DE1966836A1 - Water dilutable polyurethanes - for use as coating resins curing by oxidative drying - Google Patents

Abstract

Water-dilutable polyurethanes as coating resins curing by oxidative drying. N1-. Are made by (I) heating together (opt. in stages) (a) 25-70% unsatd. fatty acids of which 0-25% may be drying oils and which may contain up to 6% added maleic anhydride, the mixture having an iodine value of 130-390; (b) 0-30% (cyclo)aliphatic-, aromatic- or hydroxy carboxylic boxylic acids, or anhydrides of these; (c) 5-35% polyhydric org. hydroxy cpds., (d) 0-17% (esp. 13-17%) polyoxyalkylene cpds. contg. at least one (esp. at least 2) active H atoms, with an av. mol. wt. in the POA chain of 200-50.000 (esp. 2000-6000) and (e) 0-65% (esp. 0-15%) copolymerisable monomers, (II) converting the resulting OH grp. -contng. (and poss. COOH-gp. contg.) ester into an intermediate by reaction with (f) 0.05-50% isocyanates and (g) 0-60% (esp. 0-25%) unsatd mono- and/or polyalcohols in an amt. such that the total OH equiv.: NCO equiv. = 1.01 to 1.45 and opt (III) where the polyurethane contains COOH grps. converting it to water-dilutable form by adding alkali and/or strong org. bases. They are useful as binders in coating resin formulations, esp. in conjunction with water-dilutable phenolic, phenolic modified alkyd, or styrene-butadiene latex resins. The finishes can be applied by electrophoretic or mechanical means.

Description

Process for the production of water-soluble resp.

water-dispersible, oil-modified polyurethane copolymer resins.

There are several ways of working known in which an attempt has been made by Installation of polyoxyalkylene compounds, water-thinnable, air-drying binders to manufacture. In this way, water-dilutable condensation products are obtained by reaction of polyethylene glycols with polybasic carboxylic acids or adducts of e.g. maleic anhydride and a drying oil fatty acid (see U.S. Patent 2,634,245). Another known method is the production of water-dispersible Alkyd resins carried out by mixing alkyd resins containing carboxyl groups with polyethylene glycols esterified. Modification with copolymerizable binders was also used in similar binders Monomers and made with epoxy resins (see German Auslegeschrift 1 231 433). Also the combination, adducts of oxidative drying systems with isocyanates and to produce polyoxyalkylene compounds has been known in several forms (See French patent specification 1,468,487).

Although these known processes are water-thinnable binders are obtained, one has the film-forming properties of a conventional oxidative drying Resin not reached.

The aim of the present invention is to provide such water-dilutable to provide water-dispersible, air-drying synthetic resins, which have all the necessary technical paint properties and are significantly improved Drying properties with excellent film quality with high gloss after Have drying and also have great storage stability and excellent Distinguish flow properties.

The invention relates to a process for the production of water-dilutable or water-dispersible, oxidatively drying polyurethane copolymer resins, characterized in that first: I (a) 25 to 55 percent by weight unsaturated Fatty acids, of which 0 to 25 percent by weight may be present as drying oils, and optionally the unsaturated fatty acids and / or the drying oils contain up to 6 percent by weight of maleic anhydride and the mixture Has iodine numbers of about 130 to 390, (b) 2 to 15 percent by weight aliphatic, cycloaliphatic, aromatic carboxylic acids or hydroxycarboxylic acids, individually or in the mixture, or their anhydrides, if they exist, (c) 2 to 30 percent by weight polyvalent organic hydroxyl compounds, (d) 4 to 9 percent by weight polyoxyalkylene compounds, containing at least two atoms of active hydrogen, with a molecular weight of the polyoxyalkylene chain from about 2000 to 6000, individually or as a mixture.

(e) up to 65 percent by weight of partially polymerizable monomers, together or implemented in stages by heating, II the obtained hydroxyl group-bearing if necessary, carboxyl group-bearing esters in deficit by heating with (f) 5 to 25 percent by weight of diisocyanates, individually or in a mixture, and (g) 5 to 35 percent by weight of pentaerythritol triallyl ether converts, III and optionally by adding alkali and / or organic strong bases in the water-dispersible or water-thinnable state.

For the products to be manufactured according to the invention, 25 to 55 Percentage by weight of unsaturated fatty acids of natural or synthetic origin, optionally drying and / or semi-drying oils in amounts 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 add up to 6 percent by weight of maleic anhyciride The mixture used must have iodine numbers of 130 to 390.

Suitable unsaturated fatty acids are, for example: eleostearic acid, Licanic acid, parinaric acid, linolenic acid with isolated and conjugated double bonds, Linoleic acid with isolated and conjugated double bonds. Furthermore are suitable as an admixture to the unsaturated fatty acids mentioned above, those with 10 up to 30 carbon atoms, which have at least one unsaturated carbon double bond 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 at least simple unsaturated fatty acids may, however, 30 percent by weight, based on the total amount, do not exceed. However, the content of these fatty acids is preferably below 10 Weight percent. The percentage of saturated fat that is always present is burning Fatty acid mixtures, as they are obtained by saponification nati.-licl.cr oils, should not exceed 20 percent by weight, if possible even below 10 percent by weight lie. Unsaturated fatty acids that can also be used are those obtained by dimerization or oligomerization Polybasic acids obtained from unsaturated fatty acids as well as cyclized monobasic acids Acids are used. Unsaturated fatty acid mixtures are preferably used, as obtained from natural vegetable and animal unsaturated fats by saponification can be obtained.

