DE2048956A1 - Aqueous air or oven-drying paints based on dispersions or solutions of polyurethane resins - Google Patents

Description

File: 2168

Reichhold-Albert-Chemie Aktiengesellschaft 2 Hamburg 70, Iversstrasse 57

Aqueous air- or oven-drying paints based on dispersions or solutions of polyurethane resins

The aim of the present invention is to provide such water-dilutable or water-dispersed, air-drying or stoving lacquers, all of which are required paint technical properties and have significantly improved drying properties with excellent Film quality with high gloss and excellent weather resistance after drying and in addition, they are characterized by great storage stability and excellent plieft properties.

The invention relates to aqueous, air-drying or oven-drying paints based on dispersions or solutions of water-thinnable or water-dispersible, oxidatively drying polyurethanes or polyurethane mixed polymer resins, characterized in that these binders consist of: (a) 2B to 70 percent by weight of unsaturated fatty acids , of which 0 to 25 percent by weight are present as drying ? ■ Ie, and where, if necessary, the un ^ esäbhipt ^ n fatty acids w, <\ / >! ^ r the drying ^ Ie up to ύ Hewichtapr ■ ·.> / «? α *. ? ■ '';, If »in.iHureanhy.l.rii! anp "ela! 'er * t

109o.ua/1866

contain and the mixture iodine numbers from about 130 to 390 owns

(b) up to 30 percent by weight of aliphatic, cycloaliphatic, aromatic carboxylic acids or hydroxycarboxylic acids, individually or in a mixture, or their anhydrides, if they exist,

(c) 5 to 35 weight percent polyvalent organic hydroxy !links ,

(d) up to 17 percent by weight of polyoxyalkylene compounds,

"which contain at least one atom of active hydrogen,

having an average polyoxyalkylene chain molecular weight of about 200 to 50,000 individually or in a mixture,

(e) up to 65 percent by weight of polymerizable monomers,

(f) 0.05 to 50 percent by weight isocyanates, individually or in admixture, and

(g) up to 60 percent by weight of unsaturated mono- and / or Polyalcohols or mixtures thereof, selected by the selection of quantities, are present in such a way that the total hydroxyl group equivalent to the isocyanate group equivalent is 1.01 to 1.5,

^ (h) and, if applicable, as far as the polyurethane resin is carboxyl groups contains, this by adding alkali and / or organic strong bases in the water-dispersible or water-dilutable state.

Contained in a special embodiment of the invention the lacquers as polyirethane resins, those which are composed of the following components:

(a) 25 to 50 percent by weight of unsaturated fatty acids

with iodine numbers of about 130 to 3 ^ 0, (0) 2 to 30 lev / ichtprozent aliphatic, cycloarip ^H .a -

109828/1666 _{BAD 0R} , _e , _NA L

table, aromatic carboxylic acids or hydroxycarboxylic acids, individually or in a mixture, or their anhydride · ': -, as far as these exist,

(c) 5 to 35 weight percent polyvalent organic hydroxy !links,

(d) 2 to 9 percent by weight of polyoxyalkylene compounds, which contain at least one atom of active hydrogen, r.iit an average molecular weight of Polyoxyalkylene chain of about 3000,

(e) zero,

(f) 4 to 50 percent by weight isocyanates, individually or im Mixture, and

(g) 2 to 25 weight percent unsaturated ether alcohols or mixtures thereof, reacted selected by menu selection so that the total hydroxyl group equivalent to the isocyanate group equivalent was 1.01 to 1.5.

In a further special embodiment of the invention The paints contain polyurethane resins made up of the following components:

(a) 25 to 70 percent by weight unsaturated fatty acids, of which up to 25 percent by weight as a drying pie are present and the mixture has iodine numbers of about 130 to 390,

(b) 2 to 30 percent by weight aromatic polycarboxylic acids., individually or as a mixture, or their anhydrides, preferably trimellitic anhydride, if these exist are,

(c) 5 to 35 weight percent polyvalent organic hydroxy !links ,

(d) zero,

(e) zero, where component b in such amounts

109828/1665 _eAD

hold is that the condensation product has acid numbers from about 20 to about 80,

(f) 2 to 50 percent by weight isocyanates, individually or im Mixture, and

(g) zero

(h) and the carboxyl group-containing polyurethane resin than by alkali and / or organic strong bases water-dispersible or water-thinnable product is present.

In a further special embodiment of the invention The paints contain polyurethane resins made up of the following components:

(a) 25 to 70 percent by weight unsaturated fatty acids, of which up to 25 percent by weight are present as drying oils and the mixture has iodine numbers of about 130 to 390 has

(b) 2 to 30 percent by weight of aromatic polycarboxylic acids, individually or in a mixture, or their anhydrides, preferably Trimellitic anhydride, if these exist,

(c) 5 to 35 percent by weight of polyvalent organic hydroxy compounds,

(d) 2 to 9 percent by weight of polyoxyalkylene compounds, with an average molecular weight of the polyoxyalkylene chain of about 3000,

(e) zero, component b being contained in such amounts that the condensation product has Sfture numbers from about 10 to about 50,

(f) 2 to 50 percent by weight isocyanates, individually or in nemiech, and

(g) zero,

(h) and the carboxyl group-containing polyurethane resin

109828/1666

BAD UrwuiWHL

as a product that is water-dispersible or water-thinnable by alkali and / or organic strong bases is present.

Contained in a further embodiment of the invention the paints as polyurethane copolymer resins are those that are composed of the following components:

(a) 25 to 50 percent by weight unsaturated fatty acids, possessed with iodine numbers of about 130 to 390,

(b) zero,

(c) 5 to 35 weight percent polyvalent organic hydroxy !links,

(d) ¹¹ to 9 percent by weight of polyoxyalkylene compounds which contain at least one atom of active hydrogen, with an average molecular weight of the polyoxyalkylene chain of about 3000,

(e) 2 to ^l \ 5 weight percent anpolym.erisierbare Monome ran,

(f) 3 Ms 50 percent by weight isocyanates, individually or im Mixture, and

(g) 2 to 25 weight percent unsaturated mono- and / or rolyr.U'chole or mixtures thereof, is reacted selected by selection amount such that the total isocyanate group equivalent to Hydroxy1-prunpenSquivalent 1.01 am l, ^l \ 5 was.

In a further special embodiment of the invention The paints contain polyurethane polymer resins r. oil marriage, which is composed of the following components

Ui) ' ^M 5 hl ■'"/") percent by weight of unsaturated fatty acids

from about 150 to

«AD OR1G * ^NAL

109828 / U66

(b) 2 to 30 percent by weight of aromatic polycarboxylic acids, individually or as a mixture, or their anhydrides, if they exist,

(c) 5 to 35 percent by weight of polyvalent organic hydroxy compounds,

(d) zero,

(e) 2 to 45 percent by weight of polymerizable monomers of which at least one monomer has at least one free carboxyl group, the components b and e are contained in such amounts that the acid numbers of the reaction product are about 20 to be about 80,

(f) 3 to 50 percent by weight isocyanates, individually or in admixture, and

(g) 2 to 25 percent by weight of unsaturated mono- and / or Polyalcohols or mixtures thereof, reacted selected by the selection of amounts so that the total hydroxyl group equivalent to the isocyanate group equivalent was 1.01 to 1.1 * 5,

(h) and the polyurethane resin contains carboxyl groups that are strong by adding alkali and / or organic Bases in the water-dispersible or water-thinnable Condition.

In a further special embodiment of the invention The paints contain, as polyurethane copolymer resins, those that are composed of the following components:

(a) 25 to 50 percent by weight of unsaturated fatty acids with dead numbers of about 130 to 390,

(b) zero

(c) 5 to 35 weight percent polyvalent organic hydro xyl compounds,

(d)? up to 9 percent by weight of polyoxyalkylene compounds,

109828/1666 bad original

which contain at least one atom of active hydrogen, with an average molecular weight of Polyoxyalkylene chain of about 3000,

(e) 2 to 5 percent by weight of polymerizable monomers of which at least one monomer has at least one free carboxyl group, the component e is contained in such amounts that the acid numbers of the reaction product are about 20 to about Be 80,

(f) 3 to 50 percent by weight isocyanates, individually or im Mixture, and

(g) 2 to 25 percent by weight of unsaturated mono- and / or Polyalcohols or their mixtures, by choosing the amount implemented selected so that the total hydroxyl group equivalent to the isocyanate group equivalent 1.01 up to 1.1 * 5,

(h) and the polyurethane resin contains carboxyl groups that are strong by adding alkali and / or organic Bases in the water-dispersible or water-dilutable Condition.

The aqueous paints according to the invention are particularly notable characterized in that they have an improved Piementbindigkeit and the coatings produced from them Even at room temperature or at relatively low stoving temperatures, they fully display their valuable properties or practically fully develop. Furthermore, such aqueous air-drying paints or stoving paints are made Paintwork with improved adhesion and impact resistance to get as well as paintwork with particularly pronounced Plasticity, weather resistance, hardness and saponification resistance. If desired, varnishes can also be obtained that also have other characteristics, such as light resistance, flexural strength,

109828/1666 _ßA D original.

medium resistance and temperature resistance in particular Own dimensions.

As a solvent for the paints according to the invention Water used.

To achieve sufficient water dispersibility or Solubility in water, improvement of the flow properties and the gloss of pigmented paints may require

P be like organic solvents that are unlimited or at least largely miscible with water, when Dissolve with water to be used. These organic solvents can be used in amounts of about zero to 30 percent by weight, preferably 2 to 15 percent by weight, find use, and serve to help with dilution to obtain a body content of approx. 30 to 70 percent by weight of the paints with water. Suitable as such e.g. mono- and diethers of ethylene glycol, diethylene glycol with lower monohydric alcohols such as ethanol, n- and i-propanols, n- and i-butanols, such as e.g. Methyl glycol, Ethyl glycol, propyl glycol, isopropyl glycol, butyl

^ glycol, diethylene glycol diethyl ether, also acetone alcohol, lower ketones such as acetone, methyl ethyl ketone and in small amounts also methyl isobutyl ketone.

