MXPA99010341A - Dye mixture, process for its preparation and its use - Google Patents

Abstract

Red reactive azo dye mixture is used for dyeing fibrous and other material containing hydroxyl and/or carbonamido groups, e.g. cotton, wool, synthetic polyamide fibers or film or paper Dye mixture contains reactive 1-(2-arylamino-4-chloro-1,3,5-triazin-6-yl-amino)-7-vinylsulfonylphenylazo-8-hydroxy naphthalene-3,6-disulfonic acid (precursor) dye(s) (I) and 1-(2-arylamino-4-chloro-1,3,5-triazin-6-yl-amino)-7-arylazo-8-hydroxy naphthalene-3,6-disulfonic acid dye(s) (II) in 70:30 to 30:70 molar ratio. Dye mixture contains reactive 1-(2-arylamino-4-chloro-1,3,5-triazin-6-yl-amino)-7-vinylsulfonylphenylazo-8-hydroxy naphthalene-3,6-disulfonic acid (precursor) dye(s) (I) and 1-(2-arylamino-4-chloro-1,3,5-triazin-6-yl-amino)-7-arylazo-8-hydroxy naphthalene-3,6-disulfonic acid dye(s) (II) of the given formulae in 70:30 to 30:70 molar ratio:M=hydrogen (H), an alkali metal or the equivalent of an alkaline earth metal;R1, R7=H, 1-4 carbon (C) alkyl, 1-4 C alkoxy, sulfo or carboxy;R2, R8=H, 1-4 C alkyl or 1-4 C alkoxy;RA, RB=H or sulfo;R=H or 1-4 C alkyl;Y1, Y2=vinyl or ethyl with a substituent eliminated by alkali in the b-position;G, D=a benzene residue;R3, R5=H, 1-4 C alkyl,1-4 C alkoxy, halogen, sulfo or carboxy;and R4, R6=H, 1-4 C alkyl, 1-4 C alkoxy or sulfo;or G, D=a naphthalene residue;R3, R5=H, methyl, sulfo or carboxy;and R4, R6=H or sulfo.

