MXPA99004540A - Mixture of reagent azocolorants to the fibers, soluble in water, preparation of the same and use of the - Google Patents

Abstract

The present invention relates to dye mixtures of the general formulas (1) and (2) wherein M is hydrogen, ammonium, an alkali metal or equivalent of an alkaline earth metal, R1 is hydrogen or sulfo, R2 is hydrogen or sulfo, each of X1 and X2 is fluorine, chlorine, amino which can be mono- or disubstituted by lower alkyl or optionally substituted aryl and one of the radicals possesses a group of the formula -SO2-Y1-SO2-Y2, wherein each one of Y1 and Y2 is vinyl or ethyl substituted in the position by a removable alkali group, or each of X1 and X2 is optionally substituted morpholino or pyrimidino, cyanoamino, hydroxyl, lower alkoxy or optionally substituted aryloxy and wherein the -SO2- groups Y1ó-SO2Y2 are bonded to the meta benzene nuclei or to the azo or amino group, the novel dye mixtures are used to color hydroxyl and / or carboxamide containing material, preferably fiber material, such as cellulose fiber materials. slab, wool and synthetic fibers of poliami

Description

MIXTURE OF REAGENT AZOCOLORANTS TO FIBERS, SOLUBLE IN WATER, PREPARATION OF THE SAME AND USE OF THE SAME DESCRIPTIVE MEMORY The patent of E.U.A. 4,485,041, European Patent Application Publication No. 0,094,055 and German Patent No. 4,417,719 disclose dyes that conform to the general formulas (1) and (2) indicated and defined later herein. They have certain defects of application, for example insufficient strength in washing, excessive dependence on the color yield on the changing coloring parameters in the coloring process, insufficient solubility in the aqueous dye bath at higher dye concentrations in the presence of salts electrolytic electrolytes or insufficient color formation on cotton and especially viscose (good color formation results from the ability of a colorant to produce a correspondingly stronger coloration from an increased dye concentration in the dyebath). The possible consequences of these deficiencies are the scarce reproduction capacities for the colorations that are obtainable. However, it is particularly important to obtain colorations having good color rendering, ie, colorations whose hue depth is very high in relation to the amount of colorant used, for example in comparison with other colorants, because the coloration property of the colorant dye itself (high absorbency) and by the coloring characteristics of this dye, such as good affinity and high fixing performance. If mixtures of dyes having a certain color yield are used, the color yield of this dye mixture will generally be the sum total of the color yields of the individual dyes; with this, the color yield of a mixture, for example, of two dyes will be less than the resulting color yield of the dye having the highest color rendering property that is being used as a single dye in the same amount of the mixture of the two individual dyes. The present invention then provides mixtures of colorants of the azo dyes comprising one or more, such as two or three, azo dyes that conform to the general formula (1) and one or more, such as two or three, azo dyes that are they conform to the general formula (2), whose intensity of color is surprisingly higher than the sum total of the color intensities provided by the individual dyes of the dye mixture. This synergistic effect is also noted in the improved forming characteristics and the better firmness in the washing of part of the mixture of the invention in comparison with the individual dyes present in the mixture. (2) (D In these formulas: M is hydrogen, ammonium, an alkali metal or the alkaline earth metal equivalent; R1 is hydrogen or sulfo; R2 has one of the meanings of R1; X1 is fluorine or chlorine or a group of the general formula -NR3R4 or OR3, wherein R3 is H or C1-C4 alkyl or aryl (such as phenyl), which is optionally substituted, and R4 has one of the meanings of R3 or is an aryl having Y1-SO2- or Y2-SO2- (such as phenyl) or a C1-C4 alkyl group, or -NR3R4 is morpholino or pyrimidino or -NHCN optionally substituted; x has one of the meanings of X1; Y1 is vinyl or a group of the general formula -CH2-CH2-Z, wherein it is a substituent that can be removed by the action of alkali, sulfate, thiosulfate or acetyloxy; Y2 the groups -SO2-Y1 and -SO2-Y2 are arranged in the meta position or for the azo group or the amino group. In general, the azo dye of the general formula (1) and the azo dye of the general formula (2) are present in the mixture in a mixed ratio of 90: 10% by weight to 10: 90% by weight, preferably in a ratio from 70: 30% by weight to 30: 70% by weight. They are particularly preferably present in the mixture in a ratio of 55:45 to 45: 55% by weight. Preferably, in the general formulas (1) and (2), R1 = hydrogen, M = H, Li or Na and preferably each of X1 = X2 is chloro or fluoro. Also, preferably, Y1 and Y2 are -CH2-CH2-Z wherein Z = sulfate. In the preceding general formulas and also in the subsequent general formulas, the individual elements of the formulas, if they have identical or different designations within any general formula, can have meanings according to their definition that are mutually identical or different. The terms "sulfo", "thiosulfate", "phosphate" and "sulfate" cover not only the acid form, but also the salt form of the respective groups. According to the above, sulfo groups are groups that conform to the general formula -SO3M, thiosulfate groups are groups that they conform to the general formula -S-SO3M, the phosphate groups are groups that conform to the general formula -OPO3M2 and the sulfate groups are groups that conform to the general formula -OSO3M, wherein each M is as defined above . The dye mixtures of the invention may be present as a preparation in solid form or in liquid (dissolved) form. In solid form, they generally include customary electrolyte masses for water-soluble dyes especially for reagents with fibers, such as sodium chloride, potassium chloride and sodium sulfate, and may also comprise the auxiliary materials customary in commercial dyes, such as pH regulating substances capable of adjusting a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate, sodium tricitrate and disodium hydrogen phosphate, small amounts of Drying agents or, if they are present in aqueous liquid solution (including the presence of thickeners of the type customary in printing pastes), these substances ensure a long duration for these preparations, for example mold preventers. In general, the dye mixtures of the invention are present as coloring powders comprising from 10 to 80% by weight, based on the coloring powder or the preparation, of an electrolyte