The aqueous paints according to the invention can, if desired, the additives customary in water-repellent paints, such as pigments, siccatives, soluble dyes, optical Brighteners and agents to promote flow, e.g. anionic, cationic, nonionic emulsifiers and of shine included. In particular, in addition to the polyurethane resins, the lacquers can contain other lacquer binders, such as alkyd resins, amino resins, phenolic resins, epoxy resins, rosins, drying and not drying oils, cellulose derivatives and other polyurethane

10 9 82 8/1666 bad original

resins that do not match the main binder (polyurethane resin of the type indicated) are identical, dissolved and / or dispersed. The weight ratio the polyurethane resins in addition to the other paint binders should in general be expedient be greater than 1, in particular greater than 2. Fs has also generally proven to be useful when the Weight ratio of water to the total amount of binder in the paints is about 0.4 to 3, in particular is approximately from 0.5 to 1.5.

To produce lacquers, the aqueous lacquers can be applied to the objects to be lacquered using the customary methods, for example by spraying, brushing on, pouring on, rolling on, flooding, dipping or soaking and by means of electrodeposition, for example electrophoresis. Drying or baking of the coatings may contain up I8o ° n is generally expedient £ ßigerweise at room temperature or in a Finbrennen at temperatures about 80 °, in particular approximately 100 ° to 140 ⁰ C and, in function of the temperature, over a period of about from 5 to 120 minutes, in particular from about 20 to 40 minutes. Since the valuable properties of the paint are particularly effective on metals such as iron, aluminum, magnesium and alloys of these metals, the aqueous paints are particularly suitable for painting objects made of wood, masonry, concrete, paper, sheet metal, e.g. parts of car bodies , Ships and ice boxes, as well as cans, jugs, vats and appliances for industry and household. The lacquers can be used in the same way for the production of base and top coats because of their adhesive strength they are also very suitable for applying fin-coat lacquers to metals, the high surface gloss generally not requiring subsequent polishing.

109828/1666 bad ORiGiNAL

lent.

For the polyurethane resins used according to the invention in their production 25 to 70 percent by weight, preferably 35 to 55 percent by weight, of unsaturated fatty acids of natural or synthetic origin, optionally drying and / or semi-drying oils in quantities from zero to 25 percent by weight, preferably in the range from zero to 15 percent by weight, is used. the Fatty acids or oils can contain up to 6 percent by weight Incorporated maleic anhydride, the mixture used must have iodine numbers of 130 to 390.

Examples of suitable unsaturated fatty acids are: eleostearic acid, licanic acid, parinaric acid, linolenic acid with isolated and conjugated double bonds, linoleic acid with isolated and conjugated double bonds. Also suitable as an admixture with the abovementioned unsaturated fatty acids are those 10 to 30 carbon atoms, which have at least one unsaturated Carbon double bonds in the chain, all unsaturated found in natural fatty oils Fatty acids such as palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, erucic acid, arachidonic acid, Clupanodonic acid, etc. The total content of these However, at least monounsaturated fatty acids must not be 30 percent by weight, based on the total batch exceed. However, the content of these fatty acids is preferably below 10 percent by weight. The amount in saturated fatty acids, which is always present when fatty acids, such as those made more natural by saponification oils are extracted +,) should not exceed 20 percent by weight, if possible even be below 10 percent by weight. As unsaturated fatty acids, the through Dimerization or oligomerization of unsaturated fatty

+) are used,

1Q9828 / 18S6 bath

acids obtained polybasic acids as well as cyclized monobasic acids can be used. To be favoured Uses unsaturated fatty acid mixtures, such as those made from natural vegetable and animal unsaturated fats can be obtained by saponification. Additions of natural resin acids (rosin), up to a maximum of 20 Percentage by weight and / or of maleic anhydride-styrene copolymers up to a maximum of 15 percent by weight of the fatty acid mixture (a) are possible.

Those products made from fatty acids with a pyrone structure, as described in the English patents, are also suitable 827,361 and 844,620 have been described, as well as their addition products with maleic acid, fumaric acid and maleic anhydride, which are described in English patent specification 1,135,775, again the Products with a viscosity of 30-120 poise are preferred.

Natural, unsaturated, fatty substances include cottonseed oil, Lupine oil, corn oil, sesame oil, grapeseed oil, Walnut oil, perilla oil, linseed oil, wood oil, safflower oil, niticica oil and fish oil suitable. Of these, wood oil, oiticica oil, safflower oil, linseed oil and fish oil are preferred. Farther but are also suitable: Fatty acids from dehydrated castor oil, which have a high proportion of conjugated Contain linoleic acid. Here, drying and / or semi-drying oils are also used as drying and / or semi-drying oils Condensation products, e.g. from wood oil and phenolic resols and / or etherified phenolic resols, are preferred Butylphenol resoils, useful.

They are also suitable, for example, as admixtures the above-mentioned unsaturated fatty acids as component (b) other aliphatic, cycloaliphatic

109828/1666

and aromatic carboxylic acids or hydroxycarboxylic acids and / or their anhydrides, if any. As monocarboxylic acids be z.P. called: trimethyl acetic acid, Pelargonic acid, glycolic acid, lactic acid, 3-hydroxypropionic acid, α-hydroxyisobutyric acid, 2-hydroxybutyric acid, 2-hydroxynonanoic acid, 2-hydroxvoctadecanoic acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid »4-hydroxybenzoic acid, 4-hydroxyphenylacetic acid, 3-hydroxy-2-naphthoic acid, 2-Hydroxy-1-naphthoic acid, alkane monocarboxylic acid, their Carboxyl groups on tertiary or quaternary carbon atoms are bound, with 8 to 18 carbon atoms, as they are from carbon monoxide, water and monoolefins (Swiss Patent specification 390 229) are obtained, phenylacetic acid, acrylic or methacrylic acid, benzoic acid, ptert-butylbenzoic acid, 1-methylhexydrobenzoic acid, 2,4,5-trimethylhexanhydrobenzoic acid. Furthermore, as Component (b) polycarboxylic acids or their anhydrides are used e.g. phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, Tetrahydrophthalic anhydride, trimellitic acid, "" rimellitic anhydride, Hemimellitic acid, pyromellitic acid, Pyror> ellitic anhydride, prehnitic acid, prehnitic anhydride, Mellophanic acid, benzene pentacarboxylic acid, benzene pentacarboxylic acid anhydride, Maleic anhydride, citraconic anhydride, itaconic anhydride, methaconic anhydride, Aconitic anhydride, 2,6-matylene-dicarboxylic acid, diphenyl-0-0'-dicarboxylic acid, Hexachloroendomethylenetetrahydrophthalic acid.

As polyvalent organic hydroxy compounds, e.g. glycerol, pentaerythritol, di-pentaerythritol, Ethylene glycol, diethylene glycol, ^ rimethylolethane, Trimethylolpropane, diallyl ether of pentaerythritol, Mannitol, sorbitol, bisphenol-A, hydrogenated bisphenol-A,

109828 / 1B66 bad original

H _a 4-Dihydroxypheny! Methane, ¹ J, ^ - Dihydroxypheny! Butane, Jij ^ '- Dihydroxydiphenyl, Cyclohexanediol, 1,4-Cyclohexanedimethanol, 2,2, if-Trimethyl-1,3-Pentanediol, ethoxylated bisphenol-A with 1 to 6 ethylene oxide molecules, pro-oxylated bisphenol-A with 1 to 6 propylene oxide molecules, ethoxylated pentaerythritol with about 12 ethylene oxide molecules, ethoxylated * J, * f · dihydroxydiphenol with 1 to 6 ethylene oxide molecules to 6 ethylene oxide with 1 to 6 ethylene oxide molecules, 4, 4-methyl-ethoxyphenoxydmolecules with 1 to 6 ethylene oxide molecules to 6thylene oxide with 6thylene oxide molecules , 2,6-cyclohexanetriol, can be used. Phenolic resols and / or etherified phenolic resols which still have 2 to 6 free alcoholic hydroxyl groups per molecule, preferably with average molecular weights of 250 to 700, can also be used, such an addition in the range of 3 to 10 percent by weight being preferred. It is also possible to use phenolic resins based on bisphenol-A, but preferably with a low charge with formaldehyde (phenol! Formaldehyde = 1: 0.8 to 1: 1.3), as dihydric to hexahydric alcohols.

In addition, admixtures of hydroxyl groups can be used Copolymers, e.g. allyl alcohol-styrene with an average molecular weight of 500 to 3000 and 0.3 to 0.6 OH equivalent per ion g up to a maximum of 15 percent by weight, be added.

Polyoxyalkylene compounds which contain at least two active hydrogen atoms are used as component (d) Question:

propoxylated and ethoxylated (or mixed propoxy and ethoxylated) alcohols, amines and alcohol amines, which in their molecule have at least one polyoxyalkylene oxide chain with a molecular weight of at least 200 to about 50,000. These include, for example, as polyvalent basic polyols, amines or alcohol amines, the following compounds

109828/1666

Applications understood: e.g. ethylene glycol, di- _s tri- and tetraethylene glycol, butahdiol, 1,2-propanediol, 1,3-proanediol »neopentyl glycol, pentaerythritol, trimethylolpropane, bisphenol-A, ¹ l, 4'-dihydroxyphenyl methane, 1,4- Cyclohexanediol, ethylenediamine, 1,3-propanediamine, 1,3-, 1, ¹ -butanediamine, 1,2-, 1,3- »1» ¹ * - »1> 5- and 1,6-hexanediamine, phenylenediamine , Tolylenediamine, ^, il'-diaininodiphenylamine, 1,2,4- and 1,2,3-diaminobenzene and methyl-diethanolamine, butyl-diethanolamine, N-methyl-diSthanolamine, N-butyl-diethanolamine, N-oleyl-diethanolamine , N-linolenyl-diethanolamine, N-linoyl-diethanolairin, N-cyclohexyldiethanol, ^ -amino-phenol _s 2-hydroxyethy! Hydrazine.

As polyoxyalkylene compounds that have only one atom active Contain hydrogen, and in which the polyoxyalkylene chain has an average molecular weight of about 200 to 50,000 are eligible

Those from monocarboxylic acid by catalytic alkoxylation or from monocarboxylic acid and polyoxyalkylene compounds which have two atoms of active hydrogen, can be obtained by half-ester reaction. As monocarboxylic acids, e.g. triroethyl acetic acid, pelargonic acid, Acrylic acid, methacrylic acid are used. Also the monocarboxylic acids already mentioned as component (a) in the main patent can be used. From monoalcohols by alkoxylation or by etherification reaction with polyoxyalkylene compounds, which have two atoms of active hydrogen, are also polyoxyalkylene compounds, which have an active hydrogen atom. These include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, allyl, benzyl alcohol, Cyclohexanol, phenol, methyl-, ethyl-, butyl-, isobutyl-, p-tert-butylphenol and those as component (f) understood compounds mentioned.