Description

MIXTURE OF COLORANTS, PROCEDURE FOR PREPARATION AND USE OF THE SAME DESCRIPTIVE MEMORY The present invention relates to the technical field of reactive azo dyes to fibers. The dyes according to the general formulas and defined below (1) and (2) have certain defects of application, for example an excessive dependence on the color yield when changing the dyeing parameters in the dyeing process, an insufficient solubility in the dyeing process. the aqueous dye bath at higher dye concentrations in the presence of electrolyte salts or an insufficient color buildup on cotton and especially viscose (good color build-up is the result of a dye's ability to produce a correspondingly stronger dye) from an increased dye concentration in the dye bath). The possible consequences of these drawbacks are poor reproducibility for the stains that are obtained. However, it is particularly important to obtain dyes having a good color yield, ie, dyeings whose depth of surplus is very high in relation to the amount of dye used, for example, in comparison with other dyes, due to the property of the dye. coloration of the colorant itself (high extinction) and by the staining characteristics of this colorant, such as good affinity and high binding performance. If mixtures of dyes are used that have a certain color yield, the color yield of this dye mixture will generally be the average of the color yields of the individual dyes, and this is the reason why the color yield of a Mixture of, for example, two dyes will be less than the color yield obtained when the dye having a higher color yield property is used as the sole dye and in the total amount of the two individual dyes. The present invention, therefore, provides mixtures of azo dyes according to the following general formulas defined (1) and (2) whose color strength is surprisingly greater than the sum total of other forces provided by the individual colors of the dye mixture. The synergistic effect also shows improved accumulation characteristics on the part of the mixture of the invention, compared to the individual dyes in the mixture when dyeing fiber materials containing hydroxy- and carboxamido-, for example cellulose fiber materials such like cotton, and especially in the case of viscose fiber materials. Therefore, the invention provides mixtures of dyes comprising one or more, such as two or three, preferably 1 or 2, dyes of the general formula (1) and one or more, such as two or three, preferably 1 or 2 dyes of the general formula (2) in a molar ratio of the dye or dyes (1) and the dye or dyes (2) from 70:30 to 30:70, preferably 60:40 to 40:60. In these formulas: M is hydrogen, an alkali metal, such as sodium, potassium or lithium, or the equivalent of an alkaline earth metal, such as calcium, preferably hydrogen and especially sodium, potassium or lithium; R1 is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy, sulfo or carboxy, preferably hydrogen, methyl and methoxy and in particular preferably hydrogen; R2 is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, or alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy, preferably hydrogen, methyl and methoxy and in particular preferably hydrogen; G is a benzene or naphthalene radical; R3 when G is a benzene radical is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy, halogen, such as bromine or chlorine , sulfo or carboxy, preferably hydrogen, methyl, methoxy and sulfo, in particular preferably sulfo, and is hydrogen, methyl, sulfo or carboxy, preferably sulfo, when G is a naphthalene radical; R4 when G is a benzene radical is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy, or sulfo, especially hydrogen, methyl , methoxy and sulfo, particularly preferably hydrogen and sulfo, and is hydrogen or sulfo when G is a naphthalene radical; RA is hydrogen or sulfo, preferably hydrogen; D is a benzene or naphthalene radical; R5 when D is a benzene radical is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy, halogen, such as bromine and chlorine , sulfo or carboxy, preferably hydrogen, methyl, methoxy and sulfo, in particular preferably sulfo, and is hydrogen, methyl, sulfo or carboxy, preferably sulfo, when D is a naphthalene radical; R6 when D is a benzene radical is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy, or sulfo, preferably hydrogen, methyl , methoxy and sulfo, particularly preferably hydrogen and sulfo, and is hydrogen or sulfo when D is a naphthalene radical; RB is hydrogen or sulfo, preferably hydrogen; R7 is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy, sulfo or carboxy, preferably hydrogen, methyl and methoxy and in particular preferably hydrogen; R8 is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and especially methyl, or alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy, preferably hydrogen, methyl and methoxy and in particular preferably hydrogen; R is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl or ethyl, preferably hydrogen; Y1 is vinyl or ethyl which is substituted in the β-position by an alkali removable substituent, for example by chlorine, sulfate, thiosulfate, phosphate, alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, and sulfobenzoyloxy, and is preferably vinyl , ß-chloroethyl and ß-sulfatoethyl and