HK1117863A - Mixture of water-soluble fibre-reactive dyes, method for the production thereof, and use of the same - Google Patents

Description

Dye mixtures of water-soluble fibre-reactive dyes, method for the production thereof and use thereof

Technical Field

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

Background

From documents US 6,143,039, EP 0735111 and EP 0832939, for example, and from japanese references JP5-70707 and JP2-99564, a wide variety of fiber-reactive dye mixtures are known which can be used to produce a blue dyeing effect on fibers containing hydroxyl and/or carboxamido groups, such as, in particular, cellulose fibers. Furthermore, EP-A668328 describes mixtures of fiber-reactive dyes, in each of which a dye component is used as dark component.

However, these dye mixtures have certain application disadvantages, such as the amount of dye delivered being excessively dependent on changes in the dyeing parameters during the dyeing operation, or insufficient or uneven dye build-up on the cotton material, since good build-up results from the ability to provide stronger dyeings when the dye is used in the dye bath at higher concentrations. These disadvantages may cause a result that dye reproducibility is poor.

However, it is particularly important to obtain dyes having a good color yield, i.e. dyes whose deep shade correlates very strongly with the amount of dye used, for example due to the high absorbance of the dye and due to the good dyeing properties of the dye, such as high affinity and high fixation. When mixtures of dyes having a specific colour-imparting amount are used, the rule is that the colour-imparting amount of these mixtures is the sum of the colour-imparting amounts of the individual dyes, which is why, for example, the colour-imparting amount of a mixture of two dyes is lower when compared with the use of only one dye which has the property of a higher colour-imparting amount but whose amount is the same as the total amount of the two dyes. This also applies to some durable fastnesses, for example fastness to light, washing, hot pressing and chlorine. Furthermore, there is generally a negative synergistic effect on these fastnesses, the reason for which is known as enzymatic decay, so that the fastnesses of the mixtures can be lower than with the individual dyes.

Disclosure of Invention

The inventors have now surprisingly found that the colour strength of the dye mixture according to the invention described below is surprisingly higher than the sum of the colour strengths provided by the individual dyes in the dye mixture. This positive synergistic effect is also shown in the improvement in dye accumulation exhibited by the inventive mixtures when compared to the individual dyes in the mixtures, and in their fastness properties, which in some instances are superior to the average of the fastness properties of the individual dyes.

The present invention accordingly provides dye mixtures comprising at least one dye of the general formula (I) and at least one dye of the general formula (II)

Wherein

M is hydrogen or an alkali metal, ammonium, or an equivalent of an alkaline earth metal ion;

y is vinyl or of the formula CH₂CH₂A group of Z, wherein Z is a base-removable group such as chloro, acetyl, phosphato, thiosulfato, and preferably sulfato;

R¹is hydrogen or sulfo;

R²having R¹Or is methyl, methoxy, carboxyl or SO₂Y²Wherein Y is²Has one of the meanings of Y, and is preferably CH₂CH₂Cl or vinyl;

R³having R¹One of the meanings of (a);

r has R²One of the meanings of (a);

w is carbon or-SO-;

a is a group of the formula (3)

Wherein

Denotes a bond linked to formazan, an

B is a group of the general formula (4), (5), (6) or (7)

Wherein

Represents a bond to N in general formula (3);

u is a 5-or 6-membered heterocyclic ring to which N is attached, which may be substituted by thio or oxo;

preferably U is morpholino, or is a radical of the formula (8)

Wherein

E is hydrogen, C unsubstituted or substituted by methoxy, hydroxy, sulfato, sulfo or chlorine₁-C₄-alkyl, or is phenyl, unsubstituted or selected from chlorine, nitro, acetamido, sulfo, hydroxyl, carboxyl, C₁-C₄Alkanoyl radical, C₁-C₄-alkoxy and C₁-C₄-alkyl substituted by one or two substituents, E preferably being hydrogen, phenyl, 4-chlorophenyl, 3-sulfophenyl, methyl, 2-hydroxyethyl, 2-sulfoethyl or 2-sulfatoethyl;

g has one of the meanings of E, or is cyano and is preferably hydrogen;

l is phenylene or naphthylene, each of which may be substituted with up to two substituents selected from chlorine, bromine, hydroxy, C₁-C₄Alkoxy (especially methoxy), C₁-C₄Alkyl (especially methyl, ethyl), sulfo and cyano; or L is C₂-C₆Alkylene which may be interrupted by 1 to 2 hetero radicals, such as oxo, thio, amino, C₁-C₄-an alkylamino group; l is preferably phenylene, ethylene, propylene or 3-oxypentylene;

q is fluorine, chlorine, C₁-C₄Alkoxy, cyanamino, amino, C₁-C₄-alkylamino, dialkylamino, piperazinyl, morpholinyl or a group of formula (9a) or (9b)

