Indian Patents. 230125:DYE MIXTURES OF FIBER-REACTIVE AZO DYES

Title of Invention	DYE MIXTURES OF FIBER-REACTIVE AZO DYES
Abstract	Dye mixtures comprising one or more reactive dyes of the general formula (I) and one or more reactive dyes of the general formula (II),

Full Text	BLACK DYE MIXTURES OF FIBER REACTIVE AZO DYES AND USE THEREOF FOR DYEING MATERIAL CONTAINING HYDROXY-AND/OR CARBOXAMIDO GROUPS The present invention relates to the feld of fiber-reactive dyes. It describes black mixtures of fiber-reactive dyestuffs and use thereof for dyeing hydroxy- and/or carboxamido-containing fiber materia. Various patent documents disclose dye mixtures of fiber reactive dyes and their use for dyeing hydroxy- and/or carboxamido-containing fiber material in black shades. Examples are US 5,445,654 and US 5,611,821, KR 94-2560 and Sho 58- 160362. However the dyeing properties of these dye mixtures in view of special application methods, as well as their aoplicability to fiber material and the fastness properties of the dyed material, are in need of improvement in some instances. Additionally most known mixtures of reactive dyestuffs have to be dyed in the presence of 50 to 100 g/l of electrolyte salts. The patent documents WO 98/42784, WO 98/42785, WO 93/18224 and US 5,330,539 describe dyes which can be dyed in the presence of low amounts of salt but in the absence of salt they give dyeings having only very poor color strengths. As due to ecological and economic reasons the contamination of dye-house waste-water has to be reduced there is a demand for reactive dyestuffs, which are applicable in the presence of low amounts or even in the absence of electrolyte salts giving dyeings of a high color strength. It has now been found that mixtures comprising reactive dyes of formula (I) and (II) meet these requirements. The present invention thus provides dye mixtures comprising one or more reactive dyes of the general formula (I) and one or more reactive dyes of the general formula (II), where D1 and D2 each represent a group of the general formula (1) where R1 is hydrogen, (C1-C4-alkyl, aryl or substituted aryl; R2 and R3 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and A is a phenylene group of the general formula (2) where R4 and R5 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)- alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or a naphthylene group of the general formula (3) where R6 and R7 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)- alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or a polymethylene group of the general formula (4) where k is an integer greater than 1 and R8 and R9 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)- alkoxy, hydroxyl, cyano, amido, halogen or aryl; and X1 is hydrogen or -SO2-Z; or represent a phenyl group of the general formula (5) where R10 and R11 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and X2 has one of the meanings of X1; or represent a naphthyl group of the general formula (6) where R12and R13 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; X3 has one of the meanings of X1; Z is -CH=CH2, -CH2CH2Z1 or hydroxyl, where Z1 is hydroxyl or an alkali-detachable group; M is hydrogen or an alkali metal; D21 has one of the meanings of D1 or D2 or is a group of formula (7) or (8) where R22 and R23 have independently of one another one of the meanings of R and R3; R24 is hydrogen, (C1- C4)-alkyl, phenyl which is unsubstituted or substituted by (C1-C4)- alkyl, (C1-C4)-alkoxy, sulfo, halogen, carboxy; and Z22 is a group of the general formula (9) or (10) or formula (11) wherein V is fluorine or chlorine; U1, U2 are independently of one another fluorine, chlorine or hydrogen; and Q1, Q2 are independently of one another chlorine, fluorine, cyanamido, hydroxy, (C1-C6)-alkoxy, phenoxy, sulfophenoxy, mercapto, (C1-C6)-alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino,or a group of the general formula (12) or (13) where R2' is hydrogen, (C1-C6)-alkyl, sulfo-(C1-C6)-alkyl, phenyl which is unsubstituted or substituted by (C1-C4)- alkyl, (C1-C4)-alkoxy, sutfo, halogen, carboxy, acetamido, ureido; R3' and R4' have independently of one another one of the meanings of R2', or are a group of the general formula (8), or form a cyclic ring system, such as -(CH2)j- with j being 4 or 5, or alternatively -(CH2)2-E-(CH2)2- with E being oxygen, sulfur, sulfo, -NR5'- with R5' being (C1- C6)-alkyl; W is phen/lene which is unsubstituted or substituted by 1 or 2 substituents such as (C1-C4)-alkyl, (C1-C4)- alkoxy, sarboxy, sulfo, chlorine, bromine, or is (C1-C4)- alkylene -arylene or (C2-C6)-alkylene, which can be interrupted by oxygen, sulfur, sulfono, amino, carbonyl, carbonamido, or is phenylene-CONH-phenylene which is unsutstituted or substituted by (C1-C4)-alkyl, (C1- C4)-alkoxy, hydroxyl, suifo, carboxyl, amido, ureido or halogen, or naphthylene which is unsubstituted or substituted by one or two sulfo groups; and Z is as defined above; R25, R26 and R27 are (C1-C4)-alkyl or (C1-C4)-hydroxyalkyl; B' is an equivalent for an anion such as hydrogensulfate, sulfate, fluoride, chloride, bromide, dihydrogenphosphate, hydrogenphosphate, phosphate, hydroxide, acetate; R21 has one of the meanings of R24; Z21 is hydrogen, (C2-C6)-acyl, aroyl which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4)-alkoxy, sulfo, carboxyi or halogen, or has one of the meanings of Z22; and n is O or l; In the general formula (I) at least one of D1 and D2 is a group of the general formula (1), where, if A is a group ol the general formula (4), R1 is aryl or substituted aryl and where the reactive dye of the general formula (I) contains at least one -SO2-Z group. The individual symbols in the general formulae can be identical to or different from each other within the scope of their definitions. (C1-C4)-alkyl R may be straight-chain or branched and is in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, iscbutyl, sec-butyl or tert-butyl. Methyl and ethyl are preferred. The same logic applies to (C1-C4)-alkoxy groups. Aryl R is in particular phenyl. Substituted aryl R1 is in particular phenyl substituted by one, two or three independent groups selected from the group consisting of (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxy, sulfo, carboxyl, amido and halogen. Halogen R is in particular fluorine, chlorine or bromine, and fluorine and chlorine are preferred. Alkali-eliminable Z1 in the-position of the ethyl group of Z include for example halogen atoms, such as chlorine and bromine, ester groups of organic carboxylic and sulfonic acids, as of alkylcarboxylic acids, substituted or unsubstituted benzenecarboxylic acids and substituted or unsubstituted benzenesulfonic acids, such as alkanoyloxy of 2 to 5 carbon atoms, especially acetyloxy, benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxy and toluylsulfonyloxy, also acidic ester groups of inorganic acids, as of phosphoric acid, sulfuric acid and thiosulfuric acid (phosphato, sulfato and thiosulfato groups), similarly dialkylamino groups having alkyl groups of 1 to 4 carbon atoms in each case, such as dimethylamino and diethylamino. Z is preferably vinyl, -chloroethyl and particularly preferably -ulfatoethyl. The groups "sulfo", "carboxyl", "thiosulfato", "phosphato" and "sulfate-" include not only their acid form but also their salt form. Accordingly, sulfo groups are groups conforming to the general formula -SO3M, thiosulfato groups are groups conforming to the general formula -S- SO3M, carboxyl groups are groups conforming to the general formula -COOM, phosphato groups are groups conforming to the general formula -OF'O3M2 and sulfato groups are groups conforming to the general formula -OSO3M, in each of which M is as defined above. The dyes of the general formula (I) and (II) may possess different fiber-reactive groups -SO2Z within the meaning of Z. More particularly, the fiber-reactive groups -SO2Z may be on the one hand vinylsulfonyl groups and on the other -CH2CH2Z1 groups, preferably sulfatoethyisulfonyl groups. If the dyes of the general formula (I) or (II) contain vinyl-sulfonyl groups in some instances, then the fraction of the respective dye with the viny sulfonyl group is up to about 30 mol%, based on the respective amount of total dye. Alkali M is in particular lithium, sodium or potassium. M is preferably hydrogen or sodium. k is preferably 2 or 3. R1 to R13 are each preferably hydngen and R6, R7, R12 and R13 are each preferably sulfo as well. If A is phenylene and X1 is -SO2Z, the bond leading to the SO2Z-group preferably is in meta- or para-position of the nitrogen atom. In the general formula (1) the carbonamido-group preferably is in para- or meta-position of the diazo-group. If A is naphthylene, the bond leading to the nitrogen atom preferably is in -position of the naphthylene-group. If D1 or D2 have one of the meanings of the general formula (6), the diazo-group preferably is in -position of the naphthyl-group. If D1 or D2 have one of the meanings of the general formula (5) and X2 is -SO2Z, the bond leading to the SO2Z-group preferably is in meta- or para-position of the diazo-group. Examples of substrtuents A are in particular 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2-chloro-1,4-phenylene, 2-chloro-1,5-phenylene, 2-bromo- 1,4-phenylene, 2-sulfo-1,4-phenyle ie, 2-sulfo-1,5-phenylene, 2-methoxy- 1,5-phenylene, 2-ethoxy-1,5-phenyiene, 2,5-dimethoxy-1,4-phenylene, 2-methoxy-5-methyl-1,4-phenylene, 2-methyl-1,4-phenylene, 2,6-naphthylene, 2,8-naphthylene, 1-sulfo-2,6-naphtfylene, 6-sulfo-2,8-naphthylene or 1,2-ethylene and 1,3-propylene. A is particularly preferably 1,3-phenylene, 1,4-phenylene, 2-sulfo-1,4-phenylene, 2-methoxy-1,5-phenylene, 2,5-dimethoxy-1,4-phenylene, 2-methoxy-5-methyl- 1,4-phenylene or 1,2-ethylene and 1,3-propylene, and in the case of the two last- mentioned alkylene groups R is preferably phenyl or 2-sulfophenyl. In general formula (7) R22 to R24 are each preferably hydrogen and R22, R23 are each preferably sulfo as well. In general formula (8) R25 to R27 are each preferably methyl or ethyl. Anion B' preferably is sulfate or chloride. In general formulae (12) and (13) R2' to R4'are preferably hydrogen or methyl, R2' is preferably phenyl as well and R3, R4' are each preferably 2-sulfoethyl, 2-, 3- or 4-sulfophenyl, 3- or 4-trimethylammoniumphenyl-sulfate, 3- or 4- trimethylammoniumphenyl-chloride as well, or R3' and R4' form a cyclic ring system which is preferably of the formula -(CH2)2-O-(CH2)2-. W is preferably 1,3-phenylene, 1,4-phenylene, 2-sulfo-1,4-phenylene, 2-methoxy- 1,5-phenylene, 2,5-dimethoxy-1 4-phenylene, 2-methoxy-5-methyl-1,4-phenylene, 1,2-ethylene, 1,3-propylene. Q1 , Q2 are independently of ono another preferably chlorine, fluorine, cyanamido, carbamoylpyridino, carboxypyridino, or a group of the general formula (12) or (13) with the preferred R2' to R4', W and Z as described above. Examples of the groups Z21 and Z22 are 2,4-dichloro-1,3,5-triazin-6-yl, 2-chloro-4- hydroxy-1,3,5-triazin-6-yl, 2-chloro-4-methoxy-1,3,5-triazin-6-y), 2-chloro-4- phenoxy-1,3,5-triazin-6-yl, 2-chloro-4-(4-sulfophenoxy)-1,3,5-triazin-6-yl, 2-chloro- 4-methylmercapto-1,3,5-triazin-6-yl, 4-amino-2-chloro-1,3,5-triazin-6--yl, 2-chloro- 4-methylamino-1,3,5-triazin-e-yl, 2-chloro-4-morpholino-1,3,5-triazin-6-yl, 2- chloro-4-phenyiamino-1,3,5-1riazin-6-yl, 2-chloro-4-methylphe'nylamino-1,3,5- triazin-6-yl, 2-chloro-4-(2-sul1ophenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(3- sulfophenylamino)-1,3,5-tria;an-6-yl, 2-chloro-4-(4-sulfophenylamino)-1,3,5-triazin- 6-yl, 2-chloro-4-(2,5-disulfophenylamino)-1,3,5-trtazin-6-yl, 2-chloro-4-(3- trimethylammoniumphenyla nino)-1,3,5-triazin-6-yl, 2-chloro-4-(4- trimethy1ammoniumphenylamino)-1:2,5-triazin-6-yl, 2-chloro-4-cyanamido-1,3,5- triazin-6-yl, 2-chloro-4-(2-sulfoethylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(N-methyl- 2-sulfoethylamino)-1,3,5-tri azin-6-yl, 2-chloro-4-(3-carboxypyridino)-1,3,5-triazin-6- yl, 2-chloro-4-(4-carboxypyidino)-1,3,5-triazin-6-yl, 2-chloro-4-(3- carbamoylpyridino)-1,3,5-triazin-6-yl, 2-chloro-4-(4-carbamoylpyridino)-1,3,5- triazin-e-yl, 2-chloro-4-(2-(2-sulfatoethylsulfonyl)-phenylamino;-1,3,5-triazin-6-yl, triazin-6-yl, 2,4-difluoro-pyrimidin-6 yl, 4,6-difluoro-pyrimidin-2-yl, 5-chloro-2,4- difluoro-pyrimidin-6-yl, 5-chloro-4,6-difluoro-pyrimidin-2-yl, 2,3-dichlorochinoxalin- 6-carbonyl, and Z21 preferably acelyl as well. n is preferably 0 In general formula (II) the bond leading to the nitrogen atom preferably is in  position of the naphthalene. If D21 has one of the meanings of the general formula (6), the diazo-group preferably is in -position of the naphthyl-group. If D21 has one of the meanings of the general formula (5) and X2 is -SO2Z, the bond leading to the SO2Z-group preferably is ir meta- or para-position of the diazo-group. If D21 has one of the meanings of the general formula (8), the quaternary-salt preferably is in meta- or para-position of the diazo-group. Preferred dye mixtures comprise one or more compounds of the general formula (la) In the general formulae (la) and (lla) M, A, R1, Z, D21 and Z21 are each as defined above. Particularly preferably, A is phonylene and Z is vinyl or -sulfatoethyl in the general formula (la) Most preferably, A is phenylene, R1 is hydrogen and Z is vinyl or -sulfatoethyl in the general formula (la). In general, the azo dyestuffs of the formula (I) are contained in the mixture in quantity of 95 to 30% by weight and the azo dyestuffs of the formula (II) are contained in the mixture in a mixing ratio of 10 to 70% by weight, preferably in a mixing ration of 90% :10% by weight to 40%:60% by weight. The dye mixtures according to the 3 present invention may also comprise one or more red monoazo dye of the general formulae (14) or (15) in up to 10 % by weight where M and D2 are each as destined above. Particularly preferably D2 is 4-(2- sulfatoethylsulfonyl)-phenyl or 4-vinylsulfonyl-phenyl. The dyes of the formulae (14) and (15) can be synthesised by the standard methology, or are partly formed during the synthesis of compound (I). They are generally added as shading components. Dyestuffs of formula (I) are known from EP-A-1046677 and dyestuffs of formula (II) are well known from KR 84-2785, EP-A-08311, DE-A-3915305, US 5,349,057, WO 9963005-A1, EP-B-0557841, EP-B-0808343 , US 823,926, DE-A- 1 265 698, DE-A-19 43 904, F R 2 019 394.CA-A-519 978. The dye mixtures of the invention can be prepared