DE1520686A1 - Process for making alkyd resins - Google Patents

Description

Dr. Ing.E. BERKENFELD, Potentanwalt, COLOGNE, Un iversitatsstrasse 31 Attachment file number

for entry of 2; 5.1.1964 CS / name d. Note: The Research Association of

British Paint, Color cc Varnish Manufacturers,

The Paint Kesearcn Station,

l'aldegrave Road,

Teddin ^ ton, Middle sex, England

«U- ⁷ VHi ■:« - _ ~, ^ _ P

Appropriate for making alkyd resins.

The invention relates to alkyd resins and a process for their preparation and coating agents containing these resins.

ial the present invention, alkyd resins are prepared which contain combined allyl ether or methallyl ether groups, where the number of combined allyl ether or methallyl ether groups is at least equal to the number of combined polyvalent ones Alcohol residues are in the resin and this is soluble in aqueous alkali, but insoluble in 'Jasser is.

The term alkyd resins should be understood to mean a polyester which contains saturated or unsaturated fatty acids may or may not.

A simple »/ eg to produce the alkyd resins according to the invention, best to use an allyl ether or mothalyllite at least one to condense two polyvalent Aikonoles containing free hydroxyl groups with a polybasic acid. Before-

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preferably the acid or alcohol reactant should have an esterification functionality of at least three and the other reactant one Have esterification functionality of at least two.

Typical polybasic ones useful in the process of the invention Acids are the phthalic, isophthalic, tetra'hydrophthalic and Terephthalic acid, trimellitic or trlmesic acid, maleic, Pumaric and itaconic acid and adducts of unsaturated fatty acids with maleic or fumaric acid. The phthalic, trimellitic and maleic acids can be used in the form of their anhydrides. Typical allyl ethers of polyhydric alcohols are glycerol monoallyl ethers, Trimethylolpropane monoallyl ether, trimethylolethane monoallylether, Pentaerythritol mono- and di-allyl ethers, dipentaerythritol mono-, di-, tri- and tetraallyl ethers, sorbitol morio-, di-, tri- or tetra-allyl ethers and equivalent methallyl ethers.

The polybasic acids can be used in the form of their anhydrides if this is easier. The allyl ethers to be used for the process of the invention do not need pure compounds to be, but mixtures of ethers or mixtures of ethers and unsubstituted, polyvalent alcohols satisfactory results provided they tiaii on average have a composition that corresponds to that desired in the resulting alkyd resin ...

Typical polyhydric alcohols used for the purposes of the invention can be used are ethylene, propylene, neaperityl and diethylene glycols, glycerin, Triinethyiolpropane, Triuietnylul-

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ethane, pentaerythritol, dipentaerythritol and sorbitol. Monobasic Acids, straight chain monohydric alcohols and other typical alkyd modifying agents can be added to the esterification mixture possibly incorporated.

Typical monobasic acids that can be used are saturated straight-chain acids ranging from 8 (caprylic) - to l8 (stearin) -

to have
Acids such as oleic acid, polyunsaturated acids such as linoleic and linoleic and mixed acids originating from drying oils, hydroxy-substituted acids such as ricinoleic acid and aromatic acids such as benzoic and substituted benzoic acids. The monohydric alcohols can be, for example, butyl, caprylic and lauryl alcohols.

The stated reaction is carried out until not only sufficient carboxyl groups remain to convert the material into Water to dissolve. can, but enough carboxyl groups remain in order to dissolve the material in aqueous solutions of bases, e.g. ammonia or to be able to dissolve trimethylamines. The excess of hydroxyl groups nothing must be such as to make the alkyd resin water-soluble close.

The invention also includes coating agents that are a solution an alkyd resin according to the invention in aqueous alcohol, e.g. in an aqueous solution of ammonia, trimethylamine or sodium hydroxide, exhibit.

Gernäß a preferred embodiment of the invention, the amount of alkali just sufficient to χίοϊι au "the acid value of the

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To neutralize the resulting free acidity. With the alkali it is preferably a volatile alkali.

The agents according to the invention have the advantage of giving films which have high water resistance when drying in air or when hardening at temperatures of 120 C or below. If the alkyd resin is free from polyunsaturated fatty acids, you can films are obtained without discoloration on curing in the oven. Air-dried films are good color by themselves resins containing polyunsaturated fatty acids.