BATH ORIGINAL

109828/1666

But it is also possible to use the polyoxyalkylene compounds already mentioned, which contain at least two atoms of active hydrogen, with the unsaturated ones mentioned under (a) To esterify fatty acids and / or their drying oils and / or (b) mentioned monocarboxylic acids hsw. transesterify so that it only has one active hydrogen atom contain. The polyoxyalkylene compounds containing only one active hydrogen atom can be used alone or in a mixture with the polyoxyalkylene compounds which contain at least two atoms of active hydrogen, used will.

As polyoxyalkylene compounds with one or two Atoire.i Active hydrogen can also be used: compounds of the series of isotridekanol polyglycol ethers with more than 5 ethylene oxide molecules, compounds of the nonylphenoxy poly (ethylene oxide) -thanol series with more than 2 ethylene oxide molecules as well as their mono- and di-esters with orthophosphoric acid; Compounds of the series ethoxy and / or propoxylated products from ethanolamine and fatty acid, with saturated and unsaturated fatty acids among fatty acids with 4 to about 22 carbon atoms are understood, again products with unsaturated fatty acid are beneficial.

A special embodiment of the invention is thereby characterized in that the polyoxyalkylene compounds having an average molecular weight of 2000 up to 4000 amounts of 2 to 8 percent by weight are used.

Copolymerizable monomers can be used as component (e) such as vinyl or vinylidene monomers can be used individually or as a mixture. Of the monomeric vinyl or vinylidene compounds those which do not contain free carboxyl groups are preferred, with the most preferred

109828/1686

BATH ORIGINAL

Compounds of this type include styrene, styrenes substituted in the core, styrenes substituted in the side chain, such as α-methylstyrene, α-ethylstyrene, α-chlorostyrene ₃ and vinyltoluene.

As vinyl monomers that do not meet any free carboxyl groups, are also possible: alkyl esters of α, ß-unsaturated monocarboxylic acids, such as methyl acrylate, ethyl acrylate, Propyl acrylate, butyl acrylate, isobutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate and the corresponding methyl, ethyl, phenyl acrylates, propyl crotonate, butyl crotonate and the like. Further come in question:

Hydroxylalkyl esters of a, ß-unsaturated carboxylic acids, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hyro: iybutyl acrylate, 3-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate and the corresponding methacrylates, Xthacrylate, Pbenyl acrylate, 2-Hydroxyäthyliraleinat, Di- (2-hydroxyproüyD-Maleinat or the corresponding fumarates, 2-hydroxy-3-chlorodropyl acrylate, 2-hydroxy-1-phenylethyl acrylate, 2-Hydroxy-3-butoxy-propyl acrylate and the corresponding ethacrylates and phenyl acrylates.

As admixtures, the monomer mixture, individually or as a mixture, other monomers capable of partial polymerization be added, such as acrylamide, methacrylamide, etherified-N-methylolacrylamide, etherified-N-methylolmethacrylamici, Acrylonitrile, methacrylonitrile and the like. Her vinyl and / or the vinylidene content in the synthetic resin depends on the intended area of application for the cattle product.

Partially polymerizable carboxyl group-bearing monomers are also used, such as Acrylic acid. Methacrylic acid, cinnamic acid, ß-benzoylacrylic acid, Crotonic acid, ethyl crotonic acid, benzene lactic acid,

109828/1666

BATH ORIGINAL

Cyclohexenedicarboxylic acid, angelicic acid; also ct, ß-ethylenically unsaturated polycarboxylic acids or their anhydrides, insofar as they are capable of forming such as maleic acid, fumaric acid, citraconic acid, itaconic acid, methaconic acid, aconitic acid or monoesters of the aforementioned polycarboxylic acids with saturated, straight-chain monoalcohols with 1 to H carbon atoms , Maleic monomethyl esters, halogen-substituted acids such as chloroaleic acid and the like. The preferred α, β-methylenically unsaturated carboxylic acids include: acrylic acid, methacrylic acid, maleic anhydride, maleic acid and fumaric acid.

The carboxyl group-bearing monomers can alone in Mixture with one another, alone in a mixture with the first-mentioned, no carboxyl group-bearing monomers or be reacted in a mixture with the other components.

Admixtures of dicyclopentadiene and its derivatives, up to a maximum of 15 percent by weight are possible.

Esterification, transesterification or polymerization is carried out by heating at temperatures between 15O ° C to 29 ° ⁰ C, preferably at 15O ° C to 27O ⁰ C, in the presence of catalysts, for example dibutyltin dilaurate, calcium acetate, lead oxide, sodium methylate, lithiumricinoleate, Kobaltbutylphthalat, Äthylhexyltitanat.

The specified quantities reduce the esterification or Umesterungsreaktionen carried out so that mono-di- or polyesters or mixtures of these are formed, the The resulting ester products should have acid numbers from zero to 300, preferably below 40, and should have hydroxyl groups must show that uip can continue to be implemented.

109828/1666 _eA D

If components (a) to (d) have first been esterified by heating in the temperature range already mentioned, the polymerization of the monomers can be carried out without catalysts or in the presence of catalysts, such as peroxides, acids, Friedel-Crafts compounds, by heating to 120 ° C to 2 ^ O ⁰ C are carried out. In the polymerization of component (e), a procedure is preferred in which the polymerization temperature and the polymerization time are reduced by polymerization initiators in order to carry out the polymerization under conditions that are as gentle as possible.

Polymerization initiators which can be used are those known per se Find organic peroxides and / or hydroperoxides use. Also the use of the known ones Chain terminators such as mercaptans provide particularly beneficial results.

A distinction must be made between two cases A and B in the manufacture of component I. The Pall A comprises one component I, which is obtained by appropriate selection and implementation of the starting components and a hydroxy] .- ™ represents group-bearing ester which is practically free of carboxyl groups.

Such a component I according to Pall A is preferably produced when the polyurethane resin obtainable as the end product is to be water-dispersible and the water-containing polyurethane resin binder preparations are to be characterized by practically unlimited storage stability and good air-drying properties. To such polyurethanes. to obtain the best paint and binder properties, component I is usually 3 case A,
(a) 25 - * »5 Oew.i '

109828/1666

BATH ORIGINAL

(b) 2-15 wt. *

(c) 2-30% wt.

(d) H - 9 wt. J? eineir with average molecular weight from 2000 to ¹ Jooo

(e) zero - 40 wt. *
built up.

However, the above-identified polyurethane resin should be used as the sole binder or in combination with others Binders in water-dispersed form for stoving coating agents are used in the The above guide formulation for component I, case A, the proportion of (a) and (b) selected in the following range:

(a) 25 - 35 wt. *

(b) 2-30 wt. *

The preparation of component I, case A, that is, the Production of a component I which contains hydroxyl groups and is practically free of free carboxyl groups, can be done, for example, according to the following procedure:

Working method α:

Components (a), (b), (c), (d) and (e) are prepared by heating, optionally in the presence of catalysts esterified or copolymerized to about 155 to 260 ° C.

Working method ß:

Components (a), (b), (c) and (d) are raised by heating, optionally in the presence of catalysts Esterified about 155 to 26o ° C until the acid number has dropped below 1. Then the component (e) polymerized thermally or catalytically.

109828/1666

Mode of operation γ:

The components (a) and (d) are esterified at 155-200 ⁰ C and then esterified with the components (b), (c) and (e) by heating at 155 to 26O ° C and copolymerized.

Mode of operation δ:

The components (c) and (d) are esterified at 155-200 ⁰ C and then esterified with the components (a), and (e) at 155 to 26O ⁰ C and mischpolyirerisiert.

Mode of operation ε:

Components (a) and (e) are copolymerized thermally or catalytically by heating and esterified with components (b), (c) and (d) (heating to 155 to 260 ^° C.).

Working method ζ:

The component (e) with carboxyl group and / or HydroxyI- and / or amide and / or nitrile groups are esterified and / or etherified with component (d) by heating or reacted and then esterified with components (a), (b) and (e) and optionally copolymerized.

The preferred embodiments of the process include such new water-dilutable, carboxyl group-free, oil-modified polyurethane resins which are obtained according to the present invention from the following special component combinations: linseed oil fatty acid, polyethylene glycol (pole weight 3000), pentaerythritol, hydrogenated bisphenol-A, phthalic anhydride, toluene diisocyanate Triallyl ether of pentaerythritol; Linoleic acid, polyethylene glycol (molecular weight? 000), hydrogenated bisphenol-A, terephthalic acid, hydrogenated T ¹ oil diisocyanate, di-

109828/1666 sad original

20A8956

allyl ethers of trimethylolpropane; Linolenic acid, polyethylene glycol (molecular weight 3000), polyethylene glycol (molecular weight 2000), ethoxylated bisphenol-A with 2 ethylene oxide molecules, pentaerythritol, terephthalic acid, tolylene diisocyanate, dimerized tolylene diisocyanate, triallyl ether of pentaerythritol; Linoleic acid, polyethylene glycol (molecular weight 3000), pentaerythritol, hydrogenated bis-phenol-A, terephthalic acid, isobutyl methacrylate, hydrogenated tolylene diisocyanate, diallyl ether of trimethylolpropane; Fish oilate acid with an iodine number of about 150 to 210, polynropylene glycol (molecular weight 2000), polyethylene glycol (molecular weight 3000), pentaerythritol, hydrogenated bisphenol-A, terephthalic acid, tolylene diisocyanate, triallyl ether of pentaerythritol, pentaerythritol fatty acid, polyethylene anhydride 3000 molar weight, maleic anhydride glycol (3000 molar) Co-polymer containing maleic anhydride and styrene in a molar ratio of 1: 1, an acid number of 40O and a K value of 15, pentaerythritol, phthalic anhydride, toluene diisocyanate; Fish oil fatty acid, ethoxylated ethylene diamine (molecular weight 2750), allyl alcohol-styrene copolymer with 0, ^ 5 OH equivalent no 100 g _s pentaerythritol, tolylene diisocyanate, diallyl ether of trimethylolpropane; Safflower oil fatty oriura, pentaerythritol, ethoxylated H-linolenyl diethanolamine (molecular weight 2800), hydrogenated bisphenol-A, phthalic anhydride, tolylene diisocyanate, triallyl ether of pentoerythritol; Fish oil fatty acid, l ^ -cyclohexanediol, ethoxylated 1,3-propanediamine (molecular weight 3000), pentaerythritol, phthalic anhydride, lactic acid, toluylene diisocyanate, unsaturated monoalcohol with an iodine number of ΙβΟ; Linolenic acid, polyethylene glycol (weight 3000); propoxylated U , "f-nihydroxydiphenyl with two propylene oxide molecules, 1,2,6-nyclohexanetriol, pentaerythritol, toluylene diisocyanate, triallyl ether of pentaerythritol; Linoleic acid, trimethylolpropane, polyethylene glycol (molecular weight 2500), pentaerythritol, phthalic anhydride, polyphenyl isocyanate

109828/1666

- 22 of the general formula:

TjfCO

NCO

where η is 1 to 3, triallyl ether of pentaerythritol; Linolenic acid, polyethylene glycol (molecular weight 3000), pentaerythritol, methacrylic acid, toluylene diisocyanate, antimony

. isocyanate.

