DE1928931B2 - METHOD OF MANUFACTURING WATER DILUTABLE MODIFIED POLYAETHERS - Google Patents

Description

Thermosetting synthetic resins based on condensates from compounds containing epoxy groups and phenolic resins, dissolved in organic solvents, have proven themselves as binders for interior protection of containers, but also extremely well-proven for primers (see P a q u i n, »Epoxy compounds und Epoxyharze ", p. 388, Springer-Verlag Berlin / Göttingen / Heidelberg 1958).

Previous water-thinnable synthetic resins have the major disadvantage that they are not in aqueous solution are stable in storage. The pH of the neutralized products slips into the acidic area during storage from, whereby water-insoluble parts are formed.

The object of this invention is to provide such water-soluble synthetic resins available that are in characterized by extraordinary stability in an alkaline environment.

The invention therefore relates to a process for the preparation of water-dilutable modified ones Polyethers, characterized in that one

a) aromatic and / or hydroaromatic, optionally hydroxyl-containing epoxy compounds, as they are by etherification of a dihydric hydroaromatic alcohol and / or obtained a bisphenol with epihalohydrins or dihalohydrins in the presence of alkali be, or reaction products from the epoxy compounds thus obtained with mono- and / or polyalcohols with 1 to 20 carbon atoms in a straight or branched chain, the ratio from epoxy groups of the compounds containing epoxy groups to the OH groups of the mono- and polyalcohols between 1: 1 to 1: 1.5 and where the OH groups of the mono- or polyalcohols are primary or secondary,

b) hydrophilic, low molecular weight, thermosetting condensation products of mononuclear and / or binuclear Phenols with aldehydes,

c) aliphatic mono- and dioxycarboxylic acids with 2 to 20 carbon atoms or their esters with alcohols of 1 to 6 carbon atoms together by heating or reacting component a) with component b) and this intermediate product then with component c) Reacting heating, or by first reacting components b) and c) with one another by heating and then reacting this intermediate product with component a), the ratio between phenolic OH groups and epoxy groups between 1: 0.5 and 1: 2 and The temperature at the poly etherification is 100 to 150 ⁰ C and the etherification reaction is catalyzed in the usual way and the etherification reaction is catalyzed in the usual way and the etherification or transetherification with the oxycarboxylic acid or its ester by heating is continued until the resulting carboxylic acid resin has an acid or the carboxylic acid ester resin has a saponification number between 30 and 150,

d) the carboxylic acid ester resin is saponified and the addition of acids after the saponification Contains carboxylic acid resin,

e) the carboxylic acid resin by adding ammonia and / or organic nitrogen bases to the transferred water-dilutable form.

In the Austrian patent specification 244 910 a method for coating an anode in one electrical circuit described which a bath of an aqueous medium in electrical contact with comprises an anode and a cathode, wherein it is indicated as a label that one in this Bath dispersed a film-forming paint containing a polycarboxylic acid resin which at least partially is neutralized with a water-soluble amino compound and through this circuit direct current

ίο passes through with a voltage in the range of 50 to 500 volts and thereby electrically deposits the film containing this resin on the anode. Canadian patent 730 133 describes a process in which the pH value of such electrophoretic baths is kept constant by using unneutralized synthetic resin as a replenisher for the electrophoretic bath. French Patent 1,356,236 claims a process in which the pH is kept constant in electrophoretic baths by placing a dialysis membrane around the cathode, which prevents the accumulation of free amines in the anode compartment. Belgian patent 662 280 claims a process in which the pH value in electrophoretic baths is kept constant by introducing a cation exchange membrane into the bath, which prevents the accumulation of amines in the anode compartment.
British Patent 1 102 384 describes a process for the preparation of polar melamine-formaldehyde resins in which a melam containing alkoxy groups is reacted in-formaldehyde condensation product with transetherification with an oxycarboxylic acid to form a polyether. However, the polyether carboxylic acid described in this patent is unsuitable as the sole binder for electrophoretic deposition and must be mixed with another synthetic resin for plasticization. However, the synthetic resins obtained in the present invention are useful as the sole binder. The Dutch laid-open specification 6 606 824 describes a water-soluble amino resin which is obtained by reacting urea or melamine-formaldehyde condensation products containing alkoxy groups with oxicarboxylic acids with transetheration. This product is also not suitable as the sole binder for electrophoretic deposition. French patent 1,473,569 describes a condensation product of a melamine-formaldehyde resin bearing alkoxy groups with a polyfunctional hydroxycarboxylic acid. This product is also not suitable as the sole binder, but is deposited together with alkyd resins during electrophoretic deposition. In contrast, the synthetic resins produced according to the invention are suitable as sole binders for electrophoretic deposition and painting. The plasticizing polyethers used in reaction stage a), which carry hydroxyl and optionally also epoxy groups, are either

1) as reaction products of compounds containing epoxy groups, optionally also containing hydroxyl groups with mono- and / or polyalcohols with 1 to 20 carbon atoms in a straight or branched chain and / or cycloaliphatic and / or aromatic and / or heterocyclic mono- or polyalcohols or

2) directly as compounds containing hydroxyl and epoxy groups.

The embodiment belonging to item 1) can optionally also contain epoxide groups compounds containing hydroxyl groups are used, for example, to build up the reaction products will:

Polyethers with epoxy groups, such as those produced by the etherification of a dihydric hydroaromatic alcohol or diphenol, with epihalohydrins or dihalohydrins, e.g. B. with epichlorohydrin or dichlorohydrin in the presence of diphenols such as resorcinol, pyrocatechol, hydroquinone, 1,4-dihydroxinaphthalene ·. Bis - (4 - hydroxiphenyl) - methane, bis (4 - hydroxiphenyl) - methyl - phenyl methane, bis (4 - hydroxiphenyl) - toluylmethane, 4,4 '-dihydroxidiphenyl and 2,2 - bis (4 - hydroxiphenyl -) - propane, derive.

The ίο general formula comes from polyethers containing epoxy groups

CH ₂ -CH - CH ₂ - (O - R ₁ - O - CH ₂ - CHOH - CH ₂ ) "- O - R ₁ - O - CH ₂ - CH - CH ₂

O O

Here, R ₁ denotes a hydroaromatic or aromatic carbon radical and η = zero or a small number up to 10.

Particularly noteworthy are polyethers of the general formula containing epoxy groups

CH ₂ -CH-CH ₂ -I ΟΧ / '
O \

CH ₃

C- / XO-CH ₂ -CHOH-CH ₂ I

CH _a

CH ₃

CH ₃

0-CH ₂ -CH-CH ₂

which contain 2,2-bis- (4-hydroxiphenyl) propane as the starting compound, of which in turn are preferred such polyethers having a molecular weight between about 380 and about 3500 can be used.

The other components for building up the reaction products are mono- and polyalcohols with 1 up to 20 carbon atoms; Examples include methanol, ethanol, propanols, butanols, pentanols, hexanols, Fatty alcohols such as linseed oil alcohol, soybean oil alcohol, stearic alcohol, diols such as ethylene glycol, propylene glycol, Butylene glycol, hexylene glycol, neopentyl glycol, also trimethylolethane, trimethylolpropane, Pentaerythritol, glycerin and similar products.

The aromatic and / or hydroaromatic epoxy groups which may also carry hydroxyl groups Connections are made with the mono- or polyalcohols converted to the reaction products in such a way that a polyetherification takes place. the Reaction components are selected so that when using relatively low molecular weight short-chain compounds containing epoxy groups, long-chain mono- and polyalcohols for conversion are used, such as linseed oil alcohols, soybean oil alcohol or, for example, hexylene glycol. on the other hand are preferred in the conversion of high molecular weight long-chain compounds containing epoxy groups short-chain mono- and polyalcohols used The ratio of epoxy groups to those bearing epoxy groups Connections to the OH groups

the mono- and polyalcohols should be between 1: 1 to 1: 1.5. The OH groups of the used Mono- or polyalcohols should preferably be primary or secondary. Alcohols with tertiary OH groups are not suitable for the implementation.

The etherification reaction becomes organic in a known manner by means of catalysts, for example boron trifluoride Tin compounds or trimethylbenzylammonium hydroxide.