The excess of hydroxyl groups used to prepare the alkyd resin should preferably be as low as possible, for example on the order of 8 fr , if air drying compositions are required. Higher levels of excess hydroxyl, for example 20 to 23 fr ', may require curing at temperatures up to 120 ° G.

The agents according to the invention can also contain metallic dryers, preferably in the form of a water-soluble salt. For example, cobalt can be incorporated as cobalt acetate. The amount of cobalt can be between 0.03 and 0.23 p , but is preferably 0.1 ^c jo . Pigments can also be incorporated in a known manner.

The resins of the invention can be used as the sole forming agent Medium to be used in a paint; but they can also at the same time with other compatible water dispersible

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Media are used. For example, you can use emulsions at the same time or latexes of polymers or copolymers of acrylic and methacrylic acid ester, styrene or vinyl acetate can be used.

Paints composed of the resins according to the invention can can be applied in one of the known ways, e.g. by brushing, spraying, dipping or by deposition on electrical

The invention is described in more detail by means of the following examples.

example 1

A polyester resin that has an excess of 20% hydroxyl groups and had an acid number of 46 mg KOH / g, 29 »6 parts by weight (0.200 mol) phthalic anhydride and 60 parts by weight (0.160 mol) dipentaerythritol triallyl ether (produced by reacting excess Allyl bromide with the appropriate sodium derivative of dipentaerythritol) by esterification for 5 hours at '' 160 ° C and 2 1/2 hours at 175 ° C in an inert atmosphere and produced under azeotropic conditions (xylene) Xylene was subjected to a brief vacuum treatment (1 mm Hg at yO to 100 ° C) removed and the residue in dilute ammonia or a water-soluble organic base (e.g. trimethylamine Triethylamine, 2-Dlrnethylair) inoethanol) dissolved, one for neutralization the free acidity indicated by the acid value

was just sufficient ^. Amount of a base added; the whole was

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by adding water to a 50 $ solids content of the Solution brought. The viscosity of this solution was about 4 poise in aqueous trimethylamine.

Films that last an hour on glass or aluminum pads 120 C had been hardened, were hard, tack-free, good and gloss and showed excellent water resistance

Solutions that had been stored for 6 months showed no increase in viscosity.

Example 2

A polyester resin with 2.j yb hydroxyl group excess and an acid value of 33 mg KOH / g was made from 11.5 parts by weight (0.06 mol) of trimellitic anhydride, 5 * 8 parts by weight (0.04 mol) of adipic acid and 21.1 Parts by weight (0.16 mol) of alpha-allyl glycerol ether prepared by esterification at 165 ° C. for 6 hours in an inert atmosphere and under azeotropic conditions. .Xylene was removed from the reaction product by a short vacuum treatment (1 mm / Hg at yo to 100 ° C) and the residue was dissolved in dilute ammonia or in a water-soluble organic base (e.g. trimethylamine, triethylamine, 2-dimethylamineethanol, etc.), with just enough base added to neutralize the free acidity indicated by the acid value. Solutions diluted with water up to $ 50 pesticides were stable for at least 6 months when stored at room temperature. The films hardened on glass or aluminum sheets for one hour at 120.degree. C. were sufficiently hard, tack-free and had a good color and a good glaze.

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Example 3

A polyester resin with an excess of 2 ^ ρ hydroxyl groups and an acid value of 48 mg KOH / g was made from 11.5 parts by weight (0.2 mol) of trimellitic anhydride, 5.8 parts by weight (0.04 mol) of adipic acid and 54.6 parts by weight. . Parts by weight of (O, l6 mol) Pentaerythritoldiallyläther (prepared by the reaction of excess sodium Ällylbromid with the appropriate derivative of pentaerythritol) is prepared by esterification at I65 ⁰ C for 8 hours in a nitrogen atmosphere. The product was dissolved in dilute ammonia or a water-soluble organic base, such as trimethylamine triethylamine, 2-dimethylaminoethanol, etc., and exactly the amount of base added to neutralize the free acidity indicated by the acid value. Solutions diluted with water up to 50 % solids were found to be stable for 6 months when stored at room temperature.

