CH695613A5 - Fiber-reactive dye mixture, useful for colouring or printing on cellulosic or nitrogenous synthetic materials, comprises triazo compounds; dye components; further fiber-reactive dyes as nuance components; and colorless additives - Google Patents

Abstract

Mixtures (I) of heavy metal-free fiber-reactive dyes based on one or more triazo compounds (1); one or more dye components (2); at least a further fiber-reactive dyes as mixture- or nuance-components; and further colorless additives. Mixtures (I) of heavy metal-free fiber-reactive dyes based on one or more triazo compounds of formula (1); one or more dye components of formula (2); at least a further fiber-reactive dyes as mixture- or nuance components; and further colorless additives. R1, R2-O-M, -CH=CH2 or CH2CH2-Z; R3, R4CH=CH2 or CH2CH2-Z; Z : OH, Cl, Br or particularly sulfate; L1-L3H, -CH2COO-M, -CH2CH2COO-M, -CH2CH2OH or-CH2SO3-M; X1-X3, Y1-Y4H, -NH2, -NH-acetyl, -NH-CH2COO-M, 1-3C alkyl, 1-3C alkoxy, -NO2 or -SO3-M; and M : H, ammonium, trialkyl ammonium, tetraalkyl ammonium, an alkali metal or the equivalent of an alkaline earth metal. [Image] [Image].

Description

CH 695 613 A5

description

The invention relates to mixtures of heavy metal-free fiber-reactive dyes of triazo compounds and other fiber-reactive dye components and their Venwendung, and the preparation of the triazo compounds.

Fiber-reactive dyes are covalent linkages with fiber materials in dyeing and printing processes and thus often have an above-average wet fastness level. Precondition for reactions between reactive dyes with their electrophilic centers and fiber materials are nucleophilic groups such as e.g. Hydroxy or amino groups on the textile fibers, e.g. in cotton, cellulose regenerated fibers and wool. For applications in textile finishing, prefabricated mixtures of readily combinable dyes are of particular interest, since these are simple in their application and give the desired nuance with high reproducibility. For dark shades, such as black or navy, mixtures of fiber-reactive dyes are frequently used whose components have different extinction maxima in the UV / VIS range. As a result, these mixtures, as a combination dye, are able to absorb a large wavelength range of the incident light and thus give rise to textile fiber materials, e.g. a deep black color impression.

Mixtures of fiber-reactive dyes which are particularly suitable for dyeings with black or navy nuances are known and are mentioned for example in the documents WO 03/080 739 or WO 2004/069 937. By nature, however, high amounts of dye are required for very dark shades on fiber materials.

For applications in the field of textile finishing cellulosic or nitrogen-containing fiber materials reactive dyes are of particular interest, since in addition to a good level of fastness allow brilliant shades and high reproducibility of the dyeing processes. For industrial textile finishing, the dyestuffs of interest in reactive dyeing with a view to economical and also ecologically advantageous process management are of interest, which are inherently very strong in color and, moreover, thanks to a good fixation and good color build-up, even in relatively small amounts to the desired dyeing results to lead.

Fiber-reactive dyes which contain an ion of a heavy metal in the chromophore via a chelate complex, often have a high light fastness, but often lead to less brilliant dye results. In addition, such metal complexes can lead to problems with wastewater pollution in the processing plants or to metal-containing extracts from the dyed fibers. When using fiber-reactive dyes for the dyeing of fiber blends of cellulosic and synthetic fibers, such as e.g. a cotton-polyamide blended fabric, it is further advantageous if the fiber-reactive dye does not give troublesome staining of the synthetic fiber constituents. From a partial staining of the synthetic fibers with fiber-reactive dyes worse wash fastness can result. In addition, in particular with mixtures of fiber-reactive dyes, different staining of the cellulosic and the synthetic components in such fiber blends may result in a nonuniform staining result.

In the textile industry metal-free reactive dyes are thus required for dark nuances, which have sufficiently high solubilities and light fastness and which lead to dyeings with good wash fastness at low dye use.