As the one according to subsection 2) directly as hydroxyl and

Products which can be converted into compounds containing epoxy groups come as aromatic and / or hydroaromatic optionally hydroxyl-containing epoxy compounds, polyethers with epoxy groups, as they are produced by the etherification of a divalent hydroaro-

matic alcohol and / or a bisphenol with epihalohydrins or dihalohydrins, e.g. B. Epichlorohydrin or dichlorohydrin, can be obtained in the presence of alkali. These connections can be derived from diphejiols such as resorcinol,

Pyrocatechol, hydroquinone, 1,4-bis-hydroxynaphthalene.

The general formula comes from polyethers containing epoxy groups

CH ₂ - CH - CH ₂ - (O - R ₁ - O - CH ₂ - CHOH

CH ₂ ) ^ - OR ₁ -O-CH ₂ -CH-CH ₂

Here, R ₁ denotes a hydroaromatic or aromatic carbon radical and η = zero or a small number up to 10. Particularly noteworthy are polyethers of the general formula containing epoxy groups

CH ₂ -CH-CH ₂ -I O- <

CH ₃ / -0-CH ₂ - \ CHOH-CH ₂ I. -CH-CH ₂ —V ~ \ / \ /
0 CH ₃ CH ₃
> - C— / ^) - O-CH ₂ - CH ₃

where η = zero or a small number up to 10, and which contain 2,2-bis- (4-hydroxyphenyl) propane as starting compound, of which in turn those polyethers with a molecular weight between about 380 and about 3500 are preferably used.

For coating compositions which can be deposited electrophoretically, those are preferred as starting materials Polyethers with a molecular weight of 380 to about 2000. There are also those with a higher molecular weight suitable, these also result in highly corrosion-resistant films, but it is difficult to obtain high layer thicknesses to achieve. For water-thinnable coating compounds that are applied by conventional application methods be applied, such as dipping, spraying, flooding, pouring, painting, polyethers with higher Molecular weight preferred, but the molecular weight should not exceed the starting polyether.

Among phenol-aldehyde condensation products bearing methylol groups those condensation products are also to be understood, which alone heated a relatively high molecular weight, but not yet reach infusible state.

Examples of suitable thermosetting, hydrophilic, low molecular weight condensation products bearing methylol groups of the formula already explained are phenol alcohols and phenol polyalcohols, d. H., still low molecular weight by condensation of mononuclear and / or polynuclear phenols with aldehydes, such as Formaldehyde, acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural or formaldehyde-supplying compounds products obtained such as paraformaldehyde, paraldehyde, trioxymethylene. Preferred aldehyde is formaldehyde or a formaldehyde-supplying compound that is known in an alkaline medium Ways to be obtained such. B. hexamethylenetetramine.

Suitable phenols are phenol in the O, O '- p position substituted phenols such as cresol and xylenol which can still be condensed with formaldehyde. very good Resoles obtained from alkylphenols such as propyl-, butyl-, especially p-tert-butylphenol, are suitable will. Resoles 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.

It is very advantageous that at least a part of the phenol aldehyde condensation products with lower monohydric, aliphatic alcohols with 1 to 4 carbon atoms are etherified, such as methanol, ethanol, Propanols, butanols.

As oxicarboxylic acids c) are aliphatic mono- and dioxicarboxylic acids, preferably with 2 to 20 carbon atoms, suitable, for example glycolic acid, lactic acid, dimethylolpropionic acid, ricinoleic acid, oxistearic acid, Oxicaproic acid and similar aliphatic monooxicarboxylic acids with 10 to 20 carbon atoms.

These aliphatic mono- or dioxicarboxylic acids can also be used as esters with alcohols having 1 to 6 carbon atoms such as methanol, ethanol, propanols, butanols, pentanols and hexanols are used. the The polyethers can be prepared by first adding an etherified phenol-aldehyde condensation product with a mono- or dioxicarboxylic acid or its ester with the addition of a catalyst in the Heat, preferably under vacuum, is reacted until the etherification alcohol is split off the desired amount of oxicarboxylic acid residue, bound ethereally, has occurred.

When using the free mono- or dioxicarboxylic acids in the reaction as catalysts can act, working through suitable reaction conditions is to ensure that the transetheration product not gelled by undesired esterification of the carboxylic acid group, i.e. the proportions and the response time must be carefully coordinated. This can generally be achieved be by one

1. the reaction temperature in polyetherification does not choose too high, d. H. preferably below 120 ° C holds,

II. Polyetherification with the addition of an acidic catalyst, for example phosphoric acids or p-toluenesulfonic acid, carries out,

III. In the polyetherification, preference is given to using such an aliphatic oxicarboxylic acid whose carboxyl group does not tend to esterify due to steric hindrance, e.g. B. dimethylol propionic acid.

When the aliphatic oxycarboxylic acid esters are used for the same purpose, such Difficulties do not arise. The unetheration product is then used alone and / or in combination with a phenol-aldehyde condensation product of the general formula already mentioned with the plasticizing ones Polyethers that carry hydroxyl and possibly also epoxy groups are polyetherified. Here-

It should be noted that if the free oxicarboxylic acids are used, the plasticizing polyether If possible, should not carry any epoxy groups, since otherwise the polyetherification will result in undesirable esterification cannot be excluded with sufficient certainty. But it can also be an etherified phenol-aldehyde condensation product of the general formula already mentioned, preferably alone and / or in a mixture with non-etherified phenol-aldehyde condensation products, with the plasticizing hydroxyl groups, if necessary, also epoxy group-bearing polyethers be polyetherified, and the intermediate product is then with an oxicarboxylic acid or its ester etherified with elimination of the ethereal alcohol by heating. When using the oxicarboxylic acids as an etherification agent, care must be taken to ensure that the products do not gel like this has already been explained earlier.

The quantitative ratio of phenol resol to polyether can vary within wide limits. In general, the ratio between phenolic OH groups and epoxy groups is chosen between 1: 0.5 and 1: 2. The Polyverätherung takes place between 100 and 150 ⁰ C, the temperature being preferably of 120 to 130 ⁰ C. The polyetherification can be accelerated by adding catalysts. Examples of suitable catalysts of this type are boron trifluoride, p-toluenesulfonic acid and phosphoric acids. The duration of the polyetherification depends on the desired final viscosity. The quantitative ratio of component c to components a and b is chosen so that the resulting end product has an acid number or a saponification number between 30 and 150, preferably between 30 and 80. This is achieved in that the etherification or transetherification with the oxicarboxylic acid or its ester is continued by heating until the end product has reached a corresponding acid number or saponification number. The etherification of the etherified phenol resol or the intermediate product with the oxicarboxylic acid or its ester is carried out in such a way that the etherification is carried out with the addition of acidic catalysts under heat. The etherifying alcohol which is split off is removed by distillation, preferably under vacuum. The reaction is continued until the desired amount of alcohol has been removed by distillation. The catalysts used are preferably acids or acid-releasing compounds which are known per se as transetheration catalysts, e.g. B. phosphoric acids, sulfuric acid, boron trifluoride adducts and p-toluenesulfonic acid. If oxicarboxylic acid esters have been used in the transetherification, these must be saponified after the production of the end product. This is done by adding aqueous or alcoholic solutions of inorganic, strong bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide or borium hydroxide. After the saponification, the addition of acid sets free the carboxyl groups and the resulting salts have to be removed. This is preferably done by washing out the resin with water. The further development of the process is characterized by the fact that the obtained transetherification product is obtained after saponification in an aqueous alkaline medium

e) subjected to an azeotropic distillation to separate the water, then the azeotropic Entrainer removed in a vacuum by heating,

f) the distillation residue is converted into the free resin carboxylic acid by adding acid, which may be dissolved in organic solvents, and the acid added is measured in such a way that it largely neutralizes the alkali, but this acid is not present in excess of the total alkali content,
g) separating the salt formed and

h) the resin carboxylic acid by adding ammonia and / or strong organic bases in water-soluble Products transferred.

The azeotropic distillation is carried out according to methods known per se to remove the water to remove the mixture. The mixture contains the reaction products formed by saponification and excess alkaline agent.

Examples of possible azeotropic entrainers are: benzene, toluene, xylene.

After completion of the azeotropic distillation, the residue is heated to temperatures of 80 to 150 ⁰ C, preferably 80 to 100 ° C, and applying a vacuum of z. B. 12 mm of mercury from the azeotropic drag center].

