MXPA99007483A - Coloring mixture that includes azo hidrosoluble colorants reagents in fibers, preparation of the same and use of the - Google Patents

Abstract

The present invention relates to mixtures of dyes comprising one or more azo dyes of the general formula (1) and one more azo dyes of the general formula (2), wherein p is 1 or 2, R 1, R 1 and R 2 are independently hydrogen or a group of the general formula SO3MoOCH3, R5 and R6 are independently hydrogen or C1-C4 alkyl, X1 and X2 are independently fluorine or chlorine or a group of the general formula NR3R4OR3, R3 is hydrogen, C1-C4 alkyl or aryl optionally substituted, R4 has one of the meanings of R3 or aryl or alkyl (which may be substituted by SO2Y, SO3MoOCH3), optionally substituted morpholino or pyrimidino or NHCH, Y, Y1 and Y2 are independently vinyl or a group of the general formula CH2CH2Z , Z is a group that can be eliminated by the action of uncalcali, and M is a hydrogen atom, an ammonium ion or the equivalent of an alkali metal or alkaline earth metal, its preparation and its use to dye or stamp matter l containing hydroxyl groups and / or carboxy

Description

COLORING MIXTURE THAT INCLUDES AZO HIDROSOLUBLE COLORS REAGENTS IN FIBERS. PREPARATION OF THE SAME AND USE OF THE SAME DESCRIPTIVE MEMORY This invention relates to the technical field of reactive azo dyes in fibers. EP-A 534 342 and EP-A 177 449 describe dyes of formulas 1 and 2 defined later in the present invention. However, these dyes have certain defects of application, for example an excessive dependence on the color yield of the variable dyeing parameters in the dyeing process, an insufficient solubility in the dye bath aqueous at higher dye concentrations in the presence of electrolyte salts or an insufficient color build-up in cotton (good color build-up depends on the ability of a colorant to produce a correspondingly stronger dye from an increased dye concentration in the dyebath). The possible consequences of these disadvantages are poor reproducibility of the dyeings obtained. However, it is particularly important to obtain dyes having a good color yield, ie, dyeings whose hue intensity is very high in relation to the amount of dye used, for example in comparison with other dyes, due to the coloring property of the dye. dye itself (high absorbance) and due to the dyeing characteristics of this dye, 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 average of the color yields of the individual dyes. The color yield of a mixture, for example, two dyes will therefore be lower than the color yield that is obtained when the dye having the largest color rendering property is used as the only dye, but in the total amount of individual dyes. The present invention, therefore, provides blends of dyes that provide dyes having a color yield that is surprisingly higher than the average color yields of the dyeings of the individual dyes in the dye mixture. This synergistic effect is also shown in improved accumulation characteristics in the part of the blends of the invention, especially in cotton, compared to the individual dyes in the mixture. Accordingly, the invention provides mixtures of dyes consisting of one or more azo dyes of the general formula (1) and one or more azo dyes of the general formula (2): wherein p is 1 or 2, R1, R1 'and R2 are independently hydrogen or a group of the general formula SO3M or OCH3, R5 and R6 are independently hydrogen or C1-C4 alkyl, X1 and X2 are independently fluorine or chlorine or a group of the general formula NR3R4 or OR3, R3 is hydrogen, C1-C4 alkyl or optionally substituted aryl, has one of the meanings of R3 or is aryl or alkyl (which may be substituted with SO2Y, SO3M or OCH3), optionally substituted morpholino or pyrimidino or NHCN, Y, Y1 and Y2 are independently vinyl or a group of the general formula CH2CH2Z, Z is a group which can be eliminated by the action of an alkali, and is a hydrogen atom, a on ammonium or the equivalent of an alkali metal or alkaline earth metal.

In general, the azo dye of the general formula (1) and the azo dye of the general formula (2) are present in the mixtures of the invention in a mixing ratio of 90: 10% by weight to 10: 90% in weight, preferably in a ratio of 70: 30% by weight to 30: 70% by weight. Preferably, these are present in the blends of the invention in a ratio of 55:45 to 45: 55% by weight. Alkyl of C1-C4-R3, R4, R5 or Re can be straight or branched chain and can be methyl, ethyl, propyl or butyl, with ethyl and especially methyl being preferred. Aryl R3 is especially phenyl or naphthyl, of which each may be optionally substituted with SO3M. Aryl R 4 is preferably phenyl or naphthyl. Alkyl R4 preferably has 1 or 2 carbon atoms and ethyl is particularly preferred. Morpholino or pyridino R4 may be substituted by carboxyl, for example. A with the group Z which can be eliminated by the action of an alkali is in particular sulphate of the formula -OSO3M, thiosulfate of the formula -SSO3M or acetyloxy of the formula -OCOCH3, in each of which M is as defined previously. The groups -SO2Y, -SO2Y1 and -SO2Y2 are preferably placed in the meta position or for the azo or amino group, respectively.

