DE1745353A1 - Process for the production of water-dilutable synthetic resins in the form of phenoplasts carrying carboxyl groups and water-dilutable synthetic resins obtained by the process - Google Patents

Description

Process for the production of water-soluble synthetic resins in the form of of phenoplasts bearing carboxyl groups and water-diluted oils obtained by the process Synthetic Resins The present invention is concerned with the manufacture of water-soluble resins Synthetic resins based on phenoplasts containing carboxyl groups.

Previous products based on phenoplastics have the major disadvantage that they are not storage-stable in aqueous solution. The pH of the neutralized During storage, the product slips into the acidic area, making it water-insoluble Shares are formed.

In the German Auslegeschrift 1 113 775 is a method for production of essentially neutral, water-based stoving enamels from: I. water-soluble Phenolic resins, II. Plasticizing polyesters with a stature number over about 35, preferably 50 to 70, and numerous hydrophilic groups, which at least consist predominantly of preferably primary hydroxyl groups, III. a strong one water-soluble inorganic or organic nitrogen base and IV. water or a mixture of water and a solvent miscible with this, characterized in that that a relatively low molecular weight resol carboxylic acid is used as component I is, which is a (poly) methylol compound of a phenol carboxylic acid, which is a S§urezahi from about 100 to 250 and in which the total number of all to all free phenol hydroxyl groups nuclear hydrogen atoms in o- or p-position does not differ significantly from two, and that the plasticizing polyester resin (component II) has one gram hydroxyl group per 200 to 400 grams of the resin, previously described. The resole carboxylic acid used in this known process is ethereal over the phenolic hydroxyl group is linked to the carboxylic acid residue, increasing the reactivity the Resolcarbonalure is significantly reduced.

The Belgian patents 537 054 and 537 055 are alkaline Medium soluble phenolic resins are known in which the phenyl nuclei are 4,4-bis (4-hydroxyphenyl) valeric acid are substituted by aliphatic radicals and obtained by reaction with formaldehyde have been.

However, these known water-soluble binders have the disadvantage cannot be used as the sole binder, as this is insufficient are plasticizing.

In the German patent 748 932 is a method for production of curable synthetic resins from curable phenol-aldehyde resins and alcoholic hydroxyl groups containing compounds described, which is characterized in that. 8th the phenol-aldehyde resins with free hydroxyl groups containing, high-boiling or no longer distillable, oily to resinous esters from polybasic Carboxylic acids and polyhydric alcohols or mixtures of monohydric and polyhydric Alcohols with simultaneous or subsequent distilling off of the formed Reaction water heated to temperatures above 70 ° C.

However, such products are not water-soluble since they are not free Contain carboxyl groups and are therefore not suitable for water-soluble coating agents. In addition, only such oxycarboxylic acids or their Esters used in the carboxylic acid residue have free hydroxyl groups, While in the German patent 748 932 esters are used that are not have hydroxyl groups in the carboxylic acid residue but in the alcohol residue. Such products cannot convert the ester formation into water-soluble resin by saponification will.

The present invention relates to a method for producing water-converting ammonia and / or amine salts of new carboxyl groups Phenoplasts that do not have these disadvantages, characterized in that one heat-recoverable phenol-aldehyde condensation products by warming with alidatic Oxycarboxylic acids, preferably oxycarboxylic acid esters, etherified, the condensates with ester groups saponified in an alkaline medium and from this, according to methods known per se, the phenol resin carboxylic acid isolated and this with ammonia and / or strong organic nitrogen bases up added to the desired water thinnability.

The present invention also relates to the new water-dilutable Synthetic resins as such obtained after the process.

The invention also relates to the use of the new phenolic resins as sole binder or binder together with other synthetic resins in pigmented or unpigmented aqueous lacquers or coating compounds for the electrophoretic Application process, with the electrophoretically deposited films at increased Temperature can be burned in.

The invention also relates to the use of the new phenolic resin carboxylic acids as sole binders or binders together with other binders in pigmented or unpigmented water-based paints or coating materials Manufacture of coatings that are baked on at elevated temperatures.

The products according to the invention are in neutral and alkaline medium, can be stored indefinitely, especially in the presence of water.

Among recast phenol-aldehyde condensation products should also Such condensation products are to be understood as heating one relatively alone reach a high molecular weight, but not yet infusible state.

Examples of suitable thermosetting, hydrophilic, low molecular weight Phenol aldehyde condensation products are phenol alcohols and phenol phenol alcohols, i. H. still low molecular weight due to the condensation of mono- and / or polynuclear phenols with aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, Furfural etc. or compounds that provide formaldehyde, such as paraformaldehyde, paraldehyde, Trioxymethylene, products obtained. Preferred aldehyde is formaldehyde or a Formaldehyde-supplying compound obtained in a known manner in an alkaline medium become, such as B.

Hexamethylenetetramine. Suitable phenols are phenol in the o, os, p-position substituted phenols that can still be condensed with frmaldehyde, such as cresol, Xylenol. Resoles derived from alkylphenols such as propyl, butyl, in particular p-tert-butylphenol can be obtained. Resoles are also made of binuclear ones Phenols, such as diphenol, bephenol-A, are suitable, especially when per mole of phenol about 1.75 to 2.5 mol of formaldehyde have been added. When using the Resole recommends the use of a small amount of a strongly hydrophilic one Solvent, such as ethylglycol, Diethylene glycol, propyl glycol, isopropyl glycol, Butyl glycol. It is necessary that at least a part of the phenol-aldehyde condensation products etherified with lower monohydric, aliphatic alcohols with one to four carbon atoms is like methanol, ethanol, propanols, butanols.

