DE1669289A1 - Air-drying or stoving, water-dilutable coating compounds - Google Patents

Description

DR. WALTER NIELSCH

Patent attorney
2 Hamburg 70
SchloBslraße 112 P.O. Box 10914 File: 2 O 91

Telephone: 652 97 07 I O O 9 2 S

REICHHOLD CHEMIE AKTIENGESELLSCHAFT
Hamburg 70, Iversstrasse 57

Air-drying or stoving, water-thinnable coating compounds

It has long been known to produce paints by boiling phenolic resins with unsaturated oils (see: The wood oil from E. Fonrobert, Berliner Union, Stuttgart). These products which only work in organic solvents are soluble, are characterized by excellent properties, especially film properties. In the present invention, air-drying, xvas server thin synthetic resins are produced on the basis of this implementation and used as a basis for air-drying or stoving water-thinnable coating compounds, which in particular are able to meet the high requirements for the storage stability of such products.

The invention includes air-drying or stoving, i

water-thinnable coating compounds consisting of at least:

a) water and / or completely or largely water-miscible organic solvents,

b) ammonia, or

b ¹ ) strong organic nitrogen bases or mixtures of b and b ¹ ,

characterized by the content of at least one oxidatively drying carboxylic acid resin based on unsaturated fatty acids, which is resistant to saponification and at least after

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one of the following '/ experienced 1st received:

1. By heat conversion of at least one phenolic resin (I), with at least one ethylenically unsaturated fatty acid (II), with at least 14 carbon atoms.

2. By hitaeraaktion in the level A of at least one Phenolic resin (I) with at least one ester (III and IV) of ethylenically unsaturated fatty acids, with at least one monohydric and / or polyhydric alcohol and post-

P subsequent cleavage of the esters in stage B and optionally Separation of the released alcohols and any inorganic salts present.

3. By blocking any phenolic hydroxyl groups still present in the products according to 1 and / or -2 by reaction with compounds containing oxirane rings, which lead to the reaction are capable of phenolic hydroxyl groups, the reaction of the products obtained according to 2 with the Oxirane rings containing compounds preferably after

"Stage A _{takes place as stage A 1} " and the cleavage of the esters is then carried out.

4. By copolymerizing the products according to 1 and / or 2 and / or 3, which in the latter cases optionally also after stage A bsir. A. Can be done with vinyl (V) and / or vinylidene compounds (VI) in the Warin & ^ preferably in the presence of polymerization catalysts and subsequent cleavage of the esters, provided that the product is pr ^ dük ^ e after 2 or 3 in stage A or A.- copolyririfl-rt <"

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the, wherein in the preferred variant the copolymerization only takes place after stage B,

5. By modifying the products according to i and / or 2 and / or 3, which in the latter cases may also be done after stage A or v :. A ₁ can take place and / or the products after ¹ J with cyclopentadiene or dicyclopentadiene (YII) in the Wäraie.

6. By heat reaction of at least one phenolic resin (I)

with at least one with vinyl (V) and / or vinylidene Λ compound (VI) in the heat, preferably using polymerization catalysts, copolymerized ethylenically unsaturated fatty acid (II) with at least 1H carbon dioxide.

J. Through a heat reaction of at least one phenolic resin (I) with at least one ethylenically unsaturated fatty acid (II) with at least 1h carbon atoms modified by heat with cyclopentadiene or dicyclopentadiene (YII),

8. By heat reaction in stage A of at least one Phenolic resin (I) with at least one with vinyl (V) and / or vinylidene compounds (VI) copolymerized esters (III and IV) ethylenically unsaturated fatty acids (II) with mono- and / or polyhydric alcohols and the following Cleavage of the esters in stage B and, if appropriate, separation of the alcohols released and, if appropriate any inorganic salts present.

9. By heat reaction in stage A of at least one

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Phenolic resin (I) with at least one with cyclopentadiene or dicyclopentadiene (VII) heat-modified esters (III and IV) of ethylenically unsaturated fatty acids (II) with monohydric and / or polyhydric alcohols and subsequent cleavage of the esters in stage B and optionally Separation of the released alcohols and any inorganic salts present.

Io. Implementation of the products according to 1 to 9 with α, ß-ethylenically unsaturated dicarboxylic acids or, if they exist, their anhydrides (VIII) in the Marne.

The resols formed by the alkaline condensation of phenols with formaldehyde are particularly suitable as phenolic resins I. These resols can already have their molecular weight increased to a greater or lesser extent by heat condensation in an alkaline and / or acidic medium. However, it required 1st _s d? .SS the phenolic resins co selected xrerden that after its reaction with the fatty acids (II) and / or Fettsäureestern (III and IV) homogeneous products are formed. This homogeneity is achieved particularly easily with so-called oil-soluble, preferably oil-reactive phenolic resins. Resoles based on trifunctional simple phenols are therefore only suitable for reaction with unsaturated fatty acids in relatively few, particularly favorable cases, because of their pronounced alcohol solubility. The most suitable are alkylphenol resins, which can readily be condensed with unsaturated fatty acids or their esters.

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The so-called oil-reactive alkylphenol resins be used. Resoles, which only through appropriate etherification of the methylol groups in their solubility behavior the alkylphenol resins have been adjusted in terms of their boilability with the fatty acids (Ii) must be carefully checked.

The phenolic resins I which are primarily suitable in the present invention include those produced by alkaline condensation Resoles formed by phenols of the general formula with aldehydes, preferably formaldehyde. These are preferably grounded used in largely anhydrous form. OH

R = alkyl radical with 2 to 20 carbon

^ - ^ atoms or aryl radical ¹ R

The phenols of the general formula are able to bind up to 2 KoI formaldehyde per mole of phenol. Preferred Resoles are those which contain 1 to 2 moles of formaldehyde per mole of phenol condensed. The resol can through condensation In alkaline and / or acidic medium already to a greater or lesser extent in their molecular weight be enlarged vrordon, so that so-called phenolic resins are present. However, it is necessary that the phenolic resins be selected so that they react with the fatty acids (II) and / or fatty acid esters (III and IV) result in homogeneous products. Among the phenols of the general formula is p.-tert.-dutylphenol is particularly suitable.

Phenols substituted with longer alkyl chains of the general

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in a formula contribute to the elasticization of the films made from the synthetic resins according to the invention. However, the films also ground and have a lower mass resistance. To establish the desired properties, a mixture of different phenols of the general formula with substituents R of different chain lengths may therefore be recommended. Phenols of the general formula in which R is C ^ H ₁₁ J ^c 6 ^H l ^ * ^C 7 ⁱⁱ l5 » ^c ^ n » CgH ^ q are particularly suitable for elasticization.

The phenolic resins and / or resoles can also be used with alcohols have already been etherified in a known manner.