Natural, unsaturated, fatty oils include cottonseed oil, Lupine oil, corn oil, sesame oil, grape seed oil, walnut oil, perilla oil, linseed oil, wood oil, Safflower oil, oiticica oil and fish oil are suitable. Of these, wood oil, oiticica oil, Safflower oil, linseed oil, and fish oil are preferred.

Furthermore, however, are also suitable: Fatty acids from dehydrated Castor oils, which contain a high proportion of conjugated linoleic acid. Are here as drying and / or semi-drying oils, also drying and / or semi-drying oils Condensation products, e.g. from wood oil and phenolic resols and / or etherified pheno Resols, preferably butylphenol resols, can be used.

They are also suitable, for example, as an admixture with the above named unsaturated fatty acids as component (b) other aliphatic, cycloaliphatic and aromatic carboxylic acids or hydroxycarboxylic acids and / or their anhydrides, as far as existent. Examples of monocarboxylic acids are: trimethyl acetic acid, pelargonic acid, Glycolic acid, lactic acid, 3-hydroxypropionic acid, a-hydroxyisobutyric acid, 2-hydroxybutyric acid, 2-hydroxynonanoic acid, 2-hydroxyoctadecane acid, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-Hy-: 1roxybenzoic acid, 4-hydroxyphenylacetic acid, 3-hydroxy-2-naphthoic acid, 2-Hydroxy-1-naphthoic acid, alkane monocarboxylic acid whose carboxyl groups are attached to tertiary or quaternary carbon atoms are bonded, with 8 to 18 carbon atoms, as they are made from carbon monoxide, water and monoolefins (Swiss patent 990 229) are obtained, phenylacetic acid, heryl or methacrylic acid, benzoic acid, p-tert-butylbenzoic acid, 1-methylhexhydrobenzoic acid, 2,4,5-trimethylhexanhydrobenzoic acid. Polycarboxylic acids or their anhydrides can also be used as component (b) e.g. phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, Tetrahydrophthalic anhydride, trimellitic acid, trimellitic anhydride, hemimellitic acid, Pyromellitic acid, pyromellitic anhydride prehnitic acid, prehnitic anhydride, mellophanic acid, Benzene pentacerbonic acid, benzene pentacarboxylic anhydride, maleic anhydride, citraconic anhydride, Itaconic anhydride, methaconic anhydride, aconitic anhydride, 2,6-naphthylene-dicarboxylic acid, Diphenyl-O-O'-dicarboxylic acid, hexachloroendomethylenetetrahydrophthalic acid.

As polyvalent organic hydroxy compounds, as a component (c) e.g. glycerine, pentaerythritol, di-pentaerythritol, ethylene glycol, diethylene glycol, Trimethylolethane3 trimethylolpropane3 diallyl ether of pentaerythritol, mannitol, sorbitol, Bisphenol-A, hydrogenated bisphenol-A, 4,4-dihydroxyphenylmethane, 4,4-dihydroxyphenylbutane, 4,4'-dihydroxydiphenyl, cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, Ethoxylated bisphenol-A with 1 to 6 ethylene oxide molecules, propoxylated bisphenol-A with 1 to 6 propylene oxide molecules, ethoxylated pentaerythritol with about 12 ethylene oxide molecules, ethoxylated 4,4'-dihydroxydiphenol with 1 to 6 ethylene oxide molecules, ethoxylated 4,4-dihydroxyphenylmethane with 1 to 6 ethylene oxide molecules, 1,2,6-cyclohexanetriol used will. Phenol resols and / or etherified phenol resols that still contain 2 to Have 6 free alcoholic hydroxyl groups, preferably with average Molecular weights from 250 to 700 can also be used5 with one such Addition in the range of 3 to 10 percent by weight is preferred.

As component (d) there are polyoxyalkylene compounds which contain at least contain two active hydrogen atoms, with a molecular weight of the polyoxyalkylene chain from about 2000 to 6000 individually or in a mixture, in question.

As component (e), copolymerizable monomers such as vinyl or vinylidene monomer can be used individually or in a mixture. Of the monomers Vinyl resp.

Vinylidene compounds are preferred which have no free carboxyl groups contain, the most preferred compounds of this type being styrene, substituted in the core Styrenes, styrenes substituted in the side chain, such as a-methylstyrene, a-ethylstyrene, a-chlorostyrene and vinyl toluene.

