DE1900063A1 - Alkali soluble condensates of phenols and - aromatic hydroxycarboxylic acids as - Google Patents

Abstract

Reaction prods. obtained by condensation of phenols or napthols with formaldehyde (releasing cpds.) are reacted in alkaline, acidic or neutral medium with (a) urea derivatives in which one H-atom of an NH2-grp. is replaced by a grp. of formula -CH-COOH (wherein R is H or C1-9 alkyl residue) or by aromatic grps. of formulae (wherein X is H or a first-order substituent); and (b) mononuclear aromatic carboxylic and/or sulphonic acids which may contain hydroxyl or amino grps., and/or aryloxy aliphatic and/or aliphatic polycarboxylic acids with up to 8 C-atoms which may contain hydroxyl grps. Products are used in manufacture of binders and printing inks.

Description

Process for the production of alkali-soluble condensation products From the German patent specification 693 770 it is known to use aromatic hydroxyl sulfones with formaldehyde and aromatic hydroxycarboxylic acids or aryloxy fatty acids to form alkali-soluble ones Implement condensation products used in the textile and leather industries can be. These products can be used instead of tannin in dyeing and printing can be used, e.g. for the production of rubber prints with basic dyes (German Auslegeschrift 1 o88 518). Furthermore are from the German patent 1 124 959 similar condensation products are known which contain phenols as a further component contain. These condensation products are also used in a variety of ways, e.g. as an aid in rubber printing with basic dyes (German Auslegeschrift 1 128 446).

However, the known agents of this type split at temperatures above 80C formaldehyde, which is why these condensation products for the modern, on speed The deactivated methods of rubber printing are only suitable to a limited extent.

It also occurs when printing with color varnishes on the basis of the known Condensation products often crystallize when the paint dries up, which can be recognized by the veil on the dyeings.

It has now been found that alkali-soluble condensation products, which do not have this disadvantage, are obtained by reacting phenols and aromatic hydroxycarboxylic acids or aryloxy fatty acids with formaldehyde if the reaction products, which are obtained by condensation of phenols or naphthols with formaldehyde or formaldehyde-releasing compounds, are obtained in alkaline, acidic or neutral aqueous medium at temperatures between 30OC and the boiling point, in alkaline, acidic or neutral aqueous medium in any order one after the other or simultaneously with a) urea derivatives in which a hydrogen atom of an NH group is replaced by an aliphatic group of the formula in which R denotes hydrogen or an alkyl radical having 1 to 9 carbon atoms, or by aromatic groups of the formulas in which X denotes hydrogen or a substituent of the first order, is replaced, and b) mononuclear aromatic carboxylic and / or sulfonic acids, which may contain hydroxyl or amino groups, and / or aryloxy fatty acids and / or aliphatic polycarboxylic acids with up to 8 carbon atoms , which may contain hydroxyl groups, also reacts at temperatures between 30 ° C. and the boiling point.

Examples of phenols and naphthols are: phenol itself, o-, m- and p-cresols and their mixtures, p-tertiary-butylphenol, pyrocatechol and its homologues, such as the methyl, ethyl, propylcatechols and their as Technical mixtures known from pyrex, octylphenols, nonylphenols, 1,3- and 1,4-dihydroxybenzene, Alkoxyphenols, such as 2-, 3- and 4-methoxyphenol, 4,4'-dihydroxydiphenylsulfone, 4-hydroxydiphenylsulfone, Phenylhydroxynaphthylsulfone, 2,2-bis (4-hydroxyphenyl) propane, 2-hydroxydiphenyl, 4-hydroxydiphenylmethane, α-naphthol, ß-naphthol, isopropyl-ß-naphthols, phenolsulfonic acids and naphtholsulfonic acids. Phenols and naphthols are used before @@ @@ wise, which contain koi @@@@@ l @@@ acid groups. The aromatic Hydroxycarbo @ e.g. o-cresotinic acid, gallic acid and above all salicylic acid, for aryloxy fatty acids e.g. Pheno @@@@ i @@ ä @ r consideration.

The formawdehyde can be in free form, preferably in the form of the w rigen Solution or formaldehyde-releasing compounds, such as paraformaldehyde, trioxymethylene or hexamethylenetetramine can be used.

The components of group a) are urea derivatives in which a hydrogen atom of an NH2 group is replaced by an aliphatic group of the formula in which R denotes hydrogen or an alkyl radical having 1 to 9 carbon atoms, or by aromatic groups of the formulas in which X is hydrogen or a substituent of the first order is replaced. The first order substituents are alkyl groups with 1 to 12 carbon atoms, the hydroxyl group and the amino group. Examples of components of group a) are: hydantoic acid, urine propanoic acid, urine benzene carboxylic acid or urine benzene sulphonic acid, urine nonylbenzenesulphonic acid, urine xybenzene carboxylic acid, urine aminobenzo 1 carboxylic acid.