Phenolic resins based on bisphenol-A can also be used, but preferably with a charge of formaldehyde (phenol: formaldehyde 1: 0.8 to 1: 1.3). In the case of bisphenol resins, too, etherification with monohydric alcohols with 1 to 4 carbon atoms is advisable, especially if a very high charge with formaldehyde is sought. Also suitable are phenolic resins Baeis of phenol carboxylic acids, wherein the phenolic carboxylic acids, however, at least one free phenolic hydroxyl group enthr.ltan need and should be at least bifunctional, ie Ίΐο Fhe no! Carboxylic acid must attach 2 FFOL formaldehyde fortune ^ n. The use of Kresoü- and Xylenolharsen, ge ^ obenerifalls etherified cresol and Xylenolharsen must in practice ülins lfsll:? - be reviewed.

In addition to the aforementioned phenolic resins rounder and ^"T J as, äanrisc other Phenolhrrse as Äi ^ penphonolhargo and oil soluble Phe

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nolharze, which are reaction products of phenol-formaldehyde condensation products with natural resins are used. The use of terpene phenolic resins can lead to Have a beneficial effect on viscosity regulation.

Suitable unsaturated fatty acids (II) are: eleostearic acid, licanic acid, parinaric acid, linolenic acid with isolated and conjugated double bonds, linoleic acid with isolated and conjugated double bonds. These acids can be present individually or as a mixture. The total content of polyunsaturated fatty acids in the reaction product of I and II should be 20-90 % , preferably 40-75 %. These ratios also apply if their esters III and IV are used instead of the free fatty acids. In addition, all unsaturated fatty acids occurring in natural fatty oils, such as palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, erucic acid, are suitable as admixtures with the above-mentioned acids. Araelaidinsäure, Clupanod acid tert. °, etc. this overall ^ elialt this at least mono ung; esättigten fatty acids may, however, 6o% by weight (based on the Uinsotzungsprodukt I and II) must not exceed.. However, the content of these fatty acids is preferably below 3o wt. , 1. The proportion of saturated fat, which is always present when Fettsäuregemisehe, as they are obtained by saponification of natural oil, used to 2o percent. # Not exceed, possibly even lower than Io wt.%. As unsaturated fatty acids (II), the dimeric

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ization or oligomerization of unsaturated fatty acids obtained polybasic acids can be used. It is preferred to use unsaturated fatty acid mixtures such as those obtained from natural vegetable and animal unsaturated fats by saponification. Such natural unsaturated fatty oils are, for example, cotton scatoi. Lupine oil, corn oil, rapeseed oil, sesame oil, grape seed oil, walnut oil, perilla oil, linseed oil, wood oil, oiticica oil. Of these, wood oil, oiticica oil and linseed oil are preferred. In particular mixtures of tung oil and oiticica with linseed oil, the linseed oil fraction should not exceed 60 wt.%. Furthermore, fatty acids from dehydrated castor oil which contain a high proportion of conjugated linoleic acid are also suitable. Additions of natural resin acids (rosin) to a maximum of 3o % _t based on the reaction product I with II can be added under certain circumstances.

Instead of fatty acids, however, it is often advisable to use them of fatty acid esters. Both 7 ”t-acid esters can be used here monohydric and polyhydric alcohols can be used. As fatty acid esters of monohydric alcohols, the inexpensive fatty acid methyl esters are recommended, which are obtained by transesterification natural, unsaturated oils. they provide So just like the fatty acids, fatty acid mixtures represent. As Fatty acid polyol esters are primarily natural oils, i.e. glyceride esters of unsaturated fatty acids. In the the fatty acids contained in esters (III and IV) correspond the fatty acids mentioned under (II) including the selections and proportions made there. The usage

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of difatty acid glycol esters, in particular of ethylene glycol and propylene glycol, can be advantageous in controlling viscosity during the course of the reactions.

The reaction of the phenolic resins (I) with the fatty acids (II) and / or fatty acid esters (III and IV) takes place at an elevated temperature, generally between 200 and 270.degree. When using fatty acids or fatty acid glyceride esters of highly unsaturated fatty acids, a slightly lower temperature, i.e. around 200 to 24o ° C, is usually advantageous, while a higher temperature between 23o and 20 ° C may be necessary for less strongly unsaturated fatty acids. When converting phenolic resins with highly unsaturated oils (wood oil, linseed oil, oleaginous oil), it is important to ensure that temperatures and reaction times are adhered to very precisely, as this reaction -. as is well known - can very easily lead to gel formation. As a guide, it can be said that the reaction between phenolic resins and highly unsaturated fatty oils can achieve a maximum viscosity of about 1000 centipoise / 20 ° C. (measured 66% Ig in Testbensin). A gelled batch can also be worked up on a laboratory scale, since the subsequent saponification of the reaction product causes the gel to split, but this operation cannot be carried out technically.

When using fatty acids (II) or fatty acid esters of monohydric alcohols (III), in particular fatty acid methyl esters, the reaction with the phenolic resins is less critical. The viscosity here can vary within wide limits.

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however, it has proven to be beneficial if the viscosity where reaction products are measured between 100 and 300 centipoise / 20 ° C (50 / »ig in butylglycol). The reaction temperature should be around 2? o ° C.

Since phenols are known to act as antioxidants and can therefore cause a delay in drying in paint films, the reaction product of phenols with unsaturated oils and / or fatty acid monoalcohol esters with compounds containing oxirane rings that are capable of reacting with phenolic hydroxyl groups, preferably ethylene oxide or propylene oxide, can be reacted to to etherify any phenolic hydroxyl groups that may still be present. This reaction takes place in such a way that at an elevated temperature above the boiling point of the ethylene oxide or propylene oxide, if appropriate under pressure, it is reacted with about 10% of ethylene oxide or propylene oxide (based on the batch). The reaction is complete after about 2 hours, after which the excess ethylene oxide or propylene oxide is distilled off, if appropriate under vacuum. It has been found that this conversion is not absolutely necessary in every case.

To achieve solubility in water, it is necessary that the reaction product bearing carboxyl groups is made from fatty acids and phenolic resins are neutralized with ammonia and / or strong organic nitrogen bases. Is best suited for air-drying, water-permeable coating compounds, water-based ammonia solution, since synthetic resins neutralized with aqueous ammonia solution, films with the lowest GI

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When converting phenolic resin an (I) with fatty acid esters (III and IV), saponification of the ester bonds is first necessary to achieve water dilutability. This saponification can be carried out in the normal way using aqueous alkalis in the heat. After saponification, the Raaktionsgemlsch -T.it kineralsäuren is acidified, which causes the resin to precipitate and the aqueous salt solutions can be separated. Repeated washing with water is necessary to completely remove any salts present. Much more expedient than alkaline saponification is saponification with water, optionally with the addition of small blades of acidic catalysts, which is carried out in a known manner at higher temperature under pressure. It may be unnecessary to wash out the resins, so that the reaction product can be neutralized directly with ammonia or strong organic nitrogen bases. A Druckverseifung with aqueous ¹ Aimoniaklösung at about 80 to loo ° C sufficient VCN Wasserverdünnbarkelt in manehen cases to achieve.

