MXPA99006980A - Black coloring mixtures reagent to fibers and using them to dye fiber materials containing hidroxy-and / or carboxam groups - Google Patents

Abstract

The present invention relates to a mixture of dyes consisting of one or more diazo dyes composed of 1-amino-3,6-disulfo-8-naphthol as the coupling compound and two-component diazo of the aniline series containing each a fiber-reactive group of the vinylsulfone series, one or more monoazo dyes composed of a coupling component of 4-sulfo-1-amino-naphthalene and a diazo component of the aniline series containing a reactive group to the fiber of the vinylsulfone series, one or more diazo dyes composed of a 1,3-diamino-4-sulfo-benzene and two diazo components of the aniline series each containing a fiber reactive group of the vinylsulfone series, and optionally one or two monoazo dyes with 1-amino-3,6-disulfo-8-naphthol as a coupling agent to which a diazo component of the compound is coupled in the ortho-position to the amino group. aniline series replaced by a group of the vin series ilsulfone, the mixture yields deep black dyeings in fiber materials containing hydroxy- and / or carboxamido- groups, such as cellulose fibers, in particular cotton, or in for example, wool and synthetic polyamide fibers

Description

MIXTURES OF BLACK COLORANTS REAGENT TO FIBERS AND USE OF THE SAME TO DYE FIBER MATERIALS THAT CONTAIN HYDROXY-AND / OR CARBOXAMIDE GROUPS- DESCRIPTIVE MEMORY Concern for the environment and competition has increased the imposition of requirements on the use of reactive dyes, especially in the section of black dyes. Until today, not only the quality of the dyed product but also the efficiency and environmental impact of the dyeing process have been put under scrutiny. Continues the search for new reactive dyes to the fibers that provide a superior fixation in the fiber, thus providing ecological advantages. Mixtures of deep black dyes are known, for example, from Japanese Patent Application Publication Sho-58-160 362 which are based on a dark blue diazo dye of the formula (I) and an orange monoazo dye of the formula (II) (I) Contrary to these prior art mixtures, the dye mixtures of the present invention, defined below, show a higher binding value on cellulose when applied by the exhaustion methods and are environmentally advantageous thereon. The present invention provides mixtures of dyes with improved black staining properties, which consist of one or more dyes, such as one, two, or three diazo dyes that are formed with the general formula (1), optionally one or more monoazo dyes which conform with the general formula (2), one or more colorants, such as one, two or three monoazo dyes that conform to the general formula (3) and one or more colorants, such as one, two or three dyes diazo that conform to the general formula (4) Each of them being defined later, and the dye, or respective dyes, of the general formula (1) or the general formulas (1) and (2) being present in the mixture in an amount of 65 to 95% by weight, preferably from 70 to 90% by weight, and the dye, respectively dyes, of the general formula (3) being present in the dye mixture in an amount of 1 to 25% by weight, preferably 5 to 22.5% by weight, weight, and the dye, respectively dyes, of the general formula (4) being present in the colorant mixture in an amount of 1 to 25% by weight, preferably 2 to 12% by weight, calculated on the basis of 100% by weight of the dye mixture consisting of the dyes of the general formulas (1), (3) and (4) and optionally of the formula (2), while the dyes of the formulas (1) and (2) , if a dye of the general formula (2) is present in the dye mixture, they are present in a ratio of 99.5% to 94% u not with respect to the diazo dye or diazo dyes of the formula (1) and from 0.5 to 6% by weight with respect to the monoazo dye (s) of the formula (2), calculated on the total amount of dyes of the formulas (1) ) and (2). The meanings of the symbols in formulas (1) to (4) are as follows: R1 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably methoxy or hydrogen and in particular hydrogen, R2 is hydrogen, methyl , ethyl, methoxy, ethoxy, sulfo or carboxy, preferably hydrogen, R3 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably methoxy or hydrogen and in particular hydrogen, R4 is hydrogen, methyl, ethyl, methoxy , ethoxy, sulfo or carboxy, preferably hydrogen, R5 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably methoxy or hydrogen and in particular hydrogen, R6 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably hydrogen, R7 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably methoxy or hydrogen and in particular hydrogen, R8 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, hydrogen preference, R9 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably methoxy or hydrogen and in particular hydrogen, R10 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably hydrogen, and is in each case, independently of the others, vinyl or is ethyl which is substituted in the β-position by a substituent which is removed by the action of an alkali, forming a vinyl group, such as chloride, thiosulfate, sulfate, alkanoyloxy of 2 to 5 carbon atoms , such as acetyloxy, phosphate, sulfobenzoyloxy and p-toluylsulphonyloxy and Y is preferably vinyl, β-chloroethyl, β-thiosulfatoethyl or β-sulfatoethyl and is in particular preferably vinyl and β-sulfatoethyl; M is hydrogen or an alkali metal, such as lithium, sodium and potassium; the -SO2-Y groups are preferably attached to the benzene ring in the meta position or preferably in the para- position to the azo group. Both in the formulas mentioned above and in those indicated below the individual formula elements, both with different designations and with the same denomination within a formula, can within the scope of their definition, have meanings that are the same as or different from one with other. The groups "sulfo", "thiosulfate", "carboxy", "phosphate" and "sulfate" include both the acid form and the salt form of these groups. Accordingly, the sulfo groups are groups of the formula -SO3M, the thiosulfate groups are groups of the formula -S-SO3M, the carboxy groups are groups of the formula -COOM, the phosphate groups are groups of the formula -OPO3M2 