salt, which is also known as a normalizing agent. These powders may further comprise the aforementioned pH buffer substances in a total amount up to 5% by weight, based on the coloring powder. If the dye mixtures of the invention are present in aqueous solution, the total dye content of these aqueous solutions is up to about 50% by weight, for example between 5 and 50% by weight, and the content of the The electrolytic salt of these aqueous solutions is preferably less than 10% by weight, based on the aqueous solution; the aqueous solutions (liquid preparations) may include the aforementioned pH buffer substances in an amount which is generally up to 10% by weight, preferably up to 2% by weight. The dye mixtures of the present invention are preparable in a conventional manner, for example by mechanically mixing the individual dyes known from the aforementioned publications and present in solid or liquid form, in the required proportions or by synthesis by means of the usual diazotization reactions. and coupling conversion reactions with the haiogenotrizine components using appropriate mixtures of various components in a manner known to the person skilled in the art and with obtained mixing ratios. For example, in a possible process, which is preferably carried out as a reaction in a single crucible, a 2,4,6-trihaiogen-s-triazine, especially 2,4,6-trichlor or 2-triazine, is initially reacted. , 4,6-trifluoro-s-triazine, in a conventional manner with 1-amino-8-naphthol-3,6-disulfonic acid, for example at a temperature of 0 to 40 ° C, preferably from 0 to 10 ° C, and a pH from 0 to 5, preferably from 1 to 2, and then with one or more amino compounds of the general formula (3A) or 3B) (3A) (3B) (3A) 4 (3B) 4 wherein each R1, R2, Y1 and Y2 are defined above or a mixture of one or more amino compounds the general formulas (3A) and (3B) in conventional manner, for example at a temperature between 0 and 60 ° C, preferably between 20 and 40 ° C, and a pH between 2 and 8, preferably between 3 and 5. The resulting diaminohalotrizine compounds can then be coupled with a diazonium salt prepared from an identical or different amine of the general formula (3A) or 3B) or two such amines in a well-known manner to form the mixture of the dyes (1) and (2) in a conventional manner, for example at a temperature between 10 and 50 ° C, preferably between 20 and 40 ° C, and a pH between 3 and 7, preferably between 4 and 5. The dyes of the general formulas (1) and (2) wherein X1 and X2 are not halogens are prepared by reacting the mixture with the HOR3 or HNR3R4 compounds in a conventional manner, for example at a temperature between 10 and 100 ° C, preferably between 40 and 80 ° C, and a pH between 3 and 7, preferably between 4 and 5. The starting compounds of the general formula (3B) are for example 4- (β-sulfatoethylsulfonyl) aniline, 3- (β-) sulfatoethylsulfonyl) aniline, 2-sulfo-4- (β-sulfatoethylsulfonyl) aniline and 2-sulfo-5- (β-sulfatoethylsulfonyl) aniline, especially 4- (β-suldatoethylsulfonyl) aniline, and also derivatives of these compounds in which they replace ß-sulfatoethylsulfonyl with a vinylsufonyl or ß-thiosulfatoethylsulfonyl group or ß-chloroethylsulfonium. The separation from its synthesis solution of the chemically produced dye mixtures of the invention by commonly known methods, for example, has already been precipitated by reaction electrolytes, sodium chloride or potassium chloride, evaporating or spray drying the reaction solution, in which case this reaction solution may have a pH regulating substance added thereto. The dye mixtures of the invention have useful application properties. They are used to color or print hydroxyl and / or carboxamide-containing materials, for example in the form of sheet-like structures, such as paper and leather, for films composed, for example, of polyamide, or in bulk, such as polyamine or polyurethane, but especially to color and print those materials in the form of fiber. Similarly, the solutions obtained in the synthesis of the azo compounds after their mixing to form the dye mixture of the invention, if desired after the addition, or with it, of a pH regulating substance, and also if desired after concentrating or diluting, can be used directly as a liquid concentration to be colored. The present invention thus also provides the use of the dye mixture of the invention to color or print these materials or rather methods for coloring and printing these materials in a conventional manner, using a mixture of dyes of the invention as dye. The materials are preferably used in the form of fiber materials, especially in textile fiber, such as woven fabrics or yarns, in the form of skeins or rolled packages. The hydroxyl-containing materials are those of natural or synthetic origin, for example of cellulose fiber materials or their products generated and polyvinyl alcohols. The cellulose fiber materials are preferably cotton, but are also other vegetable fibers, such as flax, hemp, jute and ramie fibers; regenerated cellulose fibers are for example common viscose and viscose filaments. Carboxamides are for example synthetic and natural polyamides and polyurethanes, especially in the form of fibers, for example wool and other animal hair, silk, leather, nylon-6, 6 nylon-6, nylon-1 1 and nylon-4-. The dye mixtures of the invention can be applied to the substrates mentioned, or fixed thereon, especially the mentioned fibrous materials, by the known application techniques for water-soluble dyes, especially dyes reactive with fibers. For example, on the cellulose fibers produced from a long-range liquor by the depletion method and by means of several known binding agents with neutral salts, or without them, such as sodium chloride and sodium sulfate, colorations They have very good color yields which are improved compared to the individual dyes. It is preferably colored from an aqueous bath at temperatures between 40 and 105 ° C, if desired at temperatures up to 130 ° C at a pressure above atmospheric and, if desired, in the presence of customary coloring auxiliaries. A possible procedure is to introduce the material to the hot bath and gradually heat the bath to the desired color temperature and complete the coloring procedure at that temperature. Neutral salts that accelerate the exhaustion of dyes can not be added, if desired, to the bath until after the actual coloration temperature has been reached. The pad inking process also produces excellent color performances and very good color formation on the cellulose rows, on which the fixing can be carried out by batching at room temperature or elevated temperature, for example up to about 60 ° C. , with steam or with dry heat in a conventional manner.