As vinyl monomers that do not have free carboxyl groups, come also in question: alkyl esters of cx, 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 and phenyl acrylates; Propyl crotonate, butyl crotonate and the like. The following are also possible: Hydroxylalkyl esters the α, ß-unsaturated carboxylic acids, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate and the corresponding Methacrylates, ethacrylates, phenyl acrylates, 2-hydroxyethyl maleate, di- (2-hydroxypropyl ) maleate or the corresponding fumarates, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-1-phenylethyl acrylate) 2-hydroxy-3-butoxy-propyl acrylate and the corresponding ethacrylates and phenyl acrylates.

As an admixture, the monomer mixture, individually or in a mixture, other polymerizable monomers are added, such as acrylamide, methacrylamide, etherified N-methylolacrylamide, etherified-N-methylol methacrylamide, acrylonitrile, Methacrylonitrile and the like. The vinyl and / or vinylidene content in the synthetic resin is depending on the intended use area of the binding agent.

Partially polymerizable carboxyl groups can also be used in minor amounts Monomers are also used, such as acrylic acid, methacrylic acid, cinnamic acid, ß-benzoylacrylic acid, Crotonic acid, ethylcrotonic acid, benzene lactic acid, cyclohexenedicarboxylic acid, angelicic acid, also a, ß-ethylenically unsaturated polycarboxylic acids or their anhydrides, as far as they are able to form 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 4 carbon atoms, preferably Methanol, maleic monomethyl ester, halogen-substituted acids such as chloromaleic acid and the same. The preferred α, ß-ethylenically unsaturated carboxylic acids include: Acrylic acid, methacrylic acid, maleic anhydride, maleic acid and fumaric acid.

The carboxyl group-tagging monomers can be used alone in a mixture with one another, alone in a mixture with the first-mentioned monomers which do not carry any carboxyl groups or reacted in a mixture with the other components.

Esterification, transesterification or polymerisation takes place by heating at temperatures between 1500C to 2900C, preferably at 1500C to 2700C, in Presence of catalysts, e.g. dibutyltin dilaurate, calcium acetate, Lead oxide, sodium methylate, lithium ricinoleate, cobalt butyl phthalate, ethylhexylt itanate.

The esterification or transesterification reactions are controlled by the specified amounts carried out so that mono-di- or polyesters or mixtures of these arise, with the resulting ester products have acid numbers from zero to 300, preferably below 40, should have and must have hydroxyl groups in order to be able to continue to act to be.

So much for components (a) to (d) first by heating in the already mentioned temperature range have been esterified, the polymerization of the Monomers without catalysts or in the presence of catalysts, such as peroxides, Acids, Friedel-Crafts compounds, carried out by heating to 1200C to 2400C will. When polymerizing component (e), a procedure is preferred at which by polymerization initiators the polymerization temperature and the polymerization time is reduced, uni the polymerisation under conditions that are as gentle as possible perform.

Polymerization initiators which can be used are the organic ones known per se Find peroxides and / or hydroperoxides use. Also the use of others known chain terminators, such as mercaptans, give particularly advantageous results.

A distinction must be made between two cases A and B in the manufacture of component I. The case A includes a component I, which by appropriate selection and implementation of the starting components is obtained and a hydroxyl group-bearing Represents ester which is practically free of carboxyl groups.

Such a component I according to case A is preferably produced, if the polyurethane resin available as an end product is to be water-dispersible and the water-containing polyurethane resin binder preparations practically Unlimited storage stability and good air drying properties should be characterized. To have such polyurethanes with the best lacquer and binder properties to obtain, the component I according to case A from, (a) 25 - 45 wt .-% (b) 2 - 15% by weight (c) 2-30% by weight (d) 4-9% by weight with an average molecular weight from 2000 to 4000 (e) zero - 40 weight built up.

However, the above-identified polyurethane resin should be used as the sole binder or in combination with other binders in water-dispersed form for stoving Coating agents are used, is in the above guide formulation for the Component I, case A, the proportion of (a) and (b) selected in the following range: (a) 25-35% by weight (b) 2-30% by weight The preparation of component I, case A, that is the preparation of a component I that contains hydroxyl groups and is practically free of free carboxyl groups can, for example, according to the following procedure -take place: Procedure a: Components (a), (b), (c)) (d) and (e) are raised by heating, optionally in the presence of catalysts about 155 to 26,000 esterified or copolymerized.

Working method ß: The components (a), (b), (c) and (d) are through Heating, optionally in the presence of catalysts, to about 155 to 26,000 esterified until the acid number has dropped below 1. Then the component (e) partially polymerized thermally or catalytically.

Procedure y: Components (a) and (d) are at 155 to 2000C esterified and then with component (b), (c) and (e) by heating to 155 bis 2600C esterified and copolymerized.

Procedure g: Components (c) and (d) are at 155 to 2000C esterified and then with component (a), (c) and (e) at 155 to 2600C esterified and copolymerized.

Procedure e: Components (a) and (e) are obtained by heating thermally or catalytically copolymerized and with component (b), (c) and (d) esterified (heated to 155 to 2600C).

Procedure 5: The component (e) with carboxyl group and / or hydroxyl and / or Amide and / or nitrile groups are esterified with component (d) by heating and / or etherified or

implemented and then esterified with components (a), (b) and (e) and optionally copolymerized.