particularly preferably vinyl and ß-sulfatoethyl; Y2 has any of the meanings of Y1; the groups Y1 -SO2 and -SO2Y2 are preferably linked to the benzene nucleus in a meta or para position to the azo group and the amino group, respectively. Hereinafter, the dyes of the general formulas (1) can be referred to collectively as "dyes (1)" and dyes (2) as "dyes (2)". They are known from Japanese Patent Application Publication Sho-58-189, or they can be prepared in a manner similar to the methods described therein. In the above general formulas and also in the subsequent general formulas, the individual constituents of the formulas, whether they present identical or different designations, within the scope of their definition may have meanings that are identical or different from one another. The terms "sulfo", "thiosulfate", "carboxy", "phosphate" and "sulfate" include both the acid form and the salt form of the respective groups. Accordingly, the sulfo groups are groups corresponding to the general formula -SO3M, the thiosulfate groups are groups corresponding to the general formula -S-SO3M, the carboxy groups are groups corresponding to the general formula -COOM, the phosphate groups are groups corresponding to the general formula -OPO3M2, and the sulphate groups are groups corresponding to the general formula -OSO3M, where each M is as defined above. The groups of the general formulas (3a) and (3b) which are present in dyes (1) and (2), respectively, are for example 3- (β-sulfatoethylsulfonyl) phenyl, 4- (β-sulfatoethylsulfonyl) phenyl, 2-methyl-5- (β-sulfato-ethylsulfonyl) phenyl, 2-methoxy-5- (β-sulfatoethylsulfonyl) phenyl, 4-methyl-3- (β-sulfatoethylsulfonyl) phenyl, 2,5-dimethyl-4- (β-sulfatoethylsulfonyl) phenyl, 2,6-dimethyl-4 - (β-sulfatoethylsulfonyl) phenyl, 2-methoxy-4- (β-sulfatoethylsulfonyl) phenyl, 4-methoxy-5- (β-sulfatoethylsulfonyl) phenyl, 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) phenyl, 2,4-dimethoxy-5- (β-suphatoethylsulfonyl) phenyl, 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) phenyl 2-carboxy-5- (β-sulfate-ethylsulfonyl) phenyl, 2-sulfo- 5- (β-sulfatoethylsulfonyl) phenyl and 2-sulfo-4- (β-sulfatoethylsulfonyl) phenyl, especially 3 or 4- (β-sulfatoethyl-sulfonyl) phenyl, and also derivatives thereof wherein the β-sulfatoethylsulfonyl group is replaced by the vinylsulfonyl or β-thiosulfatoethylsulfonyl or β-chloroethylsulfonyl group. The groups according to the general formulas -G (R3, R4, RA) and (RB, R5, R6) -D-, which are presented in the dyes (1) and dyes (2), respectively, are for example 2-Sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2-sulfo-4-methoxyphenyl, 2-sulfo-4-methylphenol, 2,5-disulfo-4-methoxyphenyl, 2,5-disulfo-4-methylphenyl, 2, 5-disulfophenyl, 2,4-disulfophenyl, 2-carboxy-phenyl, 1-sulfonaphth-2-yl, 1,5-disulfonaphth-2-yl, 4,8-disulfonaphth-2-yl and 5,7-disulfonaft- 2-ilo. Among the dye mixtures of the invention, preference is given to those comprising dyes (1), wherein Y1-SO2- is vinyl and in particular preferably β-sulfatoethylsulfonyl and is attached to the phenyl radical in a position for the azo group, R1 and R2 are both hydrogen and -G (R3, R4, RA) is 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl or 1-sulfonaphth-2-yl. Among the dye mixtures of the invention, preference is also given to those comprising dyes (2), wherein (RB, R5, R6) -D- is 1, 5-disulfonaphth-2-yl, 1-sulfonaft-2 -yl, 2-sulfophenyl or 2-sulfo-4-methyl and the group of the general formula (3b) is 3- or 4-vinylsulfonylphenyl or preferably 3- or 4- (β-sulfatoethylsulfonyl) phenol, and also a those comprising dyes (2) wherein the diazo component (RB, R5, R6) -D- is 2-sulphophenyl, R is ethyl and the group of the general formula (3b) is 3-vinylsulfonylphenyl or preferably 3- ( β-sulfatoethylsulfonyl) phenyl, and also to dye mixtures of the invention comprising said dyes (2) wherein the diazo component is 1,5-disulfonaphth-2-yl, R is hydrogen and the group of the general formula ( 3b) is 2-methoxy-5-vinylsulfonylphenyl or preferably 2-methoxy-5- (β-suyfatoethylsulfonyl) phenyl. The dyes of the general formula (1), especially if the chromophore is the same, can have different groups reactive to the fibers -SO2-Y1 within the meaning of Y1 (the same applies to the dyes of the formula (2) with relation to Y2). Very particularly, the dye mixtures may contain dyes of the same chromophore according to the general formulas mentioned herein, in which the fiber-reactive groups -SO2-Y1 and S02-Y2 are, on the one hand, vinylsulfonyl groups and, on the other, β groups -chloroethylsulfonyl or β-thiosulfatoethylsulfonyl or preferably β-sulfatoethylsulfonyl. When the dye mixtures contain the respective coloring components partially as dyes having a vinylsulfonyl group, then the fraction of the respective dye having the vinylsulfonyl group is up to about 30 mol%, based on the respective dye chromophore. The dye mixtures of the invention can be prepared in a conventional manner, for example by mechanically mixing the individual dyes, either in the form of their dyes or granules or their solutions as they are synthesized or in the form of aqueous solutions of the individual dyes In general, they can also include traditional auxiliaries. The dye mixtures of the invention can