WO2002008339A2 - Black dye mixtures of fiber-reactive azo dyes, methods for their preparation and use thereof for dyeing hydroxy- and/or carboxamido-containing fiber material - Google Patents

Black dye mixtures of fiber-reactive azo dyes, methods for their preparation and use thereof for dyeing hydroxy- and/or carboxamido-containing fiber material Download PDF

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Publication number
WO2002008339A2
WO2002008339A2 PCT/EP2001/008462 EP0108462W WO0208339A2 WO 2002008339 A2 WO2002008339 A2 WO 2002008339A2 EP 0108462 W EP0108462 W EP 0108462W WO 0208339 A2 WO0208339 A2 WO 0208339A2
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Prior art keywords
dye
formula
meanings
mixture
group
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PCT/EP2001/008462
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French (fr)
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WO2002008339A3 (en
Inventor
Ronald Pedemonte
Joachim Steckelberg
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Dystar Textilfarben Gmbh & Co. Deutschland Kg
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Priority to JP2002514234A priority Critical patent/JP2004504469A/en
Priority to MXPA03000690A priority patent/MXPA03000690A/en
Priority to BR0112784-5A priority patent/BR0112784A/en
Priority to AU2001283953A priority patent/AU2001283953A1/en
Priority to EP01962866A priority patent/EP1305372A2/en
Priority to CA002417232A priority patent/CA2417232A1/en
Priority to KR10-2003-7001048A priority patent/KR20030022308A/en
Publication of WO2002008339A2 publication Critical patent/WO2002008339A2/en
Publication of WO2002008339A3 publication Critical patent/WO2002008339A3/en

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C09B67/0047—Mixtures of two or more reactive azo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C09B67/0051—Mixtures of two or more azo dyes mixture of two or more monoazo dyes
    • C09B67/0052—Mixtures of two or more reactive monoazo dyes

Definitions

  • the present invention relates to the field of fiber-reactive dyes.
  • Black-dyeing mixtures of fiber-reactive dyes are known from U.S. Patents Nos. 5,445,654 and 5,61 1 ,821 as well as from Korean Patent Application Publication No. 94-2560.
  • Deep black dye mixtures are known, for example, from Japanese Patent Application Publication Sho-58-1 60 362 which are based on a navy-blue disazo dye and an orange monoazo dye.
  • these dye mixtures have some deficiencies.
  • Y 1 is in each instance, independently of one another, vinyl or is ethyl which is substituted in the ⁇ -position by a substituent which can be eliminated by the action of an alkali, forming the vinyl group, such as chlorine, thiosulfato, sulfato, alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, phosphato, sulfobenzoyloxy and p-toluylsulfonyloxy, and is preferably vinyl, ⁇ -chloroethyl, ⁇ -thiosulfatoethyl or ⁇ -sulfatoethyl and is in particular preferably vinyl or ⁇ -sulfatoethyl; Y Y ⁇ 2 has one of the meanings of Y 1 ; ⁇ 3 has one of the meanings of Y 2 ;
  • M is hydrogen or an alkali metal, such as lithium, sodium and potassium;
  • X is fluorine or chlorine;
  • R 1 is hydrogen methyl, methoxy or a group of the formula SO 3 M, preferably hydrogen or methoxy and in particular hydrogen;
  • R 2 has one of the meanings of R 1 ;
  • Q is a group of the formula (a) or (b)
  • A is hydrogen, C, to C 6 alkyl such as methyl, ethyl, n-propyl , i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl or hexyl, preferably C-, to C 4 alkyl groups, in particular methyl and ethyl, which may be substituted by hydroxy, sulfo or sulfato or is phenyl which may be substituted by one or more halogens such as chloro, fluoro or bromo, by acetamido- or by sulfo and is preferably 4-chlorophenyl and in particular 3-metanilic or 2,5- dimetanilic acid;
  • A' is C, to C 6 alkyl such as methyl, ethyl, n-propyl , i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl or hexyl, preferably C, to C 4 alkyl groups, in particular methyl and ethyl, which may be substituted by hydroxy, sulfo or sulfato or is phenyl which may be substituted by one or more halogens such as chloro, fluoro or bromo, by acetamido- or by sulfo and is preferably 4-chlorophenyl and in particular 3-metanilic or 2,5- dimetanilic acid;
  • B has one of the meanings of A and is preferably hydrogen, methyl or ethyl
  • D has one of the meanings of A'; or the group of the formula (a) is a cyclic ringsystem such as morpholino, piperidino or piperazino, in particular morpholino, or prolino; (b) is a cyclic ringsystem such as N-methyl morpholinium or N-ethyl morpholinium, N-ethyl piperidinium, or is a bicyclic ringsystem such as N- 1 ,4-diaminobicyclo (2,2,2) octyl, or is pyridinium which may be substituted by carboxy, such as 3-carboxy-pyridinium or 4-carboxy-pyridinium, or by carboxamido, such as 3-carboxamidopyridinium, and is in particular 3- carboxy-pyridinium; n is 0 if Q is a group of the formula (a) and n is 1 if Q is a group of formula (a) and n is 1 if
  • W " is a halogenide or the equivalent of a divalent anionic group such as sulfate or carbonate and is preferably chloride or fluoride;
  • dye mixtures comprising an amount of from 50 to 95% by weight of the diazo dye of the general formula (1 ), from 1 to 30% by weight of the monoazo dye of the general formula (2) and from 1 to 20 % by weight of the dye of the general formula (3) based on the dye mixture.