The selected esters containing hydroxyl and carboxyl groups, in which at least one free carboxyl group on secondary and / or tertiary Carbon atoms are bonded (stage I), can be achieved through a coordinated selection of Acid component (b) and / or (e) in stage (I), that is to say through use especially of polycarboxylic acids (h) 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.

Another possibility, useful hydroxyl group-bearing esters in stage I from components (a), (b), (c), (d) and (e) to produce the in their molecule at least one free carboxyl group on secondary and / or tertiary ones Containing carbon atoms bonded is given by first looking at the components (a), (b), (c) and (d) by condensation to form hydroxyl-group-bearing esters which practically do not contain free carboxyl groups in their molecule, and then copolymerized with such partially polymerizable monomers as component (e), which in their molecule at least one free carboxyl group on a secondary or tertiary carbon atom bound, must contain.

In each of the working methods described here for the production of the Hydroxyl group-bearing esters of component I must have components (a) to (e) be adjusted so that component I has acid numbers from 1 to 300.

Component I, which is present as an ester bearing hydroxyl groups, which have at least one free carbxyl group on secondary and / or in their molecules contains tertiary carbon atoms (i.e. case B), can - as before protruding described - be manufactured in one step.

However, it is also a multi-stage production - preferably two-stage Manufacturing - possible. In this two-stage production, one puts in the stage I from components (a), (b), (c) and (d) or from components (a) 3 (b), (c), (d) and (e) initially produce a hydroxyl group-bearing ester 2 of either does not contain a carboxyl group, or does not contain sufficient amounts of carboxyl groups contains built-in. In a second reaction stage, polycarboxylic acid is added or polycarboxylic anhydride an additional proportion of component (b) in such amounts are added, so that the finished product after heating by esterification Component 1 has the desired acid number in the range from 1 to 300. The advantage this two or more-stage production for component I results in further processing storage-stable end products, so that the multistage production of component I belongs to the preferred embodiment.

The multi-stage produced component I (case B) can also through a subsequent copolymerization stage with the polymerizable monomers (e) be modified.

Another multistage production of component I (case B) can also consist in first converting components (a), (b), (c) and (d) into one Reacts sufficient amounts of carboxyl groups and hydroxyl groups-bearing esters and then this ester in step (e) with the polymerizable monomers implements.

Good results are obtained if one uses the component Iç which is present as a hydroxyl group-bearing ester that has at least one in its molecule free carboxyl group on secondary and / or tertiary carbon atoms contains bound, so builds up that these as reaction products from the components (a), (b), (c) g (d) and (e) with tri and / or polybasic acids as components (b) and / or their anhydrides, insofar as they are capable of forming such, are present. In in this case one must as component (b) such polycarboxylic acids with 2 to 6 carboxyl groups, in which at least one carboxyl group on a secondary and / or tertiary carbon atom is bound to use. As a hydroxyl group-bearing ester, which is in its molecule at least one free carboxyl group on secondary and / or tertiary carbon atoms are for example suitable: those made from conjugated safflower oil fatty acid, Trimethylolpropane, phthalic anhydride, polyethylene glycol, (molecular weight 3000), styrene, Methacrylic acid, those from ricinene fatty acid, pentaerythritol, adducts from bisphenol-A and 2 moles of propylene oxide, vinyl toluene and acrylic acid; those from ricinic fatty acid 3 trimethylolpropane, phthalic anhydride, methacrylamide, methacrylic acid; such 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 from icinenfatty acid, Trimethylolpropane, phthalic anhydride, trimellitic anhydride, styrene, methacrylic acid, 2-hydroxyethyl maleate.

The following isocyanates, for example, can be used as component (f) are: arylene diisocyanates or their alkylation products, such as phenylene diisocyanates, Naphthylene diisocyanate, diphenylmethane diisocyanate, Toluylene diisocyanate, Di- or triisopropylbenzene diisocyanate, xylylene diisocyanate, naphthalene-1> 4-diisocyanate, 1,1'-di-naphthyl-2,2'-diisocyanate, bisphenyl-2,4'-diisocyanate, bisphenyl-4,4'-diisocyanate, Benzophenone-3,3'-diisocyanate, fluorene-2,7-diisocyanate, anthraquinone-2,6-diisocyanate, Pyrene-3ç8-diisocyanate, chrysene-2,8-diisocyanate, 3-methoxyhexane diisocyanate, octane diisocyanate, #, # '- diisocyanate-1,4-diethylbenzene, #, #' - diisocyanate-1,4-dimethylnaphthalene, cyclohexane-1,3-diisocyanate, 1-isopropylbenzene-2,4-diisocyanate, 1-chlorobenzene-2,4-diisocyanate, 1-fluorobenzene-2,4-diisocyanate, 1-nitrobenzene-2,4-diisocyanate, 1-chloro-4-methoxybenzene-2,5-diisocyanate, azobenzene-4,4'-diisocyanate, Benzolazonaphthalene-4,4'-diisocyanate, diphenyl ether-2,4-diisocyanate, diphenyl ether-4,4'-diisocyanate.

