DE1259288B - Process for the production of real prints using the base printing methods - Google Patents

Description

Process for the production of real prints according to the methods of Base printing It has long been known to make real prints using the base printing methods Manufacture by treating the textile material with alkaline solutions of azo components the ice paint series and, after drying, with thickened diazo solutions Printed from aromatic amines, and dries the prints in the usual way completes. More recently have been used to produce water-insoluble azo dyes on the fiber amines of the heterocyclic series gained importance after diazotization and coupling with the azo components by treatment with metal donors be converted into metal complex compounds, whereby dyes are obtained, which have a high resistance and very good fastness properties. the Use of such heterocyclic amines for the production of true prints according to the methods of base printing "by printing the diazonium compounds together with the metal donating compounds and subsequent development to the azo dye with simultaneous metallization, however, caused difficulties because the metallization in many cases it was incomplete, took too long or took too long Temperatures, e.g. B._ Temperatures over 100`C '. required.

It has now been found that real prints can be produced much more easily by the methods of base printing if printing pastes are used to print the textile material primed with azo components of the ice color series. which in addition to the diazonium compound from a heterocyclic amine of the general formula where A denotes a heterocyclic 5- or 6-membered ring and B denotes a radical from the benzene or naphthalene series, a metal donating compound and optionally a metal complex-forming compound and the usual additives also contain a cationic, surface-active compound. The process is carried out in such a way that the material to be printed, e.g. B. Fabric made from vegetable fibers, such as cotton or regenerated cellulose, primed with the alkaline solution of the azo component and then dried. The material treated in this way is then printed with the printing pastes, which are expediently prepared as follows: The solid diazonium compound from the heterocyclic amine is dissolved in water containing an organic acid, for example acetic acid, or the heterocyclic amine is mixed with sodium nitrite in the usual way and hydrochloric acid diazotized and the diazo solution obtained blunted with alkali acetate. The diazo solution thus obtained is in one of the usual thickenings, for. B. starch-tragacanth thickening, stirred in and the resulting thickened diazo solution mixed with the metal donating compound, the cationic, surface-active compound and optionally other auxiliaries and optionally metal complex-forming compounds and adjusted to 1 kg. It is then dried and the metallization is completed by treatment in a hot, preferably alkaline, water bath. The metallization can also be carried out by neutral steaming at temperatures around or above 100 ° C., but the use of such high temperatures is generally not necessary in the present process, since the use of the cationic, surface-active compounds in the printing pastes means that the metallization is essential and can therefore be carried out at lower temperatures than usual.

Arylamides are found as azo components in the present process use of aromatic or heterocyclic o-oxycarboxylic acids or acyl acetic acids, for example aryl amides of 2,3-oxynaphthoic acid or those substituted in the 6-position Derivatives, of 2-oxyanthracene-3-carboxylic acid, of 2-oxycarbazole-3-carboxylic acid, of 5-oxy-1,2,1 ', 2'-benzocarbazole-4-carboxylic acid, 3-oxy-diphenylene oxide-2-carboxylic acid, 3-oxydiphenylenesulfide-2-carboxylic acid, acetoacetic acid, benzoylacetic acid or terephthaloyl-bis-acetic acid. As heterocyclic amines. come for example 2- (2'-aminoaryl-4,5-arylene-1,2,3-triazoles, 2- (2'-aminoaryl) -4,5-arylene-1,2,3-triazole-1-oxides, 8-aminoquinolines, 7-aminoindazoles, 3-aminoindazoles, 7-aminobenzimidazoles, 7-aminobenzotriazoles, 1-aminocarbazole, 2 - (2'-aminophenyl) -benzimidazole, 2- (2'-aminophenyl) -benzthiazole, 1- (2'-aminoaryl) -1,2,3,4-tetrazoles, 5- (2'-aminoaryl) -1,2,3,4-tetrazoles, 2- (2'-aminoaryl) -1.3 , 4-triazoles, 2- (2'-aminoaryl) -1,3,4-oxdiazoles, 2- (2'-aminoaryl) -1,3,4-thiodiazoles, 4-aminobenzo-2,1,3-thiodiazoles and 3-amino-1-phenyl-5-imino-4,5-dihydro-1,2,4-triazole.