As aliphatic mono- and / or dioxycarboxylic acids with 2 to 20 carbon atoms are for example products such as glycolic acid, lactic acid, dimethylolpronionic acid, Ricinoleic acid, oxystearic acid and similar aliphatic monooxyearboxylic acids with 10 to 20 carbon atoms are suitable. These oxyarboxylic acids are preferred as esters with Alcohols with 2 to 6 carbon atoms brought into use, such as methanol, ethanol, propanols, Butanols, pentanols and hexanols.

The most preferred embodiment of the present invention includes the thinning of the heat-treatable phenol-aldehyde condensation products with ricinoleic acid or ricinoleic acid esters or oxystearic acid and similar MonooxyearbonsGuren with 10 to 20 carbon atoms or their esters.

In the preferred embodiment, the ricinoleic acid or the Ricinoleic acid ester and / or oxystearic acid and / or the monooxycarboxylic acids with 10 to 20 carbon atoms or their esters up to 20% by weight due to glycolic acid, lactic acid, and / or dimethylolpropionic acid or its esters.

The above embodiments are characterized in that # the phenolic resin carboxylic acids obtained are well plasticized.

Plasticized phenolic resin carboxylic acids can, however, also be used of glycolic acid, lactic acid, dimethylolpropionic acid or their esters by reaction with the convertible Obtained phenol aldehyde condensation products if these are monovalent with long-chain, saturated and / or unsaturated5 Alcohols with 5 to 30 carbon atoms, preferably 10 to 20 carbon atoms, are etherified.

The proportion of the alkylated phenol-aldehyde condensation product for the oxycarboxylic acid or its ester is chosen in the reaction so that the resulting End product an acid number or a saponification number between 30 and 150, preferably between 30 and 80. This is achieved by the circling of the thermosetting phenol resol with oxyearhonic acid or its esters or mixtures thereof is continued by heating until the etherified condensate has a corresponding Acid or Has reached saponification number. The Umätherung des with volatile monoalcohols etherified phenol resol with the oxycarboxylic acid or its ester takes place in the Way that the conversion is carried out with the addition of acidic catalysts in the heat will. The etherifying alcohol which is split off is preferred by distillation under vacuum. The reaction is continued until the desired Amount of alcohol has been removed by distillation.

Acids or those which split off acids are preferably used as catalysts Use of compounds that are known per se as conversion catalysts, z. B. phosphoric acid, sulfuric acid, boron trifluoride adducts, p-toluenesulfonic acid.

If oxyarboxylic acid esters have been used in the etherification, these must be saponified after the production of the etherified condensate. this is done by adding aqueous or alcoholic solutions of inorganic, strong bases such as caustic soda, potassium hydroxide, calcium hydroxide or Barium hydroxide. After the saponification, the resin carboxylic acid is converted into Freedom set, and the resulting salts must be removed.

This is preferably done by washing out the Harzearaonsture with Water.

The further development of the procedure has the indicator, that the obtained transetheration product after saponification in the aqueous alkaline Environment a) subjected to an azeotropic distillation to separate off the water, then the azeotropic entrainer is removed in vacuo by heating, b) the distillation residue by adding acids, which may be used in organic solvents are converted into the free rosin carboxylic acid, and the added acid is so measures that this largely neutralizes the alkali, but the acid does not but the total alkali content is in excess, c) separates the salt formed, and d) the resin carboxylic acid by adding ammonia and / or strong organic Bases converted into water-soluble products.

The azeotropic distillation is carried out according to methods known per se, around the water from the mixture, consisting of reaction products, after saponification and remove excess alkaline agent. As an azeotropic entrainer Examples include: benzene, toluene, xylene.

After completion of the azeotropic distillation, the residue is through Heating to temperatures of 80-150 ° C., preferably 80-100 ° C., and applying a Vacuum of e.g. B. 12 mm of mercury, freed from the azeotropic entrainer.

The distillation residue obtained in this way, that from the alkali salts the phenolic resin carboxylic acid and excess alkali is mixed with acids, to obtain the free phenolic resin carboxylic acid. It is particularly important here that the added acid is measured in such a way that it largely neutralizes the alkali, but this acid is not present in excess over the entire alkali content. This Obviously, excessive acid must be avoided in order to prevent disturbances in the to avoid electrophoretic application processes. The organic acids here are For example, the following are suitable: formic acid, acetic acid, propionic acid, oxalic acid, Malonic acid, succinic acid, oxalic acid is preferred. As inorganic acids For example, hydrogen chloride, phosphoric acid or sulfuric acid can be used.

If necessary, these acids are dissolved in organic solvents are used, for which, for example, the following are suitable as organic solvents are: ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohols, such as Methanol, ethanol, propanol, glycols such as ethylene glycol, propylene glycol, ethyl glycol, Propyl glycol, butyl glycol, acetone is preferred.

After adding the acid, the batch must be stirred well, thus the implementation of the acid added with the salts of the resin carboxylic acids and the excess alkali takes place completely. It is sufficient at room temperature to work, but it is also possible to implement it by heating it up a little to accelerate, but the temperature must not be chosen so high that undesirable Reactions are triggered. After the implementation is over, the formed must Salt can be separated by filtering or centrifuging.