The starting compounds of group b) are preferably single-ring compounds aromatic carboxylic acids which may contain hydroxyl or amino groups, such as Benzoic acid, phthalic acid, salicylic acid, o-cresotinic acid, gallic acid, and aminobenzoic acids into consideration. Other compounds of group b) are aliphatic polycarboxylic acids, which can also contain hydroxyl groups, such as malonic acid, succinic acid, adipic acid, Tartaric acid, malic acid and citric acid, also aryloxy fatty acids such as phenoxyacetic acid, to call.

As examples of aromatic mononuclear amino groups Sulphonic acids are sulphanilic acid and metanilic acid.

In the case of the present ancestor, one assumes reaction products, the by condensation of phenols or naphthols mitiormaldevhyd or formaldehyde donating compounds obtained in an alkaline, acidic or neutral aqueous medium will. The quantitative ratio of phenols or naphthols to formaldehyde in these Reaction products can be varied within wide limits; for example turns to 1 mole of phenol or naphthol 1 to 8 moles of formaldehyde or the equivalent Amount of a formaldehyde-releasing substance. Products have proven to be particularly effective that of 1 mole of a phenol or naphthol and 1 to 6 moles of formaldehyde or the equivalent amount of a formaldehyde-releasing substance are produced. The alkaline The reaction medium can react with a large number of alkaline substances be evoked. Suitable alkaline compounds are z ß. Alkali metal hydroxides, such as sodium and potassium hydroxide, ammonia, primary, secondary or tertiary amines, such as ethylamine, diethylamine, triethanolamine, diethanolamine and triethanolamine. the Reaction in the acidic medium is preferably in the presence of mineral acids, such as Hydrochloric or sulfuric acid. Also medium-strength inorganic acids, such as Phosphoric acid, acidic salts of strong acids such as sodium hydrogen sulfate, and organic Acids, especially the aliphatic carboxylic acids, which are free of hydroxyl groups are, like formic acid, acetic acid, oxalic acid and trichloroacetic acid, come in for it into consideration. The reaction is advantageously carried out at pH values between 4 and 8 through. The reaction is preferably carried out in an aqueous solution or suspension by.

The reaction mixture can also contain organic solvents with water are miscible, such as methanol, ethanol, acetone, tetrahydrofuran, glycol and polyglycols contain. The condensation occurs at temperatures between 300C and the boiling point, preferably between 500 and 100 ° C. Under these conditions is the reac-.

tion generally ended after 2 to 8 hours.

Those emitted from phenols of naphthols and formaldehyde or formaldehyde Compounds obtained are reaction products according to the method of the invention reacted with the starting materials of groups a) and b). The order of these Implementation can be chosen at will. So you can either use the reaction products react simultaneously in one work stage with components a) and b) permit; but you can also start with one of the components a) or b) and then implement with the other component. Condensation products with particularly good properties are obtained, for example, if one mole of the converted phenol 0.1 to 3, preferably 0.1 to 2, mol of components a) and 0.1 to 3, preferably 0.5 to 2, moles of component b) are used.

The condensation is carried out between 300 c and the boiling point. Since components a) generally react more easily than components b), the reaction with a) is often carried out at lower temperatures and / or for a shorter period of time Time than the implementation with b). In many cases the following reaction conditions have been found proven: reaction with a) at about 40 to 60 ° C in about 1 to 4 hours; Reaction with b) at about 700 ° C. to 100 ° C. in 4 to 10 hours. At the same time Implementation of the reaction products with a) and b) is advantageously chosen for b) necessary conditions. The condensation can be followed spectroscopically in the UR because at the end of the reaction the aromatically bound -CH20H groups The resulting band at 9.7 to 9.8 1u disappears. The above times were determined that way.

The products of the process do, however, not dissolve in aqueous alkalis in neutral water and in acids, making them out of an acidic or neutral aqueous Funds can be separated easily. They are washed for further work-up expediently a few times with water and then dried under reduced pressure Pressure at around 600C. For many purposes, however, it is also sufficient to add the entire conversion mixture or the mixture from which the majority of the aqueous phase has been separated off, to dry, for example in a drying pan, on a roller or in a Spray dryer. The resins obtainable in this way do not only dissolve in alkalis and other basic agents, but also in many organic solvents, like ethanol, acetone and a mixture of ethanol and ethyl glycol, depending on their In composition, the resins have an acid number between 5 and 20. The partly colorless, Partly weakly colored and above all odorless process products are in the Heat up to 15G °: stable. You can, among other things, in the lacquer, textile and paper industry e.g., as a dispersant.