Wherein A is^-Is fluoride, chloride, or equivalent sulfate ion;

v has one of the meanings of E and is preferably hydrogen, methyl, phenyl or sulfophenyl;

T¹is hydrogen, fluorine or chlorine;

T²is hydrogen, fluorine or chlorine, with the proviso that T¹And T²Not hydrogen at the same time;

X¹is fluorine or chlorine; and is

X²Having X¹One of the meanings in (a).

In general, the dyes of the formula (I) and the dyes of the formula (II) are present in the mixture in a mixing ratio of from 90: 10% by weight to 10: 90% by weight, preferably in a ratio of from 80: 20% by weight to 20: 80% by weight. More preferably, the two dyes are present in the dye mixtures according to the invention in a mixing ratio of from 65: 35 to 35: 65% by weight.

The dye mixtures according to the invention can be present in the form of preparations in solid or liquid (dissolved) form. In the case of solid forms, these generally include the electrolyte salts customary for water-soluble dyes, in particular fibre-reactive dyes, such as sodium chloride, potassium chloride and sodium sulphate, and may additionally include auxiliaries customary for commercially available dyes, such as buffer substances capable of setting a pH of between 3 and 7 in aqueous solution, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate, sodium citrate and disodium hydrogen phosphate, or small amounts of drying agents, or, if they are present in liquid, aqueous solution form (including thickeners of the type customary in printing pastes), substances which ensure a longer life of these formulations, for example antimildew agents.

In general, the dye mixtures according to the invention are in the form of dye powders which contain from 10 to 80% by weight, based on the dye powder or the formulation, of electrolyte salts which are also referred to as standardizers. These dye powders may also comprise the abovementioned buffer substances in a total amount of up to 10% by weight, based on the dye powder. When the dye mixtures of the invention are present in aqueous solutions, the total dye content of these aqueous solutions is up to about 75% by weight, for example between 5 and 75% by weight, based on the aqueous solution, and the electrolyte salt content of these aqueous solutions is preferably less than 10% by weight, based on the aqueous solution. The aqueous solution (liquid preparation) may comprise the aforementioned buffer substances, the content of which is generally at most 10% by weight, preferably at most 2% by weight.

The dyes of the general formula (I) are known and can be synthesized in the manner described, for example, in US 4336190, US 4370145, EP-A0028788 and EP-A0028787. For example, the generic diazotization and coupling reactions may be used to form the formazan compound, while the dyes of formula (I) of the present invention are prepared by the addition of copper in a manner well known to those skilled in the art.

Dyes of the general formula (II) are known, for example from the patent literature

EP 0 021 35 1、EP 0 099 721、EP-A 629 667、

EP-A 62555 1、EP-A 626429、DE-A 4 320 632、

WO 9418381 and EP-A644239.

The dye mixtures according to the invention can be prepared in a conventional manner, for example by mechanical mixing of the individual dyes in the desired proportions in solid or liquid form.

The dye mixtures according to the invention have useful application properties. They are used for dyeing or printing materials containing hydroxyl and/or carboxamido groups, for example materials in sheet-like form (such as paper and leather) or in film form (for example made of polyamide), or materials in agglomerate form (such as polyamide and polyurethane), in particular for dyeing or printing the aforementioned materials in fiber form. Similarly, the solutions of the dye mixtures according to the invention obtained in the synthesis of the compounds can be used directly for pigmenting purposes as liquid preparations, or, where appropriate, buffer substances can be added before use, and, where appropriate, concentrated or diluted before use.

The invention therefore also relates to the use of the dye mixtures according to the invention for dyeing or printing these materials or to a process for dyeing or printing these materials in a conventional manner using one or more of the dye mixtures according to the invention as colorants. These materials are preferably used in the form of fibrous materials, especially textile fibers, such as braids or yarns, for example in the form of hanks or cheeses.

The hydroxyl-containing materials are of natural or synthetic origin, such as cellulosic fibrous materials or their remnants, and polyvinyl alcohols. The cellulosic fibrous material is preferably cotton, but also includes other plant fibers such as flax, hemp, jute and ramie fibers. Examples of regenerated cellulose fibers are viscose staple fibers and viscose filaments.