Similarly, the usual printing processes for cellulose fibers, which can be carried out either in single phase, for example by printing with a printing paste comprising sodium bicarbonate or some other acid binding agent, and emitting steam subsequently between 100 and 130 ° C, or in double phase, printing for example with neutral or weakly acidic printing paste and the subsequent fixing is already passing the printed material through an alkaline comprising hot electrolyte or over-applying with pad with an alkaline liquor for inking with pad comprising electrolyte, with the subsequent batch production of this treated material or the subsequent vapor emission or the subsequent treatment with dry heat, produces strong impressions with well-defined contours on a light white base. The appearance of the impressions is not greatly affected by variations in the fixing conditions. When heat is fixed by means of dry heat according to the usual heat-sealing procedures, hot air of 120 to 200 ° C. In addition to the virtual test at 101 and up to 103 ° C it is also possible to use superheated steam and high pressure value at temperatures up to 160 ° C. The acid binding agents which effect the fixation of the colorants of the dye mixtures of the invention on the cellulosic fibers include, for example, water-soluble basic salts of alkali metals and likewise alkaline-earth metals of inorganic or organic acids or compounds. They release alkali in the heat. They are especially suitable are the alkali metal hydroxides and the alkali metal salts of inorganic or organic acids of weak to medium, the preferred alkali metal compounds being the sodium and potassium compounds. Such acid-binding agents include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, dihydrogen phosphate and sodium acid, sodium hydrogen phosphate, sodium trichloroacetate, liquid glass or trisodium phosphate. The dye mixtures of the invention are remarkable for a high reaction yield when applied to cellulose fetal materials by coloring or printing. The cellulose colorations obtained immediately after the usual post-treatment and rinsing to remove unfixed dye portions exhibit excellent wet strengths, in particular since such unfixed dye portions are easily removed by washing because of their good solubility in cold water . The colorations and impressions obtainable with the dye mixtures of the invention have brilliant shades; especially the colorations and the impressions on materials of fiber of cellulose have good firmness in the light and good firmness in humid, such as properties of firmness in the washing, milling, water, sea water, crossed coloration and transpiración acid and also alkaline, and also good firmness in the pleating, ironing in hot flotation.