This object is achieved with the present invention, which provides mixtures of heavy metal-free fiber-reactive dyes available, which lead in comparison with conventional dye mixtures even with relatively small amount used to very dark dye results in the black and marine.

The novel mixtures comprise one or more, preferably one or two triazo compounds a) of the general formula (1),

which are prepared by diazotization of the amino-functionalized component (A) with subsequent coupling with component (B),

a)

so3m l (

(1)

2

CH 695613 A5

(A) (B)

together with one or more, preferably a dye component b) of the general formula (2),

b)

(2)

and optionally c) at least one further fiber-reactive dye as a mixing or shading component and d) optionally further colorless additives according to the prior art.

Examples of such blending or shading components are given below.

In these formulas mean:

i) Ri is -O-M and R2 is -CH = CH2 or CH2CH2-Z, or ii) R2 is -O-M and Ri is -CH = CH2 or CH2CH2-Z.

The formula (1) thus contains only one fiber-reactive group of the formula -SO 2 -CH = CH 2 or -SO 2 CH 2 CH 2 -Z.

R3 and R4 are independently of Ri and R2: -CH = CH2 or CH2CH2-Z, wherein Z is hydroxy, chloride, bromide or particularly preferably sulfate.

Li, L2 and U mean independently of one another:

-H, -CH 2 COO-M, -CH 2 CH 2 COO-M, -CH 2 CH 2 OH or -CH 2 SO 3-M.

Xi, X2 and X3 are independent of each other:

-H, -NH 2, -NH-acetyl, -NH-CH 2 COO-M, - (C 1 -C 3) -alkyl, - (C 1 -C 6 -alkoxy,

-NO 2 or -SO 3 -M,

Yi, Y2, Y3 and Y4 are independent of each other:

-H, -NH 2, -NH-acetyl, -NH-CH 2 COO-M, - (C 1 -C 3 -alkyl, - (C 1 -C 3) -alkoxy,

-NO 2 or -SO 3 -M,

M stands here, in formula (1) and in formula (2) for:

Hydrogen, ammonium, trialkylammonium, tetraalkylammonium, an alkali metal or the equivalent of an alkaline earth metal.

The groups X, -X3 and the specific substitution pattern of triazo compounds according to formula (1) affect their solubility and cellulosic fibers their fiber affinity. Similar fiber affinities of the cellulosic fibers their fiber affinity. Similar fiber affinities of the compounds of formula (1) in comparison to compounds of formula (2) allow in mixtures similar interactions between fiber material and dye fractions, which are in many dyeing processes a prerequisite for a uniform dyeing of the fiber material.

In the novel mixtures, the triazo compounds a) with 3-55 wt .-% and the dye components b) with 45-97 wt .-% are included. Optionally, additional fiber-reactive dyes in proportions of 1-20% by weight, as blending or shading components, may additionally be added as component c) without losing the advantageous properties of the original mixtures.

In this case, mixtures of 20 to 40 wt .-% triazo compounds a), 60 to 80 wt .-% of dye components b) and additionally 3-10 wt .-% of other fiber-reactive dyes c) are particularly preferred.

CH 695613 A5

Examples of preferably used further fiber-reactive dyes c) are components according to the general formulas (3), (4), (5) and (6).

[0021]

SO.sub.3M

(3)

(4)

(5)

mo3soch2ch2o2s

Cf N ^ N

A A

\ J ~ H N NH 0H

m03s n = n-ò- s02ch2ch20s03m

(6)

In the formulas (3), (4), (5) and (6) M is hydrogen, ammonium, trialkylammonium, tetraalkylammonium, an alkali metal or the equivalent of an alkaline earth metal.

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CH 695 613 A5

By the additional incorporation of Nuancierkomponenten c) in wt .-% - 1-20%, preferably 3-10 wt .-%, e.g. from yellow, orange and red components to the described dye mixture, a very large part of the possible nuances can be achieved in black and marine dyeings on suitable fiber materials. Depending on the mixing ratio of the components, both greener and redder black or navy nuances can be adjusted.

