HK1075269A - Dye mixtures of fiber reactive azodyes, production and use thereof - Google Patents

Description

Dye mixtures of fiber-reactive azo dyes, their preparation and their use

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The invention relates to the technical field of fiber-reactive azo dyes.

Mixed fibre-reactive azo dyes and their use for dyeing hydroxy-and carboxamido-containing materials to black shades are known, for example, from documents U.S. Pat. No. 5,445,654, U.S. Pat. No. 3, 5,611,821, KR 94-2560, Sho 58-160362 and EP-A-0870807. However, they have certain application drawbacks such as, for example, the colour yield being overly dependent on changing the dyeing parameters in the dyeing process or an insufficient or uneven dye build-up on the cotton (good dye build-up results from the ability of the dye to provide proportionally stronger dyeing when dyed in higher concentrations in the dye bath), or the dyeing being overly dependent on salt. The result of these defects is poor reproducibility of the dyeings obtainable. Documents WO98/42784, WO 98/42785, WO 93/18224 and US 5,330,539 disclose dyes and dye mixtures which are capable of dyeing in the presence of small amounts of salt, but provide only very weak dyeings in the absence of salt.

Due to the commercial and environmental need to reduce the salt content of dyeing wastewater, there is a need for reactive dyes that provide high dyeing intensity dyeings in the presence of small amounts of salt, even in the absence of electrolyte salts.

The present invention therefore provides dye mixtures which provide dyeings of high dyeing intensity with only very low levels, even in the absence of electrolyte salts.

Accordingly, the present invention provides dye mixtures comprising one or more, such as two or three, preferably one or two, dyes of the general formula (I) below; one or more, such as two or three, preferably one or two, dyes of the general formula (II) below; and optionally one or more, such as two or three, preferably one or two, dyes of the following formulae (III-a) to (III-f) as ingredients for mixing or shading:

wherein:

D¹and D²Each a group of the formula (1), or each a phenyl group of the formula (5), or each a naphthyl group of the formula (6),

wherein:

R¹is hydrogen, (C)₁-C₄) -an alkyl, aryl or substituted aryl group,

R²and R³Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, amido or halogen; and

a is a phenylene group of the general formula (2), or a naphthylene group of the general formula (3), or a polymethylene group of the general formula (4),

wherein:

R⁴and R⁵Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, amido or halogen;

wherein:

R⁶and R⁷Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, amido or halogen;

-(CR⁸R⁹)_k- (4)

wherein:

k is an integer greater than 1, and

R⁸and R⁹Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, cyano, amido, halogen or aryl; and

X¹is hydrogen or formula-SO₂-a group of Z;

wherein:

R¹⁰and R¹¹Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, amido or halogen; and

X²having X¹One of the meanings of (a);

wherein:

R¹²and R¹³Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, amido or halogen; and

X³having X¹One of the meanings of (a);

z is-CH ═ CH₂、-CH₂CH₂Z¹Or a hydroxyl group,

Wherein:

Z¹is a hydroxyl group or a base-eliminable group; and

m is hydrogen, an alkali metal or one equivalent of an alkaline earth metal;

D³having D¹Or D²Or a group of the general formula (7):

wherein:

R²¹and R²²Independently have R²And R³One of the meanings of (a);

R²³is hydrogen, (C)₁-C₄) -alkyl, unsubstituted phenyl or (C)₁-C₄) -alkyl-, (C)₁-C₄) -alkoxy-, sulfo-, halogen-or carboxy-substituted phenyl; and

Z²¹is a fibre-reactive radical of the general formula (8) or (9) or (10):

wherein:

v is fluorine or chlorine;

U¹and U²Independently fluorine, chlorine or hydrogen; and

Q¹and Q²Independently chlorine, fluorine, cyanamido, hydroxyl, (C)₁-C₆) Alkoxy, phenoxy, sulfophenoxy, mercapto, (C)₁-C₆) -alkylthio, pyrido, carboxypyrido, carbamoylpyrido or a group of general formula (11) or (12):

wherein:

R^2’is hydrogen or (C)₁-C₆) Alkyl, sulfo- (C)₁-C₆) -alkyl, or unsubstituted phenyl or (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -phenyl substituted by alkoxy, sulfo, halogen, carboxyl, acetamido or ureido;

R^3’and R^4’Independently have R^2’One of the meanings of (a); or in combination form- (CH)₂)_j-wherein j is 4 or 5; or in combination to form- (CH)₂)₂-E-(CH₂)₂-, where E is oxygen, sulfur, sulfo, -NR^5′-, wherein R^5′Is (C)₁-C₆) -an alkyl group; or a group of the general formula (13):

wherein:

R²⁴、R²⁵and R²⁶Each is (C)₁-C₄) -alkyl or (C)₁-C₄) -a hydroxyalkyl group; and

B^-is an equivalent of a negative ion such as a hydrogen sulfate ion, a fluoride ion, a chloride ion, a bromide ion, a dihydrogen phosphate ion, a hydrogen phosphate ion, a hydroxide ion, or an acetate ion;

w is unsubstituted phenylene or phenylene which is substituted by 1 or 2 substituents, e.g. (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, carboxy, sulfo, chloro, bromo; or is (C)₁-C₄) Alkylene-arylene or (C)₂-C₆) Alkylene which may be substituted by oxygen, sulfur, sulfo, amino,Interrupting carbonyl and formamido; or is phenylene-CONH-phenylene which is unsubstituted or substituted by (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, amido, ureido or halogen substitution; or naphthylene which is unsubstituted or substituted by one or two sulfo groups; and

z is as defined above;

r is hydrogen or (C)₁-C₄) -alkyl, or unsubstituted phenyl or (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -phenyl substituted by alkoxy, sulfo, halogen, carboxyl, acetamido or ureido; or

R is a group of formula (14):

CH₂-SO₃M (14)，

wherein M is as defined above; and

n is 1 or 2, and n is a hydrogen atom,

D⁴、D⁵、D⁶、D⁷and D⁸Having D¹、D²Or D³One of the meanings of (A), and

if R is³¹Is not a group of the formula (8) or (9), D⁴And D⁵Or D⁶And D⁸Containing at least one group of the formula-SO₂Z or Z²¹A fiber-reactive group of (a);

R³¹is hydrogen, acetyl, carbamoyl, sulfomethyl or a group of the general formula (8) or (9),

R³²is hydrogen or a sulfomethyl group,

R³³is methyl, carboxyl or has C₁-C₄-a carboxyalkyl group of an alkyl group,

R³⁴is hydrogen or a methyl group,

R³⁵is hydrogen, cyano, carbamoyl, carboxy or sulfomethyl,

R³⁶is methyl, ethyl or beta-sulfoethyl,

R³⁷is methyl, carboxyl or has C₁-C₄-a carboxyalkyl group of an alkyl group,

R³⁸is an acetamido group, a ureido group or a methyl group,

R³⁹is hydrogen, methyl or methoxy,

m is 0 or 1, and m is,

p is 1, 2 or 3, and

Z³having Z²¹One of the meanings of (a).

In the general formula (I), at least one D¹And D²A group of the general formula (1);

when A is a group of the formula (4), R¹Is aryl or substituted aryl; and the reactive dyes of the general formula (I) contain at least one-SO₂-a Z group.

The dyes of the general formula (II) contain, independently of one another, at least one-SO₂-Z or Z²¹A fiber-reactive group of (1).

Each symbol in the above and below formulae may have the same or different meanings under its definition, irrespective of whether the symbol has the same or different nomenclature.

