WO2012025279A1 - Mixtures of fibre-reactive dyes and their use in a method for trichromatic dyeing or printing - Google Patents

Mixtures of fibre-reactive dyes and their use in a method for trichromatic dyeing or printing Download PDF

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Publication number
WO2012025279A1
WO2012025279A1 PCT/EP2011/060442 EP2011060442W WO2012025279A1 WO 2012025279 A1 WO2012025279 A1 WO 2012025279A1 EP 2011060442 W EP2011060442 W EP 2011060442W WO 2012025279 A1 WO2012025279 A1 WO 2012025279A1
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Prior art keywords
formula
dye
crc
alkyl
radical
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PCT/EP2011/060442
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French (fr)
Inventor
Athanassios Tzikas
Georg Roentgen
Jean-François LANDRE
Remo Codemo
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Huntsman Advanced Materials (Switzerland) Gmbh
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Priority to CN2011800406880A priority Critical patent/CN103080414A/en
Priority to KR1020137006877A priority patent/KR20130100133A/en
Priority to EP11726813.6A priority patent/EP2609247A1/en
Priority to BR112013004125A priority patent/BR112013004125A2/en
Priority to US13/816,966 priority patent/US20130283546A1/en
Publication of WO2012025279A1 publication Critical patent/WO2012025279A1/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
    • D06P1/0096—Multicolour dyeing
    • 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
    • C09B67/0055—Mixtures of two or more disazo dyes
    • C09B67/0057—Mixtures of two or more reactive disazo 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
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0072—Preparations with anionic dyes or reactive dyes
    • C09B67/0073—Preparations of acid or reactive dyes in liquid form
    • 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
    • D06P1/0032—Determining dye recipes and dyeing parameters; Colour matching or monitoring
    • 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
    • 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
    • D06P1/382—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 reactive group directly attached to heterocyclic group
    • 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
    • D06P1/384—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 reactive group not directly attached to heterocyclic group
    • 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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • 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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D06P3/663—Natural or regenerated cellulose using reactive dyes reactive group directly attached to heterocyclic group
    • 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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D06P3/666—Natural or regenerated cellulose using reactive dyes reactive group not directly attached to heterocyclic group

Definitions

  • the present invention relates to mixtures of reactive dyes that are suitable for the dyeing or printing of nitrogen-containing or hydroxy-group-containing fibre materials and yield on such materials dyeings or prints having good reproducibility and good all-round fastness properties.
  • the present invention relates also to a method for trichromatic dyeing or printing wherein the reactive dye mixtures according to the invention are used.
  • Suitable reactive dyes should provide a unique combinability and a low sensitivity to various dyeing parameters. Furthermore, they should have sufficient substantivity and at the same time have good ease of washing off of unfixed dye. They should also have a good tinctorial yield and high reactivity, the objective being to provide especially dyeings having high degrees of fixation.
  • the present invention is therefore based on the problem of providing new mixtures of reactive dyes that are suitable especially for the reproducible trichromatic dyeing and printing of fibre materials in the desired colour shades and fulfill the above indicated requirements to the highest possible extent.
  • the present invention accordingly relates to a dye mixture, comprising at least one yellow dye of the formula
  • Ar- ⁇ represents a benzene or naphthalene radical
  • Xi is chlorine or fluorine
  • Ri is amino or CrC 6 alkyl
  • R 2 , R3, R 4 , R5, R6 and R 7 each independently of the others represent hydrogen, hydroxy, amino, CrC 6 alkyl, d-C 6 alkoxy or sulfo,
  • u is a number from 1 to 3
  • Y is vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions; at least one yellow dye of the formula
  • Ar 2 represents a benzene or naphthalene radical
  • X 2 , and X 3 independently of the other are chlorine or fluorine
  • B denotes a straight-chain or branched C 2 -C 6 alkylene radical which is unsubstituted or substituted by hydroxy, sulfo or sulfato,
  • R 8 , Rg, R1 0 and Rn each independently of the others represent hydrogen or CrC 6 alkyl which is unsubstituted or substituted by hydroxy, amino, cyano, halogen, CrC 6 alkoxy,
  • R12 and Ri 3 denote amino or CrC 6 alkyl
  • Ri 4 , Ri 5 and Ri 6 each independently of the others are hydrogen, hydroxy, amino, CrC 6 alkyl,
  • v is a number from 1 to 3;
  • Ar 3 represents a benzene or naphthalene radical
  • X 4 denotes halogen, 3-carboxypyridin-1 -yl or 3-carbamoylpyrid
  • Ri 7 is hydrogen or CrC 6 alkyl
  • Ri8 represents hydrogen, CrC 6 alkyl, CrC 6 alkoxy or sulfo
  • Z-i is hydrogen or a fibre-reactive group of the formula
  • Y-i , Y 2 and Y 3 each independently of the others denote vinyl or a radical -CH 2 -CH 2 -U and U is a group removable under alkaline conditions, and
  • k is a number from 1 to 3;
  • (R 19 ) b denotes b identical or different substituents from the group CrC 6 alkyl, CrC 6 alkoxy, sulfo and halogen,
  • X 5 is halogen
  • Z 2 is a fibre-reactive radical of formula
  • T 2 is halogen, a non-fibre-reactive substituent or a fibre-reactive radical of formula -NH-(CH 2 ) 2-3 -S0 2 -Y 7 (6a), -NH-(CH 2 ) 2- 3-0-(CH 2 ) 2-3 -S0 2 -Y 8 (6b),
  • (R2o)o-2 denotes from 0 to 2 identical or different substituents from the group halogen, CrC 6 -alkyl, d-C 6 alkoxy and sulfo,
  • Y 4 , Y5, ⁇ , Y7, ⁇ , ⁇ and ⁇ 10 each independently of the others denote vinyl or a -CH 2 -CH 2 -U radical and U is a group that is removable under alkaline conditions,
  • n are each independently of the other the number 2, 3 or 4 and
  • Hal is halogen
  • Ti is a fibre-reactive radical of the above formula (6b), (6c), (6d) or (6e) and
  • b and a are each independently of the other the number 0, 1 or 2.