in solid or in liquid (dissolved) form. In solid form they generally contain the electrolyte salts customary in the case of water-soluble and in particular fiber-reactive dyes, such as sodium chloride, potassium chloride .and sodium sulfate, and also assistants customary in commercial dyes, such as biffer substances capable of establishing a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium citrato, sodium dihydrogenphosphate and disodiumhydrogenphosphate, smell amounts of siccatives or if, they are present in liquid, aqueous solution (including the presence of thickeners of the type customary in print pastes), substances which ensure the permanence of these preparations, for example mold preventatives. In general, the dye mixtures will take the form of dye powders containing from 10 to 80 % by weight, based on the dye powder or preparation, of a strength- standardizing colorless diluent electrolyte salt. These dye powders may in addition contain the abovementioned buffer substances in a total amount of up to 10%, 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 about 50 % by weight, for example between 5 and 50 % by weight, the electrolyte salt content of these aqueous solutions preferably being below 10 % by weight, based on the aqueous solution; the acueous solutions (liquid preparations) can in general contain the abovement oned buffer substances in an amount of up to 5 % by weight, preferably up to 2 % by weight. The dye mixtures of this invention can be obtained in a conventional manner, for instance by mechanically mixing the individual dyes in solid form or in form of aqueous solutions in the requied proportions, or by synthesis by means of the customary diazotization and coupling reactions using appropriate mixtures of a diazo and the coupling components in a manner familiar to those skilled in the art and the necessary proportion;;. Thus, if the diazo components with the groups D1 and D21 according to the general formulae (I) and (II) a-e the same (D1 = D21), one option is for example to prepare aqueous suspensions of a mixture of a red monoazo dye according to the general formula (14) with the meanings of M and D2 described above, and an optionally N-substituted 2-Arr ino-7-surfo-5-naphthol or 2-Amino-6-sulfo-8- naphthol as coupling comporents, then coupling in a one-pot reaction with a diazotised aniline or naphthy amine compound of the formula D1 - NH2, with the meanings of D1 described above, at a pH between 4 and 8 forming a mixture of disazo dyes conforming to the formula (I) and monoazo dyes conforming to the formula (II) The final dyestuff can be isolated from the solution in the conventional manner, for example by salting out with an electrolyte salt, such as sodium chloride or potassium chloride, or by spray-drying. The red monoazo-dyes of general formulae (14) can be prepared by diazotizing an amino compound D2 - NH2, with the meanings of D2 described above, in a conventional manner in a strongl/ acid medium and then carrying out the first coupling reaction of 1-amino-8-naphthol-3,6-disulfonic acid or 1-amino-8-naphthol- 4,6-disulfonic acid with the diazo component at a pH below 2. Dye mixtures in which the dye chromophores contain for example not only a -chloroethylsulfonyl or -thiosulfatoethylsulfonyl or (l-suifatoethylsulfonyl group but also proportions with vinylsulfonyl groups cannot only be prepared by the above mentioned method using approoriate vinylsulfonyl starting anilines or naphthylamines, but also by reacting the dye mixture in which Z is a -chloroethyl, - thiosulfatoethyl, or -sulfatoeth/l group with an amount of alkali required for only part of these groups and converting partly said -substituted ethylsulfonyl groups into vinylsulfonyl groups. This procedure is carried out by generally known methods of converting -substituted ethylsulfonyl groups into the vinylsulfonyl group. The solution of the dye mixtures according to the invention obtained during synthesis of their individual azo dyes can also be used for dyeing directly as a liquid preparation, if appropria:e after addition of a buffer substance and if appropriate also after concentration or dilution. The reactive dye mixtures according to the invention have fiber-reactive properties and possess very good dye properties. They can therefore be used for dyeing hydroxyl- and/or carbcxamido-containing material, especially fiber material, paper and also leather. The present invention therefc re also provides for the use of the inventive dye mixtures for dyeing or printing hydroxyl- and/or carboxamido-containing materials, or methods for their application on these substrates. This includes mass coloration, for example films composed of polyamide. and printing. The materials are preferably employed in the form of fiber materials, especially in the form of textile fibers, such as woven fabrics or yams;, as in the form of hanks or wound packages. Hydroxyl-containing materials are those of natural or synthetic origin, for example cellulose fiber materials or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton, but also other vegetable fibers, such as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are for example staple viscose and filament viscose. Carboxamido-containing materia s are for example synthetic and natural polyamides and polyurethanes, especially in the form of fibers, for example wool and other animal hairs, silk, leather, nyIon-6,6, nylon-6, nylon-11 and nylon-4. The inventive reactive dye mixtures can be applied to and fixed on the substrates mentioned, especially the fiber materials mentioned, by the application techniques known for water-soluble dyes, especially fiber-reactive dyes. For instance, on cellulose fibem they produce by the exhaust method from a long liquor using various acid-binding agents and optionally neutral salts, such as sodium chloride or sodium sulfate, dyeings having very good color yields and excellent color build-up combined with high fixation yields. Dyeing is earned out in an aqueous bath at temperatures between 40 and 105°C, optionally at temperatures of up to 120°C under superatmospheric pressure, and optionally in the presence of customary dye.-ing auxiliaries. One possible procedure is to introduce the material into the warm bath and to gradually heat the bath to the desired dyeing temperature and to complete the dyeing process at that temperature. The neutral salts which accelerate the exhaustion of the inventive reactive dye mixtures may also, if desired, only be added to the bath after the actual dyeing temperature has been reached. However, the inventive reactive dye mixtures are also very useful for saltless or low-salt dyeing and can thus he dyed for example without any salt at low depth of shade, with very little salt such as not more than 5 g/l electrolyte salt at medium depth of shade and with not more than 10 g/l electrolyte salt at higher depths of shade, and in all cases strong dyeings are obtained. Low depths of shade for the purposes of this invention are depths of shade involving not more than 2 percent by weight of dye being used, based on the substrate. Medium depths of shaoe are to be understood as meaning more than 2 to not more than 4 percent by weight of dye and higher depths of shade are to be understood as meaning more than 4 to not more than 10 percent by weight of dye, based on the substrate. This provides for partly distinct reductions not only of the effluent loading of dyehouse wastewaters but also of the associated costs. The padding process likewise provides excellent color yields coupled with high fixation yields and very good color build-up on cellulose fibers, the dye mixture being allowed to become fixed an the material by batching at room temperature or at elevated temperature, for example at up to approximately 60°C, by steaming or using dry heat in a conventional manner. Similarly, the customary printirg processes for cellulose fibers, which can be carried out either single-phase, for example by printing with a print paste comprising sodium carbonate or some other acid-binding agent and a reactive dye-mixture of the invention and by subsequent steaming at 100 to 103°C, or two- phase, for example by printing with print paste comprising a neutral or weakly acidic print colour and subsecuent fixation either by passing the printed material through a hot electrolyte-comorising alkaline bath or by overpadding with an alkaline electrolyte-comprising padding liquor with subsequent batching of the alkali-overpadded material or subsequent steaming or subsequent treatment with dry heat, produce strong prints with well-defined contours and a clear white ground. The outcome of the prints is not greatly affected by variations in the fixing conditions. The fixation yields obtained with the inventive reactive dye mixtures are very high not only in dyeing but also in printing. When fixing by means of dry heat n accordance with the customary thermofix processes, hot air from 120 to 200°C is used. In addition to the customary steam at 101 to 103°C it is also possible to use superheated steam and high-pressure steam at temperatures of up to 160°C. The acid-binding agents which effect the fixation of the inventive reactive dye mixtures on the cellulose fibers include for example water-soluble basic salts of the alkali metals and the alkaline earth metals of inorganic or organic acids and likewise compounds which liberate alkali in the heat. Especially suitable are the alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic 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 dihydrogenphosphate, disodium hydrogenphosphate, sodium trichloroacetate, waterglass or trisodium phosphate. Treating the inventive dye mixtures with the acid-binding agents with or without heating, binds the dyes chemically to the cellulose fiber. Cellulose dyeings in particular, following the custorr ary aftertreatment by rinsing to remove unfixed dye portions exhibit very good wet fastnesses, in particular since such unfixed dye portions are easily washed off on account of their good solubility in cold water. Dyeings on polyurethane and polyamide fibers are customarily carried out from an acidic medium. For instance, the dyebath may include acetic acid and/or ammonium sulfate and/or acetic acid and ammonium acetate or sodium acetate in order to obtain the desired oH. To achieve useful levelness for the dyeing, it is advisable to add customary leveling aids, for example based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic acid aid/or an aminonaphthaienesulfonic acid or based on a reaction product of for example stearylamine vvith ethylene oxide. Generally the material to be dyed is introduced into the bath at a temperature of about 40°C, agitated therein for some tirm, and the dyebath is then adjusted to the desired weakly acidic pH. preferably with acetic acid, and the actual dyeing is carried out at a temperature between 60 and 98°C. However, the dyeings can also be carried out at boiling point or at temperatures of up to 120°C (under pressure). The dyeings and prints on cellulose fiber materials in particular, as already mentioned, have high color strength, good light- and wet fastnesses and also good hot press and crock fastnessses. Particularly noteworthy are the high yields of fixation obtainable on celluloso fiber materials, which can be above 90%, and also the very good color build-up, including the exhaust method using reduced neutral salt quantities or dispensing with salt altogether, depending on the depth of shade, i.e., depending on the amount of dye used. A further advantage of the inventive reactive dye mixtures is the ease with which portions unfixed in the printing or dyeing process are washed off, as a result of which the wash of the printed or dyed cellulose fiber materials can be accomplished with smaller amounts of wash liquor and, as the case may be, energy-saying temperature control during the wash. The examples hereinbelow serve to illustrate the invention. Parts and percentages are by weight, uniess otherwise stated. Parts by weight relate to parts by volume as the kilogram relates to the liter. The compounds described in the examples in terms of a formula are indicated in the form of the sodium salts as in general they are prepared and isolated in the form of their alkali metal salts, such as lithium, sodium or potassium salts, and used for dyeing in the form of this salts. The starting compounds, and components mentioned in the form of the free acid in the examples hereinbelow may be used in the synthesis as such or similarly in the form of their saits, preferably alkali metal salts. Example 1 85 parts of an electrolyte-containing dye powder which contains the navy-dyeing disazo dye of the formula (lA) in a proportion of 70% are mechanically mixed with 15 parts of an electrolyte- containing dye powder which contains the orange-dyeing monoazo dye of the formula (HA) in a 75% proportion The resulting dye mixture according to the invention, when employed according to the application and fixing methods customary in the art for fiber-reactive dyes, produces for example on cellulose fiber materials dyeings and prints in deep black shades. Example 2 80 parts of an electrolyte-containing dye powder which contains the navy-dyeing disazo dye of the formula (1A in a proportion of 75% and 20 parts of an electrolyte- containing dye powder which contains the orange-dyeing monoazo dye of the formula (HA) in a 60% proportion are dissolved in 700 parts of water and the resulting dye solution is adjusted to pH 5.5 - 6.5. Evaporating this solution affords a dye mixture which produces deep black shades on cellulosic materials when employed according to the application and fixing methods customary in the art for fiber-reactive dyes. Example 3 a) A suspension of 281 parts of 4-(fi-sulfatoethylsulfonyl)-aniline in 650 parts of ice- water and 180 parts of 30 % aqueous hydrochloric acid is diazotized with 173 parts of 40% strength aqueous sodiurr, nitrite solution. 