HK1001093B - Fibre reactive dyes and mixtures of dyes and their utilization - Google Patents

Description

The present invention relates to mixtures of fibre-reactive dyes suitable for dyeing cellulose-containing fibre materials from water baths and for printing cellulose-containing fibre materials suitable for drawing and continuous dyeing processes, and which give wet and light dyes.

Mixtures of dyes for the trichromic staining of textile fibres containing a yellow dye of the formula (1) and a red dye of the formula (2) are already known from GB-A-2226336, but the residues of A1, A2 and A3 are different.

The subject matter of the invention is mixtures of dyes characterized by the fact that they are dyes of the formulae and where A1, A2 and A3 are identical and each contains the residue of a mono-azo, polyazo, metal complex azo, anthraquinone, phthalocyanin, formazane, azomethine, dioxazine, phenazine, stilbene, triphenyl methane, xanthine, thioxanthone, nitroaryl, naphthoquinone, pyrenquinone or peryl tetracarbimide dye, R1, R2, R3, R4 and R5 independently of each other or C1-C4 alkyl, which may be substituted by halogen, hydroxy, cyan, C1-C4-alkoxy, C1-C4-alkoxy, carboxy, fluorocyclo, heterofamoyl, sulfoam or sulfoam, an aliphatic hydroxide, an aliphatic hydroxide, Z1 or Z2 or a sulphuric acid, X1 or X2 or a heterocyclo, and may contain up to five other aromatic hydroxides, and may be composed of a ring of hydrogen, bromine, sulphate or sulphur, and may be connected to each other aromatic hydroxide, and may be formed by a ring of hydrogen, bromine, sulphur or sulphur, and may be composed of a heterocycloyl or hydrogen.

The residue A1, A2 or A3 may contain the substituents common to organic dyes bound to its base.

Other examples of substituents in the residue A1, A2 and A3 respectively are: alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl or butyl, alkoxy groups with 1 to 4 carbon atoms, such as methoxy, aethoxy, propopxy, isopropoxy or butyxy, and acylamine groups with 1 to 8 carbon atoms, in particular alkaneolamine groups, such as acetyl, propionylamine or benzoylamine, phenylamine, N,N-diethyl-β-hydroxylamine, N,N-diethyl-β-sulphate, benzoyl-β-sulphate, benzoyl-β-carbonyl, N,N-diethyl-β-carbonyl, N,N-diethyl-β-carbonyl, N,N-diethyl-β-carbonyl, A,N-diethyl-β-carbonyl, A,N-diethyl-β-carbonyl, A,N-diethyl-β-carbonyl, A, A,N-diethyl-β-carbonyl, A, A,A,A,A,A,A,A,A,A,A,A,A,A,A,A,A,A,A,A,A,A,B,A,B,B,A,B,A,B,B,A,B,B,B,B,B,A,B,B,B,B,B,B,B,B,C,B,B,C,B,B,C,B,B,C,B,C,B,C,B,C,B,C,B,C,B,C,D,B,C,D,B,C,D,D,D,D,D,D,E,E,E,E,E,B,E,B,B,E,B,B,B,B,E,B,B,F,B,B,B,F,F,F,F,B,F,F,G,F,G,G,

The residue R1, R2, R3, R4 or R5 respectively, if an alkyl residue, is straight-chain or branched and may be further substituted, e.g. by halogen, hydroxy, cyan, C1-C4-alkoxy, C1-C4-alkoxycarbonyl, carboxy, sulfamoyl, sulpho or sulphate. For R1, R2, R3, R4 and R5, the following residues are given as examples: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, carboxymethyl, β-butylpropyl, β-carboxy, methoxycarbonyl, methoxycarbonyl, methoxycarbonyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, β-methyl, and β-methyl, and β-methyl.

The residues X1, X2 and X3 independently mean fluorine, chlorine, bromine, carboxypyridinium or a sulpho group.

The term aliphatic bridging link also includes cycloaliphatic residues. Thus, B can be a straight-chain or branched C1-C10 alkyl residue; in particular, an alkyl residue with 2 to 6 carbon atoms is considered, e.g. ethylene, propylene, butylene, hexylene or cyclohexylene. The B residue can contain further substituents, e.g. halogen atoms, such as fluorine, chlorine and bromine, alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl and propyl, alkoxy groups with 1 to 4 carbon atoms, such as methoxy, aethoxy, propopoxy and isopropoxy, carboxy or sulfoxyl.