  • the dyes of the formulae (1 ), (2), (3) and (4) in the dye mixtures according to the invention contain one or more than one sulfo group or carboxy group, which are each present either in free acid form or, preferably, in salt form.
  • Suitable salts are, for example, alkali metal, alkaline earth metal or ammonium salts, salts of an organic amine, or mixtures thereof.
  • ammonium lithium or, preferably sodium or potassium salts, or in the form of a salt of an organic amine, for example, a mono-, di- or tri- ethanolamine salt or mixed Na/Li or Na/Li/NH 4 salts.
  • CrC 6 alkyl groups which come into consideration for R-i to R 20 can be e.g. methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl and n-hexyl, preferably methyl and ethyl.
  • Suitable CrC 6 alkoxy groups as R 2 to Rn and Ri 4 to R 20 are e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy and n-hexoxy, preferably, methoxy and ethoxy and, especially, methoxy.
  • U there comes into consideration, for example, -CI, -Br, -F, -OSO 3 H, -SSO 3 H, -OCO-CH 3 , -OP0 3 H 2 , -OCO-C 6 H 5 , -OS0 2 -CrC 4 alkyl or -OS0 2 -N(Ci-C 4 alkyl) 2 .
  • U is preferably a group of the formula -CI, -OSO 3 H, -SSO 3 H, -OCO-CH 3 , -OCO-C 6 H 5 or -OP0 3 H 2 , especially -CI or -OS0 3 H.
  • bridging moieties B in formula (2) are ethylene, propylene, trimethylene, 2-hydroxypropanediyl, tetramethylene, 2,2-dimethylpropanediyl,
  • Halogen as substituent X 4 , X 5 or T 2 can be fluorine, chlorine or bromine, in particular fluorine or chlorine.
  • Halogen as Hal in formula (5d), (5e) or (6e) may be chlorine or bromine, in particular bromine.
  • Ar- ⁇ in formula (1 ) is preferably naphthyl subsituted by three sulfo groups.
  • R-i in formula (1 ) is preferably amino or methyl, especially amino.
  • R 2 in formula (1 ) is preferably hydrogen.
  • R 3 in formula (1 ) is preferably hydrogen.
  • R 4 in formula (1 ) is preferably amino.
  • R 5 in formula (1 ) is preferably sulfo.
  • R 6 and R 7 in formula (1 ) are preferably hydrogen.
  • R 8 , R9, R1 0 and Rn preferably represent hydrogen.
  • Ri 2 and R13 are preferably amino.
  • Ar 2 in formula (2) is preferably naphthyl subsituted by three sulfo groups.
  • B in formula (2) preferably represents ethylene, propylene or trimethylene, in particular trimethylene.
  • Ar 3 in formula (3) is preferably naphthyl subsituted by two sulfo groups.
  • Z-i is hydrogen
  • Yi is preferably vinyl or 2-sulfatoethyl.
  • R-I7 in formula (3) is preferably hydrogen or ethyl, in particular hydrogen.
  • R-I8 in formula (3) is preferably hydrogen.
  • Z 2 preferably represents vinylsulfonyl, 2-sulfatoethylsulfonyl or
  • Rig is preferably sulfo and b is 0 or 1.
  • a in formula (4) is preferably 1.
  • T-i in formula (4) is preferably a radical of formula (6c) wherein Y 9 is vinyl or 2-sulfatoethyl.
  • Suitable dyes of formula (2) are, for example, the compounds of the formulae
  • the mixtures according to the invention may contain further yellow reactive dyes, like e.g. the dye of the formulae
  • dye mixtures wherein the dye of the formula (3) corresponds to the compound of the formula (302).
  • the trichromatic mictures according to the invention contains as red component a mixture of a dye of formula (301 ) and a dye of formula (302).
  • Suitable dyes of formula (4) are, for example, the compounds of the formulae
  • the mixtures according to the invention may contain further blue reactive dyes, like e.g. the dyes of the formula
  • Z 3 is a fibre-reactive radical of formula (5a), (5b), (5c), (5d), (5e) or (5f) as defined above.
  • the dye of formula (8) is, for example, a dye of the formula
  • the dye of formula (801 ) is particularly preferred.
  • the mixture according to the invention contains the dye of formula (101 ) and the dye of formula (201 ) as defined above in a weight ratio from 4 : 1 to 1 : 4, preferably from 2 : 1 to 1 : 2, and in particular in a weight ratio from 1 : 1 to 1 : 2.
  • the mixture according to the invention contains the dye of formula (302) and the dye of formula (301 ) as defined above in a weight ratio from 4 : 1 to 1 : 4, preferably from 2 : 1 to 1 : 2, and in particular in a weight ratio from 2 : 1 to 1 : 1 .
  • the mixture according to the invention contains the dye of formula (401 ) and the dye of formula (801 ) as defined above in a weight ratio from
  • a particularly preferred embodiment of the invention is a trichromatic dye mixture comprising as yellow component a mixture of a dye of formula (101 ) and a dye of formula (201 ) as defined above, as red component a mixture of a dye of formula (301 ) and a dye of formula (302) as defined above and as blue component a mixture of a dye of formula (401 ) and a dye of formula (801 ) as defined above.
  • the dyes of formulae (1 ), (2), (3), (4) and (8) are known in some cases or they can be prepared in accordance with processes known per se.
  • Dyes of the formula (1 ) are disclosed, for example, in EP 623 655.