The products obtained in this way (.Ij 2 and 3) are already used as water-thinnable binders for :. ' Production of air-drying sn Oberzugsmassen suitable. In particular with regard to the drying speed and water resistance of the dried films, they can be further improved by copolymerization with vinyl or vinylidene compounds on (4, 5, P) and / or by adding "'velopentadiene or sicylcpentadiene (5, 7-9 ).

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The copolymerization gives synthetic resins that Films with very short dry sides result which are not due to the modification with cyclopentadiene or dicyclopentadiene can be achieved. It is therefore opposed to the copolymerization given preference to modification with cyclopentadiene.

However, the modification with cyclopentadiene is a good one The course of the films can be caused by a mixture of synthetic resins modified with cyclopentadiene with those which are produced by Copolymerization obtained with vinyl and / or vinylidene compounds, be advantageous.

A subsequent reaction (lo) of the anhydrous or largely anhydrous (water content <5%) products with α- # - ethylenically unsaturated dicarboxylic acids at temperatures between 10o - 22o C, with adduct formation taking place in a known manner, can increase the hardness of the films and to improve the water solubility of the synthetic resins, but this method does not belong to the preferred embodiment.

The best products were obtained according to method k if products according to 2, preferably according to 3, were copolymerized after stage B in an anhydrous medium, the vinyl and / or vinylidene compounds being characterized by an admixture of acrylic acid.

The reaction with vinyl and / or vinylidene compounds takes place in the heat, preferably with the action of polymerization catalysts. The implementation is preferred

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carried out with a vinyl or vinylidene monomer mixture which contains 1,800 g of at least one acid equivalent (expressed in grams) of an unsaturated carboxylic acid capable of copolymerization with the vinyl or vinylidene compounds. The reaction with vinyl and / or vinylidene compounds is preferably carried out in an anhydrous medium (water content <5%).

When using relatively weakly polar monomers, such as styrene, α-methylstyrene, vinyltoluene, 1,800 g, preferably 2 to 4 acid equivalents may be included.

The copolymerization temperature depends on the one used Catalyst system. Reaction temperatures between 120 and 160 ° C are preferred as the most favorable ranges Use of di-tert-butyl peroxide, if appropriate in Combination with a chain terminator, preferably lauryl mercaptan. At lower temperatures, the reaction mixture is often too highly viscous for easy processability. In addition, the reaction rate, which can be followed by the increase in the level of pest bodies, is at too slow for many monomers. At high temperatures, "products with a lower viscosity are obtained, even with purely thermal polymerization, however, these fall in terms of their FiIm properties worse looking.

The reaction rate can be reduced by cobalt-II-Chlorldin Quantities of 3 to 6 parts per million can be increased. The same reaction times are, however, also when the person is present received from Y ^ iA material. By using

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the water solubility of the overall system is increased by monomers containing carboxyl groups. The vinyl monomer content, based on the total solids content, of the reaction product can reach 50 % . However, the total proportion depends on the type of monomers used.

As vinyl and vinylidene monoir.;:? ' komnv..r. ^:: N primarily vinyltoluene, α-methylstyrene and styrene In embossing. In some cases, the use of acrylic acid esters cannot be avoided in order to achieve sufficient elasticity in the films. Preferred acrylic acid esters are therefore those P which are relatively stable to saponification.

Suitable alkyl esters of α, B-unsaturated monocarboxylic acids are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate and the corresponding meth-, eth-, phenyl acrylates, propyl crotonate, butyl crotonate and the like, and also aryl hydroxy ester. α, 8-unsaturated carboxylic acids, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl, 3-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate and the W correspond sponding methacrylates, Äthacrylate, phenyl acrylates, 2-Hydroxyäthylmaleinat, di- (2-hydroxypropyl) - Maleate or the corresponding fumarates, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-1-phenylethyl acrylate, 2-hydroxy-3-butoxypropyl acrylate and the corresponding meth-ethacrylates and phenyl acrylates. Also styrenes substituted in the core (ortho-metha-, para-, methyl-, ethyl-, propyl-, butylstyrene, 2, ^ 1-, 2,3-, 2,5-dimethylstyrene, 2, ^! -, 2, 3-, 2,5-dichlorostyrene) styrenes substituted in the side chain such as a-methylstyrene, a-ethylstyrene,

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α-Ch-Lorstyrene etc. in embossing. Preference is given to using vinyl monomers which are stable to saponification, and esters susceptible to saponification only to the extent that is absolutely necessary to elasticize the films, preferably 2-ethylhexyl acrylate. Monomers carrying carboxyl groups which must be capable of copolymerizing with the aforementioned monomers are suitable Acrylic acid and / or methacrylic acid, cinnamic acid, β-benzoylacrylic acid, crotonic acid, etc. Furthermore, α, β-ethylenically unsaturated polycarboxylic acids or their anhydrides, if they are able to form such as maleic acid, fumaric acid, citraconic acid, itaconic acid _, mesaconic acid, aconitic acid ™ or monoesters of the polycarboxylic acids mentioned with saturated, straight-chain monoalcohols having 1 to k carbon atoms, preferably methanol. The preferred α, 3-ethylenically unsaturated monocarboxylic acids include acrylic acid and methacrylic acid. The monomers bearing carboxyl groups can be used alone, in mixtures with one another or alone or in Mix with the monomers bearing no free carboxyl groups are reacted.

If compatibility is achieved in the overall system, other polymerizable monomers, such as acrylamide, methacrylamide, acrylonitrile, methacrylonitrile and the like, can be added to the monomer mixture individually or as a mixture. The total proportion of polymerization of vinyl or vinylidene compounds in the total resin can be 0 to 50%. ^: ^Tr u ~ ': * but found that the best results in terms of water resistance of the films are achieved when the total content of polymers made from vinyl and / or vinylidene compounds

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Is 28 to 35 wt. %. If the polymerization is not carried out to a high solids content, it is advisable to remove the excess monomer content by vacuum distillation. As has already been stated, aqueous ammonia solution is particularly suitable for neutralization. However, if the tendency of the film to yellow does not play a decisive role, as is the case, for example, with primers, strong organic nitrogen bases can also be used for neutralization . Volatile alkylamines such as triethylamine, diethylamine and trimethylamine are particularly suitable. fc Tertiary, secondary or primary alkylolamines such as triethanolamine, diethanolamine, monoethanolamine, N-dimethylethanolamine, N-methylethanolamine, N-diethanolanine, monoisopropanolamine, di-isopropanolamine, triisopropanolamine are generally to be understood as meaning those with strong organic nitrogen bases , 05 normal aqueous solutions have a pH value of ^ lo, o, measured at 25 ° C. The neutralization with aqueous ammonia solution and / or strong organic nitrogen bases should take place at room temperature or only moderately increased temperatures. It is useful to carry out the neutralization in the presence of water.

It may be necessary to achieve sufficient solubility in water be to use organic solvents that are unlimited or at least largely miscible with water. as such are e.g. Fono and dieters of ethylene glycol, Diethylene glycol with lower monohydric alcohols, Kie methanol, Ethanol, propanol, eutanol, e.g. methylglycol, Ethyl glycol, propyl glycol, isopropyl glycol, butyl glycol, di-

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ethylanglycol diethyl ether., also acetone alcohol, lower Ketones such as acetone, methyl ethyl ketone and, in small amounts, methyl isobutyl ketone. The water-thinnable synthetic resins should be 1: oo soluble or at least dispersible in water. Colloidal solutions should preferably arise, which appear clear or cloudy.