In particular, the water-soluble compounds are used as metal-releasing compounds Use of salts of copper, nickel or cobalt, for example sulfates, chlorides, Bromides, nitrates, acetates, formates and salts of organic sulfonic acids.

As complex-forming compounds that may be used can be mentioned, for example: alkali metal phosphates, e.g. B. Alkalimeta-, Alkalipyr- or alkali polyphosphates, alkanolamines, e.g. B. diethanol or triethanolamine, aliphatic Dicarboxylic acids, e.g. B. oxalic acid or maleic acid, aliphatic oxycarboxylic acids, z. B. citric acid, tartaric acid, lactic acid or gluconic acid, also aliphatic Aminocarboxylic acids, e.g. B. aminoacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid or glutamic acid.

Quaternary ammonium compounds of the general formula are preferably used as cationic surface-active agents Consider, where R is a high molecular weight organic radical with at least 8 carbon atoms, R1, R2 and R3 are alkyl, aralkyl or aryl radicals which can be substituted or can form a heterocyclic ring together with the nitrogen atom, and X is an anion.

R can be an aliphatic, straight-chain or branched hydrocarbon radical with 8 to 30 carbon atoms, which has one or more double bonds, heteroatoms, such as B. oxygen, sulfur or optionally quaternized nitrogen atoms, or functional groups, such as. B. carboxylic acid groups contained in the chain can. R can also be aromatic, hydroaromatic or cycloaliphatic Rest that can carry aliphatic side chains. The alkyl or aryl radicals R1, R2 and R3 can be identical or different and optionally have substituents contain, for example halogen atoms, alkyl, aralkyl, oxyalkyl or polyglycol ether groups. You can also together with the nitrogen atom a heterocyclic ring, for. B. form a pyridine, morpholine, imidazole or oxazole ring. The anion X can be inorganic or organic in nature and, for example, the remainder of a hydrohalic acid, such as hydrochloric or hydrobromic acid, or another inorganic one Acid, e.g. B. sulfuric acid, phosphoric acid or boric acid, or the rest of a organic carboxylic acid, e.g. B. acetic acid, formic acid, oxalic acid, lactic acid, Tartaric acid, gluconic acid, citric acid or benzoic acid, or the remainder of an organic one Sulfonic acid, e.g. B. methanesulfonic acid or benzenesulfonic acid.

Suitable quaternary ammonium compounds are, for example, dodecyl-dimethyl-benzyl-ammonium chloride, oleyl-trimethyl-ammonium chloride, distearyl-dimethyl-ammonium chloride, lauryl-dimethyl-oxyethyl-ammonium chloride, dodecyl-dioxyethyl-methyl-ammonium chloride, dodecyl-dimethyl-vinyl-ammonium chloride, dodecyl -methyl-morpholinium chloride, lauryl-pyridinium chloride, hexadecyl-N, N'-dimethyl-benzimidazolinium sulfate, dodecyl-di- (triethylene glycol ether) -benzylammonium chloride, phenylnonyl-dimethyl-benzyl-ammonium chloride, oleyl-di- (oxyethylene glycol) -ether Oleyl-dimethyl-oxyethyl-ammonium chloride, coconut-di- (triethylene glycol ether) -benzyl-ammonium chloride, coconut-dimethyl-benzyl-ammonium chloride, distearyl-dimethyl-ammonium chloride, trioctyl-methyl-ammonium chloride, coconut-dimethyl-oxypropyl-ammonium chloride, p- Diisobutylphenoxyethoxyethyl-dimethylbenzylammonium chloride, oleyl-methyl-imidazolinium chloride, dehydroabietyl-dimethyl-benzylammonium chloride or compounds of the formulas, Quaternary phosphonium compounds of the general formula can also be used as cationic, surface-active compounds or tertiary sulfonium compounds of the general formula in which R, Ri> R # 2 and Ra and X have the meaning given above, are used. Suitable quaternary phosphonium compounds are, for example, dodecyl dimethyl benzyl phosphonium chloride, dodecyl trimethyl phosphonium chloride, dodecyl dimethyl oxyethyl phosphonium chloride, coconut dimethyl benzyl phosphonium chloride, oleyl dimethyl benzyl phosphonium chloride. Examples of ternary sulfonium compounds are: dodecyl methyl benzyl sulfonium chloride, dodecyl dimethyl sulfonium chloride, dodecyl pentaoxyethyl benzyl sulfonium chloride, coconut methyl benzyl sulfonium chloride, oleyl methyl benzyl sulfonium chloride. Example 1 Cotton fabric is padded and dried on the padder with a squeeze effect of 70% with the following solution: 20 g of 2,3-oxynaphthoylaminobenzene are dissolved with 10 g of sodium castor oil, 30 cc of 38 % caustic soda and 150 cc of boiling water Water set to 11.