  • Dyes of the formula (2) are disclosed, for example, in
  • the dye mixtures according to the invention can be prepared, for example, by mixing the individual dyes together.
  • the mixing procedure is effected, for example, in suitable mills, e.g. ball mills or pin mills, as well as in kneaders or mixers.
  • the dye mixtures according to the invention can also be prepared, for example, by dissolving the reactive dyes directly in the dyebath or the printing medium. The amount of the individual reactive dyes is governed by the shade to be obtained.
  • the dye of formula (1 ) and the total amount of the dyes of formulae (2), (3), (4) and (8) are present in the dye mixtures according to the invention in a ratio by weight of, for example, from 1 :99 to 99:1 , preferably from 5:95 to 95:5 and especially from 10:90 to 90:10.
  • the reactive dyes of formulae (1 ), (2), (3), (4) and (8) and accordingly also the dye mixtures according to the invention may comprise further additives, for example, sodium chloride or dextrin.
  • the reactive dyes of formulae (1 ), (2), (3), (4) and (8) and accordingly also the dye mixtures according to the invention may comprise further auxiliaries which, for example, improve handling or increase storage stability, such as buffers, dispersants or anti-dusts.
  • auxiliaries are known to the person skilled in the art.
  • the dye mixtures according to the invention are suitable for the dyeing and printing of an extremely wide variety of materials, especially hydroxy-group-containing or nitrogen- containing fibre materials.
  • materials especially hydroxy-group-containing or nitrogen- containing fibre materials.
  • materials are paper, silk, leather, wool, polyamide fibres and polyurethanes as well as, especially, cellulosic fibre materials of all kinds.
  • Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen and hemp, as well as cellulose and regenerated cellulose.
  • the dye mixtures according to the invention and the reactive dyes according to the invention are also suitable for the dyeing or printing of hydroxy-group-containing fibres that are contained in blend fabrics, for example mixtures of cotton with polyester fibres or polyamide fibres.
  • the said textile fibre material may be in an extremely wide variety of processing forms, such as, for example, in the form of fibres, yarn, woven fabric or knitted fabric.
  • the present invention relates also to a method for the trichromatic dyeing or printing of hydroxy-group-containing or nitrogen-containing fibre materials, especially cellulosic fibre materials, which method comprises using at least one yellow dye, for example one, two or three dyes, preferably one dye, of the above-mentioned formula (1 ) and at least one yellow dye, for example one, two or three dyes, preferably one dye, of the above-mentioned formula (2), together with at least one red dye of the above-mentioned formula (3) and at least one blue dye of the above-mentioned formula (4).
  • at least one yellow dye for example one, two or three dyes, preferably one dye, of the above-mentioned formula (1 )
  • at least one yellow dye for example one, two or three dyes, preferably one dye, of the above-mentioned formula (2)
  • the method according to the invention for trichromatic dyeing and printing can be carried out in accordance with customary dyeing and printing methods, for example, according to the so- called cold pad-batch process, in which the dye is applied, together with the alkali, on the padder and is then fixed by storage for several hours at about room temperature, for example, from 25 to 35°C.
  • the method according to the invention for trichromatic dyeing and printing is carried out according to the exhaust-dyeing method, in which the goods are impregnated with aqueous, optionally salt-containing dye solutions, and the dyes are fixed after an alkali treatment or in the presence of alkali, optionally under the action of heat.
  • the dye liquors or print pastes in addition to containing water and the dyes, may also comprise further additives, for example shading dyes known per se, salts, buffer substances, wetting agents, anti-foams, levelling agents or agents that influence the properties of the textile material, for example, softeners, additives for flame-resistant finishes or dirt-, water- or oil-repellants, as well as water-softeners and natural or synthetic thickeners, e.g. alginates or cellulose ethers.
  • further additives for example shading dyes known per se, salts, buffer substances, wetting agents, anti-foams, levelling agents or agents that influence the properties of the textile material, for example, softeners, additives for flame-resistant finishes or dirt-, water- or oil-repellants, as well as water-softeners and natural or synthetic thickeners, e.g. alginates or cellulose ethers.
  • the amounts in which the individual dyes are used in the dyebaths or print pastes can vary within wide limits in dependence upon the desired depth of shade; in general, amounts of from 0.01 to 15% by weight, especially from 0.1 to 10% by weight, based on the goods being dyed or on the print paste, have proved advantageous.
  • the dyes of formulae (1 ), (2), (3), (4) and (8) used in the method according to the invention are distinguished in trichromatic dyeing or printing by uniform colour build-up, good exhaustion and fixing behaviour, good constancy of shade even in different concentrations, a low sensitivity to various dyeing parameters and, in particular, very good combinability. Dyeing times can be reduced. Furthermore, they have sufficient substantivity and at the same time have good ease of washing off of unfixed dye and can advantageously be applied at short liquor ratios, for example, at a liquor ratio of from 1 :4 to 1 :6, preferably, 1 :6.
  • the dyeings and prints produced in accordance with the method of the invention exhibit very good fastness properties, such as wash and water fastness and perspiration fastness, and good reproducibility.
  • a bleached cotton tricot fabric is introduced at 60°C into an aqueous dyebath with a liquor ratio of 1 :10 which contains 72 g/l of sodium chloride, 0.541 % by weight of the yellow dyeing reactive dye of formula (201 ), 0.361 % by weight of the yellow dyeing reactive dye of formula (101 ), 0.276 % by weight of the red dyeing reactive dye of formula (301 ), 0.413 % by weight of the red dyeing reactive dye of formula (302), 0.618 % by weight of the blue dyeing reactive dye of formula (801 ) and 0.412 % by weight of the blue dyeing reactive dye of formula (401 ).