With the mixtures according to the invention of the heavy metal-free fiber-reactive color components a), b) and optionally c), which have the properties required for industrial use to a large extent, compared to other known ready-made mixtures of fiber-reactive dyes for black and marine Nuance level dyeings in dark nuances already achieved with comparatively small amounts of dye.

The triazo compounds a) according to formula (1) have above-average extinction coefficients compared to conventional fiber-reactive dyes. The similar high solubility and the similar fiber affinity to cellulosic fiber materials of the compounds according to formulas (1) and (2) lead to an optimal combinability of these components. The molecular geometry of the triazo compounds according to formula (1) with non-linearly standing azo bonds contributes to the fact that these dyes are not blocked in the exhaust process by dyes according to formula (2) and that unfixed amounts of dye according to formula (1 ) remain well washable after a dyeing process. In continuous and semi-continuous dyeing methods, the reproducibility of de with relatively low salt concentrations is thereby achieved. In addition, the groups Li, L2, M, R ,, R2, X ,, X2 and X3 in the triazo compounds according to formula (1) can contribute significantly to improved solubility in aqueous, strongly electrolyte-containing media. High solubility of the color components is especially noticeable in deep shades such as e.g. Black required in certain staining procedures.

Dyeings of cellulosic fiber materials with fiber-reactive dyes are usually carried out in the alkaline pH range in the textile industry. When dyeing fiber blends under these typical conditions, it is seen that e.g. in cotton-polyamide blends only the cotton content is dyed very dark and the polyamide content is only very little colored. This allows a uniform appearance of the dyeing results, which facilitates a separate dyeing of the synthetic fibers. Due to the low tendency of the dye mixtures according to the invention, in particular of the triazo compounds according to formula (1), to dye the proportions of synthetic fibers in mixed fibers, a very high level of wash fastness can also be achieved with textile materials from fiber blends. It is also advantageous that all components of the dye mixtures according to the invention are obtained by reductive treatments, e.g. can be decolorized in the etching pressure, to the same extent and completely and so various effects in the textile finishing are possible. In addition to a high wet fastness level, the novel mixtures of fiber-reactive dyes advantageously also give good light fastnesses in the case of very dark shades.

Preferred triazo compounds a) here are the compounds (1a), (1b), (1c) and (1 d), in which the respective specific substitution pattern influences the dyeing property of these components so that these compounds are very good combine with the dye components according to formula (2).

S03Na

(1a)

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CH 695 613 A5

SOjNa

(1b)

S03Na

(1C)

Sosna

(1d)

Preference is given to mixtures of triazo compounds, in particular of the triazo compounds (1a) to (1d), with a dye component b) of the formula (2a) in order to achieve the desired dark shades such as black or navy (cf. Examples 5 to 11),

(2a)

The invention also includes the use of the mixture according to claims 1 to 6 with a dye content of 3 to 40 wt .-% in aqueous liquid preparations for dyeing or printing cellulosic or nitrogen-containing fiber materials.

The invention also includes the preparation of the triazo compounds a) as the basis of the mixtures according to claim 1 to 6

6

CH 695613 A5

RAS

* 2

SO.sub.3M

NH

'2

L.

two \

MO3S

(A)

(B)

The preparation is carried out by diazotization of a corresponding amino-functionalized monoazo component (A) and their coupling with a second monoazo component (B). The corresponding monoazo components are prepared by diazotization and azo coupling and partial sulfonation of suitable intermediates under the conditions customary for these reactions according to the prior art.