As substituted amino groups For example, in the case of alkylamino, N,N-dialkylamino, cycloalkylamino, N,N-dicycloalkylamino, aralkylamino and arylamino groups, mixed substituted amino groups such as N-alkylamino-N-cyclohexylamino and N-alkylamino-N-arylamino groups, and amino groups containing heterocyclic residues which may contain further condensed carbocyclic rings, and amino groups where the amino group is a member of an N-heterocyclic ring containing further phenyl heterocycles. The above mentioned heterocyclic residues may be widely or only partially hydrogenated, low or higher glycol, and may be derived from the amino group containing the cycloacetyl glycol, such as cycloacetyl, cycloacetyl, cycloacyl, cycloacyl, cycloacyl, cycloacyl, cycloacyl, cycloacyl, cycloacyl, cycloacyl, cycyl, cycloacyl, cycyl, cycloacyl, cycyl, cycyl, cycloacyl, cycyl, cycyl, cycloacyl, cycyl, cycyl, cycloacyl, cycyl, cycyl, cycloacyl, cycyl, cycyl, cycloacyl, cyc, cycloacyl, cyc, cyc, cycloacyl, cyc, cyc, cycloacyl, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, cyc, may also contain fibrous reactive residues.

As examples of the amino residue The following are specified in formula (1): -NH2, methyl ethylamine, aethylamine, propylamine, isopropylamine, butylamine, β- ((acetylamine) ethylamine, hexylamine, β-methoxyethylamine, γ-methoxypropylamine, β-methoxyethylamine, N,N-dimethylamine, N,N-diethylamine, β-chlorethylamine, β-cyanethylamine, γ-propylamine, β-carboxymethylamine, sulphonylamine, β-sulphonylamine, β-hydroxyphenylamine, N,N-diethylamine, β-diethylamine, β-hydroxyphenylamine, β-diethylamine, N,N-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, β-diethylamine, 2-diethylamine, 2-diethylamine, 2-diethylamine, 2-diethylamine, 2-dilamine, 2-dilamine, 2-dilamine, 2-dilamine, 2-dilamine, 2-dilamine, 2-dilamine, 2-dilamine, 2-dilamine, 2-dilamine, 2-dilamine, 2-dilamine, 2-dilamine, 2-dilam

In addition, consideration should be given to reagents of formulae (1) and (2), where the residue A1, A2 or A3 respectively includes another reagent residue.

An additional reagent residue, where applicable, included in A1, A2 or A3 or Z1 or Z2, shall be in particular a low molecular weight alkanoyl or alkyl sulphonyl residue substituted by a fissile atom or fissile group, a low molecular weight alkenoyl or alkenosulphonyl residue substituted by a fissile atom or fissile group, a carbonyl or sulphonyl group substituted by a fissile atom or a fissile group substituted by a carbo- or heterocyclic 4-, 5- or 6-ring carbon, or a residue directly substituted by a hydrogen atom or fissile group substituted by an aliphatic or alkenosulphonyl group, or a halophilic residue containing a halophilic or heterocyclic amino group, such as a halophilic or heterocyclic resin, or a halophilic resin, such as a halophilic or heterocyclic resin, such as a pyridine or a halophilic resin, or a halophilic resin, such as an example of a pyridine or a halophilic resin, or a halophilic resin, such as an acetylic or a heterocyclic resin.

The additional reactive residues included in A1, A2, A3, Z1 and Z2 are in particular heterocyclic residues which contain at least one fissile substituent bound to a heterocyclic residue, including those containing at least one reactive substituent bound to a 5- or 6-membered heterocyclic ring such as a monazine, diazine, triazine, e.g. pyridine, pyrimidine, pridazine, pyrazine, thiazine, oxazine or asymmetric or symmetric triazine ring, or to a similar ring system containing one or more associated aromatic substituents such as a quinine, pinothaline, phenylalanine, quinine, phenylalanine, acrylic acid, phenylalanine, and 5- or 6-membered rings, or to such rings which may contain at least one or more of the following aromatic substituents, such as quinine, pinothaline, phenylalanine, quinine, phenylalanine, acrylic acid, and 5- or 6-membered rings, and which are preferably heterocyclic or carboxylic rings, and which may contain at least one 5- or 6-membered rings, or more of such rings, and which are preferably containing a 5- or 6-membered ring.

The reactive substituents on the heterocycle include halogens (Cl, Br or F), ammonium including hydrazine, sulphonium, sulphonyl, azide- ((N3), rhodanide, thio, thiolether, oxyhether, sulphuric acid and sulphonic acid.