* In the preferred embodiment of the process, the components are selected and reacted under the stated conditions in such a way that the end products obtained, measured as 50% solutions in butyl glycol, have a viscosity according to Gardner-Holdt from RZ.

In the preparation of component I according to Pall B is a component I produced in which this component is selected by appropriate selection of the starting compounds according to type and amount and their corresponding conversion to form a hydroxyl group and carboxyl group Ester is implemented. This ester bearing hydroxyl groups and carboxyl groups should be used as component I according to Pall B. Acid numbers from 1 to 300, preferably less than ^ O. In a special preferred embodiment as component I according to case B, those hydroxyl-trapping esters which have at least one in their molecule contain free carboxyl group bonded to secondary and / or tertiary carbon atoms.

The use of component I according to case B allows polyurethane resins to be produced as end products which are both water-dispersible and, after the addition of PHi-rc-rd ®k or strong organic bases, water-dispersible or water-thinnable.

109828/1666

BATH

To the extent that the polyurethane resin obtained as the end product is produced using component I, Pall B and is mainly intended to be water-dispersible, component I must have an acid number of 1 to 20 in the structure of component I according to Pall B, and the condensed portion of condensed polyoxyalkylene compounds as well 1 and / or 2 active hydrogen atoms with an average molecular weight of the polyoxyalkylene chain 200-50000 must be between zero and 8 percent by weight, preferably from zero to 5 overall t

weight percent.

As far as the polyurethane resin available as an end product is produced via component I Pall B, and the resin is to be water-dispersible or water-dilutable or water-soluble, component I must have an acid number of 1 to ¹ JO, and the proportion of condensed polyoxyalkylene compounds must be 1 and / or 2 active hydrogen atoms with an average molecular weight of the polyoxyalkylene chain of 200 to 50,000 between zero to 8 percent by weight. In addition, the last-mentioned polyurethane resins must be mixed with alkalis and / or strong organic bases until *

the polyurethane resins achieve the desired water dispersibility, water thinnability or water solubility to have.

However, it is also possible to use component I case B to produce polyurethane resins which have free carboxyl groups and the finished polyurethane resin has SS.ure numbers below 10, and it is not necessary to add alkali or strong organic bases to such polyurethane resins in order to to achieve the desired water dispersibility, water dilutability or water solubility. Hm such special polyurethanes 109828/1666

To prepare resins according to this invention, when building up component I case B, work towards the fact that component I has an acidity of 1 to 12 and the proportion of condensed polyoxyalkylene compounds with 1 and / or 2 active hydrogen atoms in the range from 5 to 8 weight percent, and the average molecular weight of the polyoxyalkylene chain at ^2000-1 is IOOO.

The preparation of component I case B, that is, the preparation of a component I, the hydroxyl groups and Contains free carboxyl groups, can be done, for example, according to the following procedure:

The same procedures can be used as in the preparation of component I case A in the working methods α to ζ has been described.

The selected esters containing hydroxyl and carboxyl groups, in which at least one free carboxyl group are bonded to secondary and / or tertiary carbon atoms (stage I), can be obtained by carefully selecting the acid component (b) and / or (e) in stage (I), that is, by co-use especially of polycarboxylic w acids (b) and / or Hydroxymono and polycarboxylic acids (b) and / or other substituted carboxylic acids (b) in which at least one carboxyl group is bonded to a secondary or tertiary carbon atom, can be constructed .

Another possibility, useful hydroxyl ^ group-bearing Esters in stage I from components (a), (b), (c), (d) and (e) to be prepared in their molecule at least contain a free carboxyl group bonded to secondary and / or tertiary carbon atoms given by first the components (a), (b), (c) and (d) by condensation to form hydroxyl groups

109828/1666

Esters that contain practically no free carboxyl groups in their molecule, and then with such polymerizable monomers, copolymerized as component (e), which have at least one free carboxyl group on a secondary or tertiary carbon atom in their molecule bound, must contain.

r> ei any of the manufacturing methods described here of the hydroxyl group-bearing esters of component I, components (a) to (e) must be coordinated in this way be that component I acid numbers from 1 to 300 owns.

Component I, which is present as an ester bearing hydroxyl groups and which contains at least one free carboxyl group on secondary and / or tertiary carbon atoms in its molecules (ie Pall B), can - as already described above - be prepared in one step. However, multi-stage production - preferably two-stage production - is also possible. In this two-stage production, stage I is made from components (a), (b), (c) and (d) or from components (a), (b), (c), Cd) and (e) first of all an ester bearing hydroxyl groups, which either does not contain any carboxyl group or does not yet contain sufficient amounts of carboxyl groups incorporated. In a second reaction stage, by adding polycarboxylic acid or polyearboxylic acid anhydride, an additional portion of component (b) is added in such amounts that, after heating by esterification, the finished component I has the desired acid number in the range from 1 to 300, which is an advantage Two- or multi-stage production for component X results in the further processing of end products which are more stable in storage, so that multi-stage production of component I is preferred

108828/1668

- 26 embodiment heard.

The multi-stage component I (Pall B) can but also modified by a subsequent mixed polymerization stage with the polymerizable Monomnr ^ ri (e) will.

Another multistage preparation of component I (Pall B) can also consist in that you first Components (a), (b), (c) and (d) au a sufficient amount of carboxyl groups and hydroxyl groups Reacts ester and then reacts this ester in stage (e) with the polymerizable monomers.

Good results are obtained using the component I, which is present as an ester bearing hydroxyl groups, which has at least one free carboxyl group in its molecule contains bonded secondary and / or tertiary carbon atoms, builds up so that these are formed as reaction products components (a), (b), (c), (d) and (e) with tri and / or polybasic acids as component (b) and / or their Anhydrides, as far as they are able to form such, are present. In this case, one must use such polycarboxylic acids as component (b) with 2 to 6 carboxyl groups, in which at least one carboxyl group is attached to a secondary and / or tertiary carbon atom is bonded, use. As a hydroxyl group-bearing ester, which in its molecule at least containing a free carboxyl group on secondary and / or tertiary carbon atoms are for example suitable:

those made from linseed oil fatty acid, trimethylolprofjan, hydrogenated Bisphenol-A, polyethylene glycol (molecular weight 30ΟΘ), tri— mellitic anhydride, those made from linseed oil fat, polyethylene glycol (molecular weight 3000), pentaerythritol, hydrogenated bisphenol-A, phthalic anhydride; those from ricin

108828 / USfl

BATH ORIGINAL

- 57 -

fatty acid, isononanoic acid, pentaerythritol, hydrogenated Bisphenol-A, phthalic anhydride, polyethylene glycol (molecular weight 3000) 5 from tall oil fatty acid, trimethylolpropane, Adducts of bisphenol-A and 2 moles of propylene oxide, trimellitic anhydride; those from tall oil fatty acid, pentaerythritol, Adducts of bisphenol-A and 2 moles of propylene oxide, trimellitic anhydride; those from conjugated Safflower oil fatty acid, trimethylolpropane, phthalic anhydride, Polyethylene glycol (molecular weight 3000), styrene, methacrylic acid; those from ricinic fatty acid, pentaerythritol, adducts from bisphenol-A and 2 moles of propylene oxide, vinyl toluene and acrylic acid; those made from ricinic fatty acid, trimethylolpropane, Phthalic anhydride, methacrylamide, methacrylic acid; those from ricinic fatty acid, pentaerythritol, adducts from bisphenol-A and 2 moles of propylene oxide, etherified N-methylolacrylamide, acrylic acid; those made from ricinic fatty acid, Trimethylolpropane, phthalic anhydride, polyethylene glycol (molecular weight 3000), isobutyl acrylate; such from ricinic fatty acid, trimethylolpropane, phthalic anhydride, α-methylstyrene, etherified N-methylolacrylamide, Hydroxyethyl methacrylate, methacrylic acid; those made from ricinic fatty acid, Trimethylolpropane, phthalic anhydride, trimellitic anhydride, styrene, methacrylic acid, 2-hydroxyethyl maleate.