Examples of carboxamido-containing materials are synthetic and natural polyamides and polyurethanes, especially materials in the form of fibers, such as wool and other animal hair, silk, leather, nylon-6, nylon-11 and nylon-4.

The dye mixtures according to the invention can be applied to, and fixed on, the aforementioned substrates, in particular the aforementioned fibre materials, by the application techniques known for water-soluble dyes, in particular fibre-reactive dyes.

For example, dyeing on cellulose fibers by exhaust dyeing and using various acid-binding agents and optionally neutral salts (such as sodium chloride or sodium sulfate) at a long bath ratio (long liquor) gives dyeings with excellent color yield, which is an improvement over the individual dyes. A preferred application is dyeing in a water bath at a temperature between 40 and 105 ℃, optionally at a temperature of up to 130 ℃ and superatmospheric pressure, and optionally in the presence of customary dyeing auxiliaries. One possible procedure is to feed the material into a warm bath, gradually increase the bath temperature to the desired dyeing temperature, and to carry out the dyeing operation at this temperature. If desired, neutral salts can be added which accelerate dye exhaustion, but only after the actual dyeing temperature has been reached.

The pad dyeing process likewise allows excellent color yield and excellent color build-up on the cellulose fibers, and the dye can be fixed to the material by rolling (batching) in a conventional manner at room temperature or at elevated temperature (for example up to about 60 ℃, by steam treatment or by means of dry heat).

Likewise, the conventional printing processes of cellulose fibres, which can be carried out in a single stage, for example with a printing paste containing sodium bicarbonate or other acid-binding agent, followed by steam treatment at 100 to 103 ℃, can produce strongly coloured prints with a well-defined outline and a clear white background; the fixing may be carried out in two stages, for example, by printing with a neutral or weakly acidic printing ink, passing the printed material through a hot alkali bath containing an electrolyte, or by padding the material with an alkaline padding liquid containing an electrolyte, and then winding the material subjected to alkaline padding, or by steam treatment or dry heat treatment. The printing results do not suffer significantly in appearance from variations in the fixing treatment conditions.

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

The acid-binding agent for fixing the dye mixture of the present invention to the cellulose fiber includes, for example, water-soluble basic salts of alkali metals and alkaline earth metals with organic acids or inorganic acids, or compounds which liberate alkali upon heating. Particularly suitable are alkali metal hydroxides and alkali metal salts of weak to medium-strength organic or inorganic acids, the preferred alkali metal compounds being sodium and potassium compounds. Such acid-binding agents include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium trichloroacetate, water glass, or trisodium phosphate.

The significance of the dye mixtures according to the invention is the high fixing capacity when applied to cellulose fibres by the dyeing or printing process. After the customary subsequent treatment by rinsing to remove the unfixed dye fraction, the cellulose dyeings obtained exhibit excellent wet fastnesses, which are easy to wash off, in particular owing to the good solubility of the unfixed dye fraction in cold water.

The invention also provides the use of the dye mixtures according to the invention for printing inks for digital textile printing by the ink jet process.

The printing inks of the invention comprise one or more of the abovementioned reactive dyes in an amount of, for example, from 0.1 to 50% by weight, preferably from 1 to 30% by weight, more preferably from 1 to 15% by weight, based on the total weight of the ink. Combinations of the foregoing reactive dyes with other reactive dyes used in textile printing and dyeing may also be included. To use the ink in a continuous flow process, the conductivity can be set to 0.5 to 25mS/m by adding an electrolyte.

Examples of suitable electrolytes include lithium nitrate and potassium nitrate.

The dyeing ink of the present invention may contain organic solvents in a total amount of 1 to 50% by weight, preferably 5 to 30% by weight.