(C₁-C₄) The alkyl radical R may be linear or branched, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. Methyl and ethyl are preferred. The same logic applies to (C)₁-C₄) -alkoxy groups.

Aryl R is in particular phenyl. Substituted aryl radicals R¹In particular phenyl substituted with one, two or three groups independently selected from: (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, amido and halogen.

Halogen R is in particular fluorine, chlorine or bromine, preferably fluorine and chlorine.

Z is eliminable by alkali in the beta-position of the ethyl group of Z¹Including, for example, halogen atoms such as chlorine and bromine; ester groups of organic carboxylic and sulfonic acids such as alkanoyloxy groups of 2 to 5 carbon atoms, particularly acetoxy, benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxy and p-tolylsulfonyloxy, such as alkyl carboxylic acids, substituted or unsubstituted benzoic acids and substituted or unsubstituted benzenesulfonic acids; also included are ester groups of inorganic acids such as phosphoric acid, sulfuric acid, and thiosulfuric acid (phosphato, sulfato, and thiosulfato groups); analogous dialkylamino radicals having in each case an alkyl radical having 1 to 4 carbon atoms, such as dimethylamino and diethylamino.

Z is preferably vinyl or β -chloroethyl, particularly preferably β -sulfatoethyl.

The radicals "sulfo", "carboxyl", "thiosulfato", "phosphato" and "phosphato" include not only their acid forms but also their salt forms. Thus, sulfo is of the formula-SO₃The radical corresponding to M, the thiosulfato radical being of the formula-S-SO₃M is a group corresponding to the formula-COOM, carboxyl is a group corresponding to the formula-COOM, and phosphate is a group corresponding to the formula-OPO₃M₂The radicals in agreement, and the sulfato radical, being of the formula-OSO₃M is identical to the radicals, in each case M is as defined above.

The dyes of the formulae (I) to (III) may have different fibre-reactive groups-SO-within the meaning of Z₂And Z. More specifically, the fiber-reactive group-SO₂Z may be vinylsulfonyl on the one hand and-CH on the other hand₂CH₂Z¹The radical, preferably β -sulfatoethylsulfonyl. If the dyes of the formulae (I) to (III) comprise vinylsulfonyl groups in some cases, the proportion of the individual dyes having vinylsulfonyl groups is up to about 30 mol%, based on the amount of the respective total dye.

The base M is in particular lithium, sodium or potassium. M is preferably hydrogen or sodium.

R¹To R¹³Each is preferably hydrogen, R⁶、R⁷、R¹²And R¹³Each is preferably a sulfo group.

When A is phenylene and X¹is-SO₂Z is, SO₂The Z group is preferably located meta or para to the nitrogen atom. In the radical of the formula (1), the carboxamide group is preferably located in the para-or meta-position relative to the diazo group. When A is naphthylene, the bond to the nitrogen atom is preferably located in the beta-position of the naphthalene nucleus. When D is present¹Or D²In the case of a group of the formula (6), the bond to the diazo group is preferably located at the beta-position of the naphthalene nucleus.

When D is present¹Or D²Is a group of the formula (5) and X²is-SO₂Z is, SO₂The Z group is preferably located meta or para to the diazo group.

Examples of substituents A are in particular 1, 2-phenylene, 1, 3-phenylene, 1, 4-phenylene, 2-chloro-1, 5-phenylene, 2-bromo-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, 6-naphthylene, 2, 8-naphthylene, 1-sulfo-2, 6-naphthylene, 6-sulfo-2, 8-naphthylene or 1, 2-ethylene and 1, 3-propylene.

A is particularly preferably 1, 3-phenylene, 1, 4-phenylene, 2-sulfo-1, 4-phenylene, 2-methoxy-1, 5-phenylene, 2, 5-dimethoxy-1, 4-phenylene, 2-methoxy-5-methyl-1, 4-phenylene or 1, 2-ethylene and 1, 3-propylene, in the case of the last two alkylene groups, R¹Preferably phenyl or 2-sulfophenyl.

k is preferably 2 or 3.

Group D of the general formulae (5) and (6)¹To D⁸Examples of (B) are 2- (. beta. -sulfatoethylsulfonyl) phenyl, 3- (. beta. -sulfate)Ethylsulfonyl) phenyl, 4- (. beta. -sulfatoethylsulfonyl) -phenyl, 2-carboxy-5- (. beta. -sulfatoethylsulfonyl) phenyl, 2-chloro-4- (. beta.0-sulfatoethylsulfonyl) phenyl, 2-chloro-5- (. beta.1-sulfatoethylsulfonyl) phenyl, 2-bromo-4- (. beta.2-sulfatoethylsulfonyl) phenyl, 2-sulfo-4- (. beta.3-sulfatoethylsulfonyl) phenyl, 2-sulfo-5- (. beta.4-sulfatoethylsulfonyl) phenyl, 2-methoxy-5- (. beta.5-sulfatoethylsulfonyl) phenyl, 2-ethoxy-5- (. beta.6-sulfatoethylsulfonyl) phenyl, methyl-ethyl-5- (. beta.6-sulfatoethylsulfonyl) phenyl, methyl-, 2, 5-dimethoxy-4- (. beta.7-sulfatoethylsulfonyl) phenyl, 2-methoxy-5-methyl-4- (. beta.8-sulfatoethylsulfonyl) phenyl, 2-methyl-4- (. beta.9-sulfatoethylsulfonyl) phenyl, 2-or 3-or 4- (. beta. -thiosulfatoethylsulfonyl) phenyl, 2-methoxy-5- (. beta.0-thiosulfatoethylsulfonyl) phenyl, 2-sulfo-4- (. beta.1-phosphatoethylsulfonyl) phenyl, 2-or 3-or 4-vinylsulfonylphenyl, 2-sulfo-4-vinylsulfonylphenyl, 2-chloro-4- (. beta.2-chloroethylsulfonyl) phenyl, 2-chloro-5- (. beta.3-chloroethylsulfonyl) phenyl, 3-or 4- (. beta.4-acetoxyethylsulfonyl) phenyl, 6-or 8- (. beta.5-sulfatoethylsulfonyl) naphthalen-2-yl, 6- (. beta.6-sulfatoethylsulfonyl) -1-sulfonaphthalen-2-yl and 8- (. beta. -sulfatoethylsulfonyl) -6-sulfonaphthalen-2-yl, preferably 3- (. beta. -sulfatoethylsulfonyl) phenyl, 4- (. beta. -sulfatoethylsulfonyl) -phenyl, 2-sulfo-4- (. beta. -sulfatoethylsulfonyl) phenyl, 2-methoxy-5- (. beta. -sulfatoethylsulfonyl) phenyl, p-ethoxyethyl-sulfonyl, 2, 5-dimethoxy-4- (. beta. -sulfatoethylsulfonyl) phenyl, 2-methoxy-5-methyl-4- (. beta. -sulfatoethylsulfonyl) phenyl and 3-or 4-vinylsulfonylphenyl.

In the general formula (II), R is preferably hydrogen or a group of the formula (14), and M is as defined above.