in particular, 2,4-dichlorotriazinyl-6-, 2-di-β-oxythyl-amino-chlorotriazinyl-6-, 2-alkyl-amino-4-chlorotriazinyl-6-, 2-alkyl-amino-4-chlorotriazinyl-6-, such as 2-methylamino-4-chlorotriazinyl-6-, 2-ethylamino-zinzinyl-6-, or 3-propylamino-4-chlorotriazinyl-6-in particular, 2-β-oxythylamino-4-chlorotriazinyl-6--, 2-di-β-oxythyl-amino-4-chlorotriazinyl-6- and the corresponding sulphuric acid halogenates, in particular, 2-diethylamino-4-chlorotriazinyl-6-, 2-morpholine-zinyl-4-zinyl-4-zinyl-6- or 2-pyrethyl-methyl-phenylenophenyl-zinyl-zinyl-6-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl-zinyl'phenylenediamine' means a phenylenediamine containing a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenediamine, a phenylenamine, a phenylenediamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenylenamine, a phenyThe term 'methyl methacrylate' means a methacrylate of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing by weight more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of ethylene, containing more than 0,5% of the same, containing more than the same substance, containing more than the same substance, containing more than the substance, containing more than the substance, of the substance of the substance of the substance of the substance of the same substanceThe term 'methyl methacrylate' means a methacrylate of a kind used in the manufacture of a compound containing a compound containing a compound of methacrylate, a compound containing a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound containing a compound of methacrylate, a compound of methacrylate, a compound of methacrylate, a compound of methacrylate, a compound of methacrylate, a compound of methacrylate, compound of methacrylate, compound of methacrylate, compound of methacrylate, compound of methacrylate, compound of methacrylate, compound of methacrylate, compound of methacrylate, compound of methacrylate, compound of methacrylate, compound of methacrylate of methacrylate, compound of methacrylate, compound of methacrylate of methacrylate, compound of methacrylate of methacrylate, compound of methacrylate of methacrylate, compound of methacrylate of methacrylate of metcontaining in the 2-position by a nitrogen link the 1,4-bis-azabicyclo[2,2,2]-octane or 1,2-bis-azabicyclo-meth[0,3,3]-octane quaternary bonded to 2-pyridinium 4-phenylamino- or 4-o-, m- or p-sulfophenyl) aminotriazinyl-6- and corresponding 2-onium-triazinyl-6 residues, substituted in the 4-position by alkylamino- or 1,4-bis-azabicyclo[2,2,2,2]-octane or 1,4-bis-azabicyclo[0,3,3]-octane or 1,2-bis-azabicyclo[0,3,3]-octane or 4-quaternary-octane groups, such as methyl- or methyl- or ethyl- or β-hydroxyethylamino- or alkoxy- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2-ethyl- or 2- or 2-ethyl- or 2-ethyl- or 2- or 2-ethyl- or 2- or 2-ethyl- or 2- or 2- or 2- or 2- or 2- or 6-thyl- or 2- or 6-thyl- or 2- or 2- or 6-thyl- or 6-thyl- or 2- or 6-thyl- or 2- or 2- or 6-thyl- or 2- or 6-thyl- or 2- or 6-thyl- or 6-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or-or2-Chlor-4-methylthiazole-(1,3)-5-carbonyl or -4- or -5-sulfonyl, N-oxide of 4-Chlor or 4-Nitroquinoline-5-carbonyl or also the residues of 5-Chlor-2,6-Difluor-1,3-Dicyanphenyl, 2,4-Difluor-1,3,5-Tricyanphenyl, 2,4,5-Trifluor-1,3-Dicyanphenyl, 2,4,5-Dicyl-5-Methylsulfonyl-pyrimidyl-6, 2,4-Dichlor-5-Methylsulfonyl-pyrimidyl-6, 2-Fluor-5-Methylsulfonyl-6'-(2'-Sulfinylamino) -Pyrimidyl-4, 2,5-Dichlor-6-Methylfluorpyrimidyl-4.

In addition, reactive groups of the aliphatic series, such as acrylolyl, mono, di- or trichloracryloyl, such as -CO-CH=CH-Cl, -CO-CCl=CH2, -CO-CCl=CH-CH3, -CO-CCl=CH-COOH, -CO-CH=CCl-COOH, β-Chlorpropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpronyl, 2-fluor-2-chlor-3,3-difluorcyclobutan-1-carbonyl, 2,2,3,3-tetrafluor sulfonyl-carbonyl-1, or -fonyl-1-, β-sulfonyl-2,2,3,3-tetrafluor sulfonyl-butyl-1) or β-bromethyl or β-acyl-acyl-acyl-acyl, such as α-sulfonyl, β-sulfonyl-acyl or β-methyl-acyl, or β-sulfonyl-acyl, or α-sulfonyl-methyl, are to be mentioned.

For example, a C1-C8 alkyl residue, if any, or a C5-C7 cycloalkyl residue, if any, may be considered as aliphatic residue Z1 or Z2 in formula (1).

Z1 and Z2 as C1-C8 alkyl are e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl or n-octyl. The C1-C8 alkyl residues Z1 and Z2 can be substituted, e.g. by halogen, hydroxy, cyan, carboxy, C1-C4-alkoxy, C2-C4-alkanoyl, hydroxy-C2-C4-alkoxy, sulfo, sulfate, phenyl and naphthyl, whereby the acyl or naphthrestyl phenyl substitute can be widely indicated, e.g. for A1, A2 or A3. Examples are benzylon-carboxyl, β-cyanoyl, β-cyanoyl, β-ethyl, β-ethyl, β-ethyl, sulfo.

For Z1 and Z2 the cyclopentyl, cyclohexyl or cycloheptyl residue, which may be further substituted, for example, by C1-C4 alkyl, is considered to be a C5-C7-cycloalkyl.