To produce air-drying paints, it is necessary to siccativize the paints. The are suitable as siccatives cobalt, lead,

Mangen etc. connections. Preferred are those in ^

Are water dispersible.

The coating compositions according to the invention can be used unpigmented or pigmented and / or containing fillers. For example, they can be applied to wood, concrete, masonry, plaster or iron and steel as well as to non-ferrous metals, with or without pretreatment such as passivation, phonophating, electrochemical treatment, sinking, tinning or other metallization using various methods, including electrophoretic application. λ den. Pigments and / or fillers are, for example - without restricting the invention thereby - iron oxide red, carbon black, lead icochromate, strontium chromate, blanc fix, micronized barite varieties, microtalk, colloidal chalk, diatomaceous earth, china clay, titanium dioxide, chromium oxide green and others.

The use of strongly basic pip-ments, such as zinc oxide, zinc chromate, Lead carbonate, basic sulphate, red lead potassium air plumbate requires a penautn examination. These figments can

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tend to thicken or fall out. The ratio of pigment to binder depends on the type of pigment used and the proposed use. In most cases the pigment / binder ratio will be 0.5: 1 to 2: 1. Only in the case of electrophoretic application can the pigment content be below 0.5 % .

In some cases it has proven to be expedient to add dispersions to the water-thinnable coating compositions according to the invention based on styrene-butadiene copolymers, vinyl acetate homopolymers and vinyl acetate-acrylate copolymers as well as pure acrylate copolymers, individually or as a mixture. The proportions between dispersions and the coating composition according to the invention can be 5:95 to 95: 5. With small ones Proportions of dispersions in coating compositions according to the invention the properties of the coating compositions according to the invention can be modified. In these cases the modification is to be regarded as a kind of external plasticization. The dispersions must always be selected so that they dry homogeneously Films are made. Under certain circumstances, these dried films, such as dispersions, can themselves show a slight opalescence.

In the case of high proportions of dispersions, those according to the invention are used Coating compounds are more about modifying the dispersions, e.g. with regard to adhesive strength on chalking substrates.

The coating compositions according to the invention can also be used with increased Temperature can be burned in. When used as stoving enamels an admixture of water-soluble or at least

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least hydrophilic low molecular weight aldehyde condensation products such as phenol resols or arr.inoplast-forming condensation products be beneficial.

The combination of the new oxidatively drying carboxylic acid 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 cause a higher degree of crosslinking of the stoved coating compounds and thus a further improvement their paint-related properties, such as hardness, gloss, corrosion protection and the like

Thermosetting is also to be understood as meaning those condensation products which, when heated alone, reach a relatively high molecular weight but not yet 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 is sufficient to in combination with the plasticizing, oxidatively drying carbon g

Acid resins to give sufficient compatibility, i.e. baked clear lacquer films should be homogeneous, and in the aqueous coating compounds may be used in the processing concentration there is no separation of the binder components.

As thermosetting, hydrophilic, low molecular weight, aminoplast forming Condensation products apply to aldehyde reaction products of compounds which can be reacted with aldehydes such as urea, ethylene urea, dicyandiamide and aminotriazines, such as melamine, Benz.oguanamin, Acatoguanarr.in and Forr.fiu-

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anamin. The aforementioned compounds can be mixed with aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, Furfurol etc. implemented vrsrdsn. Among aldehydes are supposed to aldehyde-forming compounds, such as paraformaldehyde, paraldehyde, trioxymethylene, are also to be understood. More preferred Aldehyde is formaldehyde, the preferred aldehyde-forming 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. The nitrogen-containing polyalcohols are preferred in partially or fully alkylated or alcohol-modified Form for application.

In the present case, the etherification products of the lowest half ethers of glycol and glycol, such as ethyl glycol, ethyl diglycol with the methylol melamines, as already described in the Austrian patent 180 HoJ, have proven themselves well.

Fe Low molecular weight condensation products have a preferred position of melamine with formaldehyde with a melamine-formaldehyde ratio from 1: 4 to 1: 6, which have been almost completely etherified with methanol. There are also suitable ethers partially esterified with dicarboxylic acids containing nitrogen Polymethylol compounds, such as those obtained, for example, by transesterification of hexamethoxymethylmelamine with adipic acid. In stoving enamels according to the invention, 5 to 50 Gaw./S of this Condensation products may be included.

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The percentage in each case relates to the solids content. Combinations are preferably the oxidatively drying carboxylic acid resin in which the condensation product with aminoplastbildende Io -. 3o% by weight is included based on Peststoffgehalte.

Examples of suitable thermosetting, hydrophilic, low-molecular-weight condensation products are phenol alcohols and phenol polyalcohols, ie still low-molecular ones by condensation of mono- and / or polynuclear phenols with aldehydes, such as formaldehyde, acetaldehyde, crotonaldehyde, acrolein, a benzaldehyde, furfural, etc., or compounds that provide formaldehyde, such as Paraformaldehyde, paraldehyde, trioxymethylene, more preferred aldehyde is formaldehyde or a formaldehyde-supplying compound which is obtained in a known manner in an alkaline medium. Suitable phenols are phenols, phenols which are substituted in the ο, ο ', ρ-position but still condensable with formaldehyde, such as cresol, xylenol. Resoles obtained from alkyl phenols, such as propyl, butyl, in particular p-tert-butyl phenol, are particularly useful. Resoles made from binuclear phenols, such as diphenol, ™ bisphenol-A, are also suitable, in particular when about 1.75 to 2.5 moles of formaldehyde have been added per mole of phenol. At the Anvjendunp; The use of a small amount of a strongly hydrophilic solvent such as ethyl glycol, diethyl glycol, propyl glycol, isopropyl glycol or butyl glycol is recommended for the resols.

The resols of phenolcarboxylic acids, which

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can be obtained by condensation of formaldehyde or formaldehyde-supplying compounds with suitable phenol carboxylic acids. Among the condensable with formaldehyde, phenol carboxylic acids, the 4,4-bis ⁽¹ 4-hydroxyphenyl) valeric acid sine preferred position takes. The most favorable results are also obtained here when 1.75 to 2.5 moles of formaldehyde are bound per mole of diphenolic acid. It is advisable to neutralize the phenol carboxylic acid resols, preferably with ammonia, before mixing them with the plasticizing, oxidatively drying carboxylic acid resin. The production of other suitable phenol carboxylic acid resols is described in DAS 1 113 775, for example. The phenol carboxylic acid resols, in particular those based on 4,4-bis- (4-hydroxyphenyl) -valeric acid, are outstandingly suitable for the combinations according to the invention which are intended for use according to the invention as electrophoretically depositable coating compositions and lacquer binders. In the coating compositions and lacquer binders according to the invention, the proportion of hydrophilic phenol resols and / or phenol carbonic acid resols and / or etherified phenol resols and / or etherified phenol carbonic acid resols can be 1 to 5o wt. will amount to, preferably combinations where Io -. 3o% by weight of the phenolic resoles and / or Phenolcarbonsäureresole are included.