  • a total of 15.2 g/l of calcined sodium carbonate is added in 4 portions (1 .52 g/l, 3.04 g/l, 3.04 g/l and 7.6 g/l, respectively) to the dyebath after 45, 50, 55 and 60 minutes at 60°C. Dyeing is continued for 35 minutes. The dyed fabric is taken out of the dyeing liquor and dried. A brown shaded fabric is obtained.
  • a bleached cotton tricot (1 -4002/22) fabric is introduced at 60°C into an aqueous dyebath with a liquor ratio of 1 :10 which contains 78 g/l of sodium chloride, 0.90 % by weight of the yellow dyeing reactive dye of formula (201 ), 0.68 % by weight of the red dyeing reactive dye of formula (301 ) and 1 .29 % by weight of the blue dyeing reactive dye of formula (801 ).
  • a total of 15.8 g/l of calcined sodium carbonate is added in 4 portions (1 .58 g/l, 3.16 g/l, 3.16 g/l and 7.9 g/l, respectively) to the dyebath after 45, 50, 55 and 60 minutes at 60°C. Dyeing is continued for 35 minutes. The dyed fabric is taken out of the dyeing liquor and dried. A brown shaded fabric is obtained.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Coloring (AREA)

Abstract

Dye mixtures, comprising least one yellow dye of the formula (1), at least one yellow dye of the formula (2), at least one red dye of the formula (3), at least one blue dye of the formula (4), wherein the radicals have the definitions given in the claims, are suitable especially for the trichromatic dyeing or printing of cellulosic fibre materials and yield dyeings or prints having good reproducibility and good all-round fastness properties.

Description

Mixtures of fibre-reactive dyes and their use in a method for trichromatic dyeing or printing
The present invention relates to mixtures of reactive dyes that are suitable for the dyeing or printing of nitrogen-containing or hydroxy-group-containing fibre materials and yield on such materials dyeings or prints having good reproducibility and good all-round fastness properties. The present invention relates also to a method for trichromatic dyeing or printing wherein the reactive dye mixtures according to the invention are used.
There is a huge demand for novel reactive dye mixtures that are suitable for the reproducible trichromatic dyeing and printing of fibre materials which fulfill highest ecological and economical requirements while still providing dyeings of the desired colour shades with good fastness properties, such as wash and water fastness and perspiration fastness. Suitable reactive dyes should provide a unique combinability and a low sensitivity to various dyeing parameters. Furthermore, they should have sufficient substantivity and at the same time have good ease of washing off of unfixed dye. They should also have a good tinctorial yield and high reactivity, the objective being to provide especially dyeings having high degrees of fixation.
The present invention is therefore based on the problem of providing new mixtures of reactive dyes that are suitable especially for the reproducible trichromatic dyeing and printing of fibre materials in the desired colour shades and fulfill the above indicated requirements to the highest possible extent.
The present invention accordingly relates to a dye mixture, comprising at least one yellow dye of the formula
Figure imgf000003_0001
wherein Ar-ι represents a benzene or naphthalene radical,
Xi is chlorine or fluorine, Ri is amino or CrC6alkyl,
R2, R3, R4, R5, R6 and R7 each independently of the others represent hydrogen, hydroxy, amino, CrC6alkyl, d-C6alkoxy or sulfo,
u is a number from 1 to 3,
Y is vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions; at least one yellow dye of the formula
Figure imgf000004_0001
wherein Ar2 represents a benzene or naphthalene radical,
X2, and X3 independently of the other are chlorine or fluorine,
B denotes a straight-chain or branched C2-C6alkylene radical which is unsubstituted or substituted by hydroxy, sulfo or sulfato,
R8, Rg, R10 and Rn each independently of the others represent hydrogen or CrC6alkyl which is unsubstituted or substituted by hydroxy, amino, cyano, halogen, CrC6alkoxy,
CrC6alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato,
R12 and Ri3, denote amino or CrC6alkyl,
Ri4, Ri5 and Ri6 each independently of the others are hydrogen, hydroxy, amino, CrC6alkyl,
CrC6alkoxy or sulfo,
v is a number from 1 to 3;
at least one red dye of the formula
Figure imgf000004_0002
wherein Ar3 represents a benzene or naphthalene radical,
X4 denotes halogen, 3-carboxypyridin-1 -yl or 3-carbamoylpyrid
Ri7 is hydrogen or CrC6alkyl, Ri8 represents hydrogen, CrC6alkyl, CrC6alkoxy or sulfo,
Z-i is hydrogen or a fibre-reactive group of the formula
-S02-Y2, (7a) or -NH-CO-(CH2)2-3-S02-Y3 (7b), Y-i , Y2 and Y3 each independently of the others denote vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, and
k is a number from 1 to 3;
and at least one blue dye of the formula
Figure imgf000005_0001
wherein (R19)b denotes b identical or different substituents from the group CrC6alkyl, CrC6alkoxy, sulfo and halogen,
X5 is halogen,
Z2 is a fibre-reactive radical of formula
-S02-Y4 (5a),
-NH-CO-(CH2)m-S02- Y5 (5b),
-CONH-(CH2)n-S02- Y6 (5c),
-NH-CO-CH(Hal)-CH2-Hal (5d),
-NH-CO-C(Hal)=CH2 (5e) or
Figure imgf000005_0002
wherein T2 is halogen, a non-fibre-reactive substituent or a fibre-reactive radical of formula -NH-(CH2)2-3-S02-Y7 (6a), -NH-(CH2)2-3-0-(CH2)2-3-S02-Y8 (6b),
Figure imgf000005_0003
Figure imgf000006_0001
(R2o)o-2 denotes from 0 to 2 identical or different substituents from the group halogen, CrC6-alkyl, d-C6alkoxy and sulfo,
Y4, Y5, Υβ, Y7, Υβ, ΥΘ and Υ10 each independently of the others denote vinyl or a -CH2-CH2-U radical and U is a group that is removable under alkaline conditions,
Q is a -CH(Hal)-CH2-Hal or -C(Hal)=CH2 group,
m and n are each independently of the other the number 2, 3 or 4 and
Hal is halogen,
Ti is a fibre-reactive radical of the above formula (6b), (6c), (6d) or (6e) and
b and a are each independently of the other the number 0, 1 or 2.