Examples of suitable organic solvents are alcohols, such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, tert-butanol, pentanol, polyols, such as 1, 2-ethanediol, 1, 2, 3-propanetriol, butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 2-propanediol, 1, 3-propanediol, pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, hexanediol, D, L-1, 2-hexanediol, 1, 6-hexanediol, 1, 2, 6-hexanetriol, 1, 2-octanediol, polyalkylene glycols, such as polyethylene glycol, polypropylene glycol, alkylene glycols having 2 to 8 alkylene groups, such as monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, thioethylene glycol, thiodiethylene glycol, butyltriethylene glycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, lower alkyl ethers of polyhydric alcohols, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, tripropylene glycol isopropyl ether, polyalkylene glycol ethers, such as polyethylene glycol monomethyl ether, polypropylene glycol glycerol ether, polyethylene glycol tridecyl ether, polyethylene glycol nonylphenyl ether, amines, such as methylamine, ethylamine, triethylamine, diethylamine, dimethylamine, trimethylamine, dibutylamine, diethanolamine, triethanolamine, n-acetylethanolamine, N-formylethanolamine, ethylenediamine, urea derivatives, such as urea, thiourea, N-methylurea, N, N' -dimethylurea, ethyleneurea, 1, 1, 3, 3-tetramethylurea, amides, such as dimethylformamide, dimethylacetamide, acetamides, ketones or ketols, such as acetone, diacetone alcohol, cyclic ethers, such as tetrahydrofuran, dioxane, trimethylolethane, trimethylolpropane, 2-butoxyethanol, benzyl alcohol, gamma-butyrolactone, epsilon-caprolactam, and also sulfolane, dimethylsulfolane, methylsulfolane, dimethylsulfone, butadiene sulfone, dimethylsulfoxide, dibutylsulfoxide, N-cyclohexylpyrrolidone, N-methyl-2-pyrrolidone, N-ethylpyrrolidone, 2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 1- (3-hydroxypropyl) -2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 1, 3-bismethoxymethylimidazolidone, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, 2- (2-propoxyethoxy) ethanol, pyridine, piperidine, trimethylolpropane, 1, 2-dimethoxypropane, ethyl acetate, ethylenediamine tetraacetate, and ethylpentyl ether.

The printing ink of the present invention may further comprise conventional additives such as a viscosity modifier to set the viscosity in the range of 1.5 to 40.0 millipoise (mPas) at a temperature range of 20 to 50 ℃. Preferred inks have a viscosity of 1.5 to 20 millipoise, and particularly preferred inks have a viscosity of 1.5 to 15 millipoise.

Suitable viscosity modifiers include rheological additives, examples of which include the following: polyvinyl caprolactam, polyvinyl pyrrolidone, and their copolymers, polyether polyols, associative thickeners, polyureas, polyurethanes, sodium alginate, modified galactomannans, polyether ureas, polyurethanes, nonionic cellulose ethers.

The inks of the invention may also comprise additives with surface-active substances for setting the surface tension to 20 to 65 millinewtons per meter (mN/m), which may be adjusted as appropriate to the technology used (thermal or pressure technology). Examples of suitable surface-active substances include all kinds of surfactants, preferably nonionic surfactants, butyl diglycol, 1, 2-hexanediol.

The inks may also contain customary additives, such as fungal and bacterial growth inhibitors, in amounts of from 0.01 to 1% by weight, based on the total weight of the ink.

The ink can be prepared in a conventional manner by mixing the components in water.

The dye inks of the invention are suitable for use in ink jet printing processes for printing a wide variety of any pre-treated materials, such as silk, leather, wool, polyamide fibres and polyurethanes, especially any variety of cellulosic fibre materials. Examples of such fibrous materials are natural cellulose fibers, such as cotton, linen and hemp, and also chemical pulp and regenerated cellulose. The printing inks of the invention are also suitable for printing hydroxyl-and/or amino-containing fibres which have been pretreated in a blend of, for example, cotton, silk, wool and polyester fibres or polyamide fibres.

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

The pretreatment of textile substrates, such as cellulose and regenerated cellulose fibres and silk and wool, is carried out with an aqueous lye before printing. Bases are required for fixing the reactive dyes, examples of which are sodium carbonate, sodium bicarbonate, sodium acetate, trisodium phosphate, sodium silicate, sodium hydroxide, base donors such as sodium chloroacetate, sodium formate, hydrotropic substances such as urea, reduction inhibitors such as sodium nitrobenzenesulfonate, and thickeners which prevent the flow of the pattern (motifs) when the printing ink is applied, examples of which are sodium alginate, modified polyacrylates and highly etherified galactomannans.

These pretreatment agents are applied uniformly and quantitatively to the textile substrate by the following means: the treated substrate is then dried using a suitable applicator, for example using a 2-or 3-roll pad, using a non-contact spray technique, using a foam application, or using a suitably adapted ink-jet technique.

After printing, the textile fibre material is dried at 120 to 150 ℃ and then fixed. The ink jet prints obtained with reactive dyes can be fixed at room temperature or by saturated steam, superheated steam, hot air, microwaves, infrared radiation, laser or electron beam or other suitable energy transfer methods.

The single-stage differs from the two-stage fixation operation in that:

in single stage fixation, the chemicals required for fixation are already on the textile substrate.

In a two-stage fixation, no such pre-treatment is required. Fixing requires only a base, which is applied after ink jet printing and before the fixing operation, without an intermediate drying step. No additional additives, such as urea or thickeners, are required.