  • dye mixtures comprising an amount of from 70 to 90 % by weight of the disazo dye of the general formula (1 ), from 5 to 28 % by weight of the monoazo dye of the general formula (2) and from 2 to 1 2 % by weight of the dye of the general formula (3) based on the dye mixture.
  • the dye mixtures according to the present invention may optionally also comprise one or more monoazo dyes of the general formulae (4), (5), (6), (7), (8) or (9) in 0.5 to 25 % by weight based on the dye mixture, preferably they comprise one monoazo dye of the formulae (4), or (5), or (6), or (7), or (8), or (9) in 0.5 to 25% by weight based on the dye mixture.
  • Z is a C,-C 4 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, or is a phenylgroup, which may be substituted by chlorine nitro or sulfo, preferably methyl and ethyl;
  • Y ⁇ Y 5 , Y 6 , Y 7 Y 8 and Y 9 have one of the meanings of Y 1 .
  • X has one of the meanings of X Q' is a group of the formula (a')
  • A has one of the meanings of A or is C, to C 4 alkoxyalkyl such as methoxymethyl, methoxyethyl, ethoxyethyl, which may be substituted by a group of the formula SO 2 Y 1 , or is phenyl which is substituted by sulfo or a group of the formula SO 2 Y 1 B T has one of the meanings of A, or (a') has one of the meanings of (a).
  • the dyes according to the general formula (1 ) are known from the U.S. Patent No. 2,657,205, from Japanese Patent Application Publication Sho-58-1 60 362 and also from U.S. Pat. No. 4,257,770 and the references cited therein.
  • Monoazo dyes of the formula (2) are described in the DE-A 1 9 1 1 427.
  • Dyes of the formula (3) wherein Q is a group of formula (a) are described US 5456727 EP -A141367, 395951 , 486176, 623655, 630946, 632107, 647683.
  • Dyes of the formula (3) wherein Q is a group of formula (b) can be obtained in a conventional manner, for instance by synthesis by means of customary diazotization and coupling reactions in a manner familiar to those skilled in the art using appropriate substituted phenylamine derivatives conforming to the general formula (3-2)
  • Y is a alkali eliminable group and R and R 2 are as defined above, and coupling components, such as diaminophenylsulfonic acid in the necessary proportions to give the diazo component of the general formula (3-3).
  • R 1 , R 2 and Y are as defined above.
  • A, B, D and n are as defined above to give a claimed dyestuff of the formula (3):
  • the resulting 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.
  • an electrolyte salt such as sodium chloride or potassium chloride
  • Dyes of the general formula (4) are described in EP-A 832 939 and dyes of the general formula (5) are described in EP-B 94 055.
  • the dyes of the formulae (6) through (9) are well known in the literature and can be synthesised by the standard methology. They are generally added as shading components.
  • sulfo are groups of the formula -SO 3 M
  • thiosulfato groups are groups of the formula -S-SO 3 M
  • phosphato groups are groups of the formula -OPO 3 M 2
  • carboxy groups are groups of the formula -COOM
  • sulfato groups are groups of the formula -OSO 3 M , in which M is defined as above.
  • Carboxyamido groups are groups of the formula -CONH2.
  • the dyes of the general formulae (1 ), (2), (3), (4), (5), (6), (7), (8), (9) in particular if those corresponding to the same general formula, have the same chromophore, can have, within the meaning of Y 1 to Y 9 , structurally different fiber-reactive groups -SO 2 -Y 1 to -SO 2 -Y 9 .
  • the dye mixture can contain dyes of the same chromophore conforming to the formula (1 ) and dyes of the same chromophore conforming to formula (2) and dyes of the same chromophore conforming to formula (3) and optionally likewise of the general formula (4) through (9) in which the fiber-reactive groups -S0 2 -Y to -SO 2 -Y 9 are partly vinylsulfonyl groups and partly groups in which Y 1 to Y 9 is a ⁇ -ethyl substituted group as defined above, such as ⁇ -chloroethylsulfonyl, ⁇ - thiosulfatoethylsulfonyl or, preferably, ⁇ -sulfatoethylsulfonyl groups.
  • the proportion of the respective vinylsulfonyl dye to the respective dye with Y being a ⁇ -ethyl substituted groups as defined above, such as a ⁇ -chloro- or ⁇ -thiosulfato- or ⁇ -sulfatoethyl-sulfonyl dye, will be up to about 30 mol-%, based on the respective dye chromophore.
  • the dye mixtures of the invention can be present as a preparation in solid or liquid (dissolved) form.
  • 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 the assistants customary in commercial dyes, such as buffer substances capable of establishing a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium citrate, sodium dihydrogenphosphate and disodium hydrogenphosphate, small 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.
  • buffer substances capable of establishing a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium citrate, sodium dihydrogenphosphate and disodium hydrogenphosphate, small amounts
  • the dye mixtures take the form of dye powders, they contain, as a rule, 10 to 80 % by weight, based on the dye powder or preparation, of a strength- standardizing colorless diluent electrolyte salt, such as those mentioned above.