The products of the process are, above all, excellent laking agents for basic dyes. With auramine dyes, rhodamine dyes, Victoria blue dyes, Methyl violet, crystal violet and malachite green become water-insoluble colored lakes obtain. Despite their salt character, these are extremely organophilic, so that you can use these color lacquers for coloring organic materials, e.g. for Production of carbon paper waxes, lithograph compounds, ballpoint pen pastes. The use of the process products as a laking component is special Highlight rubber printing (flexography). The obtained with the process products Lacquers, as well as the prints and dyeings made with them, are clear and without a haze and have excellent properties, e.g. good to very good water fastness.

The parts and percentages given in the examples relate to the weight.

Example 1 75 parts of p-tert-butylphenol, 0.3 part of goat sodium hydroxide solution, 14 parts of water and 65 parts of 33% aqueous formaldehyde are heated for 2 hours to 60 ° C.

Then 69 parts of salicylic acid, 1 part, are carried one after the other at 40 ° C Hydantoic acid and 8 parts of phthalic anhydride and heats the entire reaction mixture 4 hours on The product is evaporated under reduced pressure and then pulverized.

166 parts of a slightly yellowish powder are obtained very good in aqueous alkalis, methanol, ethanol, acetone and a mixture of Ethyl glycol / ethanol dissolves.

As proof of technical progress, we use the process product a flexographic printing ink produced: 14 parts of the process are dissolved in 90 parts of ethanol and 10 parts of ethyl glycol of this solution are added 3! 0 parts of a St. rol maleic acid ester copolymer and 7 parts of the dye C.I. 45 170 added.

One with this flexographic printing ink on a rotary varnishing machine lacquered aluminum foil had water fastness according to the PriZ method according to DIN 16 524 5.

Example 2 75 parts of p-tert-butylphenol, 0.3 part of 50 sodium hydroxide solution 14 parts of water and 65 parts of 33% aqueous formaldehyde are heated for 2 hours to 60 ° C. At 40 ° C., 52 parts of salicylic acid and 14.8 parts of hydantoic acid are added to this and 8 parts of phthalic anhydride are added and the entire reaction mixture is heated 4 Hours at 1000C.

After drying under reduced pressure, the product has cooled down pulverized.

152 parts of a slightly yellowish powder are obtained good in aqueous alkalis, ethanol, acetone and a mixture of ethanol / ethylglycol solves.

The coating with a flexographic printing ink, which is made from the process product according to the information in example 1 herges @@@@@ @@@ has a water fastness from 4 to 5.

Example 3 75 parts of p-tert-butylphenol, 0.3 part of 50 sodium hydroxide solution S, 14 parts of water and 65 parts of 33% strength aqueous formaldehyde are heated for 2 hours to 60 ° C.

Then give 34.6 parts of salicylic in small, even portions re, 29.6 parts of hydantoic acid and 8 parts of phthalic anhydride at 40 ° C and holds the entire reaction mixture 4 hours' at 10000. The product thus obtained is in evaporated in a spray can dryer.

160 parts of a slightly yellowish powder are obtained, which works well in aqueous alkalis, ethanol, acetone and an ethanol / ethyl glycol mixture solves.

The coating with a flexographic printer produced according to Example 1 color has a water fastness of 4 to 5.

Example 4 75 parts of p-tert-butylphenol, 0.3 part of 50% sodium hydroxide solution, 14 parts of water and 65 parts of 33% strength aqueous formaldehyde are kept for 2 hours 600C.

Then add one after the other in small portions at 400C; 17.2 Parts of salicylic acid, 44.2 parts of hydantoic acid and 8 parts of phthalic anhydride. That The mixture is now heated to 1000C for 4 hours. The product thus obtained is in a Drying pan evaporated under reduced pressure.

After the powders of the product, 156 parts of a weak one are obtained yellowish powder that works well in aqueous alkalis, ethanol, acetone as well a mixture of ethanol / ethyl glycol dissolves.

The coating with a prepared according to the information in Example 1 Flexographic printing inks have an accuracy rating of 4 to 5.

A flexographic printing ink which, instead of the C.I. 45 170 den yellow dye C.I. Contains 41,000, the water fastness has 4.