The fixing is followed by a printing and dyeing aftertreatment, which is a prerequisite for good fastness, high brightness and defect-free white backgrounds.

The dyeings and prints obtained with the dye mixtures according to the invention have intense dark parts; especially on cellulosic fibre materials, have good light fastness and excellent moisture resistance properties, such as wash resistance, water resistance, sea water resistance, cross-dyeing resistance and acid and alkaline perspiration resistance, as well as good fastness to dry heat setting, folding and rubbing.

Furthermore, the dye mixtures according to the invention can also be used for the fibre-reactive dyeing of wool. Furthermore, wools which have been subjected to non-felting or low-felting treatment (see, for example, Lehrbuch der Textilchemie, Springer-Verlag, third edition (1972), p. 295-299, especially the Hercosett method (p. 298); J. Soc. dyers and Colourists 1972, 93-99, and 1975, 33-44, by H. Rath) can be dyed with very good fastness properties.

The dyeing procedure for the wool is here 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 dyeings having an acceptable level of dyeing, it is advisable to add customary leveling agents, based, for example, on the reaction product of cyanuric chloride with three molar amounts of aminobenzenesulfonic acid and/or aminonaphthalenesulfonic acid, or on the reaction product of, for example, stearamide with ethylene oxide. For example, it is preferred that the dye mixtures of the invention are first subjected to an exhaust process in an acid dyebath having a pH value of between about 3.5 and 5.5 under pH monitoring, and then the pH is changed to neutral towards the end of the dyeing time and optionally to a pH in the weakly basic range of up to 8.5, so that complete reactive bonds are formed between the dye mixtures of the invention and the fibers for deep dyeing. At the same time, the portion of the dye that is not reactively bound is removed.

The procedure described here is also suitable for producing dyeings on fiber materials composed of other natural or synthetic polyamides and polyurethanes. In general, the material to be dyed is introduced into a bath at a temperature of about 40 ℃ and agitated therein for a period of time, after which the bath is adjusted to the desired weakly acidic pH (preferably that of weak acetic acid) and the actual dyeing is carried out at a temperature between 60 and 98 ℃. However, the dyeing can also be carried out at boiling or in a closed dyeing apparatus at temperatures of up to 106 ℃. The dye mixtures according to the invention can also be used to advantage in customary continuous dyeing processes, owing to their excellent water solubility. The color strength of the dye mixtures according to the invention is extremely high.

The dye mixtures according to the invention provide reddish blue to greenish blue dyeings or ink-jet prints on the abovementioned materials, preferably fibrous materials. The following examples serve to illustrate the invention.

Detailed description of the preferred embodiments

The following examples are provided to illustrate the invention. The examples are prepared by mechanically mixing individual dyes in solid or liquid form in the manner of the present invention. Parts and percentages are by weight unless otherwise indicated. The compounds of the formulae described in the examples are sometimes referred to in the form of the free acid; it is usually prepared and isolated in the form of its salt, preferably a sodium or potassium salt, and used in dyeing in the form of its salt.

When the dye mixtures according to the invention are applied to the abovementioned materials, in particular cellulosic fibre materials, by the dyeing and printing application methods customary in the art, preferably those customary in the art for fibre-reactive dyes, they have excellent application properties and provide strong dyeing and printing results, with good fastness properties, in particular good tinctorial effects, in particular when the polyester is continuously dyed by the pad-steam dyeing process.

The following compounds are used as examples of dyes of formula (I):

examples of dyes of formula (II) are obtained by the following reaction: the method comprises the steps of reacting the amino formazan (2a-1) with trichlorotriazine at 0-20 ℃, and then reacting the dichlorotriazinyl compound (II-A) with N-ethyl-3-beta-vinylsulfonylaniline at room temperature to form the dye (II-B).

The following dyes corresponding to the general formula (II) are prepared in a similar manner:

examples 1 to 162

The aqueous formazan dye solutions of the formulae (I-a) to (I-E) were mixed with the copper formazans of the formulae (II-B) to (II-T) in the quantitative ratios indicated in the table and then isolated by spray drying to give the following inventive mixtures:

examples	Dye (I)	Dye (II)	Ratio (I): (II)
				1	(I-A)	(II-B)	1∶1
2	(I-A)	(II-C)	1∶1
				3	(I-A)	(II-D)	1∶1
4	(I-A)	(II-E)	1∶1
				5	(I-A)	(II-F)	1∶1