The following isocyanates, for example, can be used as component (f):

Phenylethyl isocyanate, 2, k , 5-trimethylphenyl isocyanate, Jj-cyclohexyl phenyl isocyanate, diphenyl methane ^ t isocyanate, 3, ¹ *, 6-trichlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, 3, 4,6-trifluorophenyl isocyanate, 3-Sulfofluoridphenylisocyanat, 2-chlorophenyl isocyanate, 3-Senfphenyl-isocyanate, methyl 3-isocyanato-benzylifther, Methoxymethyldiisocyanat, ^ -Äthoxyphenyl isocyanate, 4-Carbäthoxyphenyl isocyanate, H, H ^f -Dichlorodiphenylether-2-isocyanate, 3-isocyanate-benzene-

108828/1660

sulfomethylanilide, II-isocyanatoazobenzene, 1-naphthyl isocyanate, 5-nitro-1-naphthyl isocyanate, tetrahydro-1-naphthyl isocyanate, decahydro-2-naphthyl isocyanate, phenanthryl-3-isocyanate, pyrenyl-3-isocyanate, tert-butyl -isocyanate, dodecyl isocyanate, oleyl isocyanate, octadecyl isocyanate, methyl isocyanate, di-cKn-hexyD-methyl-isocyanate, 1-chlorohexyl-6-isocyanate, l-chlorobutyl-etherpropyl-isocyanate, 1-cyano-propyl-3 isocyanate, ethyl isocyanate acetic acid ester, isocyanate caproic acid ester, isocyanate linoleic acid ester, isocyanate linolenic acid ester, methyl ether propyl isocyanate, ™ isopropyl ether propyl isocyanate, cyclohexyl ether propyl isocyanate, phenyl isocyanate, phenyl isocyanate, tol isocyanate, xocyanate isocyanate, p-tolyl isocyanate, p-tolyl isocyanate or hexamethylene diisocyanate, arylene diisocyanates or their alkylation products, such as phenylene diisocyanates, naphthylene diisocyanates, diphenylmethane diisocyanates, tolylene diisocyanates, di- or triisopropylbenzene diisocyanates or triphenylmethane triisocyanates, p-isocyanatophenylthiol phosphorus acid triesters, p-isocyanatophenylthiophosphoric acid triesters, aralky! diisocyanates, such as l- (isocyanatophenyl) ethyl isocyanate or the xylylene diisocyanates, fluorine-substituted isocyanates, ethylene glycol diphenyl ether 2,2'-diisocyanate, 2,2'-diethylene flykoldiphenyl ether-2,2 ^ 1-diisocyanate, 1,1'-dinaphthyl-2, 2'-diisocyanate, pisphenyl-2, ^ '-diisocyanate, biphenyl-iJ , h ' -diisocyanate, benzophenone-3,3'-diisocyanate, fluorene-2, 7-diisocyanate, anthraquinone-2,6-diisocyanate, pyrene-3,8-diisocyanate, chrysene-2,8-cliisocyanate, 1-methylbenzene-2, ^I l, 6-triisocyanate, naphthalene-l, 3,7-triisocyanate , Biphenylmethane-2, il , U'-triisocyanate, triphenylmethane-ilj ^ jil'-triisocyanate, 3'-methoxyhexane diisocyanate, octane diisocyanate, ω, ω'-diisocyanate-1, ^ - diethylbenzene, w ^ '- diisocyanate -lj ^ -dimethylnaphthalin, cyclohexane-1,3-diisocyanate, l-IsoproDylbenzol-2,4-diisocyanate, l-chlorobenzene-2, i * diisocyanate, l-Pluorbenzol-2, ¹ J-diisocyanate, l-nitrobenzene 2, li-diisocyanate, 1-chloro- ¹ »-

109828/1666

methoxybenzene-2,5-diisocyanate, azobenzene-4,4'-diisocyanate, Benzolazonaphthalene-4,4'-diisocyanate, Diphenyl-Mther-2,4-diisocyanate, Diphenyl ether 4,4-diisocyanate, and Polyphenyl isocyanate of the general formula

NCO

CH,

where n = 1 to 3.

NCO

CiL

NCO

Isocyanates of the general types are also suitable Formula:

NCO
ι ^R 2 " MCO
J N I.
C -
I. I.
- c - H H ^V 0R

wherein R ₁ = alkyl, alkoxyalkyl, aryl, alkaryl, aralkyl, or a halogen derivative

R ₂ = lower alkylene or lower alkylidene radical R, = H or the radical

R ₁ O

As such diisocyanates, the following can be used come:

The esters of 2,6-diisocyanatecaproic acid such as methyl, Methoxymethyl, 1-4 dichloropropyl, isopropyl esters. the corresponding diester of 2, lJ-diisocyanatoglytaric acid, 2,5-diisocyanatoadipic acid, 2,6-diisocyanatopimelic acid, 2,7-Diieocyanatokorkäure, ajg-

109828/1666

acid, di-cisocyanatmethyD-cyclobutane, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated diphenylethane diisocyanate, hydrogenated diphenylpropane diisocyanate, hydrogenated diphenylbutane diisocyanate, isophorone diisocyanate, Trimethylhexanemethylene diisocyanate. Inorganic and organometallic compounds are also used Isocyanates in question, e.g. antimony triisocyanate, silicon tetraisocyanate, Dibutyltin triisocyanate, reaction products of polyhydric alcohols with polyisocyanates, e.g. the reaction product of 1 mole of trimethylolpropane with) 3 moles of toluylene diisocyanate, also containing biuret groups Polyisocyanates, e.g. the reaction product of 1 mole of water and 3 moles of hexamethylene diisocyanate and dimerized, trimerized or polymerized isocyanates.

As component (g) come unsaturated fatty alcohols with 10 to 2 ¹ I carbon atoms are suitable, which contain one or more double bonds in the molecule, that is, for example, decenol, dodecenol, Hexadecenol, oleyl alcohol, linoleyl alcohol and linolenyl alcohol. In particular, unsaturated fatty alcohols of natural fatty acids can be used as mixtures, such as those obtained by hydrogenation of drying or semi-drying oils while maintaining the double bonds.

In addition, as an admixture to component (g) to 15 percent by weight with unsaturated fatty alcohols containing about 8 to 30 carbon atoms modified Phenols, as described in German Auslegeschrift 1,268,137, can also be used. These Admixtures are preferred in those cases where the end product is used as a binder for aqueous stoving enamels which are burned in after a certain drying time to allow the water to evaporate.

109828/1666

BATH ORIGINAL

Furthermore, as component (g), individually or in a mixture, monohydric or polyhydric alcohols which contain one or more β, γ-ethylenically unsaturated ether groups, be used. The alcohol ether can, for example, from an allyl, methylallyl, ethallyl, chlorallyl or crotonyl alcohol. Particularly suitable alcohol ethers are those that only have one free Contain hydroxyl group. Examples of such compounds are glycerol diallyl ether and trimethylolpropane diallyl ether and pentaerythritol triallyl ethers.

The hydroxyl-containing esters obtained from reaction I, by heating to * 10 to 13O ° C, preferably 80 to 120 ⁰ C, with 0.05 to 50 weight percent, preferably 5 to 25 weight percent, isocyanates, individually or in a mixture, and 0 to 60 percent by weight of unsaturated mono- and / or polyalcohols or mixtures thereof are used. When using fatty alcohols, such as those obtained from natural fatty acids as mixtures by hydrogenation, the percentage of fatty acids must be taken into account.

When using unsaturated ether alcohols, the use of triallyl ethers of pentaerythritol in an amount of 5 to 35 percent by weight is advantageous. Unsaturated fatty alcohols that are obtained by modification with phenols (see German Auslegeschrift 1 268 137) »are used in cases in which products are to be manufactured that must have special anti-corrosive properties, namely in an amount of 10 to 50 , preferably 20 to 30 percent by weight. To accelerate the reaction, organometallic compounds or tertiary amines can be used as catalysts. The reaction time is about 4 to 1U hours.

109828/1688

If the implementation of components (f) and (g) with the from the first reaction stage originating hydroxyl groups and optionally also carboxyl groups Esters are not carried out together, then component (f) (isocyanate) and component (g) (more unsaturated Alcohol) to convert to an intermediate product in such a way that the isocyanate is submitted and the unsaturated one Alcohol is added in portions with thorough stirring, the reaction temperature being kept at about CO to 110.degree will. This intermediate product then becomes the initially introduced hydroxyl group-bearing ester from the first reaction stage partly with warming at about 80 ° to 120 ° C, added. In these implementations, it should be noted that that the reactants are used in such amounts that the ratio of the total HydroxyI equivalent to the isocyanate group equivalent 1.01 to 1, ^ 5, is preferably 1.05 to 1.25.

The urethanization reaction, ie, the reaction of the product I Product II, one can w of Xthylenglykole or diether of Xthylenglykole perform, in the presence or absence of an organic solvent or solvent mixture, such as ketones, Fster, Esteräther. Working with solvents in the urethanization reaction is preferred if the end products are to have a lower viscosity. After the implementation with the Monobwz. Polyisocyanates, no free isocyanate groups may be present in the resin molecule obtained. After the reaction, the resin must not contain more than 0.1 percent by weight of unreacted isocyanate.

As far as the finished polyurethane resins have free carboxyl groups, and these only with the aid of organic solvents that are unlimited or at least largely miscible with water, not in the

109828/1663

BATH ORIGINAL

water-dispersible or water-dilutable state can be transferred, water-soluble alkalis and / or strong organic nitrogen bases must be in such Quantities are added until the desired water dispersibility, Water dilutability, water solubility has been achieved.

The main alkalis that can be used are sodium hydroxide, potassium hydroxide and / or ammonia. As the organic strong bases such organic nitrogen bases are understood to be in! The above aqueous solution at 25 ⁰ C have a pH value of at least. 8

Suitable strong nitrogen bases are: volatile alkylamines, such as triethylamine, diethylamine, Trimethylamine. Also to be used are tertiary, secondary or primary alkylolamines, such as triethanolamine, diethanolamine, Monoethanolamine, N-dimethanolamine, M-methylethanolamine, N-diethanolamine, monoisopropanolamine, di-isopropanolamine, Triisopropanolamine.

The use of strongly basic pigments, such as zinc oxide, Zinc chromate, lead carbonate, basic lead sulfate, red lead, calcium plumbate, are surprisingly free from carboxyl groups Polyurethane resins possible in most cases. These pigments are not prone to thickening or thickening to failure. The ratio of pigment to binder depends on the type and type of pigment used suggested use. Tn most pulls the pigment-binder ratio becomes 0.5: 1 to 3: 1 be. Only with the electrophoretic application can the pigment content also be below 0.55? lie.

The polyurethane resins used according to the invention can be used as air-drying or stoving binding or sole

109828/1666 _ßAD

binders in the form of aqueous dispersions for coating agents alone or in combination with mixed polymer dispersions the following compositions are used:

. * 60 percent butadiene and ¹ JO% by weight of styrene. 5 wt.% Butadiene and 1J5 wt.% Styrene and 5 wt.? Butyl acrylate; ¹ IO wt.% Of butadiene, 50 wt.% Of styrene and 8 acc.% Of butyl acrylate and 2 wt. ?? Hydroxyethyl methacrylate.

| Also vinyl acetate homopolymers and vinyl acetate-acrylate copolymers as well as pure acrylate copolymers or others Dispersions can be mixed in. The proportions between dispersions and that of the invention coating masses can be 5:95 to 95: 5.

