DE19607851A1 - Readily soluble polyfunctional reactive dyes - Google Patents

Abstract

Polyfunctional reactive dyes of formula (I), with a bridge containing 2 monohalo- or monocarboxypyridinium-triazine groups, are new; in which D = the residue of a mono-, poly- or metal complex azo, anthraquinone, phthalocyanine, formazan, azomethin, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, pyrenequinone or perylenetetracarbimide dye; R = hydrogen (H), methyl, ethyl or hydroxyethyl; R<1>, R<2> = H or optionally substituted 1-4C alkyl; X = halogen or carboxypyridinium; B = an aliphatic bridge; at least one of R<1>, R<2> and B contains sulpho, sulphato and/or carboxy substituent(s). The bridged disazo dyes of formulae (II) and (III) are excluded. Also claimed are solid dye formulations, especially powders or granulates, containing 30-95 wt.% dye(s) (I) and 5-15 wt.% buffer(s).

Description

The invention relates to new polyfunctional reactive dyes, their preparation and use.

Polyfunctional reactive dyes - especially those with two monohalogen triazine residues are described in GB 1461125. The state of the art Known dyes still have disadvantages with regard to their application technical characteristics.

The present invention relates to reactive dyes of the formula

wherein
D for the remainder of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, pyrenequinone - or perylene tetracarbimide dye,
R for hydrogen is methyl, ethyl or hydroxyethyl,
R¹ and R² independently of one another for hydrogen or optionally substituted C₁-C₄-alkyl,
X for halogen or carboxypyridinium and
B represents an aliphatic bridge member,
with the proviso that at least one of the radicals R¹, R² or B contains at least one substituent from the series sulfo, sulfato and carboxy,
except the dyes of the formulas

and

The dyes excluded by disclaimer are known from Biul. Inf .: Barwniki Srodki Pomocnicze 1981, 25 (2), 32-5.

The alkyl radicals mentioned in the meaning of R¹ and R² can be straight-chain or branched and are optionally substituted by halogen, hydroxy, cyano, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl, carboxy, sulfamoyl, sulfo or sulfato. The following radicals may be mentioned as examples of R 1 and R 2:
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, carboxymethyl, β-carboxyethyl, β-carboxypropyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, β-methoxyethyl, β-ethoxyethyl, β-methoxypropyl, β- Chloroethyl, γ-bromopropyl, β-hydroxyethyl, β-hydroxybutyl, β-cyanoethyl, sulfomethyl, β-sulfoethyl, aminosulfonylmethyl and β-sulfatoethyl.

Preferably R1 and R2 are independently hydrogen, methyl or Ethyl, especially hydrogen.

The aliphatic bridge member in the definition of B is preferably a C₂- C₁₂-alkylene radical, which is selected by 1 to 3 members from the group -NH-, -N (CH₃) -, -O- can be interrupted, in particular a C₂-C₆ alkylene radical, preferably a radical of the formula

where the meanings as Ethylene and propylene are of particular interest.  

The radical X is preferably halogen, such as fluorine, chlorine, bromine, in particular Fluorine.

The radicals mentioned in the meaning of D can be used for these radicals be substituted in the usual way. As examples of substituents under D radicals mentioned are: alkyl groups with 1 to 4 carbon atoms such as Methyl, ethyl, propyl, isopropyl or butyl; Alkoxy groups with 1 to 4 carbons atoms of matter such as methoxy; Ethoxy, propoxy, isopropoxy or butoxy; Acylamino groups with 1 to 8 carbon atoms such as acetylamino, propionylamino or Benzoylamino; Amino; Alkylamino with 1 to 4 carbon atoms such as methyl amino, ethylamino, propylamino, isopropylamino or butylamino, phenylamino, N, N-di-β-hydroxyethlamino, N, N-di-β-sulfatoethylamino, sulfobenzylamino, N, N- Disulfobenzylamino; Alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy residue such as methoxycarbonyl or ethoxycarbonyl; Alkylsulfonyl with 1 to 4 Koh lenstoffatom such as methylsulfonyl or ethylsulfonyl; Trifluoromethyl; Nitro; Cyano; Halogen such as fluorine, chlorine or bromine; Carbamoyl; N-alkylcarbamoyl with 1 up to 4 carbon atoms in the alkyl radical such as N-methylcarbamoxyl or N-ethylcar bamoyl; Sulfamoyl, N-alkylsulfamoyl with 1 to 4 carbon atoms such as N- Methylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl or N-butyl sulfamoyl, N- (4-hydroxyethyl) sulfamoyl, N'N-di- (β-hydroxyethyl) sulfamoyl, N- Phenylsulfamoyl; Ureido; Hydroxy; Carboxy; Sulfomethyl or sulfo. Before the radicals mentioned under D contain one or more sulfones acid groups.