Examples	Dye (I)	Dye (II)	Ratio (I): (II)
				6	(I-A)	(II-G)	1∶1
7	(I-A)	(II-H)	1∶1
				8	(I-A)	(II-J)	1∶1
9	(I-A)	(II-K)	1∶1
				10	(I-A)	(II-L)	1∶1
11	(I-A)	(II-M)	1∶1
				12	(I-A)	(II-N)	1∶1
13	(I-A)	(II-O)	1∶1
				14	(I-A)	(II-P)	1∶1
15	(1-A)	(II-Q)	1∶1
				16	(I-A)	(II-R)	1∶1
17	(I-A)	(II-S)	1∶1
				18	(I-A)	(II-T)	1∶1
19	(I-A)	(II-B)	2∶1
				20	(I-A)	(II-C)	2∶1
21	(I-A)	(II-D)	2∶1
				22	(I-A)	(II-E)	2∶1
23	(I-A)	(II-F)	2∶1
				24	(I-A)	(II-G)	2∶1
25	(I-A)	(II-H)	2∶1
				26	(I-A)	(II-J)	2∶1
27	(I-A)	(II-K)	2∶1
				28	(I-A)	(II-L)	2∶1
29	(I-A)	(II-M)	2∶1
				30	(I-A)	(II-N)	2∶1
31	(I-A)	(II-O)	2∶1
				32	(I-A)	(II-P)	2∶1
33	(I-A)	(II-Q)	2∶1
				34	(I-A)	(II-R)	2∶1
35	(I-A)	(II-S)	2∶1
				36	(I-A)	(II-T)	2∶1
37	(I-A)	(II-B)	1∶2

Examples	Dye (I)	Dye (II)	Ratio (I): (II)
				38	(I-A)	(II-C)	1∶2
39	(I-A)	(II-D)	1∶2
				40	(I-A)	(II-E)	1∶2
41	(I-A)	(II-F)	1∶2
				42	(I-A)	(II-G)	1∶2
43	(I-A)	(II-H)	1∶2
				44	(I-A)	(II-J)	1∶2
45	(I-A)	(II-K)	1∶2
				46	(I-A)	(II-L)	1∶2
47	(I-A)	(II-M)	1∶2
				48	(I-A)	(II-N)	1∶2
49	(I-A)	(II-O)	1∶2
				50	(I-A)	(II-P)	1∶2
51	(I-A)	(II-Q)	1∶2
				52	(I-A)	(II-R)	1∶2
53	(I-A)	(II-S)	1∶2
				54	(I-A)	(II-T)	1∶2
55	(I-B)	(II-B)	1∶1
				56	(I-B)	(II-C)	1∶2
57	(I-B)	(II-D)	1∶1
				58	(I-B)	(II-E)	1∶2
59	(I-B)	(II-F)	1∶1
				60	(I-B)	(II-G)	2∶1
61	(I-B)	(II-H)	1∶2
				62	(I-B)	(II-J)	2∶1
63	(I-B)	(II-K)	1∶1
				64	(I-B)	(II-L)	2∶1
65	(I-B)	(II-M)	1∶2
				66	(I-B)	(II-N)	1∶1
67	(I-B)	(II-O)	2∶1
				68	(I-B)	(II-P)	1∶1
69	(I-B)	(II-Q)	1∶2

Examples	Dye (I)	Dye (II)	Ratio (I): (II)
				70	(I-B)	(II-R)	1∶2
71	(I-B)	(II-S)	2∶1
				72	(I-B)	(II-T)	1∶2
73	(I-C)	(II-B)	1∶1
				74	(I-C)	(II-C)	2∶1
75	(I-C)	(II-D)	1∶1
				76	(I-C)	(II-E)	1∶2
77	(I-C)	(II-F)	1∶1
				78	(I-C)	(II-G)	2∶1
79	(I-C)	(II-H)	1∶2
				80	(I-C)	(II-J)	2∶1
81	(I-C)	(II-K)	1∶1
				82	(I-C)	(II-L)	2∶1
83	(I-C)	(II-M)	1∶2
				84	(I-C)	(II-N)	1∶1
85	(I-C)	(II-O)	2∶1
				86	(I-C)	(II-P)	1∶1
87	(I-C)	(II-Q)	1∶2
				88	(I-C)	(II-R)	1∶2
89	(I-C)	(II-S)	2∶1
				90	(I-C)	(II-T)	1∶2
91	(I-D)	(II-B)	1∶1
				92	(I-D)	(II-C)	1∶2
93	(I-D)	(II-D)	1∶1
				94	(I-D)	(II-E)	1∶2
95	(I-D)	(II-F)	1∶1
				96	(I-D)	(II-G)	2∶1
97	(I-D)	(II-H)	1∶2
				98	(I-D)	(II-J)	2∶1
99	(I-D)	(II-K)	1∶1
				100	(I-D)	(II-L)	2∶1
101	(I-D)	(II-M)	1∶2