be present as a preparation in solid or liquid (dissolved) form. In solid form, generally include traditional electrolyte salts for water-soluble dyes and especially reagents to fibers, such as sodium chloride, potassium chloride and sodium sulfate, and additionally may comprise traditional auxiliaries in commercial dyes, such as pH-regulating substances to establish a pH in an aqueous solution of between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate, and disodium acid phosphate, and small amounts of drying agents, or, if found present in a liquid, aqueous solution (including the presence of traditional thicknesses in printing pastes), can also include substances that ensure a longer life for these preparations, for example, substances that prevent the formation of mold. In general, the dye mixtures of the invention are presented as coloring powders containing from 10 to 80% by weight, based on the coloring powder or the preparation, of an electrolyte salt which is also known as a stabilizing agent. These coloring powders can also include the aforementioned buffer substances in a total amount of up to 5% by weight, based on the coloring powder. If the dye mixtures of the invention are presented 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 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 separation of its synthesis solution from the mixtures of chemically prepared dyes of the invention can be carried out by generally known methods, for example by precipitation from the reaction medium by electrolytes, for example sodium chloride or potassium chloride, or by evaporating or drying by spraying the reaction solution, in this case a pH regulating substance can be added to this reaction solution. The dye mixtures of the invention have useful application properties. They are used to dye or print materials containing hydroxy and / or carboxamide, for example in the form of sheet-like structures, such as paper and leather, or to films, for example composed of polyamide, or bonded, such as, for example, polyamide and polyurethane, but especially for dyeing or printing these materials in the form of fiber. Also, the solutions obtained in the synthesis of the dye mixtures of the invention, can be used directly as liquid preparations for dyeing, if desired after the addition of a pH regulating substance, or also after concentrating or diluting. Therefore, the present invention relates to the use of the dye mixtures of the invention for dyeing or printing these materials, or the processes for dyeing or 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 the form of textile fibers, such as woven fabrics or yarns, in the form of skeins or rolled packages. The hydroxy-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 ramin fibers; Regenerated cellulose fibers are for example short viscose fibers and viscose filaments. The materials containing carboxamide group are for example synthetic and natural polyamides and polyurethanes, especially in the form of fibers, for example wool and other animal, silk, leather, nylon-6,6, nylon-6, nylon-11 and nylon-4. The dye mixtures of the invention can be applied to and fixed onto said substrates, especially the aforementioned fiber materials, by the application of known techniques for water-soluble dyes, especially fiber-reactive dyes. For example, on cellulose fibers they produce by means of the depletion method from a long solution using various acid binding agents, and optionally neutral salts, such as sodium chloride or sodium sulfate, dyes that have very good color yields and which are better in comparison with the individual dyes. The application is preferably of an aqueous bath at temperatures between 40 and 105 ° C, optionally at a temperature of up to 130 ° C under superatmospheric pressure, and optionally in the presence of traditional staining aids. A possible procedure 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 that temperature. If desired, only the neutral salts which accelerate the exhaustion of the dyes can also be added to the bath after the actual dyeing temperature has been reached. The impregnation processes also provide excellent color yields and very good color build-up on cellulose fibers, and the dyes are allowed to settle on the material by dosing preferably at room temperature or at elevated temperature, for example up to 60 ° C, when applying steam or use dry heat in a conventional way. Similarly, traditional printing processes for cellulose fibers, which can be carried out either in a single phase, for example by printing with a printing paste containing sodium bicarbonate or other acid binding agent and by subsequent vaporization of 100 ° at 103 ° C, or in two phases, for example by printing with a weakly acidic or neutral printing paste and subsequent fixing by passing the printed material through an alkaline hot bath containing electrolyte or over-impregnation with an alkaline solution comprising electrolyte with Subsequent dosing of this treated material or subsequent vaporization or subsequent treatment with dry heat, produces strong impressions with well-defined contours and a transparent clear background. The appearance of the impressions is not greatly affected by the variations in the fixing conditions.