In the general formula (II), D³Preferably 2- (. beta. -sulfatoethylsulfonyl) phenyl, 3- (. beta. -sulfatoethylsulfonyl) phenyl, 4- (. beta. -sulfatoethylsulfonyl) phenyl, 2-sulfo-4- (. beta. -sulfatoethylsulfonyl) phenyl, 2-methoxy-5- (. beta. -sulfatoethylsulfonyl) phenyl, 2, 5-dimethoxy-4- (. beta. -sulfatoethylsulfonyl) phenylEthylsulfonyl) phenyl, 2-methoxy-5-methyl-4- (. beta. -sulfatoethylsulfonyl) phenyl, 6- (. beta. -sulfatoethylsulfonyl) -1-sulfonaphthalen-2-yl, 2-, 3-or 4-vinylsulfonylphenyl, 1-sulfo-4- (2, 4-difluoropyrimidin-6-yl) amino-2-phenyl, 1-sulfo-4- (4, 6-difluoropyrimidin-2-yl) amino-2-phenyl, 2-sulfo-4- (2, 4-difluoropyrimidin-6-yl) amino-1-phenyl or 2-sulfo-4- (4, 6-difluoropyrimidin-1-yl) amino-1-phenyl.

In the general formula (II), when D³In the case of the group of the formula (6), the bond to the diazo group is preferably located at the beta-position of the naphthalene nucleus of (6).

In the general formula (7), R²¹To R²³Each is preferably hydrogen, R²¹And R²²Preferably a sulfo group.

In the general formulae (11) and (12), R²' to R⁴' in each case preferably hydrogen or methyl, R²' is preferably phenyl, R³And R⁴Each preferably 2-sulfoethyl, 2-, 3-or 4-sulfophenyl, 3-or 4-trimethylphenylammonium sulfate, 3-or 4-trimethylphenylammonium chloride, or R³' and R⁴' combine to form a ring system, which preferably conforms to the formula- (CH)₂)₂-O-(CH₂)₂-。

W is preferably 1, 3-phenylene, 1, 4-phenylene, 2-sulfo-1, 4-phenylene, 2-methoxy-1, 5-phenylene, 2, 5-dimethoxy-1, 4-phenylene, 2-methoxy-5-methyl-14-phenylene, 1, 2-ethylene, 1, 3-phenylene.

Group Q in the formula (9)¹And Q²Independently of one another, fluorine, chlorine, hydroxyl, methoxy, ethoxy, phenoxy, 3-sulfophenoxy, 4-sulfophenoxy, methylmercapto, cyanamido, amino, methylamino, ethylamino, morpholino, piperidino, phenylamino, methylphenylamino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 2, 4-disulfophenylamino, 2, 5-disulfophenylamino, 3-trimethylammonium phenylamino, 4-trimethylammonium phenylamino, 2-sulfoethylAlkylamino, N-methyl-2-sulfoethylamino, pyrido, 3-carboxypyrido, 4-carboxypyrido, 3-carbamoylpyrido, 4-carbamoylpyrido, 2- (2-sulfatoethylsulfonyl) phenylamino, 3- (2-sulfatoethylsulfonyl) phenylamino, 4- (2-sulfatoethylsulfonyl) phenylamino, N-ethyl-3- (2-sulfatoethylsulfonyl) phenylamino, N-ethyl-4- (2-sulfatoethylsulfonyl) phenylamino, 2-carboxy-5- (2-sulfatoethylsulfonyl) phenylamino), 2-chloro-4- (2-sulfatoethylsulfonyl) phenylamino, N-methyl-2-sulfoethylamino, 2-chloro-5- (2-sulfatoethylsulfonyl) phenylamino, 2-bromo-4- (2-sulfatoethylsulfonyl) phenylamino, 2-sulfo-5- (2-sulfatoethylsulfonyl) phenylamino, 2-methoxy-5- (2-sulfatoethylsulfonyl) phenylamino, 2, 5-dimethoxy-4- (2-sulfatoethylsulfonyl) phenylamino, 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) naphthalen-2-ylamino, 8- (2-sulfatoethylsulfonyl) -6-sulfonaphthalen-2-ylamino, 3- (2- (2-sulfatoethylsulfonyl) ethylcarbamoyl) phenylamino, 4- (2- (2-sulfatoethylsulfonyl) ethylcarbamoyl) phenylamino, 3- (2- (vinylsulfonyl) ethylcarbamoyl) phenylamino, 4- (N-methyl-2- (2-sulfatoethylsulfonyl) ethylcarbamoyl) 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) ethyl sulfonylYl) phenylcarbamoyl) phenylamino, 3- (2-sulfatoethylsulfonyl) propylamino, N-methyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino, N-phenyl-N- (3- (2-sulfatoethylsulfonyl) propyl) -amino.

Preference is given to the group Q in the formula (9)¹And Q²Independently of one another, are fluorine, chlorine, cyanamide, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 3-trimethylammonium phenylamino, 4-trimethylammonium phenylamino, N-methyl-2-sulfoethylamino, 3-carboxypyrido, 4-carboxypyrido, 3-carbamoylpyrido, 4-carbamoylpyrido, 3- (2-sulfatoethylsulfonyl) phenylamino, 4- (2-sulfatoethylsulfonyl) phenylamino, 3- (vinylsulfonyl) phenylamino, 4- (3- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 4- (4- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 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.

Particular preference is given to the group Q in the formula (9)¹And Q²Independently of one another, fluorine, chlorine, cyanamide, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 3-trimethylammonium phenylamino, 4-trimethylammonium phenylamino, 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.

In the general formula (13), the group R²⁴To R²⁶Each is preferably methyl or ethyl.

The negative ion B-is preferably a sulfate ion or a chloride ion.

In the general formula (13), the quaternary ammonium group is preferably located meta or para to the free bond on the benzene nucleus.

Group Z²¹Examples of (a) are 2, 4-difluoropyrimidin-6-yl, 4, 6-difluoropyrimidin-2-yl, 5-chloro-2, 4-difluoropyrimidin-6-yl, 5-chloro-4, 6-difluoropyrimidin-2-yl, 4, 5-difluoropyrimidin-6-yl, 5-chloro-4-fluoropyrimidin-6-yl, 2, 4, 5-trifluoropyrimidin-6-yl, 4, 5-dichloropyrimidin-6-yl, 2, 4-dichloropyrimidin-6-yl, 4-fluoropyrimidin-6-yl, 4-chloropyrimidin-6-yl, or a compound having Q as shown in the above examples¹And Q²An exemplary radical of the formula (9) or 2, 3-dichloroquinoxaline-6-carbonyl.

Z²¹Preferably 2, 4-difluoropyrimidin-6-yl, 4, 6-difluoropyrimidin-2-yl, 5-chloro-2, 4-difluoropyrimidin-6-yl, 5-chloro-4, 6-difluoropyrimidin-2-yl or a compound having Q as defined above¹And Q²Preferred radicals are those of the general formula (9).

Z²¹Particularly preferably 2, 4-difluoropyrimidin-6-yl, 5-chloro-2, 4-difluoropyrimidin-6-yl or a compound having Q as defined above¹And Q²Particularly preferred groups of (3) are those of the formula (9).

Preferred mixtures comprise one or more dyes of the general formula (Ia) and one or more dyes of the general formula (IIa) and, if desired, one or more dyes of the general formulae (IIIa) to (IIIf):

in the general formulae (Ia) and (Ila), M, A, R¹、Z、D³And R are each as defined above.

In the formula (Ia), it is particularly preferred that A is phenylene and Z is vinyl or β -sulfatoethyl.

In the general formula (Ia), most preferably A is phenylene, R¹Is hydrogen and Z is vinyl or beta-sulfurAn acid ethyl group.

The dye mixtures according to the invention comprise from 30 to 95% by weight, preferably from 50 to 90% by weight, of the disazo dye of the formula (I), and from 5 to 70% by weight, preferably from 10 to 50% by weight, of the monoazo dye of the formula (II), and from 0 to 40% by weight, preferably from 5 to 25% by weight, of the dyes of the formulae (IIIa) to (IIIf).