The electrolyte-free phenolic resin acidic acids are then added of ammonia and / or strong organic bases, such as. B. trimethylamine, triethanolamine, Triisopropanolamine, diglycolamine, diethylamine, piperidine, pyridine, morpholine, diethanolamine, N-dimethylethanolamine, N-methylethanolamine, converted into their salts.

Strong organic bases should be secondary or tertiary Amines are understood to have at least a pH value in 50% aqueous solution of 9 reach. It is not necessary to use the carboxyl groups of the phenol resin carboxylic acid to neutralize completely, but it is enough to use as much ammonia and / or amine admit that the products are at least water-dilutable.

When choosing the aliphatic oxyarboxylic acids or their esters is the use of ricinoleic acid, oxystearic acid and similar monooxycarboxylic acids with 10 to 20 carbon atoms or their esters are particularly advantageous because the resulting Phenolic resin carbonic acids through the ricinoleic acid residues. other monooxycarboxylic acids internally plasticized with 10 to 20 carbon atoms. When using other Murzkettiger of aliphatic oxycarboxylic acids with 2 to 6 carbon atoms, it is advisable to use plasticizing Components to be used. The use of alcohols is particularly suitable for this with 10 to 20C atoms, such as e.g. B. lauryl alcohol, myristyl alcohol, palmityl alcohol, Stearyl alcohol, linseed oil alcohol, soybean oil alcohol. Monohydric alcohols with 6-30 carbon atoms, preferably 10-20 carbon atoms, can either together with the aliphatic oxycarboxylic acids be introduced into the etherified phenolic resin by ether, or else their incision 1n the resin takes place together with the etherification of the phenol resin. Pas quantity ratio These alcohols to the etherified phenolic resins depend on the desired elastic properties of the end product.

The new water-dilutable resins obtained by the process according to the invention Phenolic acids can be used as sole binders in aqueous coating agents be used.

Also mixtures of the new water-thinnable phenolic resin carboxylic acid with other water-thinnable resins are possible.

It is particularly noteworthy that the new water-thinnable phenolic resin carboxylic acids have a previously unknown storage stability even in aqueous alkaline solution.

The phenolic resin carboxylic acid, which according to the process of the invention are also suitable for electrophoretic deposition. Here The products plasticized internally with RicinolsSure are particularly suitable because this creates relatively elastic coatings. If especially nicely plasticized Resin carboxylic acids are required, those resin carboxylic acids are preferred which in addition to ricinoleic acid, the monohydric alcohols with 6-30 carbon atoms already mentioned contained ethereally bound. If the products for electrophoretic coating are to be used, the viscosity of the products should be between 95 and 235 cP, measured at 25 ° C 1: 1 in butyl glycol, move.

The pH of the aqueous solution should be between 7 and 9, preferably between 7 and 8. It is best to use a small amount of a hydrophilic Solvents to be used, such as ethyl glycol, diethyl glycol, propyl glycol, isopropyl glycol, Butyl glycol.

When using the products prepared according to the invention for Conventionally applied water-based paints, the viscosity range is not as substantial, because the processing viscosity of the solvent additive is adjusted can.

Preferred embodiment of the culer stand from conversion products with the following structure: A p.-tert.-butylphenol resol, which per mole of phenol Contains 1 mole of glycolic acid and 1 mole of linseed oil fatty alcohol. The acid number is 100-105, the viscosity is preferably 95-235 cP (1: 1 in butylglycol 20 ° C).

The same product with scja oil fatty alcohol instead of linseed oil fatty alcohol built up.

The same product made with stearyl alcohol instead of soy fatty alcohol.

The above products are made with lactic acid instead of glycolic acid.

Reaction product from 1 mole of p.-tert.-butylphenol resol, which per 1 mole of phenol contains 1 mole of glycolic acid and 1 mole of lauryl alcohol. The product has a Acid number of 120 and a preferred viscosity between 95-235 cP (1: 1 in Butyl glycol measured at 20 ° C).

A bisphenol A resole with a formaldehyde charge of approx. 2, which per mole of phenol 1 mole of glycolic acid and 1 mole of soya oil alcohol are bound in an ethereal manner contains. The acid number of the product is about 90. The preferred viscosity is between 95-235 cP (measured 1: 1 in butyl glycol at 20 ° C).

The same product made with linseed oil alcohol instead of soybean oil alcohol.

Diesel products made with lactic acid instead of glycolic acid.

A phenol resol based on bisphenol A, which is charged with formaldehyde of about 3, 5-3, 8 and which per mole of resole 1 mole of glycolic acid and 1 mole Linseed fatty alcohol contains ether-like bonds, with the remaining methylol groups at least are partially etherified with butanol. The S acid number is 70-80, the preferred one Viscosity 95-235 cP (measured 1: 1 in butyl glycol at 20 ° C).

The same product as above, but with 2 moles of linseed fatty alcohol and 1 mole of glycolic acid per mole of resole instead of 1 mole of linseed oil fatty alcohol. The product has an acid number of 50-60 and a preferred viscosity of 95-230 cP (measured 1: 1 in butyl glycol at 20 ° C).

The same products with soybean oil fatty alcohol instead of linseed fatty alcohol built up.

The same products made with lactic acid instead of glycolic acid.