Preferred dye mixtures of the invention comprise azo dyes of the general formulas (1) and (2) wherein p is 2, and the two -SO3M groups are in positions 1 and 5, R1, R, R2, R5 and R6 are each hydrogen, X1 and X2 are each chloro or fluoro, Y, Y1 and Y2 are each -C2H4OSO3M, and M is hydrogen, lithium or sodium.

The dye mixtures of the invention can be present as a preparation in solid or liquid (dissolved) form. In solid form, they generally include the usual electrolyte salts for water-soluble dyes and especially for the reactive dyes in the fibers, such as sodium chloride, potassium chloride and sodium sulfate, and may additionally consist of the usual auxiliaries in commercial dyes , as pH regulating substances capable of fixing a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium citrate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate, sodium tricitrate and disodium hydrogen phosphate, small amounts of desiccants; if they are present in aqueous, liquid solution (including the presence of thickeners of the usual type in the stamping pastes), they can also include substances that ensure a long life for these preparations, for example for prevention of mold.

The dye mixtures of the invention are generally present as powder preparations including an electrolyte salt or a standardization agent of 10 to 80% by weight, based on the preaparaicon. The aforementioned pH buffer substances are generally present in a total amount of up to 5% by weight, based on the preparation. If the dye mixtures of the invention are present in aqueous solution, the total dye content of these aqueous solutions will be up to 50% by weight, for example between 5 and 50% by weight, and the electrolyte salt content of these aqueous solutions will preferably be below 10% by weight, based on the aqueous solution. Aqueous solutions (liquid preparations) can 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 invention can be prepared in a conventional manner, for example by mechanically mixing the required amounts of the known individual dyes from the aforementioned EP-A documents, either in solid or liquid form, or by synthesis by means of the customary diazotization and coupling reactions and by the conversion reactions with the halotriazine component using appropriate mixtures of such components in a manner that will be familiar to those skilled in the art and using the amounts required for this purpose.

For example, a possible method comprises reacting a compound of the general formula (3A) (3A) wherein M is as defined above, with a trihalotriazine, especially trichlorotriazine or trifluorotriazine, in a conventional manner, such as for example at a temperature between -10 and 60 ° C, preferably between 0 and 40 ° C, and at a pH between 0 and 8, preferably between 3 and 5, and subsequently reacting the resulting product with a mixture of one or more amino compounds of the general formula (3B) and one or more amino compounds of the general formula (3C) (3B) (3C) wherein R1, R1 ', R5, R6 Y and Y2 are each as defined above, in a conventional manner, such as for example at a temperature between 0 and 60 ° C, preferably between 0 and 40 ° C, a pH between 2 and 8, preferably between 3 and 5, and then reacting the resulting diaminohalotriazine compounds with a mixture of diazonium salt prepared in a well-known manner from an amine of the general formula (3D) (3D) and a naphthylamine of the general formula (3E) wherein R2, Y1, M and p are each as defined above, in a conventional manner, for example at a temperature between 10 and 50 ° C, preferably between 20 and 35 ° C and at a pH between 3 and 7, preferably between 4 and 5, to form the mixture of azo dyes 1 and 2 of the invention. The dyes of formulas 1 and 2 wherein X1 and X2 are not halogen are obtained by reacting the mixture with the compounds HOR3 or HNR3R4, wherein R3 and R4 are each as defined above in a conventional manner, for example to a temperature between 10 and 100 ° C, preferably between 40 and 80 ° C, and at a pH between 3 and 7, preferably between 4 and 5.