319 parts of 1-amino-8-napthol-3,6- disulfonic acid are added and the first coupling forming a red monoazo dye according to the general formula (14) is carried out at a pH between 1 and 1.3 and at a temperature below 20°C. Durinc the reaction the pH is maintained with about 140 parts of sodium bicarbonate. b) In a separate vessel to a suspension of 500 parts of 4-amino-N-(3-(- sulfatoethylsulfonyl)-phenyl)-benzamide in 2750 parts of ice-water, adjusted to pH 6.5-7 with about 90 parts of sodium carbonate, are added 217 parts of 40% strength aqueous sodium nitrite solution. This suspension is pumped into a slurry of 780 parts of ice, 630 parts ice-water and 450 parts concentrated hydrochloric acid. After stirring for 2 hours at 5-10°C excess r itrite is destroyed using sulfamic acid and the resulting diazo suspension is pumped into solution (a). Immediately afterwards 70 parts of 6- acetylamino-1-hydroxynaphth alene-3-sulfonic acid are added to the reaction mixture. The pH is raised to 5-6 by addition of sodium carbonate at a temperature below 25°C and after the coupling is complete the 85:15 mixture of the dyes (IB)jand (IIB) is isolated by spray-drying. Alternatively the obtained dye solution can be buffered at pH 5.5 - 6 by adding a sodium phosphate buffer. By further diluting with water or by evaporating the solution, this liquid dye mixture can then be standardized to the desired strength for a liquid preparation. The dye mixture affords deep black shades on cellulosic materials. Examples 4 to 634 The table examples which follow describe further dye mixtures according to the invention of the dyes conforming to the formulae (I) and (II) as the sodium salts and the mixing ratios of the dyes by percent by weight. When employed according to the application and fixing methods customary in the art for fiber-reactive dyes, these dye mixtures produce, for example, on cellulose fiber materials, navy to deep black dyeings. Examples 97- 191 Examples 1, 2 and 4-96 were repeated using dye (IB) instead of dye (IA). Examples 192-286 Examples 1, 2 and 4-96 were repeated using dye (IC) instead of dye (IA): Examples 287 - 381 Examples 1, 2 and 4 - 96 were repealed using dye (ID) instead of dye (IA): Examples 382 - 476 Examples 1, 2 and 4 - 96 were repeated using dye (IE) instead of dye (IA): Dye mixtures prepared according to examples 1, 2 or 3 Examples 539 - 570 Examples 507 - 538 were repeated ising dye (IG) instead of dye (IF): Examples 571 - 602 Examples 507 - 538 were repeated using dye (IH; Instead of dye (IF): Examples 603 - 634 Examples 507-538 were repeated using dye (IJ) instead of dye (IF): Dyeing example 1 2 parts of a dyestuff mixture according to example 1, 2 or 3 are dissolved in 999 parts of water and 5 parts of sodium carbonate, 0,7 parts of sodium hydroxide (as a 32,5% solution in water) and 1 part of a wetting agent, if necessary, are added. 100g of a cotton fabric are brought into the dye bath. The temperature of the dye bath is held at 25°C for 10 minutes, then raised to 40 - 60°C within 30 minutes and dyeing is continued for another 60 - 90 minutes at this temperature. Afterwards the dyed fabric is first rinsed with water for 2 minutes and then rinsed with desalted water for 5 minutes. Afterwardes the fabric is neutralized for 10 minutes at 40°C in 1000 parts of an aqueous solution containing 1 part of 50% acetic acid. The cotton fabric is rinsed with desalted water at 70°C and soaped at the boiling point for 15 minutes, again rinsed and air-dried or ironed, resulting a deep navy to grey dyeing with very good fastness properties. Dyeing example 2 4 parts of a dyestuff mixture according to example 1, 2 or 3 are dissolved in 999 parts of water and 5 parts of sodium chloride, 7 parts of sodium carbonate, 0,7 parts of sodium hydroxide (as a 32,5% solution in water) and 1 part of a wetting agent, if necessary, are added. 100g of a cctton fabric are brought into the dye bath. The dyeing and aftertreatment process is carried out as described in dyeing example 1, resulting a deep navy to black dyeing with very good fastness properties. Dyeing example 3 8 parts of a dyestuff mixture according to example 1, 2 or 3 are dissolved in 997 parts of water and 10 parts of sodium chloride, 10 parts of sodium carbonate, 1,3 parts of sodium hydroxide (as a 32,5% solution in water) and 1 part of a wetting agent, if necessary, are added. 100c of a cotton fabric are brought into the dye bath. The dyeing and aftertreatment process is carried out as described in dyeing example 1, resulting a deep black dyeing with very good fastness properties. WE CLAIM: 1. Dye mixtures comprising one or more reactive dyes of the general formufa (I) and one or more reactive dyes of the general formula (II), where D1 and D2 each represent a group of the general formula (1) where R1 is hydrogen, (C1-C4)-alkyl, aryl or phenyl substituted by one, two or three independent groups selected from the group consisting of (C1-C4)- alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, amido and halogen; R2 and R3 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxy, amido or halogen; and A is a phenylene group of the general formula (2) where R4 and R5 ae independently hydrogen, (C1-C4)-alkyl, (C1-C4)- alkoxy, hydroxy), sulfo, carboxyl, amido or halogen; or a naphthylene group of the general formula (3) where R6 and R7 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)- alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or a polymethylene group of the genera! formula (4) where k is an integer greater than 1 and R8 and R9 are ndependently hydrogen, (C1-C4)-alkyl, (C1-C4)- alkoxy, hydroxyl, cyano, amido, halogen or aryl; and X1 is hydrogen or -SO2-2; or represent a phenyl group of the general formula (5) where R10 and R11 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, amido, or halogen; and X2 has one of the meanings of X1; or represent a naphthyl group of the general formula (6) where R12and R13 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo carboxyl, amido, ureido or halogen; X3 has one of the meanings of X1; Z is -CH=CH2, -CH2CH2Z1 or hydroxyl, where Z1 is hydroxyl or an alkali-detachable group; M is hydrogen or an alkali metal; D21 has one of the meanings of D1 or D2 or is a group of formula (7) or (8) where R22 and R23 have independently of one another one of the meanings of R2 and R3; R24 is hydrogen, (C1- C4)-alkyl, phenyl which is unsubstituted or substituted by (C1-C4)- alkyl, (C1-C4)-alkoxy, sulfo, halogen, carboxy; and Z22 is a group of the general formula (9) or (10) or formula (11) wherein V is fluorine or chlorine; U1, U2 are independently of one another fluorine, chlorine or hydrogen; and Q1, Q2 are independently of one another chlorine, fluorine, cyanamido, hydroxy, (C1-C6)-alkoxy, phenoxy, sulfcphenoxy, mercapto, (C1-C6)-alkylmercapto, pyridine carboxypyridino, carbamoylpyridino, or a group of the general formula (12) or (13) where R2' is hydrogen, (C1-C6)-alkyl, sulfo-(C1-C6)-alkyl, phenyl which is unsubstituted or substituted by (C1-C4)- alkyl, (C1-C4)-alkoxy, sulfo, halogen, carboxy, acetamido, ureido; R3' and R4' have independently of one another one of the meanings of R2', or form a cyclic ring system, such as -(CH2)j- with j being 4 or 5, or alternatively -(CH2)2-E- (CH2)2- with E beir.g oxygen, sulfur, sulfo, -NR5'- with R5' being (C1-C6)-alkyl; W is phenylene which is unsubstituted or substituted by 1 or 2 substituents such as (C1-C4)-alkyl, (C1-C4)-alkoxy, carboxy, sulfo, chlorine, bromine, or is (C1-C4)-alkylene- arylene or (C2-C6)-alkylene, which can be interrupted by oxygen, sulfur, sulfono, amino, carbonyl, carbonamido, or is phenylene-CONH-phenylene which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido or halogen, or naphthylene which is unsubstituted or substituted by one or two sulfo groups and Z is as defined above; R25, R26 and R27 are (C1-C4)-alkyl or (C1-C4)-hydroxyalkyl; B" is an equivalent for an anion such as hydrogensulfate, sulfate, fluoride, chloride, bromide, dihydrogenphosphate, hydrogenphosphate, phosphate, hydroxide, acetate; R21 has one of the meanings o R24; Z21 is hydrogen, (C2-C6)-acyl, aroyl which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4)-alkoxv, sulfo, carboxyl or halogen, or has one of the meanings of Z22; and n is 0 or 1; wherein in the general formula (I) al least one of D1 and D2 is a group of the general formula (1); wherein, if A is a group of the general formula (4), R1 is aryl or phenyl substituted by one, two or three independent groups selected from the group consisting of (C1-C4)-alkyl, (C1-C4)-alkoxy, hydrox/l, sulfo, carboxyl, amido and halogen; and where the reactive dye of the geneml formula (I) contains at least one -S02-Z group. 2. Reactive dye mixtures according to claim 1 with the substituents R1 to R5, R8 to R11, R21 and R24 being hydrogen, R6 R7. R12, R13, R22 and R23 being hydrogen or sulfo and R25, R26 and R27 being melhyl. 3. Reactive dye mixtures according to at least one of claims 1 to 2 wherein Z is vinyl, -chloroethyl or -sulfatoethyl. 4. Reactive dye mixtures according to at least one of the claims 1 to 3 wherein n is 0 in general formula (II). 5. Reactive dye mixtures according to claim 4 which comprise one or more dyes according to the general formula [la) and one or more dyes of the general formula (lla) wherein M, A, R1, Z, D21 and Z21 are as defined in claim 1. 6. Reactive dye mixtures according to claim 4 wherein R1 is hydrogen, A is phenylene and Z is vinyl or -sulfatothyl in the general formula (la) and D21 and Z21 in general formula (lla) are as defined in claim 1. 7. Reactive dye mixtures according to at least one of claim 1 to 6 wherein D21 in general formula (II) has one of the meanings of 3-(-sulfatoethylsulfonyl)-phenyl, 4-(ft-sulfatoethylsulfonyl)-phenyl, 2-slfo-4-(-sulfatoethylsulfonyl)-phenyl, 2-methoxy-5-(-sulfatoethylsulfonyl)-phenyl, 2,5-dimethoxy- 4-(-sulfatoethylsulfonyl)-phenyl, 2-methoxy-5-methyl-4-(-sulfatoethylsulfonyl)- phenyl, 6-(-sulfatoethylsulfonyl)-1-sulfo-naphth-2-yl, 3- or 4-vinylsulfonyl-phenyl, 4-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl, 4-(4-(2- sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl, 3-(3-(2-sulfatoethylsulfonyl)- phenylcarbamoyl)-phenyl, 3-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)- phenyl,1-sulfo-4-(2,4-difluoro-pyrimiclin-6-yl)-amino-2-phenyl or 1-sulfo-4-(4,6- difluoro-pyrimidin-2-yl)-amino-2-phenyl, 2-sulfophenyl, 4-methyl-2-sulfophenyl or 1,5-disulfonaphth-2-yl. 8. Reactive dye mixtures according to at least one of claim 1 to 7 wherein Z21 in general formula (II) has one of the meanings of 2,4-dichloro-1,3,5-triazin-6-yl, 2- chloro-4-morpholino-1,3,5-triazi i-6-yl, 2-chloro-4-(3-sulfophenylamino)-1,3,5- triazin-6-yl, 2-chloro-4-(4-sulfophenylamino)-1,3,5-triazin-6-yl, 2-chloro-4- cyanamido-1,3,5-triazin-6-yl, 2-chloro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)- 1,3,5-triazin-6-yl, 2-chloro-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin- 6-yl, 2-chloro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(4- (vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(N-methyl-N-(2-(2- sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl, 2-chloro-4-(N-phenyl-N-(2-(2- sulfatoethylsulfonyl)-ethyl)-aminci)-1,3,5-triazin-6-yl, 2-fluoro-4-morpholino-1,3,5- triazin-6-yl, 2-fluoro-4-(2-sulfophenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(3- sulfophenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(4-sulfophenylamino)-1,3,5-triazin- 6-yl, 2-fluoro-4-(3-trimethylammoniumphenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4- (4-trimethylammoniumphenylami io)-1,3,5-triazin-6-yl, 2-fluoro-4-(3-(2- sulfatoethylsulfonyl)-phenylaminc )-1,3,5-triazin-6-yl, 2-fluoro-4-(4-(2- sulfatoethylsulfonyl)-phenylaminc)-1,3,5-triazin-6-yl, 2-fluoro-4-(3-(vinylsulfonyl)- phenylamino)-1,3,5-triazin-6-yl, 2fluoro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5- triazin-6-yl, 2-fluoro-4-(N-methyl-M-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5- triazin-6-yl, 2-fluoro-4-(N-phenyl-M-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5- triazin-6-yl, 2,4-difluoro-pyrimidin-o-yl, 4,6-difluoro-pyrimidin-2-yl, 5-chloro-2,4- difluoro-pyrimidin-6-yl, 5-chloro-4,3-difluoro-pyrimidin-2-yl, 2,3-dichlorochinoxalin- 6-carbonyl, and acetyl. 9. A dye mixture according to at least one of the claims 1 to 8 wherein a dye of formula (I) is present in the mixture; in an amount of from 30 to 95% by weight; a dye of the formula (II) is present in the mixture in an amount of from 5 to 70% by weight. 10. A dye mixture according to at least one of the claims 1 to 9 comprising a monoazo dye of formula (14) in a total amount of 0.5 to 6.0% by weight and/or a monoazo dye of formula (15) in a total amount of 0.5 to 6.0% by weight. wherein D2 and M are as defined n claim 1. 11. A dye mixture according to onu or more of the claims 1 to 10 comprising at least one dye of general formula (I) in uo to 95 % by weight. 12. A process for the preparation of the dye mixtures according to at least one of the claims 1 to 11 comprising mechanically mixing the individual dyes of the formulae (I) and (II) in solid form or in form of aqueous solutions in the required proportions. 13. A process for the preparation of the dye mixtures according to at least one of the claims 1 to 11, under the proviso that D1 and D21 in the general formulae (I) and (II) have the same meaning, by diazotizing an amine of the general formula (16) D2-NH2 (16), wherein D2 is as described in claim 1, in a conventional manner in a strongly acidic medium and then carrying out the coupling reaction of the 1-amino-8-napthol-3,6- disulfonic acid or 1-amino-8-naptho -4,6-disulfonic acid with the diazo component at a pH below 2 to form the red compound (14) followed by diazotation of an amine of the general formula (17) D1-NH; (17), wherein D1 is as described in claim I, in a conventional manner in a strongly acidic medium and then carrying out the second coupling reaction with the monoazo dye product (14) to form the disazo dye conforming to the formula (I) at a pH between 4 and 8 and followed by addition of an aqueous solution of the optionally N-substituted 2-Amino-7-sulfo-5-naphthol or 2-Amino-6-su!fo-8-naphthol to the coupling reaction to form the dye conforming to the formula (II) which is carried out in the same pH-range between 4 and 7.5 followed by isola ion of the dyestuff mixture from the solution in the conventional manner. 14. A process for dyeing hydroxy- and/or carboxamido -containing fiber material, in which dyes are applied to the material and the dyes are fixed to the material by means of heat or with the aid of an alkali or by means of heat and with the aid of an alkali, which comprises dye mixtures as claimed in one or more of the claims 1 to12. Dated this 31st day of OCTOBER, 2003 Dye mixtures comprising one or more reactive dyes of the general formula (I) and one or more reactive dyes of the general formula (II),