The distillation residue thus obtained, which consists of the alkali metal salts of the resin carboxylic acid and excess alkali, is mixed with acids in order to obtain the free resin carboxylic acid. It is particularly important here that the acid added is measured in such a way that it largely neutralizes the alkali, but that this acid is not present in excess of the total alkali content. This excess of acid must obviously be avoided in order to avoid disturbances in the electrophoretic application process. Organic acids are preferred for neutralization. The following are, for example, suitable organic acids: formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid; oxalic acid is preferred. As inorganic acids, for. B. usable: hydrochloric, phosphoric or sulfuric acid.
These acids are optionally used dissolved in organic solvents, for which the following are suitable as organic solvents, for example:

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, and butyl glycol. Preferred becomes acetone.

Inorganic acids are preferably used dissolved in organic solvents. To the addition of the acid, the batch must be thoroughly stirred so that the implementation of the added Acid with the salts of the resin carboxylic acids and the excess alkali takes place completely. It is sufficient to work at room temperature, but it is also possible to reduce the reaction by a small amount To accelerate heating, however, the temperature must not be chosen so high that undesirable Reactions are triggered. After the reaction has ended, the salt formed must be separated, for example by nitration or centrifugation.

The electrolyte-free end products that no longer contain epoxy groups are then added

109 522/374

of ammonia and / or strong organic nitrogen bases, such as B. trimethylamine, triethanolamine, triisopropanolamine, üiglykolamin, diethylami ^ piperidine, Pyridine, morpholine, diethanolamine, η-dimethylethanolamine, N-methylethanolamine, in their salts convicted.

Under strong organic nitrogen bases, secondary or tertiary amines are to be understood to mean at least reach a pH of 9 in 50 ° / _o aqueous solution. It is not necessary to completely neutralize the carboxyl groups of the end product; it is sufficient to add enough amine for the products to be at least dilutable with water.

When selecting the tricarboxylic acids or their esters, the use of ricinoleic acid or their esters are advantageous, as the resulting end products are internally plasticized by the ricinoleic acid residues will.

The obtained by the inventive method new water-thinnable polyether resins can be used as sole binders in aqueous coating agents be used. Mixtures of the new water-thinnable polyether resins with other water-thinnable ones Resins are possible. It is particularly noteworthy that the new water-thinnable Polyether resins have a previously unknown storage stability even in aqueous alkaline solution.

The products that are obtained by the process according to the invention are also suitable for the electrophoretic one Suitable for deposition. Here, those with ricinoleic acid and / or oxistearic acid and similar can be used aliphatic monooxicarboxylic acids with 10 to 20 carbon atoms internally plasticized products are suitable be, since this results in relatively elastic coatings, especially if as component a) the Products according to section 2 have been used. In case the products for electrophoretic coating are to be used, the viscosity of the products should be between 95 and 235 cP Move 1: 1 in butyl glycol at 25 ° C. This can be achieved once by using as component a) a correspondingly high molecular weight polyether is used, or by the fact that the reaction with the component b) is continued until the desired final viscosity is reached.

The pH of the aqueous solution should be between 7 and 9, preferably between 7 and 8. It recommends to use a small amount of a hydrophilic solvent such as ethyl glycol, diethylene glycol, Propyl glycol, fsopropyl glycol, butyl glycol. When using the manufactured according to the invention Products for conventionally applied paints, the viscosity range is not so important because the processing viscosity of the solvent additive can be adjusted. Of course the resins must always remain soluble in suitable solvents.

According to the preferred embodiments of the method of the invention, the following are made Process products received:

1. The polyether of an epoxy resin having an epoxide equivalent 230-280, a refractive index of 1.5830 and a viscosity of 500 to 1000 cP at 20 ⁰ C 70 ° / _o strength measured in butylglycol, which in a known manner by alkaline condensation of bisphenol A was obtained with epichlorohydrin, with p.-tert-butyldimethylolphenol, which is etherified with methanol or ethanol or propanols or butanols or mixtures of these components and which contains 0.81 mol of ricinoleic acid in ether-like bonds per mole of butylphenol, the ratio between the epoxide groups and the phenolic hydroxyl groups is 1: 1. The viscosity of the preferred polyether is in the range zwisehen 95 and 235 cps, measured at 20 ⁰ C, 1: 1 in butyl glycol, the acid number of between 50 and 80th

2. The polyether of the epoxy resin described above, made of a phenolic resin based on bisphenol A, with a formaldehyde charge of about 2, which is etherified with methanol or ethanol or propanols or butanols or mixtures of these alcohols and which is 1.5 per mole of phenol resol Contains mole of ricinoleic acid bonded like an ether, the ratio between the epoxy groups and the moles of phenol resol is 1: 1. The phenolic resole has a viscosity of 95-235 cP, measured at 20 ⁰ C 1: 1 in butyl glycol, and an acid number zwisehen 90 and 110th

3. The polyether of the epoxy resin described above with a phenol resol based on bisphenol A with a formaldehyde charge of about

3.5 to 3.8, which is etherified with methanol and ethanol or propanols or butanols or mixtures of these alcohols, and which contains 1.5 to 1.7 moles of ricinoleic acid per mole of phenol resol. The PoIyäther has a viscosity 95-235 cP, measured at 20 ⁰ C 1: 1 in butyl glycol, and an acid number between 80 and 100.

4. The polyether of the epoxy resin described above with the tertiary butylphenol resol described above, which contains 1 mole of butyl glycolate ether-like per mole of phenol resol. The polyether has a viscosity between 95 and 235 cP, measured 1: 1 in butylphenol at 20 ^° C., and an acid number between 100 and 120.

5. The polyether of the epoxy resin described above with 1 mol of a tertiary butylphenol resol, which contains 2 moles of ricinoleic acid bound in ethereal fashion per mole of phenol resol, and 1 mole of one Tertiary butylphenol resol, which is etherified with methanol or ethanol, the ratio between the epoxy groups and phenolic hydroxyl groups is 1: 1. The polyether has a viscosity between 95 and 235 cP and an acid number between 50 and 80.

6. The polyether of the epoxy resin described above with 1 mole of a phenol resol based Bisphenol A with a formaldehyde charge of about 2, which is 2 moles of ricinoleic acid per mole of phenol resol contains ether-like bound, and part of a phenol resol based on bisphenol A with a Formaldehyde charge of about 2 which with methanol or ethanol or propanols or butanols or mixtures of these alcohols is completely etherified.

7. The polyether of the epoxy resin described above with p.-tert-butyldimethylolphenol, wel-

clies contains 2 moles of ricinoleic acid bound ether-like per mole of phenol, the ratio between the epoxy groups and the phenolic hydroxyl groups being 1: 1. The viscosity of the polyether is between 95 and 235 cP, measured at 2O ⁰ C 1: 1 in butyl glycol, the acid number between 100 and 120.

The invention also relates to the use of the modified polyether resins in water-thinning

binders and / or coating agents as sole binders or in a mixture with other binders for stoving enamels. A preferred use of the new polyether resins is in use as Sole binder or in a mixture with other binders in electrophoretically depositable coating compounds.

The synthetic resins used according to the invention can be unpigmented or pigmented and / or Containing fillers can be used. You can, for example, on wood, concrete, masonry, or plaster also iron and steel as well as non-ferrous metals, with or without pretreatment such as passivation, Phosphating, electrochemical treatment, galvanizing, tinning or other metallization after various methods, including electrophoretic application, can be applied. Pigments and / or fillers are, for example - without limiting the invention thereby - iron oxide red, Soot black, lead silicon chromate, strontium chromate, blanc fix, micronized barite varieties, microtalk, colloidal chalk, diatomaceous earth, china clay, titanium dioxide and chromium oxide green.

The use of strongly basic pigments such as zinc oxide, zinc chromate, lead carbonate, basic lead sulphate, red lead or calcium plumbate requires careful examination. These pigments can tend to thicken or precipitate. The ratio of pigment to binder depends on the type of pigment used and the proposed use. In most cases the pigment to binder ratio will be 0.5: 1 to 2: 1. Only for the electrophoretic application of the pigment content can / ₀ ° are also less than 0.5.

The synthetic resins used according to the invention have to be stoved at an elevated temperature. When used as stoving enamels, water-soluble or at least hydrophilic substances can be added low molecular weight aldehyde condensation products, such as. B. phenolic resols or aminoplast-forming Condensation products, be advantageous.