Example 1: Component (1a)

In a first reaction vessel 62 parts of 4 - ((2- (sulfoxy) ethyl) sulfonyl) aniline are suspended with 200 parts of ice water and 35 parts of hydrochloric acid (32%) admixed. After cooling to 0-5 ° C in an ice bath, 100 parts of ice are added and diazotized by adding 16 parts of sodium nitrite. The reaction mixture is stirred for 40 min at 0-5 ° C and then added 1 part of sulfamic acid. Thereafter, this suspension is added to a solution of 40 parts of m-phenylenediamine-4-sulfonic acid in 100 parts of ice water and the reaction mixture is stirred for 15 h at 0-5 ° C.

In a second reaction vessel, 77 parts of p-amino-azo-benzene-3,4-disulfonic acid are suspended in 100 parts of ice water and 35 parts of hydrochloric acid (32%) are added. After cooling to 0-5 ° C in an ice bath, 100 parts of ice are added and diazotized by adding 17 parts of sodium nitrite. The reaction mixture is stirred for 40 min at 0-5 ° C and then added 1 part of sulfamic acid.

Thereafter, the solution in the first reaction vessel is added to the suspension with the diazotized monoazo component from the second reaction vessel, the pH adjusted to 6.4 by addition of sodium carbonate and stirred for 8 h at 0-5 ° C. The triazo component (1a) is now obtained by spray or sheet drying of the reaction solution as an orange powder.

Example 2: Component (1b)

In a first reaction vessel 38 parts of p-sulfanilic acid are suspended with 200 parts of ice water and 35 parts of hydrochloric acid (32%) admixed. After cooling to 0-5 ° C in an ice bath, 100 parts of ice are added and diazotized by adding 16 parts of sodium nitrite. The reaction mixture is stirred for 40 min at 0-5 ° C and then added 1 part of sulfamic acid. Thereafter, this suspension is added to a solution of 40 parts of m-phenylenediamine-4-sulfonic acid in 100 parts of ice water and the reaction mixture is stirred for 15 h at 0-5 ° C. In a second reaction vessel, 78 parts of 4 '- ((2- (sulfoxy) ethyl) sulfonyl) -4-aminoazobenzene added under cooling in portions at 25 ° C in 200 parts of 65% oleum. Thereafter, the mixture is stirred for 4 h at 40 ° C and after complete sulfonation, the reaction mixture was added to 800 parts of ice and the precipitated aminoazo suction filtered, washed with saturated brine, the paste suspended in 100 parts of ice water and 35 parts of hydrochloric acid (32%). After cooling to 0-5 ° C in an ice bath, 100 parts of ice are added and diazotized by adding 18 parts of sodium nitrite. The reaction mixture is stirred for 40 min at 0-5 ° C and then added 1 part of sulfamic acid.

Thereafter, the solution in the first reaction vessel is added to the suspension with the diazotized monoazo component from the second reaction vessel, the pH is adjusted to 6.4 by adding sodium carbonate and during 8

S03Na

(1a)

7

CH 695613 A5

Stirred at 0-5 ° C h. The triazo component (1b) is now obtained by spray or sheet drying of the reaction solution as an orange powder.

S03Na

(1b)

Example 3: Component (1c)

and 35 parts of hydrochloric acid (32%) added. After cooling to 0-5 ° C in an ice bath, 100 parts of ice are added and diazotized by adding 16 parts of sodium nitrite. The reaction mixture is stirred for 40 min at 0-5 ° C and then added 1 part of sulfamic acid. Thereafter, this suspension is added to a solution of 40 parts of m-phenylenediamine-4-sulfonic acid in 100 parts of ice water and the reaction mixture is stirred for 15 h at 0-5 ° C.

In a second reaction vessel, 38 parts of p-sulphanilic acid are suspended with 200 parts of ice water and 35 parts of hydrochloric acid (32%) are added. After cooling to 0-5 ° C in an ice bath, 100 parts of ice are added and diazotized by adding 18 parts of sodium nitrite. The reaction mixture is stirred for 40 min at 0-5 ° C. Then, this suspension is added to a solution of 50 parts of 1-N-acetyl-meta-phenylenediamine-4-sulfonic acid and 20 parts of sodium carbonate in 100 parts of ice water and the reaction mixture is stirred for 15 h at 0-5 ° C. After complete coupling reaction, 40 parts of hydrochloric acid (32%) are added and diazotized by adding 16 parts of sodium nitrite. The reaction mixture is again stirred for 40 min at 0-5 ° C and then added 1 part of sulfamic acid.