  • These dye powders may in addition contain the abovementioned buffer substances in a total amount of up to 5 %, based on the dye powder.
  • the total dye content of these aqueous solutions is up to about 50 % by weight, the electrolyte salt content of these aqueous solutions preferably being below 10 % by weight, based on the aqueous solutions.
  • Liquid preparations can in general contain the abovementioned 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 instance by mechanically mixing the individual dyes in the required proportions or by synthesis by means of the customary diazotization and coupling reactions using appropriate mixtures of the diazo and coupling components in a manner familiar to those skilled in the art and the necessary proportions.
  • One option is for example to prepare aqueous suspensions of the coupling components 1 - amino-8-naphthol-3,6-disulfonic acid, a sulfonaphtylamine, and, as diazo components, aniline compounds of the formula (10).
  • the dye mixture can be produced by diazotizing 4-( ⁇ - sulfatoethylsulfonyDaniline in a conventional manner in a strongly acid medium and then carrying out the coupling reaction of the 1 -amino-8-napthol-3,6- disulfonic acid with the diazo component at a pH below 1 .5 to form the compound (4).
  • the second coupling reaction with the monoazo dyes (4) products to form the disazo dyes conforming to the formula (1 ) is carried out at a pH between 3 and 6.5.
  • the coupling reaction to form the dye conforming to the formula (2) is carried out at a pH between 3 and 6.5.
  • a dyestuff of the general formula (3) To the dye mixture thus obtained is added a dyestuff of the general formula (3).
  • the resulting dyestuff mixture 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.
  • Dye mixtures which contain the respective dye components in form of the vinylsulfonyl dye can be prepared by the above mentioned method using appropriate vinylsulfonyl starting anilines, or alternately by reacting the dye mixture in which Y 1 to Y 9 is a ⁇ -chloroethyl, ⁇ -thiosulfatoethyl, or ⁇ -sulfatoethyl radical with an appropriate amount of alkali by generally known methods.
  • the respective dye with Y 1 to Y 9 being a ⁇ -ethyl substituted group is reacted with the required amount of alkali to convert said ⁇ -substituted ethylsulfonyl groups into vinylsulfonyl groups in the required proportion.
  • the dye mixtures of the instant invention are well suitable for dyeing (which includes printing) hydroxy- and/or carboxamido-containing fiber materials by the application and fixing methods numerously described in the art for fiber-reactive dyes, in deep black shades with good color build-up and good wash-off in respect of unfixed dye portions. Moreover, the dyeings obtained surprisingly show very little or no staining on polyamide fibers.
  • the present invention therefore also provides for use of the inventive dye mixtures for dyeing (including printing) hydroxy- and/or carboxamido-containing fiber materials and processes for dyeing such materials using a dye mixture according to the invention by applying the dye mixture to the substrate in dissolved form and fixing the dyes on the fiber by the action of an alkali or by heating or both.
  • Hydroxy-containing materials are natural or synthetic hydroxy-containing materials, for example cellulose fiber materials, including in the form of paper, or their regenerated products and polyvinyl alcohols.
  • Cellulose fiber materials are preferably cotton but also other natural vegetable fibers, such as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are for example staple viscose and filament viscose.
  • Carboxamido-containing materials are for example synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-1 1 , and nylon-4.
  • inventive dye mixtures are by generally known processes for dyeing and printing fiber materials by the known application techniques for fiber- reactive dyes. Since the dyes 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 exhaust dyeing processes. Applied in this way for example to cellulose fibers from a long liquor ratio at temperatures between 40 and 105°C, optionally at temperatures up to 1 30°C, under superatmospheric pressure, and optionally in the presence of customary dyeing assistants with the use of acid-binding agents and optionally neutral salts, such as sodium chloride or sodium sulfate, they produce dyeings in very good color yields with excellent color build-up and consistent shade.
  • One possible procedure is to introduce the material into the warm bath, gradually heat the bath to the desired dyeing temperature, and complete the dyeing process at that temperature.
  • the neutral salts which speed up the exhaustion of the dyes can also if desired not be added to the bath until the actual dyeing temperature has been reached.
  • the conventional printing processes for cellulose fibers which can either be carried out in single-phase, for example by printing with a print paste containing sodium bicarbonate or some other acid-binding agent and the colorant, and subsequent steaming at from 100 to 1 03°C, or in two phases, for example by printing with a neutral or weakly acid print paste containing the colorant and subsequent fixation either by passing the printed material through a hot electrolyte-containing alkaline bath or by overpadding with an alkaline electrolyte-containing padding liquour and subsequent batching of this treated material or subsequent steaming or subsequent treatment with dry heat, produce strong prints with well defined contours and a clear white ground. Changing fixing conditions has only little effect on the outcome of the prints.
  • the hot air used in dry heat fixing by the customary thermofix processes has a temperature of from 1 20 to 200°C.
  • the customary steam at from 101 to 103°C, it is also possible to use superheated steam and high pressure steam at up to 1 60°C.
  • Acid-binding agents responsible for fixing the dyes to cellulose fibers are for example water-soluble basic salts of alkali metals and of alkaline earth metals of inorganic or organic acids, and compounds which release alkali when hot.