Full Text

BLACK DYE MIXTURES OF FIBER REACTIVE AZO DYES AND USE THEREOF
FOR DYEING MATERIAL CONTAINING HYDROXY-AND/OR CARBOXAMIDO
GROUPS
The present invention relates to the feld of fiber-reactive dyes. It describes black
mixtures of fiber-reactive dyestuffs and use thereof for dyeing hydroxy- and/or
carboxamido-containing fiber materia.
Various patent documents disclose dye mixtures of fiber reactive dyes and their
use for dyeing hydroxy- and/or carboxamido-containing fiber material in black
shades. Examples are US 5,445,654 and US 5,611,821, KR 94-2560 and Sho 58-
160362. However the dyeing properties of these dye mixtures in view of special
application methods, as well as their aoplicability to fiber material and the
fastness properties of the dyed material, are in need of improvement in some
instances. Additionally most known mixtures of reactive dyestuffs have to be dyed
in the presence of 50 to 100 g/l of electrolyte salts. The patent documents WO
98/42784, WO 98/42785, WO 93/18224 and US 5,330,539 describe dyes which
can be dyed in the presence of low amounts of salt but in the absence of salt they
give dyeings having only very poor color strengths.
As due to ecological and economic reasons the contamination of dye-house
waste-water has to be reduced there is a demand for reactive dyestuffs, which are
applicable in the presence of low amounts or even in the absence of electrolyte
salts giving dyeings of a high color strength.
It has now been found that mixtures comprising reactive dyes of formula (I) and
(II) meet these requirements.
The present invention thus provides dye mixtures comprising one or more
reactive dyes of the general formula (I)

and one or more reactive dyes of the general formula (II),

where
D1 and D2 each represent a group of the general formula (1)

where
R1 is hydrogen, (C1-C4-alkyl, aryl or substituted aryl;
R2 and R3 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy,
hydroxyl, sulfo, carboxyl, amido or halogen; and
A is a phenylene group of the general formula (2)

where

R4 and R5 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-
alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or
a naphthylene group of the general formula (3)

where
R6 and R7 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-
alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or
a polymethylene group of the general formula (4)

where
k is an integer greater than 1 and
R8 and R9 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-
alkoxy, hydroxyl, cyano, amido, halogen or aryl; and
X1 is hydrogen or -SO2-Z;
or represent a phenyl group of the general formula (5)

where
R10 and R11 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy,
hydroxyl, sulfo, carboxyl, amido or halogen; and