Examples	Dye (I)	Dye (II)	Ratio (I): (II)
				102	(I-D)	(II-N)	1∶1
103	(I-D)	(II-O)	2∶1
				104	(I-D)	(II-P)	1∶1
105	(I-D)	(II-Q)	1∶2
				106	(I-D)	(II-R)	1∶2
107	(I-D)	(II-S)	2∶1
				108	(I-D)	(II-T)	1∶2
109	(I-E)	(II-B)	1∶1
				110	(I-E)	(II-C)	1∶2
111	(I-E)	(II-D)	1∶1
				112	(I-E)	(II-E)	1∶2
113	(I-E)	(II-F)	1∶1
				114	(I-E)	(II-G)	2∶1
115	(I-E)	(II-H)	1∶2
				116	(I-E)	(II-J)	2∶1
117	(I-E)	(II-K)	1∶1
				118	(I-E)	(II-L)	2∶1
119	(I-E)	(II-M)	1∶2
				120	(I-E)	(II-N)	1∶1
121	(I-E)	(II-O)	2∶1
				122	(I-E)	(II-P)	1∶1
123	(I-E)	(II-Q)	1∶2
				124	(I-E)	(II-R)	1∶2
125	(I-E)	(II-S)	2∶1
				126	(I-E)	(II-T)	1∶2

Dyeing example 1

To a solution of 3 parts of the dye mixture from example (8) and 999 parts of water are added 5 parts of sodium chloride, 7 parts of sodium carbonate, 0.7 part of sodium hydroxide (in the form of a 32.5% strength aqueous solution) and 1 g of customary wetting agents.

100 g of bleached cotton knit fabric are placed in the dye bath, the temperature of which is maintained at 25 ℃ under constant mechanical agitation and is heated to 60 ℃ at a rate of 1 ℃/min. Keeping the temperature of the dye liquor for 60-90 minutes. The dyed material was then removed and rinsed by boiling for 5 minutes and then holding at 60 ℃ for 5 minutes. The dyed fabric was neutralized with 1000 parts of 0.05% acetic acid at 40 ℃ for 10 minutes, rinsed at 70 ℃ and then soaped with a laundry detergent for 15 minutes. After further rinsing, the dyed material is dried and the bright blue dyeing obtained has excellent fastness properties.

Dyeing example 2

Textile fabrics consisting of mercerized cotton were pad-dyed with a dip containing 35 g/l anhydrous sodium carbonate, 100 g/l urea and 150 g/l low viscosity sodium alginate solution (6%) and then dried. The wet pick-up (wet pick-up) was 70%. The fabric thus pretreated was printed with an aqueous ink containing the following components using a drop-on-demand (bubble jet) ink jet printing head:

2% of the dye mixture of example (1)

20% of sulfolane

0.01% of Mergal K9N

77.99% water.

The blot was completely dried. The fixation was carried out with saturated steam at 102 ℃ for 8 minutes. The print is then rinsed with warm water, subjected to fastness cleaning with hot water at 95 ℃, rinsed with warm water and then dried. The result obtained is a bluish red print with excellent various work fastnesses.

Claims (10)

1. A dye mixture comprising at least one dye of the general formula (I) and at least one dye of the general formula (II),

wherein

M is hydrogen or an alkali metal, ammonium, or the equivalent of an alkaline earth metal ion;

y is vinyl or of the formula CH₂CH₂A group of Z, wherein Z is a base-removable group;

R¹is hydrogen or sulfo;

R²having R¹Or is methyl, methoxy, carboxyl or SO₂Y²Wherein Y is²Has one of the meanings of Y;

R³having R¹One of the meanings of (a);

r has R²One of the meanings of (a);

w is carbon or-SO-;

a is a group of the formula (3)

Wherein

Denotes a bond linked to formazan, an

B is a group of the formula (4), (5), (6) or (7)

Wherein

Represents a bond to N in general formula (3);

u is a 5-or 6-membered heterocyclic ring to which N is attached, which may be substituted by thio or oxo; or is a group of the formula (8)