The dyes of the formulae (1 ), (2), (3) and (4) in the dye mixtures according to the invention contain one or more than one sulfo group or carboxy group, which are each present either in free acid form or, preferably, in salt form. Suitable salts are, for example, alkali metal, alkaline earth metal or ammonium salts, salts of an organic amine, or mixtures thereof.
Examples that may be mentioned are ammonium, lithium or, preferably sodium or potassium salts, or in the form of a salt of an organic amine, for example, a mono-, di- or tri- ethanolamine salt or mixed Na/Li or Na/Li/NH4 salts.
CrC6alkyl groups which come into consideration for R-i to R20 can be e.g. methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl and n-hexyl, preferably methyl and ethyl.
Suitable CrC6alkoxy groups as R2 to Rn and Ri4 to R20 are e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy and n-hexoxy, preferably, methoxy and ethoxy and, especially, methoxy. As leaving group U there comes into consideration, for example, -CI, -Br, -F, -OSO3H, -SSO3H, -OCO-CH3, -OP03H2, -OCO-C6H5, -OS02-CrC4alkyl or -OS02-N(Ci-C4alkyl)2. U is preferably a group of the formula -CI, -OSO3H, -SSO3H, -OCO-CH3, -OCO-C6H5 or -OP03H2, especially -CI or -OS03H.
Examples of preferred bridging moieties B in formula (2) are ethylene, propylene, trimethylene, 2-hydroxypropanediyl, tetramethylene, 2,2-dimethylpropanediyl,
2-methylpentanediyl and hexamethylene.
Halogen as substituent X4, X5 or T2 can be fluorine, chlorine or bromine, in particular fluorine or chlorine.
Halogen as Hal in formula (5d), (5e) or (6e) may be chlorine or bromine, in particular bromine.
Ar-ι in formula (1 ) is preferably naphthyl subsituted by three sulfo groups.
R-i in formula (1 ) is preferably amino or methyl, especially amino.
R2 in formula (1 ) is preferably hydrogen.
R3 in formula (1 ) is preferably hydrogen.
R4 in formula (1 ) is preferably amino.
R5 in formula (1 ) is preferably sulfo.
R6 and R7 in formula (1 ) are preferably hydrogen.
In formula (2) R8, R9, R10 and Rn preferably represent hydrogen.
Ri2 and R13 are preferably amino.
Ar2 in formula (2) is preferably naphthyl subsituted by three sulfo groups. Preferably B in formula (2) preferably represents ethylene, propylene or trimethylene, in particular trimethylene.
Ar3 in formula (3) is preferably naphthyl subsituted by two sulfo groups.
Preferably Z-i is hydrogen.
Yi is preferably vinyl or 2-sulfatoethyl.
R-I7 in formula (3) is preferably hydrogen or ethyl, in particular hydrogen. R-I8 in formula (3) is preferably hydrogen.
In formula (4) Z2 preferably represents vinylsulfonyl, 2-sulfatoethylsulfonyl or
-NHCO-CBr=CH2Br.
Rig is preferably sulfo and b is 0 or 1. a in formula (4) is preferably 1.
T-i in formula (4) is preferably a radical of formula (6c) wherein Y9 is vinyl or 2-sulfatoethyl.
Preference is given to dye mixtures, wherein the dye of the formula (1 ) corresponds to the compound of the formula
Figure imgf000008_0001
Suitable dyes of formula (2) are, for example, the compounds of the formulae
Figure imgf000009_0001
Preference is given to dye mixtures, wherein the dye of the formula (2) corresponds to the compound of the formula (201 ).
In addition to the dyestuffs of formulae (1 ) and (2), the mixtures according to the invention may contain further yellow reactive dyes, like e.g. the dye of the formulae
Figure imgf000010_0001
Figure imgf000010_0002
-9-
Figure imgf000011_0001
Figure imgf000011_0002
Figure imgf000011_0003
(308) or
Preference is also given to dye mixtures, wherein the dye of the formula (3) corresponds to the compound of the formula (301 ).
Preference is also given to dye mixtures, wherein the dye of the formula (3) corresponds to the compound of the formula (302).
In a preferred embodiment the trichromatic mictures according to the invention contains as red component a mixture of a dye of formula (301 ) and a dye of formula (302).
Suitable dyes of formula (4) are, for example, the compounds of the formulae
Figure imgf000012_0002
2/025279
- 11 -
Figure imgf000013_0001
Figure imgf000014_0001
In addition to the blue dyestuffs of formulae (4), the mixtures according to the invention may contain further blue reactive dyes, like e.g. the dyes of the formula
Figure imgf000014_0002
wherein Z3 is a fibre-reactive radical of formula (5a), (5b), (5c), (5d), (5e) or (5f) as defined above.
The dye of formula (8) is, for example, a dye of the formula
Figure imgf000014_0003
N
Figure imgf000015_0001
The dye of formula (801 ) is particularly preferred.
In a preferred embodiment the mixture according to the invention contains the dye of formula (101 ) and the dye of formula (201 ) as defined above in a weight ratio from 4 : 1 to 1 : 4, preferably from 2 : 1 to 1 : 2, and in particular in a weight ratio from 1 : 1 to 1 : 2.
In a further preferred embodiment the mixture according to the invention contains the dye of formula (302) and the dye of formula (301 ) as defined above in a weight ratio from 4 : 1 to 1 : 4, preferably from 2 : 1 to 1 : 2, and in particular in a weight ratio from 2 : 1 to 1 : 1 .
