Hoechst Aktiengesellschaft

Hoechstaktiengesellschaft

Reinhard Mohr

Kurt Hohmann

Manfred Hahnke

Rudolf Neeb

Eberhard Mundlos

Peter Mischke

Erwin Fleckenstein

Rudolf Lowenfeld

Konrad Lohe

Luis Herz

Norbert Kollodzeiski

Chlorozincate salts of benzothiazonium azo compounds are prepared by reacting benzothiazolium azo compounds with an dialkylsulfate having from 1 to 4 carbon atoms in the alkyl radicals, which process comprises carrying out the reaction in an aqueous medium at a temperature of from 10.degree. to 80.degree. C. in the presence of an acid acceptor and the alkylation with the use of from 1.8 to 2.5 mols of the dialkylsulfate, calculated on the starting azo dyestuff, at a pH not exceeding 7. The prepared benzothiazolium azo compound is precipitated as chlorozincate salt, especially with the use of an alkali metal chloride. According to this process, the chlorozincate salts are obtained in higher purity. A perceptible decomposition of the benzothiazolium azo compound does not occur. Chemicals, for example the alkylation agent and acid-binding agents need be used in a small quantity. In addition to this economy and to the less pollution of the waste water, the process has the advantage that it can be carried out with the use of a small reaction volume.

Process for the preparation of chlorozincate salts of benzo thiazolium

Improvement of a process for spin-dyeing acid-modified polymers or copolymers of acrylonitrile in which cationic quaternary dyestuffs are added to the spinning mass and spun according to the wet-spinning procedure. The improvement is characterized by using dyestuffs characterized by a migration factor M of 20 or less than 20, by a combination index K of less than 2.5 and a cation weight of more than 310. Migration factor M and combination index K are known values in the dyestuff field or can be determined. The dyestuff to be used according to the invention can belong to the most different classes of dyestuffs; they fix rapidly on the polymer, and thus they do not color, or color only to a minor extent, the coagulation, stretching and washing baths although they are soluble in water and aqueous solutions of these baths. The fibers and filaments obtained by the process of the invention have outstanding fastnesses to wet processing and, owing to the absence of dyestuff aggregates at the surface of the fiber such as occur when spin-dyeing with pigments, very good fastnesses to dry and wet rubbing. The fibers are intense, absolutely transparent and free from specks.

Process for spin-dyeing of acid-modified polymers of copolymers of

Fiber material composed of acid-modified homopolymers or copolymers of acrylonitrile (PAC fibers) which has been obtained by a wet spinning process, has not been dried and is still in a swollen condition (gel form), can be dyed advantageously and in fast colors by means of soluble dyes, the molecule of which contains several groups, namely more than one quaternary grouping and/or a strongly basic grouping carrying no charge, which exert a basic action towards the acid groups of the fiber substance. The chromophore of this colorant can belong to the category of monoazo or diazo dyes, methine, azamethine or diazamethine dyes or naphthalactam dyes. In accordance with the invention, after substantially removing the non-aqueous spinning solvent by washing, the spun material, as a moist gel, is dyed continuously or discontinuously from an aqueous dyebath; the fibers can be stretched before the dye is applied, during the dyeing process itself or immediately afterwards. By virtue of their special nature, the dyes of the type designated above, which have a strong fixing action, produce optimum fixing rates when dyeing PAC gels and, in the subsequent production stages, do not cause any noticeable soiling, as a result of dye which has bled out, on components of machines and operating baths, such as stretching or after-treatment baths. Investigations of penetration of the fiber by the dye, of the fixing rate and of the resulting fastness properties, such as fastness to wet processing, have shown no disadvantages compared with conventional dyes.

Process for dyeing, in the gel state, fiber material composed of wet

Process for spin-dyeing of acid-modified polymers of acrylonitrile by

Zinc chloride complex compounds to which the structure of the general formula (1) ##STR1## can be assigned, in which the individual radicals in the formula have the following meanings: Rhu 1 is a hydrogen atom or an optionally substituted lower alkyl group; R.sup.2 is a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted phenyl radical; R.sup.3 is a hydrogen atom or an optionally substituted lower alkyl group; R.sup.4 is a hydrogen atom, an optionally substituted lower alkyl group or an optionally substituted phenyl radical; R.sup.5 is a hydrogen atom or a halogen atom or a lower alkyl group or a lower alkoxy group, or R.sup.1 and R.sup.5 together form the o-phenylene radical; R.sup.6 is a hydrogen atom or a halogen atom or a lower alkyl group or a lower alkoxy group; Z is a hydrogen atom or a halogen atom or a lower alkyl group or a cyano, carboxylic acid, carbamoyl or sulfamoyl group or a carbamoyl or sulfamoyl group which is monosubstituted or disubstituted by lower alkyl, or a trifluoromethyl or lower carbalkoxy group, a lower alkoxy group which can be substituted by cyano, an acyloxy group, an acylamino group, a lower alkylamino group or a lower dialkylamino group. They are prepared by reacting a nitroso compound of the formula (2) ##STR2## in which R.sup.3, R.sup.4, R.sup.6 and Z have the meanings mentioned above, with an m-aminophenol of the formula (3) ##STR3## in which R.sup.1, R.sup.2 and R.sup.5 have the meanings mentioned above, in the presence of zinc chloride and in the absence of a base. The zinc chloride complex compounds of the formula (1) can be converted by eliminating the radical Z in the formula or by removing, by oxidative means, this radical Z, in the formula, which is in the ortho-position in relation to the nitrogen atom, or the other hydrogen atom which is in the ortho-position, into the phenoxazine dyestuffs of the formula (4) ##STR4## in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 have the meanings mentioned above and Z.sub.1 denotes a halogen atom, a lower alkyl group, a cyano, carboxylic acid, carbamoyl or sulfamoyl group, a carbamoyl or sulfamoyl group which is monosubstituted or disubstituted by lower alkyl, or a trifluoromethyl or lower carbalkoxy group or a hydrogen atom and X.sup.(-) represents and anion.