After complete reaction, the solution from the first reaction vessel is then added to the suspension in the second reaction vessel, the pH is increased to 5.0 by addition of sodium carbonate and then stirred for 5 h at 0-5 ° C. After complete coupling reaction, the triazo component (1c) is obtained by spray or sheet drying of the reaction solution as a brown powder.

Soana

(1c)

Example 4: Component (1d)

In a first reaction vessel 38 parts of p-sulfanilic acid are suspended with 200 parts of ice water and 35 parts of hydrochloric acid (32%) admixed. After cooling to 0-5 ° C in an ice bath, 100 parts of ice are added and diazotized by adding 16 parts of sodium nitrite. The reaction mixture is stirred for 40 min at 0-5 ° C and then added 1 part of sulfamic acid. Thereafter, this suspension is added to a solution of 40 parts of m-phenylenediamine-4-sulfonic acid in 100 parts of ice water and the reaction mixture is stirred for 15 h at 0-5 ° C. In a second reaction vessel, 62 parts of 4 - ((2- (sulfoxy) ethyl) sulfonyl) aniline are suspended with 200 parts of ice water and 35 parts of hydrochloric acid (32%) admixed. After cooling to 0-5 ° C in an ice bath, 100 parts of ice are added and diazotized by adding 16 parts of sodium nitrite. The reaction mixture is stirred for 40 min at 0-5 ° C. Then, this suspension is added to a solution of 50 parts of 1-N-acetyl-meta-phenylenediamine-4-sulfonic acid and 20 parts of sodium carbonate in 100 parts of ice water and the reaction mixture is stirred for 15 h at 0-5 ° C. After complete coupling reaction, 40 parts of hydrochloric acid (32%) are added and diazotized by adding 17 parts of sodium nitrite. The reaction mixture is again stirred for 40 min at 0-5 ° C and then added 1 part of sulfamic acid. After complete reaction, the solution from the first reaction vessel in the

8th

CH 695 613 A5

Added suspension in the second reaction vessel, the pH increased by the addition of sodium carbonate to 5.0 and then stirred for 5 h at 0-5 ° C. After complete coupling reaction, the triazo component (1 d) is obtained by spray or sheet drying of the reaction solution as a brown powder.

The triazo compounds a) according to formula (1), diazo compounds b) according to formula (2) and optionally other fiber-reactive dyes can be mixed as solids and as components dissolved in aqueous media.

Example 5

A dye mixture is prepared by mechanical mixing, which contains 29 parts of the triazo compound according to formula (1a) and 71 parts of the diazo compound according to formula (2a). Optionally, this mixture may be mixed with a portion of sodium dihydrogen phosphate and dissolved in softened water. This solution can be filtered and then dried via a spray-drying process.

Example 6

A dye mixture is prepared by mechanical mixing, which contains 26 parts of the triazo compound according to formula (1a), 6 parts of the monoazo compound according to formula (6) and 68 parts of the diazo compound according to formula (2a). Optionally, this mixture may be dissolved in softened water, filtered and then dried via a spray-drying process.

Example 7

A dye mixture is prepared by mechanical mixing, which contains 25 parts of the triazo compound according to formula (1b) and 75 parts of the diazo compound according to formula (2a). Optionally, this mixture may be dissolved in softened water, filtered and then dried via a spray or sheet drying process.

Example 8

A dye mixture is prepared by mechanical mixing, which contains 24 parts of the triazo compound of formula (1b), 8 parts of the diazo compound of formula (3) and 68 parts of the diazo compound of formula (2a). Optionally, this mixture may be mixed with a portion of sodium dihydrogen phosphate, dissolved in softened water, filtered and then dried via a spray-drying process.