The aromatic residue for Z1 and Z2 is in particular phenyl or naphthyl and phenyl or naphthyl residues substituted, for example, by C1-C4 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, C1-C4 alkoxy such as methoxy or aethoxy, halogens such as fluorine, chlorine or bromine, carboxy, hydroxy or sulpho.

For Z1 and Z2 a furan, thiophen, pyrazol, pyridine, pyrimidine, quinoline, benzimidazole, benzthiazole and benzoxazole residue in particular is considered as a heterocyclic residue, whereby the said residues may be replaced by the substitutes specified for A1, A2 and A3 respectively.

If Z1 and Z2 together with the nitrogen atom which binds them, including where appropriate another heteroatom, form a nitrogen-containing heterocyclic ring, this is e.g. the piperidinyl, piperazinyl or morpholinyl residue.

The preferred colouring matters of the reagents of formulae (1) and (2) are characterised by: (b) The weight ratio of the dyes of the formulae (1): ((2) 5:95 to 95:5, in particular 30:70 to 70:30, is: or -NH- ((CH2) 2-NH-CO-CH3 is,e) X1, X2 and X3 are independently fluorine or chlorine, in particular fluorine,f) R1, R2, R3, R4 and R5 are independently hydrogen, methyl or ethyl. In particular, R3 and R4 mean hydrogen,g) A1, A2 and A3 are each mono- or disazo dye residues, metal complex azo dye residues or formase dye residues.

The following shall be indicated for the reaction dye mixtures of the reagents of formulae (1) and (2): (a) X1, X2 and X3 mean fluorine, (b) R3 and R4 mean one hydrogen atom each, (c) R2 has the same meaning as R5, (d) A1, A2 and A3 are each azo, metal complex azo or formase residue.

Mixtures of dyes of the reactive dyes of formulae (1) and (2) are of particular importance, where A1, A2 and A3 are a residue of the following formulae (3) to (15) respectively: where R6 stands for 0 to 3 substituents from the group C1-C4-alkyl, C1-C4-alkoxy, halogen, carboxy and sulpho group. where R6 stands for 0 to 3 substituents from the group C1-C4-alkyl, C1-C4-alkoxy, halogen, carboxy and sulpho group. where R7 is for substituents 0 to 4 from the group of halogens, nitro, cyan, trifluoromethyl, sulfamoyl, carbamoyl, C1-C4-alkyl, C1-C4-alkoxy, amino, acetylamino, ureido, hydroxy, carboxy,Sulphomethyl and sulfo are independent of each other, where R8 is C1-C4-alkanoyl or benzoyl. where R8 is C1-C4-alkanoyl or benzoyl. where R9 stands for 0 to 3 substituents from the group C1-C4-alkyl, C1-C4-alkoxy, halogen, carboxy and sulpho group. where R12 and R10 are independently hydrogen, C1-C4-alkyl or phenyl, and R11 is hydrogen, cyano, carbamoyl or sulphomethyl. where R9 stands for 0 to 3 substituents from the group C1-C4-alkyl, C1-C4-alkoxy, halogen, carboxy and sulpho group. where R13 stands for 0 to 2 substituents from the group C1-C4-alkyl, C1-C4-alkoxy, halogen, carboxy and sulpho group; and Z is β-sulphatethyl, β-thiosulphatethyl, β-phosphatethyl, β-acylloxytethyl, β-halogenethyl or vinyl. containing R14 for 0 to 2 substituents from the C1-C4 alkyl group,C1-C4 is alkoxy, halogen, carboxy and sulfo; and Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatethyl, β-acyloxyethyl, β-halogenethyl or vinyl.

The heavy metal complexes of the reaction dyes of formula (1) are also of particular importance, the most suitable heavy metals being copper, nickel, cobalt or chromium, and the preferred are copper complex azo dyes, especially those of formula (3) to (13), which contain the copper atom bound to the azo fragment by an oxygen atom in each ortho position.

Examples of azo dyes that are suitable as metal complexes are: The metal atoms are preferred to be Cu (1:1 complex) or Cr and Co (1:2 complex). Cr and Co complexes can contain the azure bond of the above formula once or twice, i.e. they can be symmetrical or asymmetrical with any other ligand.

The preferred material is copper complexes such as In the above formulae, the residues R24 to R26 mean hydrogen or C1-C4-alkyl. Preferably, the residues R24 to R26 mean hydrogen, methyl or ethyl. The aromatic rings in the above dyes can be further substituted. The benzene rings are mainly methyl, ethyl, methoxy, aethoxy, methylsulfonyl, ethylsulfonyl, carboxy, acetyllamine or chlorine, and the naphthalene rings are mainly methoxy, carboxy, acetylamine, nitro or chlorine.

