EP2118214A2

EP2118214A2 - Mixtures of fibre-reactive azo dyes

Info

Publication number: EP2118214A2
Application number: EP08708240A
Authority: EP
Inventors: Stefan Ehrenberg; Stefan Meier; Christian Schumacher
Original assignee: Dystar Textilfarben GmbH and Co Deutschland KG
Current assignee: Dystar Colours Distribution GmbH
Priority date: 2007-02-06
Filing date: 2008-01-28
Publication date: 2009-11-18
Also published as: CA2677474A1; CN101595186A; MX2009008335A; TW200848474A; US20090320217A1; WO2008095802A3; DOP2009000185A; WO2008095802A2; KR20090122187A; DE102007005795A1; JP2010520926A; BRPI0807130A2

Abstract

The invention relates to one or more dyes of general formula (I) and one or more dyes of general formula (II), where D1, D2, D3 RA, RB, RC, Z1 and M have the meanings given in claim 1 and a method for production and use thereof.

Description

DyStar Textile dyes GmbH & Co. Germany KG 2007 / D502Ausl Dr. med. My

Mixtures of fiber-reactive azo dyes

The invention is in the technical field of fiber-reactive azo dyes.

Dye mixtures of fiber-reactive azo dyes and their use for dyeing hydroxy- and carbonamido-group-containing materials in golden yellow to orange shades are known, for example, from EP 1 000 982 A2 and from CN 1861695 A. However, these have certain application-related deficiencies, such as a not yet sufficient color structure at low dye concentrations, which ultimately affects the economics of the dyeing process. As a result, there is still a need for new reactive dyes or reactive dye mixtures having improved properties, such as steep color structure with good fastness properties. In addition, they must also have good dyeing yields and have a high reactivity, in particular dyeings with high degrees of fixation to be delivered.

With the present invention dye mixtures have now been found which have these properties described above in a high degree. The new dye mixtures are characterized mainly by high Fixierausbeuten and easy leachability of not fixed to the fiber fractions. In addition, the dyeings have good fastness properties, such as high light fastness and very good wet fastness.

The invention relates to dye mixtures which contain one or more dyes of the general formula (I) and one or more dyes of the general formulas (II)

in which D ¹ , D ² and D ³ independently of one another represent a group of the general formula (III)

stand in which

R ¹ and R ² independently of one another are hydrogen, (C ₁ -CO-Al kVl, (C ₁ -C ₄ ) -alkoxy,

Hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; and

X ^{1 is} hydrogen, sulfo, a group of the formula -SO ₂ -Z ² , wherein

Z ^{2 is} -CH = CH ₂ or -CH ₂ CH ₂ Z ³ and

Z ^{3 is} hydroxy or an alkali cleavable group; or for a group of the formula (IV)

stands; or in which

D ¹ , D ² and D ³ independently of one another represent a group of the general formula (V) wherein

R ³ and R ^{4 are} independently hydrogen, (C _r C ₄ ) alkyl, (C _r C ₄ ) alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halo; and X ^{2 has} one of the meanings of X ¹ ;

or in which

D ¹ , D ² and D ^{3 are} independently of one another a group of the general formula (VI)

stand in which

R ⁵ and R ⁶ independently of one another have one of the meanings of R ¹ ; R ^{7 is} hydrogen, (C _r C ₄ ) alkyl, unsubstituted or substituted by (C _r C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, sulfo, halogen or carboxy-substituted phenyl; and Z ^{4 represents} a group of the general formula (VII), (VIII) or (IX)

stands; wherein

V is fluorine or chlorine;

Mean U ¹ and U ² are independently fluorine, chlorine or hydrogen; and Q ¹ and Q ² are independently chlorine, fluorine, cyanamido, hydroxyl, (C ₁ -C ₆₎ - alkoxy, phenoxy, sulfophenoxy, mercapto, (CrCeJ-alkylmercapto , Pyridino,

Carboxypyridino, carbamoylpyridino or a group of the general formula (X) or (Xl) _R ⁸ , R ⁹

W VV-S SOU ₂ Z ^ ⁵ _(χ) ^S DR ¹⁰ _{(χ |)}

mean, in which

R ^{8 is} hydrogen, (C _r C ₆ ) alkyl, sulfo (C _r C ₆ ) alkyl, phenyl or by (C _r C ₄ ) alkyl, (Ci-C ₄ ) alkoxy, hydroxy, sulfo, halogen , Carboxy, acetamido, ureido substituted phenyl;

R ⁹ and R ¹⁰ independently of one another have one of the meanings of R ⁸ or together represent a group of the formula - (CH ₂ ) _r or the formula - (CH ₂ ) 2-E- (CH ₂ ) 2-, where j is 4 or 5, E is oxygen, sulfur, sulfonyl or -NR ¹¹ and R ^{11 is} (C ₁ -C ₆ ) -alkyl; W is phenylene, by 1 or 2 substituents from the series (C _r _C4) alkyl, (C ₁ -C ₄₎ - alkoxy, carboxy, sulfo, chlorine and bromine-substituted phenylene, (C _r _C4) alkylene- phenylene, (C ₂ -C ₆₎ alkylene which is interrupted by oxygen, sulfur, sulfonyl, amino, carbonyl or carbonamido, (C ₂ -C ₆₎ -alkylene, phenylene-CONH-phenylene, (by 1 or 2 substituents from the series C _r C ₄₎ alkyl, (C _r C ₄₎ -alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido and halogen substituted phenylene-CONH- phenylene, naphthylene or is substituted by one or two sulfo groups naphthylene; and Z ^{5 has} one of the meanings of Z ² ;

or in which

D ¹ , D ² and D ³ independently of one another represent a group of the general formula (XII)

stand in which

R ^{12 is} hydrogen, (C 1 -C ₄ ) -alkyl, aryl or substituted aryl;

R ¹³ and R ^{14 are} independently hydrogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; and A for a group of the general formula (XIII)

stands in which

R ¹⁵ and R ¹⁶ independently of one another are hydrogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen; or A is a group of the general formula (XIV)

stands in which

R ¹⁷ and R ¹⁸ independently of one another are hydrogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen; or

A for a group of the general formula (XV) where k is an integer greater than 1; R ¹⁹ and R ²⁰ independently of one another are hydrogen, (C _r C ₄ ) -alkyl, (C ₁ -CO-alkoxy,

Hydroxy, cyano, amido, halo or aryl; and

X ^{3 has} one of the meanings of X ¹ ;

R ^{A is} hydrogen or a group of general formula (XVII) -CH ₂ -SO ₃ M (XVII);

R ^{B is} acetamido, ureido, methyl, methoxy or a group of general formula (XVIII)

(XVIII) in which

Q ³ and Q ⁴ independently of one another are one of the meanings of Q ¹ ; R ^{c is} hydrogen, methyl, methoxy or sulfo; Z ^{1 has} one of the meanings of Z ⁴ ; and

M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal; where the dyes of the general formulas (I) and (II) contain at least one fiber-reactive group of the formula -SO ₂ Z ² or Z ⁴ or of the formula (XVIII) or Z ¹ , and where compounds of the formula (A)

wherein

D ^{4 represents} a group of the formula (B) or (C)

stands in which

E ^A ( _0-3 ) ^{ur |} d F_ ^B _(0- 3) are the same or different and are 0 to 3 groups selected from hydrogen, -SO ₃ M, -OH, -COOM, -F, -Cl, -Br, (dC ₄₎ alkyl or

(C _r C ₄ ) alkoxy; p and q are a number from 0 to 2;