Zinc chloride complex compounds

Novel azamethine compounds of the formula (1) ##STR1## in which R is alkyl of from 1 to 4 carbon atoms optionally substituted, Alk is alkyl of from 1 to 4 carbon atoms, Y is the methine radical or a nitrogen atom, R.sub.1 is hydrogen or alkyl of from 1 to 4 carbon atoms optionally substituted, alkylene is an alkylene group of from 2 to 6 carbon atoms, Z is a group of the formula (2a) or 2(b) ##STR2## in which R.sub.2 is alkyl of from 1 to 4 carbon atoms optionally substituted, R.sub.3 is alkyl of from 1 to 4 carbon atoms optionally substituted, or is phenyl unsubstituted or substituted by chlorine, alkyl of from 1 to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms, nitro, carbalkoxy of from 2 to 5 carbon atoms and/or carbamoyl, R.sub.4 is hydrogen or alkyl of from 1 to 4 carbon atoms optionally substituted, or R.sub.2 and R.sub.3 together with the nitrogen atom form a heterocyclic ring containing optionally nitrogen, oxygen or sulfur as a further hetero atom, or R.sub.2 and R.sub.3 or R.sub.2, R.sub.3 and R.sub.4 together with the positive nitrogen form a heterocyclic ring containing optionally nitrogen, oxygen or sulfur as a further hetero atom, the benzene nucleus A is unsubstituted or substituted by halogen, nitro, cyano, sulfamoyl, alkyl of from 1 to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms and/or carbalkoxy of from 2 to 5 carbon atoms, the benzene nucleus B is unsubstituted or substituted by halogen, nitro, alkyl of from 1 to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms and/or carbalkoxy of from 2 to 5 carbon atoms, n is the integer 1 or 2, and X.sup.(-) is the equivalent of a colorless anion. These novel compounds can be prepared in usual manner analogously to known processes using the corresponding indoline and alkoxyaniline derivatives as starting compounds with optional subsequent alkylation. The novel azamethine compounds are well suitable as dyestuffs, soluble in water and in acids as well as in various organic solvents, for the dyeing of preferably acid-modified aromatic polyesters, acid-modified polyamides and acid-modified polyacrylonitrile materials, especially those in the form of fibres or in the mass by means of a spin-dyeing procedure.

Quaternary and basic azamethine compounds and their use as colorants

Chlorozincate salts of thiazolium azo compounds are prepared by reacting thiazolium azo compounds with an dialkylsulfate having from 1 to 4 carbon atoms in the alkyl radicals, which process comprises carrying out the reaction in an aqueous medium at a temperature of from about 10.degree. to 50.degree. C. in the presence of a zinc compound capable of binding acid, and with the use of from 1.8 to 2.5 mols of the dialkylsulfate, calculated on the starting azo dyestuff, at a pH not exceeding 8, preferably at 3-7. The prepared thiazolium azo compound is precipitated as chlorozincate salt, especially by means of an alkali metal chloride. According to this process, the chlorozincate salts are obtained in higher purity. A perceptible decomposition of the thiazolium azo compound does not occur. Chemicals, for example the alkylation agent and acid-binding agents need be used in a small quantity. In addition to this economy and to the less pollution of the waste water, the process has the advantage that it can be carried out with the use of a small reaction volume.

Process for the preparation of chlorozincate salts of thiazolium azo

A dyeing process has been found which enables to dye uniformly polyacrylonitrile fiber materials, by using as dyestuffs basic azo dyestuffs being non-quarternized and containing neither cationic quaternary ammonium groups nor cationic N-substituted or N-unsubstituted iminium groups, said azo dyestuffs containing on the other hand at least one unsubstituted or substituted amino group, hydrazino group, amidino group or guanidino group capable of forming salts. The very dyeing process as such is carried out according to usual processing data for dyeing polyacrylonitriles in a slightly acid medium. Especially with the use of several of these dyestuffs for polychromic dyeing, such as trichromic dyeing, special advantages are obtained, insofar that even at cut-rate dyeing periods and for preparing light color shades, there are obtained even dyes with constant color shades, when using these dyestuffs having good migrating properties.