Example 5 75 parts of p-tert-butylphenol, 0.3 part of goat sodium hydroxide solution, 14 parts of water and 65 parts of 33% strength aqueous formaldehyde are heated for 2 hours 60 ° C. Then 69 parts of salicylic acid and 1.1 parts of urine propanoic acid are carried in succession and 8 parts of phthalic anhydride at 40 to 500C and heated to 1000C for 4 hours.

The work-up and the applied examination are carried out in the same way Example 1.

162 parts of a slightly yellowish powder are obtained.

Water fastness of the paintwork: 5.

Example 6 75 parts of p-tert-butylphenol, 0.3 part of 50% sodium hydroxide solution, 14 parts of water and 65 parts of 33% strength aqueous formaldehyde are heated for 2 hours to 60 ° C.

16.5 parts of urine propanoic acid and 51.8 parts are now added one after the other Add salicylic acid and 8 parts of phthalic anhydride at 40 to 45 ° C and heat it up total reaction mixture 4 hours to 10000. The product is in a drying pan evaporated under reduced pressure and pulverized after cooling.

There are 164 parts of a slightly yellowish, in aqueous alkalis, ethanol, Acetone and an ethanol / ethyl glycol mixture of readily soluble powder.

The painting with a prepared according to the information in Example 1 Flexographic printing inks have a water fastness rating of 4 to 5.

A coating with a flexographic printing ink that replaces the dye C.I. 45 170 the dye C.I. Contains 41,000, also has the water fastness 4 to 5.

Example 7 75 parts of p-tert-butylphenol, 0.3 part of 50% sodium hydroxide solution, 14 parts of water and 65 parts of 33% strength aqueous formaldehyde are heated for 2 hours to 60 ° C.

Then add 69 parts of salicylic acid, 1.5 parts of urine benzoic acid (o) and 8 parts of phthalic anhydride are added at 40 ° C. and the entire reaction mixture is heated 4 hours to 10000.

The work-up and the application-related testing are carried out as described in example 1.

165 parts of a slightly brownish-tinged powder are obtained dissolves well in ethanol / ethyl glycol.

Water fastness of the paintwork: 4 to 5.

Example 8 75 parts of p-tert-butylphenol, 0.3 part of 50% sodium hydroxide solution, 14 parts of water and 65 parts of 33% aqueous formaldehyde are heated to 60 ° C. for 2 hours held.

This is followed by 51.8 parts of salicylic acid, 22.6 parts of urine benzoic acid (o) and 8 parts of phthalic anhydride at 40 ° C. and the reaction mixture is heated for 4 hours to 1000C.

The work-up and the technical application test are carried out in the same way Example 1.

There are 168 parts of a slightly brownish, in an ethanol / Ethyl glycol mixture obtained easily soluble powder.

Water fastness of the paintwork: 4.

Example 9 75 parts of p-tert-butylphenol, 0.5 part of 50% strength potassium hydroxide solution, 14 parts of water and 65 parts of 33% strength aqueous formaldehyde are heated for 2 hours to 60 ° C.

Then 69 parts of salicylic acid, 8.6 Parts of urine-benzenesulphonic acid (o) and 8 parts of phthalic anhydride are added and the mixture is heated 4 hours at 1000C.

The processing and the technical application test are carried out as for example. 1 described.

163 parts of a gray-tinged powder are obtained, which is good in Ethanol and a mixture of v @@ ethanol / ethyl glycol dissolves.

Coatings with flexographic printing inks that are derived from the process product the details of Example 1 are produced, have the following water fastnesses: with Dye C.I. 45 170: Water fastness §t C.I. 41 000: water fastness 4 to 5.

Example 10 75 parts of p-tert-butylphenol, 0.5 part of 50% strength potassium hydroxide solution, 14 parts of water and 65 parts of 33% strength aqueous formaldehyde are heated to 60 ° C. for 2 hours warmed up.

Then one sets at 50 ° C one after the other and in small, evenly large servings 51.5 parts salicylic acid, 27.0 parts urine benzene sulfonic acid (o) and 8 parts of phthalic anhydride are added and the entire reaction mixture is heated 4 Hours at 100 ° C.

The product is placed in a steam-heated drying pan under reduced pressure Pressure evaporated and powdered after cooling.

171 parts of a gray-tinged powder are obtained, which is dissolved in acetone, Ethanol and Xthylglycol / Xthanol dissolve.

Finishing with flexographic printing inks according to the information in the example 1 have the following water fastness properties according to the test method according to DIN 16 524: with dye C.I. 45 170 4, C.I. @ 1,000 4.