Z ^A and Z ^{B are} a group of the formula (Da), (Db), (Dc) or (Dd),

-SO ₂ -Y ^A (Da) -CONH- (CH ₂ ) _r -SO ₂ -Y ^A (Db) -NHCONH (Hal) CH ₂ Hal (Dc) -NHCOCH (Hal) = CH ₂ (Dd) r a Number from O to 5;

Hal halogen;

Y ^{A is} vinyl, β-chloroethyl, β-bromoethyl, β-acetylethyl, β-sulfatoethyl, β-phenoxyethyl, β-phosphatoethyl or a -CH ₂ -CH ₂ -U group; U is a group which can be split off under the action of alkali; and M is defined as above; at most in an amount of 1% by weight, based on the total colorant content. (C _r C ₄₎ alkyl groups may be straight or branched and is especially methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl. Preferred are methyl and ethyl. The same applies to (C 1 -C ₄ ) -alkoxy groups, which are therefore preferably methoxy and ethoxy. The same applies analogously to alkylene groups, which stand in particular for etylene, propylene and butylene. Aryl is in particular phenyl or naphthyl, preferably phenyl. Substituted aryl preferably has one, two or three independent substituents selected from the group consisting of (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxy, hydroxyl, sulfo, carboxy, amido and halogen. Halogen is especially fluorine, chlorine and bromine, with fluorine and chlorine being preferred.

In particular, lithium, sodium and potassium are those which stand for M; an equivalent of an alkaline earth metal for M is in particular the equivalent of calcium. M is preferably hydrogen or sodium.

For Z ³ standing under alkali action cleavable groups are for example halogen atoms, such as chlorine and bromine, ester groups of organic carboxylic and sulfonic acids, for example alkylcarboxylic acids, optionally substituted benzene and optionally substituted benzenesulfonic, especially alkanoyloxy of 2 to 5 carbon atoms such as acetyloxy, and benzoyloxy, Sulfobenzoyloxy, phenylsulfonyloxy and toluenesulfonyloxy, further acidic ester groups of inorganic acids, such as phosphoric acid, sulfuric acid and thiosulfuric acid (phosphato, sulfato and thiosulfato), as well dialkylamino groups with alkyl groups of 1 to 4 carbon atoms, such as dimethylamino and diethylamino.

Z ³ is preferably vinyl, β-chloroethyl and particularly preferably β-sulfatoethyl.

The groups "sulfo", "carboxy", "thiosulfato", "phosphato", and "sulfato" include both their acid form and their salt form, accordingly corresponding to sulfo groups of the general formula -SO ₃ M, thiosulfato groups of the general formula -S- SO ₃ M, carboxy groups of the general formula -COOM, phosphato groups, groups of the general formula -OPO ₃ M ₂ and sulphato groups of the general formula -OSO ₃ M, where M is in each case as defined above. Insofar as the dyes of the general formulas (I) and (II) have fiber-reactive groups -SO ₂ Z ² or -SO ₂ Z ⁵ , these may be present partly as vinylsulfonyl groups and partly as -CH ₂ CH ₂ Z ³ , preferably as β-sulfatoethylsulfonyl Groups, are present. The proportion of the particular dye with the vinylsulfonyl group is in particular up to about 30 mol%, based on the respective total amount of dye.

The radicals R ¹ and R ² are preferably hydrogen, (C _r _C4) alkyl, (C _r _C4) -alkoxy, sulfo or carboxyl, and particularly preferably hydrogen, methyl, methoxy or sulfo.

The radicals R ³ to R ⁶ and R ¹² to R ²⁰ are preferably hydrogen, R ³ to R ⁶ , R ¹⁷ and R ¹⁸ are also preferably sulfo.

The radicals R ⁷ to R ¹⁰ are preferably hydrogen or methyl, R ⁷ and R ⁸ are also preferably phenyl and R ⁹ and R ¹⁰ also preferably 2-sulfoethyl, 2-, 3- or 4-sulfophenyl. In addition, R ⁹ and R ^{10 are} preferably together - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -. The radicals R ^A and R ^c are preferably hydrogen, while the radical R ^{B is} preferably acetamido or ureido.

Accordingly, preferred dye mixtures according to the invention are those in which

R ¹ and R ^{2 are} hydrogen, methyl, methoxy or sulfo; R ³ to R ^{6 are} hydrogen or sulfo;

R ⁷ and R ^{8 are} hydrogen or phenyl;

R ⁹ and R ^{10 are} hydrogen, 2-sulfoethyl, 2-, 3- or 4-sulfophenyl or together -

(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -;

R ^{11 is} hydrogen or methyl; R ¹² to R ¹⁶ , R ¹⁹ , R ²⁰ , R ^A and R ^{c are} hydrogen;

R ¹⁷ and R ^{18 are} hydrogen or sulfo; and

R ^{B means} acetamido or ureido. If in the group of the general formula (IM) X ^{1 is} -SO ₂ Z ² , this is preferably in the meta or para position to the diazo group.

In the group of the general formula (V), the bond which leads to the diazo group is preferably bonded to the naphthalene nucleus in the β-position. Preferred groups of the general formula (IM) and (V) are 4-sulfophenyl, 2,4-disulfophenyl, 2,5-disulfophenyl, 4,8-disulfo-naphth-2-yl, 6,8-disulfo-naphth-2 -yl, 1,5-disulfo-naphth-2-yl, 4,6,8-trisulfo-naphth-2-yl, 3,6,8-trisulfo-naphth-2-yl, 2- (β-sulfatoethylsulfonyl) -phenyl , 2-sulfo-4- (4-sulfo-phenylazo) -phenyl, 3- (β-sulfatoethylsulfonyl) -phenyl, 4- (β-sulfatoethyl-sulfonyl) -phenyl, 2-carboxy-5- (β-sulfatoethylsulfonyl) -phenyl , 2-chloro-4- (β-sulfato-ethylsulfonyl) -phenyl, 2-chloro-5- (β-sulfatoethylsulfonyl) -phenyl, 2-bromo-4- (β-sulfato-ethylsulfonyl) -phenyl, 2-sulfo -4- (β-sulfatoethylsulfonyl) -phenyl, 2-sulfo-5- (β-sulfato-ethylsulfonyl) -phenyl, 2-methoxy-5- (β-sulfatoethylsulfonyl) -phenyl, 2-ethoxy-5- (β- sulfatoethylsulfonyl) -phenyl, 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) -phenyl, 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) -phenyl, 2-methyl-4- (β-sulfatoethyl- sulfonyl) -phenyl, 2- or 3- or 4- (β-thiosulfatoethylsulfonyl) -phenyl, 2-methoxy-5- (β-thiosulfatoethylsulfone yl) -phenyl, 2-sulfo-4- (β-phosphatoethylsulfonyl) -phenyl, 2- or 3- or 4-vinylsulfonyl-phenyl, 2-sulfo-4-vinylsulfonyl-phenyl, 2-chloro-4- (β- chloroethylsulfonyl) -phenyl, 2-chloro-5- (β-chloroethylsulfonyl) -phenyl, 3- or 4- (β-acetoxyethylsulfonyl) -phenyl, 6- or 8- (β-sulfatoethylsulfonyl) -naphth-2-yl, 6 (β-sulfatoethylsulfonyl) -1-sulfonaphth-2-yl and 8- (β-sulfatoethylsulfonyl) -6-sulfonaphth-2-yl, of which preference is given to 3- (β-sulfatoethylsulfonyl) -phenyl, (β-sulfatoethylsulfonyl) -phenyl, 2-sulfo-4- (β-sulfatoethylsulfonyl) -phenyl, 2-methoxy-5- (β-sulfatoethylsulfonyl) -phenyl, 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) - phenyl, 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) -phenyl and 3- or 4-vinylsulfonyl-phenyl.