Manufacturing instructions for thermosetting, etherified phenol-formaldehyde condensation products Etherified phenol resol 1,500 parts of p-tert-butylnhenol resol are used with such Amounts of methanol added that the water content of the reaction mixture, based on Methanol, is not more than 20% by weight. Then with concentrated hydrochloric acid adjusted to a pH value of 1 and heated to 60 ° C for 2 to 3 hours. Of the The solid grain content of a neutralized sample increases by approx. 2-3%. After that, will the methanol is distilled off in vacuo, the temperature not exceeding 60.degree shall be. The reaction mixture is washed twice with water to remove the excess Remove SSure. The mixture is then vacuumed up to an internal temperature concentrated from 100 ° C. The pest content of the etherified resole is 92% by weight.

The "butylphenol resol used" is prepared as follows been : 60 p-tert-butylphenol and 80 g of 30% strength by weight aqueous formaldehyde solution react with each other under the action of strong alkalis in a known manner at 40 ° C, until the level of free formaldehyde has dropped to almost zero. With the help of stronger Acids, the resol is broken down and washed salt-free with water.

Etherified phenol resol 2686.5 g of p-tert-butylphenol resol dehydrated in vacuo to 90 ° C., then 1650 g of n-butanol and 835 g of toluene are added. The mixture is heated to boiling and the water by azeotropic distillation removed, the solvent mixture being returned to the reaction vessel. After about 40 g of water have been removed, 8 g of 85% strength by weight phosphoric acid are added and continue the azeotropic distillation until no more water passes over, then the acid is neutralized with calcium hydroxide added in solid form. The product is concentrated in vacuo to a temperature of 110 ° C and then filtered.

The solids content is approx. 92% by weight.

Etherified phenol resol 3 209 g bisphenol A and 365 S 30% by weight 82.5 g of 40% strength by weight sodium hydroxide solution are added to formaldehyde. The mixture is kept at 30 ° C until the formaldehyde charge is approx. 3. 7. Then the resol is decomposed with dilute hydrochloric acid and treated several times Washed electrolyte-free with water. It will 738 g n-butanol and 370 ß toluene added. After adding 5 g of phosphoric acid, an azeotropic Circular distillation carried out, with the solvent back in the mixture is returned. The distillation is continued until there is no water more passes. Then the phosphoric acid is neutralized with calcium hydroxide and the mixture concentrated in vacuo. The solids content of the resol is approx. 92% by weight.

Example 1 309 g of the etherified phenol resol 2.525 g of ricinol only methyl ester and 1 g of p-toluenesulfonic acid are mixed. The mixture is under vacuum up heated to a temperature of 150 ° C. The reaction is continued at 150 ° C until until 110 g of distillate have passed over. The etherified condensate becomes aqueous Potash lye saponified and then acidified with dilute sulfuric acid. That Resin is carefully removed from electrolytes and from by washing several times with water Excess acids freed, then the resin is with as much triethylamine added until the pH value reaches 8. The resin. is indefinitely indestructible in water. The aqueous solution is suitable for electrodeposition.

Example 2 360 g of etherified phenol resol 3 and 300 g of ricinoleic acid methyl ester were with the addition of 0.5 gt p-toluenesulfonic acid under vacuum for so long at 100-110 ° C heated until the viscosity is 120-130 eP (1: 1 measured in butylglycol at 20 ° C) amounts to. The saponification number is 92. The product is treated with 5N aqueous sodium hydroxide solution saponified and with the Acidified equivalent amount of 5N sulfuric acid. Then enough triethylamine is added to the resin until the pH reaches 8 Has. The resin is infinitely dilutable with water and for electrophoretic purposes Suitable for deposition.

Example 3 360 g of etherified phenol resol 3, 300 g of ricinol acid methyl ester and 260 g of soybean oil fatty alcohol are added with 0.5 g-p-toluenesulfonic acid under Vacuum heated to 100 to 110 ° C until the viscosity is 120-130 cP (1: 1 measured in butyl glycol at 20 ° C). The saponification number is 67. The product is saponified with -5 N sodium hydroxide solution and with the equivalent amount of 5 N sulfuric acid acidified. Then enough triethylamine is added until the pH is 8. The product can be diluted indefinitely with water and is added when stoved 170 ° C for 30 minutes on iron sheets highly elastic coatings.

Example 4. The procedure is as in Example 1, but this is etherified phenol resol 2 replaced by 250 g etherified phenol resol 1. The received The product can be diluted indefinitely with water and is highly elastic when stoved Coatings.

The invention also relates to the use of the new condensates in water-thinnable binders and / or coating agents as the sole binder or in a mixture with such binders for stoving enamels. A preferred use The new condensate is used as a sole binder or mixed with other binders in electrophoretic separable coating compounds The coating compositions used according to the invention can be unpigmented or pigmented and / or containing fillers can be used. For example, you can click Wood, concrete, masonry, plaster or iron and steel as well as non-ferrous metals, with or without pretreatment such as passivation, phosphating, electrochemical treatment, Zinc plating, tinning or other metallization by various processes including the electrophoretic method of application. Pigments and / or fillers are for example - without limiting the invention thereby - iron oxide red, Ru # black, Lead silicon chromate, strontium chromate, BlancFix, micronized barite varieties, microtalk, colloidal chalk, diatomaceous earth, china clay, titanium dioxide, chrome oxide green and others.

The use of strongly basic pigments, such as zinc oxide, zinc chroma, Lead carbonate, basic lead sulfate, red lead or calcium plumbate requires an exact Test. These pigments can tend to thicken or to kiss. The ratio the pigment to the binder depends on the type of pigment used and the suggested use. In most cases this will be the pigment to binder ratio 0.5: 1 to 2: 1. Only with the electrophoretic application can the The pigment retention can also be less than 0.5% by weight.