The following can be used as diisocyanates: The esters of 2,6-diisocyanate caproic acid, such as methyl, methoxymethyl, 1,2-dichloropropyl, isopropyl esters. The corresponding diesters of 2D4-diisocyanatoglutaric acid, 2,5-diisocyanatoadipic acid, 2,6-diisocyanatopimelic acid, 2,7-diisocyanatocorkic acid, 2,9-diisocyanatosebacic acid, Di- (isocyanatomethyl) -cyclobutane, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated diphenylethane diisocyanate, hydrogenated diphenylpropane diisocyanate, hydrogenated Diphenylbutane diisocyanate, isophorone diisocyanate, trimethylhexanemethylene diisocyanate The resulting hydroxyl group-bearing esters from reaction I are through Heating to 40 to 140 ° C, preferably 80 to 1200G, with 5 to 25 percent by weight Diisocyanates, used individually or as a mixture.

The urethanization reaction, i.e. the conversion of the product I to the Product II, you can in the presence or absence of an organic solvent or Solvent mixture, such as ketones, esters, ester ethers of ethylene glycol kole or diether of ethylene glycols. Working with solvents in the urethanization reaction, it is preferred if the end products have a lower one Should have viscosity. After the reaction with the mono- or polyisocyanates there must be no free isocyanate groups in the resin molecule obtained.

A maximum of 0.1 percent by weight in the resin after the reaction unreacted isocyanate may be contained.

To achieve sufficient water dispersibility or

Water solubility, improvement of flow properties and gloss It may be necessary in the case of pigmented coating agents for the new polyurethane resins being organic solvents that interact with water indefinitely or at least largely are miscible, to be used when dissolving with water. These organic solvents can in amounts of about zero to 40 percent by weight, preferably 10 to 40 percent by weight, Find use and serve to help when diluting with water to a body level from about 30 to 70 percent by weight of the resin solution, clear solutions are obtained. As such e.g. mono- and diethylene glycols, diethylene glycol with lower ones are suitable monohydric alcohols such as ethanol, n- and i-propanols, n- and i-butanols, such as e.g. Methylglycol, ethylglycol, propylglycol, isepropylglycol, butylglycol, dithyfenglycol diethyl ether, also acetone alcohol, lower ketones such as acetone, methyl ketone and in small amounts also methyl isobutyl ketone.

As far as the finished polyurethane copolymer resins have free carboxyl groups own, and these alone with the aid of organic solvents that Unlimited or at least largely miscible with water are, cannot be converted into the water-dispersible or water-dilutable state must have water-soluble alkalis and / or strong organic nitrogen bases be added in such amounts until the desired water dispersibility, Water dilutability, water solubility has been achieved.

The main alkalis are sodium hydroxide, potassium hydroxide and / or Ammonia can be used. Such organic nitrogen bases are used as organic strong bases understood that in 10% aqueous solution at 25 0C a pH value of at least 8 have.

Suitable strong nitrogen bases are: volatile alkylamines, such as triethylamine, Diethylamine, trimethylamine. You can also use tertiary, secondary or primary Alkylolamines, such as triethanolamine, diethanolamine, monoethanolamine, N-dimethylethanolamine, N-methylethanolamine, N-diethanolamine, monoisopropanolamine, di-isopropanolamine, triisopropanolamine The novel polyurethane copolymer resins according to the invention can be used in coating compositions unpigmented or pigmented, and / or containing fillers, can be used. For example, you can use plastics, paper, cardboard, concrete, masonry, Plaster or iron and steel as well as non-ferrous metals, with or without pretreatment, such as passivation, phosphating, electrochemical treatment, galvanizing, tinning or other metallization by various methods using such Pigments or other resins that change when a DC voltage is applied to the Deposit anode, including the electrophoretic application, applied will. Pigments and / or fillers are for example - without the use hereby to restrict - iron oxide red, carbon black, lead silica chromate, strontium chromate, blanc Fix> micronized barite varieties, microtalk, colloidal chalk, diatomaceous earth3 China clay, Titanium dioxide, chromium oxide green and others.

The use of strongly basic pigments, such as zinc oxide, zinc chromate, Lead carbonate, basic lead sulfate, red lead, calcium plumbate, is surprising in This is possible in most cases with carboxyl-free polyurethane resins. These pigments are not prone to thickening or failure. The ratio of the pigment to the binder depends on the type of pigment used and the one proposed Purpose of use. In most cases this will be the pigment to binder ratio 0.5: 1 to 3: 1.

The pigment content can only be used in electrophoretic applications are below 095.

The polyurethane copolymer resins produced according to the invention can be used as air-drying or stoving binders or sole binders in the form of aqueous dispersions for coating agents alone or in combination with copolymer dispersions the following compositions are used: 60 wt .-% butadiene and 40 wt .-% Styrene; 5% by weight butadiene and 45% by weight styrene and 5% by weight butyl acrylate; 40 wt% Butadiene, 50% by weight of styrene and 8% by weight of butyl acrylate and 2% by weight of hydroxyethyl methacrylate, Also vinyl acetate homopolymers and vinyl acetate-acrylate copolymers as well as pure acrylate copolymers or other dispersions can be mixed in. The proportions between Dispersions and the coating composition according to the invention can be 5:95 to 95: 5.