  • 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.
  • These acid-binding agents are for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate and disodium hydrogenphosphate.
  • the dyeings of polyurethane and polyamide fibers are customarily carried out from an acid medium.
  • the dyebath 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.
  • customary leveling assistants 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.
  • the material to be dyed is introduced into the bath at a temperature of about 40°C and agitated therein for some time, the dyebath is then adjusted to the desired weakly acid, preferably weakly acetic acid, pH, and the actual dyeing is carried out at temperature between 60 and 98°C.
  • the dyeings can also be carried out at the boil or at temperatures up to 120°C (under superatmospheric pressure).
  • a dye mixture according to the invention is prepared by diazotizing a suspension of 281 parts of 4-( ⁇ -sulfatoethylsulfonyl)aniline in 650 parts of ice-water and 1 80 parts of 30 % aqueous hydrochloric acid with 1 73 parts of 40 % strength aqueous sodium nitrite solution.
  • 1 20 parts of 1 -amino-8-napthol-3,6-disulfonic acid are added and the first coupling is carried out at a pH between 1 and 1 .3 and at a temperature below 20°C (the pH is maintained with about 50 parts of sodium bicarbonate).
  • 72 parts 1 -Aminonaphtaline-4-sulfonic acid are added to the mixture and the pH is raised to 6 with sodium carbonate at a temperature below 30°C.
  • the resulting dye mixture comprises the dyes of the formulae (A), (D) and (C) in a the ratio of about 70 % : 22 % : 8 %.
  • This dye solution can be adjusted to pH 4.5 by adding 5 parts of 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.

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Abstract

The present invention discloses a dye mixture comprising a disazo dye conforming to the formula (1), a monoazo dye conforming to the formula (2), and monazo dye conforming to the formula (3) in which (1), (2) and (3) are defined as given in claim 1, a method for its preparation and a process for dyeing hydroxy- and/or carboxamido containing fiber material in which an inventive dye mixture is applied to the material.

Description

DyStar Textilfarben GmbH & Co. Deutschland KG
Description
Black Dye Mixtures of Fiber-Reactive Azo Dyes, Methods for their Preparation and Use Thereof for Dyeing Hydroxy- and/or Carboxamido-containing Fiber Material
The present invention relates to the field of fiber-reactive dyes.
Black-dyeing mixtures of fiber-reactive dyes are known from U.S. Patents Nos. 5,445,654 and 5,61 1 ,821 as well as from Korean Patent Application Publication No. 94-2560. Deep black dye mixtures are known, for example, from Japanese Patent Application Publication Sho-58-1 60 362 which are based on a navy-blue disazo dye and an orange monoazo dye. However these dye mixtures have some deficiencies.
With the present invention, deep black-dyeing dye mixtures of improved properties have unexpectedly been found, comprising a disazo dye conforming to the general formula (1 ),
Figure imgf000002_0001
a monoazo dye conforming to the general formula (2),
Figure imgf000003_0001
and a dye of the general formula (3)
Figure imgf000003_0002
(3)
wherein
Y1 is in each instance, independently of one another, vinyl or is ethyl which is substituted in the β-position by a substituent which can be eliminated by the action of an alkali, forming the vinyl group, such as chlorine, thiosulfato, sulfato, alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, phosphato, sulfobenzoyloxy and p-toluylsulfonyloxy, and is preferably vinyl, β-chloroethyl, β-thiosulfatoethyl or β-sulfatoethyl and is in particular preferably vinyl or β-sulfatoethyl; Y Y^2 has one of the meanings of Y1; γ3 has one of the meanings of Y2;
M is hydrogen or an alkali metal, such as lithium, sodium and potassium; X is fluorine or chlorine; R1 is hydrogen methyl, methoxy or a group of the formula SO3M, preferably hydrogen or methoxy and in particular hydrogen; R2 has one of the meanings of R1 ; Q is a group of the formula (a) or (b)
Figure imgf000004_0001
(a) (b) wherein
A is hydrogen, C, to C6 alkyl such as methyl, ethyl, n-propyl , i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl or hexyl, preferably C-, to C4 alkyl groups, in particular methyl and ethyl, which may be substituted by hydroxy, sulfo or sulfato or is phenyl which may be substituted by one or more halogens such as chloro, fluoro or bromo, by acetamido- or by sulfo and is preferably 4-chlorophenyl and in particular 3-metanilic or 2,5- dimetanilic acid;
A' is C, to C6 alkyl such as methyl, ethyl, n-propyl , i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl or hexyl, preferably C, to C4 alkyl groups, in particular methyl and ethyl, which may be substituted by hydroxy, sulfo or sulfato or is phenyl which may be substituted by one or more halogens such as chloro, fluoro or bromo, by acetamido- or by sulfo and is preferably 4-chlorophenyl and in particular 3-metanilic or 2,5- dimetanilic acid;
B has one of the meanings of A and is preferably hydrogen, methyl or ethyl;
B' has one of the meanings of A'
D has one of the meanings of A'; or the group of the formula (a) is a cyclic ringsystem such as morpholino, piperidino or piperazino, in particular morpholino, or prolino; (b) is a cyclic ringsystem such as N-methyl morpholinium or N-ethyl morpholinium, N-ethyl piperidinium, or is a bicyclic ringsystem such as N- 1 ,4-diaminobicyclo (2,2,2) octyl, or is pyridinium which may be substituted by carboxy, such as 3-carboxy-pyridinium or 4-carboxy-pyridinium, or by carboxamido, such as 3-carboxamidopyridinium, and is in particular 3- carboxy-pyridinium; n is 0 if Q is a group of the formula (a) and n is 1 if Q is a group of formula
(b) ; W" is a halogenide or the equivalent of a divalent anionic group such as sulfate or carbonate and is preferably chloride or fluoride;
Preference is given to dye mixtures comprising an amount of from 50 to 95% by weight of the diazo dye of the general formula (1 ), from 1 to 30% by weight of the monoazo dye of the general formula (2) and from 1 to 20 % by weight of the dye of the general formula (3) based on the dye mixture.