Example 9

A dye mixture is prepared by mechanical mixing, which 10 parts of the triazo compound of formula (1c), 10 parts of the triazo compound of formula (1 d), 5 parts of the monoazo component according to formula (5) and 75 Contains parts of the diazo compound according to formula (2a). Optionally, this mixture may be dissolved in softened water, filtered and then dried via a spray or sheet drying process.

Example 10

A dye mixture is prepared by mechanical mixing, which contains 10 parts of the triazo compound according to formula (1c) and 90 parts of the diazo component according to formula (2b).

9

CH 695613 A5

O-CH3

oh no

m03s0ch2ch202s

H3C-O

MO3S

n = n

SO.sub.3M

n = n so2ch2ch2oso3m

.(2 B)

Optionally, this mixture can be dissolved in softened water, this solution filtered and then dried over a spray or sheet drying process to a residual moisture content of <5%.

Example 11

An aqueous liquid formulation is prepared by mechanical mixing, which consists of 70% water, 20% diazo component according to formula (2a), 7% triazo component according to formula (1a), 1% of component (5) and to a total of 2% of glycols, pH buffer substances and biocides. Due to the good solubility of the color component contained, in particular that of the triazo compound (1a), no undesired changes in viscosity, precipitations or crystallizations occur in this liquid formulation even after prolonged storage.

The ink-jet printing process (ink-jet) enables cost-effective and time-saving printing of textile fiber materials with dyes. When using fiber-reactive dyes on cellulosic fiber materials, the problem may arise here that the required color intensity can not be achieved in master patterns with very dark shades. By using the dye mixtures according to the invention in a liquid ink formulation, very dark nuances in the marine and black areas are now achieved in the inkjet printing process, similar to dyeing processes for cellulosic fiber materials. For the preparation of an aqueous black reactive ink, the triazo component according to formula (1a) in a proportion of 4%, the diazo component according to formula (2a) in an amount of 9% can be used. The inks further contain water as main solvents, antimicrobials, pH buffers, surfactants, rheology additives, and antifoaming agents, and are prepared by mechanical mixing and subsequent filtration.

The novel mixtures of Examples 5 to 12 are preferably suitable for dyeing or printing cellulosic or nitrogen-containing fiber materials.

Six parts of the mixture from Example 5 are dissolved in 80 parts of water and then treated with 20 parts of a solution of sodium silicate (250 ml / l sodium water glass 38 ° Bé) and sodium hydroxide (77 g / l). This solution is then applied by means of a padding method to a Textiiprobe from mercerized cotton and there, as usual in Klotz-Kaltver-Weil method, with air excluded at room temperature. After an 18-hour residence time, the texti-sample is rinsed out and all non-fixed constituents are washed out by washing at 100 ° C. After drying, a dyeing with a very dark shade of black is achieved, which has good fastness properties.

To shorten the residence time, the fiber material can be dwelled at elevated temperature instead of at room temperature in the pad-cold-dwell method. The dye mixture according to the invention can be used in a similar manner as in Example 13 in such a method in which instead of 18 hours at room temperature for only 45 minutes at 70 ° C is dwelling. The dyeing results in a deep black color, which has good wash fastness.

Example 15

By using the mixture of Example 6 and under similar conditions as in Example 13, a dark black is achieved, which has a slightly redder shade of black due to the Nuancierkomponente (6) compared to the dyeing result of Example 13 and good fastness properties having.

The dye mixture from Example 7 is added to a proportion of 6% by weight of a textile sample of cotton in a typical dyeing process for the textile industry according to the exhaust method with the addition of sodium chloride (80 g / l), soda (5 g / l). and sodium hydroxide (1.1 g / l). In a typical for the exhaust process

Example 12

Example 13

Example 14

Example 16

10

CH 695 613 A5

Dyeing process, the dye is now fixed at 60 ° C for 60 min on the fiber material. The now black Textiiprobe is rinsed, neutralized with dilute acetic acid solution (0.5 ml / l) and the unfixed components by a soaping process at 100 ° C washed out. After drying, a dyeing with a very dark shade of black is achieved, which has good fastness properties.