In addition, the dye mixtures of the invention can also be used for reactive dyeing with wool fibers. Also, the wool to which was given a non-plush or underlaid finish (see H.Rath, Lehrbuch der Textilchemie, Springer-Verlag, 3rd Edition (1972), pp. 295-299, especially finished by the so-called Hercosett procedure (p.298); J. Soc. Dyers and Colourists 1972, 93-99, and 1975, 33-44) can be colored as in the present. The procedure of coloring on wool in a conventional manner acid medium. For example, and / or ammonium sulfate, sodium acetate, to the dye bath of the desired pH. To obtain a coloration it is advisable to add a usual unifying agent, for example on the basis of a reaction product of cyanuric chloride with 3 times the molar amount of an aminobenzenesulfonic acid and / or an aminonaphthalenesulfonic acid or on the basis of a reaction product. for example of stearylamine with ethylene oxide. For example, the mixture of dyes of the invention is preferably subjected to the depletion process initially from an acid dye bath having a pH of about 3.5 to 5.5 with pH control and then the pH is varied, towards the end of the time of coloration, at the neutral or perhaps weakly alkaline range up to a pH of 8.5 to produce, especially for very deep colorations, the complete reactive link between the dyes of the dye mixtures of the invention and the fiber. At the same time, the unreacted dye portion is reactive The process described herein also applies to the production of dyes on fiber materials composed of other natural polyamides or of synthetic polyamides and polyurethane. In general, the material to be colored is introduced into the bath at a temperature of about 40 ° C, stirred there for some time, then the dye bath is adjusted to the desired weakly acidic pH, preferably weak acetic acid, and Real coloration is carried out at a temperature of 60 and 98 ° C. However, it is also possible to carry out boiling dyes or sealed staining apparatus at temperatures up to 106 ° C. Since the water solubility of the dye mixtures of the invention is very good, they can also be used with advantage in customary continuous dyeing processes. The color intensity of the dye mixtures of the invention is very high. The dye mixtures of the invention produce bright red colorations between yellowish and bluish on said materials, preferably fiber materials. The examples below in the present. The parts and percentages are by weight, unless indicated otherwise. The parts by weight are related to the parts by volume as well as the kilogram are related to the liter. The compounds described in the examples in terms of a formula are indicated in the formula of the free acids; in general, they are prepared and isolated in the form of their salts, preferably sodium or potassium salts, and used to color in the form of their salts. The mentioned starting compounds in the free acid form in the following examples, especially the examples of tables, can be used similarly in the synthesis as such or in the form of their salts, preferably alkali metal salts, such as sodium salts or potassium.