The reagents of formulae (1) and (2) are known in isolation or can be produced by adding one or two organic dye equivalents of formulae (1) and (2). or a dye precursor, at least one aequivalent of an s-triazine, at least one aequivalent of a diamine of the formula or an amine equivalent of the formula in any order, wherein A1, A2, A3, R1, R2, R3, R4, R5, B, Z1 and Z2 have the meanings given in the formulae (1) and (2) or, in the case of dye precursors, transfer the intermediate products obtained to the desired dyes and, if necessary, follow a further conversion reaction.

The production of the final dyes from intermediate products is mainly coupled production, which leads to azo dyes.

Since the individual steps of the process described above can be performed in different sequences, sometimes simultaneously, several variations of the process are possible.

The structure of the starting materials will determine which of the possible process variants will give the best results or under which special conditions, e.g. at which condensation temperature, the reaction is most advantageous to carry out.

Since hydrolysis of a halogen triazine residue occurs under certain conditions, an intermediate containing acetylamin groups must be siphoned to separate the acetyl groups before condensation with a halogen triazine. e.g. in the production of a secondary condensation product from a combination of the formula (25) with the triazine and the dye of the formula (24) or a precursor, the reaction which is preferably carried out first, that of the triazine with the combination of the formula (25) or with the dye or a precursor of the dye, varies from case to case and depends mainly on the binding of the solutions involved and the basicity of the acyclic amine groups.

The following are individual possible starting materials that can be used to produce the reagents of formulae (1) and (2).

Colouring matters of the formula (24)

For the purposes of heading 2910, the expression 'other' means: Other

The metal atoms are preferred to be Cu (1:1 complex) or Cr and Co (1:2 complex). Cr and Co complexes can contain the azure bond of the above formula once or twice, i.e. they can be symmetrical or asymmetrical with any other ligand. Other

In this formula, Pc stands for the Cu or Ni-phthalocyanin residue, and the total number of substituents on the Pc scaffold is 4. Other

In the above formulae, the residues R17 to R22 mean hydrogen or C1-C4 alkyl, and the residues R15 and R16 mean hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkanoyl amino, urea or halogen, whereby the residues R15 and R16 belonging to the same formula are independent of each other. Preferably, the residues R17 to R22 mean hydrogen, methyl or ethyl, and the residues R15 and R16 mean hydrogen, methyl, ethyl, methoxy, aethoxy, acetylamine, urea or chlorine. The aromatic rings in the above dyes may be further similar, which are substituted by methanol, especially methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, methanol, met

The following are to be classified as triazines:

The following substances are to be classified in the same heading as the active substance:

Diamonds of the formula (25)

It's called 1,2-diaminethane, 1,3-diaminopropane.

Amine of the formula (26)

Dimethylamine, dimethylamine, aethylamine, diethylamine, hydroxypropylamine, diethylamine, propylamine, isopropylamine, butylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, propylamine, propylamine, isopropylamine, isopropylamine, isopropylamine, isopropylamine, isophylamine, isophylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, dimethylamine, propylamine, dimethylamine, propylamine, propylamine, isophylamine, isophylamine, isophylamine, is

The mixture of dyes in the present invention may be obtained by mixing the individual dyes, for example in suitable mills, such as ball and pen mills, and in kneaders or mixers.

The dye mixtures can also be prepared by spray drying of the aqueous dye mixtures.

The invention also concerns a method for dyeing and printing cellulose-containing fibre materials with dye mixtures containing reactive dyes of formulae (1) and (2). The fibre materials include, for example, natural cellulose fibres such as cotton, linen and hemp, and cellulose and regenerated cellulose. The dye mixtures are also suitable for dyeing or printing hydroxyl group fibres contained in mixed fabrics, e.g. from mixtures of baumonium cotton with polyamide fibres, or in particular polyester fibres.

The dye mixtures of the invention can be applied to and fixed on the fibre material in various ways, in particular in the form of aqueous dye solutions and printing pastes. They are suitable for both extrusion and dyeing using the Foulard dyeing process, whereby the product is impregnated with aqueous, possibly salty dye solutions and the dye substances are fixed after an alkali treatment or in the presence of alkali, possibly by thermal action. After fixation, the dyes or prints are treated with cold and hot water, possibly by the addition of a dispersive agent, and the diffusion of the unfixed proportions is facilitated by a spray. The usual dyeing and printing methods are used.

The colour mixtures are characterised by a good fixation and very good build-up properties. They can be used after the extrusion process over a very large temperature range and are therefore also very suitable for dyeing cotton-polyester mixed fabrics under the conditions recommended for such fabrics. The fixation grades are high and the difference between the degree of extrusion and fixation is remarkably small, i.e. the loss of soap is very low. The colour mixtures of the reactive chemical mixtures of the molds (1) and (2) are also suitable for printing, especially on cotton, but also for printing of sticky materials, e.g. of wool or of fabrics containing fibres of wool or silk, which contain fibres of wool or silk.