Special preference is given to dye mixtures comprising an amount of from 70 to 90 % by weight of the disazo dye of the general formula (1 ), from 5 to 28 % by weight of the monoazo dye of the general formula (2) and from 2 to 1 2 % by weight of the dye of the general formula (3) based on the dye mixture.
The dye mixtures according to the present invention may optionally also comprise one or more monoazo dyes of the general formulae (4), (5), (6), (7), (8) or (9) in 0.5 to 25 % by weight based on the dye mixture, preferably they comprise one monoazo dye of the formulae (4), or (5), or (6), or (7), or (8), or (9) in 0.5 to 25% by weight based on the dye mixture.
Figure imgf000006_0001
(5)
Figure imgf000006_0002
(6)
Figure imgf000007_0001
Figure imgf000007_0002
wherein
Z is a C,-C4-alkyl, such as methyl, ethyl, n-propyl, i-propyl, or is a phenylgroup, which may be substituted by chlorine nitro or sulfo, preferably methyl and ethyl; Y\ Y5, Y6, Y7 Y8 and Y9 have one of the meanings of Y1. X, has one of the meanings of X Q' is a group of the formula (a')
Figure imgf000008_0001
(a') wherein A, has one of the meanings of A or is C, to C4 alkoxyalkyl such as methoxymethyl, methoxyethyl, ethoxyethyl, which may be substituted by a group of the formula SO2Y1, or is phenyl which is substituted by sulfo or a group of the formula SO2Y1 BT has one of the meanings of A, or (a') has one of the meanings of (a).
The dyes according to the general formula (1 ) are known from the U.S. Patent No. 2,657,205, from Japanese Patent Application Publication Sho-58-1 60 362 and also from U.S. Pat. No. 4,257,770 and the references cited therein. Monoazo dyes of the formula (2) are described in the DE-A 1 9 1 1 427. Dyes of the formula (3) wherein Q is a group of formula (a) are described US 5456727 EP -A141367, 395951 , 486176, 623655, 630946, 632107, 647683. Dyes of the formula (3) wherein Q is a group of formula (b) can be obtained in a conventional manner, for instance by synthesis by means of customary diazotization and coupling reactions in a manner familiar to those skilled in the art using appropriate substituted phenylamine derivatives conforming to the general formula (3-2)
Figure imgf000008_0002
wherein Y is a alkali eliminable group and R and R2 are as defined above, and coupling components, such as diaminophenylsulfonic acid in the necessary proportions to give the diazo component of the general formula (3-3).
Figure imgf000009_0001
wherein R1, R2 and Y are as defined above.
Reacting this intermediate at pH 9,5-1 ,5 with cyanuric halogenide gives the azo dye conforming to the formula (3-4):
Figure imgf000009_0002
wherein X is fluorine or chlorine, and by reaction with a compound of the general formula Q' at pH 2-9 eventually under heating wherein Q' is a group of the formula:
H .N. 1 B^ I ^A
D
B A
(b)'
(a)' or
in which
A, B, D and n are as defined above to give a claimed dyestuff of the formula (3):
Figure imgf000010_0001
with X, Y, W, n, Q', R1 and R2 as defined above
The resulting 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.
Dyes of the general formula (4) are described in EP-A 832 939 and dyes of the general formula (5) are described in EP-B 94 055.
The dyes of the formulae (6) through (9) are well known in the literature and can be synthesised by the standard methology. They are generally added as shading components.
The groups "sulfo", "thiosulfato", "phosphato," „carboxy" and "sulfato" include both the acid form and the salt form of these groups. Accordingly, sulfo groups are groups of the formula -SO3M , thiosulfato groups are groups of the formula -S-SO3M , phosphato groups are groups of the formula -OPO3M2 , carboxy groups are groups of the formula -COOM and sulfato groups are groups of the formula -OSO3M , in which M is defined as above. Carboxyamido groups are groups of the formula -CONH2.