Then it is printed with the printing paste described below, dried, treated for 30 to 40 seconds in a hot, aqueous bath at 95 ° C, which contains 20 ccm sodium hydroxide solution of 38 "Be and 20 g soda in one liter of water, rinsed with hot water and finally soaped for 2 minutes at 95 ° C in a bath in one liter of water Contains 3 g of soap and 1 g of soda, rinsed and dried.

Printing paste 27 g of 2- (2'-amino-4 ', 5'-diethoxyphenyl) -6-methoxy-benzotriazole-1-oxide in the form of a diazonium compound prepared in the usual way are in Dissolved 20 cc of acetic acid, 50%, and 150 cc of water. The solution becomes neutral in 500 g Starch-tragacanth thickening 40: 1000 stirred in. Then 8 g of copper sulfate are dissolved in 50 ccm of water, 20 g of diethyl sulfide, 20 g of dodecyl-dimethyl-benzyl-ammonium chloride, 50% and 30 g emulsified mineral oil added. Subsequently, water is applied 1 kg set.

A brown print is obtained, the hue of which when using non-ionic or anion-active products, such as. B. the product of action of about 10 moles of ethylene oxide to 1 mole of nonylphenol, the product of action of about 20 moles of ethylene oxide 1 mole of octodecyl alcohol or the condensation product of an aminoalkyl sulfonic acid and a higher molecular weight fatty acid instead of dodecyl - dimethyl - benzyl - ammonium chloride, 50% ,. only after a steaming time of 5 to 10 minutes at 120 ° C is achieved.

If the following compounds are used instead of dodecyl-dimethyl-benzylammonium chloride, 50%, the same result is achieved: Example 2. Cotton fabric is padded and dried on the padder with a squeeze effect of 70% with the following solution: 20 g of 2,3-oxynaphthoylaminobenzene are dissolved with 10 g of sodium castor oil, 30 cc of sodium hydroxide solution at 38 ° Be and 150 cc of boiling water and mixed with boiling water Water set to 11.

It is then printed with the printing paste described below, dried, treated for 30 to 40 seconds in a hot, aqueous bath at 95 ° C. which contains 20 cc of 38 % sodium hydroxide solution and 20 g of soda in one liter of water, rinsed with hot water and then rinsed for 2 minutes Soaped at 95 ° C in a bath containing 3 g of soap and 1 g of soda per liter of water, rinsed and dried.

Printing paste 5 g of 3-amino-6-chloroindazole in the form of a standard Diazonium compounds prepared in this way are in 15 ccm hydrochloric acid of 20 ° B6 and Dissolve 200 cc of water. The solution is in 500 g of neutral starch - tragacanth - thickening 40: 1000 stirred in. Then 6 g of sodium tartrate, dissolved in 20 ccm of water, 6 g of cobalt chloride, dissolved in 20 cc of water, 20 cc of dioxydiethyl sulfide, 20 cc of dodecyl-dimethylbenzyl-ammonium chloride and 20 cc of emulsified mineral oil added. Then with water to 1 kg set.

A green print is obtained, the color of which when using non-ionic or anion-active products instead of dodecyl-dimethyl-benzylammonium chloride is only reached after a steaming time of 5 to 10 minutes at 120 ° C.

Claims (1)

Claim: Process for the production of real prints by the methods of base printing, characterized in that printing pastes are used for printing the textile material primed with azo components of the ice color series, which, in addition to the diazonium compound, consist of a heterocyclic amine of the general formula where A denotes a heterocyclic 5- or 6-membered ring and B denotes a radical from the benzene or naphthalene series, a metal donating compound and optionally a metal complex-forming compound and the usual additives also contain a canonical, surface-active compound.