In a special embodiment of the coating compositions according to the invention it has been found that in addition to or in place of the phenol resols with lower, monohydric, aliphatic alcohols with 1-4 carbon atoms, such as methanol. Ethanol, pro

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panol, butanol, preferably methanol, etherified phenol resols, in particular alkylphenol resols, can be used as components. The combination of the oxidatively drying carboxylic acid resins with etherified phenolic resols in the coating compound has the advantage of achieving a somewhat higher storage stability of the water-containing coating compounds and of improving the corrosion resistance of the stoved films. The phenol resols already mentioned and phenolcarboxylic acid resols, preferably p-tert-butylphenol resols, which have already been mentioned, can be used as phenol resols for the etherification and can be contained as a component in the coating composition. The degree of etherification and the proportion of etherified phenol resols or phenol resol carboxylic acids in the coating compositions according to the invention are adjusted so that homogeneous films are formed after baking. The proportions between oxidatively drying carboxylic acid resins and thermosetting condensation products, in particular in the case of etherified phenol resols, in the coating compositions according to the invention are between 1 and 50% by weight , the preferred range is 10 to 30% by weight, based in each case on solid resin. i

The stoving enamels combined in this way can themselves be brought together its components are manufactured in the usual way. In general, it is advantageous to use the water-soluble Salts of ammonia or amines or mixtures of ammonia and amines and oxidatively drying carboxylic acid resins with the others Components in the form of concentrated aqueous solutions, which may contain minor amounts of water-soluble organic May contain solvents, mix and then,

109ΪΪ9 / 1884

if necessary, the concentrations and pH of the mixed solutions to the desired values. The pH of the desired solution should generally be appropriate about 7.5-9.0, in particular about 8; if necessary, he can use the resins after a long period of storage Ammonia or organic strong nitrogen bases can be adjusted.

The combined stoving enamels can contain the relevant customary additives, for example minor amounts of water-soluble organic solvents, in the presence of which the components of the stoving enamel have been prepared, and / or other solvents, such as monoalkyl ethers of di- and triethylene glycol, and compounds of hexavalent chromium, such as Ammonium dichromate _s soxvie soluble dyes, pigments, flow improvers, corrosion inhibitors, stabilizers and / or hardening catalysts.

The combined stoving lacquers can be applied to the objects to be lacquered using the usual methods; they are particularly suitable for painting 'sheet metal. It is a special feature of the paints that they can also be deposited on the metal sheets by the electrophoresis process a period of time approximately from Io to δα, preferably approximately from 2o to 6c min »take place,

luftti-o ζ-knenaen lacquers can, if necessary, unc "py ^ i-feiscii

109819/1884

in all cases advantageously as an additional component at least one soluble in the lacquer system, different from the oxidatively drying carboxylic acid resin, in the case of relevant water-thinnable, air-drying paints are common Contain additional resin, whereby when choosing the type and quantity, the compatibility must be taken into account.

Bai the use of the coating compositions according to the invention as The addition of hydroxyl-containing binders has an effect on stoving enamels Compounds, especially those containing hydroxyl groups Amines, preferably polyamines, are favorable. Particularly suitable polyhydroxy polyamines are not in the laid out documents of the German patent application R 41 805 IVc / 22 g. Of these, am best the fully hydroxylated polyamines.

Production of the phenolic resin 1

At p.-tert.-butylphenol 1.5 Get formaldehyde are deposited in aqueous alkaline media in a known manner, the temperature should not überschreiton 70 ⁰ C. The resulting p.-tort.-butylphenol resol is decomposed with sulfuric acid and excess acid and salt present are removed by washing several times with water. The water is then distilled off within as short a time as possible, it being possible, under certain circumstances, to work under vacuum. The resin is kept at 115 to 120 ^° C. until the melting point of approximately 50 to 60 ^° C. is reached.

Production of the phenolic resin 2
The procedure is the same as for the production of phenolic resin 1,

109819/1884

however, nonylphenol is used instead of p.-tert.-butylphenol. In the case of the nonylphenol resin, the condensation is ended as soon as there is no more water due to vacuum distillation · The ilonylphenol resin is viscous at room temperature.

Production of the phenolic resin 3

The same procedure was used for the production of phenolic resin 1, however, bisphenol A was used instead of p-tert-butylphenol and only 1.1 moles of formaldehyde per mole of bisphenol A ^ used. The condensation was ended as soon as a melting point of approx. 100 ° C. had been reached after the water had been completely removed had been.

Example 1 according to the invention

80 parts of phenolic resin 1 are reacted with 12o parts of linseed oil fatty acids by heating at 25o ° C for three hours. At the end of this experiment, the viscosity, when consumed 4o / 5ig in white spirit, is approx. 8o cP / 20 ° C. A sample of this resin is diluted to 50 % with ethylglycol and mixed with aqueous ammonia solution, | loo #ig - based on acid number - neutralized. It is diluted with water to 3o % pest body content. It is siccative with cobalt-containing siccative (Cyclodex 0.1% , cobalt based on pest bodies) and a film with a thickness of 9 μ is drawn with a doctor blade. This film is bone dry in about two hours.

Example 2 according to the invention

33 T of phenolic resin 1 and 66 T of wood oil are kept at 2oc to 2lA until the viscosity drops to 600 to 650 cP /? C " ^J Q

109819/1884 * ° «*» * «.

has risen. The reaction takes place under an inert gas. Ansehliessenä is cooled and reacted at 100 ° C with 5 T propylene oxide. It is kept under reflux for about 2 hours at 100 to 120 ° C. When the reaction has ended, the excess propylene oxide is removed by vacuum distillation. The viscosity is approx. 75o cP / 20 ° C; the saponification number approx. 115. With an excess of 10 to 20 % above the theoretical saponification number, the resin is saponified with potassium hydroxide solution, which has mainly been dissolved in othancl. The saponification takes place under reflux and under a nitrogen atmosphere. After about 3 hours of refluxing, the saponification is complete. ™

It is neutralized with hydrochloric acid diluted 1: 1 with water until the resin precipitates out of the solution. The decomposition water is separated, whereupon the remaining resin solution three times is washed with water. With the neutralization Ammonia, the resin according to Example 2 is suitable as a binder for air-dry, generally water-soluble paints.

Example according to the invention 3

With regard to the drying properties, the bars according to Example 2 can be improved by copolymerization with vinyl compounds. For this purpose, the resin obtained after washing by aseotropic distillation is freed from water by aseotropic distillation. no more water collects, we remove remaining water and uas xylene under vacuum distillation. The Taniperatur icann while on l5o "C anstsi- ^ s. From aera waterproof HaZ ¹ S iällt after verblierenes sodium chloride _from? Obtained by Jil ^ ration ao" etrennt ^ ill. The viscosity btf ^ MSST i8o to 25c Jr ^ Sun ⁰ O ₅ 56 5ig in

White spirit measured.