and the Sulfate groups are groups of the formula -OSO3M, in which M is as defined above. The dyes according to the general formula (1) are known from the patents E.U.A. Nos. 2,657,205, 3,387,914, 4,072,463 and 4,257,770, and dyes of the general formula (2) are known, for example from European Patent Application Publication No. 0,832,939. The dyes of the general formula (3) are known from German Offenlegungsschrift Nr. 19 11 427 and the dyes of the general formula (4) have been described in Korean Patent Specification No. 90-4223. The dyes of the general formulas (1), (2), (3) and (4), in particular if those corresponding to the same general formula, have the same chromophore, may have, within the meaning of Y, groups - SO2-Y structurally different fiber reagents. In particular, the dye mixture can contain dyes of the same chromophore according to the formula (1) and / or dyes of the same chromophore according to the formula (3) and / or (4) and optionally similarly of the formula (2) in which the -SO2-Y groups reactive to the fiber are partially vinylsulfonyl groups and partially groups in which Y is a group substituted with β-ethyl as defined above, such as β-chlororethylsulfonyl, β thiosulfatoethylsulfonyl or, preferably, β-sulfatoethylsulfonyl groups. If the dye mixtures contain the respective dye components in the form of a vinylsulfonyl dye, the proportion of the vinylsulfonyl dye relative to the respective dye in which Y is a group substituted with β-ethyl as defined above, such as a dye of β-chloro- or β-thiosulfate- or β-sulfatoethyl-sulfonyl will be up to 30 mol%, based on the chromophore of the respective dye. Preference is given here to mixtures of dyes in which the proportion of vinylsulfonyl dye to dye substituted with β-ethyl, such as β-sulfatoethylsulfonyl dye is in terms of the molar ratio between 5:95 and 30:70. The radicals of formulas (5), (6), (7), (8) and (9) in the dyes of the formulas (1), (2), (3) and (4) are, for example, 2- (β-sulfatoethylsulfonyl) phenyl, 3- (β-sulfatoethylsulfonyl) phenyl, 3- or 4-vinylsulfonylphenyl, 4- (β-sulfatoethylsulfonyl) phenyl, 2-carboxy-5- (β-sulfatoethylsulfonyl) phenyl, 4-methoxy-3- (β-sulfatoethylsulfonyl) -phenyl, 2-ethoxy-4- or -5 (β-sulfatoethylsulfonyl) phenyl, 2-methyl-4- (β-sulfatoethylsulfonyl) -phenyl, 2-methoxy-5- or -4- (β-sulfatoethylsulfonyl) phenyl, 2,4-diethoxy-5- (β-sulfatoethylsulfonyl) phenyl, 2, 4-dimethoxy-5- (β-sulfatoethylsulfonyl) phenyl, 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) phenyl, 2-methoxy-5-methyl-4- (β-sulfatoethyl-sulfonyl) phenyl, 2- 3- or 4- (β-thiosulfatoethylsulfonyl) phenyl, 2-methoxy-5- (β-thiosulfate-ethylsulfonyl) phenyl, 2-sulfo-4- (β-phosphatoethylsulfonyl) phenyl, 2-sulfo-4-vinylsulfonyl-phenyl and 3- or 4- (β-acetoxyethylsulfonyl) phenyl and their corresponding vinylsulfonyl derivatives. The radicals of the general formulas (5) to (9) preferably independently of one another are 3-vinylsulfonylphenyl, 4-vinylsulfonylphenyl, 3- (β-sulfatoethylsulfonyl) phenyl and 4- (β-sulfatoethylsulfonyl) phenyl, and if the groups vinylsulfonyl as well as β-sulfatoethylsulfonyl are present in the dye mixtures, the molar ratio between the vinylsulfonyl portions and the β-sulfatoethylsulfonyl portions is between 5:95 and 30:70. The dye mixtures of the invention can be present as a preparation in solid or liquid (dissolved) form. In solid form they generally contain the customary electrolyte salts in the case of water-soluble dyes and in particular of dyes reactive to the fibers, such as sodium chloride, potassium chloride and sodium sulfate, and in addition the customary auxiliaries in the commercial dyes, such as pH regulating substances which can establish a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate and disodium monophosphate, small amounts of desiccants or, if is that they are present in liquid, aqueous solution (including the presence of thickeners of the type customary in the stamping pastes), substances that ensure the permanence of these preparations, for example antifungals. If the dye mixtures are in the form of dye powders, they contain, as a rule, from 10 to 80% by weight, based on the powder or dye preparation, of a colorless, concentration-normalizing electrolyte salt, such as like those mentioned above. These dye powders may also contain the aforementioned buffer substances in a total amount of up to 5%, based on the dye powder. If the dye mixtures of the invention are present in aqueous solution, the total dye content of these aqueous solutions is up to 50% by weight, the electrolyte salt content of these aqueous solutions being preferably below 10% by weight. Weight, based on aqueous solutions (liquid preparations) can generally contain the aforementioned buffer substances in an amount of up to 5% by weight, preferably up to 2% by weight. The dye mixtures of the invention can be obtained in a conventional manner, for example by mechanically mixing the individual dyes in the required proportions or partially by synthesis with the usual diazotization and coupling reactions using appropriate mixtures of the diazo and coupling components in a familiar to those skilled in the art and in the necessary proportions. One option is, for example, to prepare aqueous solutions of the two coupling components: 1-amino-8-naphthol-3,6-disulfonic acid and 1-amino-naphthalene-4-sulfonic acid and of the aniline compounds of the formulas (10), (11) and (12) as the diazo components wherein R1, R2, R3, R4, R5, R6 and Y are each as defined above, in the same batch of reaction in the appropriate proportions, diazotizing these aniline compounds in a conventional manner in a strongly acidic medium and performing the coupling reaction of the 1-amino-8-naphthol-3,6-disulfonic acid and 1-amino-naphthalene-4-sulfonic acid first to a pH below 1.5 to produce the monoazo dyes of the formulas (2) and (3) and thereafter the second coupling reaction with the monoazo dye of the formula (2) at a pH between 3 and 6 and at a temperature of 10 to 20 ° C to form the diazo compound according to formula (1). The solution of the dyes of the formulas (1) and (3) and optionally of the formula (2) is then mixed with an aqueous solution of the dye or dyes of the formula (4) prepared in the usual and known manner.