The coating compositions used according to the invention must be used with increased Temperature can be burned in. When used as stoving enamels, admixing of water soluble or at least hydrophilic low molecular weight aldehyde condensation products, such as B. Phenolresclen or aminoplast-forming condensation production, advantageous be.

The mixing of the new water-soluble precondensate resins with relatively low molecular weight, at least hydrophilic, thermosetting resins Condensation products, such as aminoplast-forming reaction products and / or phenol resols and / or etherified phenol resols cause greater crosslinking of the stoved Pull-in masses 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 warming that are heated alone, a relatively high molecular weight, but not yet reach infusible state. It is also not absolutely necessary that the admixed condensate products by themselves have solubility in water ; it is only necessary that their hyclronhilic character be sufficient to combine with the new water-soluble precondensate resins, which may have a plasticizing effect to give sufficient tolerance, d. H. Baked clear lacquer films should be homogeneous, and in the aqueous topcoat 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, for example, to aldehyde reaction products of such compounds that can be reacted with aldehydes, such as urea, ethylene urea, dicyandiamide and aminotriazines such as melamine, benzoguanamine, acetoguanamine and formguanamine. The aforementioned compounds can be mixed with aldehydes such as formaldehyde, acetaldehyde, Crotonaldehyde, acrolein, benzaldehyde, furfural, etc., are implemented. Among aldehydes aldehyde-forming compounds such as paraformaldehyde, paraldehyde, trioxymethylene, be understood. Preferred aldehyde is formaldehyde, the preferred Aldehyde-forming compounds are melamine and urea. The implementation takes place in the Uhlichen molar ratios, e.g. B. with urea resins in a usual formaldehyde molar ratio from 1: 1.5 to 1: 4, in the case of melamine resins in a formaldehyde molar ratio of 1: 1.5 to 1: 6.

The nitrogen-containing polyalcohols come preferably in partial or fully alkylated or alcohol-modified form for use.

In the present case, the ethereal products have also done well the lowest half ethers of glycol and diglycol, such as ethylglycol, ethyldiglycol proven with the methylolmelamines, as already mentioned in the Austrian patent specification -180 407 are written.

Low molecular weight condensation products have a preferred position of melamine with formaldehyde with a melamine-formaldehyde ratio of 1: 4 up to 1: 6, which have been almost completely etherified with methanol. It suit also partially esterified ethers of nitrogen-containing polymethylol compounds with dicarboxylic acids, how they z. B. obtained by transesterification of hexamethoxymethylmelamine with adipic acid will. 5 to 50% by weight of these can be used in stoving enamels used according to the invention Condensation products may be included.

Preferred water-dilutable melamine condensation products, which are im Mixture with the new condensates of the present invention as Uherzursmittel can be used are those that are etherified by reacting with alcohols Aminotriazine-formaldehyde condensation products that are at least 1 mole volatile Alcohol residue contained in the ether bond, with alinatic hydroxycarboxylic acid esters have been obtained by heating and those in French patent specification 1 544 219 have been written. The percentages relate to the solids content. To be favoured Combinations of the new condensate in which the aminoplast-forming condensation product with 10 - 30% by weight, based on solids content, is included.

The stoving enamels combined in this way can be put together its components are produced in the usual manner. In general it is advisable to the water soluble salts of ammonia or amines or mixtures of ammonia and Amines and the carboxylic acid resins according to the invention with the other components in Form of concentrated aqueous solutions, the possibly minor amounts may contain water-soluble organic solvents, mix and then, if necessary, adjust the concentration and pH of the mixed solutions set the desired values. The pH of the desired solution should in general expediently about 7.5-9.0, in particular about 8; if necessary, can after a longer storage period of the resins with ammonia or strong organic nitrogen bases be adjusted.

The combined stoving enamels can contain the relevant customary additives included, e.g. B. minor amounts of water-soluble organic solvents, in the presence of which the components of the stoving enamel have been produced, and / or other solvents, such as monoalkyl ethers of di- and triethylene glycol, and compounds of hexavalent chromium, such as ammonium dichromate, as well as soluble dyes, pigments, Leveling agents, anti-corrosion agents, stabilizers and / or curing catalysts.

The combined stoving enamels can be made using the usual Methods applied to the objects to be painted; they are suitable especially for painting sheet metal. Here it is a particular advantage of the paints, that they can also be deposited on the metal sheets using the electronhoresis method. The enamels can be stoved at temperatures from about 80 to 200, preferably from about 100 to 180 ° C and depending on the baking temperature over a period of time about 10 to 80, preferably about 20 to 60 minutes.

The lacquers can be used advantageously in practically all FR1 oils as an additional component of at least one soluble in the paint system The precondensation resin is different for the relevant water-thinnable stoving enamels Usual additional resin included, with the selection according to type and amount on the Compatibility is to be observed.

When using the synthetic resins according to the invention as a binder for stoving enamels, the addition of compounds containing hydroxyl groups has an effect, especially amines containing hydroxyl groups, preferably polyamines, are favorable.

In a special embodiment, the coating agents according to the invention contain at least one compound according to the general formula as a strong ormanic nitrogen base: where the substituents and symbols have the following meanings: x = zero or an integer between 1 and 6.

Such polyhydroxypolyamines according to the above are preferred general formula obtained by the complete substitution of the hydrogen atoms of Polyamines are characterized by the 2-hydroxypropyl radical. In particular the through exhaustive implementation of diethylenetriamine and diethylenetetramine with propylene oxide obtained polyhydroxypolyamines.