When fixed by dry heat according to the traditional heat-sealing procedures, hot air of 120 to 200 ° C. In addition to traditional 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 fixation of the colorants of the dye mixtures of the invention on cellulose fibers include, for example, water-soluble basic salts of alkali metals and also alkaline earth metals of inorganic or organic acids or alkali-releasing compounds. the heat, and also alkali metal silicates. Especially suitable are the alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids, the preferred alkali metal compounds are 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 diacid phosphate, disodium hydrogen phosphate, sodium trichloroacetate, trisodium phosphate or water glass The dye mixtures of the invention are characterized by their high fixing performance when applied to cellulose fiber materials by dyeing or printing. The cellulose stains obtained following the traditional after-treatments by rinsing to remove unfixed dye portions show excellent moisture resistance in particular since said unfixed dye portions are easily washed due to their good solubility in cold water.

The dyeings and prints obtainable with the dye mixtures of the invention have bright tones; especially the stains and impressions on cellulose fiber materials have light resistance and especially very good resistance to moisture, such as washing, brining, water, sea water, cross-dyeing and acid and alkaline perspiration resistance properties , as well as resistance to pleating, hot pressing and rubbing. In addition, the dye mixtures of the invention can also be used for reactive dyeing of wool fibers. Likewise, wool that has received a non-felted or low-felting finish (see, for example, H. Rath, Lehrbuch der Textilchemie, Springer-Verlag, 3rd Edition (1972), pp. 295-299, especially the finishing by the Hercosett procedure (p.298); J. Soc. Dyers and Colourists 1972, 93-99, and 1975, 33-44) can be stained with very good strength properties. The wool dyeing process of the present invention is carried out in conventional manner from an acid medium. For example, acetic acid and / or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate which can be added to the dye bath to obtain the desired pH. To obtain an acceptable level stain, it is recommended to add a traditional leveling agent, for example based on the reaction product of cyanide chloride with three times the molar amount of an aminobenzenesulfonic acid and / or an aminonaphthalenesulfonic acid or based on 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 a dye bath having an acidic pH of about 3.5 to 5.5 under pH control and then the pH is, towards the end of time from staining, changed to neutral and perhaps a weakly alkaline pH up to 8.5 to achieve, especially for very deep stains, the complete reactive binding between the dyes of the dye mixtures of the invention and the fiber. At the same time, the portion of dye that does not reactively bind is removed. The process described herein also applies to the production of dyes on fiber materials composed of other natural and / or synthetic polyamides and polyurethanes. In general, the material to be dyed 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 acetic acid, and the current dyeing is performed at a temperature between 60 and 98 ° C. However, the dyeings can also be carried out in a boiling or sealing dyeing apparatus 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 traditional continuous dyeing processes. The color strength of the dye mixtures of the invention is very high.

The dye mixtures of the invention dye the mentioned materials, preferably fiber materials, in bright yellow shades to bluish red shades. The following examples serve to illustrate the invention. The parts and percentages are by weight, unless indicated otherwise. The parts by weight are related to the parts by volume as the kilograms are related to the liters. The compounds described in the examples in terms of a formula are in the form of free acids; in general they are prepared and isolated in the form of their salts, preferably sodium or potassium salts, and used to dye in the form of their salts. The starting compounds mentioned in the following examples, especially the examples in the tables, can also be used in the synthesis in the free acid form or in the form of their salts, preferably alkali metal salts, such as sodium or potassium salts .

EXAMPLE 1 1000 parts of an aqueous solution containing 164 parts of the dye indicated below the formula (A-1), such as a synthesis solution of this dye, and 1000 parts of an aqueous solution containing 175 parts of the dye indicated below the formula (B-1), such as a synthesis solution of this dye (where M is as defined above, preferably sodium) are mixed together. The dye mixture of the invention is isolated from the combined solution in a molar mixture ratio of dye (A-1) to dye (B-1) of 50:50 in a conventional manner, for example by spray drying the dye solution . The dye mixture resulting from the invention which may contain electrolyte salts of the synthesis, such as sodium chloride and sodium sulfate, have very good dyeing properties and provides for example on cellulose fiber materials, such as cotton or fibers. of regenerated cellulose, strong red and level stains when applied by a traditional depletion staining procedure for fiber-reactive dyes.