Another way to synthesize the dye mixture of the invention can be by preparing strongly acid solutions or suspensions of the compounds 1-amino-8-naphthol-3,6-disulfonic acid, 1-amino-naphthalene-4-sulfonic acid and , 3-diamino-benzene-4-sulfonic acid in the appropriate proportions, by adding the aqueous solutions or suspensions of the diazotized aniline compounds of the general formulas (10), (11) and (12), defined above, and of the compounds of aniline of the general formulas (13) and (14) wherein R7, R8, R9, R10 and Y are as defined above, the anilines of the formula (10) to (14) being preferably the same compounds, and performing the first coupling reactions at a pH below 1.5 and at a temperature between 10 and 20 ° C and after that the second coupling reactions at a pH between 3 and 6 and at a temperature of 10 to 20 ° C. The dye mixtures according to the invention obtained in this way can be separated in a conventional manner, for example by adding in excess an electrolyte salt such as sodium chloride, potassium chloride or lithium chloride, or by spray drying. Mixtures of dyes of the invention in which the chromophores contain, for example, not only a β-chlororethylsulfonyl or β-thiosulfatoethylsulfonyl or β-sulfatoethylsulfonyl group, but also proportions with vinylsulfonyl groups can be prepared not only by the aforementioned method, but also by using the appropriate starting vinyl sulphonyl anilines by reacting the dye mixture in which Y is a β-chlororethyl or β-thiosulfatoethyl or β-sulfatoethyl radical, with an amount of alkali required for only a part of these groups and becoming part of said groups β-substituted ethylsulfonyl in vinylsulfonyl groups. This measurement is carried out by generally known methods for converting β-substituted ethylsulfonyl groups into vinylsulfonyl groups. The dye mixtures of the present invention are well suited for dyeing (which includes embossing) fiber materials containing hydroxy- and / or carboxamido groups by the methods of application and fixation numerously described in the art of fiber-reactive dyes, with intense black shades with good color accumulation, good washing resistance and very good fiber fixation. In addition, the obtained dyeings can easily fade. Therefore, the present invention also provides the use of novel dye mixtures for dyeing (including printing) fiber materials containing hydroxy- and / or carboxamido- groups and methods for dyeing such fiber materials using a dye mixture. according to the invention by applying the dye mixture in dissolved form to the substrate and fixing the dyes in the fiber by the action of an alkali or by heating or both.