Examples of the starting compounds of the general formula (3A) are the sodium salt and the potassium salt of 8-hydroxy-3,5-disulfo-1-naphthylamine or preferably of the 8-hydroxy-3,5-disulphide. 1 -naphthylamine itself. Examples of the starting compounds of the general formulas (3B), (3C) and (3D) are 4- (β-sulfatoethylsulfonyl) aniline, 3- (β-sulfatoethylsulfonyl) aniline 4- (β-sulfatoethylsulfonyl) -2-aminoanisole , 3- (β-sulfatoethylsulfonyl) -5-aminoanisole, 2-sulfo-4- (β-sulfatoethylsulfonyl) aniline, 2-sulfo-5- (β-sulfatoethylsulfonyl) aniline, and further derivatives of these compounds in which the group β-sulfatoethylsulfonyl is replaced by vinylsulfonyl, β-thiosulfatoethylsulfonyl or β-chloroethylsulfonyl. A preferred starting compound is 4- (β-sulfatoethylsulfonyl) aniline. Examples of starting compounds of the general formula (3E) are 1-sulfo-2-naphthylamine, 1,5-disulfo-2-naphthylamine, 1,4-disulfo-2-naphthylamine and 6,8-disufo-2-naphthylamine. . The separation from its synthesis solution of the dye mixtures of the invention produced chemically can be effected by commonly known methods, for example either by precipitation of the reaction medium by means of electrolytes, for example sodium chloride or sodium chloride. potassium, or by evaporation or spray drying of 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 can be used for dyeing or printing hydroxyl- and / or carboxamido-containing materials, for example in the form of sheet-like structures, such as paper and skin or films, for example composed of polyamide, or in bulk, such as, for example, polyamide and polyurethane, but especially for the dyeing or printing of these materials in the form of fiber. Similarly, the solutions obtained in the synthesis of the dye mixtures of the invention, if desired after the addition of a pH regulating substance, and also if desired after concentration or dilution, can be used directly as liquid preparations for had. The present invention thus also provides for the use of the dye mixtures of the invention for dyeing or embossing these materials, or instead of for processes for dyeing or printing these materials in a conventional manner, using a mixture of dyes of the invention as colorant. The materials are preferably used in the form of fiber materials, especially in the form of textile fibers, such as spun fabrics or yarns, such as in the form of skeins or winding packages. The hydroxyl-containing materials are those of natural or synthetic origin, for example cellulose fiber materials or their regenerated products and polyvinyl alcohols. The cellulose fiber materials are preferably cotton, but also other vegetable fibers, such as flax, hemp, jute and ramia fibers; the regenerated cellulose fibers are for example viscose in segments and viscose in filament.

The carboxamide-containing materials are for example synthetic and natural polyamides and polyurethanes, especially in the form of fibers, for example wool and other animal coats, silk, leather, nylon-6, 6, nylon-6, nylon-1 1 and nylon-4. The dye mixtures of the invention can be applied to and fixed onto said substrates, especially the fiber materials mentioned, by known application techniques for water-soluble dyes, especially dyes that react on fibers. For example, on cellulose fibers they produce, from a long liquid by the depletion method and by means of several acid-binding agents with or without neutral salts, such as sodium chloride or sodium sulfate, dyes which have very good color yields that are improved compared to the individual dyes. These are preferably applied from an aqueous bath at temperatures between 40 and 105 ° C, if desired at temperatures up to 130 ° C under superatmospheric pressure, and if desired in the presence of usual staining aids. A possible method is to introduce the material into the warm bath and gradually heat the bath to the desired staining temperature and complete the staining procedure at this temperature. Neutral salts that accelerate the exhaustion of the dyes may if desired not be added to the bath until after the current dyeing temperature has been reached. The process with pads also produces excellent color performances and a very good color build-up on cellulose fibers, on which the fixing can be effected by batching at room temperature or elevated temperature, for example up to 60 ° C, by vaporization or with dry heat in a conventional way. Similarly, the usual stamping processes for cellulose fibers, which can be carried out either in a single phase, for example by stamping with a stamping paste consisting of sodium bicarbonate to some other acid binding agent and by vaporization Subsequently from 100 to 103 ° C, or from two phases, for example by stamping with a neutral or weakly acid stamping paste and subsequent fixing either by passing the printed material through an alkaline bath consisting of hot electrolyte or by over-application with pad of an alkaline solution for pad containing the electrolyte and subsequent separation in batches of this treated material or subsequent vaporization or subsequent treatment with dry heat, produce strong prints with well-defined contours and a clear white background . The appearance of these impressions is not affected mainly by variations in the fixing conditions. When fixed by means of dry heat according to the usual heat-setting procedure, hot air of 120 to 200 ° C is used. In addition to the usual steam at 101 to 103 ° C it is also possible to use superheated steam and high pressure steam at temperatures up to 160 ° C.