677 T of this dehydrated resin are mixed with a mixture consisting of: 142 T styrene, 385 T alpha-methylstyrene, 46 T acrylic acid, 2o T di-tert-butyl peroxide added.

The temperature is then kept at 150 to 160 ° C until a solids content of 83 % has been reached (Ig resin is weighed into a metal dish - 8.5 cm in diameter - diluted with 2 ml of ethanol and placed in a drying cabinet at Ho C for one hour dried). The excess monomer is distilled off in vacuo. The viscosity is approx. 250 to 28o cP / 2o ° C measured 1: 1 butyl glycol. A sample of this resin is diluted to 50 % pest body content with ethyl glycol, neutralized 100% with concentrated ammonia solution (based on acid number, 8l, 5) and diluted with water to 1% pest body content. The solution is desiccated with cobalt siccative (Cyclodex), 0.1 % cobalt based on solid resin.

A film drawn on a glass plate with a layer thickness of 90 μ is dust-dry within half an hour. After the film has dried for four days at room temperature, the film can be moistened with a wet cotton ball for four hours without the film becoming cloudy. The pH value of the application solution was 9.5, the viscosity of the Ho £ igen solution was about 1.600 cP / 20 ° Ci after three weeks of storage of the Ho igen solution in a closed vessel at 50 ° C, the pH value 9, 3, the viscosity of the Ho £ igen solution approx. 1,3oo cP / 20 ° C. After a further 21 days of storage, i.e. a total of H2 days of storage at 5o ° C, the pH value was 9.1, <3ie viscosity 1.25o cP / 2o ° C,

1Ö9819 / 1Ö84

Even after 42 days of storage, the film was dust-dry after 30 minutes, also in terms of water resistance after 4 days Air drying at room temperature showed no change. Both at the beginning and after 42 days of storage if the material was 1: oo was s e rl ö s 1 i ch without re-neutralization being necessary.

Example 4 according to the invention

150 parts of the resin dehydrated by the method described in example 3 according to example 2 are treated at 150 ° C. within 2 1/2 hours with a mixture consisting of: 25 parts of 2-ethylhexyl acrylate, 4 l parts of vinyltoluene, 5.7 parts Acrylic acid and 2.4 T di-tert-butyl peroxide and kept at this temperature until the pest body content is approx. 98 % . The pest body content is determined at 100 ° C. The product is diluted to 50 % pest body content with ethyl glycol and 100% neutralized with concentrated ammonia solution (based on theoretical acid number) and adjusted to 40% pest body content with water.

A film drawn from a sample with a layer thickness of 90 μm which had been siccativated with cobalt siccative (Gyclodex) was dust-dry within 3 ° minutes and showed good water resistance after storage for 4 days. The 40 % resin solution had a pH value of 9.3 and was 1: od water-soluble. Despite the incorporation of the 2-ethylhexyl acrylate, this resin also proved to be storage-stable. After 14 days of storage at 50 ° C., the pH had dropped to 9.0, but the solution was clear and 100% water-dilutable. The resin according to the example

109819/1884

4 results in comparison with the resin according to Example 3 films with essential higher elasticity.

Example 5 according to the invention

19o T of the "phenolic resin 2 is reacted with 114 T linseed oil and k ^ S T heating oil at 22o to 23o ° C under inert gas until the viscosity is 2oo to 25o cP / 20 ° C, 66%, measured in white spirit. The The batch is cooled and reacted with 37 ¹ P propylene oxide at 100 ° C. The propylene oxide is fed in at the rate allowed by the reflux distillation

tion to I3o C removes the excess propylene oxide. the After vacuum distillation is complete, the viscosity is 66 liters of white spirit, approx. 18o to 22o cP; the saponification number is 125 - 13o.

600 parts of this resin are saponified with 83 parts of potassium hydroxide, which has been dissolved in 2oo parts of water and 2oo parts of ethanol, under nitrogen at about 90 ° C. for 5 hours. When the hydrolysis is complete, it is acidified with concentrated hydrochloric acid, the resin precipitating out. After the separation water has been separated off, the resin is washed four times with 500 p of water each time. The washed resin is freed from water by azeotropic distillation at approx. 150 ° C. and xylene. After the water has been completely removed, the solvent is stripped off in vacuo. The filtered resin solution has a pest body content of at least 99 % ; the viscosity is approx. 8o to 9o eP / 2o ° C, 66 ySig measured in solid terms «

300 T of this dehydrated resin are at 15c ° 0 Inn & ih

109019/1394

of 2 1/2 hours with a mixture consisting of: 63 parts of styrene, 171 parts of α-methylstyrene, 2o, 5 parts of acrylic acid and 8.5 parts of di-tert-butyl peroxide. The temperature is held until a pest body content of approx. 82 to 83 % is reached. It may be necessary to add 1 part of DI-tert-butyl peroxide at certain intervals.

As soon as the solids content has been reached, the excess monomer is distilled off in vacuo. After vacuum distillation, the solids content is 99.5%, the viscosity is approx. 8o to 9o cP, 50 % ± g dissolved in butyl glycol. λ

The acid number of the resin is 89. A sample of the resin is diluted to 50 % pest body content with ethyl glycol and neutralized with concentrated ammonia solution loc% (based on acid number) and adjusted to ^ o% pest body with water. A film drawn with 90% of a sample drawn with cobalt desiccative (Cyclodex) is dust-dry in about 2 hours. The viscosity of the 40% solution is approx. I3o cP / 2o ° C. The water resistance of the films obtained according to Example 5 is not as high as those films obtained from resins according to Example 3 after drying ^{for 1 J day.}

Example 6 according to the invention

Instead of in the example 2 to 5 carried out with potassium hydroxide saponification of the reaction product of phenol resins and Fettsäureestern the cleavage of these products can also alone with water in the presence of small amounts of any acid which will act catalytically _s performed.

1 09S1§ / 1884

-32- ib69289

375 T of the reaction product from 25o T phenolic resin 1, 15o T linseed oil and 6οο T wood oil, which was brought to a viscosity of approx. 40 cP / 2o ^o C ₅ 2: 1 in ^{white spirit at 23o to 2 1} Io ^{0 C,} are heated with 125 T of dionized water and 3.7 T of para-toluenesulfonic acid in a 1 liter autoclave to approx. This temperature was maintained for about 6 to 8 hours. Thorough mixing of the reaction components was ensured during this period. After 6 hours of saponification, the acid number was Io7. After neutralization with concentrated ammonia solution, the resin could be diluted with water.

Example 7 according to the invention

As in Example 6, the pressure saponification was carried out with concentrated ammonia solution and water. 375 parts of the resin as in Example 6 were mixed with 75 parts of concentrated ammonia solution and 50 parts of water and kept in the autoclave at 100 to Ho ⁰ C for 17 hours. The acid number after this holding time was 50. After addition of ethyl glycol in a ratio of 1: 1 based on the solids contents, the f resin was diluted with water to a solids content of about 2o%. Upon further dilution, the resin was only water-dilutable in the form of an emulsion.