In a further preferred embodiment the mixture according to the invention contains the dye of formula (401 ) and the dye of formula (801 ) as defined above in a weight ratio from
4 : 1 to 1 : 4, preferably from 2 : 1 to 1 : 2, and in particular in a weight ratio from 1 : 1 to 1 : 2.
A particularly preferred embodiment of the invention is a trichromatic dye mixture comprising as yellow component a mixture of a dye of formula (101 ) and a dye of formula (201 ) as defined above, as red component a mixture of a dye of formula (301 ) and a dye of formula (302) as defined above and as blue component a mixture of a dye of formula (401 ) and a dye of formula (801 ) as defined above.
The dyes of formulae (1 ), (2), (3), (4) and (8) are known in some cases or they can be prepared in accordance with processes known per se. Dyes of the formula (1 ) are disclosed, for example, in EP 623 655. Dyes of the formula (2) are disclosed, for example, in
EP 478 503. Dyes of the formulae (3) and (4) are disclosed, for example, in US 7,641 ,724. Dyes of the formula (8) are disclosed, for example, in WO 2005/090485.
The dye mixtures according to the invention can be prepared, for example, by mixing the individual dyes together. The mixing procedure is effected, for example, in suitable mills, e.g. ball mills or pin mills, as well as in kneaders or mixers. The dye mixtures according to the invention can also be prepared, for example, by dissolving the reactive dyes directly in the dyebath or the printing medium. The amount of the individual reactive dyes is governed by the shade to be obtained. The dye of formula (1 ) and the total amount of the dyes of formulae (2), (3), (4) and (8) are present in the dye mixtures according to the invention in a ratio by weight of, for example, from 1 :99 to 99:1 , preferably from 5:95 to 95:5 and especially from 10:90 to 90:10.
The reactive dyes of formulae (1 ), (2), (3), (4) and (8) and accordingly also the dye mixtures according to the invention may comprise further additives, for example, sodium chloride or dextrin.
If desired, the reactive dyes of formulae (1 ), (2), (3), (4) and (8) and accordingly also the dye mixtures according to the invention may comprise further auxiliaries which, for example, improve handling or increase storage stability, such as buffers, dispersants or anti-dusts. Such auxiliaries are known to the person skilled in the art.
The dye mixtures according to the invention are suitable for the dyeing and printing of an extremely wide variety of materials, especially hydroxy-group-containing or nitrogen- containing fibre materials. Examples thereof are paper, silk, leather, wool, polyamide fibres and polyurethanes as well as, especially, cellulosic fibre materials of all kinds. Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen and hemp, as well as cellulose and regenerated cellulose. The dye mixtures according to the invention and the reactive dyes according to the invention are also suitable for the dyeing or printing of hydroxy-group-containing fibres that are contained in blend fabrics, for example mixtures of cotton with polyester fibres or polyamide fibres.
The said textile fibre material may be in an extremely wide variety of processing forms, such as, for example, in the form of fibres, yarn, woven fabric or knitted fabric.
The present invention relates also to a method for the trichromatic dyeing or printing of hydroxy-group-containing or nitrogen-containing fibre materials, especially cellulosic fibre materials, which method comprises using at least one yellow dye, for example one, two or three dyes, preferably one dye, of the above-mentioned formula (1 ) and at least one yellow dye, for example one, two or three dyes, preferably one dye, of the above-mentioned formula (2), together with at least one red dye of the above-mentioned formula (3) and at least one blue dye of the above-mentioned formula (4).
The method according to the invention for trichromatic dyeing and printing can be carried out in accordance with customary dyeing and printing methods, for example, according to the so- called cold pad-batch process, in which the dye is applied, together with the alkali, on the padder and is then fixed by storage for several hours at about room temperature, for example, from 25 to 35°C. Preferably, the method according to the invention for trichromatic dyeing and printing is carried out according to the exhaust-dyeing method, in which the goods are impregnated with aqueous, optionally salt-containing dye solutions, and the dyes are fixed after an alkali treatment or in the presence of alkali, optionally under the action of heat.
The dye liquors or print pastes, in addition to containing water and the dyes, may also comprise further additives, for example shading dyes known per se, salts, buffer substances, wetting agents, anti-foams, levelling agents or agents that influence the properties of the textile material, for example, softeners, additives for flame-resistant finishes or dirt-, water- or oil-repellants, as well as water-softeners and natural or synthetic thickeners, e.g. alginates or cellulose ethers.
The amounts in which the individual dyes are used in the dyebaths or print pastes can vary within wide limits in dependence upon the desired depth of shade; in general, amounts of from 0.01 to 15% by weight, especially from 0.1 to 10% by weight, based on the goods being dyed or on the print paste, have proved advantageous.
The dyes of formulae (1 ), (2), (3), (4) and (8) used in the method according to the invention are distinguished in trichromatic dyeing or printing by uniform colour build-up, good exhaustion and fixing behaviour, good constancy of shade even in different concentrations, a low sensitivity to various dyeing parameters and, in particular, very good combinability. Dyeing times can be reduced. Furthermore, they have sufficient substantivity and at the same time have good ease of washing off of unfixed dye and can advantageously be applied at short liquor ratios, for example, at a liquor ratio of from 1 :4 to 1 :6, preferably, 1 :6. The dyeings and prints produced in accordance with the method of the invention exhibit very good fastness properties, such as wash and water fastness and perspiration fastness, and good reproducibility.
The following Examples serve to illustrate the invention. Unless otherwise indicated, temperatures are given in degrees Celsius, parts are parts by weight and percentages relate to percent by weight. Parts by weight relate to parts by volume in a ratio of kilograms to litres.