The mixing of the new water-soluble polyethers with relatively low molecular weight, at least hydrophilic, thermosetting condensation products such as aminoplast-forming reaction products and / or Phenol resols and / or etherified phenol resols, causes a higher degree of cross-linking of the baked-in Coating compounds and thus a further improvement in their technical coating properties, such as hardness, gloss and corrosion protection.

Thermosetting is also to be understood as meaning those condensation products which. heated alone, reach a relatively high molecular weight, but not yet infusible state. It is also it is not absolutely necessary that the admixed condensation products have solubility in water on their own exhibit; it is only necessary that their hydrophilic character be sufficient to be used in combination with the new water-soluble polyether acid resins which may have a plasticizing effect are sufficiently compatible to yield, d. That is, stoved clearcoat films should be homogeneous and in the aqueous coating compositions There must be no separation of the binder components in the processing concentration.

Aldehyde reaction products are considered to be thermosetting, hydrophilic, low molecular weight, aminoplast-forming condensation products of 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 and furfural are implemented. Aldehydes should also include aldehyde-forming Compounds such as paraformaldehyde, paraldehyde and trioxymethylene are to be understood. The preferred aldehyde is formaldehyde, the preferred aldehyde-forming compounds are melamine and Urea. The reaction takes place in the usual molar ratios, e.g. B. with urea resins in one usual formaldehyde molar ratio of 1: 1.5 to 1: 4, with melamine resins in a formaldehyde molar ratio from 1: 1.5 to 1: 6. The nitrogen-containing polyalcohols are preferably partially or completely alkylated or alcohol-modified form for use.

In the present case, the etherification products are also good the lowest half ethers of glycol and diglycol such as ethyl glycol or ethyl diglycol Proven with the methylolmelamines, as already described in Austrian patent 180 407 have been described.

Low molecular weight condensation products of melamine with formaldehyde have a preferred position with a melamine-formaldehyde ratio of 1: 4 to 1: 6, which is almost completely etherified with methanol have been. Ethers of nitrogen-containing polymethylol compounds partially esterified with dicarboxylic acids are also suitable, how they z. B. obtained by transesterification of hexamethoxymethylmelamine with adipic acid will. When used in baking enamels, 5 to 50 percent by weight of these condensation products can be added be included in them.

Preferred water-dilutable melamine condensation products that are mixed with the new polyether resins of the present invention can be used as a coating agent, are those that by Reaction of aminotriazine-formaldehyde condensation products etherified with alcohols, the Contains at least 1 mol of volatile alcohol residue in the ether bond, with aliphatic hydroxycarboxylic acid esters by heating and in French patent 1,544,219 are described.

The percentage in each case relates to the solids content.
Combinations of the new polyether carboxylic acid resin in which the aminoplast-forming condensation product is contained in 10 to 30 percent by weight, based on the solids content, are preferred. The stoving enamels themselves combined in this way can be produced in the usual way by bringing their components together. In general, it is advantageous to mix the water-soluble salts of ammonia or amines or mixtures of ammonia and amines and the eneuen polyether carboxylic acid resins with the other components in the form of concentrated aqueous solutions, which may contain minor amounts of water-soluble organic solvents, and then if necessary to adjust the concentrations and pH of the mixed solutions to the desired values. The pH of the desired solution should in general expediently be about 7.5 to 9.0, in particular 8; If necessary, he can after a long period of storage of the resins with ammonia or

organic strong nitrogen bases can be simulated.

The combined stoving enamels can contain the relevant customary additives, eg. B. subordinate 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, also compounds of hexavalent chromium, such as ammonium dichromate and soluble ones Dyes, pigments, flow improvers, anti-corrosion agents, Stabilizers and / or curing catalysts.

The combined stoving enamels can be applied to the enamels to be painted using the customary methods Objects are applied, they are particularly suitable for painting sheet metal. Here it is A particular advantage of the paints is that they are deposited on the metal sheets even after the electrophoresis process can be. The stoving of the paint can occur with

R ₂ H

R ₃ -O-CC

H H \

Temperatures approximately from 80 to 200, preferably approximately from 100 to 180 ^° C. and depending on the stoving temperature in a time span approximately from 10 to 80, preferably approximately from 20 to 60 minutes. The lacquers can optionally and practically in all cases advantageously contain as an additional component at least one additional resin which is soluble in the lacquer system and different from the polyether resin and is customary in the case of relevant water-thinnable stoving lacquers, the type and amount being selected for compatibility.

When using the coating compositions prepared according to the invention as binders for stoving enamels the addition of compounds containing hydroxyl groups, especially those containing hydroxyl groups, has an effect Amines, preferably polyamines, favorably. In a particular embodiment, they contain according to the invention produced coating agent as a strong organic nitrogen base at least one compound

ao according to the general formula

MR,'

C —C —O —R, '

/ HH

where the substituents and symbols have the following meanings:

Y is - CHr, - C ₂ H ₄ -, - C ₃ H ₆ -, - C ₄ H ₈ -, - CH ₂ - N - CH ₂ -;

R ₂

R ₁ is H, CH ₃ , C ₂ H ₅ , CH ₂ - C - O - R ₃ ;

H
R ₂

R ₁ 'is H, Ch ₃ , C ₂ H ₅ , CH ₂ -COR ₃ ;

H
R ₂ is H, CH ₃ , C ₂ H ₅ ;

R ₂ 'is H, CH ₃ , C ₂ H ₅ ;

CH,,

R ₃ is H, (CH ₂ - CH ₂ -O- ) _x - H, | CH ₂ -CO -H

H J _x

CH ₃ \ R ₃ 'is H, (CH ₂ -CH ₂ -O) ₂ -H, (CH ₂ - CO - H

H J _x and
χ means zero or an integer between 1 and 6.

Those polyhydroxypolyamines according to the above general formula, which are preferred complete substitution of the hydrogen atoms of polyamines by the 2-hydroxypropyl radical are. In particular the exhaustive conversion of diethylenetriamine and diethylenetetramine polyhydroxypolyamines obtained with propylene oxide. The manufacture of the above Polyhydroxipolyamines are described in French patent 1,497,222.

Manufacturing instructions for thermosetting, etherified Phenol-formaldehyde condensation products

Etherified phenolic resole 1

500 g of p-tert-butylphenol resol are mixed with such amounts of methanol that the water content of the reaction mixture, based on methanol, is not more than 20 percent by weight. The pH is then adjusted to 1 with concentrated hydrochloric acid and the mixture is heated ^{to 60 ° C. for 2 to 3 hours.} The solids content of a neutralized sample rises by about 2 to ^3% · is then distilled off in vacuo the methanol, the temperature of 60 ⁰ C should not be exceeded. The reaction mixture is washed twice with water to remove the excess acid. Subsequently, the mixture in vacuum is concentrated up to an internal temperature of 100 ⁰ C. The solids content of the etherified resol is 92%.

The butylphenol resol used was produced as follows:

60 g of p-tert-butylphenol and 80 g of 30% aqueous formaldehyde solution are allowed to ^{react with one another in a known manner at about 40 °} C. under the action of strong alkalis until the free formaldehyde content has fallen to almost zero. With the help of strong acids, the resol is broken down and washed salt-free with water.

Etherified phenolic resole 2

686.5 g p-tert-Butylphenolresol be dehydrated in vacuum to 90 ⁰ C, then 1.1650 g of n-butanol and 835 g of toluene added. The mixture is heated to the boil and the water is removed by azeotropic distillation, the solvent mixture being returned to the reaction vessel. After about 40 g of water have been removed, 8 g of 85% phosphoric acid are added and the azeotropic distillation is continued 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 HO ⁰ C and then nitrated. The solids content is about 92 percent by weight.