The acid binding agents which effect the fixing of the colorants of the dye mixtures of the invention on the cellulose fibers include, for example, water-soluble basic salts of the alkali metals and also alkaline earth metals of inorganic or organic acids or compounds which they release alkali in the heat. Especially suitable are the alkali metal hydroxides and the alkali metal salts of weak to medium organic or inorganic acids, 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, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium trichloroacetate, water glass or trisodium phosphate. . The dye mixtures of the invention are remarkable for high fixing performance when applied to cellulose fiber materials by dyeing or stamping. The cellulose dyeings obtained following the usual post-treatment by rinsing to remove unfixed dye portions exhibit excellent wet firmness, in particular because such unfixed dye portions are easily rinsed thanks to their good solubility in cold water. The dyes and prints that can be obtained with the dye mixtures of the invention have bright shades; Especially those dyed and printed on cellulose fiber materials have good light fastness and very good wet firmness, such as firm properties to washing, grinding, water, salt water, cross-stain and acid perspiration firmness and also alkaline, besides good firmness to folding, hot ironing and carving. Additionally, the dye mixtures of the invention can also be used for reactive dyeing in wool fiber. Moreover, the wool to which a non-felted or low-felt finish has been given (see H. Rath, Lehrbuch der Textilchemie, Springer-Verlarg, 3rd Edition (1972), pp. 295-299, especially the finish). by the so-called Hercosett procedure (p.298), J. Soc. Dyers and Colourists 1972, 93-99 and 1975, 33-44) can be dyed with very good fixing properties. The method of dyeing wool is carried out here in a conventional manner from an acidic medium. For example, acetic acid and / or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate can be added to the dye bath to obtain the desired pH. To obtain a dyeing of acceptable uniformity, it is advisable to add a usual leveling agent, for example on the basis of a reaction product of cyanuric chloride with three times the molar amount of a aminobenzenesulfonic acid and / or an aminonaphthalenesulfonic acid or on the basis of a reaction product of for example stearylamine with ethylene oxide. For example, the dye mixture of the invention is preferably subjected to the depletion process initially from an acid dye bath having a pH of 3.5 to 5.5 under a pH control and the pH is then towards the end of time dyeing, changed to the neutral and perhaps weakly alkaline scale up to a pH of 8.5 to extract, especially for very deep dyeing, all the reactive link between the dyes of the dye mixture of the invention and the fiber. At the same time, the dye portion not prone to react is removed. The process described herein also applies to the production of dyeings on fiber materials composed of other natural polyamides or synthetic polyamides and polyurethane. In general, the material to be dyed is introduced into the bath at a temperature of 40 ° C, is stirred therein for some time, the dyebath is then adjusted to the desired pH, weakly acidic, preferably weakly acetic acid, and the current dyeing is carried out at a temperature between 60 and 98 ° C. However, the dyeings can also be carried out with boiling or in dyeing apparatuses sealed at temperatures of up to 106 ° C. Because the water solubility of the dye mixtures of the invention is very good, they can also be used with advantage in usual continuous dyeing processes. The color strength of the dye mixture of the invention is very high. The dye mixtures of the invention produce bright dyes, from yellowish red to bluish red on the mentioned materials, preferably fiber materials. The examples hereinafter serve to illustrate the invention. Parts and percentages are by weight, unless otherwise specified. The parts by weight are related to the parts by volume as the kilogram is related to the liter. The compounds described in the examples in terms of a formula are indicated in the form 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 stain in saline form. The aforementioned starting compounds in the form of the free acid in the following examples, especially the examples in the table, can also be used in the synthesis as such or in the form of their salts, preferably alkali metal salts, such as sodium or potassium salts.