Wherein

E is hydrogen, C unsubstituted or substituted by methoxy, hydroxy, sulfato, sulfo or chlorine₁-C₄-alkyl, or is phenylSaid phenyl group being selected from chloro, nitro, acetamido, sulfo, hydroxy, carboxy, C₁-C₄Alkanoyl radical, C₁-C₄-alkoxy and C₁-C₄-alkyl substituted by one or two substituents;

g has one of the meanings of E, or is cyano;

l is phenylene or naphthylene, each of which may be substituted by up to two substituents selected from chlorine, bromine, hydroxy, C₁-C₄Alkoxy, especially methoxy, C₁-C₄-alkyl, especially methyl or ethyl, sulfo, and cyano; or L is C₂-C₆Alkylene, which may be interrupted by 1 to 2 hetero groups;

q is fluorine, chlorine, C₁-C₄Alkoxy, cyanamino, amino, C₁-C₄-alkylamino, dialkylamino, piperazinyl, morpholinyl or a group of formula (9a) or (9b)

Wherein A-is fluoride, chloride, or the equivalent of sulfate;

v has one of the meanings of E;

T¹is hydrogen, fluorine or chlorine;

T²is hydrogen, fluorine or chlorine, with the proviso that T¹And T²Not hydrogen at the same time;

X¹is fluorine or chlorine; and is

X²Having X¹One of the meanings in (a).

2. Dye mixture according to claim 1, wherein

M is hydrogen or an alkali metal;

y is vinyl or of the formula CH₂CH₂A group of Z, wherein Z is sulfato, chloro, acetyl, phosphato or thiosulfato;

R¹is hydrogenOr a sulfo group;

R²is SO₂Y²Wherein Y is²Is CH₂CH₂Cl or vinyl;

R³having R¹One of the meanings of (a);

r has R²One of the meanings of (a);

w is carbon or-SO-;

a is a group of the formula (3)

Wherein

Denotes a bond linked to formazan, an

B is a group of the general formula (4), (5), (6) or (7)

Wherein

Represents a bond to N in general formula (3);

u is morpholino, or a group of the formula (8)

Wherein

E is hydrogen, phenyl, 4-chlorophenyl, 3-sulfophenyl, methyl, 2-sulfoethyl, 2-hydroxyethyl or 2-sulfatoethyl;

g is hydrogen;

l is phenylene or naphthylene, each of which may be substituted by methoxy or methyl, ethyl, sulfo or cyano; or L is C₂-C₆Alkylene which may be substituted by oxy, thio, amino or C₁-C₄-an alkylamino group is interrupted;

q is fluorine, chlorine, C₁-C₄Alkoxy, cyanamino, amino, C₁-C₄-alkylamino radicalDialkylamino, piperazinyl, morpholinyl or a radical of the formula (9a) or (9b)

Wherein A-is fluoride, chloride, or the equivalent of sulfate;

v is hydrogen, methyl, phenyl or sulfophenyl;

T¹is hydrogen, fluorine or chlorine;

T²is hydrogen, fluorine or chlorine, with the proviso that T¹And T²Not hydrogen at the same time;

X¹is fluorine or chlorine; and is

X²Having X¹One of the meanings in (a).

3. A dye mixture according to claim 1 which comprises one or more formazan dyes according to formula (I) in a mixing ratio of 90: 10 to 10: 90% by weight with one or more formazan dyes according to formula (II).

4. A dye mixture according to claim 1 which comprises one or more formazan dyes according to formula (I) and one or more formazan dyes according to formula (II) in a mixing ratio of from 70: 30% to 30: 70% by weight.

5. Use of a dye mixture as claimed in at least one of claims 1 to 4 for dyeing or printing hydroxyl-and/or carboxamido-containing material, preferably fiber material.

6. A process for preparing a dye mixture as claimed in one or more of claims 1 to 3, by mechanical mixing of the individual dyes of the general formulae (I) and (II) in solid or liquid form in the desired proportions.

7. A process for dyeing or printing hydroxyl-and/or carboxamido-containing material, preferably fibrous material, by applying one or more dyes in dissolved form to the material and fixing the dye(s) to the material by heating or with the aid of an alkaline agent or both, which comprises using as dye a dye mixture according to at least one of claims 1 to 4.

8. Dye preparations comprising reactive dyes according to one or more of claims 1 to 4 for dyeing and printing carboxamido-and/or hydroxyl-containing material, especially fiber material.

9. An aqueous printing ink for printing textiles by the inkjet process, comprising from 0.01 to 40% by weight, based on the total weight of the ink, of one or more reactive dye mixtures as claimed in claims 1 to 4.

10. A process for dyeing, conventional printing and ink-jet printing textile fibre materials, which comprises using one or more reactive dyes as claimed in claims 1 to 4.