The materials containing hydroxy groups are natural or synthetic materials containing hydroxy groups, for example cellulose fiber materials, even in the form of paper, or their regenerated products and polyvinyl alcohols. The cellulose fiber materials are preferably cotton but also other natural fibers of vegetable origin, such as the fibers of flax, hemp, jute and ramie; the regenerated cellulose fibers are, for example, discontinuous viscose and filament viscose. The materials containing carboxamido groups are, for example, synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal coats. Silk, leather, nylon-6,6, nylon-6, nylon-11 and nylon-4. The application of the dye mixtures of the invention is carried out by known processes for dyeing and printing fiber materials by the application of known techniques for the dyes reactive to the fibers. Since the colorants of the dye mixtures according to the invention are highly compatible with one another, the dye mixtures of the invention are also advantageously useful in the exhaustion dyeing processes. For example, applied in this manner to cellulose fibers of a large solution ratio at temperatures between 40 and 105 ° C, optionally at temperatures up to 130 ° C, under pressure above atmospheric pressure, and optionally in the presence of the customary staining auxiliaries using acid-binding agents and optionally neutral salts, such as sodium chloride or sodium sulfate, these produce dyes in very good color yields with excellent color build-up and consistent hue. A possible procedure is to introduce the material into the warm bath, gradually heat the bath to the desired staining temperature and complete the dyeing procedure at that temperature. Furthermore, if desired, the neutral salts, which accelerate the exhaustion of the dyes, are not added to the bath until the dyeing temperature is reached. Similarly, conventional stamping processes for cellulose fibers, which can be performed either in a single phase, for example by stamping with a stamping paste containing sodium bicarbonate or some other acid binding agent and the dye, and the subsequent vaporization between 100 and 103 ° C, or in two phases, for example by stamping with a neutral or slightly acidic stamping paste containing the colorant and the subsequent setting either by passing the stamped material through a hot alkaline bath containing the electrolyte or by padding an alkaline pad solution containing the electrolyte and subsequent separation in batches of this treated material or subsequent vaporization or subsequent treatment with dry heat, produce strong stamping with contours well defined and a clear white background. Changing the fixing conditions only has little effect on the result of the prints. The degrees of fixation obtained with the dye mixtures of the invention are very high not only in the dyeing but also in the stamping. The hot air used in the fixation with dry heat by means of customary heat setting procedures has a temperature from 120 to 200 ° C. In addition to the usual steam between 101 and 103 ° C, it is also possible to use superheated steam and high pressure steam up to 160 ° C. The acid-binding agents responsible for fixing the dyes to the cellulose fibers are, for example, water-soluble basic salts of alkali or alkaline-earth metals of organic and inorganic acids, and compounds that liberate alkalis when heated. Particularly suitable are the alkali metal hydroxides and the alkali metal salts of weak and medium strength organic and inorganic acids, with the preferred alkali metal compounds being the sodium and potassium compounds. These acid-binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium formate, sodium biphosphate and disodium monophosphate. The treatment of the dyes of the dye mixture of the invention with the acid-binding agents with or without heating chemically bonds the dyes to the cellulose fibers; especially those dyed in cellulose, after they have been given the usual post-treatment rinse to remove the portions of dye that were not fixed, show excellent properties of firmness in wet, in particular because the portions of dye that do not they were fixed are easily washed due to their good solubility in cold water. The stains of polyurethane and polyamide fibers are customarily made in an acid medium. The staining bath may contain, for example, acetic acid and / or ammonium sulfate and / or acetic acid and ammonium acetate or sodium acetate to bring it to the desired pH. To obtain a dyeing with acceptable uniformity it is advisable to add customary uniformity aids, for example based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or based on a reaction product of for example, stearylamine with ethylene oxide. In general, the material to be dyed is introduced into the bath at a temperature of about 40 ° C and is stirred therein for some time, then the dye bath is adjusted to the desired weak acid pH, preferably at a pH of acetic acid, and normal dyeing is carried out at a temperature between 60 and 98 ° C. However, the dyeings can also be carried out at boiling temperature or at temperatures up to 120 ° C (at a pressure higher than atmospheric). The following examples illustrate the invention. The parts and percentages are by weight, unless otherwise indicated. The parts by weight have the same ratio to parts by volume as the kilogram to the liter.