The dyes and prints on cellulose fibre materials produced with the dye mixtures of the invention have a high color intensity and a high fiber-dystyrene bonding stability, both in the acid and alkaline ranges, and also good lightfastness and very good wet-holding properties, such as washing, water, sea water, over-dying and sweat resistance, as well as good pleating, bending and rubbing resistance and very good chlorination resistance.

The colouring matters of formulae (1) and (2) are either in the form of their free sulphonic acid or preferably as their salts such as the alkaline, alkaline earth or ammonium salts or as salts of an organic amine, for example sodium, lithium or ammonium salts or the salt of triethanolamine.

The following examples are intended to illustrate the invention. Temperatures are given in degrees Celsius, parts are weight parts, percentages are weight percentages, unless otherwise stated. Weight parts are volume parts in the ratio of kilogram to liter.

The production of mono- and disazo-intermediate compounds is not described in the following examples, but is easily seen from the general description.

Example 1: For the manufacture of the dye mixtures containing a dye of formula and a dye of formula (102), in a mixer (1) 40 parts of the dye of formula (101) and 60 parts of the dye of formula (102) are mixed homogeneously and 100 parts of the mixture are obtained, hereinafter referred to as dye mixture A1;a2) 5 parts of the dye of formula (101) and 95 parts of the dye of formula (102) are mixed homogeneously and 100 parts of the mixture are obtained, hereinafter referred to as dye mixture A2;a3) 10 parts of the dye of formula (101) and 90 parts of the dye of formula (102) are mixed and 100 parts of the mixture are obtained,hereinafter referred to as A3 dye; for the manufacture of the mixture of dyes containing the dye of formula and contains the dye of formula (104) are mixed in a mixer (b) 20 parts of the dye of formula (103) and 80 parts of the dye of formula (104) are mixed homogeneously; To produce the dye mixture containing the dye of formula and the dye of formula (106) mix in a mixer (c) 20 parts of the dye of formula (105) and 80 parts of the dye of formula (106) homogeneously; for the manufacture of the mixture of dyes containing the dye of formula the colouring matter of the formula and contains, in a mixer, 20 parts of the dye of formula (107) and 80 parts of the dye of formula (108) are mixed homogeneously to give 100 parts of the mixture,hereinafter referred to as 'Dye Mix D'; for the manufacture of the mixture of dyes containing the dye of formula and the colouring matter of the formula contains, in a blender, 20 parts of the dye of formula (109) and 80 parts of the dye of formula (110) are mixed homogeneously; for the manufacture of the mixture of colouring matter containing the formula and the formula (f) 30 parts of the dye of formula (111) and 70 parts of the dye of formula (112) are mixed homogeneously in a mixer to give 100 parts of the mixture, hereinafter referred to as dye mixture F.

Example 2

27.3 parts of the formula When no diazotizable amino groups are detectable, the dye solution is moved to 0 to 5° and a pH of 5-7 with 0.75 parts ethylene and 2.2 parts morpholine. The pH of the reaction mixture is then raised to 7.5 by adding sodium carbonate and the temperature is slowly raised to 25°. After condensation, a mixture of the dyes of the formulas and It is an orange powder and colours cotton in golden yellow tones.

If 5,8 parts methylic acid, 2,7 parts o-toluidine, 2,7 parts N-methylaniline or 3,0 parts N-ethylaniline are used instead of 2,2 parts morpholine, mixtures of the dye of the formula with a colourant C.I. Depending on the molar ratios of the amines or diamines used, mixtures of dyes with different mixing ratios are obtained.

The following diamines may be used instead of ethylene diamine, e.g. 1,3-propylene diamine, 1,2-propylene diamine, n-butylene diamine, 1-methyl-n-propylene diamine, n-hexylene diamine, 2-ethyl-n-butylene diamine, 2-hydroxy-n-propylene diamine, piperazine.

If the chromophores listed in column I of the following table are used instead of the chromophore indicated above and if the other examples are followed, further colouring agents are obtained which colour cotton in the tones indicated in column II.

Example 3

27.3 parts of the formula When no diazotizable amino groups are detectable, the dye solution is replaced at 0 to 5° and a pH of 5-7 by 2 to 2.5 parts ethylene diamine. The pH of the reaction mixture is then raised to 7.5 by adding sodium carbonate and the temperature is slowly raised to 25°. After the condensation is completed, the dye solution is acylated with 2 to 5 parts acetanid at pH 8-9. and It is an orange powder and colours cotton in golden yellow tones.

Other acyclic agents, in particular aliphatic, aromatic or heterocyclic carbon chlorides, may be used instead of acetane hydride, such as acetyl chloride, propionyl chloride, propionic anhydride, 2-propanic acid, carboxypropionyl chloride, butyryl chloride, benzoyl chloride, 4-methylbenzoyl chloride, benzyl carbon chloride, 4-sulfobenzyl carbon chloride and pyridine 3-carbon chloride.

The diamine or chromophore listed in the following example 2 may be used instead of the ethylene diamine and the chromophore indicated.