Optionally, the dye mixtures according to the invention may also comprise up to 10% by weight, preferably up to 5% by weight, of one or more monoazo dyes of the general formula (15) or (16)

Wherein M and D²The definitions of the above are respectively. Particularly preferred is D²Is 4- (2-sulfatoethylsulfonyl) phenyl or 4-vinylsulfonylphenyl.

Dyes of the formula (I) are known from EP-A1046677 and dyes of the formula (II) are known from WO9610610, WO 9725377, WO 9947608 and EP-A922735.

The dyes of the general formulae (15) and (16) are obtainable by standard synthetic methods or are formed in some cases during the synthesis of the dyes of the general formula (I). They are commonly used as shading components.

The dye mixtures according to the invention can be present in the formulations in solid or liquid (dissolved) form. In solid form, they contain, according to the requirements of some extent, electrolyte salts which are customarily used in water-soluble dyes, in particular fibre-reactive dyes, such as sodium chloride, potassium chloride and sodium sulfate; and may additionally contain auxiliaries commonly used in industrial dyes, such as buffer substances capable of adjusting the pH of an aqueous solution to 3 to 7, such as sodium acetate, sodium citrate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate and disodium hydrogen phosphate; dye auxiliary agent, dust-proof agent and a small amount of drier; when they are present in the form of liquid, aqueous solutions (comprising thickeners conventionally used in printing pastes), they may also comprise substances which ensure a long life of these formulations, such as mildewcides.

When present in solid form, the dye mixtures of the invention are generally powders or granules which comprise electrolyte salts, which are generally referred to hereinafter as a formulation with or without at least one of the abovementioned auxiliaries. In this formulation, the dye mixture is present in an amount of 10 to 90% by weight, based on the formulation in which it is contained. The total amount of buffer substances present is generally up to 5% by weight, based on the formulation.

When the dye mixtures according to the invention are present in the form of aqueous solutions, the total dye content of these aqueous solutions is up to 50% by weight, for example from 5 to 50% by weight, the electrolyte salt content of these aqueous solutions preferably being less than 10% by weight, based on the aqueous solution; the aqueous solutions (liquid preparations) may contain the abovementioned buffer substances in general up to 5% by weight and preferably up to 2% by weight.

The dye mixtures of the invention can be prepared in a conventional manner: for example, dye mixtures are prepared by total mechanical mixing of individual dyes, whether present as dye powders or granules or synthetically obtained solutions or in the form of aqueous solutions, which may additionally contain customary auxiliaries; or by conventional diazotization and coupling of a mixture of the appropriate diazo component and coupling component in the desired proportions.

For example, when the formulae (I) and (II) bear a radical D²And D³The diazo component of (D) has the same meaning²＝D³) In this case, the amines of the general formula (17) are diazotized in a conventional manner and the diazo compounds obtained are then reacted in an aqueous medium at a pH below 3 with a mixture of 4-amino-5-hydroxynaphthalene-2, 7-disulfonic acid or 4-amino-5-hydroxynaphthalene-1, 7-disulfonic acid and optionally N-substituted 6-amino-4-hydroxynaphthalene-2-sulfonic acid or 3-amino-5-hydroxynaphthalene-2, 7-disulfonic acid to give a mixture of two red monoazo dyes of the formulae (15) and (II),

D²-NH₂ (17)

wherein D²The definition of (A) is as above.

The amine of the formula (18) is subsequently diazotized in a conventional manner, and the diazo compound obtained is then coupled in a second stage with the mixture of monoazo dyes of the formulae (15) and (II) obtained in the first stage at a pH of from 3 to 7.5 to give a mixture of dyes of the formulae (I) and (II),

D¹-NH₂ (18)，

wherein D²The definition of (A) is as above.

Alternatively, when formulae (I) and (II) bear D¹And D³The diazo component of (D) has the same meaning¹＝D³) When this is the case, the amines of the general formula (18) in which D is present can be diazotized in a conventional manner¹The diazo compound obtained is then reacted with an aqueous solution or suspension of a mixture of a red monoazo dye of the general formula (15) and optionally substituted 6-amino-4-hydroxynaphthalene-2-sulfonic acid in the stated proportions, first at a pH below 3 to give a mixture of two red monoazo dyes of the general formulae (15) and (II), and when the acid coupling is complete, the pH is increased to 4 to 7.5 and a second coupling of the monoazo dye of the general formula (15) is carried out to give a mixture of the two red monoazo dyes of the general formulae (15) and (II)

(I) And (II) a mixture of two dyes.

The amines of the general formula (17) can be used to prepare red monoazo dyes of the general formula (15) by conventional diazotization, in which D²The diazo compound obtained is then coupled in a first stage with 4-amino-5-hydroxynaphthalene-2, 7-disulfonic acid and/or 4-amino-5-hydroxynaphthalene-1, 7-disulfonic acid in an aqueous medium at a pH below 2, as defined in claim 1.

The dye mixtures according to the invention can be isolated in a conventional manner, suitably after addition of one or more, for example two or three, yellow components of the formulae (IIIa) to (IIIf) in solid form or in the form of an aqueous solution, by salting out, for example using sodium chloride or potassium chloride, or by spray drying.

In addition, the solutions of the dye mixtures of the general formulae (I) and (II) obtained as a result of the synthesis can be used directly as liquid preparations for dyeing, suitably after addition of one or more, for example two or three, yellow components of the general formulae (IIIa) to (IIIf) in solid form or in the form of aqueous solutions, and suitably after addition of buffer substances and suitable concentration or dilution.

Dye mixtures which contain vinylsulfonyl as active group in addition to β -chloroethylsulfonyl or β -thiosulfatoethylsulfonyl or β -sulfatoethylsulfonyl can be synthesized not only starting from appropriately substituted vinylsulfonylanilines or naphthylamines but also by reacting dye mixtures in which Z is β -chloroethyl, β -thiosulfatoethyl or β -sulfatoethyl with the desired moiety of a base and converting the β -substituted ethylsulfonyl into vinylsulfonyl. This transformation is carried out in a manner well known to the person skilled in the art.

The dye mixtures of the invention have useful application properties. They can be used for dyeing and printing hydroxyl-and/or carboxamido-containing materials, for example in the form of sheet-like structures such as paper and leather, or in the form of films such as films composed of polyamide, or in the form of blocks such as polyamide and polyurethane, but are used in particular for dyeing and printing these materials in the form of fibers.

The present invention therefore also provides for the use of the dye mixtures according to the invention for dyeing or printing these materials or for dyeing or printing these materials in a conventional manner by using the dye mixtures according to the invention or the individual components thereof (dyes), respectively, as colorants together. Preferably, the material used is a fibrous material, in particular a woven fabric or yarn in the form of a fabric, such as in a bundle or package.

Hydroxyl-containing materials are those from natural or synthetic sources, such as cellulosic fibre materials or regenerated products thereof and polyvinyl alcohol. The cellulose fiber material is preferably cotton, and other plant fibers such as flax, hemp, jute and ramie fibers are also selected; regenerated cellulose fibers are, for example, short and long viscose, and chemically modified cellulose fibers, such as aminated cellulose fibers or those described in WO 96/37641 and WO 96/37642 and in EP 0538785 and EP 0692559.

Carboxamido-containing 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, nylon-6, nylon-6, nylon 11 and nylon-4.