The dyes of the general formulae (1 ), (2), (3), (4), (5), (6), (7), (8), (9) in particular if those corresponding to the same general formula, have the same chromophore, can have, within the meaning of Y1 to Y9, structurally different fiber-reactive groups -SO2-Y1 to -SO2-Y9. In particular, the dye mixture can contain dyes of the same chromophore conforming to the formula (1 ) and dyes of the same chromophore conforming to formula (2) and dyes of the same chromophore conforming to formula (3) and optionally likewise of the general formula (4) through (9) in which the fiber-reactive groups -S02-Y to -SO2-Y9 are partly vinylsulfonyl groups and partly groups in which Y1 to Y9 is a β-ethyl substituted group as defined above, such as β-chloroethylsulfonyl, 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 respective vinylsulfonyl dye to the respective dye with Y being a β-ethyl substituted groups as defined above, such as a β-chloro- or β-thiosulfato- or β-sulfatoethyl-sulfonyl dye, will be up to about 30 mol-%, based on the respective dye chromophore. Preference is here given to the dye mixtures in which the proportion of vinylsulfonyl dye to said β-ethyl substituted dye, such as β-sulfatoethylsulfonγl dye is in terms of the molar ratio 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 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 the assistants customary in commercial dyes, such as buffer substances capable of establishing a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium citrate, sodium dihydrogenphosphate and disodium hydrogenphosphate, small 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. If the dye mixtures take the form of dye powders, they contain, as a rule, 10 to 80 % by weight, based on the dye powder or preparation, of a strength- standardizing colorless diluent electrolyte salt, such as those mentioned above. These dye powders may in addition contain the abovementioned 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 about 50 % by weight, the electrolyte salt content of these aqueous solutions preferably being below 10 % by weight, based on the aqueous solutions. Liquid preparations can in general contain the abovementioned 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 instance by mechanically mixing the individual dyes in the required proportions or by synthesis by means of the customary diazotization and coupling reactions using appropriate mixtures of the diazo and coupling components in a manner familiar to those skilled in the art and the necessary proportions. One option is for example to prepare aqueous suspensions of the coupling components 1 - amino-8-naphthol-3,6-disulfonic acid, a sulfonaphtylamine, and, as diazo components, aniline compounds of the formula (10).
Figure imgf000012_0001
Thus the dye mixture can be produced by diazotizing 4-(β- sulfatoethylsulfonyDaniline in a conventional manner in a strongly acid medium and then carrying out the coupling reaction of the 1 -amino-8-napthol-3,6- disulfonic acid with the diazo component at a pH below 1 .5 to form the compound (4). The second coupling reaction with the monoazo dyes (4) products to form the disazo dyes conforming to the formula (1 ) is carried out at a pH between 3 and 6.5. Then, by addition of the aqueous solution of the sulfo- napthylamine the coupling reaction to form the dye conforming to the formula (2) is carried out at a pH between 3 and 6.5. To the dye mixture thus obtained is added a dyestuff of the general formula (3). The resulting dyestuff mixture 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.
Dye mixtures which contain the respective dye components in form of the vinylsulfonyl dye can be prepared by the above mentioned method using appropriate vinylsulfonyl starting anilines, or alternately by reacting the dye mixture in which Y1 to Y9 is a β-chloroethyl, β-thiosulfatoethyl, or β-sulfatoethyl radical with an appropriate amount of alkali by generally known methods. If the dye mixtures contain the respective dye components in the form of a vinylsulfonyl dye within the proportion as defined above, the respective dye with Y1 to Y9 being a β-ethyl substituted group is reacted with the required amount of alkali to convert said β-substituted ethylsulfonyl groups into vinylsulfonyl groups in the required proportion.
The dye mixtures of the instant invention are well suitable for dyeing (which includes printing) hydroxy- and/or carboxamido-containing fiber materials by the application and fixing methods numerously described in the art for fiber-reactive dyes, in deep black shades with good color build-up and good wash-off in respect of unfixed dye portions. Moreover, the dyeings obtained surprisingly show very little or no staining on polyamide fibers.
The present invention therefore also provides for use of the inventive dye mixtures for dyeing (including printing) hydroxy- and/or carboxamido-containing fiber materials and processes for dyeing such materials using a dye mixture according to the invention by applying the dye mixture to the substrate in dissolved form and fixing the dyes on the fiber by the action of an alkali or by heating or both.
Hydroxy-containing materials are natural or synthetic hydroxy-containing materials, for example cellulose fiber materials, including in the form of paper, or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton but also other natural vegetable fibers, such as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are for example staple viscose and filament viscose.
Carboxamido-containing materials are for example synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-1 1 , and nylon-4.
Application of the inventive dye mixtures is by generally known processes for dyeing and printing fiber materials by the known application techniques for fiber- reactive dyes. Since the dyes 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 exhaust dyeing processes. Applied in this way for example to cellulose fibers from a long liquor ratio at temperatures between 40 and 105°C, optionally at temperatures up to 1 30°C, under superatmospheric pressure, and optionally in the presence of customary dyeing assistants with the use of acid-binding agents and optionally neutral salts, such as sodium chloride or sodium sulfate, they produce dyeings in very good color yields with excellent color build-up and consistent shade. One possible procedure is to introduce the material into the warm bath, gradually heat the bath to the desired dyeing temperature, and complete the dyeing process at that temperature. The neutral salts which speed up the exhaustion of the dyes can also if desired not be added to the bath until the actual dyeing temperature has been reached. Similarly, the conventional printing processes for cellulose fibers, which can either be carried out in single-phase, for example by printing with a print paste containing sodium bicarbonate or some other acid-binding agent and the colorant, and subsequent steaming at from 100 to 1 03°C, or in two phases, for example by printing with a neutral or weakly acid print paste containing the colorant and subsequent fixation either by passing the printed material through a hot electrolyte-containing alkaline bath or by overpadding with an alkaline electrolyte-containing padding liquour and subsequent batching of this treated material or subsequent steaming or subsequent treatment with dry heat, produce strong prints with well defined contours and a clear white ground. Changing fixing conditions has only little effect on the outcome of the prints. Not only in dyeing but also in printing the degrees of fixation obtained with dye mixtures of the invention are very high. The hot air used in dry heat fixing by the customary thermofix processes has a temperature of from 1 20 to 200°C. In addition to the customary steam at from 101 to 103°C, it is also possible to use superheated steam and high pressure steam at up to 1 60°C.