In the group of the general formula (X), W preferably denotes 1, 3-phenylene, 1,4-phenylene, 2-sulfo-1, 4-phenylene, 2-methoxy-1, 5-phenylene, 2,5-dimethoxy 1, 4-phenylene, 2-methoxy-5-methyl-1, 4-phenylene, 1, 2-ethylene or 1, 3-propylene.

Preferred examples of the groups Q ¹ and Q ² or Q ³ and Q ⁴ are independently fluorine, chlorine, hydroxyl, methoxy, ethoxy, phenoxy, 3-sulfophenoxy, 4-sulfophenoxy, methylmercapto, cyanamido, amino, methylamino, ethylamino, morpholino, piperidino, phenylamino, methylphenyl-amino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 2,4-disulfophenylamino, 2,5-disulfophenylamino, 2-sulfoethylamino, N-methyl-2-sulfoethylamino, pyridino, 3-carboxypyridino, 4-carboxypyridino, 3-carbamoylpyridino, 4-carbamoyl-pyridino, 2- (2-sulfatoethylsulfonyl) -phenylamino, 3- (2-sulfatoethylsulfonyl) - phenylamino, A- (2-sulfatoethyl-

sulfonyl) -phenylamino, N-ethyl-3- (2-sulfatoethylsulfonyl) -phenylamino, N-ethyl-4- (2-sulfatoethylsulfonyl) -phenylamino, 2-carboxy-5- (2-sulfatoethyl-sulfonyl) -phenylamino ), 2-chloro-4- (2-sulfatoethylsulfonyl) -phenylamino, 2-chloro-5- (2-sulfatoethylsulfonyl) -phenylamino, 2-bromo-4- (2-sulfatoethylsulfonyl) -phenylamino, 2- Sulfo-4- (2-sulfatoethylsulfonyl) -phenyl-amino, 2-sulfo-5- (2-sulfatoethylsulfonyl) -phenylamino, 2-methoxy-5- (2-sulfato-ethylsulfonyl) -phenylamino, 2.5- Dimethoxy-4- (2-sulfatoethylsulfonyl) -phenyl-amino, 2-methoxy-5-methyl-4- (2-sulfatoethylsulfonyl) -phenylamino, 2-methyl-4- (2-sulfatoethylsulfonyl) -phenylamino, 2- (Vinylsulfonyl) -phenylamino, 3- (vinylsulfonyl) -phenylamino, 4- (vinylsulfonyl) -phenylamino), N-ethyl-3- (vinylsulfonyl) -phenylamino, N-ethyl-4- (vinylsulfonyl) -phenylamino, 6 - (2-sulfatoethylsulfonyl) -naphth-2-ylamino, 8- (2-sulfatoethylsulfonyl) -naphth-2-ylamino, 8- (2-sulfatoethylsulfonyl) -6-sulfonaphth-2-ylamino, 3 - (2- (2-sulfatoethylsulfonyl) ethyl car bamoyl) -phenylamino, 4- (2- (2-sulfatoethylsulfonyl) -ethylcarbamoyl) -phenyl-amino, 3- (2- (vinylsulfonyl) -ethylcarbamoyl) -phenylamino, 4- (2- (2-vinylsulfonyl) - ethylcarbamoyl) -phenylamino, 4- (N-methyl-2- (2-sulfatoethylsulfonyl) -ethyl-carbamoyl) -phenylamino, 4- (N-phenyl-2- (2-sulfatoethylsulfonyl) -ethylcarbamoyl) -phenylamino, 4- ( 3- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 4- (4- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 3- (3- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino , 3- (4- (2-sulfatoethylsulfonyl) -phenyl-carbamoyl) -phenylamino, 3- (2-sulfatoethylsulfonyl) -propylamino, N-methyl-N- (2- (2-sulfatoethylsulfonyl) -ethyl) -amino, N -Phenyl-N- (2- (2-sulfato-ethylsulfonyl) -ethyl) -amino, N-phenyl-N- (2- (2-sulfatoethylsulfonyl) -propyl) -amino and 2- [2- (2-chloro -ethylsulfonyl) -ethoxy] -ethylamino. In particular, Q ¹ and Q ² for fluorine or chlorine and Q ³ and Q ⁴ have one of the other meanings mentioned here.

Particularly preferably, the groups Q ¹ and Q ² or Q ³ and Q ⁴ independently of one another are fluorine, chlorine, cyanamido, morpholino, 2-sulfophenylamino, 3

Sulfo-phenylamino, 4-sulfophenylamino, N-methyl-2-sulfoethylamino, 3-carboxypyridino, 4-carboxypyridino, 3-carbamoylpyridino, 4-carbamoylpyridino, 3- (2-sulfatoethyl-sulfonyl) -phenylamino, 4- (2-sulfatoethylsulfonyl ) -phenylamino, 3- (vinylsulfonyl) -phenylamino, 4- (vinylsulfonyl) -phenylamino), 4- (3- (2-sulfatoethylsulfonyl) -phenyl-carbamoyl) -phenylamino, 4- (4- (2-sulfatoethylsulfonyl ) - phenylcarbamoyl) -phenyl-amino, 3- (3- (2-sulfatoethylsulfonyl) -phenylcarbamoyl) -phenylamino, 3- (4- (2-sulfatoethylsulfonyl) -phenylcarbamoyl) -phenylamino, N-methyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino, N-phenyl-N- (2- (2-sulfatoethylsulfonyl) -ethyl) -amino or 2- [2- (2-chloro-ethylsulfonyl) -ethoxy] ethylamino.

In particular, Q ¹ and Q ^{2 are} fluorine or chlorine and Q ³ and Q ⁴ have one of the other meanings mentioned here.

Very particularly preferably, the groups Q ¹ and Q ² or Q ³ and Q ⁴ independently of one another are fluorine, chlorine, cyanamido, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 3- (2-sulfatoethylsulfonyl) -phenylamino, 4- (2-sulfatoethylsulfonyl) -phenylamino, 3- (vinylsulfonyl) -phenylamino, 4- (vinylsulfonyl) -phenylamino), N -methyl-N- (2- (2-sulfatoethylsulfonyl) -ethyl) -amino, N-phenyl-N- (2- (2-sulfatoethylsulfonyl) -ethyl) -amino or 2- [2- (2-chloro-ethylsulfonyl) -ethoxy] -ethylamino. In particular, Q ¹ and Q ^{2 are} fluorine or chlorine and Q ³ and Q ⁴ have one of the other meanings mentioned here.

The groups Z ¹ and Z ⁴ preferably denote 2,4-difluoropyrimidin-6-yl, 4,6-difluoropyrimidin-2-yl, 5-chloro-2,4-difluoro-pyrimidin-6-yl, 5 Chloro-4,6-difluoro-pyrimidin-2-yl, 4,5-difluoro-pyrimidin-6-yl, 5-chloro-4-fluoro-pyrimidin-6-yl, 2,4,5-trichloro-pyrimidine -6-yl, 4,5-dichloro-pyrimidin-6-yl, 2,4-dichloro-pyrimidin-6-yl, 4-fluoro-pyrimidin-6-yl or 4-chloro-pytimidin-6-yl or the group of the general formula (VIII) having the preferred meanings given above for Q ¹ and Q ² .