Process for dyeing uniformly polyacrylonitrile fiber materials

Azo-dyestuff of the formula ##STR1## in which D represents nitrophenylene, ##STR2## DINITRO-PHENYLENE, NITRO-CYANO-PHENYLENE, NITRO-CHLORO-PHENYLENE, NITRO-BROMO-PHENYLENE, TRICHLORO-PHENYLENE, NITRO-DICHLORO-PHENYLENE, DINITRO-CHLORO-PHENYLENE, DINITRO-CYANO-PHENYLENE, NITRO-BROMO-CYANO-PHENYLENE, DINITRO-BROMO-PHENYLENE, PHENYLAZO-PHENYLENE, ##STR3## R represents hydrogen, chlorine, lower alkyl, lower alkoxy, --O--CH.sub.2 --CN, --NH--CO--lower alkyl, --NH--COO lower alkyl or ##STR4## n stands for the integer 1 or 2, X represents cyano, --CO--NH.sub.2 or --COO-lower alkyl, R.sub.1 represents hydrogen, lower alkyl, lower alkylene-OH, lower alkylene-CN, lower alkylene-OCO-lower alkyl or lower alkenyl, and R.sub.2 represents lower alkyl, lower alkylene-O-CO-lower alkyl or lower alkylene-COO-lower alkyl, said dyestuffs being suitable for the dyeing or printing of synthetic fibrous materials, such as fibers of cellulose-di-, -21/2- or -triacetat, polyamides, polyurethanes, polyolefines, polycarbonates and particularly of linear polyesters, the dyeings or prints obtained being distinguished by a very good build up, tinctorial strength and a series of very good fastness properties.

Water-insoluble monoazo-dyestuffs for synthetic fibrous materials

It has been found that nickel-containing polyolefins can be dyed and printed in deep colors and with very good to excellent fastness properties when a thiazole-azo-(3-cyano-2,6-dihydroxypyridine) dyestuff is used.

Process for dyeing and printing nickel-containing polyolefins

New basic azo dyestuffs of the formula ##STR1## where D.sup.(+) is the radical of an aromatic or heterocyclic diazo component containing a quaternary nitrogen atom,

Quaternary basic azodyestuffs containing a propenyl amino radical

A process for the direct preparation of pure thiazolazo compounds had been found with the use of a 2-aminothiazole as diazo or azo component in a coupling process wherein the 2-aminothiazole used therein is subjected to the usual coupling reaction, if used as diazocomponent after diazotation, without intermediate isolation after its preparation in known manner. This process avoids the preparation of the 2-aminothiazoles as starting compounds in its solid form and the expensive purification of these instable compounds and yields now very pure azo products.

Process for preparing an azo compound from a 2-aminothiazole diazo

New valuable basic oxazine dyestuffs of the formula ##STR1## in which R is hydrogen or lower alkyl, R.sub.1 is hydrogen or lower alkyl substituted by halogen, lower alkoxy, cyano or hydroxy, R.sub.2 and R.sub.3 each is hydrogen or lower alkyl or lower alkyl substituted by halogen, lower alkoxy, cyano or hydroxy, or R.sub.1 and R.sub.2 form together with the nitrogen atom the pyrrolidino, piperazino, piperidino or morpholino ring, and the phenyl nucleus a is substituted by lower alkyl, lower alkoxy, acetyl, cyano, halogen, phenoxy or trifluoromethyl, and X.sup.(.sup.-) is an anion has been found which are well suitable for the dyeing or printing of tanned cellulose fibers, silk, leather, or acetate rayon, synthetic polyamide fibers or acid-modified polyester and polyamide fibers and fibers containing polyacrylonitrile or polyvinylidene cyanide. The dyeings and prints obtained are bright and color-intensive and have good fastnesses to light and to wet processing.

Basic oxazine dyestuffs

Dyestuffs of the formula ##EQU1## IN WHICH Alk is lower alkyl and in which the phenyl nucleus may be further substituted by nonionic substituents, n is 2 to 6 and x is a number of 1 up to but excluding 2, are useful for dyeing polymers containing acidic groups. These dyestuffs yield stable compositions containing 20 to 40 % by weight of one or more of said dyestuffs, 20 to 40 % by weight of an organic solvent, 20 to 40 % by weight of a nonionic dispersant of the alkylphenolpolyglycolether or fat alcohol polyglycolether type and up to 20 % by weight of water.

N-Alkyl nitro phenyl diethylene triamine dyeing of acid modified

Dyestuffs of the formula ##EQU1## IN WHICH Alk is lower alkyl and in which the phenyl nucleus may be further substituted by nonionic substituents and n is 2 to 6, are useful for dyeing polymers containing acidic groups. These dyestuffs yield stable compositions containing 20 to 40 % by weight of one or more of said dyestuffs, 20 to 40 % by weight of an organic solvent, by weight of an organic solvent, 20 to 40 % by weight of a nonionic dispersant of the alkylphenol polyglycolether or fat alcohol polyglycolether type and up to 20 % by weight of water.

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Offenbach am Main, Germany

Reinhard Mohr