Acid-binding agents responsible for fixing the dyes to cellulose fibers are for example water-soluble basic salts of alkali metals and of alkaline earth metals of inorganic or organic acids, and compounds which release alkali when hot. Of particular suitability 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. These acid-binding agents are for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate and disodium hydrogenphosphate.
Treating the dyes of the dye mixtures according to the invention with the acid- binding agents with or without heating bonds the dyes chemically to the cellulose fiber; especially the dyeings on cellulose, after they have been given the usual aftertreatment of rinsing to remove unfixed dye portions, show excellent wet fastness properties, in particular since the unfixed dye portions are readily washed off because of their good cold water solubility.
The dyeings of polyurethane and polyamide fibers are customarily carried out from an acid medium. The dyebath 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 of acceptable levelness it is advisable to add customary leveling assistants, 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 agitated therein for some time, the dyebath is then adjusted to the desired weakly acid, preferably weakly acetic acid, pH, and the actual dyeing is carried out at temperature between 60 and 98°C. However, the dyeings can also be carried out at the boil or at temperatures up to 120°C (under superatmospheric pressure).
The examples which follow illustrate the invention. Parts and percentages are by weight, unless otherwise stated. The parts by weight bear the same relation to parts by volume as the kilogram to the liter.
Example 1
200 parts of an electrolyte-containing dye powder which contains the navy- dyeing disazo dye of the formula (A)
Figure imgf000017_0001
in a proportion of 50% are mechanically mixed with 75 parts of an electrolyte- containing dye powder which contains the orange-dyeing monoazo of the formula (B) in a 70% proportion
Figure imgf000017_0002
and a 25 parts of an electrolyte-containing dye powder which contains the yellow-dyeing azo dye of the formula (C) in a 60% proportion
Figure imgf000017_0003
(C ) 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
A dye mixture 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 1 80 parts of 30 % aqueous hydrochloric acid with 1 73 parts of 40 % strength aqueous sodium nitrite solution. 1 20 parts of 1 -amino-8-napthol-3,6-disulfonic acid are added and the first coupling is carried out at a pH between 1 and 1 .3 and at a temperature below 20°C (the pH is maintained with about 50 parts of sodium bicarbonate). 72 parts 1 -Aminonaphtaline-4-sulfonic acid are added to the mixture and the pH is raised to 6 with sodium carbonate at a temperature below 30°C.
To the resulting solution containing the dyes of formulae (A) and (D) are added 50 parts of a yellow dye of the formula (C). The resulting dye mixture comprises the dyes of the formulae (A), (D) and (C) in a the ratio of about 70 % : 22 % : 8 %.
Figure imgf000018_0001
This dye solution can be adjusted to pH 4.5 by adding 5 parts of 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 3 to 1 12
The table examples which follow describe further dye mixtures according to the invention of the dyes conforming to the formulae (1 )-(9) as the sodium salts of the β-sulfatoethyl, 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, deep black dyeings.
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001

Claims

Patent Claims:
A dye mixture, comprising a disazo dye conforming to the formula (1 ), a monoazo dye conforming to the formula
(2), and monazo dye conforming to the formula (3)
Figure imgf000038_0001
(3) wherein
Y1 is in each instance, independently of one another, vinyl or is ethyl which is substituted in the β-position by a substituent which can be eliminated by the action of an alkali, forming the vinyl group, such as chlorine, thiosulfato, sulfato, alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, phosphato, sulfobenzoyloxy and p-toluylsulfonyloxy;
Y2 has one of the meanings of Y1;
Y3 has one of the meanings of Y2;
M is hydrogen or an alkali metal, such as lithium, sodium and potassium; X is fluorine or chlorine;
R1 is hydrogen methyl, methoxy or a group of the formula SO3M;
R2 has one of the meanings of R1;
Q is a group of the formula (a) or (b)
Figure imgf000039_0001
(a) (b) wherein
A is hydrogen, C, to C6 alkyl such as methyl, ethyl, n-propyl , i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl or hexyl, which may be substituted by hydroxy, sulfo or sulfato or is phenyl which may be substituted by one or more halogens such as chloro, fluoro or bromo, by acetamido- or by sulfo; A' is C, to C6 alkyl such as methyl, ethyl, n-propyl , i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl or hexyl, which may be substituted by hydroxy, sulfo or sulfato or is phenyl which may be substituted by one or more halogens such as chloro, fluoro or bromo, by acetamido- or by sulfo; B has one of the meanings of A;
B' has one of the meanings of A'; D has one of the meanings of A'; or the group of the formula
(a) is a cyclic ringsystem such as morpholino, piperidino or piperazino;
(b) is a cyclic ringsystem such as N-methyl morpholinium or N-ethyl morpholinium, N-ethyl piperidinium, or is a bicyclic ringsystem such as N- 1 ,4-diaminobicyclo (2,2,2) octyl, or is pyridinium which may be substituted by carboxy, such as 3-carboxy-pyridinium or 4-carboxy- pyridinium, or by carboxamido, such as 3-carboxamidopyridinium; n is 0 if Q is a group of the formula (a) and n is 1 if Q is a group of formula
(b) ; W" is a halogenide or the equivalent of a divalent anionic group such as sulfate or carbonate.