The groups Z ¹ and Z ⁴ particularly preferably represent 2,4-difluoropyrimidin-6-yl, 4,6-difluoropyrimidin-2-yl, 5-chloro-2,4-difluoropyrimidin-6-yl or 5-chloro-4,6-difluoro-pyrimidin-2-yl or the group of the general formula (VIII) having the abovementioned particularly preferred meanings for Q ¹ and Q ² .

Very particularly preferably, the groups Z ¹ and Z ^{2 are} 2,4-difluoropyrimidin-6-yl or 5-chloro-2,4-difluoro-pyrimidin-6-yl or the group of the general formula (VIII) having the above very particular preferred meanings for Q ¹ and Q ² .

In the group of the general formula (XII), the carbonamide group is preferably in para or meta position to the diazo group. In the case where A is phenylene and X ^{3 is} -SO ² Z ² , the -SO ² Z ² group is preferably in the meta or para position to the nitrogen atom. In the case where A is naphthylene, the bond leading to the nitrogen atom is preferably bonded to the naphthalene nucleus in the β-position. Preferred examples of substituents standing for A are 1, 2-phenylene, 1, 3

Phenylene, 1, 4-phenylene, 2-chloro, 4-phenylene, 2-chloro-1, 5-phenylene, 2-bromo-1, 4-phenylene, 2-sulfo-1, 4-phenylene, 2-sulfo 1, 5-phenylene, 2-methoxy-1, 5-phenylene, 2-ethoxy-1, 5-phenylene, 2,5-dimethoxy-1, 4-phenylene, 2-methoxy-5-methyl-1, 4- phenylene, 2-methyl-1, 4-phenylene, 2,6-naphthylene, 2,8-naphthylene, 1-sulfo-2,6-naphthylene, 6-sulfo-2,8-naphthylene or 1, 2-ethylene and 1, 3-propylene.

A particularly preferably represents 1, 3-phenylene, 1, 4-phenylene, 2-sulfo-1, 4-phenylene, 2-methoxy-1, 5-phenylene, 2,5-dimethoxy-1, 4-phenylene, 2 -Methoxy-5-methyl-1, 4-phenylene, 1, 2-ethylene or 1, 3-propylene, wherein in the case of the two last-mentioned alkylene groups, the radical R ^{12 is} preferably phenyl and 2-sulfophenyl.

If A is a group of the general formula (XV), k is preferably the number 2 or 3. D ¹ and D ² preferably represent a group of the general formula (III) or (VI), the group of the general formula (III) being particularly preferred. In very particularly preferred dye mixtures according to the invention, D ¹ and D ^{2 have} the abovementioned preferred meanings.

D ³ is preferably a group of the general formula (V), particularly preferably a group of the general formula (V) in which R ³ , R ⁴ and X ^{2 are} hydrogen or sulfo.

Z ¹ preferably represents a group of the general formula (VIII) in which Q ¹ and Q ^{2 have} the abovementioned preferred meanings. In particular, Q ^{1 is} fluorine or chlorine and C 2 H has one of the other preferred meanings. Z ¹ particularly preferably represents a group of the general formula (VIII) in which Q ^{1 is} fluorine or chlorine and Q ^{2 is} cyanamido, morpholino, 2-sulfophenyl-amino, 3-sulfophenylamino, 4-sulfophenylamino, N-methyl-2 sulfoethylamino, 3

Carboxypyridino, 4-carboxypyridino, 3-carbamoylpyridino, 4-carbamoylpyridino, 3- (2-sulfatoethylsulfonyl) -phenylamino, 4- (2-sulfatoethylsulfonyl) -phenylamino, 3- (vinylsulfonyl) -phenylamino, 4- (vinylsulfonyl) - phenylamino), 4- (3- (2-sulfatoethylsulfonyl) -phenyl-carbamoyl) -phenylamino, 4- (4- (2-sulfatoethylsulfonyl) -phenyl-carbamoyl) -phenyl-amino, 3- (3- (2 -Sulfatoethylsulfonyl) phenylcarbamoyl) - phenylamino, 3- (4- (2-sulfatoethylsulfonyl) phenylcarbamoyl) -phenylamino, N-methyl-N- (2- (2-sulfatoethyl-sulfonyl) -ethyl) -amino, N-phenyl -N- (2- (2-sulfatoethyl-sulfonyl) -ethyl) -amino, or 2- [2- (2-chloro-ethylsulfonyl) -ethoxy] -ethylamino. With very particular preference Z ¹ thus represents a group of the general formula (VIII) in which Q ^{1 is} fluorine or chlorine and Q ^{2 is} cyanamido, morpholino, 2-

Sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 3- (2-sulfatoethylsulfonyl) -phenylamino, 4- (2-sulfatoethylsulfonyl) -phenylamino, 3- (vinylsulfonyl) -phenylamino, 4- (vinylsulfonyl) - phenylamino), N-methyl-N- (2- (2-sulfatoethylsulfonyl) -ethyl) -amino, N-phenyl-N- (2- (2-sulfatoethylsulfonyl) -ethyl) -amino, or 2- [2- (2- 2-chloroethylsulfonyl) -ethoxy] -ethylamino. Particularly preferred dye mixtures according to the invention contain one or more dyes of the general formula (Ia)

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

R ^1a , R ^1b , R ^2a and R ^2b are each independently hydrogen, methyl, methoxy or sulfo;

Z ² and Z ₅ independently of one another are vinyl or β-sulfatoethyl; and D ³ , R ^B , R ^c and M are as defined above.

The dye mixtures according to the invention contain the dye or the dyes of the general formula (I) in an amount of 1 to 99 wt .-%, preferably 10 to 90 wt .-% and the dye or dyes of the general formula (II) in an amount of 1 to 99 wt .-%, preferably 10 to 90 wt .-%, each based on the total amount of dye.

In preferred dye mixtures according to the invention, compounds of the formula (A) are present in an amount of 0.5% by weight, based on the total dye content, while particularly preferred inventive compounds contain no compounds of the formula (A).

The dyes according to the invention can be present as a preparation in solid or in liquid (dissolved) form. In solid form they generally contain the usual in water-soluble and especially fiber-reactive dyes

Electrolyte salts, such as sodium chloride, potassium chloride and sodium sulfate, and may further contain the usual in commercial dyes aids, such as

Buffer substances capable of adjusting a pH between 3 and 7 in aqueous solution, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate, sodium tricitrate and disodium hydrogen phosphate, small amounts of siccatives or, if they are in liquid, aqueous solution (including the Content of thickening agents, as are customary in printing pastes), substances which ensure the durability of these preparations, such as, for example, mildewproofing agents.

In solid form, the dye mixtures according to the invention are generally in the form of electrolytic salt-containing powders or granules (hereinafter generally referred to as preparation) with, if appropriate, one or more of the abovementioned auxiliaries. In the preparations, the dye mixture to 20 to 90 wt .-%, based on the preparation contained. The buffer substances are generally present in a total amount of up to 5% by weight, based on the preparation.

If the dye mixtures according to the invention are present in aqueous solution, the total dye content in these solutions is up to about 50 wt .-%, such as between 5 and 50 wt .-%, while the electrolyte salt content is preferably below 10 wt .-%, based on the aqueous solution is. The aqueous solutions or liquid preparations can also contain buffer substances, generally in an amount of up to 5% by weight, preferably in amounts of from 0.1 to 2% by weight.

The dye mixtures according to the invention can be prepared by customary methods known to the person skilled in the art. For example, by mechanical mixing of the individual dyes, in the form of dye powders or granules or in the form of aqueous solutions, for example

Synthesis solutions, which may still contain conventional adjuvants may be present.