The preparation of the aforementioned polyhydroxypolyamines is in French patent 1,497,222.

Example 5 The resin described in Example 2 was de-metered with Water diluted to 40% by weight solids content and placed in a ceramic suction mill with a pigment mixture of iron oxide red (BAYER 510 F) and basic lead silicochromate (Oucor M 50) rubbed off in a ratio of 9: 1 that the pigment / binder ratio Is 0.6: 1. The paste is mixed with water to a solids content of 10 wt diluted. The solution is poured into a steel basin 10 x 10 x 18 cm and placed in it are passivated sheets (Bonder 1025/5 Metallgesellschaft) by applying a DC electrical voltage at constant voltage in the range between 100-120 V coated for 2 minutes. The sheets are then baked at 170 ° C. for 30 minutes. The result is smooth, sufficiently elastic upper layers.

Example 6 The rosin carboxylic acid, which was prepared according to Example 1, is neutralized with N, N, N ', N', N ', -Pentakis- (2-hydroxypropyl) - diethylenetriamine, until the aqueous solution has a pH of 8. An advantage of this resin is, because the coating agents made with this water-thinnable synthetic resin can be applied in thick layers and this even with rapid heating can be baked in without splashing paint material.

Example 7 The procedure is as in Example 6, but by adding neutralized by N, N. N ', N', N ", N" -hexakis- (2-hydroxypropyl) -triethylenetetramine. The same effects are produced from it when the is burned in Coating agent, as described in Example 6, achieved.

Example 8 The resin carboxylic acid obtained according to Example 2 is neutralized with N, Na N'-, N'-tetrakis- (2-hydroxypropyl) -ethylenediamine, until the aqueous solution has a pH value of 8 (measured in 20% aqueous Solution).

The resin can be mixed with water in any proportion. With deionized Water is adjusted to a solids content of 60% by weight. Made from it Coating agents can be applied in thick layers and by rapid heating can be baked in without the paint material being splashed.

Example 9 The resin solution neutralized with triethylamine according to the example 1 is diluted with deionized water to a solids content of 40% by weight. The solution is rubbed off in a ball mill with a pigment / binder ratio of 0.8: 1. The solution is then diluted to the desired viscosity with butanol brought and applied by dipping or spraying on iron sheet. After-burn-in 30 minutes at 170 ° C. result in clear, hard, elastic coatings.

Example 10 The procedure is as in Example 9, but the resin solution is used according to Example 2. Similar results are obtained.

Example 11 The procedure is as in Example 9, but the resin solution used according to Example 4. Similar results are obtained.

Example 12 The procedure is as in Example 5, but the resin solution is used according to Example 4. Similar results are obtained.

Example 13 The procedure is as in Example 5, but the resin solution is used according to Example 1. Similar results are obtained, Example 14 Die Resin solution, obtained according to example 2 according to the invention, is made with hexamethoxymethylmelamine (Cymel 300 Cyanamid) mixed in a weight ratio of 8: 2. The solution is with Deionized water to a solids content of 40 wt .-% and then diluted rubbed off in a ball mill in a ratio of 1: 0.8 with titanium dioxide. The solution is diluted to the desired viscosity with butanol and sprayed or Dipping applied to sheet iron. After baking, give 150 ° C for 30 minutes hard, relatively light-colored coatings.

Example 15 309 g of the etherified phenol resol 2, 260 g of linseed oil fatty alcohol, 132 g of butyl glycolate and 1 g of paratoluene sulfonic acid are mixed. The mixture is heated to a temperature of 150 ° C to about 60 g. Distillate passed are.

It is saponified with aqueous potassium hydroxide and then with the acidified equivalent amount of dilute sulfuric acid. The precipitated resin will Carefully freed from electrolytes by washing several times with water and then so much triethylamine is added until the pH has reached 8. The resin is Can be diluted indefinitely with water.

Example 16 The procedure is as in Example 15, but instead of Linseed oil fatty alcohol Soya oil fatty alcohol is used. The cooking will as indicated in Example 15 carried out.

Example 17 The procedure is as in Example 15, but instead of 260 g of linseed oil fatty alcohol 260 g of stearyl alcohol are used.

The cooking is carried out as indicated in Example 15.

Example 18 The procedure is as in Example 15, but the Butyl glycolate replaced by ethyl lactate. Instead of 132 g of butyl glycolate 132 g of ethyl lactate are used.

In a special embodiment of the invention, the after the process according to the invention produced water-thinnable synthetic resins based on phenoplasts containing carboxyl groups mixed with new types Amino resin products used as binders for stoving enamels. These new amino resin products are obtained by aromatic and / or hydroaromatic epoxy compounds, which contain at least two epoxy groups in the molecule, by heating with amino resin products precondensed, a) using amino resin condensation products which and / or contain aliphatic mono- and / or dicxycarboxylic acid esters bound in ethereal fashion b) the precondensate with an aliphatic mono- and / or dioxycarboxylic acid and / or preferred. the esters of which are etherified by heating, c) the precondensates according to a) or b) saponified with ester groups in an alkaline medium - and the resin carboxylic acid therefrom isolated. d) and these with ammonia and / or ntarkon organic nitrogen bases Hardened to the desired water dilutability. Making this new Amino batch products is in French patent 1,594 114 described in detail. Example 19 shows one embodiment of this binder combination.