Those hardened for one hour on glass or aluminum panels at 120 ° C Films were hard, tack-free, and exhibited good color as well as a good shine. The pigmentation of these water-soluble Resins can be done by means of conventional ball mills, using rutile titanium dioxide A paint can be used for pigmentation in an amount of 0.9 parts pigment per 1 part solids be produced, the hard, tough films of good color when cured at 120 ° C for one hour.

Example 4

A polyester resin with an excess of 2 × 5 hydroxyl groups and an acid ^{value of 1} Jj ra & KÖH / g was made from 11 parts by weight (0.06o mol)

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Trimellitic anhydride, 5.8 parts by weight (O, O4O mol) adipic acid, 43.1 parts by weight (0.120 moles) sorbltol tetraallyl ether and 4.24 Parts by weight (0.040 mol) of diethylene glycol by esterification 175 C for 4 hours in an inert atmosphere under azeotropic conditions Conditions (xylene) produced. Xylene was removed by a brief vacuum treatment (1 mm Hg at 90 to 100 ° C) and the residue in dilute ammonia or a water-soluble organic base, such as trimethylamine triethylamine, 2-Dimethylaminoethanol, dissolved, the exact amount of base added was to neutralize the free acidity indicated by the acid value of the resin, and the whole was done through Adding water to a 50 pound solution Brought solids content. ·

On glass and aluminum surfaces at 120 C for one hour cured films were hard, tack-free, of good color and gloss, and excellent water resistance.

Solutions stored for 6 months showed only a slight increase the viscosity.

Example 5

A polyester resin with 8 yes hydroxyl groups excess and an acid value of 55 mg KOH / g was made from 19.2 parts by weight (0.100 mol) of trimellitic anhydride, 9.7 parts by weight (Ό, Οβγ mol) of adipic acid, 57.0 parts by weight. Parts (0.167 mol) of sorbitol tetraallyl ether and 7.1 parts by weight (0.067 mol) of diethylene glycol by esterification at 175 ° G for 4 1/2 hours in an inert atmosphere and under a ^ eotropic conditions (xylene). Xylene was through

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a short vacuum treatment (l ram HG at 90 to 100 ° C) removed and the residue dissolved in dilute ammonia, but preferably in a volatile water-soluble tertiary organic base, such as trimethylamine, and added exactly the amount of base that is necessary to neutralize the acid value specified free acidity is required; the whole was prepared by adding water to a solution of 50 'jb Fe st oxygen content accommodated.

Polyester resins of this type, which are produced, for example, with a lower hydroxyl excess than that of Examples 1-4, were particularly useful for drying in air. With a content of 0.05 to 0.25 / ^y *, preferably 0.1 > Cobalt added as cobalt acetate, films of around 20 μ were dried in three to four hours and soon after drying were tack-free. After aging for 24 hours, they had good color and gloss.

The pigmentation of this water-soluble resin can be carried out by means of usual ball mills and a paint can be prepared if, for example, rutile titanium dioxide is used for pigmentation in an amount of 0.9 parts pigment: 1 part Solids used. Added at $ 0.10 as cobalt acetate Cobalt and triethylamine as the base dry films of 20 yu in 5 1/2 hours with excellent shine. A tack-free condition was achieved in another 1-2 hours and within several For days the films got tough and tough.

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Example 6 .

A polyester resin with 25 % excess hydroxyl groups and an acid value of 57 mg KOH / g was prepared from 19.2 parts by weight (0.100 mol) of trimellitic anhydride, 9.73 parts by weight (0.067 mol) of adipic acid and 65.07 parts by weight (0.267 mol) pentaerythritol ß-dimethallyl ether (produced by reacting an excess of ß-methallyl chloride with the appropriate sodium derivative of pentaerythritol) produced by esterification at 175 ° C for 6 hours in an inert atmosphere and under azeotropic conditions (xylene) .. Xylene was removed from the product by a brief vacuum treatment (1 mm Hg at 90 to 100 C) and the residue was dissolved in dilute ammonia or a water-soluble organic base such as trimethylamine, triethylamine or 2-dimethylaminoethanol, and used to neutralize the free through the Acid value, indicated acidity, just sufficient amount of base added.In aqueous trimethylamine the viscosity was about 5 poise, ßat 120 ° C for one hour on glass s and aluminum

from

Panel cured films were hard, glossy, tack free, and particularly good in color. The pigmentation of this water-soluble alkyd resin can be done by conventional ball mills, and a paint can be made using rutile titanium dioxide used for pigmentation in an amount of 0.9 parts pigment to 1 part solid, the hard, tough films of very good color when cured at 120 ° C for one hour.