X2 has one of the meanings of X1;
or represent a naphthyl group of the general formula (6)

where
R12and R13 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy,
hydroxyl, sulfo, carboxyl, amido or halogen;
X3 has one of the meanings of X1;
Z is -CH=CH2, -CH2CH2Z1 or hydroxyl,
where
Z1 is hydroxyl or an alkali-detachable group;
M is hydrogen or an alkali metal;
D21 has one of the meanings of D1 or D2 or is a group of formula (7) or (8)

where
R22 and R23 have independently of one another one of the meanings of R
and R3;
R24 is hydrogen, (C1- C4)-alkyl, phenyl which is unsubstituted or

substituted by (C1-C4)- alkyl, (C1-C4)-alkoxy, sulfo, halogen, carboxy;
and
Z22 is a group of the general formula (9) or (10) or formula (11)

wherein
V is fluorine or chlorine;
U1, U2 are independently of one another fluorine, chlorine or
hydrogen; and
Q1, Q2 are independently of one another chlorine, fluorine,
cyanamido, hydroxy, (C1-C6)-alkoxy, phenoxy, sulfophenoxy,
mercapto, (C1-C6)-alkylmercapto, pyridino, carboxypyridino,
carbamoylpyridino,or a group of the general formula (12) or
(13)

where
R2' is hydrogen, (C1-C6)-alkyl, sulfo-(C1-C6)-alkyl, phenyl
which is unsubstituted or substituted by (C1-C4)- alkyl,
(C1-C4)-alkoxy, sutfo, halogen, carboxy, acetamido,
ureido;
R3' and R4' have independently of one another one of the
meanings of R2', or are a group of the general formula
(8), or form a cyclic ring system, such as -(CH2)j- with j
being 4 or 5, or alternatively -(CH2)2-E-(CH2)2- with E

being oxygen, sulfur, sulfo, -NR5'- with R5' being (C1-
C6)-alkyl;
W is phen/lene which is unsubstituted or substituted by
1 or 2 substituents such as (C1-C4)-alkyl, (C1-C4)-
alkoxy, sarboxy, sulfo, chlorine, bromine, or is (C1-C4)-
alkylene -arylene or (C2-C6)-alkylene, which can be
interrupted by oxygen, sulfur, sulfono, amino, carbonyl,
carbonamido, or is phenylene-CONH-phenylene which
is unsutstituted or substituted by (C1-C4)-alkyl, (C1-
C4)-alkoxy, hydroxyl, suifo, carboxyl, amido, ureido or
halogen, or naphthylene which is unsubstituted or
substituted by one or two sulfo groups; and
Z is as defined above;
R25, R26 and R27 are (C1-C4)-alkyl or (C1-C4)-hydroxyalkyl;
B' is an equivalent for an anion such as hydrogensulfate, sulfate,
fluoride, chloride, bromide, dihydrogenphosphate,
hydrogenphosphate, phosphate, hydroxide, acetate;
R21 has one of the meanings of R24;
Z21 is hydrogen, (C2-C6)-acyl, aroyl which is unsubstituted or substituted by
(C1-C4)-alkyl, (C1-C4)-alkoxy, sulfo, carboxyi or halogen, or has one of the
meanings of Z22; and
n is O or l;
In the general formula (I) at least one of D1 and D2 is a group of the general
formula (1), where, if A is a group ol the general formula (4), R1 is aryl or
substituted aryl and where the reactive dye of the general formula (I) contains at
least one -SO2-Z group.
The individual symbols in the general formulae can be identical to or different
from each other within the scope of their definitions.

(C1-C4)-alkyl R may be straight-chain or branched and is in particular methyl,
ethyl, n-propyl, isopropyl, n-butyl, iscbutyl, sec-butyl or tert-butyl. Methyl and ethyl
are preferred. The same logic applies to (C1-C4)-alkoxy groups.
Aryl R is in particular phenyl. Substituted aryl R1 is in particular phenyl substituted
by one, two or three independent groups selected from the group consisting of
(C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxy, sulfo, carboxyl, amido and halogen.
Halogen R is in particular fluorine, chlorine or bromine, and fluorine and chlorine
are preferred.
Alkali-eliminable Z1 in the-position of the ethyl group of Z include for example
halogen atoms, such as chlorine and bromine, ester groups of organic carboxylic
and sulfonic acids, as of alkylcarboxylic acids, substituted or unsubstituted
benzenecarboxylic acids and substituted or unsubstituted benzenesulfonic acids,
such as alkanoyloxy of 2 to 5 carbon atoms, especially acetyloxy, benzoyloxy,
sulfobenzoyloxy, phenylsulfonyloxy and toluylsulfonyloxy, also acidic ester groups
of inorganic acids, as of phosphoric acid, sulfuric acid and thiosulfuric acid
(phosphato, sulfato and thiosulfato groups), similarly dialkylamino groups having
alkyl groups of 1 to 4 carbon atoms in each case, such as dimethylamino and
diethylamino.
Z is preferably vinyl, -chloroethyl and particularly preferably -ulfatoethyl.
The groups "sulfo", "carboxyl", "thiosulfato", "phosphato" and "sulfate-" include not
only their acid form but also their salt form. Accordingly, sulfo groups are groups
conforming to the general formula -SO3M, thiosulfato groups are groups
conforming to the general formula -S- SO3M, carboxyl groups are groups
conforming to the general formula -COOM, phosphato groups are groups
conforming to the general formula -OF'O3M2 and sulfato groups are groups
conforming to the general formula -OSO3M, in each of which M is as defined
above.
The dyes of the general formula (I) and (II) may possess different fiber-reactive
groups -SO2Z within the meaning of Z. More particularly, the fiber-reactive groups
-SO2Z may be on the one hand vinylsulfonyl groups and on the other -CH2CH2Z1
groups, preferably sulfatoethyisulfonyl groups. If the dyes of the general

formula (I) or (II) contain vinyl-sulfonyl groups in some instances, then the fraction
of the respective dye with the viny sulfonyl group is up to about 30 mol%, based
on the respective amount of total dye.
Alkali M is in particular lithium, sodium or potassium. M is preferably hydrogen or
sodium.
k is preferably 2 or 3.
R1 to R13 are each preferably hydngen and R6, R7, R12 and R13 are each
preferably sulfo as well.
If A is phenylene and X1 is -SO2Z, the bond leading to the SO2Z-group preferably
is in meta- or para-position of the nitrogen atom. In the general formula (1) the
carbonamido-group preferably is in para- or meta-position of the diazo-group. If A
is naphthylene, the bond leading to the nitrogen atom preferably is in -position of
the naphthylene-group. If D1 or D2 have one of the meanings of the general
formula (6), the diazo-group preferably is in -position of the naphthyl-group. If D1
or D2 have one of the meanings of the general formula (5) and X2 is -SO2Z, the
bond leading to the SO2Z-group preferably is in meta- or para-position of the
diazo-group.
Examples of substrtuents A are in particular 1,2-phenylene, 1,3-phenylene,
1,4-phenylene, 2-chloro-1,4-phenylene, 2-chloro-1,5-phenylene, 2-bromo-
1,4-phenylene, 2-sulfo-1,4-phenyle ie, 2-sulfo-1,5-phenylene, 2-methoxy-
1,5-phenylene, 2-ethoxy-1,5-phenyiene, 2,5-dimethoxy-1,4-phenylene,
2-methoxy-5-methyl-1,4-phenylene, 2-methyl-1,4-phenylene, 2,6-naphthylene,
2,8-naphthylene, 1-sulfo-2,6-naphtfylene, 6-sulfo-2,8-naphthylene or 1,2-ethylene
and 1,3-propylene.
A is particularly preferably 1,3-phenylene, 1,4-phenylene, 2-sulfo-1,4-phenylene,
2-methoxy-1,5-phenylene, 2,5-dimethoxy-1,4-phenylene, 2-methoxy-5-methyl-
1,4-phenylene or 1,2-ethylene and 1,3-propylene, and in the case of the two last-
mentioned alkylene groups R is preferably phenyl or 2-sulfophenyl.

In general formula (7) R22 to R24 are each preferably hydrogen and R22, R23 are
each preferably sulfo as well.
In general formula (8) R25 to R27 are each preferably methyl or ethyl.
Anion B' preferably is sulfate or chloride.
In general formulae (12) and (13) R2' to R4'are preferably hydrogen or methyl, R2'
is preferably phenyl as well and R3, R4' are each preferably 2-sulfoethyl, 2-, 3- or
4-sulfophenyl, 3- or 4-trimethylammoniumphenyl-sulfate, 3- or 4-
trimethylammoniumphenyl-chloride as well, or R3' and R4' form a cyclic ring
system which is preferably of the formula -(CH2)2-O-(CH2)2-.
W is preferably 1,3-phenylene, 1,4-phenylene, 2-sulfo-1,4-phenylene, 2-methoxy-
1,5-phenylene, 2,5-dimethoxy-1 4-phenylene, 2-methoxy-5-methyl-1,4-phenylene,
1,2-ethylene, 1,3-propylene.
Q1 , Q2 are independently of ono another preferably chlorine, fluorine, cyanamido,
carbamoylpyridino, carboxypyridino, or a group of the general formula (12) or (13)
with the preferred R2' to R4', W and Z as described above.
Examples of the groups Z21 and Z22 are 2,4-dichloro-1,3,5-triazin-6-yl, 2-chloro-4-
hydroxy-1,3,5-triazin-6-yl, 2-chloro-4-methoxy-1,3,5-triazin-6-y), 2-chloro-4-
phenoxy-1,3,5-triazin-6-yl, 2-chloro-4-(4-sulfophenoxy)-1,3,5-triazin-6-yl, 2-chloro-
4-methylmercapto-1,3,5-triazin-6-yl, 4-amino-2-chloro-1,3,5-triazin-6--yl, 2-chloro-
4-methylamino-1,3,5-triazin-e-yl, 2-chloro-4-morpholino-1,3,5-triazin-6-yl, 2-
chloro-4-phenyiamino-1,3,5-1riazin-6-yl, 2-chloro-4-methylphe'nylamino-1,3,5-
triazin-6-yl, 2-chloro-4-(2-sul1ophenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(3-
sulfophenylamino)-1,3,5-tria;an-6-yl, 2-chloro-4-(4-sulfophenylamino)-1,3,5-triazin-
6-yl, 2-chloro-4-(2,5-disulfophenylamino)-1,3,5-trtazin-6-yl, 2-chloro-4-(3-
trimethylammoniumphenyla nino)-1,3,5-triazin-6-yl, 2-chloro-4-(4-
trimethy1ammoniumphenylamino)-1:2,5-triazin-6-yl, 2-chloro-4-cyanamido-1,3,5-
triazin-6-yl, 2-chloro-4-(2-sulfoethylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(N-methyl-
2-sulfoethylamino)-1,3,5-tri azin-6-yl, 2-chloro-4-(3-carboxypyridino)-1,3,5-triazin-6-
yl, 2-chloro-4-(4-carboxypyidino)-1,3,5-triazin-6-yl, 2-chloro-4-(3-
carbamoylpyridino)-1,3,5-triazin-6-yl, 2-chloro-4-(4-carbamoylpyridino)-1,3,5-
triazin-e-yl, 2-chloro-4-(2-(2-sulfatoethylsulfonyl)-phenylamino;-1,3,5-triazin-6-yl,