In addition, the new water-soluble oil-modified polyurethane copolymer resins in combination with styrene-butadiene copolymer dispersions as binders for coating agents3 which can be processed by means of mechanical or electrophoretic application, can be used.

The polyurethane copolymer resins according to the invention are used for high proportions of dispersions more to a modification of the dispersions, e.g. with regard to adhesive strength chalking surfaces.

The invention also relates to the use of the new oxidative drying Polyurethane copolymer resins in water-dispersible or water-thinnable Binders and / or coating agents as sole binders for air-drying or also burn-in lacquers or in a mixture with other binders for air-drying Lacquer or even for stoving enamels. A use of the new polyurethane copolymer resins is used as a sole binder or in a mixture with other binders in electrophoretically depositable coating masses, together with such pigments, which are deposited on the anode when a direct voltage is applied.

The air-drying binders used according to the invention can can also be baked in at elevated temperatures. When used as a binder in stoving enamels, an admixture of water-soluble or at least hydrophilic, low molecular weight aldehyde condensation products> such as phenol resols and / or aminoplast-forming condensation products, be advantageous.

The mixing of the new water-soluble polyurethane copolymer resins with relatively low molecular weight, at least hydrophilic, thermosetting Condensation products, such as aminoplast-forming reaction products and / or phenol resols and / or etherified phenol resols) causes a higher degree of crosslinking of the stoved Films and thus a further improvement in their technical coating properties, such as Hardness, gloss, corrosion protection and the like.

Such condensation products are also to be understood as thermosetting that are heated alone) a relatively high molecular weight, but not yet reach infusible state. It is also not absolutely necessary that the admixed condensation products have solubility in water on their own; it is only necessary that their hydrophilic character be sufficient to combine with the plasticizing new water-soluble polyurethane resins sufficient To give compatibility, i.e. baked clear lacquer films should be homogeneous; and in the aqueous coating agents made from them, in the processing concentration there is no separation of the binder components.

The new water-soluble Polyurethane copolymer resins also with fatty acid esters containing carboxyl groups, Fatty acid adduct esters, in particular attached maleic acid and water-thinnable Alkyd resins with an acid number between 30 to 120 can be used.

As thermosetting, hydrophilic, low molecular weight, aminoplast-forming Condensation products apply to aldehyde reaction products of those with aldehydes convertible compounds such as urea, thyene urea, dicyandiamide and aminotriazines, such as melamine, benzoeguanamine, acetoguanamine and formguanamine. The aforementioned compounds can with aldehydes) such as formaldehyde, acetaldehyde, crotonaldehyde5 acrolein, benzaldehyde, Furfural and the like can be implemented. The aldehydes should also include aldehyde-forming Compounds such as paraformaldehyde, paraldehyde, trioxymethylene are contemplated will.

The preferred aldehyde is formaldehyde, the preferred aldehyde-binding agents 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 for melamine resins in a formaldehyde molar ratio of 1: 1.5 to 1: 6.

In the present case, they have proven to be good binders for stoving enamels also the etherification products of the lowest half ethers of glycol and diglycol, like ethylglycol, ethyl diglycol with the methylolmelamine, proven as they are already in the Austrian patent 180 407 were 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 have been almost completely etherified with methanol, are also suitable ethers partially esterified with dicarboxylic acids or ethers etherified with hydroxycarboxylic acids nitrogen-containing polymethylol compounds, such as those produced by transesterification of hexamethoxymethylmelamine with adipic acid. In stoving enamels according to the invention, 5 to 50 percent by weight of these condensation products should be included.

Examples of suitable thermosetting, hydrophilic, low molecular weight Condensation products are phenol alcohols, i.e. still low molecular ones, through condensation obtained products of monohydric or polyhydric phenols with aldehydes how Formaldehyde, acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural etc., or Formaldehyde-producing compounds, such as paraformaldehyde, paraldehyde and trioxymethylene. Preferred aldehyde is formaldehyde or a formaldehyde-producing compound which is obtained in an alkaline medium in a known manner, such as hexamethylenetetramine. Suitable phenols are phenol substituted in the o-, ot-p-position, but with formaldehyde condensable phenols such as cresol or xylenol. Phenols are very suitable that from alkylphenols, such as propyl, butyl, especially p.-tert.-butylphenol, obtained will. Resoles are also made from binuclear phenols, such as diphenol and bisphenol-A, suitable. In particular, those resols based on bisphenol-A are suitable, the pro Moles of bisphenol-A contain approximately 1.75 to 2.5 moles of formaldehyde attached. very good One can also call resoles phenolic acid, which is produced by condensation of formaldehyde or formaldehyde-yielding compounds with suitable phenol carboxylic acids have been using. Among the phenol carboxylic acids condensable with formaldehyde 4,4-bis (4-hydroxyphenyl) valeric acid occupies a preferred position. The best results are also obtained when 1.75 to 2.5 moles of formaldehyde are bound per mole of phenolic acid. The production of other suitable phenol carboxylic acid resols is described e.g. in the German Auslegeschrift 1 113 775. The phenol carbonic acid resols, in particular those based on 4,4-bis (4-hydrophenyl) valeric acid are suitable good to combine for the products according to the invention, those according to the invention Use as electrophoretically depositable coating compounds and lacquer binders are determined. It is very advantageous if at least a part of the formaldehyde condensation products etherified with lower monohydric aliphatic alcohols with 1 to 4 carbon atoms is, such as ethanol, methanol) propanols, butanols. Preferred water-dilutable Phenol resols are those5 produced by the reaction of phenol ald: 2h-d condensation products which have been etherified with alcohol with aliphatic monooxy- or dioxycarboxylic acids or their esters, were obtained, as described in the laid-out documents of Belgian patent 724,923.