Example 7

A polyester resin with a 25 % excess of hydroxyl groups and an acid value of 32 mg KOH / g was made from 11.84 parts by weight (0. QoI mol)

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Trimellitic anhydride, 6 parts by weight (O, .O4l mol) of adipic acid and 6 $, 43 parts by weight (0.164 mol) Sorbitoltetra-ß-methallyläther (prepared by reaction of an excess of beta-methallyl chloride with the appropriate sodium derivative of sorbitol) by esterification at 175 C for 6 hours in an inert atmosphere and under azeotropic conditions (xylene). Xylene was removed from the "product" by a brief vacuum treatment (1 mm Hg at 90 to 100 ° C.) and the residue was dissolved in dilute ammonia or a water-soluble organic base such as trimethylamine, triethylamine, 2-dimethylaminoethanol, etc., whereby for Neutralization of the free acidity indicated by the acid value the just sufficient amount of base was added The solution in aqueous trimethylamine had a viscosity of about 3 poise .. Films cured on glass and aluminum panels at 120 ° C for one hour were hard, glossy, tack-free and of particularly good color.

Example 8 ■

A polyester resin with 36 % excess hydroxyl groups and an acid value of 47% KOH / g was made from 19.20 parts by weight (0.1 mol) of trimellitic anhydride, 4.87 parts by weight (0.053 mol) of adipic acid and 61 parts by weight (0.25 mol) pentaerythritol di-ß-methallyl ether (produced by reacting excess ß-methallyl chloride with the appropriate sodium derivative of pentaerythritol) by esterification at 175 ° G for 3 hours in an inert atmosphere and under azeotropic conditions (xylene) . Xylene was removed from the product by brief vacuum treatment (1 mm HG at 90 to 100 ° C), and the

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permanent product in dilute ammonia or a water-soluble organic base such as trimethylamine triethylamine, 2-dimethylamine ethanol, etc. dissolved and just sufficient to neutralize the free acidity indicated by the acid value Amount of base added. The solution, in aqueous trimethylamine, had a viscosity of about 10 poise. Films cured on glass and aluminum panels at 120 ° C for one hour were very hard, elastic, shiny, tack-free and of particularly good color. the

24-hour water resistance (tested by immersion in cold water) excellent.

The pigmentation of the water-soluble alkyd resin can be carried out by means of usual ball mills take place; if you use rutile titanium dioxide for pigmentation in an amount of 0.9 parts pigment: 1 part solid If used medium, a dye can be produced which will produce hard, tough films of good color when cured at 120 ° C results in an hour.

Example 9 ■

A polyester resin with an excess of 8 fr hydroxyl groups (see Example 5) and an acid value of 35 mg KOH / g was prepared from 19.2 parts by weight (0.1 mol) of trimellitic anhydride; 9 * 75 parts by weight (0.067 mol) of adipic acid, 6.95 parts by weight (0.067 mol) of neopentyl glycol, 28.5 parts by weight (0.082 mol) of sorbitol tetraallyl ether and 53.17 parts by weight (0.083 mol) of sorbitol tetra- ß-methallyl ether (prepared by reacting an excess ß-methallyl chloride with the appropriate sodium derivative of sorbitol) by esterification at 1 ~ { ^[ J> ° C for about 5 hours in an inert atmosphere and under a: -. eotropic conditions (xylene ) manufactured. ^ yIoI win-n.? n-tiü dom product by a kurao vacuum

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treatment (1 mm Hg at 90 to IQO ⁰ C) removed and the residue

fleeting

in dilute ammonia, preferably in a bo is on. water-soluble tertiary organic base such as dissolved Trimethylamine and accurately added to the amount of base sufficient to neutralize the free acidity indicated by an acid value of the resin, and the whole was transferred by adding water into a solution with ¹ J) OFO Feststoflgehalt. U films that 0.05 to 0.2% ^, having preferably 0.1 f> added as cobalt acetate cobalt of about 20, about dried in '$ hours and soon they were tack-free after drying. After aging for 24 hours, they showed good color and gloss.