EXAMPLE 1 700 parts of a dye powder are electrically mixed with electrolyte, which contains the blue dye diazo dye of the formula (A) in a proportion of 50% with 143 parts of a dye powder with electrolyte, which contains the dye monoazo dyeing orange of the formula (B) in a proportion of 70%, and with 71 parts of a dye powder with electrolyte, which contains the yellow dyeing diazo dye of the formula (C) in a proportion of 70%. The resulting dye mixture according to the invention containing the dyes of formulas (A), (B) and (C) in a proportion of 70: 20: 10%, produces, when used in accordance with the methods of application and fixation customary in the art for dyes reactive to fibers, for example on cellulose fiber materials, dyed and printed with shades of intense black color.

EXAMPLE 1a A mixture of dyes according to the invention is prepared by diazotizing a suspension of 281 parts of 4-. { β-sulfatoethylsulfonyl) aniline in 650 parts of ice water and 180 parts of 30% aqueous hydrochloric acid with 173 parts of 40% aqueous sodium nitrite solution. 112 parts of 1-amino-8-naphthol-3,6-disulfonic acid are added and the first coupling reaction is carried out at a pH between 1 and 1.3 and at a temperature below 20 ° C (the pH is maintained with approximately 50 parts of sodium bicarbonate), then 45 parts of 1-naphthylamino-4-sulfonic acid and 9.4 parts of 1,3-phenylenediamine-4-sulfonic acid are added and the pH is slowly raised to a pH between 5 and 6 with sodium carbonate, and the coupling reaction is carried out at 20 ° C and within that pH range. The result is a solution of dyes of intense black color containing the dyes of the formulas (A), (B) and (C) in the proportion mentioned in example 1 (70%: 20%: 10%).

This dye solution can be adjusted to a pH of 4.5 by adding 5 parts of sodium phosphate buffer. This liquid mixture of dyes can be standardized to the desired concentration for a liquid preparation, further diluting with water or evaporating the solution. The mixture of dyes produces shades of intense black color in cellulose.

EXAMPLE 1 b To properly prepare a dye mixture according to the invention, the process according to example 1 a is carried out using, however, an aqueous acid suspension of the diazonium salt prepared from 272 parts, instead of 281 parts, of 4- (β-sulfatoethylsulfonyl) aniline. A solution of dyes of intense black color is obtained which contains the dyes of the formulas (A), (B) and (C) as well as of the formula (D) in a ratio of approximately 69: 20: 8: 3%. In addition, this solution can be adjusted to a pH of 4.5 by adding 5 parts of a sodium phosphate buffer solution. Additionally it can be diluted with water or concentrated, and the liquid mixture of dyes obtained in this way can be standardized to the desired concentration for the liquid preparation. The mixture of dyes produces shades of intense black color in cellulose.

EXAMPLE 2 The method described in example 1a can be used to prepare a similar dye mixture by varying the amounts used of the starting compounds, for example the amount of 1-amino-8-naphthol-3,6-disulfonic acid in an amount of 120 parts, and the amount of 1,3-phenylenediamine-4-sulfonic acid in an amount of 4.7 parts. The result obtained is a mixture of dyes in which the dyes of the formulas (A), (B) and (C) are present in approximately 75%: 20%: 5% ratio. The dye mixture can be separated from the synthesis solution, for example by spray drying, or it can also be used directly as a liquid for dyeing. Used according to the methods of application and fixation customary in the technique of dyes reactive to the fibers, it produces in the cellulose fiber materials for example dyed and printed in deep black.