The dye mixtures according to the invention can be applied and fixed to the materials, in particular the fibre materials, by the application techniques known for water-soluble dyes, in particular fibre-reactive dyes. For example, the dye mixtures of the present invention produce dyeings on fibers with excellent dye yields by the exhaust process using a variety of acid binding agents and optionally neutral salts such as sodium chloride or sodium sulfate at large and small bath ratios such as liquor to fabric ratios of 5: 1 to 100: 1, preferably 6: 1 to 30: 1. Preferably at 45 to 105 c, optionally at superatmospheric pressure up to 130 c, but preferably in an aqueous bath at 30 to 95 c, in particular at 45 to 65 c, in the presence or absence of customary dyeing auxiliaries. One possible method in this context is to introduce the material into a warm bath and gradually heat the warm bath to the desired dyeing temperature and complete the dyeing process at this temperature. Neutral salts to promote exhaustion of the dye may be added to the dye bath as required after the actual dyeing temperature is reached.

The pad dyeing process likewise provides excellent dye yields and excellent dye build-up on cellulosic fibers, which can be fixed in a conventional manner in batches by room temperature or at elevated temperatures, e.g. at temperatures up to about 60 ℃, in a continuous manner, e.g. by pad-dry-pad steaming process, steaming or dry heat treatment.

Similarly, conventional printing processes for cellulose fibers produce well-defined contours and a clear white undertone, which can be carried out in one stage, such as by printing with a printing paste containing sodium bicarbonate or some other acid binding agent, and subsequently steaming at a temperature of 100 to 103 ℃; or in two stages, such as by printing with neutral or weakly acidic printing dyes, followed by fixing by overbiadding the printed material through a hot alkaline bath containing an electrolyte or with a padding liquor containing a basic electrolyte and then over-padding the package of material over-padded with alkali or by steaming or subsequent dry heat treatment of the over-padded material with alkali. Changes in the fixing conditions have only a minor effect on the printing result.

When fixing by dry heat treatment according to the conventional hot fixing method, hot air of 120 to 200 ℃ is used. In addition to conventional steam at 101 to 103 ℃, superheated steam and high-pressure steam up to 160 ℃ may be used.

Acid binding agents used to fix the dyes of the dye mixtures of the invention to the cellulose fibres are, for example, water-soluble basic salts of alkali metals and alkaline earth metals of inorganic or organic acids, or compounds which release alkali on heating, and also alkali metal silicates. Particularly suitable are alkali metal hydroxides and alkali metal salts of weak to moderately acidic inorganic or organic acids, the preferred alkali metal compounds being sodium and potassium compounds. These acid-binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogen phosphate and disodium hydrogen phosphate, sodium trichloroacetate, sodium phosphate or water glass or mixtures thereof, for example mixtures of aqueous sodium hydroxide solution and water glass.

The dye mixtures according to the invention have outstanding tinctorial strength when applied to cellulosic fibre materials by dyeing or printing in the absence or in the presence of very small amounts of alkali or alkaline earth metal compounds. For example, a light shade requires no electrolyte salt, a medium shade requires at most 5g/L of electrolyte salt, and a dark shade requires at most 10g/L of electrolyte salt.

According to the invention, light shades mean the use of 2% by weight of dye, based on the substrate to be dyed, medium shades mean the use of 2 to 4% by weight of dye, based on the substrate to be dyed, and dark shades mean the use of 4 to 10% by weight of dye, based on the substrate to be dyed.

Dyeings and prints obtained using the dye mixtures according to the invention can have bright shades; more particularly, the dyeings and prints on cellulosic fibre materials have good light fastness and particularly good wet fastnesses, such as fastness to washing, grinding, water, sea water, cross-dyeing and acidic and alkaline perspiration, and also fastness to pleating, hot pressing and rubbing. In addition, the cellulosic dyeings obtained after conventional post-treatment with rinsing to remove the unfixed dye moieties exhibit excellent wet fastness, particularly because the unfixed dye moieties are easy to wash off due to their good solubility in cold water.

In addition, the dye mixtures according to the invention can also be used for the fibre-reactive dyeing of wool. In addition, wool which has been subjected to a non-felting finish and a low-felting finish (cf. for example H.Path, Lehrbuch der Textuchemie, Springer Vertag, third edition (1972), page 295-299, especially by Hercosett processes (298); J.Soc.Dyers and Colourists, 1972, 93-99 and 1975, 33-44) can be dyed to very good fastness properties. The process for dyeing wool herein is carried out in a conventional manner in an acidic medium. For example, acetic acid and/or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate may be added to the dye bath to obtain the desired pH. In order to obtain dyes with acceptable levelling properties, it is advisable to add conventional levelling agents, such as levelling agents based on the reaction products of cyanuric chloride with tripling molar amounts of aminobenzenesulfonic acid and/or aminonaphthalenesulfonic acid, or based on the reaction products of, for example, octadecylamine with ethylene oxide. For example, the dye mixtures according to the invention are preferably subjected to an initial exhaustion of the dyebath which is acid and controlled to a pH of about 3.5 to 5.5, and then becomes neutral as the dyeing time approaches the end pH and optionally is weakly alkaline, with a pH of at most 8.5, to produce a completely reactive bond between the dyes of the dye mixtures according to the invention and the fibers, in particular for deep-dyeing. At the same time, the dye moiety that is not actively bound is removed.

The process described herein is also applicable to the formation of dyeings on fibrous materials composed of other natural polyamides or synthetic polyamides and polyurethanes. Generally, the material to be dyed is introduced into a dye bath at a temperature of about 40 ℃ with stirring for a certain time, and the dye bath is then adjusted to the desired weakly acidic pH, preferably with weak acetic acid, and the actual dyeing is carried out at a temperature of 60 to 98 ℃, however, the dyeing can also be carried out at the boiling point or at a temperature of up to 106 ℃ in a sealed dyeing apparatus. The dye mixtures according to the invention can also be used advantageously in conventional continuous dyeing processes, since they have excellent water solubility. The dye mixtures according to the invention have a high tinctorial strength.

The dye mixtures according to the invention make it possible to dye the materials, preferably fibrous materials, to deep blue to blackish shades having good fastness properties.

The examples which follow serve to illustrate the invention. Parts and percentages are by weight unless otherwise indicated. Parts by weight versus parts by volume refer to kilograms versus liters. The compounds described in the examples with the formula are all shown in the form of the sodium salts, since they are usually prepared and isolated as salts, preferably as sodium or potassium salts, and used for dyeing in the form of salts. The starting compounds described in the examples below can be used in the synthesis in the form of the free acids or likewise in the form of their salts, preferably in the form of alkali metal salts, such as sodium or potassium salts.

Example 1

70 parts of an electrolyte-containing dye powder comprising 70% parts of a deep blue disazo dye of the formula (IA), 20 parts of an electrolyte-containing dye powder comprising 75% parts of an orange-red monoazo dye of the formula (IIA) and 10 parts of an electrolyte-containing dye powder comprising 70% parts of a yellow disazo dye of the formula (IIIf-1) are mechanically mixed with one another.

The resulting dye mixtures according to the invention provide black-black dyeings and prints on, for example, cotton under the dyeing conditions customary for reactive dyes.

Example 2

Dissolving 70 parts of an electrolyte-containing dye powder comprising 70% parts of a deep blue disazo dye of the formula (IA), 20 parts of an electrolyte-containing dye powder comprising 80% parts of a red monoazo dye of the formula (IIB) and 10 parts of an electrolyte-containing dye powder comprising 70% parts of a yellow disazo dye of the formula (IIIc-1) in 500 parts of water,

and adjusting the pH value of the obtained solution to 5.5-6.5. The dye solution is evaporated or spray dried to give a dye mixture which provides a jet black dyeing and printing on cotton under the dyeing conditions customary for reactive dyes.