Etherified phenolic resole 3

209 g of bisphenol A and 365 g of 30 ° / ₀ sodium formaldehyde are added to 82.5 g of 4O ° / cent sodium hydroxide solution. The mixture is kept at 30 ^° C. until the formaldehyde charge is about 3.7. The resol is then broken down with dilute hydrochloric acid and washed free of electrolytes by repeated treatment with water. 738 g of n-butanol and 370 g of toluene are added. After the addition of 5 g of phosphoric acid, an azeotropic circulation distillation is carried out, the solvent being returned to the mixture. The distillation is continued until no more water passes over. The phosphoric acid is then neutralized with calcium hydroxide and the mixture is concentrated in vacuo. The solids content of the resol is about 92%.

example 1

300 g of an epoxy resin with an epoxy equivalent weight of 450 to 525 and a viscosity of 100 to 17OcP. measured at 25 ⁰ C, 40% in butyl diglycol, which was obtained in a known manner by condensation of 2.2- (p.-oxy) phenyl propane with epichlorohydrin is charged with 160 g of etherified phenolic resole 2 mixed. The mixture is ^{kept at 150 °} C. for 2 hours. Then 1 g of a 50% solution of 85% phosphoric acid in isobutanol and 280 g of ricinoleic acid are added. The mixture is heated under vacuum at 140 to 150 ⁰ C and retains 50% in butyl glycol at 25 ° C at this temperature until the viscosity measured, is 260 to 300 cP. The product is then diluted to a solids content of 80% with isopropyl glycol, and triethylamine is added until the pH is 8.5. It is then diluted with water to a solids content of 40%. The aqueous solution has a very long shelf life and can be used to refill electrophoretic baths.

Example 2

309 g of the etherified phenol resol 2, 525 g of ricinoleic acid methyl ester and 1 g of p-toluenesulfonic acid are mixed. The mixture is heated up to a temperature of 150 ^{° C. under vacuum.} The reaction is continued at 15O ⁰ C for so long until HO g of distillate passed. 72.5 g of this intermediate are with 62.2 g of an epoxy resin having an epoxide equivalent 230-280, a refractive index of 1.5830 and a viscosity of 500 to 1000 cP at 25 ⁰ C 70% ig measured in butylglycol, which in a known Way obtained by alkaline condensation of bisphenol A with epichlorohydrin, mixed under inert gas. To this 31.2 g of etherified butylphenol resol 2 and 2 g of a 50% methanolic solution of benzyltrimethylammonium hydroxide are added. The mixture is heated to 150 ° C. After 30 minutes the viscosity has reached 115 cP, measured at 20 ° C. 1: 1 in butyl glycol. The product has a saponification number of 90. The polyether is saponified with aqueous potassium hydroxide solution and then acidified with dilute sulfuric acid. The resin is carefully freed from electrolytes and excess acid by washing it several times with water, then enough triethylamine is added to the resin until the pH reaches 8. The resin is indefinitely soluble in water. The aqueous solution is suitable for electrophoretic deposition.

Example 3

155 g of etherified phenol resol 2, 78 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 to 1000 cP at 25 ° C, measured 70% in butyl glycol, which is measured in a known manner by alkaline Condensation of bisphenol A with epichlorohydrin has been obtained, and 3 g of a 50% methanolic solution of benzyltrimethylammonium hydroxide are mixed. The mixture is ^{heated to 140 °} C. for 2 hours. The viscosity is then 19OcP, measured at 2O ⁰ C 2: 1 in butyl glycol. There are 120 g of ricinoleic acid methyl ester and 4 g

109 522/374

p-Toluenesulfonic acid is added, and the product is ^{heated under vacuum at 140 °} C. until 53 g of distillate have passed over. The viscosity of the product is 920 cP, measured at 20 ° C 2: 1 in butyl glycol, and the saponification number is 90. The product is saponified with 5 η-sodium hydroxide solution, acidified with the equivalent amount of 5 η-sulfuric acid, and the water is removed from the Mixture removed by azeotropic distillation with xylene. The product is then filtered. Sufficient triethylamine is then added until the pH value of 8 is reached. The xylene is removed in vacuo. The resulting clear resin has unlimited solubility in water, it has an acid number of 80 and a viscosity of 230 cP, measured at 20 ° C. 1: 1 in butyl glycol. It can be used for electrophoretic deposition and produces hard, elastic coatings after baking.

Example 4

110 g of etherified phenol resol 1 and 133 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 to 1000 cP at 2O ⁰ C, 70% measured in butyl glycol, which in a known manner by alkaline Condensation of bisphenol A obtained with epichlorohydrin are mixed under inert gas. To this end, 2 g of a 50 ° / ₀ methanol solution of benzyl trimethylammonium hydroxide. The mixture is ^{kept at 140 °} C. for 4 hours. Then 150 g of ricinoleic acid methyl ester and 4 g of p-toluenesulfonic acid are added, and the mixture is ^{heated to 160 °} C. under reduced pressure. The reaction is continued until the viscosity of the product, measured at 50% g ^m butyl glycol at 20 ^° C., is about 100 cP. The product has a saponification number of 96. It is saponified with aqueous potassium hydroxide solution and then acidified with dilute sulfuric acid. The resin is carefully freed from electrolytes and excess acid by washing it several times with water. Then enough triethylamine is added to the resin until the pH value 8 is reached. The resin is indefinitely soluble in water.

Example 5

148 g phenolic resole etherified 3 and 37.5 g of an epoxy resin having an epoxy equivalent 230-280 with a refractive index of 1.5830 and a viscosity of 500 to 1000 cP, measured at 20 ⁰ C 70% in "butyl glycol, in which known way was obtained by alkaline condensation of bisphenol a with epichlorohydrin, and 2 g of a 50 ° / ₀ by weight methanolic solution of benzyltrimethylammonium hydroxide of sodium cobaltnitrite the mixture is heated to 130 to 140 ° C until the viscosity measured. 2: 1 in butylglycol is at 2O ⁰ C, about 280 cP. Then 96 g of ricinoleic acid and 4 g of p-toluenesulfonic acid are added. the product is heated 16O ⁰ C under vacuum and the reaction is continued until the viscosity, measured 50 ° / oig is in butyl glycol at 2O ⁰ C, 115 cP. The product has a saponification number of 80. It is saponified with 5 η sodium hydroxide solution and then acidified with 5-η sulfuric The precipitated resin is by repeated Wa. electrolytes with water and then treated with enough triethylamine until the pH value 8 is reached. The resin is indefinitely soluble in water.

Example 6

160 phenol resol 2 and 120 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 to 1000 cP, measured at 2O ⁰ C 70 ° / ₀ ig in butyl glycol, which in a known manner by alkaline condensation was obtained from bisphenol a with epichlorohydrin, and 2 g of a 50 ° / ₀ methanol solution of benzyltrimethyl ammonium hydroxide are mixed. The mixture is ^{heated to 140 °} C. until the viscosity, measured 2: 1 in butyl glycol at 20 ^° C., is 170 cP. Then 150 g of ricinoleic acid methyl ester and 4 g of p-toluenesulfonic acid are added, and the mixture is ^{heated to 160 °} C. under vacuum until the viscosity, measured 50% in butyl glycol at 20 ^° C., is 100 to 105 cP. The product has a saponification number of 80. It is saponified with 5 η-sodium hydroxide solution, acidified with the equivalent amount of η-sulfuric acid, and the resin is freed from electrolytes by washing several times with water. Triethylamine is then added until the pH is 8. The resin can be diluted indefinitely in water and is suitable for electrophoretic painting.

Example 7

320 g of etherified phenol resol 2 and 200 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 to 1000 cP / 20 ° C 70% in butyl glycol, which is produced in a known manner by alkaline condensation of bisphenol A. obtained with epichlorohydrin are mixed together. Then 2 g of a 50 ° / ₀ methanolic solution of benzyltrimethylammonium hydroxide added. The mixture is kept at 130 to 140 ^° C. under an inert gas until the viscosity, measured 2: 1 in butyl glycol at 20 ^° C., is 115 cP. 600 g of methyl ricinoleate and 4 g of p-toluenesulfonic acid are added. The mixture is heated under vacuum at 12 to 20 mm of mercury until the viscosity, measured at 20 ° C. 1: 1 in butyl glycol, is 95 to 100 cP. The saponification number is 100. The product is saponified with 20% methanolic potassium hydroxide solution and acidified with the equivalent amount of concentrated hydrochloric acid. Then enough triethylamine is added until the pH is 8. The methanol is distilled off in vacuo and the product is filtered. It can be diluted indefinitely with water. The resin is saponified with the anionic melamine resin described in Austrian patent 284 443, which is a reaction product of 780 g of hexamethoxymethylmelamine, 200 g of butyl glycolate, 296 g of n-butanol and has been made water-soluble by adding triethylamine in a ratio of 8: 2 mixed. In the electrophoretic coating process, lacquers with elastic coatings are produced on steel sheets after baking at 150 ^° C. for 30 minutes.