EXAMPLE 3 The method described in example 1 a can be used to prepare a similar dye mixture by varying the amounts used of the starting compounds, for example the amount of 1-amino-8-naphthol-3,6-disulfonic acid in an amount of 104 parts, and the amount of 1-naphthylamino-4-suphonic acid in an amount of 56 parts. The result obtained is a mixture of dyes in which the dyes of the formulas (A), (B) and (C) are present at approximately 65%: 25%: 10%. The dye mixture can be separated from the synthesis solution, for example by spray drying, or it can also be used directly as a liquid for dyeing. Used according to the methods of application and fixation customary in the technique of dyes reactive to the fibers, it produces in the cellulose fiber materials for example dyed and printed in deep black.

EXAMPLE 4 The method described in example 1a can be used to prepare a similar dye mixture by varying the amounts used of the starting compounds, for example the amount of 1-amino-8-naphthol-3,6-disulfonic acid in an amount of 112 parts, the amount of 1-naphthylamino-4-sulfonic acid in an amount of 50 parts, and the amount of 1,3-phenylenediamine-4-sulfonic acid in an amount of 7 parts. The result obtained is a mixture of dyes in which the dyes of formulas (A), (B) and (C) are present in approximately 70% ratio: 22.5%: 7.5%. The dye mixture can be separated from the synthesis solution, for example by spray drying, or it can also be used directly as a liquid for dyeing. Used according to the methods of application and fixation customary in the technique of dyes reactive to the fibers, it produces in the cellulose fiber materials for example dyed and printed in deep black.

EXAMPLE 5 The method described in example 1a can be used to prepare a similar dye mixture by varying the amounts used of the starting compounds, for example the amount of 1-amino-8-naphthol-3,6-disulfonic acid in an amount of 143 parts, the amount of 1-naphthylamino-4-sulfonic acid in an amount of 2.2 parts, and the amount of 1,3-phenylenediamine-4-sulfonic acid in an amount of 47 parts. The result obtained is a mixture of dyes in which the dyes of formulas (A), (B) and (C) are present in approximately 90% ratio: 1%: 9%. The dye mixture can be separated from the synthesis solution, for example by spray drying, or it can also be used directly as a liquid for dyeing. Used according to the methods of application and fixation customary in the technique of dyes reactive to the fibers, it produces in the cellulose fiber materials for example dyed and printed in deep black.

EXAMPLE 6 The method described in example 1a can be used to prepare a similar dye mixture by varying the amounts used of the starting compounds, for example the amount of 1-amino-8-naphthol-3,6-disulfonic acid in an amount of 143 parts, the amount of 1-naphthylamino-4-sulfonic acid in an amount of 11.1 parts, and the amount of 1,3-phenylenediamine-4-sulfonic acid in an amount of 9.4 parts. The result obtained is a mixture of dyes in which the dyes of formulas (A), (B) and (C) are present in approximately 90%: 5%: 5% ratio. The dye mixture can be separated from the synthesis solution, for example by spray drying, or it can also be used directly as a liquid for dyeing. Used according to the methods of application and fixation customary in the technique of dyes reactive to the fibers, it produces in the cellulose fiber materials for example dyed and printed in deep black.

EXAMPLE 7 The method described in Example 1 a can be used to prepare a similar dye mixture by varying the amounts used of the starting compounds, for example the amount of 1-amino-8-naphthol-3,6-disulfonic acid in the an amount of 135.5 parts, the amount of 1-naphthylamino-4-sulfonic acid in an amount of 11.1 parts, and the amount of 1,3-phenylenediamine-4-sulfonic acid in an amount of 18.8 parts. The result obtained is a mixture of dyes in which the dyes of formulas (A), (B) and (C) are present in approximately 85%: 5%: 10% ratio. The dye mixture can be separated from the synthesis solution, for example by spray drying, or it can also be used directly as a liquid for dyeing. Used according to the methods of application and fixation customary in the technique of dyes reactive to the fibers, it produces in the cellulose fiber materials for example dyed and printed in deep black.

