM B-117-64)

after 120 hours slight rust formation on

Cross section, single vesicles

painted over with machine paint
according to example 3, ^r -

no attack after 300 hours

Example 5 ' As indicated in Example 1, 75 parts of A4 and 43.5 parts of PA 2 (solids ratio 60: 40) are reacted to give an acid number of 15.7 mg KOH / g and an LItI of 12.9 ml / g. The emulsion produced therefrom according to Example 1 has a pH of 9> 6 and shows an emulsion stability of more than 3 months at 40.degree.

From 20 parts of the emulsion (based on solid resin), 80 parts solid resin of a commercially available acrylate dispersion (Mowilith LDM 7760 / Hoechst), 0.6 parts of the siccative mixture also used in the other examples, as well as 5 parts of the coalescing agent recommended for processing the dispersion (e.g. Texanol) becomes an unpigmentie ^ tej

^: . ^: "2370

Wood varnish produced and adjusted to application viscosity with deionized water. The varnish shows a stability of more than k weeks at HO ° C and shows, due to its surface hardness, a scratch resistance, as it is required for the parquet sealing. Applied to a glass plate, the lacquer is dry to the touch after 15 minutes, dust-dry after 30 minutes and touch-proof after 3 1/2 hours.

A comparative paint without the one produced according to the invention The emulsion remains thermoplastic and scratchy in the long run. sensitive.

Example 6 ; As indicated in Example 1, 75 parts of a '5 and 43.5 parts of PA 2 (solids ratio 6O: 4o) are reacted up to an acid number of 16.2 mg KOH / g and a b ^ I of 13.6 ml / g and processed into an emulsion with a pH of 9.5. The emulsion stability at 40 ° C is more than 3 months.

A wood glaze made from 100 parts of the emulsion is used for the test! (based on solid resin), 3 parts of siccative mixture (see example i), 2 parts of anti-skinning agent, 2 parts of flow control agent, k parts of fungicide and 20 to 30 parts of a color paste (LUCOMYL paste / BASF) produced, which with deionized water to a solids content of $ 20 is diluted.

The first coat can be painted over after one hour, the second coat is touchable after 2k hours. In terms of weather resistance, the paints correspond to those of commercially available solvent-based varnishes.

Claims (1)

2370 Claim: Process for the preparation of aqueous emulsions of oxidatively drying polyethylene glycol-modified Alkyd resins, characterized in that one (l) 25 to 50, preferably 30 to 45 wt .- ^ one Copolymer from 30 - 55 percent -. * $> Unsaturated fatty acids, 10 - 25 wt .- $ methacrylic acid and 30 - 60 wt .- ^ vinyl or Vinylidenver- . bonds which have no other functional groups besides the double bond, with 5 to 15i preferably 8 to 12 wt .- ^ polyethylene glycol (PEG) with a molecular weight between 1000 and 3000 and 35-70, preferably 40 to 65 wt .- ^ o of for the Production of alkyd resins, customary polyols Monocarboxylic acids and dicarboxylic acids to an acrylic-modified alkyd resin with an acid number of kO to 70 mg KOH / g, a limiting viscosity number D> 7J """, from 5 to 8 ml / g, the percentages being those contained in the reaction product Get shares and add up to 100, and (il) 30 to 50 wt .- ^ of this component with 50 to 70 wt .- ^ of an alkyd resin with a content of drying fatty acids from 15 to 50 $, an acid number of less than 5 mg KOH / g, a hydroxyl number of 50 to 150 mg KOH / g and a limiting viscosity number M of 8 to 13 ml / g ³ 2370 1 at 160 to 200 ° C, preferably using a partially esterified azeotropic bleeding agent until an acid number of 10 to 25 mg KOH / g and a limiting viscosity ity number iJYpi CHCl 20 ° ^{FROM 10 to 1} ^ ^ml / & is reached, 5 and ³ " (ill) the alkyd resin combination thus obtained, which has a PEG content of 3 ° is 6 5 ^, below Neutralization of the acid groups with inorganic or organic bases, preferably ammonia, or 10 organic amines and with the addition of a maximum of 20% by weight of organic auxiliary solvents, in Water emulsified.