EXAMPLE 1 a) A suspension of 319.2 parts of 1-aminium-8-naphthol-3,6-disulfonic acid is mixed in 1000 parts of water and 300 parts of ice, with 190.1 parts of cyanuric chloride with complete stirring; reaction batch is further stirred for four hours between 0 and 15 ° C and at a pH between 1.7 and 2.2 adjusted by means of sodium bicarbonate. b) The solution of the dichlorotriazine compound of part a) is combined with a solution or a pH of 5.5 to 6.0 of 133.0 parts of 4- (β-sulfatoethylsulfonyl) anilino and 156 parts of 1-amino-8-naphthol- acid. 3,6-disulfonic acid in 640 parts of water. The pH is maintained at approximately 5 and the reaction mixture is heated to a temperature of 35 to 45 ° C within one to two hours. c) The diazonium salt of the component diazo is prepared separately: a solution with pH of 6.7 to 6.8 is mixed with 410.4 parts of 4- (β-sulfatoethylsulfonyl) aniline in 500 parts of water, with 192 parts of a solution Aqueous sodium nitrite at 40% intensity. This mixture is added with complete stirring to a mixture of 800 parts of crushed ice and 160 parts of an aqueous hydrochloric acid at 31% intensity. The mixture is subsequently stirred at 0 ° C and up to 5 ° C for one hour and then, as usual, the nitrous acid is decomposed in excess with a little amidosulfonic acid. c) The secondary condensation product prepared according to item b) is combined with the diazonium salt solution described according to clause c). To carry out the coupling reaction, the mixture of strongly acidic action is adjusted with sodium carbonate still pH 4.5 to 5.0 at a temperature of about 15 ° C and the temperature is raised to 20 and up to 25 ° C. Be agitated continuously at that pH and that temperature for a few hours until the coupling is over. d) A pH between 6.0 and 6.5 is then fixed by means of sodium carbonate, the batch is clarified by filtration and the filtrate is dried by sprinkling, providing approximately 1650 parts of a powder in which it comprises an electrolytic salt, predominantly chloride. sodium and sodium sulfate, and about 42% of the sodium salt of the compound of formula A). and about 28% of the sodium salt of the compound of the formula (B) This mixture has very good dye property and is applied by the methods of application and fixation common in the art for dyes reactive with fibers to the materials mentioned in the description part, such as cellulose fiber materials, especially cotton and Viscose produces chlorination and strong red impressions that have very good firmness properties, especially very good firmness properties in washing, in light, alkalis, acids, water, sea water, perspiration and rubbing. Cloning is also notable for its high degree of fixation and good formation on cellulose materials.

EXAMPLE 2 47.5 parts of cyanuric chloride and 79.8 parts of 1-amino-8-naphthol-3,6-disulfonic acid are rapidly added, with complete stirring, to a mixture of 330 parts of water and 140 parts of ice, the batch is stirred Subsequent approximately 3.5 hours at a pH between 1.5 and 2.0, and a temperature between 10 and 15 ° C, and that primary condensation product is clarified by diatomaceous earth and filtration. The pH is then adjusted to 5 by means of calcium carbonate, and 33.2 of 3- (β-sulfatoethylsulfonyl) aniline and 39.1 parts of 1-amino-8-naphthol-3,6-disulfonic acid are inhibited and the batch is stirred for 2 to 3 hours at a temperature of 18 to 22 ° C, then it is poured at 50 and up to 55 ° C and kept at that temperature for 30 minutes while the pH of 4.0 to 4.0 is maintained constant by means of calcium carbonate . The batch is stirred for a few more hours at 18 to 20 ° C. The solution is combined with a suspension (conventionally produced by diazotization with sodium nitrite and sulfuric acid in aqueous medium) of the disodium salt of 101.2.1 parts of 3- (β-sulfatoethylsulfonyl) aniline, then the coupling mixture is strongly adjusted acid at a pH of 4.0 to 4.5 by means of calcium carbonate at a temperature of about 10 ° C, stir for a few more hours at 10 to 14 ° C and within this pH range, the calcium sulphate is separated by filtration with suction, washed with water, and the calcium fibers are precipitated in the combined filtrate and wash liquor by means of sodium oxalate at a pH of 4.5 to 5.0 and at a temperature of 30 ° C. Stirring for one hour is followed by filtration and the dye mixture of the invention is isolated by filtering by spray drying.

This produces about 390 parts of a dark red powder which, as well as the electrolyte salts, is about 44% strength with respect to the sodium salt of the compound of the formula (C) and about 28% intensity with respect to the sodium salt of the compound of the formula (D) This mixture of dyes of the invention has very good application properties and is applied by the printing methods and colorations that are common in the art for fiber-reactive dyes to cellulose fiber materials, for example, produce strong red colorations and prints that have very good manufacturing properties and firmness in use, especially firmness in light, firmness properties in washing, perspiration, water and seawater, and also resistance to the chlorinated water in the tap (chlorinated water in the bath). The binding performance of this mixture of dyes of the invention on cellulose fiber materials is very high.