triazin-6-yl, 2,4-difluoro-pyrimidin-6 yl, 4,6-difluoro-pyrimidin-2-yl, 5-chloro-2,4-
difluoro-pyrimidin-6-yl, 5-chloro-4,6-difluoro-pyrimidin-2-yl, 2,3-dichlorochinoxalin-
6-carbonyl, and Z21 preferably acelyl as well.
n is preferably 0
In general formula (II) the bond leading to the nitrogen atom preferably is in 
position of the naphthalene. If D21 has one of the meanings of the general formula
(6), the diazo-group preferably is in -position of the naphthyl-group. If D21 has
one of the meanings of the general formula (5) and X2 is -SO2Z, the bond leading
to the SO2Z-group preferably is ir meta- or para-position of the diazo-group. If D21
has one of the meanings of the general formula (8), the quaternary-salt preferably
is in meta- or para-position of the diazo-group.
Preferred dye mixtures comprise one or more compounds of the general formula
(la)

In the general formulae (la) and (lla) M, A, R1, Z, D21 and Z21 are each as defined
above.
Particularly preferably, A is phonylene and Z is vinyl or -sulfatoethyl in the
general formula (la)

Most preferably, A is phenylene, R1 is hydrogen and Z is vinyl or -sulfatoethyl in
the general formula (la).
In general, the azo dyestuffs of the formula (I) are contained in the mixture in
quantity of 95 to 30% by weight and the azo dyestuffs of the formula (II) are
contained in the mixture in a mixing ratio of 10 to 70% by weight, preferably in a
mixing ration of 90% :10% by weight to 40%:60% by weight.
The dye mixtures according to the 3 present invention may also comprise one or more
red monoazo dye of the general formulae (14) or (15) in up to 10 % by weight

where M and D2 are each as destined above. Particularly preferably D2 is 4-(2-
sulfatoethylsulfonyl)-phenyl or 4-vinylsulfonyl-phenyl. The dyes of the formulae (14)
and (15) can be synthesised by the standard methology, or are partly formed during
the synthesis of compound (I). They are generally added as shading components.
Dyestuffs of formula (I) are known from EP-A-1046677 and dyestuffs of formula
(II) are well known from KR 84-2785, EP-A-08311, DE-A-3915305, US
5,349,057, WO 9963005-A1, EP-B-0557841, EP-B-0808343 , US 823,926, DE-A-
1 265 698, DE-A-19 43 904, F R 2 019 394.CA-A-519 978.
The dye mixtures of the invention can be prepared in solid or in liquid (dissolved)
form. In solid form they generally contain the electrolyte salts customary in the
case of water-soluble and in particular fiber-reactive dyes, such as sodium
chloride, potassium chloride .and sodium sulfate, and also assistants customary in
commercial dyes, such as biffer substances capable of establishing a pH in
aqueous solution between 3 and 7, such as sodium acetate, sodium borate,

sodium bicarbonate, sodium citrato, sodium dihydrogenphosphate and
disodiumhydrogenphosphate, smell amounts of siccatives or if, they are present
in liquid, aqueous solution (including the presence of thickeners of the type
customary in print pastes), substances which ensure the permanence of these
preparations, for example mold preventatives.
In general, the dye mixtures will take the form of dye powders containing from 10
to 80 % by weight, based on the dye powder or preparation, of a strength-
standardizing colorless diluent electrolyte salt. These dye powders may in
addition contain the abovementioned buffer substances in a total amount of up to
10%, 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 about
50 % by weight, for example between 5 and 50 % by weight, the electrolyte salt
content of these aqueous solutions preferably being below 10 % by weight, based
on the aqueous solution; the acueous solutions (liquid preparations) can in
general contain the abovement oned buffer substances in an amount of up to 5 %
by weight, preferably up to 2 % by weight.
The dye mixtures of this invention can be obtained in a conventional manner, for
instance by mechanically mixing the individual dyes in solid form or in form of
aqueous solutions in the requied proportions, or by synthesis by means of the
customary diazotization and coupling reactions using appropriate mixtures of a
diazo and the coupling components in a manner familiar to those skilled in the art
and the necessary proportion;;.
Thus, if the diazo components with the groups D1 and D21 according to the
general formulae (I) and (II) a-e the same (D1 = D21), one option is for example to
prepare aqueous suspensions of a mixture of a red monoazo dye according to the
general formula (14) with the meanings of M and D2 described above, and an
optionally N-substituted 2-Arr ino-7-surfo-5-naphthol or 2-Amino-6-sulfo-8-
naphthol as coupling comporents, then coupling in a one-pot reaction with a
diazotised aniline or naphthy amine compound of the formula D1 - NH2, with the
meanings of D1 described above, at a pH between 4 and 8 forming a mixture of
disazo dyes conforming to the formula (I) and monoazo dyes conforming to the
formula (II)

The final dyestuff can be isolated from the solution in the conventional manner, for
example by salting out with an electrolyte salt, such as sodium chloride or potassium
chloride, or by spray-drying.
The red monoazo-dyes of general formulae (14) can be prepared by diazotizing an
amino compound D2 - NH2, with the meanings of D2 described above, in a
conventional manner in a strongl/ acid medium and then carrying out the first
coupling reaction of 1-amino-8-naphthol-3,6-disulfonic acid or 1-amino-8-naphthol-
4,6-disulfonic acid with the diazo component at a pH below 2.
Dye mixtures in which the dye chromophores contain for example not only a
-chloroethylsulfonyl or -thiosulfatoethylsulfonyl or (l-suifatoethylsulfonyl group but
also proportions with vinylsulfonyl groups cannot only be prepared by the above
mentioned method using approoriate vinylsulfonyl starting anilines or
naphthylamines, but also by reacting the dye mixture in which Z is a -chloroethyl, -
thiosulfatoethyl, or -sulfatoeth/l group with an amount of alkali required for only part
of these groups and converting partly said -substituted ethylsulfonyl groups into
vinylsulfonyl groups. This procedure is carried out by generally known methods of
converting -substituted ethylsulfonyl groups into the vinylsulfonyl group.
The solution of the dye mixtures according to the invention obtained during
synthesis of their individual azo dyes can also be used for dyeing directly as a
liquid preparation, if appropria:e after addition of a buffer substance and if
appropriate also after concentration or dilution.
The reactive dye mixtures according to the invention have fiber-reactive
properties and possess very good dye properties. They can therefore be used for
dyeing hydroxyl- and/or carbcxamido-containing material, especially fiber
material, paper and also leather.
The present invention therefc re also provides for the use of the inventive dye
mixtures for dyeing or printing hydroxyl- and/or carboxamido-containing materials,
or methods for their application on these substrates. This includes mass
coloration, for example films composed of polyamide. and printing. The materials

are preferably employed in the form of fiber materials, especially in the form of
textile fibers, such as woven fabrics or yams;, as in the form of hanks or wound
packages.
Hydroxyl-containing materials are those of natural or synthetic origin, for example
cellulose fiber materials or their regenerated products and polyvinyl alcohols.
Cellulose fiber materials are preferably cotton, but also other vegetable fibers,
such as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are for
example staple viscose and filament viscose.
Carboxamido-containing materia s are for example synthetic and natural
polyamides and polyurethanes, especially in the form of fibers, for example wool
and other animal hairs, silk, leather, nyIon-6,6, nylon-6, nylon-11 and nylon-4.
The inventive reactive dye mixtures can be applied to and fixed on the substrates
mentioned, especially the fiber materials mentioned, by the application techniques
known for water-soluble dyes, especially fiber-reactive dyes.
For instance, on cellulose fibem they produce by the exhaust method from a long
liquor using various acid-binding agents and optionally neutral salts, such as
sodium chloride or sodium sulfate, dyeings having very good color yields and
excellent color build-up combined with high fixation yields. Dyeing is earned out in
an aqueous bath at temperatures between 40 and 105°C, optionally at
temperatures of up to 120°C under superatmospheric pressure, and optionally in
the presence of customary dye.-ing auxiliaries. One possible procedure is to
introduce the material into the warm bath and to gradually heat the bath to the
desired dyeing temperature and to complete the dyeing process at that
temperature. The neutral salts which accelerate the exhaustion of the inventive
reactive dye mixtures may also, if desired, only be added to the bath after the
actual dyeing temperature has been reached.
However, the inventive reactive dye mixtures are also very useful for saltless or
low-salt dyeing and can thus he dyed for example without any salt at low depth of
shade, with very little salt such as not more than 5 g/l electrolyte salt at medium

depth of shade and with not more than 10 g/l electrolyte salt at higher depths of
shade, and in all cases strong dyeings are obtained.
Low depths of shade for the purposes of this invention are depths of shade
involving not more than 2 percent by weight of dye being used, based on the
substrate. Medium depths of shaoe are to be understood as meaning more than 2
to not more than 4 percent by weight of dye and higher depths of shade are to be
understood as meaning more than 4 to not more than 10 percent by weight of
dye, based on the substrate.
This provides for partly distinct reductions not only of the effluent loading of
dyehouse wastewaters but also of the associated costs.
The padding process likewise provides excellent color yields coupled with high
fixation yields and very good color build-up on cellulose fibers, the dye mixture
being allowed to become fixed an the material by batching at room temperature or
at elevated temperature, for example at up to approximately 60°C, by steaming or
using dry heat in a conventional manner.
Similarly, the customary printirg processes for cellulose fibers, which can be
carried out either single-phase, for example by printing with a print paste
comprising sodium carbonate or some other acid-binding agent and a reactive
dye-mixture of the invention and by subsequent steaming at 100 to 103°C, or two-
phase, for example by printing with print paste comprising a neutral or weakly
acidic print colour and subsecuent fixation either by passing the printed material
through a hot electrolyte-comorising alkaline bath or by overpadding with an
alkaline electrolyte-comprising padding liquor with subsequent batching of the
alkali-overpadded material or subsequent steaming or subsequent treatment with
dry heat, produce strong prints with well-defined contours and a clear white
ground. The outcome of the prints is not greatly affected by variations in the fixing
conditions.
The fixation yields obtained with the inventive reactive dye mixtures are very high
not only in dyeing but also in printing.