Alternatively, they can also be obtained in the desired proportions by diazotization and coupling reactions of suitable mixtures of diazo and coupling components which are familiar to the person skilled in the art.

Dye mixtures which, in addition to β-chloroethylsulfonyl or β-thiosulfatoethylsulfonyl or β-sulfatoethylsulfonyl groups, also have vinylsulfonyl groups as reactive radicals can be synthesized not only starting from correspondingly substituted vinylsulfonylanilines or naphthylamines, but also by reacting dye mixtures in which Z ^{3 is} .beta.-chloroethyl, .beta.-thio-sulfatoethyl or .beta.-sulfatoethyl, with an amount of alkali required for the desired proportion and conversion of said .beta.-substituted ethylsulphonyl groups into vinylsulphonyl groups. This transfer takes place in a manner familiar to the person skilled in the art.

The dyes of the general formula (I) are known and described in EP 0 785 237 A1. Dyes of the general formula (II) are also known and numerous described in the literature. Both dyes of the general formula (I) and dyes of the general formula (II) are accessible via standard synthesis methods known to the person skilled in the art.

The dye mixtures according to the invention have valuable performance properties and can be used for dyeing and printing materials containing carbonamide and / or hydroxyl groups. The materials mentioned can be present, for example, in the form of fabrics such as paper and leather, in the form of films, such as polyamide films or in the form of a composition, for example of polyamide or polyurethane.

In particular, however, they are in the form of fibers of the materials mentioned. Thus, the dye mixtures according to the invention are used for dyeing and printing cellulosic fiber materials of all kinds. Prefers They are also suitable for dyeing or printing polyamide fibers or blended fabrics made of polyamide with cotton or polyester fibers. It is also possible to use the dye mixtures of the invention to print textiles, paper or other materials by the inkjet process.

The present invention thus also relates to the use of the dye mixtures according to the invention for dyeing or printing carbonamide- and / or hydroxyl-containing materials or processes for dyeing or printing such materials in conventional procedures, in which one uses a dye mixture according to the invention as a colorant. The dye mixtures according to the invention provide on these materials, preferably fiber materials, orange to red colorations with very good fastness properties.

Advantageously, the resulting in the production of solutions of the dye mixtures according to the invention, optionally after addition of a buffer substance, optionally after concentration or dilution, can be supplied directly as a liquid preparation of the dyeing use.

For the purposes of the present invention, the term fiber materials or fibers is understood to mean, in particular, textile fibers which may be in the form of woven fabrics, yarns or in the form of strands or wound bodies.

Carbonamidgruppenhaltige materials are for example synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hair, silk, leather, polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4.

Hydroxy-containing materials are those of natural or synthetic origin such as cellulosic fiber materials or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton, but also other plant fibers, such as linen, hemp, jute and ramie fibers. Regenerated cellulose fibers are, for example, rayon and viscose rayon.

The dye mixtures according to the invention can be applied and fixed on the abovementioned materials, in particular on the fiber materials mentioned, according to the application techniques known for water-soluble, in particular, those known for fiber-reactive dyes.

On cellulose fibers are obtained by the exhaust process both from short, as well as from long liquor using a variety of acid-binding agents and optionally neutral salts, such as sodium chloride or sodium sulfate, dyeings with very good, color yields. Preferably, the extraction process at a pH of 3 to 7, in particular at a pH of 4 to 6 dyed. The liquor ratio can be chosen within a wide range and is for example between 1: 3 and 1: 100, preferably between 1: 5 and 1: 30. It is preferably dyed in an aqueous bath at temperatures between 40 and 105 ⁰ C, optionally at a temperature up to 130 ⁰ C under pressure, and optionally in the presence of conventional dyeing auxiliaries. To increase the wet fastness of the dyed material can be removed in a post-treatment unfixed dye. This aftertreatment is carried out in particular at a pH of 8 to 9 and at temperatures of 75 to 80 ^° C.

One can proceed in such a way that one brings the material into the warm bath and this gradually heats up to the desired temperature and the

Dyeing process leads to an end. If desired, the neutral salts which accelerate the removal of the dyes can also be added to the bath only after the actual dyeing temperature has been reached.

After the padding process, excellent color yields and a very good color composition are also obtained on cellulose fibers, it being possible to fix them in the usual way by lingering at room temperature or elevated temperature, for example up to about 60 ^° C., by steaming or with dry heat. Also according to the usual printing processes for cellulose fibers, the single-phase - for example by printing with a sodium bicarbonate or other acid-binding agent containing printing paste and subsequent steaming at 100 to 103 ⁰ C, - or two-phase - for example by printing with neutral or weakly acidic ink and subsequent fixing either by passing through a hot electrolyte-containing alkaline bath or by over-padding with an alkaline electrolyte-containing padding liquor and then lingering or steaming or treatment with dry heat of the alkaline padded material, - can be obtained strong prints with good contour and a clear white fund. The failure of the prints is only slightly dependent on changing fixing conditions.

In the fixation by means of dry heat according to the usual heat setting method used hot air from 120 to 200 ⁰ C. In addition to the usual steam of 101 to 103 ⁰ C and superheated steam and pressure steam of temperatures up to 160 ⁰ C can be used.

The acid-binding and the fixing of the dyes on the cellulose fibers causing agents are, for example, water-soluble basic salts of alkali metals and also alkaline earth metals of inorganic or organic acids or compounds which release alkali in the heat. In particular, the alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids may be mentioned, of the alkali metal compounds preferably the sodium and potassium compounds are meant. Such acid-binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium trichloroacetate, water glass or trisodium phosphate.

The dye mixtures according to the invention are characterized by cellulose fiber materials when used in the known dyeing and printing process by an excellent color strength and a steep course of the build-up curve. Furthermore, those with the dye mixtures according to the invention Available dyeings and prints on cellulose fiber materials good light fastness and especially good wet fastness, such as washing, Walk, water, seawater, dyeing and acid, and alkaline perspiration, furthermore a good pleating, ironing fastness and rubbing fastness.

Furthermore, the dyeings and prints after the usual post-treatment by rinsing to remove unfixed dye fractions excellent wet fastness, especially since unfixed dye fractions can be easily washed out because of their good solubility in cold water.

The dye mixtures according to the invention can also be used for the fiber-reactive dyeing of wool. Felt-free or low-felt wool (compare, for example, H. Rath, textbook of Textilchemie, Springer-Verlag, 3rd edition (1972), pp. 295-299, in particular the equipment according to the so-called Hercosett method (page 298); Soc. Dyers and Colorists 1972, 93-99, and 1975, 33-44) can be dyed with very good fastness properties. The process of dyeing wool is carried out here in the usual and well-known Därbeweise from an acidic environment. For example, acetic acid and / or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate may be added to the dyebath to obtain the desired pH. In order to achieve a usable levelness of the dyeing, it is advisable to add conventional leveling agents, for example based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic acid and / or an aminonaphthalenesulfonic acid or on

Base of a reaction product of, for example, stearylamine with ethylene oxide. Thus, for example, the dye mixture according to the invention is preferably first subjected to the exhaust process from acid dyebath having a pH of about 3.5 to 5.5 under the control of the pH and the pH then, towards the end of the dyeing time, in the neutral and optionally slightly alkaline range shifted to a pH of 8.5, especially in order to achieve high color depths full reactive binding between the dyes of the dye mixtures according to the invention and the fiber bring about. simultaneously the non-reactively bound dye fraction is removed.