Example 8

The procedure is as in Example 7, but instead of the ricinoleic acid methyl ester, a mixture of 260 g of soybean oil fatty alcohol and 70 g of butyl glycolate is added. The mixture is heated to 15O ⁰ C, until the viscosity was approximately 50 cP achieved. Then Va-

Those polyhydroxypolyamines according to the above general formula, which are preferred complete substitution of the hydrogen atoms of polyamines by the 2-hydroxypropyl radical are. In particular the exhaustive conversion of diethylenetriamine and diethylenetetramine polyhydroxypolyamines obtained with propylene oxide. The manufacture of the above Polyhydroxipolyamines are described in French patent 1,497,222.

Manufacturing instructions for thermosetting, etherified Phenol-formaldehyde condensation products

Etherified phenolic resole 1

500 g of p-tert-butylphenol resol are mixed with such amounts of methanol that the water content of the reaction mixture, based on methanol, is not more than 20 percent by weight. The pH is then adjusted to 1 with concentrated hydrochloric acid and the mixture is heated ^{to 60 ° C. for 2 to 3 hours.} The solids content of a neutralized sample rises by about 2 to 3 ° in / _0th The methanol is then distilled off in vacuo, the temperature of 60 ° C. not being exceeded. The reaction mixture is washed twice with water to remove the excess acid. Subsequently, the mixture in vacuum is concentrated up to an internal temperature of 100 ⁰ C. The solids content of the etherified resol is 92%.

The butylphenol resol used was produced as follows:

60 g of p-tert-butylphenol and 80 g of aqueous formaldehyde solution 30% strength is left in a known manner at about 40 ° C. under the action of strong alkalis react with each other until the free formaldehyde content has dropped to almost zero. With the help of stronger Acids, the resol is broken down and washed salt-free with water.

Etherified phenolic resole 2

686.5 g p-tert-Butylphenolresol be dehydrated in vacuum to 90 ⁰ C, then 1.1650 g of n-butanol and 835 g of toluene added. The mixture is heated to the boil and the water is removed by azeotropic distillation, the solvent mixture being returned to the reaction vessel. After removal of about 40 g water 8 g of 85 ° / ₀ by weight phosphoric acid are added and the azeotropic distillation continued until no water passes more, then the acid is neutralized with added in solid form calcium hydroxide. The product is concentrated in vacuo to a temperature of HO ⁰ C and then nitrated. The solids content is about 92 percent by weight.

Etherified phenolic resole 3

82.5 g of 40% sodium hydroxide solution are added to 209 g of bisphenol A and 365 g of 30% strength formaldehyde. The mixture is kept at 3O ⁰ C for so long, until the formaldehyde is charged about 3.7. The resol is then broken down with dilute hydrochloric acid and washed free of electrolytes by repeated treatment with water. 738 g of n-butanol and 370 g of toluene are added. After the addition of 5 g of phosphoric acid, an azeotropic circulation distillation is carried out, the solvent being returned to the mixture. The distillation is continued until no more water passes over. The phosphoric acid is then neutralized with calcium hydroxide and the mixture is concentrated in vacuo. The solids content of the resol is about 92 ° / ₀ .

■ '

example 1

300 g of an epoxy resin with an epoxy equivalent weight of 450 to 525 and a viscosity of 100 to 17OcP, measured at 25 ° C, 40 ° / ₀ in butyl diglycol, which in a known manner by condensation of 2,2- (p.-oxy) phenylpropane was obtained with epichlorohydrin, is mixed with 160 g of the etherified phenol resol 2. The mixture is kept at 150 ° C. for 2 hours. Then 1 g of a 50% solution of 85% phosphoric acid in isobutanol and 280 g ricinoleic acid is added. The mixture is heated under vacuum at 140 to 150 ° C and maintains 50% in butyl glycol at 25 ⁰ C at this temperature until the viscosity measured, is 260 to 300 cP. The product is then diluted to a solids content of 80% with isopropyl glycol, and triethylamine is added until the pH is 8.5. It is then diluted with water to a solids content of 40%. The aqueous solution has a very long shelf life and can be used to refill electrophoretic baths.

Example 2

309 g of the etherified phenol resol 2, 525 g of ricinoleic acid methyl ester and 1 g of p-toluenesulfonic acid are mixed. The mixture is heated up to a temperature of 150 ^{° C. under vacuum.} The reaction is continued at 150 ° C. until 110 g of distillate have passed over. 72.5 g of this intermediate product are measured with 62.2 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 to 1000 cP at 25 ° C. 70% in butyl glycol, which is known in the known Way obtained by alkaline condensation of bisphenol A with epichlorohydrin, mixed under inert gas. To this 31.2 g of etherified butylphenol resol 2 and 2 g of a 50% methanolic solution of benzyltrimethylammonium hydroxide are added. The mixture is heated to 150 ⁰ C. After 30 minutes the viscosity has reached 115 cP, measured at 20 ° C. 1: 1 in butyl glycol. The product has a saponification number of 90. The polyether is saponified with aqueous potassium hydroxide solution and then acidified with dilute sulfuric acid. The resin is carefully freed from electrolytes and excess acid by washing it several times with water, then enough triethylamine is added to the resin until the pH reaches 8. The resin is indefinitely soluble in water. The aqueous solution is suitable for electrophoretic deposition.

Example 3

155 g of etherified phenol resol 2, 78 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 to 1000 cP at 25 ⁰ C, 70% measured in butyl glycol, which is measured in a known manner by alkaline Condensation of bisphenol A with epichlorohydrin has been obtained, and 3 g of a 50% methanolic solution of benzyltrimethylammonium hydroxide are mixed. The mixture is ^{heated to 140 °} C. for 2 hours. The viscosity is then 19OcP, measured at 2O ⁰ C 2: 1 in butyl glycol. There are 120 g of ricinoleic acid methyl ester and 4 g

109 522/374

p-Toluenesulfonic acid is added, and the product is ^{heated under vacuum at 140 °} C. until 53 g of distillate have passed over. The viscosity of the product is 920 cP, measured at 20 ⁰ C 2: 1 in butyl glycol, and the saponification number is 90. The product is saponified with 5 η sodium hydroxide solution, acidified with the equivalent amount of 5 η sulfuric acid, and the water is removed from the Mixture removed by azeotropic distillation with xylene. The product is then filtered. Sufficient triethylamine is then added until the pH value of 8 is reached. The xylene is removed in vacuo. The resulting clear resin has unlimited solubility in water, it has an acid number of 80 and a viscosity of 230 cP, measured at 20 ° C. 1: 1 in butyl glycol. It can be used for electrophoretic deposition and produces hard, elastic coatings after baking.

Example 4

110 g phenolic resole etherified 1 and 133 g of an epoxy resin having an epoxide equivalent 230-280, a refractive index of 1.5830 and a viscosity of 500 to 1000 cP at 20 ⁰ C, 70 ° measured _o / ig in butylglycol, which in a known manner obtained by alkaline condensation of bisphenol A with epichlorohydrin are mixed under inert gas. To this end, 2 g of a 50 ° / ₀ methanol solution of benzyl trimethylammonium hydroxide. The mixture is ^{kept at 140 °} C. for 4 hours. Then 150 g of methyl ricinoleate and 4 g of p-toluenesulfonic acid are added, and the mixture is heated to 160 ° C. under reduced pressure. The reaction is continued until the viscosity of the product, measured _50/0 ig is in butyl glycol at 20 ° C, about 100 ° cP. The product has a saponification number of 96. It is saponified with aqueous potassium hydroxide solution and then acidified with dilute sulfuric acid. The resin is carefully freed from electrolytes and excess acid by washing it several times with water. Then enough triethylamine is added to the resin until the pH value 8 is reached. The resin is indefinitely soluble in water.

Example 5

148 g of etherified phenol resol 3 and 37.5 g of an epoxy resin with an epoxy equivalent weight of 230 to 280, with a refractive index of 1.5830 and a viscosity of 500 to 1000 cP, at 20 ° C 70 ° / _? which was obtained in known manner by alkaline condensation of bisphenol A with epichlorohydrin, and 2 g of a 50 ° / ₀ by weight methanolic solution of benzyltrimethylammonium hydroxide of sodium cobaltnitrite strength measured in butyl glycol. The mixture is heated to 130 to 140 ° C, until the viscosity, measured 2: 1 in butyl glycol at 20 ⁰ C, is about 280 cP. Then 96 g of ricinoleic acid methyl ester and 4 g of p-toluenesulfonic acid are added. The product is heated under vacuum to 160 ° C, and the reaction is continued until the viscosity measured is 50% in butyl glycol at 2O ⁰ C, 115 cP. The product has a saponification number of 80. It is saponified with 5η sodium hydroxide solution and then acidified with 5η sulfuric acid. The precipitated resin is freed from electrolytes by washing it several times with water and then adding enough triethylamine until the pH value 8 is reached. The resin is indefinitely soluble in water.