EXAMPLE 1 a) A suspension of 319.2 parts of 1-amino-8-naphthol-3,6-disulfonic acid in 1000 parts of water and 300 parts of ice is mixed with 190.1 parts of cyanuric chloride with careful agitation. The reaction batch is subsequently stirred for four hours between 0 and 15 ° C and at a pH between 1.7 and 2.2 (maintained by the use of sodium bicarbonate). b) The solution of the dichlorotriazine compound obtained in accordance with a) is combined with a solution at pH 5.5 - 6.0 of 281.0 parts of 4- (β-sulfatoethylsulfonyl) aniline in 640 parts of water. The pH is maintained around 5 and the reaction mixture is heated to 30-45 ° C in the course of 1 to 2 hours. c) A solution of pH 6.7-6.8 of 140.5 parts of 4- (β-sulfatoethylsulfonyl) aniline and 151.5 parts of 2-naphthylamino-1,5-disulfonic acid in 500 parts of water is mixed with 171 parts of a solution of aqueous sodium nitrite at 40% concentration. This mixture is added with careful agitation to a mixture of 800 parts of crushed ice and 160 parts of 31% aqueous hydrochloric acid. The stirring is continued between 0 ° C and 5 ° C for another hour, and then, usually, the excess of nitrous acid is destroyed with a little amidosulfonic acid. c) The secondary condensation product prepared in accordance with b) is combined with the diazonium salt solution prepared in accordance with c). To effect the coupling reaction, the strongly acidic reaction mixture is adjusted to pH 4.5-6.5 with sodium bicarbonate at about 15 ° C and heated to 20-25 ° C. This is subsequently stirred at that pH and temperature for a few more hours until the coupling is complete. d) The batch is then adjusted to a pH between 6.0 and 6.5 by sodium carbonate and clarified, and the filtrate is spray dried. This yields about 1650 parts of an electrolyte salt powder (predominantly sodium chloride and sodium sulfate) comprising about 40% of the sodium salt of the compound of the formula (1a) and about 40% of the sodium salt of the compound of the formula (2a) (2a) This mixture exhibits good dyeing properties and, when applied to the materials mentioned in the part of the description, such as cellulose fiber, especially cotton and viscose, by application and fixation methods customary in the fiber reactive dyeing technique, supplies dyed deep red and prints that have very good firmness properties, especially good firmness properties to washing, light, alkalis, acids, water, seawater, perspiration and carving . The dyeings are also notable for their high degree of fixation and good accumulation in cellulose-based materials.

EXAMPLE 2 A mixture of 330 parts of water and 140 parts of ice is rapidly mixed with 47.5 parts of cyanuric chloride and 79.8 parts of 1-amino-8-naphthol-3,6-disulfonic acid by careful agitation, the batch is subsequently agitated by approximately 3.5 hours at a pH between 1.5 and 2.0 and at a temperature between 10 and 15 ° C, and the solution of this primary condensation product is clarified by diatomaceous earth and filtration. Then the pH is adjusted to 5 with calcium carbonate, and 70.3 parts of 3- (β-sulfatoethylsulfonyl) aniline are added, the batch is stirred at 18-22 ° C for two to three hours, then heated to 50-55. ° C and is maintained at that temperature for 30 minutes while the pH is kept constant at 4.0 - 4.5 by means of calcium carbonate. Agitation is subsequently continued at 18-20 ° C for a few hours. The solution is combined with a conventionally prepared suspension (diazotization by means of sodium nitrite and sulfuric acid with aqueous medium) of the diazonium salt of 35 parts of 3- (β-sulfatoethylsulfonyl) aniline and 38 parts of 2-naphthylamino acid. 1,5-D-sulfonic acid, the strongly acidic coupling mixture is then adjusted to pH 4.0-6.5 by means of calcium carbonate at about 10 ° C and subsequently stirred at 10-14 ° C and within that range of pH for a few more hours. Calcium sulfate is filtered with suction, and washed with water, and the calcium ions in this combined filtrate and wash liquor are precipitated with sodium oxalate at a pH of 4.5 - 5.0 and at a temperature of 30 ° C. After stirring for one hour, the batch is filtered, and the dye mixture of the invention is separated from the filtrate with spray drying. This yields approximately 280 parts of a dark red powder which, as well as the electrolyte salts, consists of about 40% of the sodium salt of the compound of the formula (1 b) and about 40% of the sodium salt of the compound of the formula (2b) (2b) This dye mixture of the invention has very good application properties and, applied by stamping and dyeing processes customary in the art for reactive dyes in fibers, it produces in cellulose fiber materials, for example, dyed and colored prints strong red that have very good firmness to the manufacture and performance, of which the firmness to the light, the firmness to the washing, the firmness to the perspiration, the firmness to the water and the firmness to the water of sea and besides the stability to water chlorinated can be mentioned in particular. The fixing speed in cellulose fiber materials of this dye mixture of the invention is very high.