The pigmentation of this water-soluble resin can be carried out by means of conventional ball mills; If, for example, rutile titanium dioxide is used for pigmentation in an amount of 0.9 part pigment: 1 part solid, a paint with 0.1 % cobalt (added as cobalt acetate) and trimethylamine as base can be produced. Films of about 20 u dry in about 3 hours with excellent gloss. A tack-free level is reached soon thereafter and within a few days the films become hard and tough. ·

for game 10

A polyester resin with an 8 % excess of hydroxyl groups (see example t>) and an acid value of 62 mg KOH / g was made from iy, 2 parts by weight (0.1 mol) of trimellitic anhydride, ⁽ j / f3 parts by weight

(0.067 mole) of adipic acid, ^{1 part by} weight (0.167 mole) of sorbitol tetraallyi ether and 2.6 parts by weight (0.067 mole) of the product which

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by heating at 2050 ° to 240 ° C for two hours 30.67 parts by weight (0.333 moles) of glycerin and 93.33 parts by weight (0.333 mol) Soj abohnenöl fatty acids was obtained by esterification at 175 ° C for 4 1/2 hours in an inert atmosphere and produced under azeotropic conditions (xylene). Xylene was subjected to a brief vacuum treatment (1 mm Hg at yO up to 100 ° C) and the residue in dilute ammonia, but preferably dissolved in a volatile water-soluble tertiary organic base, such as trimethylamine, and the amount added those used to neutralize the acid converted by the resin indicated free acidity is just sufficient, and the whole thing was made by adding water to a solution with ^ O / O pesticide content brought.

Films of about 20 μ with 0.0 to 0.2 ^ ^%, preferably (added as cobalt acetate) with 0.1 ¹ ^ cobalt, dried in about 3 hours and were tack-free after soon your drying. After aging for 24 hours, they showed good color and gloss.

The pigmentation of this water-soluble resin can be done using suitable ball mills? if rutile titanium dioxide is used for pigmentation in an amount of 0.9 parts pigment 1 part solids, a paint with 0.1 $ cobalt (added as cobalt acetate) and trimethylamine as base can be produced. Films of about 20 and dry in about 3 hours with excellent gloss, lilne tack-free stage was reached soon after. Over the course of several days, the films became tough and tough.

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Example Il 15th

Üin polyester resin with 8; i> An excess of hydroxyl groups (see Example 5) and an acid value of 5½ mg KOH / g resulted in 19 * 2 Part by weight (0.1 mol) of trimellitic anhydride, 9.7 to 5 parts by weight (0.067 'Mi) adipic acid, 57 parts by weight (0.167 moles) sorbitol tetraallyl ether and 44 parts by weight (0.067 moles) of the product ,,, das by heating 27.2 parts by weight (0.200 moles) of pentaerythritol and 112 parts by weight (0.400 moles) of soybean oil fatty acids during 2 hours at 2 ^ 0 to 240 C, by esterification

o, ■ 'inert

tion at 173 0 for 4 1/2 hours in a / atmosphere and azeotropically see! Conditions (xylene) was prepared. The xylene was removed from the product by a brief vacuum treatment (1 mm Hg at 90 to 100 ° C.). removed and the residue dissolved in dilute ammonia, 'preferably in a volatile water-soluble tertiary organic base, e.g. trimethylamine, and the amount of Ease added which is just sufficient to neutralize the free acidity indicated by the acid value of the resin? the whole was -übergeführt oxygen content by adding water in a solution containing Fe ^ O fo st.

With 0.5 to 0.25 but preferably 0.1 ii _t fi cobalt (added as cobalt acetate) dried films of about 20 yes in approximately> hours, and they were & ald after drying tack-free. After aging for 24 hours, they showed good gloss and color.