Example 19 A) Preparation of a new amino resin product: 95 g of hexamethoxymethylmelamine and 250 g of an epoxy resin with an epoxy equivalent weight of 230 to 280, a refractive index of 1.5830 and a viscosity of 500 - 1000 cP at 20 ° C, 70% in butyl glycol measured, which in a known manner by alkaline condensation obtained from bisphenol A with epichlorohydrin are mixed together. To this end, 2 g of a 50% strength methanolic solution of benzyltrimethylammonium hydroxide are added given. The mixture is kept under an inert gas at 130 ° C until the viscosity 120 cP, measured at 20 ° C. 2: 1 in butyl glycol. Then 300 g of ricinoleic acid methyl ester and 3 g of paratoluenesulfonic acid were added. The product is heated to 160 ° C. in vacuo and held until the viscosity is 100 to 105 cP, measured at 20 1: 1 in butyl glycol. The resin has a saponification number of 85. Then that will Product saponified with 5 normal aqueous sodium hydroxide solution, with the equivalent Amount of 5 n-sulfuric acid neutralized and the resin by washing several times with Electrolytes are carefully removed from the water. So much triethylamine is then added until the pH has reached 7.5 to s. The resin is unlimited bordered in the water dilutable and is suitable for electrophoretic deposition.

B) Production of the stoving enamel: The resin solution obtained according to Example 4 will with. the amino resin product solution prepared according to A) in a ratio of 8: 2 mixed. The mixture is made with deionized water on a ceramic ball mill rubbed off with titanium dioxide Kronos RM 59 (titanium company) so that the pigment / binder ratio Is 0.5: 1. Paste is never made to a solid content with deionized water diluted by 10% by weight. This solution is then given under those given in Example 5 Electrophoretically deposited conditions. After baking at 150 ° C during Hard, smooth coatings result for 30 minutes.

In a further special embodiment of the invention, the Resins according to the invention with novel ammonia or amine salts of precondensates a mixture of carboxyl group-bearing phenoplasts and epoxy resins combined, the new carboxyl group-bearing precondensates being obtained by a process have been, which is characterized in that aromatic and / or hydroaromatic Enoxide compounds that contain at least two epoxide groups in the Melekül through Rumen precondensed with thermosetting phenol-aldehyde condensation products, using a) such thermosetting phenol-aldehyde condensation products which Oxycarboxylic acid esters contain ether-like bound, and / or 1)) the precondensate with an oxycarboxylic acid and / or preferably its ester around ether, c) the PrScondensates saponified according to a) or b) with ester groups in an alkaline medium, then the Resin carboxylic acid isolated, d) and this with ammonia and / or strong organic Nitrogen bases are added until the desired water dilutability is achieved.

The manufacture of these new carboxyl group-bearing phenoplasts is described in detail in French patent 1,594,115.

Example 20 A) Preparation of a new carboxyl group-bearing precondensate a) Production of the etherified phenolic resol as the starting product. Etherified phenolic resol 2,686.5 g of p-tert-butylphenol resol are dehydrated in vacuo to 90 ° C, then 1650 g of n-butanol and 835 s of toluene are added. The mixture will boil heated and the water removed by azeotropic distillation, the solvent mixture is returned to the reaction vessel. After removing approx. 40 g of water 85% strength by weight phosphorus acid is added for 8 seconds and the azeotropic distillation is carried out continued until no more water can be filmed, then the acid is with in Calcium hydroxide added in solid form is neutralized. The product is in vacuum concentrated to a temperature of linos and then filtered.

The solids content is approx. 92% by weight. b) Preparation of the precondition 155 g of etherified phenol resol 2, 78 g of an epoxy resin with an epoxy equivalent weight from 230 to 280, a refractive index of 1.5830 and a viscosity of. 500-1000 cP measured at 25 ° C, 70% in butylglylol, which in a known manner by alkaline Condensation of bisphenol A with epichlorohydrin was obtained, and 3 g of a 50 Qew .-% strength methanolic solution of benzyltrimethylammonium hydroxide are mixed. The mixture is heated to 140 ° C. for 2 hours. The viscosity is then 190 cP, measured at 20 ° C 2: 1 in butyl glycol.

There are 120 g of ricinoleic acid methyl ester and 4 g of paratoluene sulfonic acid added and the product is heated at 140 ° C under vacuum until 53 g Distillate have passed. The viscosity of the product is 920 cP, measured at 20oC 1: 1 in butyl glycol, and the saponification number is 90. The product will saponified with 5N sodium hydroxide solution, acidified with the equivalent amount of 5N sulfuric acid, and the water is removed from the mixture by azeotropic distillation with xylene. The product is then filtered. So much triethylamine is then added until the pH value of 8 is reached. The xylene is removed in vacuo. The emerging clear resin is indefinitely soluble in water; it has an acid number of 80 and a Viscosity of 230 cP, measured at 20OC 1: 1 in butyl glycol. It is for the electrophoretic Deposition can be used and results in hard, elastic coverings after baking.

B) Production of the stoving enamel: The one obtained according to Example 4 Resin solution is mixed with the precondensate solution containing carboxyl groups obtained according to A) mixed in a ratio of 8: 2. The solution is made up to 40% by weight with deionized water Solids content diluted and on a ceramic XugelmUhle with a pigment mixture made of Eisenexy -red. (Bayer 510 F) and basic lead silica chromate (Onkor M 50) im Ratio 9: 1 abraded so that the pigment / binder ratio is 0.8: 1 The paste is brought to the desired viscosity by diluting with butanol. It is applied to sheet iron by brushing, dipping or spraying. To Baking for 30 minutes at 170.degree. C. results in hard, smooth coatings with very good corrosion resistance.