Example 1 :
A bleached cotton tricot fabric is introduced at 60°C into an aqueous dyebath with a liquor ratio of 1 :10 which contains 72 g/l of sodium chloride, 0.541 % by weight of the yellow dyeing reactive dye of formula (201 ), 0.361 % by weight of the yellow dyeing reactive dye of formula (101 ), 0.276 % by weight of the red dyeing reactive dye of formula (301 ), 0.413 % by weight of the red dyeing reactive dye of formula (302), 0.618 % by weight of the blue dyeing reactive dye of formula (801 ) and 0.412 % by weight of the blue dyeing reactive dye of formula (401 ). A total of 15.2 g/l of calcined sodium carbonate is added in 4 portions (1 .52 g/l, 3.04 g/l, 3.04 g/l and 7.6 g/l, respectively) to the dyebath after 45, 50, 55 and 60 minutes at 60°C. Dyeing is continued for 35 minutes. The dyed fabric is taken out of the dyeing liquor and dried. A brown shaded fabric is obtained.
The evolution of the shade during the dyeing steps (exhaustion and fixation) is monitored by measuring the h coordinates (CIELab sysystem) from the remission curves of the respective samples (spectrophotometer Datacolor SF 600). Independent from reaction parameters like dyeing time, temperature, amount of salt or alkali, the measured shade values vary within narrow limits, i.e. the dye mixture according to the invention allows a very good shade control.
Comparative Example 2:
A bleached cotton tricot (1 -4002/22) fabric is introduced at 60°C into an aqueous dyebath with a liquor ratio of 1 :10 which contains 78 g/l of sodium chloride, 0.90 % by weight of the yellow dyeing reactive dye of formula (201 ), 0.68 % by weight of the red dyeing reactive dye of formula (301 ) and 1 .29 % by weight of the blue dyeing reactive dye of formula (801 ). A total of 15.8 g/l of calcined sodium carbonate is added in 4 portions (1 .58 g/l, 3.16 g/l, 3.16 g/l and 7.9 g/l, respectively) to the dyebath after 45, 50, 55 and 60 minutes at 60°C. Dyeing is continued for 35 minutes. The dyed fabric is taken out of the dyeing liquor and dried. A brown shaded fabric is obtained.
The evolution of the shade during the dyeing steps (exhaustion and fixation) is monitored by measuring the h coordinates (CIELab sysystem) from the remission curves of the respective samples (spectrophotometer Datacolor SF 600). Depending on reaction parameters like dyeing time, temperature, amount of salt or alkali, the measured shade values vary within a considerable range.

Claims

What is claimed is:
1 . A dye mixture, comprising at least one yellow dye of the formula
Figure imgf000020_0001
wherein Ar-ι represents a benzene or naphthalene radical,
Xi is chlorine or fluorine,
Ri is amino or CrC6alkyl,
R2, R3, R4, R5, R6 and R7 each independently of the others represent hydrogen, hydroxy, amino, CrC6alkyl, d-C6alkoxy or sulfo,
u is a number from 1 to 3,
Y is vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions; at least one yellow dye of the formula
Figure imgf000020_0002
wherein Ar2 represents a benzene or naphthalene radical,
X2, and X3 independently of the other are chlorine or fluorine,
B denotes a straight-chain or branched C2-C6alkylene radical which is unsubstituted or substituted by hydroxy, sulfo or sulfato,
R8, Rg, R10 and Rn each independently of the others represent hydrogen or CrC6alkyl which is unsubstituted or substituted by hydroxy, amino, cyano, halogen, CrC6alkoxy,
CrC6alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato,
R12 and Ri3, denote amino or CrC6alkyl,
Ri4, Ri5 and Ri6 each independently of the others are hydrogen, hydroxy, amino, CrC6alkyl, CrC6alkoxy or sulfo, v is a number from 1 to 3;
at least one red dye of the formula
Figure imgf000021_0001
wherein Ar3 represents a benzene or naphthalene radical,
X4 denotes halogen, 3-carboxypyridin-1 -yl or 3-carbamoylpyridin-1 -yl,
Ri7 is hydrogen or CrC6alkyl,
R18 represents hydrogen, CrC6alkyl, d-C6alkoxy or sulfo,
Zi is hydrogen or a fibre-reactive group of the formula
S02-Y2, (7a) NH-CO-(CH2)2. (7b),
Y-i , Y2 and Y3 each independently of the others denote vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, and
k is a number from 1 to 3;
and at least one blue dye of the formula
Figure imgf000021_0002
wherein (R19)b denotes b identical or different substituents from the group CrC6alkyl, CrC6alkoxy, sulfo and halogen,
X5 is halogen,
Z2 is a fibre-reactive radical of formula
-S02-Y4 (5a),
-NH-CO-(CH2)m-S02- Y5 (5b),
-CONH-(CH2)n-S02- Y6 (5c),
-NH-CO-CH(Hal)-CH2-Hal (5d), -NH-CO-C(Hal)=CH2 (5e) or
Figure imgf000022_0001
wherein T2 is halogen, a non-fibre-reactive substituent or a fibre-reactive radical of formula -N H-(CH2)2-3-S02-Y7 (6a), -N H-(CH2)2-3-0-(CH2)2-3-S02-Y8 (6b),
Figure imgf000022_0002
(R2o)o-2 denotes from 0 to 2 identical or different substituents from the group halogen, CrC6-alkyl, d-C6alkoxy and sulfo,
Y4, Y5, Υβ, Y7, Υβ, ΥΘ and Υ10 each independently of the others denote vinyl or a -CH2-CH2-U radical and U is a group that is removable under alkaline conditions,
Q is a -CH(Hal)-CH2-Hal or -C(Hal)=CH2 group,
m and n are each independently of the other the number 2, 3 or 4 and
Hal is halogen,
ΤΊ is a fibre-reactive radical of the above formula (6b), (6c), (6d) or (6e) and
b and a are each independently of the other the number 0, 1 or 2.