EXAMPLES 3 TO 77 The examples in the following tables describe more fully the dye mixtures according to the invention of monozoic compounds of the general formulas (1) and (2) in terms of their components. They can be prepared according to the invention either by mechanically mixing the dyes individually or chemically, for example in a manner similar to one of the above operating examples, with the aid of starting components (cyanuric chloride, cyanuric bromide or cyanuric fluoride, acid 1-amino-8-naphthol-3,6-disulfonic or an amino compound (3A) and / or (3B) as a second condensation component and an additional amino compound (3A) and / or (3B) as a diazo component and optionally with an amine of the general formula HNR3R4 or a compound of the general formula HOR3.

The dye mixtures of the invention have very good application properties and are applied by the usual dyeing and printing methods in the art, preferably by the methods of application and fixation common in the art for dyes reactive with fibers, to the materials mentioned in the description part, especially cellulose fiber materials, produce colorations and strong impressions which have good firmness properties and good color formation in the shade indicated in the respective example in the table. The numerical ratios indicated in the MR column specify the molar ratio in percentage of the colorant or the dyes (1) to the colorant or the dyes (2) in which the dyes are present in the respective dye mixture.

NJ NJ 00

Claims (7)

NOVELTY OF THE INVENTION CLAIMS

1. - A mixture of dyes comprising one or more azo dyes that conform to the general formula (1) and one or more azo dyes that conform to the general formula (2). wherein M is hydrogen, ammonium, an alkali metal or the alkaline earth metal equivalent; R1 is hydrogen or sulfo; R2 has one of the meanings of R1; X1 is fluorine or chlorine or a group of the general formula -NR3R4 or OR3, wherein R3 is H or C1-C4 alkyl or aryl (such as phenyl), which is optionally substituted, and R4 has one of the meanings of R3 or is an aryl having Y1-SO2- or Y2-SO

2. (such as phenyl) or a C 1 -C 4 alkyl group, or -NR 3 R 4 is optionally substituted morpholino or pyrimidino or -NHCN; X2 has one of the meanings of X1; Y1 is vinyl or a group of the general formula -CH2-CH2-Z, where it is a substituent that can be removed by the action of alkali, sulfate, thiosulfate or acetyloxy; Y2 the groups -SO2-Y1 and -SO2-Y2 are arranged in the meta position or for the azo group or the amino group. 2. The mixture of dyes according to claim 1, comprising one or more azo dyes that conform to the general formula (1) and one or more azo dyes that conform to the general formula (2) in a mixing ratio 90: 10% by weight to 10: 90% by weight.

3. The mixture of dyes according to claim 1, comprising one or more azo dyes that conform to the general formula (1) and one or more azo dyes that conform to the general formula (2) in a mixing ratio from 70: 30% by weight to 30: 70% by weight.

4. The mixture of dyes according to claim 1, comprising one or more azo dyes that conform to the general formula (1) and one or more azo dyes that conform to the general formula (2) in a mixing ratio from 55: 45% by weight to 45: 55% by weight.

5. The use of a dye mixture according to at least one of claims 1 to 4, for coloring or printing hydroxyl and / or carboxamide-containing material, preferably fiber material.

6. A process for coloring or printing hydroxyl and / or carboxamide containing material, preferably fiber material, by applying one or more dyes in dissolved form to the material and fixing the dye or dyes on the material by means of heat or with the aid of an alkaline agent or by means of both measures, which comprises using a mixture of dyes according to at least one of claims 1 to 4 as dyes.

7. A method according to claim 6, further characterized in that the material to be colored is a fiber material. SUMMARY OF THE INVENTION Mixtures of dyes of the general formulas are described (D (2) wherein M is hydrogen, ammonium, an alkali metal or equivalent of an alkaline earth metal, R1 is hydrogen or sulfo, R2 is hydrogen or sulfo, each of X1 and X2 is fluorine, chlorine, amino which can be mono- or disubstituted for lower alkyl or optionally substituted aryl and one of the radicals possesses a group of the formula -SO2-Y1 or -SO2-Y2, wherein each of Y1 and Y2 is vinyl or ethyl substituted in the β-position by a removable group of alkali, or each of X1 and X2 is optionally substituted morpholino or pyrimidino, cyanoamino, hydroxyl, lower alkoxy or optionally substituted aryloxy and wherein the groups -SO2-Y1 or -SO2-Y2 are bonded to the benzene nuclei meta or para to the azo or amino group; the novel ones are used mixtures of dyes for coloring hydroxyl and / or carboxamide containing material, preferably fiber material, such as cellulose fiber materials, wool and synthetic polyamide fibers. GC / xma * jtc * sff P99-409