A dye mixture as claimed in claim 1 wherein the dye of formula (1 ) is present in the mixture in an amount of from 50 to 95% by weight; the dye of the formula (2) is present in the mixture in an amount of from 1 to 30% by weight; the dye of the formula (3) is present in the mixture in an amount of from 1 to 20 % by weight.
A dye mixture as claimed in claim 1 comprising a monoazo dye of formula (4) in a total amount of 0.5 to 6.0% by weight and a monoazo dye of formula (5) in a total amount of 0.5 to 6.0% by weight, calculated on 100% by weight of the dye mixture.
Figure imgf000040_0001
Figure imgf000041_0001
wherein:
Y4, Y5 have one of the meanings of Y1;
M is as defined in claim 1 .
4. A dye mixture according to claim 1 -3 comprising a monoazo dye of formula (6) in a total amount of O.
5.- 25% by weight based on the dye mixture
Figure imgf000041_0002
(6) wherein
Y6 has one of the meanings of Y
M is as defined in claim 1 . A dye mixture according to claim 1 -3 comprising a monoazo dye of formula
(7) in a total amount of O.5.- 25% by weight based on the dye mixture
Figure imgf000042_0001
wherein
Y7 has one of the meanings of Y1 M is as defined in claim 1 .
A dye mixture according to claim 1 -3 comprising a monoazo dye of formula (8) in a total amount of O.5.- 25% by weight based on the dye mixture.
Figure imgf000042_0002
wherein Z is a C|-C4-alkyl, such as methyl, ethyl, n-propyl, i-propyl, or is a phenylgroup, which may be substituted by chlorine nitro or sulfo
has one of the meanings of Y1
M is as defined in claim 1 .
A dye mixture according to claim 1 -3 comprising a monoazo dye of formula (9) in a total amount of O.5.- 25% by weight based on the dye mixture
Figure imgf000043_0001
Wherein:
X, has one of the meanings of X; Q' is a group of the formula (a')
Figure imgf000043_0002
(a') in which
A, has one of the meanings of A or is an aryl or alkyl group that is substituted by sulfo or a group of the formula SO2Y\"
B, has one of the meanings of A or
(a') has one of the meanings of (a); γ9 is vinyl or is ethyl which is substituted in the β-position by a substituent which can be eliminated by the action of an alkali, forming the vinyl group, such as chlorine, thiosulfato, sulfato, alkanoyloxy of 2 to 5 carbon atoms, such as acetyloxy, phosphato, sulfobenzoyloxy and p- toluylsulfonyloxy and M is hydrogen or an alkali metal, such as lithium, sodium or potassium.
8. A dye mixture according to claim 1 -3 comprising more than one of the formulae (6), (7), (8) or (9) in up to a total of 25 % by weight based on the dye mixture.
9. A process for the preparation of the dye mixture as claimed in one or more of claims 1 -8 comprising mechanically mixing the individual dyes of the formulae (1 ) to (9) in the required proportions.
1 0. A process for the preparation of the dye mixture according to claim 1 by diazotizing an aniline component of 4-(β-sulfatoethylsulfonyl)aniline in a conventional manner in a strongly acid medium and then carrying out the coupling reaction of the 1 -amino-8-napthol-3,6-disulfonic acid with the diazo component at a pH below 1 .5 to form the compound (4) followed by the second coupling reaction with the monoazo dye (4) products to form the disazo dye conforming to the formula (1 ) which is carried out at a pH between 3 and 6.5 and by addition of the aqueous solution of the sulfo- napthylamine the coupling reaction to form the dye conforming to the formula (2) which is carried out at a pH between 3 and 6.5 and subsequent addition to the dye mixture of a dyestuff of the general formula (3) followed by the isolation of the dyestuff mixture from the solution in the conventional manner, for example by salting out with an electrolyte salt.
1 1 . 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 dyes of the mixture as claimed in claim 1 .
PCT/EP2001/008462 2000-07-25 2001-07-21 Black dye mixtures of fiber-reactive azo dyes, methods for their preparation and use thereof for dyeing hydroxy- and/or carboxamido-containing fiber material WO2002008339A2 (en)

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BR0112784-5A BR0112784A (en) 2000-07-25 2001-07-21 Black dye mixtures of azo fiber reactive dyes, methods for preparing and dyeing them, hydroxy and / or carboxamide-containing fiber material
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