This water-soluble resin can be pigmented by means of conventional ball mills if rtutll-titanium dioxide is used for pigmentation in a ratio of ½ parts of pigment; 1 part FeGtstoff Vfrrwenaet, an an ^ trio hut with 0.1 % cobalt

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(added as Kobal.tacetat) and trimethylamine are produced as a base; Films of about 20 and dry in about 4 hours' with excellent gloss. A tack-free state was achieved soon thereafter, and within a few days the films became hard and tough.

Example 12

A solution of the resin described in Example 5 and containing cobalt as a dry matter in aqueous trimethylamine is pigmented by grinding with titanium dioxide, taking into account a pigment: resin ratio = 5: 2.

The pigment paste is then applied with an emulsion of an exterior plasticize polyvinyl acetate, an alkyl acrylate, methacrylate copolymer, Viryl acetate / alkyl acrylate copolymer or a 8tyrene-butadiene copolymer, such as those commercially available are available, mixed in a ratio of Allyl resin to emulsion polymer of 1: 4 (this is a pigment: medium ratio - 1: 2).

The coating compositions produced in this way gave hard films with good properties ■ Shine.

If you have a 45 ° photoelectric rearview gloss meter is used, you can read off the following values for the gloss, the Werto for emulsion paints that are made without an allyl resin, but have the same pigment: medium ratio of 1: 2, are given in kjammern:

009841 / 01S9 · · _ u BATH

Externally plasticized polyvinyl acetate

emulsion with a particle size of 0.6 μ ........ 75 (5); Acrylic acid copolymer emulsion with a

Particle size < 0.1 μ .... 83 (6j5);

Vinyl acetate / acrylate copolymer emulsion

with a particle size <Ο, 25 μ 78 (50) j

emulsion
Styrene / butadiene copolymer with a

Particle size 0.2-: 0.3 µ .100 (73);

Example l'j

A polyester resin with an 8 % excess of hydroxyl groups (see Example "3) and an acid value of 0 mg KOH / g was made from b, K parts by weight (0.053 mol) of trimellitic anhydride, y, üj parts by weight (0.067 mol) of phthalic anhydride, 2u , 2 parts by weight (0.067 moles) of the product obtained by heating 95.33 parts by weight (0.333 moles) of soy fatty acids and 32.67 parts by weight (0.333 moles) of maleic anhydride, 6.93 parts by weight (0.067 moles) Neopentyl glycol and 57 parts by weight (0.167 mol) of SorbJltotetraallyläther at 220 ° C for 2 hours, by esterification at 173 ° C for about 3 1/2 hours in an inert atmosphere and under azeotropic conditions (xylene) removed by a brief vacuum treatment (1 mm Hg at y0-100 ° C) and the residue was dissolved in dilute ammonia, preferably in a volatile water-soluble tertiary organic base, e.g. Trirrtethylarnin, and the amount of base was added that was just sufficient to aie by the acid value of the resin to neutralize free acidity is specified, and the whole was brought by adding water to a solution having a Peststoffgehalt of 30 x /). \

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Films with 0.05 to 0.2 ^ %> preferably with 0.1 # cobalt (added as cobalt acetate) of about 20 μ dried in about> 1/2 hours and were tack-free soon after drying For hours, they showed good color and gloss.

The pigmentation of this water-soluble resin can be carried out by means of conventional ball mills, for example a rutile titanium dioxide can be used for the pigmentation in a ratio of 0.2 parts pigment: 1 part solids. A paint can (added as cobalt acetate) with Oji% cobalt are prepared and trimethylamine as a base, and the films of about 20 μ dried in about 4 hours with excellent gloss and color, ssin tack-free state was reached soon thereafter and were within a few days Films hard and tough.