The procedure described here also applies to the production of dyeings on fiber materials from other natural polyamides or from synthetic polyamides and polyurethanes. For dyeing these materials, it is possible to use the customary dyeing and printing processes described in the literature and known to the person skilled in the art (see, for example, H. -K. Rouette, Handbuch der Textilveredlung, Deutscher Fachverlag GmbH, Frankfurt am Main). In general, the material to be dyed at a temperature of about 40 ⁰ C introduced into the bath, there for some time moved therein, the dyebath then adjusted to the desired weakly acid, preferably weakly acetic acid, pH and the actual color in a Temperature between 60 and 98 ° C performed. The dyeings can also be carried out at boiling temperature or in closed dyeing apparatus at temperatures up to 106 ⁰ C. Since the water solubility of the dye mixtures according to the invention is very good, they can also be used with advantage in conventional continuous dyeing processes. The color intensity of the dye mixtures according to the invention is very high.

The present invention also relates to inks for digital textile printing by the ink-jet process, which are characterized in that they contain a Farbstoffmichung invention.

The inks according to the invention comprise a dye mixture according to the invention, for example in amounts of from 0.1% by weight to 50% by weight, preferably in amounts of

1 wt .-% to 30 wt .-% and particularly preferably in amounts of 1 wt .-% to 15

Wt .-% based on the total weight of the ink. Of course, the

Inks also mixtures of Farbstoffmichungen invention and others

Dyes used in textile printing. For the use of inks in the continuous flow process, a conductivity of 0.5 to 25 mS / m can be set by addition of electrolyte.

Suitable electrolytes are, for example: lithium nitrate, potassium nitrate. The inks of the invention may contain organic solvents having a total content of 1-50%, preferably 5-30% by weight. Suitable organic solvents are, for example, alcohols, for. For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, tert. Butanol, pentyl alcohol, polyhydric alcohols z. B, 1, 2-ethanediol, 1, 2,3-propanetriol, butanediol, 1, 3

Butanediol, 1, 4-butanediol, 1, 2-propanediol, 2,3-propanediol, pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, hexanediol, D, L-1, 2-hexanediol, 1, 6- Hexanediol, 1, 2,6-hexanetriol, 1, 2-octanediol, polyalkylene glycols, e.g. B.: Polyethylene glycol, polypropylene glycol, alkylene glycols having 2 to 8 alkylene groups, eg. B.: Monoethylene glycol, diethylene glycol, triethylene glycol,

Tetraethylene glycol, thioglycol, thiodiglycol, butyl triglycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, lower alkyl ethers of polyhydric alcohols, e.g. B .: ethylene glycol monomethyl ether, ethylene glycol, diethylene glycol, diethylene, diethylene, diethylene glycol monohexyl ether, triethylene, triethylene or tripropylene, tetraethylene glycol monomethyl ether, tetraethylene, tetraethylene, propylene glycol, propylene glycol, propylene glycol, Tripropylenglykolisopropylether, polyalkylene such. B.: Polyethylene glycol monomethyl ether, polypropylene glycol glycerol ether, Polyethylenglykoltridecylether, Polyethylenglykolnonylphenylether, amines, such as. Example: methylamine, ethylamine, triethylamine, diethylamine, dimethylamine, trimethylamine, dibutylamine, diethanolamine, triethanolamine, N-formylethanolamine, ethylenediamine, urea derivatives such. For example: urea, thiourea, N-methylurea, N, N'-epsilon dimethylurea, ethyleneurea, 1, 1, 3,3-tetramethylurea, N-acetylethanolamine, amides, such as. For example: dimethylformamide, dimethylacetamide, acetamide, ketones or ketoalcohols, such as. B.: Acetone, diacetone alcohol, cyclic ethers, such as. B .; Tetrahydrofuran, trimethylolethane, trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol, gamma-butyrolactone, epsilon-caprolactam, also sulfolane, dimethylsulfolane, methylsulfolane, 2,4-dimethylsulfolane, dimethylsulfone, butadienesulfone, dimethylsulfoxide, dibutylsulfoxide, N-cyclohexylpyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-pyrrolidone, 2-pyrrolidone, 1- (2 Hydroxyethyl) -2-pyrrolidone, 1- (3-hydroxypropyl) -2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolinone, 1,3-bisethoxymethylinnidazolidine, 2- (2- Methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, 2- (2-propoxyethoxy) ethanol, pyridine, piperidine, butyrolactone, trimethylpropane, 1, 2-dimethoxypropane, dioxane, ethyl acetate, ethylenediaminetetraacetate Ethyl penthyl ether, 1,2-dimethoxypropane and trimethylpropane. Furthermore, the inks of the invention may contain the usual additives, such as viscosity moderators to adjust viscosities in the range of 1, 5 to 40.0 mPas in a temperature range of 20 to 50 ⁰ C. Preferred inks have a viscosity of 1.5 to 20 mPas and particularly preferred inks have a viscosity of 1.5 to 15 mPas. Suitable viscosity moderators are theological additives, for example: polyvinylcaprolactam, polyvinylpyrrolidone and their co-polymers polyetherpolyol, associative thickener, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane, nonionic cellulose ethers. As further additives, the inks according to the invention can be surface-active

Substances for the adjustment of surface tensions from 20 to 65 mN / m, which may be adjusted depending on the method used (thermal or piezo technology). Suitable surface-active substances are, for example: surfactants of all kinds, preferably nonionic surfactants, butyldiglycol and 1,2-hexanediol.

Further, the inks may still contain conventional additives such as fungicidal and bacterial growth inhibiting agents in amounts of from 0.01 to 1% by weight based on the total weight of the ink.

The inks of the invention may be prepared in the usual manner by mixing the components in water.

The inks according to the invention are suitable for use in ink-jet printing Process for printing a variety of prepared materials, such as silk, leather, wool, cellulose-containing fiber materials of all kinds and polyurethanes, and in particular polyamide fibers. The printing inks of the invention are also suitable for printing pretreated hydroxy-containing or amino-containing fibers contained in blend fabrics, z. As mixtures of cotton, silk, wool with polyester fibers or polyamide fibers.

In contrast to conventional textile printing, in which the printing ink already contains all fixing chemicals and thickeners for a reactive dye, in ink-jet printing the auxiliaries have to be applied to the textile substrate in a separate pretreatment step.

The pretreatment of the textile substrate, such as, for example, cellulose and cellulose regenerated fibers, as well as silk and wool, takes place before printing with an aqueous alkaline liquor. To fix reactive dyes requires alkali, such as sodium carbonate, sodium bicarbonate, sodium acetate,

Trisodium phosphate, sodium silicate, sodium hydroxide, alkali donors such as sodium chloroacetate, sodium formate, hydrotropic substances such as urea, reduction inhibitors such as sodium nitrobenzenesulfonates, as well as thickeners that prevent the flow of motifs during application of the ink, these are, for example, sodium alginates, modified polyacrylates or highly etherified galactomannans.

These pre-preparation reagents are applied uniformly to the textile substrate in a defined amount using suitable application devices, for example a 2- or 3-roll padder, with non-contact spray technologies, by foam application or with appropriately adapted inkjet technologies, and then dried.

After printing, the textile fiber material is dried at 120 to 150 ⁰ C and then fixed. The fixation of the inkjet prints prepared with reactive dyes can be carried out at room temperature, or with saturated steam, with superheated steam, with hot air, with microwaves, with infrared radiation, with laser or electron beams or with other suitable types of energy transfer. One distinguishes one- and two-phase fixation processes: In single-phase fixation, the chemicals necessary for fixation are already on the textile substrate.

In the case of two-phase fixation, this pretreatment can be omitted. For fixing only alkali is needed, which is applied after the ink-jet printing before the fixing without intermediate drying. Other additives such as urea or thickener can be dispensed with.