2. A dye mixture according to claim 1 , wherein the dye of the formula (1 ) corresponds to the compound of the formula
Figure imgf000023_0001
3. A dye mixture according to claim 1 or 2, wherein the dye of the formula (2) corresponds to the c
Figure imgf000023_0002
4. A dye mixture according to any of the preceding claims, wherein the dye of the formula (3) corresponds to the compound of the formula
Figure imgf000023_0003
5. A dye mixture according to any of the preceding claims, wherein the dye of the formula (3) corresponds to the compound of the formula
Figure imgf000023_0004
6. A dye mixture according to any of the preceding claims, wherein the dye of the formula (4) corresponds to the compound of the formula
Figure imgf000024_0001
7. A dye mixture according to any of the preceding claims additionally containing a blue dye of the formula
Figure imgf000024_0002
wherein Z3 is a fibre-reactive radical of formula (5a), (5b), (5c), (5d), (5e) or (5f) as defined in claim 1 .
8. A dye mixture according to any of the preceding claims containing a dye of formula (101 ) as defined in claim 2 and a dye of formula (201 ) as defined in claim 3 in a weight ratio from 4 : 1 to 1 : 4.
9. A dye mixture according to any of the preceding claims containing a dye of formula (301 ) as defined in claim 4 and a dye of formula (302) as defined in claim 5 in a weight ratio from 4 : 1 to 1 : 4.
10. A dye mixture according to any of the preceding claims containing a dye of formula (401 ) as defined in claim 6 and a dye of formula
Figure imgf000025_0001
in a weight ratio from 4 : 1 to 1 : 4.
1 1 . A trichromatic dye mixture comprising as yellow component a mixture of a dye of formula (101 ) and a dye of formula (201 ) as defined in claim 8, as red component a mixture of a dye of formula (301 ) and a dye of formula (302) as defined in claim 9 and as blue component a mixture of a dye of formula (401 ) and a dye of formula (801 ) as defined in claim 10.
12. A method for the trichromatic dyeing or printing of hydroxy-group-containing or nitrogen- containing fibre materials, which method comprises using at least one yellow dye of the formula
Figure imgf000025_0002
wherein Ar-ι represents a benzene or naphthalene radical,
Xi is chlorine or fluorine,
Ri is amino or CrC6alkyl,
R2, R3, R4, R5, R6 and R7 each independently of the others represent hydrogen, hydroxy, amino, CrC6alkyl, d-C6alkoxy or sulfo,
u is a number from 1 to 3,
Y is vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions; at least one yellow dye of the formula
Figure imgf000026_0001
wherein Ar2 represents a benzene or naphthalene radical,
X2, and X3 independently of the other are chlorine or fluorine,
B denotes ethylene, propylene, trimethylene, tetramethylene, pentamethylene or
hexamethylene,
R8, Rg, R-io and Rn each independently of the others represent hydrogen or CrC6alkyl which is unsubstituted or substituted by hydroxy, amino, cyano, halogen, CrC6alkoxy,
CrC6alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato,
Ri2, Ri3, Ri4, Ri5 and Ri6 each independently of the others are hydrogen, hydroxy, amino,
CrC6alkyl, d-C6alkoxy or sulfo,
v is a number from 1 to 3;
at least one red dye of the formula
Figure imgf000026_0002
wherein Ar3 represents a benzene or naphthalene radical,
X4 denotes halogen, 3-carboxypyridin-1 -yl or 3-carbamoylpyridin-1 -yl,
Ri7 is hydrogen or CrC6alkyl,
R18 represents hydrogen, CrC6alkyl, CrC6alkoxy or sulfo,
Zi is hydrogen or a fibre-reactive group of the formula
-S02-Y2, (7a) or -NH-CO-(CH2)2-3-S02-Y3 (7b),
Y-i , Y2 and Y3 each independently of the others denote vinyl or a radical -CH2-CH2-U and U is a group removable under alkaline conditions, and
k is a number from 1 to 3; at least one blue dye of the formula
Figure imgf000027_0001
wherein (Ri9)b denotes b identical or different substituents from the group CrC6alkyl, CrC6alkoxy, sulfo and halogen,
X5 is halogen,
Z2 is a fibre-reactive radical of formula
Figure imgf000027_0002
-NH-CO-(CH2)m-S02- Y5 (5b), -CONH-(CH2)n-S02- Y6 (5c), -NH-CO-CH(Hal)-CH2-Hal (5d), -NH-CO-C(Hal)=CH2 (5e) or
Figure imgf000027_0003
wherein T2 is halogen, a non-fibre-reactive substituent or a fibre-reactive radical of formula -NH-(CH2)2.3-S02-Y7 (6a), -NH-(CH2)2.3-0-(CH2)2-3-S02-Y8 (6b),
Figure imgf000027_0004
(R2o)o-2 denotes from 0 to 2 identical or different substituents from the group halogen, CrC6-alkyl, d-C6alkoxy and sulfo,
Y4, Υδ, Υβ, Y7, Υβ, ΥΘ and Υι0 each independently of the others denote vinyl or a -CH2-CH2-U radical and U is a group that is removable under alkaline conditions,
Q is a -CH(Hal)-CH2-Hal or -C(Hal)=CH2 group,
m and n are each independently of the other the number 2, 3 or 4 and
Hal is halogen,
ΤΊ is a fibre-reactive radical of the above formula (6b), (6c), (6d) or (6e) and
b and a are each independently of the other the number 0, 1 or 2.
13. A method according to claim 12, wherein cellulosic fibre material, especially cotton- containing fibre material, is dyed or printed.
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