Example according to the invention 8

8o T of the resin solution described in Example 5 with a solids content of 40 % are intimately mixed with 20 T of a 40 % aqueous dispersion obtained by emulsion polymerization of 60 % styrene and 40 % butadiene according to methods known per se. One of one with cobalt siccative

109819/1884

ο, Ι % siccativated sample with 9o μ attached film is dust-dry in approx. 2 hours. The water resistance of the films obtained according to Example 8 is somewhat worse after storage for 4 days than that of the films obtained from the resins according to Example 5, but the elasticity of the films is significantly improved.

Example according to the invention 9

The resin obtained according to Example 5 with a solids content of 40 % is rubbed in a ceramic ball mill with TiC4 pigment (Bayer RM 57) so that the pigment / binder ratio is 1: 1. A high-gloss film drawn with 90 P from a sample which has been siccative with cobalt siccative o, l 'siccative is dust-dry after about 3 hours.

Example according to the invention Io

125 parts of the phenolic resin 1 are reacted with 75 parts of linseed oil fatty acid methyl ester and 300 g of wood oil fatty acid methyl ester at 270 ° C. under an inert gas until the viscosity is measured directly from 75 ° to 850 cP / 20 ° C. The mixture is then cooled to 150 ° C. and a mixture of 4.5 parts styrene, 284 parts α-ethylstyrene and 35 parts acrylic acid with 1.45 parts di-tert-butyl peroxide is added to the product over 21/2 hours. The temperature is maintained until a solids content of approx. 82 - 83 ^ has been reached. The excess monomer is then atdistilled in vacuo. The viscosity is then Ho cP / 20 ° C., 50 % in butyl glycol, the solids _{content is 98.5% and} the saponification number is 14 l.

486 g of the Harros are mixed with a solution of 78 T potassium hy-

109819/1884

saponified hydroxide in 100 T water and 100 T methanol under nitrogen at about 90 ° C for k hours. It is then acidified with concentrated hydrochloric acid, whereupon the resin precipitates. The washing water is separated off and the resin is washed with water until the pH of the washing water is neutral. Then 615 g of the resin are diluted with 80 g of methyl glycol. The solids content of the resin is 98.5%, acid number 129. The product is neutralized with concentrated ammonia 100%, based on the theoretical acid number, and adjusted to a solids content of U0% with ethyl glycol. A sample siccative with cobalt desiccative (Cyclodex) 0.1% and with a layer thickness of 90 μm was dust-dry in 30 minutes.

Example 11 according to the invention:

50 parts by weight of an oxidatively drying carboxylic acid resin, ψ according to Example 5 with a solids content of 99%, are adjusted with butyl glycol to a solids content of 80% by weight, with triethylamine, 100%, based on the acid number, neutralized and with Water adjusted to a solids content of ¹ ^ O wt.%.

109819/1884

A sample drawn on a glass plate gives after Baking for 30 minutes at 170 ° C gives a clear tough film.

Example 12 according to the invention;

80 parts by weight of an oxidatively drying carboxylic acid resin according to Example 5 with a solids content of 99 # with 20 parts by weight of an etherified with n-butanol

ρ -Butylphenolresols mixed, the mixture is diluted with Xthylglykol to a solids content of 8o wt # and with triethylamine, 100 $ strength, based on the acid number, neutralized and washed with water to a solids content of 6o by weight -. adjusted.%.

This coating compound is poured onto a sheet of steel and, after the penetration, results in
a clear hard film.

• and gives after baking] 50 minutes at 170 ^° C

In a particular embodiment, the invention contains Ooerzugmittel as strong organic nitrogen case at least one compound according to the general formula:

i R

2-ί-Ο-

H H "χ H

* Nc- (y) _x - c - ν

^{Η Η R} 1 where the substituents and symbols have the following meanings! Y = CHg-, C ₂ H ₄ -, C 1 -C ₄ Hg-, C 4 Hg-, CH ₂ -N -CHg-J

R ₁ = S-, CH ₅ -, C ₂ H-, CH-COR ^;

^R 2

R ₁ = H-, CH ₃ -, C ₂ H ₅ -, CH ₂ -COR

2 3 2 5
ι

R ₂ = H-, CH ₃ -, C ₂ H ₅ -;

:H

R ₃ = H-, (CH ₂ - CH ₂ - 0 -) _χ -Η, - (CH ₂ - C - 0) _χ - Η and

^{: H} 3 R, = H-, - (CH, - CH, - O) -H, - (CH, - C - 0) - H and

χ = zero or an integer between 1 and 6. Such polyhydroxy polyamines according to the above are preferred general formula obtained by the complete substitution of the hydrogen atoms of polyamines by the 2-hydroxypropyl radical are marked. especially the by exhaustive implementation of dxäthylenetriamine and diethylenetetramine Pclyhydroxypolyamines obtained with propylene oxide.

Example 13:

100 g of the resin according to Example 3 with a solids content of about 98% are diluted with butyl glycol to a solids content of 50%, then ^{mixed with Ν, Ν, Ν 1} , N'-tetrakis (2-hydroxypropyl) ethylenediamine and then mixed with Ammonia completely neutralized. It is then diluted to a solids content of 40% with water. The solution is siccativated with cobalt siccative (Cyclodex), 0.1% cobalt based on solid resin. A film with a thickness of 90 μ drawn on a glass plate is dust-dry after 2 hours.

109819/1884

Claims (1)