Example 3

a) 281 parts of 4- (. beta. -sulfatoethylsulfonyl) aniline are suspended in 650 parts of ice water and 180 parts of 30% hydrochloric acid and diazotized by dropwise addition of 173 parts of 40% sodium nitrite. 223 parts of 4-amino-5-hydroxynaphthalene-2, 7-disulfonic acid and 72 parts of 6-amino-4-hydroxynaphthalene-2-sulfonic acid are added and the coupling of the first step is carried out at a pH of from 1 to 1.8 and below 20 ℃ to form a mixture of two red monoazo dyes according to the formulae (15-1) and (IIC). The pH range is adjusted and maintained during the coupling by adding a total of about 150 parts of sodium bicarbonate.

b) In a second, single reaction vessel 280 parts of 4-amino-N- (3- ((β -sulfatoethyl) -sulfonyl) phenyl) benzamide are suspended in 1600 parts of ice water, adjusted to a pH of 6.5-7 with about 35 parts of sodium carbonate and mixed with 122 parts of a 40% sodium nitrite solution. The suspension is added dropwise to a mixture of 450 parts of ice, 350 parts of ice water and 255 parts of concentrated hydrochloric acid. After subsequent stirring at 5-10 ℃ for 2 hours, excess nitrite is reduced with sulfamic acid and the resulting diazo suspension is pumped into the red monoazo dye mixture of a). Subsequently adjusting the pH of the reaction mixture to 5-6 with sodium carbonate at a temperature below 25 ℃ and, after the coupling reaction has ended, adding 110 parts of the yellow monoazo dye of the formula (IIIa-1) in the form of an aqueous solution to the reaction mixture and isolating by spray drying the resulting mixture of dyes (IB), (IIC) and (IIIa-1) in a ratio of 73: 16: 10.

Alternatively, the pH of the resulting dye solution may be buffered to a pH in the range of 5.5 to 6 by the addition of a phosphate buffer and adjusted by further dilution or concentration to give a liquid formulation of defined strength.

The resulting dye mixture of the invention dyes cotton to black shades.

Example 4

a) 178 parts of 4- (. beta. -sulfatoethylsulfonyl) aniline are suspended in 420 parts of ice water and 115 parts of 30% hydrochloric acid and diazotized by dropwise addition of 110 parts of 40% sodium nitrite solution. 201 parts of 4-amino-5-hydroxynaphthalene-2, 7-disulfonic acid are added and the coupling of the first step is carried out at a pH of from 1 to 1.3 and below 20 ℃ to form the red monoazo dye of the formula (15-1). The pH range was adjusted and maintained by adding a total of about 90 parts of sodium bicarbonate during the coupling.

b) 353 parts of 4-amino-N- (3- ((β -sulfatoethyl) -sulfonyl) phenyl) benzamide are suspended in 1950 parts of ice water in a second single reaction vessel, adjusted to a pH of 6.5-7 with about 65 parts of sodium carbonate and mixed with 154 parts of 40% sodium nitrite solution. The suspension was added dropwise to a mixture of 550 parts of ice, 450 parts of ice water and 320 parts of concentrated hydrochloric acid. After subsequent stirring at 5-10 ℃ for 2 hours, the excess nitrite is reduced with sulfamic acid and the resulting diazo suspension is pumped into a solution of the red monoazo dye a). The reaction mixture was mixed with 80 parts of 3-amino-5-hydroxynaphthalene-2, 7-disulfonic acid.

Subsequently, the pH is first adjusted to 1.5-2.5 using sodium bicarbonate and kept in this range below 25 ℃ and acid coupled with 3-amino-5-hydroxynaphthalene-2, 7-disulfonic acid to form the red monoazo dye of the formula (IID). After the coupling is complete, the pH is stabilized at 5 to 6 by adding sodium carbonate and the reaction mixture obtained after the second coupling reaction of the monoazo dye of the formula (15-1) is mixed with 100 parts of the yellow disazo dye of the formula (IIIe-1).

The resulting mixtures of dyes (IB), (IID) and (IIIe-1) were isolated by spray drying in a ratio of 70: 20: 10.

The resulting dye mixture of the invention dyes cotton to black shades.

Example 5

406 parts of 4-amino-N- (3- ((β -sulfatoethyl) sulfonyl) phenyl) benzamide are suspended in 2250 parts of ice water, the pH of the suspension is adjusted to 6.5 to 7 with about 75 parts of sodium carbonate and 177 parts of a 40% sodium nitrite solution are added. The suspension is added dropwise to a mixture of 630 parts of ice, 520 parts of ice water and 370 parts of concentrated hydrochloric acid. After subsequent stirring at 5-10 ℃ for 2 hours, the excess nitrite is reduced with sulfamic acid and the resulting diazo suspension is pumped into 426 parts of an aqueous solution of the red monoazo dye (15-1), the preparation of which is described in example 4 a). The reaction mixture is then mixed with 80 parts of 3-amino-5-hydroxynaphthalene-2, 7-disulfonic acid and 38 parts of 5-hydroxy-1- (4-sulfophenyl) -1H-pyrazole-3-carboxylic acid. Subsequently, acidic coupling forms the red monoazo dye of formula (IID) below 25 ℃ by first adjusting the pH to 1.5-2.5 with sodium bicarbonate and maintaining it within this range. After the acidic coupling, the pH is stabilized at 5-6 by adding sodium carbonate and, after the end of the second coupling reaction, the dyes (IB), (IID) and (IIIc-1) are isolated by spray drying to give a mixture of 70: 20: 10.

The resulting dye mixture of the invention dyes cotton to black shades.

Example 6

350 parts by weight of 4-amino-N- (4- ((β -sulfatoethyl) sulfonyl) phenyl) benzamide are suspended in 2000 parts of ice water, the pH of the suspension is adjusted to 6.5 to 7 with about 44 parts of sodium carbonate, and 152 parts of 40% sodium nitrite solution are added. The suspension is added dropwise to a mixture of 560 parts of ice, 440 parts of ice water and 320 parts of concentrated hydrochloric acid. After subsequent stirring at 5-10 ℃ for 2 hours, excess nitrite is reduced with sulfamic acid and the resulting diazo suspension is pumped into an aqueous solution of 474 parts (15-1) of red monoazo dye and 173 parts of red monoazo dye of the formula (IIC) and prepared analogously to example 3 a). The reaction mixture is then mixed with 44 parts of 4- (-5-hydroxy-3-methylpyrazol-1-yl) benzenesulfonic acid and subsequently adjusted to a pH of 5 to 6 with sodium carbonate at below 25 ℃. After the coupling has ended, a mixture of the three dyes (IA), (IIC) and (IIIc-2) in a ratio of 73: 16: 11 is obtained by separation by spray drying.

Alternatively, the dye solution obtained may also be buffered at a pH in the range of 5.5 to 6 by adding a phosphate buffer and adjusted by further dilution or further concentration to give a liquid formulation of defined strength.

The resulting dye mixture of the invention dyes cotton to black shades.