Example 17

By using the mixture of Example 8 and under similar conditions as in Example 16, a dark black is achieved, which has a slightly greener shade of black due to the Nuancierkomponente (3) compared to the dyeing result of Example 16 and good fastness properties having.

Example 18

An aqueous solution of the mixture of Example 5 with a concentration of 50 g / l is applied by means of a conventional padding process in the textile industry on cotton fiber material, this then dried at 110 ° C to a residual moisture content of 30% and by means of a Block method, a solution of 200 g / l sodium chloride, 20 g / l sodium carbonate and 5 g / l sodium hydroxide applied. The fiber material is then treated for 60 seconds by means of saturated steam at a temperature of 100 ° C, thereby fixing the fiber-reactive components of the mixture. After a soaping process, a level black coloration of the fiber material is recognizable, which has good washfastness.

Example 19

The dye mixture from Example 10 is used in a proportion of 3% by weight of a textile sample of cotton in a dyeing process typical for the textile industry according to the exhaustion process with the addition of sodium chloride (40 g / l), soda (5 g / l). and sodium hydroxide (0.8 g / l). In this dyeing process, the dye is fixed at 60 ° C for 60 min on the fiber material. The fibrous material is then rinsed, neutralized with dilute acetic acid solution (0.5 ml / l) and the unfixed components washed out by a sudging process at 100 ° C. After drying, a level dyeing is achieved with a hue greenish navy blue, which has good fastness properties.

Example 20

From the liquid formulation described in Example 11, 40 parts are diluted with 160 parts of water and added to 15 parts of a strongly alkaline solution containing potassium carbonate and potassium hydroxide. About a padding method, this solution is now applied as usual in Klotz cold dwell method, with a liquor pick-up of 60% on cotton fiber material and then dwelled for 18 hours at room temperature. After washing, the fiber material is neutralized by means of a dilute solution of acetic acid (0.5 ml / l), and unfixed dye portions are washed out by a soapy process. As a dyeing result, a deep black color is achieved, which has good wet and wash fastness.

Example 21

With a liquor pick-up of 65%, a liquor containing 35 g / l sodium bicarbonate, 40 g / l urea and 5 g / l nitrobenzenesulfonic acid is applied to a fiber material made of cotton in a padding process and then dried the fiber material. An aqueous black ink according to Example 12 is printed on this material by means of a drop-on-demand type with piezo element. The pressure is fixed after drying for 8 min at 102 ° C in saturated steam, then rinsed cold, washed out by boiling, rinsed and dried. As a result, a deep black printing with good washing fastness is obtained.

Example 22

On wool dyeings with high wet fastness can be achieved with suitable fiber-reactive dyes. In order to dye wool in a very dark shade of black with the dye mixture according to the invention, a dye mixture according to Example 5 is used in a proportion of 6% with respect to the weight of the fiber material made of wool. In a dyeing process typical for the wool extraction process, the dye is fixed onto the wool fibers by means of an acid donor at pH 5 at 100 ° C. for 90 minutes. The now black Textiiprobe is rinsed out and after drying a coloring with a very dark hue in a neutral deep black nuance is achieved.

Example 23

Fiber material consisting of 80% cotton and 20% polyamide is dyed with the dye mixture of Example 5 analogously to a dyeing process as in Example 16. As a result of this dyeing process shows that the proportion of cotton has a deep black color, the proportion of polyamide was only slightly stained and that the dyed fiber material has good wash fastness.

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CH 695 613 A5

Example 24

Fiber material consisting of 90% regenerated cellulose cellulose and 10% polyurethane fibers is dyed with the dye mixture of Example 5 analogously to a dyeing process as in Example 16. As a result of this dyeing process shows that the proportion of regenerated cellulose fiber has a deep black color, the proportion of polyurethane fibers was not stained and that the dyed fiber material has good wash fastness.