After the fixation, the post-treatment is carried out, which is the prerequisite for good fastness, high brilliance and a perfect white foundation. The prints made with the inks of the present invention, especially on polyamide, have high color strength and high fiber-dye bonding stability in both acidic and alkaline ranges, as well as good fastness to light and very good wet fastness properties such as washing, water, seawater -, over-dyeing and perspiration, as well as a good pleating, ironing and rubbing fastness.

The following examples serve to illustrate the invention. The parts are by weight, the percentages are by weight unless otherwise stated. Parts by weight refer to parts by volume such as kilograms to liters. The compounds described by formula in the examples are in the form of

Sodium salts, since they are generally prepared and isolated in the form of their salts, preferably sodium or potassium salts, and used in the form of their salts for dyeing. The starting compounds mentioned in the following examples, in particular table examples, can be used in the synthesis in the form of the free acid or else in the form of their salts, preferably alkali metal salts, such as sodium or potassium salts.

example 1

20 parts of an electrolyte-containing dye powder containing the orange dye of the formula (Ib)

contains in 75% and 80 parts of an electrolyte-containing dye powder containing the yellow dye of the formula (IIb)

contains in 75%, are dissolved in 500 parts of water and the resulting dye solution adjusted to pH 5.5-6.5. Evaporation of this dye solution gives a dye mixture which gives yellow to golden yellow dyeings and prints on cotton under the dyeing conditions customary for reactive dyestuffs.

Alternatively, the dye solution obtained can also be buffered by addition of a phosphate buffer at pH 5.5-6 and adjusted by further dilution or concentration as a liquid brand of certain strength.

Example 2

20 parts of an electrolyte-containing dye powder containing the orange dye of the formula (Ib) in a proportion of 70% and 80 parts of an electrolyte-containing dye powder containing the golden yellow dye of the formula (Mc) contained in 70% proportion, are mechanically mixed together. The resulting dye mixture according to the invention gives yellow dyeings and prints under the dyeing conditions customary for reactive dyestuffs, for example on cotton.

Example 3

20 parts of an electrolyte-containing dye powder containing the orange disazo dye of the formula (1-1) in 75% and 80 parts of an electrolyte-containing dye powder containing the yellow azo dye of the formula (Md)

in 65%, are dissolved in 500 parts of water and the resulting dye solution adjusted to pH 5.5-6.5. Evaporation of this dye solution gives a dye mixture which gives yellow dyeings and prints on cotton under the dyeing conditions customary for reactive dyestuffs. Alternatively, the dye solution obtained can also be buffered by addition of a phosphate buffer at pH 5.5-6 and adjusted by further dilution or concentration as a liquid brand of certain strength.

Examples 4 to 22

The following examples describe further dye mixtures according to the invention in which the dyes of the general formulas (I) and (II) are each listed in the form of the sodium salts and which can be prepared by the processes described in Examples 1 to 3. The mixing ratios are given in percent by weight. The Dyestuff mixtures provide, according to the dyeing methods customary for reactive dyes, for example on cotton, yellow to orange-yellow dyeings.

Example 23

2 parts of a dye mixture obtained according to Example 1 and 50 parts of sodium chloride are dissolved in 999 parts of water and added 5 parts of sodium carbonate, 0.7 parts of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent. In this dye bath is added 100 g of a cotton fabric. The temperature of the dyebath is first held at 25 ° C for 10 minutes, then increased in 30 minutes to final temperature (40-80 ⁰ C) and held this temperature for another 60-90 minutes. Thereafter, the dyed fabric is first 2 minutes with drinking water and then 5 Rinsed with e-water for a few minutes. The dyed product is neutralized at 40 ^° C. in 1000 parts of an aqueous solution containing 1 part of 50% acetic acid for 10 minutes. With E-water is rinsed at 70 ⁰ C and then soaped for 15 minutes with a detergent, rinsed again and dried. This gives an orange to red coloration with very good fastness properties.

Comparable results are obtained by repeating the process described with the dye mixtures obtained according to Examples 2 and 3.

Example 24 4 parts of a dye mixture obtained according to Example 1 and 50 parts

Sodium chloride is dissolved in 998 parts of water and 5 parts of sodium carbonate, 2 parts of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent added. In this dye bath is added 100 g of a cotton fabric. Further processing is carried out as indicated in Example 23. This gives a strong orange to red coloration with very good fastness properties.

Example 25

A textile fabric consisting of mercerized cotton is padded with a liquor containing 35 g / l of sodium carbonate, 100 g / l of urea and 150 g / l of a low-viscosity Na alginate solution (6%) and then dried. The fleet intake is 70%. An aqueous ink containing 2% of the dye mixture according to Example 1 20% sulfolane 0.01% Mergal K9N 77.99% water is printed onto the textile thus pretreated with a drop-on-demand (bubble jet) inkjet print head. The print is completely dried. The fixation takes place by means of saturated steam at 102 ⁰ C for 8 minutes. Subsequently, the pressure is rinsed warm, subjected to hot water at 95 ° C a fastness wash, rinsed warm and then dried. This gives a bluish red print with excellent use fastness.

Example 26 A textile fabric consisting of mercerized cotton is padded with a liquor containing 35 g / l of sodium carbonate, 50 g / l of urea and 150 g / l of a low-viscosity Na alginate solution (6%) and then dried. The fleet intake is 70%. On the thus pretreated textile is an aqueous ink containing 8% dye mixture according to Example 1 20% 1, 2-propanediol 0.01% Mergal K9N and 71, 99% water with a drop-on-demand (bubble jet) inkjet print head printed. The print is completely dried. The fixation takes place by means of saturated steam at 102 ⁰ C for 8 minutes.

Subsequently, the pressure is rinsed warm, subjected to a fastness wash with hot water at 95 ° C, rinsed warm and then dried. This gives a bluish red print with excellent use fastness.

Example 27

A textile fabric consisting of mercerized cotton is padded with a liquor containing 35 g / l of sodium carbonate, 100 g / l of urea and 150 g / l of a low-viscosity Na alginate solution (6%) and then dried. The fleet intake is 70%. An aqueous ink containing 8% of dye mixture according to Example 1, 15% N-methylpyrrolidone 0.01 Mergal K9N and 77.99% water is printed on the textile thus pretreated with a drop-on-demand (bubble jet) inkjet print head , The print is completely dried. The fixation takes place by means of saturated steam at 102 ⁰ C for 8 minutes. Then the pressure is rinsed warm, with hot Water at 95 ° C subjected to a fastness wash, rinsed warm and then dried. This gives a bluish red print with excellent use fastness.