Example 6

160 phenol resol 2 and 120 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 to 1000 cP, measured at 20 ⁰ C 70 ° / ₀ ig in butyl glycol, which in a known manner by alkaline Condensation of bisphenol A with epichlorohydrin was obtained, and 2 g of a 50% ^{en me-}

ίο ethanol solution of benzyltrimethylammonium hydroxide are mixed. The mixture is ^{heated to 140 °} C. until the viscosity, measured 2: 1 in butyl glycol at 20 ^° C., is 170 cP. Then, 150 g ricinoleic acid and 4 g of p-toluenesulfonic acid are added and the mixture is heated under vacuum to 160 ° C, until the viscosity, measured 5O ° / oig> ⁿ butyl glycol at 20 ⁰ C, 100 to 105 cP. The product has a saponification number of 80. It is saponified with 5 η-sodium hydroxide solution, acidified with the equivalent amount of η-sulfuric acid, and the resin is freed from electrolytes by washing several times with water. Triethylamine is then added until the pH is 8. The resin can be diluted indefinitely in water and is suitable for electrophoretic painting.

Example 7

320 g of etherified phenol resol 2 and 200 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 to 1000cP / 20 ° C 70 ° / ₀ in butyl glycol, which in a known manner by alkaline condensation of Bisphenol A obtained with epichlorohydrin are mixed together. Then 2 g of a 50 ° / ₀ methanolic solution of benzyltrimethylammonium hydroxide added. The mixture is maintained under an inert gas so long as at 130 to 140 ° C, until the viscosity, measured 2: 1 in butyl glycol at 20 ⁰ C, is 115 cP. 600 g of methyl ricinoleate and 4 g of p-toluenesulfonic acid are added. The mixture is heated under vacuum at 12 to 20 mm of mercury until the viscosity, measured at 20 ° C. 1: 1 in butyl glycol, is 95 to 100 cP. The saponification number is 100. The product is saponified with 20 ° / ₀ methanolic potassium hydroxide solution and acidified with equivalent amount of concentrated hydrochloric acid. Then enough triethylamine is added until the pH is 8. The methanol is distilled off in vacuo and the product is filtered. It can be diluted indefinitely with water. The resin is saponified with the anionic melamine resin described in Austrian patent 284 443, which is a reaction product of 780 g of hexamethoxymethylmelamine, 200 g of butyl glycolate, 296 g of n-butanol and has been made water-soluble by adding triethylamine in a ratio of 8: 2 mixed. In the electrophoretic coating process, lacquers with elastic coatings are produced on steel sheets after baking at 150 ^° C. for 30 minutes.

Example 8

The procedure is as in Example 7, but instead of the ricinoleic acid methyl ester, a mixture of 260 g of soybean oil fatty alcohol and 70 g of butyl glycolate is added. The mixture is heated to 15O ⁰ C, until the viscosity was approximately 50 cP achieved. Then Va-

applied and further heated until the viscosity of the thinnable synthetic resin-made coating

95 to 100 cP. The saponification number is 50. The further work-up then takes place as in the previous one Example given. The product can be diluted indefinitely with water.

Example 9

The resin prepared according to the invention according to Example 1 is diluted with deionized water to 40% solids content and rubbed off in a ceramic ball mill with a pigment mixture of iron oxide red and basic lead silica chromate in a ratio of 9: 1 so that the pigment binder ratio is 0.6: 1. The pastes produced are diluted with water to a solids content of 16%. The resin solution is poured into a steel basin measuring 10 × 10 × 18 cm in height and passivated metal sheets are coated in it for about 2 minutes by applying an electrical direct voltage at a constant voltage in the range between 100 and 150 volts. The sheets are connected as anode and have dimensions 8.5 x 11.5 x 0.1 cm. The deposited films then give smooth surfaces when stoved. The stoving conditions are 30 minutes at 170 ^° C.

Example 10

The resin produced according to the invention according to example 6 is mixed with an anionic melamine resin according to example 9 of Austrian patent specification 284 443 in a ratio of 8: 2. The mixture is diluted to 40% solids with deionized water and rubbed in a ceramic ball mill with a pigment mixture of iron oxide red and basic lead silica chromate in a ratio of 9: 1 so that the pigment binder ratio is 0.6: 1. The pastes produced are diluted with water to a solids content of 10%. The resin is electrophoretically deposited under the conditions described above in a steel basin with the dimensions described above. The deposited films are smooth, hard and sufficiently elastic; the stoving temperature of the films is 150 ^° C. and the stoving time is 30 minutes.

The anionic melamine resin used was made as follows:

390 g of hexamethoxymethylmelamine, 150 g of n-butanol and 140 g of butyl glycolate are mixed and 0.1 g of p-toluenesulfonic acid is added as a catalyst, and the mixture is ^{heated to 100 to 110 °} C. until no more distillate passes over. Then vacuum is applied and the unreacted portion of alcohol and ester is distilled off. Then 100 ml of 5 η NaOH and 100 ml of water are added. It is refluxed for 1 hour. The water is then removed by azeotropic distillation using benzene as an entrainer. The benzene is then distilled off in vacuo, and a solution of 30 g of oxalic acid in 100 g of acetone at 30 ^° C. is added to the mixture. It is stirred well and then filtered. Then the resin is neutralized with triethylamine. It can be diluted with water indefinitely.

B e i s ρ i e 1 11

The polyether resin carboxylic acid, which was prepared according to Example 1, is Ν, Ν, Ν ', Ν', Ν '', - Pentkis- (2-hydroxypropyl) -diethylenetriamine neutralized until the aqueous solution has a pH of 8. One advantage of this example is that those with this detergent can be applied in thick layers, even when heated quickly without splashing be baked into paint material.

Example 12

The procedure is as in Example 10, but by adding N, N, N ', N'N ", N" -hexakis- (2-hydroxypropyl) -triethylenetetramine neutralized. This results in the same effects when burning in the from it produced coating agent, as described in Example 10, achieved.

Example 13

The polyether resin carboxylic acid obtained according to Example 2 is treated with N, N, N ', N'-tetrakis- (2-hydroxypropyl) -ethylenediamine neutralized 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 set to a solids content of 50 percent by weight. Coating agents made therefrom can be applied in thick layers and can be baked on by rapid heating, without splashing paint material.

Example 14

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

Example 15

The procedure is as in example 13, but the resin solution according to example 2 is used.

Example 16
The procedure is as in example 13, but the

45 resin solution according to Example 5 used.

Example 17

The procedure is as in example 8, but the resin solution according to example 2 is used.

Example 18

The procedure is as in example 8, but the resin solution according to example 5 is used.

Example 19

The resin solution obtained according to Example 8 according to the invention is mixed with hexamethoxymethylmelamine in a weight ratio of 8: 2. The solution is diluted with deionized water to a solids content of 40 percent by weight and then rubbed off with titanium dioxide in a ball mill in a ratio of 1: 0.8. The solution is diluted to the desired viscosity with butanol and applied to sheet iron by spraying or dipping. After stoving for 30 minutes at 150 ^° C., hard, relatively light-colored coatings result.

Example 20

309 g of veratherten phenolic resole 2, 260 g Leinoltettalkohol, 132 g Glykolsaurebutylester, 1 g of p-toluenesulfonic acid are mixed, the mixture is heated to a temperature of 15O ⁰ C, were transferred to about 60 g of distillate Then vacuum is applied and the heating as long continued until no distillate passes to this intermediate product, 120 g of an epoxy resin with a Epoxyaqui- \ alentgewicht 230-280, a refractive index of 1.5830 and a viscosity of 500 to 1000 cP, at 25 ⁰ C 70% in. butylglycol measured, which has been obtained in known manner by alkaline condensation of bisphenol a with Epichlorhydrm added thereto under an inert gas after the addition of 3 g of a 50 ° / _o by weight methanolic solution of Benzyltrimethylammomumhydroxid as long heated at 150 ⁰ C until the viscosity of 115 cP, measured at 2O ⁰ C 11 in butyl glycol, has reached The product has a saponification number of about 90. It is saponified with aqueous potassium hydroxide and ans Finally acidified with the equivalent amount of dilute sulfuric acid. The precipitated resin is carefully freed from electrolytes by washing several times with water and then treated with so much Tnathylamm until the pH value 8 is reached. The resin can be diluted with water indefinitely

Example 21

The procedure is as in Example 19, but Soy fatty alcohol is used instead of Lemolfettdlkohol The cooking is done up to the same viscosity as in Example 19 given, carried out

Example 22

The procedure is as in Example 19, but instead of 260 g linseed oil fatty alcohol, 260 g stearyl alcohol is used. as indicated in Example 19 carried out.