When fixing by means of dry heat n accordance with the customary thermofix
processes, hot air from 120 to 200°C is used. In addition to the customary steam
at 101 to 103°C it is also possible to use superheated steam and high-pressure
steam at temperatures of up to 160°C.
The acid-binding agents which effect the fixation of the inventive reactive dye
mixtures on the cellulose fibers include for example water-soluble basic salts of
the alkali metals and the alkaline earth metals of inorganic or organic acids and
likewise compounds which liberate alkali in the heat. Especially suitable are the
alkali metal hydroxides and alkali metal salts of weak to medium inorganic or
organic 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 dihydrogenphosphate, disodium
hydrogenphosphate, sodium trichloroacetate, waterglass or trisodium phosphate.
Treating the inventive dye mixtures with the acid-binding agents with or without
heating, binds the dyes chemically to the cellulose fiber. Cellulose dyeings in
particular, following the custorr ary aftertreatment by rinsing to remove unfixed dye
portions exhibit very good wet fastnesses, in particular since such unfixed dye
portions are easily washed off on account of their good solubility in cold water.
Dyeings on polyurethane and polyamide fibers are customarily carried out from an
acidic medium. For instance, the dyebath may include acetic acid and/or
ammonium sulfate and/or acetic acid and ammonium acetate or sodium acetate
in order to obtain the desired oH. To achieve useful levelness for the dyeing, it is
advisable to add customary leveling aids, for example based on a reaction
product of cyanuric chloride with three times the molar amount of an
aminobenzenesulfonic acid aid/or an aminonaphthaienesulfonic acid or based on
a reaction product of for example stearylamine vvith ethylene oxide. Generally the
material to be dyed is introduced into the bath at a temperature of about 40°C,
agitated therein for some tirm, and the dyebath is then adjusted to the desired
weakly acidic pH. preferably with acetic acid, and the actual dyeing is carried out

at a temperature between 60 and 98°C. However, the dyeings can also be carried
out at boiling point or at temperatures of up to 120°C (under pressure).
The dyeings and prints on cellulose fiber materials in particular, as already
mentioned, have high color strength, good light- and wet fastnesses and also
good hot press and crock fastnessses. Particularly noteworthy are the high yields
of fixation obtainable on celluloso fiber materials, which can be above 90%, and
also the very good color build-up, including the exhaust method using reduced
neutral salt quantities or dispensing with salt altogether, depending on the depth
of shade, i.e., depending on the amount of dye used. A further advantage of the
inventive reactive dye mixtures is the ease with which portions unfixed in the
printing or dyeing process are washed off, as a result of which the wash of the
printed or dyed cellulose fiber materials can be accomplished with smaller
amounts of wash liquor and, as the case may be, energy-saying temperature
control during the wash.
The examples hereinbelow serve to illustrate the invention. Parts and
percentages are by weight, uniess otherwise stated. Parts by weight relate to
parts by volume as the kilogram relates to the liter. The compounds described in
the examples in terms of a formula are indicated in the form of the sodium salts
as in general they are prepared and isolated in the form of their alkali metal salts,
such as lithium, sodium or potassium salts, and used for dyeing in the form of this
salts. The starting compounds, and components mentioned in the form of the free
acid in the examples hereinbelow may be used in the synthesis as such or
similarly in the form of their saits, preferably alkali metal salts.

Example 1
85 parts of an electrolyte-containing dye powder which contains the navy-dyeing
disazo dye of the formula (lA)

in a proportion of 70% are mechanically mixed with 15 parts of an electrolyte-
containing dye powder which contains the orange-dyeing monoazo dye of the
formula (HA) in a 75% proportion

The resulting dye mixture according to the invention, when employed according to
the application and fixing methods customary in the art for fiber-reactive dyes,
produces for example on cellulose fiber materials dyeings and prints in deep black
shades.
Example 2
80 parts of an electrolyte-containing dye powder which contains the navy-dyeing
disazo dye of the formula (1A in a proportion of 75% and 20 parts of an electrolyte-
containing dye powder which contains the orange-dyeing monoazo dye of the
formula (HA) in a 60% proportion are dissolved in 700 parts of water and the resulting
dye solution is adjusted to pH 5.5 - 6.5. Evaporating this solution affords a dye
mixture which produces deep black shades on cellulosic materials when employed

according to the application and fixing methods customary in the art for fiber-reactive
dyes.
Example 3
a) A suspension of 281 parts of 4-(fi-sulfatoethylsulfonyl)-aniline in 650 parts of ice-
water and 180 parts of 30 % aqueous hydrochloric acid is diazotized with 173 parts
of 40% strength aqueous sodiurr, nitrite solution. 319 parts of 1-amino-8-napthol-3,6-
disulfonic acid are added and the first coupling forming a red monoazo dye according
to the general formula (14) is carried out at a pH between 1 and 1.3 and at a
temperature below 20°C. Durinc the reaction the pH is maintained with about 140
parts of sodium bicarbonate.
b) In a separate vessel to a suspension of 500 parts of 4-amino-N-(3-(-
sulfatoethylsulfonyl)-phenyl)-benzamide in 2750 parts of ice-water, adjusted to pH
6.5-7 with about 90 parts of sodium carbonate, are added 217 parts of 40% strength
aqueous sodium nitrite solution. This suspension is pumped into a slurry of 780 parts
of ice, 630 parts ice-water and 450 parts concentrated hydrochloric acid. After stirring
for 2 hours at 5-10°C excess r itrite is destroyed using sulfamic acid and the resulting
diazo suspension is pumped into solution (a). Immediately afterwards 70 parts of 6-
acetylamino-1-hydroxynaphth alene-3-sulfonic acid are added to the reaction mixture.
The pH is raised to 5-6 by addition of sodium carbonate at a temperature below 25°C
and after the coupling is complete the 85:15 mixture of the dyes (IB)jand (IIB) is
isolated by spray-drying.
Alternatively the obtained dye solution can be buffered at pH 5.5 - 6 by adding a
sodium phosphate buffer. By further diluting with water or by evaporating the
solution, this liquid dye mixture can then be standardized to the desired strength for a
liquid preparation.
The dye mixture affords deep black shades on cellulosic materials.

Examples 4 to 634
The table examples which follow describe further dye mixtures according to the
invention of the dyes conforming to the formulae (I) and (II) as the sodium salts and
the mixing ratios of the dyes by percent by weight. When employed according to the
application and fixing methods customary in the art for fiber-reactive dyes, these dye
mixtures produce, for example, on cellulose fiber materials, navy to deep black
dyeings.

Examples 97- 191
Examples 1, 2 and 4-96 were repeated using dye (IB) instead of dye (IA).
Examples 192-286
Examples 1, 2 and 4-96 were repeated using dye (IC) instead of dye (IA):

Examples 287 - 381
Examples 1, 2 and 4 - 96 were repealed using dye (ID) instead of dye (IA):

Examples 382 - 476
Examples 1, 2 and 4 - 96 were repeated using dye (IE) instead of dye (IA):

Dye mixtures prepared according to examples 1, 2 or 3

Examples 539 - 570
Examples 507 - 538 were repeated ising dye (IG) instead of dye (IF):

Examples 571 - 602
Examples 507 - 538 were repeated using dye (IH; Instead of dye (IF):

Examples 603 - 634
Examples 507-538 were repeated using dye (IJ) instead of dye (IF):

Dyeing example 1
2 parts of a dyestuff mixture according to example 1, 2 or 3 are dissolved in 999
parts of water and 5 parts of sodium carbonate, 0,7 parts of sodium hydroxide (as a
32,5% solution in water) and 1 part of a wetting agent, if necessary, are added. 100g
of a cotton fabric are brought into the dye bath. The temperature of the dye bath is
held at 25°C for 10 minutes, then raised to 40 - 60°C within 30 minutes and dyeing
is continued for another 60 - 90 minutes at this temperature. Afterwards the dyed
fabric is first rinsed with water for 2 minutes and then rinsed with desalted water for 5
minutes. Afterwardes the fabric is neutralized for 10 minutes at 40°C in 1000 parts of
an aqueous solution containing 1 part of 50% acetic acid. The cotton fabric is rinsed
with desalted water at 70°C and soaped at the boiling point for 15 minutes, again
rinsed and air-dried or ironed, resulting a deep navy to grey dyeing with very good
fastness properties.

Dyeing example 2
4 parts of a dyestuff mixture according to example 1, 2 or 3 are dissolved in 999
parts of water and 5 parts of sodium chloride, 7 parts of sodium carbonate, 0,7 parts
of sodium hydroxide (as a 32,5% solution in water) and 1 part of a wetting agent, if
necessary, are added. 100g of a cctton fabric are brought into the dye bath. The
dyeing and aftertreatment process is carried out as described in dyeing example 1,
resulting a deep navy to black dyeing with very good fastness properties.
Dyeing example 3
8 parts of a dyestuff mixture according to example 1, 2 or 3 are dissolved in 997
parts of water and 10 parts of sodium chloride, 10 parts of sodium carbonate, 1,3
parts of sodium hydroxide (as a 32,5% solution in water) and 1 part of a wetting
agent, if necessary, are added. 100c of a cotton fabric are brought into the dye bath.
The dyeing and aftertreatment process is carried out as described in dyeing example
1, resulting a deep black dyeing with very good fastness properties.

WE CLAIM:
1. Dye mixtures comprising one or more reactive dyes of the general formufa (I)

and one or more reactive dyes of the general formula (II),

where
D1 and D2 each represent a group of the general formula (1)
where
R1 is hydrogen, (C1-C4)-alkyl, aryl or phenyl substituted by one, two or
three independent groups selected from the group consisting of (C1-C4)-
alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, amido and halogen;
R2 and R3 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy,
hydroxyl, sulfo, carboxy, amido or halogen; and
A is a phenylene group of the general formula (2)

where
R4 and R5 ae independently hydrogen, (C1-C4)-alkyl, (C1-C4)-
alkoxy, hydroxy), sulfo, carboxyl, amido or halogen; or
a naphthylene group of the general formula (3)

where
R6 and R7 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-
alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or
a polymethylene group of the genera! formula (4)

where
k is an integer greater than 1 and
R8 and R9 are ndependently hydrogen, (C1-C4)-alkyl, (C1-C4)-
alkoxy, hydroxyl, cyano, amido, halogen or aryl; and
X1 is hydrogen or -SO2-2;
or represent a phenyl group of the general formula (5)

where
R10 and R11 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy,
hydroxyl, sulfo, carboxyl, amido, or halogen; and
X2 has one of the meanings of X1;
or represent a naphthyl group of the general formula (6)

where
R12and R13 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy,
hydroxyl, sulfo carboxyl, amido, ureido or halogen;
X3 has one of the meanings of X1;
Z is -CH=CH2, -CH2CH2Z1 or hydroxyl,
where
Z1 is hydroxyl or an alkali-detachable group;
M is hydrogen or an alkali metal;
D21 has one of the meanings of D1 or D2 or is a group of formula (7) or (8)

where
R22 and R23 have independently of one another one of the meanings of R2
and R3;
R24 is hydrogen, (C1- C4)-alkyl, phenyl which is unsubstituted or
substituted by (C1-C4)- alkyl, (C1-C4)-alkoxy, sulfo, halogen, carboxy;
and
Z22 is a group of the general formula (9) or (10) or formula (11)