Claims

claims

1. dye mixture containing one or more dyes of the general formula (I)

and one or more dyes of the general formulas (II)

wherein

D, D and D independently of one another represent a group of the general formula (III)

stand in which

R ¹ and R ² independently of one another are hydrogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen; and X ^{1 is} hydrogen, sulfo, a group of the formula -SO ₂ -Z ² , wherein Z ^{2 is} -CH = CH ₂ or -CH ₂ CH ₂ Z ³ , and

stands; or in which D ¹ , D ² and D ³ independently of one another represent a group of the general formula (V) wherein

R ³ and R ^{4 are} independently hydrogen, (C 1 -C ₄ ) alkyl, (C 1 -C ₄ ) alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; and X ^{2 has} one of the meanings of X ¹ ;

or in which

stand in which

R ⁵ and R ⁶ independently of one another have one of the meanings of R ¹ ; R ^{7 is} hydrogen, (C _r C ₄ ) alkyl, unsubstituted or substituted by (C _r C ₄ ) alkyl, (C _r C ₄ ) alkoxy, sulfo, halogen or carboxy-substituted phenyl; and Z ^{4 represents} a group of the general formula (VII), (VIII) or (IX)

stands; wherein

V is fluorine or chlorine;

U ¹ and U ² independently of one another denote fluorine, chlorine or hydrogen;

Q ¹ and Q ² are independently chlorine, fluorine, cyanamido, hydroxyl, (CrC ₆₎ - alkoxy, phenoxy, sulfophenoxy, mercapto, _(Ci-C6) -alkylmercapto, pyridino,

Carboxypyridino, carbamoylpyridino or a group of the general formula (X) or (Xl)

.R ⁸ , R ⁹

- N _{s 5} -N

W-SOZ ^s p ¹⁰

^U2 (X) ^R (XI), in which

R ^{8 is} hydrogen, (C _r C ₆ ) alkyl, sulfo (C _r C ₆ ) alkyl, phenyl or by (Ci-C ₄ ) alkyl, (CrC ₄ ) alkoxy, hydroxy, sulfo, halogen, carboxy , Acetamido, ureido is substituted phenyl;

R ⁹ and R ¹⁰ independently of one another have one of the meanings of R ⁸ or together represent a group of the formula - (CH ₂ ) _r or the formula - (CH ₂ ) 2-E- (CH ₂ ) 2-, where j is 4 or 5, E is oxygen, sulfur, sulfonyl or -NR ¹¹ and R ^{11 is} (CrC ₆ ) -alkyl; W is phenylene, by 1 or 2 substituents from the series (C _r _C4) alkyl, (C _r _C4) - substituted alkoxy, carboxy, sulfo, chlorine and bromine phenylene, (dC ₄₎ alkylene- phenylene, ( C ₂ -C ₆ ) -alkylene, (C ₂ -C ₆ ) -alkylene interrupted by oxygen, sulfur, sulfonyl, amino, carbonyl or carbonamido, phenylene-CONH-phenylene, by 1 or 2 substituents from the series (CrC ₄ ) Alkyl, (C 1 -C ₄ ) alkoxy, hydroxy, sulfo, carboxy, amido, ureido and halogen substituted phenylene-CONH-phenylene, naphthylene or naphthylene substituted by one or two sulfo groups; and Z ^{5 has} one of the meanings of Z ² ;

or in which

stand in which

R ^{12 is} hydrogen, (C 1 -C ₄ ) alkyl, aryl or substituted aryl; R ¹³ and R ¹⁴ independently of one another are hydrogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -

Alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; and

A for a group of the general formula (XIII) stands in which

stands in which

R ¹⁷ and R ¹⁸ independently of one another are hydrogen, (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) -alkoxy,

Hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; or A is a group of the general formula (XV) where k is an integer greater than 1;

R ¹⁹ and R ²⁰ are independently hydrogen, (CrC ₄₎ alkyl, (Ci-C ₄₎ -alkoxy, hydroxyl, cyano, amido, halogen or aryl; and

X ^{3 has} one of the meanings of X ¹ ;

R ^{A is} hydrogen or a group of the general formula (XVII)

-CH ₂ -SO ₃ M (XVII);

II), in which

wherein

D ^{4 represents} a group of the formula (B) or (C)

stands in which

E ^A ( _0-3 ) ^{ur |} d E ^B ( _O- 3) are the same or different and 0 to 3 groups selected from the group consisting of hydrogen, -SO ₃ M, -OH, -COOM, -F, -Cl, -Br, (C 1 -C ₄ ) -alkyl or

(C 1 -C ₄ ) alkoxy; p and q are a number from 0 to 2;

Z ^A and Z ^{B are} a group of the formula (Da), (Db), (Dc) or (Dd),

-SO ₂ -Y ^A (Da) -CONH- (CH ₂ ) r -SO ₂ -Y ^A (Db) -NHCONH (Hal) CH ₂ Hal (Dc) -NHCOCH (Hal) = CH ₂ (Dd) r a Number from O to 5;

Hal halogen;

Y ^{A is} vinyl, β-chloroethyl, β-bromoethyl, β-acetylethyl, β-sulfatoethyl, β-phenoxyethyl, β-phosphatoethyl or a -CH ₂ -CH ₂ -U group; U is a group which can be split off under the action of alkali; and M is defined as above; at most in an amount of 1% by weight, based on the total colorant content.

2. dye mixture according to claim 1, characterized in that R ¹ and R ^{2 is} hydrogen, methyl, methoxy or sulfo;

R ³ to R ^{6 are} hydrogen or sulfo; R ⁷ and R ^{8 are} hydrogen or phenyl; R ⁹ and R ^{10 are} hydrogen, 2-sulfoethyl, 2-, 3- or 4-sulfophenyl or together - (CH ₂ ) 2 -O- (CH ₂ ) 2-; R ^{11 is} hydrogen or methyl; R ¹² to R ¹⁶ , R ¹⁹ , R ²⁰ , R ^A and R ^{c are} hydrogen; R ¹⁷ and R ^{18 are} hydrogen or sulfo; R ^{B is} acetamido or ureido; and

Z ² and Z ^{5 are} vinyl, ß-chloroethyl or ß-sulfatoethyl.

3. dye mixture according to claim 1 and / or 2, characterized in that D ¹ and D ^{2 represent} a group of the general formula (IM) or (VI).

4. dye mixture according to one or more of claims 1 to 3, characterized in that D ^{3 is} a group of the general formula (V), in which R ³ , R ⁴ and X ^{2 is} hydrogen or sulfo, stands.

5. dye mixture according to one or more of claims 1 to 4, characterized in that Z ^{1 is} a group of general formula (VIII), wherein Q ^{1 is} fluorine or chlorine and Q ² cyanamido, morpholino, 2-sulfophenyl amino, 3 Sulfo-phenylamino, 4-sulfophenylamino, 3- (2-sulfatoethylsulfonyl) -phenylamino, 4- (2-sulfatoethylsulfonyl) -phenylamino, 3- (vinylsulfonyl) -phenyl-amino, 4- (vinylsulfonyl) -phenylamino), N -methyl N- (2- (2-sulfatoethylsulfonyl) ethyl) amino, N-phenyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino or 2- [2- (2-chloroethylsulfonyl) - ethoxy] -ethylamino stands.

6. A dye mixture according to one or more of claims 1 to 5, characterized in that it contains one or more dyes of the general formula (Ia) and one or more dyes of the general formula (IIa)

wherein R ^1a , R ^1b , R ^2a and R ^2b independently represent hydrogen, methyl, methoxy or sulfo;

Z ² and Z ₅ independently represent vinyl or β-sulfatoethyl; and D ³ , R ^B , R ^c and M are as defined in claim 1.

7. dye mixture according to one or more of claims 1 to 6, characterized in that it contains the dye or the dyes of the general formula (I) in an amount of 1 to 99 wt .-%, preferably 10 to 90 wt .-% and the dye (s) of the general formula (II)

in an amount of 1 to 99 wt .-%, preferably 10 to 90 wt .-%, each based on the total amount of dye.

8. A process for the preparation of a dye mixture according to one or more of claims 1 to 7, characterized in that the individual dyes are mechanically mixed together.

9. Use of a dye mixture according to one or more of claims 1 to 7 for dyeing or printing carbonamide and / or hydroxyl-containing materials.

10. Ink for digital textile printing by the ink-jet process, characterized in that it contains a dye mixture according to one or more of claims 1 to 7.