Claims

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Claims (21)

Claims 1. A method for producing an alkyd resin, characterized in that that one containing at least two free hydroxyl groups Allyl ether or methallyl ether of a polyhydric alcohol with a polybasic acid to produce an alkyd hares is condensed, which is soluble in aqueous alkali, insoluble in water and boundr allyl ether or methallyl ether groups contains, the number of bound allyl ether or methally 1 ether groups at least equal to the number of bound polyvalent ones There is residual alcohol in the resin. 2. The method according to claim 1, characterized in that these / ither groups come from one or more of the following ethers: Glycerine monoallyl ether, trimethylolpropane monoallyl ether, Trimethylol ethane monoallyl ether, pentaerythritol monoallyl ether, Pentaerythritol diallyl ether, dipentaerythritol mono-, di-, trioder tetra-allyl ether, sorbitol mono-, di-, tri- or tetra-allyl ether or equivalent methallyl ethers. 2. - The method according to claim 1 or 2, characterized in that that one of the reactants, acid or alcohol, is a Esterification functionality of at least three and the other Reaction participants have an esterification functionality most vogfalndest has two. 4. The method according to any one of claims 1 ->, characterized in that daft as mehrbasiache acid Phthai-, I * ophthai-, terephthalic, trimellitic, trimesic ■ _# maleic, or itaconic Fumar.- "tture is used. 0 09841/0169 BADORiGINAU - 19 - 5. The method according to any one of claims 1-4, characterized in that the ether is one or more of the following ethers contains 1 Glyeerinmonoallyläther, Trimethylolpropanraonoallyläther, Trim «ethyl ethane monoallyl ether, pentaerythritol ranoallyl ether, Pentaerythritol diallyl ether, dipentaerythritol roono, dl, tri or tetra-allyl ether. Sorbitol mono-, di-, tri- or tetraallyl ethers or equivalent methyl ethers. 6. The method according to any one of claims 1-5, characterized in that the ether is mixed with an unsubstituted polyhydric alcohol. 7. The method according to claim 6, characterized by dai as polyhydric alcohol, ethylene glycol, propylene glycol, diethyleneflycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol or sorbitol is used. 8. The method according to any one of claims 1-7 »characterized in that the esterification mixture is also a monobasic Acid, a straight monohydric alcohol, or other typical alkyd modifying agent is incorporated. 9. The method according to claim 8, characterized in that that the monobasic acid is a saturated straight-chain acid with 10 to 18 carbon atoms, a "monounsaturated acid", a " polyunsaturated acid «, a hydroxy-substituted acid or an aromatic acid is used. 0 0 9 8 A 1/0 1 6 9 - 20 - BATH ORIGINAL " 10. The method according to claim y, characterized by Use of oils In-, Lina! -, linolenic acid, one of a kind mixed acid, castoroleic acid, benzoic acid or a substituted benzoic acid derived from drying oil. 11. The method according to claim 8, characterized in that the monohydric alcohol is butyl, caprylic or lauryl alcohol is used. 12. The method according to any one of claims 1-11, characterized indicated that the implementation will be carried out until insufficient carboxyl groups remain to be able to dissolve the mass in water, but sufficient carboxyl groups remain, in order to be able to dissolve the reaction product in aqueous solutions of bases. 13. Modification of the method according to claim 4, dadtrch characterized dag as polybasic acid tetrahydrophthalic acid or an adduct of an unsaturated fatty acid with maleic or Fumaric acid is used 14. The method according to claim 6, characterized in that because neopentyl glycol is used as a polyhydric alcohol. 15. The method according to claim b, characterized in that that "a" saturated straight-chain "acid" with 8 to 9 carbon atoms is used as the monobasic acid. π o 9 a u w η ι s 9 BATH 16. Coating composition "characterized by a solution of an alkyd resin in aqueous alkali" characterized in that the Alkyd resin soluble in aqueous alkali, but insoluble in water and contains bound allyl ether or imethallyl ether groups, and the number of allyl ether or methallyl ether groups at least is equal to the number of bound polyhydric alcohol residues in the resin. 17 * coating composition according to claim Ιό, characterized in that that the amount of alkali present is just sufficient to neutralize the acidity indicated by the acid value of the resin. IB. Coating compound according to Claim Ib or 17, characterized in that that the alkali is volatile. 19. Coating composition according to one of claims 16-18, characterized marked that it also contains a metallic dryer. 20. Coating composition according to claim Ii), characterized in that that the metallic dryer is in the form of a water-soluble salt. 21. Coating composition according to claim ly or 20, characterized in that, since the metal is cobalt. It. Coating composition according to claim 20, characterized in that that the Kubalt is presented in the form of the KobaLta budget. π 0 9 q 41 / π 1 e η BATH ORIGINAL. -: · «" -