Example 4

2 parts of the dye mixtures A1, A2 or A3 obtained in examples 1a1, 1a2 or 1a3 are dissolved in 400 parts of water; to this are added 1500 parts of a solution containing 53 g of sodium chloride per litre. This dye bath is entered at 40°C with 100 parts of cotton fabric. After 45 minutes 100 parts of a solution containing 16 g of sodium hydroxide and 20 g of anhydrous Na2CO3 are added. The temperature of the dye bath is maintained at 40°C for another 45 minutes.

Example 5

2 parts of the dye D obtained in the example 1d are dissolved in 400 parts of water; to this are added 1500 parts of a solution containing 53 g of sodium chloride per litre. In this dye bath 100 parts of cotton fabric are added at 35°C. After 20 minutes 100 parts of a solution containing 16 g of sodium hydroxide and 20 g of anhydrous Na2CO3 are added. The temperature of the dye bath is maintained at 35°C for another 15 minutes. The temperature is then raised to 60°C within 20 minutes. The temperature is maintained at 60°C for another 35 minutes. The orange dye is then rinsed for a quarter of an hour, dried with a very high-ionogenic cooking soap, and washed and preserved. The product is characterized by its good moisture and moisture-resistant properties, especially the original product.

Example 6

Eight parts of the dye F obtained in the example 1f are dissolved in 400 parts of water, to which are added 1400 parts of a solution containing 100 g of sodium sulphate per litre. This dye bath is entered at 25°C with 100 parts of cotton fabric. After 10 minutes, 200 parts of a solution containing 150 g of trinitrium phosphate per litre are added. Then the temperature of the dye bath is raised to 60°C within 10 minutes. The temperature is maintained at 60°C for another 90 minutes.

Example 7

The resulting solution is used to foil a cotton fabric so that it increases by 70% of its weight and then rolls it up into a ball. The cotton fabric is stored at room temperature for 3 hours. The gold-yellow coloured product is then rinsed, soaped with a non-cyanogenic detergent for a quarter of an hour, rinsed and dried. The product is characterised by good moisture-preserving properties, particularly its very dark colour.

Example 8

6 parts of the dye D obtained in the following way are dissolved in 50 parts of water. To this are added 50 parts of a solution containing 16 g of sodium hydroxide and 0.04 litre of water glass (38°Bé) per litre. The resulting solution is used to foil a cotton fabric so that it increases by 70% of its weight and then rolls up onto a sole. The cotton fabric is thus stored at room temperature for 10 hours. Afterwards, the orange-colored product is rinsed, for a quarter of an hour with a non-nitionogenic detergent cooking soap, washed and dried again.

Example 9

2 parts of the dye F obtained in the manner described in example 1f are dissolved in 100 parts of water with the addition of 0.5 parts of m-nitrobenzolsulfonic acid sodium. The resulting solution is then impregnated with a cotton fabric, increasing it by 75% of its weight, and then dried. The fabric is then impregnated with a 20°C warm solution containing 4 g of sodium hydroxide and 300 g of sodium chloride per litre, squeezed to 75%, dampens the blue colour for 30 seconds at 100 to 102°C, rinsed, soaked for a quarter of an hour in a very moist 0,3% solution of a non-organic substance, and dried. The product is characterised by good moisture-resistant properties, particularly its moisture-resistant properties.

Example 10

Three parts of the dye mixtures A1, A2 and A3 obtained in examples 1a1, 1a2 or 1a3 are rapidly stirred into 100 parts of a stock thickness containing 50 parts of 5% sodium alginate thickness, 27.8 parts of water, 20 parts of urea, 1 part m-nitrobenzene sulphonic acid sodium and 1.2 parts of sodium hydrocarbonate, sprinkled. The resulting paste is used to print a cotton fabric, dry and steam the cooked printed fabric for 2 minutes at 102 °C in a saturated steam. The gold-printed fabric is then rinsed, if necessary very dry soaped and polished, and then cut. The product obtained is characterized by good moisture-resistant properties, especially the characteristics of the product.

Example 11

5 parts of the dye D obtained in the following manner are sprayed, by rapid agitation, in 100 parts of a stock thickening agent containing 50 parts of 5% sodium alginate thickening agent, 36.5 parts of water, 10 parts of urea, 1 part of m-nitrobenzene sulphonic acid sodium and 2.5 parts of sodium hydrocarbonate. The resulting paste, which is stable and meets the technical requirements, is used to print a cotton fabric, dry and steam the resulting orange printed fabric for 8 minutes at 102 °C in saturated steam. The printed fabric is then rinsed, if necessary with boiling soap and rinsed again, and then dried. The product obtained is characterized by good moisture-resistant properties, in particular by very good stability.