The new water-soluble oil-modified polyurethane resins can also be used in combination with styrene-butadiene copolymer dispersions as a binder for coating media, which is applied by means of mechanical or electrophoretic application can be processed wisely.

The invention also relates to the use of the new ™ water-soluble oil-modified polyurethane resins in combination with styrene-butadiene copolymer dispersions, as a binder for coating agents, which are by means of mechanical or electrophoretic application process.

In the case of high proportions of dispersions, the polyurethane resins serve more to modify the dispersions, e.g. with regard to adhesion to chalking surfaces.

As thermosetting, hydrophilic, low molecular weight, aminoplast-forming Condensation products are aldehyde reaction products of those reactable with aldehydes

10 98 2 8/1866 bad original

bonds such as urea, ethylene urea, dicyandiamide and aminotriazines such as melamine, benzoeguanamine, acetoguanamine and formguanamine. The aforementioned compounds can be mixed with aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde, Acrolein, benzaldehyde, furfural and the like can be implemented. The aldehydes should also include aldehyde-forming Compounds such as paraformaldehyde, paraldehyde, trioxymethylene, be considered. The preferred aldehyde is formaldehyde, the preferred aldehyde-binding compounds are melamine and urea. The conversion takes place in the usual molar ratios, e.g. with urea resins in a usual formaldehyde molar ratio of 1: 1.5 to 1: 4, in the case of melamine resins in a formaldehyde molar ratio from 1: 1.5 to 1: 6.

In the present case, the etherification products of the lowest are also good as binders for stoving enamels Half ethers of glycols and diglycols, such as ethylglycol, ethyl diglycol with methylolmelamines, have proven their worth already in the Austrian patent specification 180 t} 07 have been described.

Low molecular weight condensation products have a preferred position of melamine with formaldehyde with a melamine-formaldehyde ratio of 1: 4 to 1: 6, which is almost have been completely etherified with methanol. Partially esterified or partially esterified with dicarboxylic acids are also suitable. ethers of nitrogen-containing polymethylol compounds etherified with hydroxycarboxylic acids, such as those produced by transesterification from hexamethoxymethylmelamine with adipic acid. In stoving enamels according to the invention may contain 5 to 50 percent by weight of these condensation products.

Examples of suitable thermosetting, hydrophilic, never-

109828/1666

Drigmolecular condensation products are phenol alcohols, i.e. still low molecular weight products of monohydric or polyhydric phenols with aldehydes obtained by condensation, such as formaldehyde, acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural, etc., or formaldehyde-yielding Compounds such as paraformaldehyde, paraldehyde, trioxymethylene. The preferred aldehyde is formaldehyde or a formaldehyde-supplying compound which is found in an alkaline medium is obtained in a known manner, such as hexamethylenetetramine. Suitable phenols are phenol in o-, o'-p-position substituted but condensable with formaldehyde Phenols such as cresol or xylenol. Phenols, which are derived from alkylphenols, such as propyl, Butyl phenol, in particular p-tert-butyl phenol, can be obtained. Resoles made from binuclear phenols, such as diphenol and bisphenol-A, are also suitable. In particular are Resoles based on bisphenol-A are suitable which add about 1.75 to 2.5 moles of formaldehyde per mole of bisphenol-A contain. One can also very well as resols phenol carboxylic acid, which is produced by condensation of formaldehyde or Formaldehyde-producing compounds with suitable phenol carboxylic acids have been obtained. Under the

P phenolcarboxylic acids condensable with formaldehyde, the ¹ Ij ¹ I-BiS (^ - hydroxyphenyl) valeric acid occupies a preferred position. The most favorable results are also obtained when from 1.75 to 2.5 ^M formaldehyde ol bound per mole of phenol carboxylic acid. The preparation of other suitable phenol carbonic acid resols is described in German Auslegeschrift 1,113,775, for example. The phenol carbonic acid resols, in particular those based on ¹ I ₁ ¹ I-BiS ( ¹ L-hydrophenyl) -valeric acid, are well suited for combination for the products according to the invention, which are intended for use according to the invention as electrophoretically depositable coating compositions and lacquers. It is very advantageous if at least part of the form

109828/1666

aldehyde condensation products etherified with lower monohydric aliphatic alcohols with 1 to M C-Afcomen is like ethanol, methanol, propanols, butanols. Preferred water-dilutable phenolic resols are those which by reaction of phenolaldehyde condensation products etherified with alcohol with aliphatic monooxy- or dioxycarboxylic acid or their esters, were obtained, as in the laid-out documents of the Belgian patent 724 923.

Combinations with the new polyurethane resins j in which aminoplast-forming or phenoplast-forming are preferred Condensation products with 10 to 30 percent by weight, based on pesticide content.

For the electrophoretic application process, it is advantageous not only to add the thermosetting condensation products of the type already explained above, namely phenoplasts and / or aminoplasts, but to subject the components to a reaction. The reaction, which can be referred to as precondensation, is generally carried out at temperatures of 70 ° to 120 ° C., where possible, by carrying out the reaction appropriately, care must be taken that the components are not esterified, but rather polyetherification takes place. A suitable reaction procedure consists, for example, in carrying out the reaction of the components in the presence of an acidic catalyst, such as phosphoric acid, p-toluenesulfonic acid or benzoic acid, at temperatures between JO ⁰ O to 120 ⁰ C. The heating is stopped immediately when the r.Hnre number has decreased by about 10 units compared to the initial value of the acid number of the reaction mixture. This can preferably be achieved by using etherified, hydrophilic, thermosetting condensation products as phenoplasts and / or aminoplasts. In order to have sufficient circulation

109828/1668 _BAD original

achieve, it is also advantageous to carry out the reaction under vacuum.

The binders for stoving enamels combined in this way can be produced in the usual way by combining their components Way to be made. In general, it is convenient to use the water-soluble salts of other synthetic resins of ammonia or amines, or mixtures of ammonia and Amines and the new polyurethane resins, with the other components in the form of concentrated aqueous solutions that "where appropriate, minor amounts of water-soluble organic Solvents can contain, mix and then, if necessary, adjust the concentration and pH of the mixed solutions to the desired values. The pH of the desired solution should in »general expediently approx. 7.5 to 9.0, in particular approx. 8.0; if necessary, it can be used after a long period of storage the resins can be adjusted with ammonia or organic strong nitrogen bases.

Production of the polyurethane resin 1: A mixture of 580 g of linseed oil fatty acid, 98 g of polyethylene glycol (molecular weight 3000), 18 | g of pentaerythritol, 122 g of hydrogenated bisphenol A, 96 g of phthalic anhydride, 0.06 g of dibutyltin dilaurate and 2 ml of triphenyl phosphite are esterified to an acid number of 5 at 155 ° to 210 ° C. within seven hours, with water being separated off. A vacuum was then applied at 180 ° to 200 ° C. in order to remove residual water. After the cooling to 90 ⁰ C, 122 g of methyl ethyl ketone, 61 »g of pentaerythritol and 0.04 g Triallylather Pibutylzinndilaurat were added. Thereafter, under intensive reflux at a boiling temperature of 11Ί to Il6 ° C within 6 hours

g of toluene diisocyanate and then within Hours a further 30 g of toluene diisoeyanate was added dropwise.

109821/1668

BAD ORiQiNAl.

After a further hour, 840 g of butyl glycol were added and under vacuum the entire amount of methyl ethyl ketone distilled off.

Example 1:

14o g of the polyurethane resin 1 were ground with 196 F. water and 84 g titanium dioxide (rutile) in a ball mill for 48 hours. The paint batch was siccativized with 1.63 g of water-dilutable cobalt salt (6% Co metal) and drawn onto glass plates with a wet film thickness of 120 y. The dried coatings showed the following properties:

Pendulum hardness after 48 hours (DIN 53157 sec) 43 Pendulum hardness after 168 hours (DIN 53157 sec) 92 Resistance to gloss (B. Lange):

Initial gloss after storage for 1 week / 20 ° C 105 gloss after storage for 4 weeks in daylight 92 Gloss after storage for 4 weeks in the dark 95 Gloss after storage for 1 week quartz lamp 95 These coatings are characterized by their extraordinary UV resistance, as they are comparable to those available commercially Painting lacquer systems practically show a much faster reduction in gloss when exposed to UV radiation. Degree of yellowing:

Initial value after storage for 1 week / 20 ° C -1.22 after storage for 4 weeks in daylight 2.50 after storage for 4 weeks in the dark, 3.66 after storage for 1 week quartz lamp 2.47

It is noteworthy that the yellowing resistance is extremely good, although the synthetic resin used is aromatic® Polyisocyanate incorporated, contains.

Manufacture of the polyurethane resin 2:

A mixture of 570 g safflower fatty acid, 96 g poly-

109828/1666 _ßAD original

- 4o -

Ethylene glycol (molecular weight 3000), 184 g of pentaerythritol, 132 g of hydrogenated bisphenol A, 96 g of phthalic anhydride, 0.06 g of dibutyltindilaurate and 2 ml of triphenyl phosphite were esterified at 155 ° to 23O ⁰ C within 9 hours with water separation to the SSurezahl. 6 The mixture was then applied at I80 to 200 ⁰ C vacuum to remove Reatwasser su. After the cooling to 100 ⁰ C 137 g of methyl ethyl ketone, 0.04 g of dibutyltin dilaurate and 72 g of pentaerythritol Triallyläther conces- ^ were setst. Thereafter were added dropwise with vigorous reflux at a boiling temperature ™ of about 114 to 116 ⁰ C within 7 hours, 138 g of toluene diisocyanate and then further period of 6 hours 36 g of tolylene diisocyanate. After a further hour, 852 g of butyl glycol were added and the entire amount of methyl ethyl ketone was distilled off under reduced pressure. The water dilutability was unlimited. The aqueous resin solution, applied as a film, dried in two hours after corresponding desiccation.