35

40

Example 23

The procedure is as in Example 7, but the Butyl glycolate replaced by ethyl lactate Instead of 70 g butyl glycolate, 65 g are used Lactic acid ethyl ester used

Example 24

The resin-containing pigment paste prepared according to Example 9 was distinguished m test experiments by storage at 50 ⁰ C during 3 weeks by an unusual stability After this test storage, the pigment paste was used for refilling a wassen gen electrophoresis bath, as has been described already been extensively described in Example 9 The Bath showed no change in its deposition properties compared to a freshly prepared bath

Example 25

A Production of a carboxyl group-bearing phenolic plastic resin

60

a) Production of the etherified phenol resol as the starting product

686.5 g of ρ-tert-butylphenol resol are in a vacuum

dehydrated to 9O ⁰ C, then 1659 g of n-butanol and
835 g of toluene were added

The mixture is heated to boiling and the solvent mixture is recycled to the reaction vessel after the removal of about 40 g of water are _cent, phosphoric acid was added 8 g of 85 ° / and continued azeotropic distillation as long as the water is removed by azeotropic distillation, until no water passes over then the acid with m zugefugtem solid form calcium hydroxide neutralized the product is concentrated under vacuum up to a temperature of 110 ⁰ C and then filtered, the Festkorpergehalt amounts to about 92 percent by weight

b) 309 g of the etherified phenol resol obtained above according to a)
525 g of methyl ricinolate and

1 g of paratoluenesulfonic acid are mixed

The mixture is heated under vacuum up to a temperature of 150 ⁰ C. The reaction is continued at 150 ⁰ C for so long, is passed through 110 g of distillate The veratherte condensate obtained is saponified with aqueous potassium hydroxide solution and then with dilute sulfuric acid acidified The resin is prepared by Repeated washing with water carefully freed of electrolytes and excess acid, then the resin is replaced with enough triethylamine until the pH value 8 is reached.The resin has unlimited solubility in water, the aqueous solution is suitable for electrophoretic deposition

B Production of the stoving enamel

The resin solution obtained according to Example 6 is mixed with the compound obtained according to A) carboxyl-phenol resin solution in the ratio 8 2 The solution is diluted with deionized water to 40 ° / ₀ Festkorpergehalt and on a ceramic ball mill with a pigment mixture of Eisenoxydrot and basic Bleisihkochromat in the ratio 9 1 rubbed off 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. After baking for 30 minutes at 170 ^° C., the result is hard, smooth Coatings with very good corrosion resistance

Example 26

The resin solution obtained according to Example 2 is mixed with the phenol plastic, which is described under A) in Example 25, in the ratio 7-3. The mixture is diluted with deionized water to a solids content of 40% so abraded in a ratio of 9 1 in that the pigment / Bmdemittelverhältnis 0.5 1 amounts the solution is diluted with water to ₀ Festkorpergehalt L0 ° / and deposited under the conditions indicated in example 9 conditions After baking during 30 minutes at 13O ⁰ C resulting hard, smooth coatings with very good corrosion resistance

Claims (10)

Claims 1 Process for the production of water-thinnable modified polyethers, characterized in that that a) aromatic and / or hydroaroma muffles, if applicable hydroxyl-containing epoxy compounds, as they are produced by etherification of a dihydric hydroaromatic alcohol and dihydric hydroaromatic alcohol and / or a bisphenol with epihalohydrins or dihalohydrins in the presence can be obtained from alkali, or reaction products from the epoxy compounds thus obtained with mono- and / or polyalcohols with 1 to 20 carbon atoms in a straight or branched chain, the ratio being of epoxy groups of the compounds containing epoxy groups to the OH groups of the mono- and polyalcohols between 1: 1 to 1: 1.5 and where the OH groups of the mono- or polyalcohols are primary or secondary are, b) hydrophilic, low molecular weight, thermosetting condensation products of one and / or binuclear phenols with aldehydes, c) aliphatic monocarboxylic and dioxycarboxylic acids with 2 to 20 carbon atoms or their esters with alcohols of 1 to 6 carbon atoms together by heating or reacting component a) with component b) and this intermediate product then with component c) Reacting heating, or by first reacting components b) and c) with one another by heating and then reacting this intermediate product with component a), the ratio between phenolic OH groups and epoxy groups between 1: 0.5 and 1: 2 and the temperature at which Polyverätherung 100 to 150 ⁰ C, and catalyzes the etherification reaction in the usual manner, and wherein the etherification or Umätherung continues with the hydroxycarboxylic acid or its ester by heating until the carboxylic acid formed an acid resin or the Carbonsäureesterharz a Has a saponification number between 30 and 150, d) the carboxylic acid ester resin is saponified and the addition of acids after the saponification Carboxylic acid resin, e) the carboxylic acid resin by adding ammonia and / or organic nitrogen bases converted into the water-dilutable form. 2. The method according to claim 1, characterized in that the conversion of high molecular weight long-chain compounds containing epoxy groups, short-chain mono- or polyalcohols are used will. 3. The method according to any one of claims 1 to 2, characterized in that as epoxy groups Polyethers those with the general formula - O - CH, - CHOH - CH, - CH ₃ CH ₃ ■ Ο - CH ₂ - CH- where η is zero or a small number up to 10, and which contain 2,2-bis- (4-hydroxylphenyl) propane as the starting compound are used. 4. The method according to one or more of claims 1 to 3, characterized in that as aliphatic mono- and dioxicarboxylic acids with up to 20 carbon atoms glycolic acid, lactic acid, dimethylolpropionic acid, Ricinoleic acid, oxistearic acid and oxicaproic acid can be used. 5. Procedure according to one or more of the claims 1 to 4, characterized in that the quantitative ratio of component c) to the components a) and b) is chosen so that the R, H R, - O - C - C H H 55 I / NC- (Y) ₃₁ -CN carboxylic acid resin has an acid number or the carboxylic acid ester resin has a saponification number between 30 and 80, this being achieved by continuing the etherification or transetherification with the oxicarboxylic acid or its ester for so long by heating, until the carboxylic acid resin has reached a corresponding acid number or the carboxylic acid ester resin has reached a saponification number. 6. The method according to one or more of claims 1 to 5, characterized in that one as organic nitrogen base compounds with the general formula HR ₂ CCOR ₃
HH 109 522/374 where the substituents and symbols have the following meanings: R ₁ Y is - CH.r, - C ₂ H ₄ -, C ₃ H ₆ -, C ₄ H ₈ -, - CH ₂ - N - CH ₂ -; R ₁ is H, CH ₃ , C ₂ H ₈ , CH ₂ - C - O - R ₃ ; H
R ₂ R ₁ 'is H, CH ₃ , C ₂ H ₅ , CH ₂ - C - O - R ₃ ; R ₂ is H, CH ₃ , C ₂ H ₅ ;
R ' ₂ is H, CH ₃ , C ₂ H ₅ ; R ₃ is H, (CH ₂ - CH ₂ - O - ) _x - H, CH ₂ -C - O | - H; R ₃ 'is H, (CH ₂ - CH ₂ - O) _x - H, / CH ₃ CH ₂ -CO - H χ is zero or an integer between 1 and 6. 7. Use of the modified polyethers obtained according to one of claims 1 to 6 as Sole binder in aqueous coating agents. 8. Use of the modified polyethers obtained according to one of claims 1 to 6 as binders in combination with other, commonly used, water-thinnable resins in aqueous Coating agents. 9. Use of the modified polyethers obtained according to one of the patent claims 1 to 6 as a binder for electrophoretic painting processes. 10. Use according to claim 9 of such modified polyethers as the starting compound Contain condensed polyether with a molecular weight of 380 to about 2000, for the Purpose mentioned in claim 9.