EXAMPLES 2 TO 13 The examples of the above tables describe the mixtures of the dyes of the invention additional according to the invention comprising dyes whose formulas (where M is as defined above) are indicated in the following table. The mixtures possess very good application properties and provide on the materials mentioned in the part of the description, especially cellulose fiber materials, when applied by the methods of application of staining and printing traditional in the art, preferably by the methods of application and fixation traditional in the art for dyes reactive to fibers, strong red stains and prints that have very good strength properties and good color build-up. The numerical relationships reported in the RM column specify the ratio of the molar mixture of the two dyes to each molar%.

Claims (15)

NOVELTY OF THE INVENTION CLAIMS

1. - A mixture of dyes comprising one or more dyes of the general formula (1) and one or more dyes of the general formula (2) in a molar ratio of the dyes (1) to the dyes (2) from 70:30 to 30 : 70 wherein: M is hydrogen, an alkali metal, or the equivalent of an alkaline earth metal; R1 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, sulfo or carboxy; R2 is hydrogen, alkyl of 1 to 4 carbon atoms, or alkoxy of 1 to 4 carbon atoms; G is a benzene or naphthalene radical; R3 when G is a benzene radical is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen, sulfo or carboxy, and is hydrogen, methyl, sulfo or carboxy when G is a radical of naphthalene; R4 when G is a benzene radical is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or sulfo, and is hydrogen or sulfo when G is a naphthalene radical; RA is hydrogen or sulfo; D is a benzene or naphthalene radical; R5 when D is a benzene radical is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen, sulfo or carboxy, and is hydrogen, methyl, sulfo or carboxy, when D is a radical of naphthalene; R6 when D is a benzene radical is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, or sulfo, and is hydrogen or sulfo when D is a naphthalene radical; RB is hydrogen or sulfo; R7 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, sulfo or carboxy; R8 is hydrogen, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, R is hydrogen or alkyl of 1 to 4 carbon atoms; Y1 is vinyl or ethyl which is substituted in the β-position by an alkali removable substituent; Y2 has any of the meanings of Y1;

2. A mixture of dyes according to claim 1, further characterized in that R1 is hydrogen, methyl or methoxy.

3. A mixture of dyes according to claim 1 or 2, further characterized in that R2 is hydrogen, methyl or methoxy.

4. - A mixture of dyes according to claim 1, further characterized in that R1 and R2 are hydrogen.

5. A mixture of dyes according to claims 1 to 4, further characterized in that R7 is hydrogen, methyl or methoxy.

6. A mixture of dyes according to claims 1 to 5, further characterized in that R8 is hydrogen, methyl or methoxy.

7. A mixture of dyes according to claims 1 to 4, further characterized in that R7 and R8 are hydrogen.

8. A mixture of dyes according to any of claims 1 to 7, further characterized in that R3 is hydrogen or sulfo, R4 is sulfo and RA is hydrogen.

9. A mixture of dyes according to any of claims 1 to 8, further characterized in that R5 is hydrogen or sulfo, R6 is sulfo and RB is hydrogen.

10. A mixture of dyes according to any of claims 1 to 9, further characterized in that Y1 is vinyl or ß-sulfatoethyl.

11. A mixture of dyes according to any of claims 1 to 10, further characterized in that Y2 is vinyl or β-sulfatoethyl.

12. - A mixture of dyes according to any of claims 1 to 11, further characterized in that the group Y1-SO2- is attached to the benzene nucleus in a meta or para position to the azo group.

13. A mixture of dyes according to any of claims 1 to 12, further characterized in that the group -SO-Y2 is attached to the benzene nucleus in a meta or para position to the amino group.

14. A mixture of dyes according to any of claims 1 to 13, further characterized in that R is hydrogen.

15. A mixture of dyes according to any of claims 1 to 14, further characterized in that the dye or dyes of the general formula (1) and the dye or dyes of the general formula (2) are presented in a molar ratio from 60:40 to 40:60.