EXAMPLES 3 TO 46 The table of examples which follows describes additional mixtures of the invention of dyes of the general formulas (1) and (2). these can be prepared in a manner according to the invention either by mechanical mixing of the individual dyes or also chemically for example in a manner similar to one of the above operating examples, starting from starting components (cyanuric chloride or cyanuric fluoride, 1-amino-8-naphthol-3,6-disulfonic acid, amino compounds of the formula 3D and 3E as secondary condenon components and amino compounds of the formula 3D and 3E as diazo components and optionally with an amine of the formula general HNR3R4 or alcohol of the general formula HOR3). The dye mixtures of the invention have very good application properties and provide in the materials mentioned in the description especially in cellulose fiber materials when they are applied by dyeing and stamping methods customary in the art, of reactive dyes in the fibers, dyed and strong prints that have good firmness properties and a good accumulation of color in the hue reported in the respective examples chart. The numerical relationships reported in column RM specify the weight ratio in percent of the colorant or dyes of the general formula (1) to the colorant or dyes of the general formula (2) in which the dyes are present in the respective mixture of dyes t? £

Claims (9)

1. NOVELTY OF THE INVENTION azo gene in gru 15 hydr a C4 is optionally substituted morpholino or pyrimidino or NHCN, Y, Y1 and Y2 are
2. 2. - The dye mixtures according to claim 1, further characterized in that the mixing ratio of the azo dye of the general formula 1 to the azo dye of the general formula 2 is in the range of 90: 10 wt% to 10:90 % in weigh.
3. 3. The dye mixtures according to claim 1, further characterized in that the mixing ratio of the azo dye of the general formula 1 to the azo dye of the general formula 2 is in the range of 70: 30% by weight to 30. : 70% by weight.
4. 4. The dye mixtures according to claim 1, further characterized in that the mixing ratio of the azo dye of the general formula 1 to the azo dye of the general formula 2 is in the range of 55: 45% by weight to 45%. : 55% by weight.
5. 5. The dye mixtures according to one or more of claims 1 to 4, further characterized in that p is 2, and two of the -SO3M groups are in positions 1 and 5, R1, R1, R2, R5 and R6 are each hydrogen, X1 and X2 are each chlorine or fluorine, Y, Y1 and Y2 are each - C2H4OSO3M, and M is hydrogen, lithium or sodium.
6. 6. A process for preparing a dye mixture according to one or more of claims 1 to 5, comprising mechanically mixing the required amounts of the azo dyes of the general formulas 1 and 2 in solid or liquid form.
7. 7. - A process for preparing a dye mixture according to one or more of claims 1 to 5, which comprises reacting a compound of the general formula (3A) (3A) wherein M is as defined in claim 1, with a trihalotriazine, in a conventional manner, and subsequently reacting the resulting product with a mixture of one or more amino compounds of the general formula (3B) and one or more amino compounds of the general formula (3C) (3B) (3C) wherein R1, R1 ', R5, R6, Y and Y2 are each as defined in claim 1, in a conventional manner and then the resulting diaminohalotriazine compound has to be reacted with a mixture of diazonium salt prepared in a manner well known of an amine of the general formula (3D) (3D) and a naphthylamine of the general formula (3E) wherein R2, Y1, M and p are each as defined in claim 1, in a conventional manner to form the mixture of azo dyes 1 and 2 and, if necessary, react the resulting mixture with HOR or HNR3R4 compounds , wherein R3 and R4 are each as defined in the claim 1, in a conventional manner.
8. 8. The use of the dye mixtures according to one or more of claims 1 to 5 for dyeing or printing material containing hydroxyl groups and / or carboxamido, preferably fiber material.
9. 9. A process for dyeing or printing material containing hydroxyl and / or carboxamide groups, preferably fiber material, by applying one or more dyes in dissolved form to the material and fixing the dye or dyes in the material by heat or with the aid of an alkaline agent or with the aid of both measures, which comprises using the dye mixture according to one or more of claims 1 to 5. SUMMARY OF THE INVENTION The present invention relates to mixtures of dyes comprising one or more azo dyes of the general formula (1) and one more azo dyes of the general formula (2) where p is 1 or 2, R > 1, D R1 and R are independently hydrogen or a group of the general formula SO3M or OCH3, R5 and R6 are independently hydrogen or C? -C alkyl, X1 and X2 are independently fluorine or chlorine or a group of the general formula NR3R4 or OR3, R3 is hydrogen, d-C4 alkyl or optionally substituted aryl, R4 has one of the meanings of R3 or is aryl or alkyl (which may be substituted by SO2Y, SO3M or OCH3), optionally substituted morpholino or pyrimidino or NHCH, Y, Y1 and Y2 are independently vinyl or a group of the general formula CH2CH Z, Z is a group that can be eliminated by the action of an alkali, and M is a hydrogen atom, an ammonium ion or the equivalent of an alkali metal or alkaline earth metal, its preparation and its use for dyeing or printing material containing hydroxyl and / or carboxamido groups. P99 / 958 JT / mvh * aom * ald * jtc.