Example 25

A dyeing as described in Example 13 is followed by printing of the deep black fiber material with a printing paste, which is composed of a thickener, an alkali donor, a wetting agent and a reductively acting component. As is usual in a typical process in the etching pressure, the thus printed fiber material is dried at 105 ° C for 5 minutes and then treated for 10 minutes at 102 ° C in saturated steam. After washing and a soaping process, it becomes clear that the printed areas could be completely decolorized.

Claims (9)

claims 1. Mixtures of heavy metal-free fiber-reactive dyes, based on a) one or more triazo compounds of the general formula (1) (1) with b) one or more dye components of the general formula (2) (2) and c) optionally at least one further fiber-reactive dye as mixing or shading components and d) optionally further colorless additives. In these formulas mean: i) R 1 is -O-M and R 2 is -CH = CH 2 or CH 2 CH 2 -Z, or ii) R 2 is -O-M and R i, -CH = CH 2 or CH 2 CH 2 -Z, R3 and R4 are independently of R, and R2 is -CH = CH2 or CH2CH2-Z, where Z is hydroxy, chloride, bromide or more preferably sulfate. Lì, L2 and l_3 mean independently of each other: -H, -CH 2 COO-M, -CH 2 CH 2 COO-M, -CH 2 CH 2 OH, or -CH 2 SO 3-M, Xì, X2 and X3 are independent of each other: -H, -NH2, -NH-acetyl, -NH-CH2COO-M, - (C, -C3) -alkyl, - (C, -C3-alkoxy, -NO 2 or -SO 3 -M, Yi, Y2, Y3 and Y4 are independent of each other: -H, -NH 2, -NH-acetyl, -NH-CH 2 COO-M, - (C 1 -C 3) -alkyl, - (C 1 -C 6 -alkoxy, -NO 2 or -SO 3 -M, M stands here, in formula (1) and in formula (2) for: 12 CH 695 613 A5 Hydrogen, ammonium, trialkylammonium, tetraalkylammonium, an alkali metal or the equivalent of an alkaline earth metal. 2. Mixtures according to claim 1, characterized in that they consist of one or two components a) and a component b) and optionally a component c). 3. Mixtures according to claim 2, characterized in that they contain as the fiber-reactive dye component b) the compound (2a). (2a) 4. Mixtures according to claims 1 to 3, characterized in that the components a) to 3-55 wt .-%, the components b) to 45-97 wt .-% and the components c) in addition to 1-20 wt .-% are included. 5. A mixture according to claim 4, characterized in that the components a) to 20-40 wt .-%, as component b) the compound (2a) to 60-80 wt .-% and other fiber-reactive dyes c) in addition to 3 -10 wt .-% are included. 6. Mixtures according to claims 1 to 5, characterized in that they contain as further fiber-reactive dyes c) those of the general formula (3) to (6) as mixing or Nuancierkomponenten. SO.sub.3M (3) CI , N ^ N / = \ jl mo3soch2ch2o2s - // w n n O ch3 oh hn 3 (4) UH, J03-M mo3soch2ch2o2s-y-n = n h3c-o (5) 13 CH 695613 A5 mo3soch2ch2o2s Cl A N NAA mo3s N = N SO.sub.3M so2ch2ch2oso3m (6) 7. The use of dye mixtures according to claims 1 to 6 for the dyeing or printing of cellulosic or nitrogen-containing fiber materials. 8. Use of the mixtures according to claims 1 to 6 with a dye content of 3 to 40 wt .-% in aqueous liquid preparations, for dyeing or printing cellulosic or nitrogen-containing fiber materials. 9. The preparation of the triazo compound of the general formula (1) according to claim 1, by diazotization of an amino-functional monoazo compound of the general formula (A) and subsequent coupling with a monoazo compound (B). (A) "mo3s (B) 14