Example 7

a) 281 parts of 4- (. beta. -sulfatoethylsulfonyl) aniline are suspended in 650 parts of ice water and 180 parts of 30% hydrochloric acid and diazotized by dropwise addition of 173 parts of 40% sodium nitrite. 174 parts of 4-amino-5-hydroxynaphthalene-2, 7-disulfonic acid, 87 parts of 6-amino-4-hydroxynaphthalene-2-sulfonic acid and 17 parts of 2, 4-diaminobenzenesulfonic acid are added and the coupling of the first step is carried out at a pH of from 1 to 1.8 and below 20 ℃ to form a mixture of three monoazo dyes of the formulae (15-1), (IIC) and (IIIa-1). The pH was adjusted and maintained within the stated range during the coupling by addition of solid sodium bicarbonate.

b) In a second single reaction vessel 255 parts of 4-amino-N- (3- ((β -sulfatoethyl) -sulfonyl) phenyl) benzamide are suspended in 1500 parts of ice water, adjusted to a pH of 6.5-7 with about 32 parts of sodium carbonate and mixed with 111 parts of 40% sodium nitrite solution. The suspension is added dropwise to a mixture of 410 parts of ice, 320 parts of ice-water and 235 parts of concentrated hydrochloric acid. After subsequent stirring at 5-10 ℃ for 2 hours, the excess nitrite is reduced with sulfamic acid and the resulting diazo suspension is pumped into a mixture of the three red monoazo dyes of a). Subsequently, the reaction mixture was adjusted to a pH of 5-6 with sodium carbonate at a temperature below 25 ℃ and after the end of the second coupling reaction a mixture of the dyes (IB), (IID) and (IIIb-1) in the ratio of 67: 23: 10 was isolated by spray drying.

The resulting dye mixture of the invention dyes cotton to black shades.

Examples 8 to 159

The examples in the table below further describe the dye mixtures of the general formulae (I) to (III) according to the invention, each described in the form of the sodium salt. The mixing ratio is expressed as a weight percentage. The dye mixtures dye cotton, for example, to black shades by the dyeing methods customary for reactive dyes.

Dye mixtures of examples 1 or 2

Examples 32 to 57

Examples 1, 2 and 8-31 were repeated using dye (IB) instead of dye (IA).

Examples 58 to 83

Examples 1, 2 and 8-31 were repeated using dye (IC) instead of dye (IA):

examples 84 to 109

Examples 1, 2 and 8-31 were repeated using dye (ID) instead of dye (IA):

example 110-

Examples 1, 2 and 8-31 were repeated using dye (IE) instead of dye (IA):

example 3 ofDye mixtures

Examples of the embodiments	Dyes of the general formula (I)	Dyes of the general formula (II)	Dyes of the general formula (III)	(I) The ratio of (II) to (III)
					136	(IA)	(IIC)	(IIIf-1)	75∶15∶10
137	(IB)	(IIG)	(IIIc-1)	68∶22∶10
					138	(IC)	(IIC)	(IIIb-2)	72∶18∶10
139	(IC)	(IIG)	(IIIe-1)	70∶20∶10
					140	(ID)	(IIC)	(IIIa-1)	73∶16∶11
141	(ID)	(IIG)	(IIIf-1)	74∶16.10
					142	(IE)	(IIC)	(IIIb-3)	75∶15∶10
143	(IE)	(IIG)	(IIIf-2)	73∶17∶10

Dye mixtures of example 4

Dye mixture of example 7

Application example 1

2 parts of the dye obtained in examples 1 to 7 are dissolved in 999 parts of water, 5 parts of sodium carbonate, 0.7 part of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent are added. To this dye bath was added 100g of cotton fabric. The temperature of the dye bath is first maintained at 25 ℃ for 10 minutes, then raised to the final temperature (40-60 ℃) within 30 minutes and maintained at this temperature for a further 60-90 minutes. The dyed material was then rinsed initially with tap water for 2 minutes and then with deionized water for 5 minutes. The dyed material was neutralized for 10 minutes at 40 ℃ in 1000 parts of an aqueous solution containing 1 part of 50% acetic acid. This was followed by rinsing with deionized water at 70 c, then soaping with detergent at the boil for 15 minutes, rinsing again and drying. Strongly dark blue to gray dyeings having excellent fastness properties are obtained.

Application example 2

4 parts of the dye obtained in examples 1 to 7 and 5 parts of sodium chloride are dissolved in 999 parts of water, and 5 parts of sodium carbonate, 0.7 part of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent are added. To this dye bath was added 100g of cotton fabric. The rest of the procedure was as described in application example 1. Strongly deep blue to black dyeings having excellent fastness properties are obtained.

Application example 3

8 parts of the dye obtained in examples 1 to 7 and 10 parts of sodium chloride are dissolved in 997 parts of water, 5 parts of sodium carbonate, 1.3 parts of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent are added. To this dye bath was added 100g of cotton fabric. The rest of the procedure was as described in application example 1. A dark-black dyeing having excellent fastness properties is obtained.

Claims (16)

1. A reactive dye mixture comprising one or more, such as two or three, preferably one or two, dyes of the general formula (I) below; one or more, such as two or three, preferably one or two, dyes of the general formula (II) below; and optionally one or more, such as two or three, preferably one or two, dyes of, for example, the following formulae (IIIa) to (IIIf) as constituents for mixing or shading:

wherein:

D¹and D²Each a group of the formula (1), or each a phenyl group of the formula (5), or each a naphthyl group of the formula (6),

wherein:

R¹is hydrogen, (C)₁-C₄) -an alkyl, aryl or substituted aryl group,

R²and R³Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, amido or halogen; and

a is a phenylene group of the general formula (2), or a naphthylene group of the general formula (3), or a polymethylene group of the general formula (4),

wherein:

R⁴and R⁵Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, amido or halogen;

wherein:

R⁶and R⁷Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, amido or halogen;

-(CR⁸R⁹)_k- (4)

wherein:

k is an integer greater than 1, and

R⁸and R⁹Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, cyano, amido, halogen or aryl; and

X¹is hydrogen or formula-SO₂-a group of Z;

wherein:

R¹⁰and R¹¹Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, amido or halogen; and

X²having X¹One of the meanings of (a);

wherein:

R¹²and R¹³Independently hydrogen, (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, amido or halogen; and

X³having X¹One of the meanings of (a);

z is-CH ═ CH₂、-CH₂CH₂Z¹Or a hydroxyl group, or a mixture thereof,

wherein:

Z¹is a hydroxyl group or a base-eliminable group; and

m is hydrogen, an alkali metal or one equivalent of an alkaline earth metal;

D³having D¹Or D²Or a group of the general formula (7):

wherein:

R²¹and R²²Independently have R²And R³One of the meanings of (a);

R²³is hydrogen, (C)₁-C₄) -alkyl, unsubstituted phenyl or (C)₁-C₄) -alkyl-, (C)₁-C₄) -alkoxy-, sulfo-, halogen-or carboxy-substituted phenyl; and

Z²¹is a fiber-reactive heterocyclic group;

r is hydrogen or (C)₁-C₄) -alkyl, unsubstituted phenyl or (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -phenyl substituted by alkoxy, sulfo, halogen, carboxyl, acetamido or ureido; or is a group of formula (14):

CH₂-SO₃M (14)，

wherein M is as defined above; and

n is 1 or 2, and n is a hydrogen atom,

D⁴、D⁵、D⁶、D⁷and D⁸Having D¹、D²Or D³One of the meanings of (A), and

if R is³¹Is not a group of the formula (8) or (9), D⁴And D⁵Or D⁶And D⁸Containing at least one group of the formula-SO₂Z or Z²¹A fiber-reactive group of (a);

R³¹is hydrogen, acetyl, carbamoyl, sulfomethyl or a group of the general formula (8) or (9),

R³²is hydrogen or a sulfomethyl group,

R³³is methyl, carboxyl or has C₁-C₄-a carboxyalkyl group of an alkyl group,

R³⁴is hydrogen or a methyl group,

R³⁵is hydrogen, cyano, carbamoyl, carboxy or sulfomethyl,

R³⁶is methyl, ethyl or beta-sulfoethyl,

R³⁷is methyl, carboxyl or has C₁-C₄-a carboxyalkyl group of an alkyl group,

R³⁸is an acetamido group, a ureido group or a methyl group,

R³⁹is hydrogen, methyl or methoxy,

m is 0 or 1, and m is,

p is 1, 2 or 3, and

Z³having Z²¹One of the meanings of (a);

wherein, in the general formula (I), D¹And D²At least one of them is a group of the general formula (1); and when A is a group of the formula (4), R¹Is aryl or substituted aryl; and the reactive dyes of the general formula (I) contain at least one-SO₂-a Z group.