EXAMPLE 8 To prepare a dye mixture in which some of the dyes have a β-sulfatoethylsulfonyl group while the remainder has a vinylsulfonyl group, the solution of the novel dye mixture prepared in Example 1 is used as the starting point. 25% by volume of this solution is separated, adjusted with sodium carbonate to a pH between 8 and 10 and subsequently stirred at 30 to 40 ° C for another 30 minutes, during which the ß-sulfatoethylsulfonyl groups are transformed into vinylsulfonyl groups. After that sulfuric acid is used to lower the pH between 4.0 and 5.0, and this solution is added from the vinylsulfonyl dye mixture to the original solution of the b-sulfatoethylsulfonyl dye mixture. The result is an aqueous solution of dyes according to formulas (A-1), (B-1) and (C-1) where Y is 25% vinyl and 75% β-sulfatoethyl. The filtrate is adjusted with 5 parts of sodium phosphate buffer at a pH of 4.5. This aqueous solution can be adjusted to the desired concentration for a liquid preparation by adding or evaporating water, and can be used directly for dyeing. When the methods of application and fixation used in the technique of dyes reactive to the fibers are used, shades of intense black color are produced.

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. - A mixture of dyes consisting of one or more diazo dyes according to the general formula (1), optionally one or two monoazo dyes according to the general formula (2), one or more monoazo dyes according to the general formula (3) and one or more diazo dyes according to the general formula (4) (1 ) wherein R1 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy; R2 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy; R3 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy; R 4 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy; R5 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy: R6 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy; R7 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy; R8 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy; R9 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy; R10 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy; And it is in each case, independently of the others, vinyl or is ethyl that is substituted in the position β by a substituent that is eliminated by the action of an alkali, forming a vinyl group; M is hydrogen or an alkali metal; the -SO2-Y groups are preferably attached to the benzene ring in the meta position or preferably in the para position with respect to the azo group; the dye, respectively dyes, of the general formula (1) or of the general formulas (1) and (2) being present in the mixture in an amount of 65 to 95% by weight, and the dye mixture being present in the dye mixture. dye, respectively dyes, of the general formula (3) in an amount of 1 to 25% by weight, and the dye, respectively dyes, of the general formula (4) being present in the dye mixture in an amount of 1 to 25% by weight, calculated on the basis of 100% by weight of the dye mixture consisting of the dyes of the general formulas (1), (3) and (4) and optionally of the formula (2), while the dyes of the formulas (1) and (2), if a dye of the general formula (2) is present in the dye mixture, are present in a ratio of 99.5% to 94% with respect to the dye diazo or diazo dyes of the formula (1) and from 0.5 to 6% by weight with respect to the monoazo dye (s) of the formula (2), calculated on the total amount of dyes of formulas (1) and (2).

2. A mixture of dyes in accordance with the claim 1, which consists of one or more diazo dyes of the formula (1) and optionally one or two monoazo dyes according to the formula (2) in a total amount of 70 to 90% by weight, one or more monoazo dyes of the formula (1) in an amount of 5 to 22.5% by weight and one or more dyes of the formula (4) in an amount of 2 to 12% by weight.

3. A mixture of dyes according to claim 1, further characterized in that R1, R3, R5, R7 and R9 are each independently of the other hydrogen or methoxy and R2, R4, R6, R8 and R10 are each hydrogen .

4. - A mixture of dyes in accordance with the claim 1, further characterized in that each of R1 to R10 are hydrogen.

5. - A mixture of dyes in accordance with the claim 1, further characterized in that Y is in each case, independently of the others, vinyl or is ethyl which is substituted in the position β by chlorine, thiosulfate, sulfate, alkanoyloxy of 2 to 5 carbon atoms, phosphate, sulfobenzoyloxy or p-toluylsulfonyloxy .

6. - A mixture of dyes according to claim 1, further characterized in that Y is in each case, independently of the others, vinyl or β-sulfatoethyl.

1. - A mixture of dyes according to claim 1, further characterized in that the group or groups -SO2-Y are attached to the benzene nucleus in the meta position or in the para position with respect to the azo group or groups.

8. - A mixture of dyes according to claim 1, further characterized in that the group or groups -SO2-Y are attached to the benzene nucleus in the para- position with respect to the azo group or groups.

9. - The use of a dye mixture according to claim 1, for dyeing fiber material containing hydroxy- and / or carboxamide groups.

10. - A process for dyeing fiber material containing hydroxy- and / or carboxamide- groups, characterized in that the dyes are applied to the material and these are fixed to the material by heat or with the help of an alkali or by heat and the aid of a alkali, which consists in using as colorants a mixture of colorants according to and as defined in claim 1.