Combinations with the new polyurethane copolymer resins are preferred, in which ainoplast-forming resp.

phenoplast-forming condensation products with 10 to 30 percent by weight5 based on solids content.

For the electrophoretic application process, it is advantageous to use the namely, thermosetting condensation products of the type already explained above Phenoplasts and / or aminoplasts, not just to be mixed in, but the components subject to a reaction.

The reaction, which can be referred to as precondensation, takes place in general at temperatures from 70 ° to 1200 ° C., with a suitable reaction procedure It is important to ensure that the components are not esterified, but rather if possible a polyvertherun takes place. A suitable reaction procedure exists, for example therein5 that the reaction of the components in the presence of an acidic catalyst5 such as phosphoric acid 5 p-toluenesulfonic acid or benzoic acid, at temperatures between 700C to 1200C. The heating is stopped immediately when the Acid 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 in that hydrophilic5 thermosetting condensation products etherified as phenoplasts and / or aminoplasts come into use. To a to achieve sufficient airtightness, it is also advantageous to carry out the reaction under vacuum.

The binders for stoving enamels combined in this way can be used Bringing their components together in the usual way. In general it is convenient to use the water-soluble salts of other synthetic resins from 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, which optionally may contain minor amounts of water-soluble organic solvents5 to mix and then, if necessary, the concentration and pH of the mixed Adjust solutions to the fourth desired. The pH of the desired solution should in general be expediently about 7.5 to 9.0, in particular about 890; if required9 after a long period of storage of the resins with ammonia or organic strong nitrogen bases are reproduced The produced from the binders Combined stoving enamels can contain the usual additives, e.g. minor amounts of water-soluble organic solvents5 in their The presence of the components of the stoving enamel have been produced, and / or other solvents, such as monoalkyl ethers of di- and trithylene glycol, and compounds of the six-component chromium 3 such as ammonium dichromate as well as soluble dyes, pigments, Flow improvers, anti-corrosion agents 5 stabilizers and / or curing catalysts.

The combined stoving enamels can be made using the usual Methods on the objects to be painted be applied; they are particularly suitable for painting sheet metal. Here it is a special one The advantage of the paints is that they can also be applied to the metal sheets after the electrophoresis process can be deposited. The stoving of the paint can take place at temperatures around from 800 to 2000C, preferably from about 1000 to 1800G, and depending on the baking temperature in a period of about 10 to 80, preferably about from 20 to 60 minutes.

Example 1: 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 at 1550C to 2200C within 9 hours with water separation up to Acid number of 7 esterified. Thereafter, a vacuum was applied at 2000C to remove residual water to remove. After cooling to 140 ° C., 316 g of xylene were added and at a reflux temperature of 1580C within 7 hours, a mixture of 274 g styrene, 6 g p-tert-butyl peroxide and 8 g dodecyl mercaptan were added dropwise. The reaction mixture was polymerized for a further 12 hours and in order to achieve a solids content of 80% another 18 g of p-tert.-butyl peroxide had to come in 4 parts at intervals of 2 hours to be added. After that, vacuum was applied to xylene and small Remove residual monomers.

After cooling to 70 ° C., 60 g of acetone and 68 g of triallyl ether were added of the pentaerythritol added, and at reflux temperature of 1060C to 1080C were 148 g of tolylene diisocyanate were added dropwise over the course of 8 hours.

After a further hour, 236 g of butyl glycol were added, and The entire amount of acetone was distilled off under vacuum. After that, the resin with triethylamine adjusted to a pH of 7 and at 800C Diluted up to 700C with 1960 g of water.

The finely divided dispersion dried after desiccation with 0.12% Co-metal (calculated on solid resin) with a wet film thickness of 120 μm in 2 1/2 hours.