Example 21 The resin solution obtained according to Example 1 is with the Phenoplast, which is described under A) in Example 20, mixed in a ratio of 7: 3. The mixture is mixed with deionized water to a solids content of 40 wt .-% diluted. The solution is mixed with a pigment mixture of iron oxide red (Bayer 510 F) and basic lead silica chromate (Onkor M 50) in a ratio of 9: 1 so rubbed that the pigment / binder ratio is 0.5: 1. The solution is made with water diluted to 10% by weight solids content and among those specified in Example 5 Conditions deposited. After baking for 30 minutes at 130 ° C hard, smooth coatings with very good corrosion resistance.

Example 22 340 g of etherified phenol resol 2 70 g of dimethylolpropionic acid are mixed and heated under vacuum to 150 - 160 ° C and held until until approx. 100 g of distillate (butanol) have passed. The product then has a viscosity of 150 cP measured 1: 1 in butyl glycol at 20 ° C and an acid number of 90.

The product is diluted to 8N% solids with isopropyl glycol. The neutralized resin can be diluted with water without limitation at pH 8.5.

It is used as the sole binder for electrophoretic coating less suitable, but is ideally suited as a hardening additive to be plasticized Electrophoresis resins.

Claims (15)

Claims 1) Process for the production of ammonia and / or Amine salts of new phenoplasts containing carboxyl groups, characterized in that that thermosetting phenolaldehyde condensation products can be produced by heat treatment with aliphatic Mono- and / or dioxycarboxylic acids, preferably their esters, etherified, the tondensates saponified with ester groups in an alkaline medium, the etherified phenolic resin earhonic acid separated by methods known per se and the separated phenol resin carbonic acid with ammonia and / or strong organic nitrogen compounds up to the desired water dilutability offset. 2) Method according to claim 1, characterized in that as Mono --- uride / or dioxycarboxylic acids, preferably with 2 to 20 carbon atoms, or their Esters, glycolic acid, lactic acid, dimethylolpropionic acid and preferably richinoleic acid, Oxystearic acid and similar aliphatic monooxycarboxylic acids with 10 to 2n carbon atoms used, the esters preferably esterified with alcohols having 1 to 6 carbon atoms can be used. 3) Method according to one or more of the preceding claims, characterized in that when using short-chain Oxycarbcnsäuren with 2 to 6 carbon atoms as etherifying agents as plasticizing component monoalcohols with 10 to 20 carbon atoms are also used. 4) Method according to one or more of claims 1 to 3, characterized characterized in that richnelic acid or ricinelic acid ester is used as the oxycarboxylic acid and this up to 29 wt .-% by glycolic acid, lactic acid and / or dimethylelpronionic acid or their ester is replaced. 5) Method according to one of claims 1 to 4, characterized that one uses such thermosetting phenol aldehyde condensation products with long-chain, saturated and / or unsaturated, monohydric alcohols with 6 to 30 carbon atoms, preferably 10 to 20 carbon atoms, are etherified. 6) Method according to one or more of claims 1 to 5, characterized characterized in that the oxycarboxylic acid or its ester is used in such amounts that the end product has acid numbers between 3n to 150, preferably 3n to 80. 7) Further development of the method after one or more. reren of claims 1 to 6, characterized in that the obtained Umätherungsprdukt after saponification in an aqueous alkaline medium a) an azeotropic distillation to separate the water, then the azeotropic entrainer removed in vacuo by heating, b) the distillation residue by adding Acids that are dissolved are converted into the free resin carboxylic acid and thereby the added acid such that it largely neutralizes the alkali, but this acid is not in excess of the total alkali content, c) that which is formed Salt separates, and d) the resin carboxylic acid by adding ammonia and / or strong organic bases converted into water-soluble products. 8) Method according to one or more of the preceding claims, characterized in that at least one compound having the general formula as the strong organic nitrogen base: is used, where the substituents and symbols have the following meanings: xs zero or a whole number between 1 and 6 and where those polyhydyoxypolyamines according to the above general formula, which are obtained by complete substitution of the hydrogen atoms of polyamines by the 2-hydroxyproyl radical, have been preferred, in particular those obtained by the exhaustive reaction of diethylenetriamine and diethylenetetramine with propylene oxide obtained polyhydroxypolyamines. 9) New resins available according to one or more of the claims 1 to 13 described procedures. 10) Use of the resins according to claim 9 as the sole binder in Stoving enamels. 11) Use of the resins according to claim 9 as the sole binder in Baths for the electrophoretic application process. 12) Use of the resins according to claim 9 mixed with other binders for stoving enamels. 13) Use of the resins according to claim 9 in a mixture with others Binders for the electrophoretic application process. 14) Use of the resins according to # claim 9 mixed with water-thinnable etherified aminotriazine-formaldehyde condensation products, alcohols and aliphatic Hydroxycarboxylic acids contain ether-like bound. 15) Use of the resins according to claim 9 mixed with water-dilutable resins etherified aminotriazine-formaldehyde condensation products, the alcohols and aliphatic Hydroxycarboxylic acids contain ether-like bound and with aromatic and / or hydroaromatic epoxy compounds containing at least two epoxy groups contained in the molecule, connected by PrScondensation.