Claims (17)

1. A process for preparing dye mixtures consisting of the dyes of the formulae and in which A₁, A₂ and A₃ are identical and are each the radical of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, pyrenequinone or perylenetetracarbimide dye, R₁, R_2, R₃, R₄ and R₅, independently of one another, are hydrogen or C₁-C₄alkyl, which can be substituted by halogen, hydroxyl, cyano, C₁-C₄alkoxy, C₁-C₄alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato, B is an aliphatic bridging member, and Z₁ and Z₂ are hydrogen or an aliphatic, aromatic or heterocyclic radical, or Z₁ and Z₂, together with the nitrogen atom linking them, form a five- to seven-membered ring, which apart from C atoms can contain further heteroatoms, and X₁, X₂ and X₃, independently of one another, are fluorine, chlorine, bromine, sulfo or carboxypyridinium, characterized in that it comprises reacting one or two equivalents of an organic dye of the formula or a dye precursor, at least one equivalent of an s-triazine, and in total at least one equivalent of diamine of the formula and amine of the formula where A₁, A₂, A₃, R₁, R₂, R₃, R₄, R₅, B, Z₁ and Z₂ are each as defined above, in any desired order, or, in the case where dye precursors are used, converting the intermediates obtained into the desired dyes and, if desired, subsequently carrying out a further conversion reaction.
2. A process according to claim 1 for preparing dye mixtures consisting of the dyes of the formulae (1) and (2) wherein the radicals A₁, A₂, A₃, Z₁ and Z₂, independently of one another, contain fibre-reactive radicals.
3. A process according to any one of claims 1 or 2 for preparing dye mixtures consisting of the dyes of the formulae (1) and (2) wherein the weight ratio of the dyes of the formulae (1):(2) is 5:95 to 95:5, in particular 30:70 to 70:30.
4. A process according to any one of claims 1 to 3 for preparing dye mixtures consisting of the dyes of the formulae (1) and (2) wherein B is C₁-C₁₀alkylene which is unsubstituted or substituted by halogen, C₁-C₄alkyl, C₁-C₄alkoxy, carbonyl or sulfo.
5. A process according to any one of claims 1 to 4 for preparing dye mixtures consisting of the dyes of the formulae (1) and (2) wherein B is ethylene, 1,2- or 1,3-propylene, n-butylene, 1-methyl-n-propylene, n-hexylene or 2-ethyl-n-butylene.
6. A process according to any one of claims 1 to 5 for preparing dye mixtures consisting of the dyes of the formulae (1) and (2) wherein the radical -N(Z₁)Z₂ is -NH₂, or -NH-(CH₂)₂-NH-CO-CH₃.
7. A process according to any one of claims 1 to 6 for preparing dye mixtures consisting of the dyes of the formulae (1) and (2) wherein X₁, X₂ and X₃ are each fluorine or chlorine.
8. A process according to claim 7 for preparing dye mixtures consisting of the dyes of the formulae (I) and (2) wherein X₁, X₂ and X₃ are each fluorine.
9. A process according to any one of claims 1 to 8 for preparing dye mixtures consisting of the dyes of the formulae (1) and (2) wherein R₁, R₂, R₃, R₄ and R₅, independently of one another, are hydrogen, methyl or ethyl.
10. A process according to claim 9 for preparing dye mixtures consisting of the dyes of the formulae (1) and (2) wherein R₃ and R₄ are hydrogen.
11. A process according to any one of claims 1 to 10 for preparing dye mixtures consisting of the dyes of the formulae (I) and (2) wherein A₁, A₂ and A₃ are each a monoazo or disazo dye radical or formazan dye radical.
12. A process according to claim 1 for preparing dye mixtures consisting of the dyes of the formulae (1) and (2) wherein B is C₁-C₁₀alkylene which is unsubstituted or substituted by halogen, C₁-C₄alkyl, C₁-C₄alkoxy, carboxyl or sulfo,

    Z₁ and Z₂, independently of one another, are each hydrogen, β-acetylaminoethyl, C₁-C₈alkyl which is unsubstituted or substituted by halogen, hydroxyl, cyano, carboxyl, C₁-C₄alkoxy, C₂-C₄alkanoyl, hydroxy-C₂-C₄alkoxy, sulfo, sulfato, phenyl or naphthyl, C₅-C₇cycloalkyl which is unsubstituted or substituted by C₁-C₄alkyl, or phenyl or naphthyl which is unsubstituted or substituted by C₁-C₄alkyI, C₁-C₄alkoxy, halogen, carboxyl, hydroxyl or sulfo, or Z₁ and Z₂, together with the nitrogen atom linking them, form a piperidinyl, piperazinyl or morpholino ring and

    X₁, X₂ and X₃ are identical and are each fluorine or chlorine.
13. A process for the dyeing and printing of cellulosic fibre materials using a dye mixture, characterized in that it comprises using a dye mixture obtainable according to any one of claims 1 to 12.
14. A process according to claim 13 for the dyeing and printing of cotton.
15. Use of a dye mixture obtainable according to claim 1 for the dyeing and printing of cellulosic fibre materials.
16. A dyeing or printing preparation comprising a dye mixture according to claims 1 to 12.