Example 11 70 parts of p-nonylphenol, 0.3 parts of 50% sodium hydroxide solution, 14 parts of water and 55 parts of 33% strength aqueous formaldehyde are heated for 2 hours ouch 6000 Then mn 2 parts urineoxybenzenecarboxylic acid and heated for 2 hours at 40 ° C. Then 70 parts of phenoxyacetic acid are added and the mixture in 4 hours dehydrated at 100 ° C and after after cooling, the product is pulverized. 165 parts of powder are obtained.

The coating with a flexographic printing ink, produced according to the information in example i, has a water fastness of 4 to 5.

Example 12 40 parts of p, p'-dioxydiphenyl sulfone, 1 part of 50% sodium hydroxide solution and 60 parts of 33% strength aqueous formaldehyde are heated to 100 ° C. for 2 hours. then 70 parts of gallic acid and 5 parts of adipic acid are added and the mixture is 4 Heated for hours from fOOC. Then 3 parts of ureinonylbenzenesulfonic acid are added heated to 1000C for 2 hours and evaporated to dryness at 100 ° C. After pulverizing 160 parts of condensation product are obtained.

Water fastness 4 to 5 (flexographic printing ink produced according to the information in example 1).

Example 13 90 parts of p, p'-dioxydiphenylpropane, 10 parts of phenolsulfonic acid, 15 parts of 50% strength sodium hydroxide solution and 50 parts of 33% strength formaldehyde are held for 4 hours At 40 ° C., 30 parts of sulfanilic acid and 40 parts of salicylic acid are added and heated to 400C for 4 hours. Then 2 parts of uraminobenzenearboxylic acid are added, heated to 100 ° C for 4 hours and evaporated to dryness at 100 ° C. After puvlerizing 170 parts of condensation product are obtained.

Water fastness of the paintwork (see example 1) 4.

Example 14 94 parts of phenol, 100 parts of water, 50 parts of 33% strength aqueous Formaldehyde and 3 parts of 96% sulfuric acid are heated to 100 ° C. for 5 hours. After the aqueous layer has been separated off, 90 parts of salicylic acid are added and 5 parts of ureinonylbenzenesulfonic acid, heated 1/2 hour to HOoG and leaves in 3 hours at 40 ° C 50 parts Add formaldehyde dropwise. The mixture is then stirred until the formaldehyde odor has disappeared, evaporate to dryness at 1000C and pulverized. 180 parts of condensation product are obtained.

Claims (8)

Claims 1. A process for the preparation of alkali-soluble condensation products by reacting phenols and aromatic hydroxyc; bonic acids or aryloxy fatty acids with formaldehyde, characterized in that the reaction products obtained by condensation of phenols or naphthols with formaldehyde or formaldehyde-releasing compounds in an alkaline, acidic or neutral medium can be obtained at temperatures between 30 ° C. and the boiling point, in an alkaline, acidic or neutral medium in any order, one after the other or simultaneously with a) urea derivatives in which a hydrogen atom of an NH2 group is replaced by an aliphatic group of the formula in which R is hydrogen or an alkyl radical having 1 to 9 carbon atoms, or by aromatic groups of the formulas in which X is hydrogen or a substituent of the 1st order, has been replaced, and b) mononuclear aromatic carboxylic and / or sulfonic acids, which may contain hydroxyl or amino groups, and / or aryloxy fatty acids and / or aliphatic polycarboxylic acids with up to 8 C- Atoms, which can contain hydroxyl groups, also converts at temperatures between 300C and the boiling point. 2. The method according to claim 1, characterized in that one of Starts out reaction products by condensation of 1 mole of a phenol or Naphthol with 1 to 6 moles of formaldehyde or the equivalent amount a formaldehyde-releasing substance can be obtained. 3. Process according to claims 1 and 2, characterized in that as phenol p-tert-butylphenol is ver @@@ det. 4. The method according to claims 1 to 3, characterized in that that a mixture of salicylic acid and phthalic acid is used as (b). 5. The method according to claims 1 to 3, characterized in that that the condensation of phenols or naphthols with formaldehyde in alkaline Medium performs. 6. The method according to claims 1 to 5, characterized in that that the reaction product first with (a) at about 40 ° C to 60 ° C and then with (b) Reacts at about 70 ° C to 10,000. 7. The method according to claims 1 to 5, characterized in, that the reaction product is reacted first with (b) and then with (a). 8. The method according to claims 1 ba?, D a d u r c h g e k e n n note that you can get the reaction product with (a) and @@@ @@ @@@@ at about 700C to 100 ° C.