wherein
V is fluorine or chlorine;
U1, U2 are independently of one another fluorine, chlorine or
hydrogen; and
Q1, Q2 are independently of one another chlorine, fluorine,
cyanamido, hydroxy, (C1-C6)-alkoxy,
phenoxy, sulfcphenoxy, mercapto, (C1-C6)-alkylmercapto,
pyridine carboxypyridino, carbamoylpyridino, or a group of
the general formula (12) or (13)

where
R2' is hydrogen, (C1-C6)-alkyl, sulfo-(C1-C6)-alkyl, phenyl
which is unsubstituted or substituted by (C1-C4)- alkyl,
(C1-C4)-alkoxy, sulfo, halogen, carboxy, acetamido,
ureido;
R3' and R4' have independently of one another one of the
meanings of R2', or form a cyclic ring system, such as
-(CH2)j- with j being 4 or 5, or alternatively -(CH2)2-E-
(CH2)2- with E beir.g oxygen, sulfur, sulfo, -NR5'- with
R5' being (C1-C6)-alkyl;
W is phenylene which is unsubstituted or substituted by
1 or 2 substituents such as (C1-C4)-alkyl, (C1-C4)-alkoxy,
carboxy, sulfo, chlorine, bromine, or is (C1-C4)-alkylene-
arylene or (C2-C6)-alkylene, which can be interrupted by

oxygen, sulfur, sulfono, amino, carbonyl, carbonamido, or
is phenylene-CONH-phenylene which is unsubstituted or
substituted by (C1-C4)-alkyl, (C1-C4-alkoxy, hydroxyl,
sulfo, carboxyl, amido, ureido or halogen, or naphthylene
which is unsubstituted or substituted by one or two sulfo
groups and
Z is as defined above;
R25, R26 and R27 are (C1-C4)-alkyl or (C1-C4)-hydroxyalkyl;
B" is an equivalent for an anion such as hydrogensulfate, sulfate,
fluoride, chloride, bromide, dihydrogenphosphate,
hydrogenphosphate, phosphate, hydroxide, acetate;
R21 has one of the meanings o R24;
Z21 is hydrogen, (C2-C6)-acyl, aroyl which is unsubstituted or substituted by
(C1-C4)-alkyl, (C1-C4)-alkoxv, sulfo, carboxyl or halogen, or has one of the
meanings of Z22; and
n is 0 or 1;
wherein in the general formula (I) al least one of D1 and D2 is a group of the
general formula (1);
wherein, if A is a group of the general formula (4), R1 is aryl or phenyl substituted
by one, two or three independent groups selected from the group consisting of
(C1-C4)-alkyl, (C1-C4)-alkoxy, hydrox/l, sulfo, carboxyl, amido and halogen; and
where the reactive dye of the geneml formula (I) contains at least one -S02-Z
group.
2. Reactive dye mixtures according to claim 1 with the substituents R1 to R5, R8 to
R11, R21 and R24 being hydrogen, R6 R7. R12, R13, R22 and R23 being hydrogen or
sulfo and R25, R26 and R27 being melhyl.
3. Reactive dye mixtures according to at least one of claims 1 to 2 wherein Z is vinyl,
-chloroethyl or -sulfatoethyl.

4. Reactive dye mixtures according to at least one of the claims 1 to 3 wherein n is 0
in general formula (II).
5. Reactive dye mixtures according to claim 4 which comprise one or more dyes
according to the general formula [la)

and one or more dyes of the general formula (lla)

wherein M, A, R1, Z, D21 and Z21 are as defined in claim 1.
6. Reactive dye mixtures according to claim 4 wherein R1 is hydrogen, A is
phenylene and Z is vinyl or -sulfatothyl in the general formula (la) and D21 and Z21
in general formula (lla) are as defined in claim 1.
7. Reactive dye mixtures according to at least one of claim 1 to 6 wherein D21 in
general formula (II) has one of the meanings of 3-(-sulfatoethylsulfonyl)-phenyl,
4-(ft-sulfatoethylsulfonyl)-phenyl, 2-slfo-4-(-sulfatoethylsulfonyl)-phenyl,
2-methoxy-5-(-sulfatoethylsulfonyl)-phenyl, 2,5-dimethoxy-
4-(-sulfatoethylsulfonyl)-phenyl, 2-methoxy-5-methyl-4-(-sulfatoethylsulfonyl)-
phenyl, 6-(-sulfatoethylsulfonyl)-1-sulfo-naphth-2-yl, 3- or 4-vinylsulfonyl-phenyl,
4-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl, 4-(4-(2-
sulfatoethylsulfonyl)-phenylcarbamoyl)-phenyl, 3-(3-(2-sulfatoethylsulfonyl)-
phenylcarbamoyl)-phenyl, 3-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-
phenyl,1-sulfo-4-(2,4-difluoro-pyrimiclin-6-yl)-amino-2-phenyl or 1-sulfo-4-(4,6-

difluoro-pyrimidin-2-yl)-amino-2-phenyl, 2-sulfophenyl, 4-methyl-2-sulfophenyl or
1,5-disulfonaphth-2-yl.
8. Reactive dye mixtures according to at least one of claim 1 to 7 wherein Z21 in
general formula (II) has one of the meanings of 2,4-dichloro-1,3,5-triazin-6-yl, 2-
chloro-4-morpholino-1,3,5-triazi i-6-yl, 2-chloro-4-(3-sulfophenylamino)-1,3,5-
triazin-6-yl, 2-chloro-4-(4-sulfophenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-
cyanamido-1,3,5-triazin-6-yl, 2-chloro-4-(3-(2-sulfatoethylsulfonyl)-phenylamino)-
1,3,5-triazin-6-yl, 2-chloro-4-(4-(2-sulfatoethylsulfonyl)-phenylamino)-1,3,5-triazin-
6-yl, 2-chloro-4-(3-(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(4-
(vinylsulfonyl)-phenylamino)-1,3,5-triazin-6-yl, 2-chloro-4-(N-methyl-N-(2-(2-
sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-triazin-6-yl, 2-chloro-4-(N-phenyl-N-(2-(2-
sulfatoethylsulfonyl)-ethyl)-aminci)-1,3,5-triazin-6-yl, 2-fluoro-4-morpholino-1,3,5-
triazin-6-yl, 2-fluoro-4-(2-sulfophenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(3-
sulfophenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-(4-sulfophenylamino)-1,3,5-triazin-
6-yl, 2-fluoro-4-(3-trimethylammoniumphenylamino)-1,3,5-triazin-6-yl, 2-fluoro-4-
(4-trimethylammoniumphenylami io)-1,3,5-triazin-6-yl, 2-fluoro-4-(3-(2-
sulfatoethylsulfonyl)-phenylaminc )-1,3,5-triazin-6-yl, 2-fluoro-4-(4-(2-
sulfatoethylsulfonyl)-phenylaminc)-1,3,5-triazin-6-yl, 2-fluoro-4-(3-(vinylsulfonyl)-
phenylamino)-1,3,5-triazin-6-yl, 2fluoro-4-(4-(vinylsulfonyl)-phenylamino)-1,3,5-
triazin-6-yl, 2-fluoro-4-(N-methyl-M-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-
triazin-6-yl, 2-fluoro-4-(N-phenyl-M-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino)-1,3,5-
triazin-6-yl, 2,4-difluoro-pyrimidin-o-yl, 4,6-difluoro-pyrimidin-2-yl, 5-chloro-2,4-
difluoro-pyrimidin-6-yl, 5-chloro-4,3-difluoro-pyrimidin-2-yl, 2,3-dichlorochinoxalin-
6-carbonyl, and acetyl.
9. A dye mixture according to at least one of the claims 1 to 8 wherein a dye of
formula (I) is present in the mixture; in an amount of from 30 to 95% by weight; a dye
of the formula (II) is present in the mixture in an amount of from 5 to 70% by weight.
10. A dye mixture according to at least one of the claims 1 to 9 comprising a
monoazo dye of formula (14) in a total amount of 0.5 to 6.0% by weight and/or a
monoazo dye of formula (15) in a total amount of 0.5 to 6.0% by weight.

wherein D2 and M are as defined n claim 1.
11. A dye mixture according to onu or more of the claims 1 to 10 comprising at least
one dye of general formula (I) in uo to 95 % by weight.
12. A process for the preparation of the dye mixtures according to at least one of the
claims 1 to 11 comprising mechanically mixing the individual dyes of the formulae (I)
and (II) in solid form or in form of aqueous solutions in the required proportions.
13. A process for the preparation of the dye mixtures according to at least one of the
claims 1 to 11, under the proviso that D1 and D21 in the general formulae (I) and (II)
have the same meaning, by diazotizing an amine of the general formula (16)
D2-NH2 (16),
wherein D2 is as described in claim 1, in a conventional manner in a strongly acidic
medium and then carrying out the coupling reaction of the 1-amino-8-napthol-3,6-
disulfonic acid or 1-amino-8-naptho -4,6-disulfonic acid with the diazo component at
a pH below 2 to form the red compound (14) followed by diazotation of an amine of
the general formula (17)
D1-NH; (17),
wherein D1 is as described in claim I, in a conventional manner in a strongly acidic
medium and then carrying out the second coupling reaction with the monoazo dye
product (14) to form the disazo dye conforming to the formula (I) at a pH between 4
and 8 and followed by addition of an aqueous solution of the optionally N-substituted
2-Amino-7-sulfo-5-naphthol or 2-Amino-6-su!fo-8-naphthol to the coupling reaction to
form the dye conforming to the formula (II) which is carried out in the same pH-range
between 4 and 7.5 followed by isola ion of the dyestuff mixture from the solution in
the conventional manner.

14. A process for dyeing hydroxy- and/or carboxamido -containing fiber material, in
which dyes are applied to the material and the dyes are fixed to the material by
means of heat or with the aid of an alkali or by means of heat and with the aid of an
alkali, which comprises dye mixtures as claimed in one or more of the claims 1 to12.
Dated this 31st day of OCTOBER, 2003

Dye mixtures comprising one or more reactive dyes of the
general formula (I)
and one or more reactive dyes of the general formula (II),

Documents:

« Previous Patent

Next Patent »

Patent Number

230125

Indian Patent Application Number

1402/KOLNP/2003

PG Journal Number

09/2009

Publication Date

27-Feb-2009

Grant Date

25-Feb-2009

Date of Filing

31-Oct-2003

Name of Patentee

DYSTAR TEXTILFARBEN GMBH & CO. DEUTSHLAND KG.

Applicant Address

INDUSTRIEPARK HOECHST, GEBAUDE B 598, 65926 FRANKFURT

Inventors:

#	Inventor's Name	Inventor's Address
1	EICHHORN, JOACHIM	HORTENSIENRING 17, 65929 FRANKFURT AM MAIN
2	PEDEMONTE, RONALD	206 HORN TASSEL CT. WESLEY CHAPEL, NC 28079

PCT International Classification Number

C09B 67/22

PCT International Application Number

PCT/EP2002/05822

PCT International Filing date

2002-05-28

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/295,193	2001-06-01	U.S.A.