Example 2: A mixture of 436 g of ricineal fatty acid, 98 g of polyethylene glycol (Molar weight 3000), 74 g of pentaerythritol, 152 g of an adduct from one mole of bisphenol-A and two moles of propylene oxide, 0.04 g of dibutyltin dilaurate and 2 ml of triphenyl phosphite were esterified at 1550 to 2200C up to acid number 3. After cooling down to 14,000, 294 g of xylene were added and at a reflux temperature of 153 ° C. A mixture of 340 g of styrene and 18 g of methacrylic acid was obtained within 4 hours and 6 g of 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. To After cooling to 70 ° C., 124 g of acetone were converted into 92 g of triallyl ether of pentaerythritol added, and at reflux temperature of 860 to 880C were within 8 hours 82 g of tolylene diisocyanate were added dropwise. After a further hour, 320 g of butyl glycol were added added, and the entire amount of acetone was distilled off under vacuum.

The resin was then adjusted to pH 7 with triethylamine and diluted with water to 50% solids.

The finely divided dispersion dried after appropriate drying in 2 1/2 hours.

Claims (13)

Claims 0 Process for the production of water-dilutable resp. water-dispersible, oxidatively drying polyurethane copolymer resins, characterized in that first: I (a) 25 to 55 percent by weight unsaturated Fatty acids, of which 0 to 25 percent by weight may be present as drying oils, and optionally the unsaturated fatty acids and / or the drying oils contain up to 6 percent by weight of maleic anhydride and the mixture Has iodine numbers of about 130 to 390, (b) 2 to 15 percent by weight aliphatic, cycloaliphatic, aromatic carboxylic acids or hydroxycarboxylic acids, individually or in the mixture, or their anhydrides, if they exist, (c) 2 to 30 percent by weight polyvalent organic hydroxyl compounds, (d) 4 to 9 percent by weight polyoxyalkylene compounds, containing at least two atoms of active hydrogen, with a molecular weight of the polyoxyalkylene chain from about 2000 to 6000, individually or in admixture, (e) to 65 percent by weight of polymerizable monomers together or in stages Heating converts, II the hydroxyl group-bearing obtained, if necessary carboxyl group-bearing esters in deficit by heating with (r) 5 to 25 percent by weight Diisocyanates, individually or as a mixture, and (g) 5 to 35 percent by weight of pentaerythritol triallyl ether implements, III and optionally by adding alkali and / or organic strong bases in the water-dispersible or water-dilutable state convicted. 2. The method according to claim 1, characterized in that as aromatic carboxylic acids, polycarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, Tetrahydrophthalic acid, trimellitic acid or their anhydrides are used. Method according to one or more of Claims 1 and 2, characterized characterized in that the polyvalent organic hydroxyl compounds glycerol, Pentaerythritol, di-pentaerythritol, trimethylolpropane, hydrogenated bisphenol-A, 4,4-dihydroxyphenylmethane, 4,4'-dihydroxyphenylmethane, 4,4'-dihydroxydiphenyl, cyclohexanediol, ethoxylated Bisphenol-A with 1 to 6 ethylene oxide molecules, propylated bisphenol-A with 1 to 6 propylene oxide molecules, ethoxylated pentaerythritol, 1,2,6-cyclohexanetriol used. 4. The method according to one or more of claims 1 to 3, characterized characterized in that the implementation of components (a) to (e) by esterification, Transesterification by heating at temperatures between 15000 to 2900C, preferably takes place at 1500C to 270 ° C, in the presence of catalysts. 5. Procedure according to an or. several of claims 2 to 4, characterized characterized in that the obtained hydroxyl groups, if necessary carboxyl group-bearing ester from reaction I by heating to 40 to 1300C, preferably 80 to 12,000, with 5 to 25 percent by weight, preferably 10 to 25 Weight percent, Diisocyanates, individually or as a mixture, reacted. 6. The method according to claim 5, characterized in that the implementation of product I to product II in the presence of an organic solvent or Solvent mixture, such as ketones, esters, ester ethers of ethylene glycols or ethers the ethylene glycols. 7. The method according to any one of claims 1 to 6, characterized in that that one uses as component (I) those hydroxyl-bearing esters which are in their molecule has at least one free carbaxyl group on the secondary and / or tertiary Contain carbon atoms bonded. 8. The method according to claim 7, characterized in that the hydroxyl and carboxyl group-containing esters in which at least one free carboxyl group is bound to secondary and / or tertiary carbon atoms (stage I), used are made by using polycarboxylic acids (b) and / or hydroxymono- and Polycarboxylic acids (b) and / or other substituted carboxylic acids (b) in which at least one carboxyl group on a secondary or tertiary carbon atom is bound to be built. 9. The method according to claim 8, characterized in that as hydroxyl and carboxyl group-containing esters, in which at least one free Carboxyl group is bonded to secondary and / or tertiary carbon atoms, those are used that are made up of components (a), (b), (c), (d) and (e) in one step or have been produced in several stages. 10. The method according to any one of claims 1 to 9, characterized in, that polyoxyalkylene compounds with an average molecular weight of about 3000 are used. 11. The method according to any one of claims 1 to 10, characterized in that that the resins are neutralized. 12. Use of the according to one or more of claims 1 to 11 available oil-modified polyurethane resins as air-drying or stoving Binding or Sole binder in the form of aqueous solutions and dispersions for coating agents. 13. Use of the oil-modified polyurethane resins according to claim t2 together with water, if necessary with organic solvents that contain Water are minimally or at least largely miscible.