Potentanwalt rt * T 2 Hamburg 70 * ^T file: 2091 112. P.O. Box 10914 Tel .: 652 97 07 PATENT CLAIMS 1. Air-drying or stoving, water-thinnable Excess ring at least consisting of: s.) water and / or completely or largely with Water-miscible organic solvents, b) ammonia, or b ¹ ) strong organic nitrogen bases or mixtures ε-us b and b ^f , characterized by the content of at least one oxidatively drying carboxylic acid resin on the basis unsaturated fatty acid, which is resistant to saponification and get ντο r the irt by at least one of the following methods: 1. By heat conversion of at least one phenolic resin (l), with at least one ethylenically unsaturated one Fatty acid (il), with at least 14 carbon atoms, or 2. By heat reaction in stage A ("at least one phenolic resin (I) with at least one ester (III and IV) of ethylenically unsaturated fatty acids, with at least one-ni one-finished and / or polyhydric alcohol and subsequent cleavage of the ester in in stage B and f; if necessary, separation of the released alcohols and any inorganic salts present; or '). L ¹ U ¹ Oh ri ^ U.'U-rurr; Phenolic hydroxyl groups still present in the products according to 1 and / or 2 by reaction. - 1 - 10981Ö / 188A bad original 1b69289 . action with phenolic hydroxyl groups are capable, the reaction of the products obtained according to 2 with the compounds containing oxirane rings, preferably after stage A as stage A-, and the cleavage takes place the ester then takes place. or "By copolymerization of the products according to 1 and / or 2, which in this case preferably takes place after stage A, and / or the products 3> * which in this case preferably _{takes place after stage A 1} , with vinyl (V) and / or vinylidene compounds (VI) in the heat, preferably in the presence of polymerization catalysts; and cleavage of the esters, provided that products according to 2 or 3 were copolymerized in stage A, the copolymerization not taking place until after stage B in the preferred variant. or 5 · By modifying the products according to 1 and / Ό-ler 2, and / or 5, in the latter case also refer to the Stage A or A, can take place and / or the products 4 with cyclopentadiene or dicyclopentadlene (VIl) in the heat; or 6. By heat reaction of at least one phenolic resin (i) with at least one with vinyl (ν) and / or vinylidene compound (VI) in the heat, preferably using polymerization catalysts, copolymerized ethylenically unsaturated fatty acid (il) with at least I ¹ TC- Atoms; or 7 · Γ-by heat reaction of at least one phenolic resin *: (X) - 'with at least one with cyclopentadiene or Bicy ^ Iocontadiene (VIl) Ethyleniron * i £ g-i-.ii-tierter modified in the heat Fatty acid (il) with at least 14 carbon atoms; - 2 109819/1884 bad 166y289 or 8. By heat reaction in stage A of at least one phenolic resin (i) with at least one with vinyl (V) and / or vinylidene compounds (VI) copolymerized esters (III and IV) Ethylenically unsaturated fatty acids (II) with mono- and / or polyhydric alcohols and the following Cleavage of the esters in stage B and optionally Separation of the released alcohols and any inorganic salts present; or ■ 9. By heat reaction in stage A of at least one phenolic resin (l) with at least one with cyclopentadiene or dicyclopentadiene (VIl) modified in heat a Esters (III and IV) of ethylenically unsaturated fatty acids (II) with mono- and / or polyhydric alcohols and the following Cleavage of the esters in stage B and, if appropriate, separation of the alcohols released and, if appropriate inorganic salts present; or 10. Implementation of the products according to 1 to 9 with α, B-ethylenic unsaturated dicarboxylic acids or, if they exist, their anhydrides (VIII) in the heat. 2. Coating compositions according to claim 1, additionally containing at least one which is soluble in the solvent (a) and different from the binders (1 to 10) in stoving enamels and / or air-drying lacquers, water-thinnable synthetic resin commonly used. 3. Coating compositions according to claim 1 or 2, additionally containing at least one soluble in the solvent (a) in the presence of at least one binder (1 to 10) different from the binders (1 to 10) in stoving enamels and / or air-drying enamels 109819/1884 common synthetic resin. " ⁿ fbbyz89 '' Coating compositions according to one or more of Claims 1 to 3, additionally containing at least one aqueous dispersion based on styrene-butadiene copolymers,
Vinyl acetate homopolymers, vinyl acetate-acrylate copolymers and pure acrylate copolymers. 5.Oberzugsmassen according to one or more of claims 1 to Μ-, containing 5 to 50 wt.% Aminoplast-forming
Condensation products. 6L top tensile compositions according to one or more of claims 1 to 5 ₃ containing 1 to 50% by weight of phenolic co-oxidation products. 7.Oberzugsmassen according to one or more of the claims 1 to 6, characterized in that at least one compound is used as the organic nitrogen base in the top coat according to the general formula: R ₉ HH R- I 'i 1 R ₃ -OCC .. CCOR ₁₁ , H H N-C- (Y) -C-N is included, where the substituents and symbols have the following meanings: i ¹
Y = CH ₂ -, C ₂ H ₄ -, C ₃ H ₆ -, -C ₄ H ₈ , CH ₂ -N-CH ₂ -; ^R l = H-, CH ₃ -, C ₂ H ₅ -, CH ₂ -COR ₃ ; 109819/1884 = H-, -CH ₃ , C ₂ H_-, -CH ₂ - C - O - R,; Ϊ2 R ₂ = H-, -CH ₃ -, C ₂ H ₅ -; 2 * = H, -CH, -, ₀ C H, -; ₃ -, C ₂ H ₅ CH-ι 3 R ₃ = H-, -CCH ₂ -CH ₂ -O-) _χ -Η, - (CH ₂ -CO) _x -H and 9 ^Η 3
= H-, - (CH ₂ -CH ₂ -O) _x -H ₅ -CCH ₂ - C - O) H and x = 0 and an integer between 1 and 109819/1884 8. Coating compositions according to claim 1, characterized in: that such oxidatively drying carboxylic acid resins are contained, in which the reaction of the phenolic resins (I) with the fatty acids (II) and / or fatty acid esters (III and IV) at an elevated temperature generally between 200 is carried out to 27O ° C, wherein, in use of fatty acids and polyunsaturated fatty acids Fettsäureglycerxdestern at about 200 to 2 ^{1 0} IO C and using Fettsäureme ± L_ lcr; Irern at about 270 ° C ^ have been implemented. 9) coating compositions according to claim 1, characterized in that such oxidatively drying carboxylic acid resins are contained which as reaction products of phenolic resins and highly unsaturated fatty oils up to a viscosity of about 1000 centipoise / 20 ⁰ C (measured 66% in white spirit) are present. ^ 10) Coating compositions according to claim 1, characterized in that they contain oxidatively drying carboxylic acid resins which are contained as conversion products using fatty acids (II) or fatty acid esters of monohydric alcohols (III), in particular fatty acid methyl esters, these reaction products having a viscosity between 100 and 300 centipoii; ν ti D ⁰ C (measured 50% in butyl glycol). 109819/1884 11) coating compositions according to claim 1, characterized in that such oxidatively drying carboxylic acid resins are included, in the preparation of which by copolymerization according to item M ^ of claim 1 with vinyl and / or vinylidene compounds, the reaction has taken place in the heat, preferably under the action of polymerization catalysts , preferably the reaction with a vinyl or. Vinylidene monomer mixture has been carried out ₉ that in 1800 g at least one acid equivalent (expressed in grams) or for copolymerization with the vinyl or. Has contained vinylidene compounds capable unsaturated carboxylic acid. 12) coating compositions according to claim 11, characterized in that such oxidatively drying carboxylic acid resins contain are, in their manufacture and use of relative weakly polar monomers, such as styrene, α "* methyl-styrene, Vinyltoluene in 1800 g, preferably 2 to 4 acid equivalents have been used. 13) coating compositions according to claim 6, characterized in that " that as a phenoplast-forming con-lensate resols from one Phenol of the general formula
OH where R is an alkyl radical having 2 to 20 carbon atoms or denotes an aryl radical and contains formaldehyde, which is practically anhydrous. 109819/1884 IH Upper slip mass according to claim 13, characterized in that that the phenoplast building is based on p.-tert.-buty! phenol. 15) coating compositions according to claim 13 or 14, characterized in that that the contained phenoplastbxldende condensate an accumulated formaldehyde content of Contains 1 to 2 moles per mole of phenol. 16) coating compositions according to claim 1 number 2, characterized __ marked that the contained drying carboxylic acid resin contains fatty acids from wood oil and / or oiticica oil and / or linseed oil as condensed fatty acids. 109819/1884