Example 2:

Under the same conditions as in Example 1, " wrote, the polyurethane resin 2 was tested as an applied paint film. The following values were determined:

Gloss resistance (B. Lange):

Initial gloss after storage for 1 week / 20 ° C 100 gloss after storage for 4 weeks in daylight 100 Gloss after storage for 4 weeks in the dark 97 Gloss after storage for 1 week quartz lamp 94 This Hars also shows very good properties, the yellowing resistance being further improved.

109828/1666 "dormin".

Example 3:

300 ρ polyurethane resin 1 (100 g) were diluted with 80 g of butyl glycol and 100 g of acetone, mixed with 220 g of water and stirred. The entire amount of acetone was then distilled off. After adding 60 g of butyl glycol, a fine dispersion is obtained which can be diluted with water without limitation. In addition, 165 g of water and 300 g of titanium dioxide (rutile) were added. The mixture was ground in a ball mill for 48 hours. After desiccation, the dried films showed the same properties as described in Example 1. The leveling properties of the paint dispersion are in an improved form compared to Example 1, since the paint batch is less viscous.

Preparation of the polyurethane resin 3: A mixture of 280 g of ficine fatty acid (iodine number 155, linoleic acid content 9.11 54 wt. 55), 220 g isononanoic acid, 192 g pentaerythritol, 124 g hydrogenated bisphenol, 118 g phthalic anhydride, 92 g polyethylene glycol (molecular weight 3000 ), 0.06 p; Dibutyltindilaurate and 2 ml of triphenyl phosphite were esterified at 155 ° to 210 ⁰ C within 10 hours under Wasserabscheidunp · until the acid number of 8.5. The mixture was then applied at l8o ° C to 200 ⁰ C vacuum to remove residual water. After cooling to 70 ° C., 45 g of acetone, 0.04 g of dibutyltin dilaurate and 84 g of triallyl ether of pentaerythritol were added. Thereafter, 132 g of tolylene diisocyanate were added dropwise at 106 ° C. to 100 ° C. over the course of six hours and then a further 34 g of tolylene diisocyanate over the course of six hours. After a further hour, 372 g of acetone, 296 g of butyl glycol and 824 g of water were added and then the entire amount of acetone was distilled off.

109828/1666

BATH ORIGINAL

-I ₁₂ -

Example 4:

80 g of the 50% polyurethane resin 3 and 10 g of the liquid Hexamethyl ethers of Hexamethylolmelamina were mixed with water adjusted to a pest body content of 50 # and siccativated with 0.08 $ K water-soluble cobalt metal content. A coating produced with this was dried at 100 ° C. for one hour. The film had a wet film thickness of 90μ. The film showed very good surface hardness and good solvent resistance to gasoline fc and fuel ©]. The tendency to yellowing was low.

Example 5:

In 38 of a Looj & strength polyurethane resin 1 g wurdenbei 55 ° - 6O ⁰ C 38 g of an aqueous 50 $ strength by weight acrylate Mischpoly- merisat-Dispersic λ stirred and added dropwise at the same temperature within hours before "" 38 g of water ·· ^'v.. h Ί> ^: ϊ "Ία1βιΊ ftf α ι -at der .-. f.orige clear coat approach with Ko- - 'tr ^ ikkativ ^ 0, -OBji water-soluble cobalt metal content calculated on solid total resin amount) added and drawn on glass plates with a wet film thickness of 120μ . The dried coatings showed very good water resistance and, in pigmented form, high gloss. It is noteworthy that this water-based clear lacquer contains no other solvents apart from water.

Production of the polyurethane resin H : The process for the production of the polyurethane resin 1 was repeated, using instead of 164 ρ tolylene diisocyanate, 102 g of tolylene diisocyanate and 5Ί g of methoxymethyl isocyanate, the only difference being that the amount of wethoxymethyl isocyanate at ' ¹ O ⁰ C afterwards the addition of the toluene diisocyanate ^ was added dropwise over the course of two hours.

109928/1866 bath

Example 6: '

The procedure described in Example 4 was followed, but the polyurethane resin 4 was used. The coatings applied to glass plates were baked at 130 ° C. and were characterized by good quality Surface hardness, elasticity and adhesion.

Preparation of the polyurethane resin 5 'A mixture of 58 g tall oil fatty acid ¹ I, I86 g trimethylolpropane, 134 ε of an adduct of one mole bisphenol A and two moles of propylene oxide, 0.04 g of dibutyltindilaurate and 2 ml of triphenyl phosphite were added at 155 ° to 23O ° C Esterified up to S acid number 2. 148 g of trimellitic anhydride were then added and ^{esterification was continued at 170 °} C. up to an acid number of 42. A vacuum was then applied at 170 ° C. in order to remove residual water. After the cooling to 8O ⁰ C, 107 g of acetone were zugeeetzt and at reflux temperature of 80 ° to 82 ° C over 6 hours, 92 g of toluylene diisocyanate were added dropwise. The reaction mixture was kept at reflux temperature for a further hour, diluted with 465 g of butyl glycol and adjusted to pH 7 with triethylamine.

Example 7:

100 g of the polyurethane resin 5 were mixed with 80 g of water and 70 g of titanium dioxide (rutile) in a ball mill for 48 hours rubbed. The paint batch was with 1.2 g of water-thinnable organic cobalt salt (6jC Co-metal) siccativates and drawn onto glass plates with a wet film thickness of 120n. The dried coatings stood out very good flow properties and high hardness; they are also non-yellowing.

109828/1686 _b ad

Preparation of the polyurethane resin 6: A mixture of 374 g of ricinic fatty acid, 386 g of an adduct of one mole of bisphenol A and 2 moles of propylene oxide, 124 g of trimethylolpropane, 46 g of phthalic anhydride, 0.04 g of dibutyltin dilaurate and 2 ml of triphenyl phosphite were at 155 ° to 23O ° C esterified up to acid number 2. Subsequently, 92 g of trimellitic anhydride was added and esterified at 180 ° to 185 ⁰ C continued until the acid number of the 25th Thereafter, a vacuum was applied at 180 ° to 185 ° C. in order to remove residual water. After the Ab-P cool to 77 ⁰ C were added 136 g of acetone, at reflux temperature of 84 ° to 86 ⁰ C over 10 hours 96 g of toluylene diisocyanate were added dropwise. The reaction mixture was held at reflux temperature for a further hour and then diluted with 128 g of butyl glycol. A vacuum was applied to distill off acetone. The resin, which had an acid number of 23, was adjusted to pH 7 with triethylamine.

Example 8:

An approximately 10Jige solution of the polyurethane resin 6 was obtained from 220 g 90% resin with 20 g isopropyl glycol and ψ 176O g water and placed in an electrophoresis tank with a volume of about 2 liters. The cathode / anode distance was 16 cm. The area of the cathode and anode was 115 cm each. The resin was deposited in 2 minutes by applying a voltage of 180 volts. The metal sheets were rinsed with water and ^{baked at 130 °} C. for 30 minutes. The film layer thickness was 35 4θμ. The film obtained showed very good water resistance and hardness. The deposition was carried out in a further experiment in the presence of a water-soluble siccative (0.2 $ Co metal content based on solid resin) and the film was dried ^{at about 20 ° C.} The film

109828/1666

showed good resistance properties after drying for a few hours.

Preparation of the polyurethane copolymer resin 7: A mixture of 622 g of linseed oil fatty acid, 120 g of polyethylene glycol (molecular weight 3000), 94 g of pentaerythritol, 188 g of an adduct of one mole of bisphenol A and two moles of propylene oxide, 0.06 g of dibutyltin dilaurate and 2 ml of triphenyl phosphite were used esterified 155 ⁰ C to 22O ° C within 9 hours with removal of water until the acid value of the 7th Thereafter, a ^{vacuum was applied at 200 °} C. in order to remove residual water. Mach taken place cooling to l40 ° C, 316 g of xylene were added and at reflux temperature of 158 ⁰ C within 4 hours a mixture of 274 g of styrene, 6 g of p-tert-butyl peroxide and 8 g dodecylmercaptan was added dropwise. The reaction mixture was polymerized for a further 12 hours and, in order to achieve a solids content of B0% , a further 18 g of p-tert-butyl peroxide had to be added in 4 parts at intervals of 2 hours. A vacuum was then applied to remove xylene and small residual monomers. After the cooling to 70 ° C 60 g of acetone and 68 g of Triallylather were Pentaeryfchr-iüs iugeaetzt, and at reflux temperature of 106 ° C to 108 ⁰ g within 8 hours 148 tolylene diisocyanate were added dropwise. After a further hour, 236 g of butyl glycol were added and the entire amount of acetone was distilled off under vacuum. Thereafter, the resin was adjusted with triethylamine to a pH value of 7 and diluted at 80 ⁰ C to 70 ⁰ C with I960 g water.

Example 9:

80 g of polyurethane resin 7 and 10 g of liquid hexamethyl ether of hexamethylolmelamines were placed on a Feet-

109828/1668

body content of 5Ο5ί and siccativated with 0.08 # water-soluble cobalt metal content. Hereby produced coating was dried at 100 ⁰ C for one hour. The film had a wet film thickness of 90 y. The film showed very good surface hardness and good solvent resistance to gasoline and fuels. The tendency to yellow was low.

Preparation of the polyurethane copolymer dispersion 8: A mixture of 372 g of ricineal fatty acid, 214 g of one

Ψ Adduct of one mole of bisphenol-A and two moles of propylene oxide, 94 g of trimethylolpropane, 48 g of phthalic anhydride, 0.04 g of dibutyltin dilaurate and 2 ml of triphenyl phosphite were esterified at 155 ° to 220 ° C up to an acid number of 2. After the cooling to IO I ^{1 0} C 286 g of xylene were added and at reflux temperature of 153 ⁰ C within 4 Stimden a mixture of 382 g of styrene, 62 g methacrylic acid, and 6 g of p-tert-butyl peroxide was added dropwise. The reaction mixture was polymerized for a further 4 hours and, in order to achieve a solids content of 80, a further 2 % p-tert-butyl peroxide had to be added. Then vacuum was applied,

fc to remove xylene and small residual monomers. After the cooling to 70 ⁰ C, 132 g of acetone and 106 g Triallyläther of pentaerythritol were added and at reflux temperature of 86 ° to 88 ⁰ C g within 8 hours 86 tolylene diisocyanate were added dropwise. After a further hour, 132 g of butyl glycol were added and the entire amount of acetone was distilled off under vacuum. The resin was then adjusted to a pH of 7 with triethylamine and diluted to a solids content of 50 μl with water.