2. Dye mixture according to claim 1, wherein the heterocyclic reactive group Z²¹Is a fibre-reactive radical of the general formula (8) or (9) or (10):

wherein:

v is fluorine or chlorine;

U¹、U²independently fluorine, chlorine or hydrogen; and

Q¹、Q²independently chlorine, fluorine, cyanamido, hydroxyl, (C)₁-C₆) Alkoxy, phenoxy, sulfophenoxy, mercapto, (C)₁-C₆) -alkylthio, pyrido, carboxypyrido, carbamoylpyrido or a group of general formula (11) or (12):

wherein:

R^2’is hydrogen or (C)₁-C₆) Alkyl, sulfo- (C)₁-C₆) -alkyl, or unsubstituted phenyl or (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -phenyl substituted by alkoxy, sulfo, halogen, carboxyl, acetamido or ureido;

R^3’and R^4’Independently have R^2’One of the meanings of (a); or in combination form- (CH)₂)_j-wherein j is 4 or 5; or combined to form-(CH₂)₂-E-(CH₂)₂-, where E is oxygen, sulfur, sulfo, -NR^5’-, wherein R^5’Is (C)₁-C₆) -an alkyl group; or a group of the general formula (13):

wherein:

R²⁴、R²⁵and R²⁶Each is (C)₁-C₄) -alkyl or (C)₁-C₄) -a hydroxyalkyl group; and

B^-is an equivalent of a negative ion such as a hydrogen sulfate ion, a fluoride ion, a chloride ion, a bromide ion, a dihydrogen phosphate ion, a hydrogen phosphate ion, a hydroxide ion, or an acetate ion;

w is unsubstituted phenylene or phenylene which is substituted by 1 or 2 substituents, such as (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, carboxy, sulfo, chloro, bromo; or is (C)₁-C₄) Alkylene-arylene or (C)₂-C₆) Alkylene which may be interrupted by oxygen, sulfur, sulfo, amino, carbonyl, carboxamide groups; or is phenylene-CONH-phenylene which is unsubstituted or substituted by (C)₁-C₄) Alkyl radicals, (C)₁-C₄) -alkoxy, hydroxy, sulfo, carboxy, amido, ureido or halogen substitution; or naphthylene, which is unsubstituted or substituted by one or two sulfo groups; and

z is as defined in claim 1;

3. a reactive dye mixture according to either one or both of claims 1 and 2, wherein the substituent R¹To R⁵、R⁸To R¹¹And R²³Each is hydrogen, R⁶、R⁷、R¹²、R¹³、R²¹And R²²Each is hydrogen or sulfo, and R²⁴、R²⁵And R²⁶Each is methyl.

4. A reactive dye mixture according to at least one of claims 1 to 3, wherein Z is vinyl, β -chloroethyl or β -sulfatoethyl.

5. A reactive dye mixture according to at least one of claims 1 to 4, wherein the group Q in the formula (9)¹And Q²Independently of one another, fluorine, chlorine, cyanamide, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 3-trimethylammonium phenylamino, 4-trimethylammonium phenylamino, 3- (2-sulfatoethylsulfonyl) phenylamino, 4- (2-sulfatoethylsulfonyl) phenylamino, 3- (vinylsulfonyl) phenylamino, 4- (vinylsulfonyl) phenylamino, N-methyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino or N-phenyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino.

6. A reactive dye mixture according to one or more of claims 1 to 5, comprising at least one dye of the general formula (Ia) and at least one dye of the general formula (IIa),

m, A, R therein¹、Z、D³And R are each as defined in claim 1.

7. A reactive dye mixture according to claim 6, wherein in formula (Ia), A is phenylene and Z is vinyl or β -sulfatoethyl; in formula (IIa), R is hydrogen or sulfomethyl, D³Is as defined in claim 1.

8. A reactive dye mixture as claimed in one or more of claims 1 to 7, comprising from 30 to 95% by weight of the dye of the formula (I) and from 5 to 70% by weight of the dye of the formula (II).

9. The reactive dye mixture of claim 8, further comprising 3 to 50% by weight of at least one dye of formulae (IIIa) - (IIIf).

10. A reactive dye mixture according to one or more of claims 1 to 9, comprising from 0.5 to 6% by weight each of one or more monoazo dyes of the formula (15) and/or one or more monoazo dyes of the formula (16),

wherein D²And M are each as defined in claim 1.

11. A reactive dye mixture according to one or more of claims 1 to 10, comprising up to 95% by weight of more than one deep blue disazo dye of the formula (I).

12. A process for the preparation of a dye mixture as claimed in one or more of claims 1 to 11, which comprises mechanically mixing the dyes of the formulae (I) and (II) and, if used, of the formula (III) in the solid form or in the form of an aqueous solution in the desired proportions.

13. A process for the preparation of a dye mixture as claimed in claim 1 to 10, wherein the radicals D are present in the general formulae (I) and (II)²And D³The process comprises diazotizing an amine of the general formula (17) in a conventional manner,

D²-NH₂ (17)，

wherein D²Is as defined in claim 1, wherein,

then reacting the diazo compound with a mixture of 4-amino-5-hydroxynaphthalene-2, 7-disulfonic acid or 4-amino-5-hydroxynaphthalene-1, 7-disulfonic acid and optionally N-substituted 6-amino-4-hydroxynaphthalene-2-sulfonic acid or 3-amino-5-hydroxynaphthalene-2, 7-disulfonic acid to give the monoazo dyes of the formulae (15) and (II),

the amine of the general formula (18) is then diazotized in a conventional manner,

D¹-NH₂ (18)，

wherein D¹Is as defined in claim 1, wherein,

the diazo compound obtained is then coupled in a second stage with the mixture of monoazo dyes of the general formulae (15) and (II) obtained in the first stage to give a mixture of dyes of the general formulae (I) and (II).

14. A process for preparing dye mixtures according to one or more of claims 1 to 10, wherein the radicals D are present in the general formulae (I) and (II)¹And D³The diazo component of (a), the process comprising:

in a first stage, the amines of the general formula (18) in which D is present are diazotized in a conventional manner¹Defined as in claim 1, and reacting the diazo compound obtained with a mixture of a red monoazo dye of the general formula (15) and optionally N-substituted 6-amino-4-hydroxynaphthalene-2-sulfonic acid or 3-amino-5-hydroxynaphthalene-2, 7-disulfonic acid in the stated proportions to give a mixture of monoazo dyes of the general formulae (15) and (II),

a second coupling of the monoazo dye of the general formula (15) is then carried out to give a mixture of two dyes of the general formulae (I) and (II).

15. An aqueous liquid formulation comprising a dye mixture according to one or more of claims 1 to 13 in a total dye content of from 5 to 50% by weight.

16. Use of a reactive dye mixture according to one or more of claims 1 to 14 for dyeing and printing hydroxyl-and/or carboxamido-containing fibre materials.