109828/1668

BATH ORIGINAL

Example 10:

In 600 g of Poly-Vuhandispersien 8 (502), 5 g of water and 30) % titanium dioxide ( ^r util) were added. The mixture was ground in a ball mill for 3 hours. According to SikkatiM .ε ^ ung, de. e ^ ro '.; l? .e' ^s n films very good mechanics: be properties,

Production cn Po: / urethanwisrT ·, olyr ^ risatdispersion 9: A mixture of ice ^! O6 £ "icinenfitts ^ ur-e, 98 g of polyethylene glycol (molar weight 3000 \. $ Pentaerythritol _v 152 g of an adduct? Aas a» 1 B ^ spiu-nol-f: u.; 1 two moles of propylene oxide, 0.04 g of dibutyl tin dilaurate and 2 ml Triphenylnhosphit were esterified at 155 ° to 22O ⁰ C until the acid number. 3 erfolptem After cooling to l40 ° C, 294 g of xylene were added and at reflux temperature of 153 ° C within 4 hours, a mixture of

g styrene, 18 g methacrylic acid and 6 g butyl peroxide were added dropwise. The reaction mixture was polymerized for a further 2 hours. A vacuum was then applied to remove xylene and small residual monomers. After the cooling to 7O ⁰ C 12 * 1 g of acetone, 92 g Triallyläther of pentaerythritol were added and at reflux temperature of 86 ° to 88 ⁰ C g within 8 hours 82 tolylene diisocyanate were added dropwise. After a further hour, 320 g of butyl glycol were added and the entire amount of acetone was distilled off under vacuum. The resin was then adjusted to a pH of 7 with triethylamine and diluted with water to 50 μl of pest bodies.

Example 11:

80 g of the 50% polyurethane dispersion 9 and 10 g of the liquid Hexamethyl ether of hexamethylolmelamine wura

«AD ORIGINAL f 1 HG ti

* kB -

adjusted with water to a pest body content of 50% and siccativated with 0.08 $ 5 water-soluble cobalt metal content. Hereby produced coating was dried at 120 ⁰ C for one hour. The film had a wet film thickness of 9μ. The film showed a very good surface hardness and good solvent resistance to gasoline and other fuels ¹¹ · The yellowing tendency was low.

109828/1665

Claims (1)

Patent claims: 1.) Aqueous, air-drying or oven-drying paints based on dispersions or solutions of water-thinnable paints or water-dispersible, oxidatively drying polyurethanes or polyurethane copolymer resins, thereby characterized in that they are composed of such polyurethane resins as binders: (a) 25 to 70 percent by weight of unsaturated fatty acids, of which 0 to 25 percent by weight as drying oils are present, and optionally the unsaturated fatty acids and / or the drying oils contain up to 6 percent by weight of maleic anhydride and the mixture contains iodine numbers of has about 130 to 390, (b) up to 30 percent by weight of aliphatic, cycloaliphatic, aromatic carboxylic acids or hydroxycarboxylic acids, individually or in a mixture, or their anhydrides, if they exist, (c) 5 to 35 percent by weight of polyvalent organic hydroxy compounds, ° (d) up to 17 percent by weight of polyoxyalkylene compounds, containing at least one atom of active hydrogen, with an average molecular weight the polyoxyalkylene chain from about 200 to 50,000, individually or as a mixture, (e) up to 65 percent by weight of polymerizable monomers, (f) 0.05 to 50 percent by weight of isocyanates, individually or in admixture, and (g) up to 60 percent by weight of unsaturated mono- and / or polyalcohols or their mixtures, selected by quantity , are present in such a way that the total hydroxyl group equivalent to the isocyanate group equivalent is 1.01 to 1 * J5, 109828/1666 (h) and, if applicable, as far as the polyurethane resin Contains carboxyl groups, this by adding alkali and / or organic strong bases in the water-dispersible or water-dilutable state is present, contain. 2.) Paints according to claim 1, characterized in that these such polyurethane resins are made of: (a) 25 to 50 percent by weight of unsaturated fatty acids with iodine numbers of about 130 to 390, (b) 2 to 30 percent by weight of aliphatic, cycloaliphatic, aromatic carboxylic acids or hydroxycarboxylic acids, individually or as a mixture, or their anhydrides, if they exist, (c) 5 to 35 percent by weight of polyvalent organic hydroxy compounds, (d) 2 to 9 weight percent polyoxyalkylene compounds containing at least one atom of active hydrogen contain, with an average molecular weight of the polyoxyalkylene chain of about 3000, (e) zero, (f) k to 50 percent by weight isocyanates, individually or in a mixture, and (g) 2 to 25 weight percent unsaturated! Ethereal alcohols or their mixtures * »by quantity selection see above selected implemented so that the total hydroxyl group equivalent to the isocyanate group equivalent 1.01 until 1, * »was 5, contain· 3.) Paints according to claim 1, characterized in that ale polyurethane resins are those from the following Components are constructed: 109828/1668 bad original (a) 25 to 70 percent by weight of unsaturated fatty acids, of which up to 25 percent by weight as drying oils are present and the mixture iodized grinds from about 130 to? 90, (b) 2 to 30 percent by weight of aromatic polycarboxylic acids, individually or in oenic, or their anhydrides, / or preferably trimellitic anhydride, if these exist, (c) 5 to 35 percent by weight of polyvalent organic hydroxy compounds, (d) zero, (e) zero, where component b is contained in such amounts that the condensation product has acid numbers of about 20 to about 80, (f) 2 to 50 percent by weight isocyanates, individually or in admixture, and (p) zero, (h) and the polyurethane resin containing carboxyl groups with alkali and / or organic strong bases mixed, water-dispersible or »water-thinnable Product is present, are included. ) Paints according to claim 1, characterized in that as polyurethane resin, those made up of the following components: (a) 25 to 70 percent by weight of unsaturated fatty acids, of which up to 25 percent by weight as drying oils are present and the mixture has iodine numbers of about 130 to 390, (b) 2 to 30 percent by weight of aromatic polycarboxylic acids, individually or as a mixture, or their anhydrides, preferably trimellitic anhydride, as far as that are existent, (c) 5 to 35 percent by weight of polyvalent organic hydroxyl compounds, (d) 2 to 9 percent by weight of polyoxyalkylene compounds, with an average molecular weight of the polyoxyalkylene chain of about 3000, (e) zero, component b being contained in such amounts that the condensation product has acid numbers from about 10 to about 50, (f) 2 to 50 percent by weight isocyanates, individually or % in a mixture, and (g) zero, (h) and the carboxyl group-containing polyurethane resin as being strong by alkali and / or organic Bases water-dispersible or water-thinnable product is present, contain. 5.) Paints according to claim 1, characterized in that the polyurethane copolymer resin used as those consisting of the following components are built up: (a) 25 to 50 percent by weight of unsaturated fatty acids, ^ with iodine numbers from about 130 to 390, * (b) zero, (c) 5 to 35 percent by weight of polyvalent organic hydroxyl compounds, (d) H to 9 percent by weight of polyoxyalkylene compounds, containing at least one atom of active hydrogen, with an average molecular weight the polyoxyalkylene chain of about 3000, (e) 2 to 45 percent by weight of polymerizable monomers, (f) 3 to 50 percent by weight isocyanates, individually or in admixture, and (g) 2 to 25 percent by weight of unsaturated mono- and / 109828/1666 or polyalcohols or mixtures thereof, reacted selected by the selection of amounts so that the total hydroxyl group equivalent to the isocyanate group equivalent was 1.01 to 1.45, contain. 6.) Paints according to claim 1, characterized in that the polyurethane copolymer resins used are those consisting of are composed of the following components: (a) 25 to 50 percent by weight unsaturated fatty acids with iodine numbers of about 130 to 390, (b) 2 to 30 percent by weight of aromatic polycarboxylic acids, individually or in a mixture, or their anhydrides, as far as these exist, (c) 5 to 35 percent by weight of polyvalent organic hydroxy compounds, (d) zero, (e) 2 to 45 percent by weight of polymerizable monomers of which at least one monomer has at least one free carboxyl group, where components b and e are contained in such amounts that the acid numbers of the reaction product be about 20 to about 80, (f) 3 to 50 percent by weight isocyanates, individually or in admixture, and (g)? up to 25 percent by weight of unsaturated mono- and / or polyalcohols or mixtures thereof, by selecting the amount reacted selected so that the total hydroxyl group equivalent to the isocyanate group equivalent Was 1.01 to 1.45, (h) and the polyurethane resin contains carboxyl groups that are formed by adding alkali and / or organic strong bases in water dispersible or water be in a dilutable state, contain. 109828/1666 7.) Paints according to claim 1, characterized in that as polyurethane copolymer resins, those made up of the following components: (a) 25 to 50 percent by weight of unsaturated fatty acids with iodine numbers of about 130 to 390, (b) zero, (c) 5 to 35 percent by weight of polyvalent organic hydroxy compounds, (d) 2 to 9 weight percent polyoxyalkylene compounds containing at least one atom of active hydrogen contain, with an average molecular weight of the polyoxyalkylene chain of about 3000, (e) 2 to M5 percent by weight of polymerizable monomers, of which at least one monomer has at least one free carboxyl group, where component e is contained in such amounts that the acid number of the reaction product is about 20 to about 80, (f) 3 to 50 weight percent isocyanates, individually or in the mixture, and (g) 2 to 25 percent by weight of unsaturated mono- and / or polyalcohols or mixtures thereof, by selecting the amount so selected implemented that the total hydroxyl group equivalent to the isocyanate group equivalent was 1.01 to 1. ** 5, (h) and the polyurethane resin contains carboxyl groups that are formed by adding alkali and / or organic strong bases in water dispersible or water be in a dilutable state, contain. 8.) Paints according to one of claims 1 to 7, characterized in that that these as further binders 5 to percent by weight aminoplast-forming and / or pheno- 109828/1666 - 55 plastbil le ". Contain all condensation products. 9.) lacquers na Λ one of the Ancprl <; he ι big j _f characterized. That this -ils further binder component copolymer · _; he “hold ions. 10.) Use of the in the Ansj / · ch ^ -; 1 to 9 mentioned lacquers al ·. electrophoretically separable coating medium. BATH