Reactive dyes of the formula (1), in which D is the residue of an azo dye, contain as substituents especially methyl, ethyl, methoxy, ethoxy, acetyl amino, benzoylamino, amino, chlorine, bromine, ureido, hydroxy, carboxy, sulfo methyl or sulfo and fiber-reactive residues. Suitable fiber-reactive residues are those with the OH or NH groups of the fiber under dyeing conditions react to form covalent bonds.

The radicals mentioned under D preferably contain at least one sulfo group, especially 1-4 sulfo groups and preferably 1 to 3 sulfo groups.

In the context of formula (1), dyes are preferred in which D represents the rest a monoazo, disazo, anthraquinone, dioxazine, phthalocyanine or For Mazan dye is available.  

Particularly preferred radicals D are mono- or disazo dye radicals of the formulas

D¹-N = N- (MN = N) _u -K- (2)

and

-D¹-N = N- (MN = N) _u -K (3)

wherein
D¹ for the remainder of a diazo component of the benzene or naphthalene series,
M for the rest of a middle component of the benzene or naphthalene series,
K for the rest of a coupling component of the benzene, naphthalene, pyrazolone, 6-hydroxypyridone (2) or acetoacetic acid arylamide series and
u represents the number 0 or 1,
where D 1, M and K are optionally substituted by substituents customary for azo dyes, such as. B. the above are substituted. D particularly preferably represents the remainder of a monoazo or disazo dye of the formulas

wherein
R³ represents C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, carboxy or sulfo,
R⁴ represents halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, amino, acetylamino, ureido, hydroxy, carboxy, sulfomethyl or sulfo,
R⁵ represents C₁-C₄ alkanoyl, benzoyl or an optionally substituted halotriazinyl radical,
R⁶ and R⁷ independently of one another represent hydrogen, C₁-C₄-alkyl or phenyl,
R⁸ represents hydrogen cyano, sulfo, chlorine, carbamoyl or sulfomethyl,
Z represents β-sulfatoethyl, β-thiosulfatocthyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl,
in the event that the above-mentioned substituents occur more than once on the same molecule or part of a molecule, as is indicated by the index behind the parenthesis, these may be the same or different.

The residues of formulas (4) to (20) can be in the phenyl or naphthyl rings still contain as a further substituent a radical of the formula -SO₂Z, wherein Z β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acylethyl, β-halogen is ethyl or vinyl. Z is preferably β-sulfatoethyl or vinyl, in particular Vinyl.

Further particularly preferred radicals D are formazan dye radicals of the formulas

wherein the benzene nuclei are optionally 1 to 2 times the same or different C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylsulfonyl, halogen or carboxy are further substituted.

Also particularly preferred residues D are phthalocyanine dye residues formula

wherein
Pc represents the rest of a metal phthalocyanine, in particular the rest of a copper or nickel phthalocyanine,
W¹ and W² independently of one another are OH or -NR¹⁰R¹¹, where R¹¹ and R¹¹ independently of one another are hydrogen or C₁-C₄-alkyl optionally substituted by hydroxy or sulfo, preferably hydrogen;
R¹² represents hydrogen or C₁-C₄-alkyl,
E represents a phenylene radical or a C₂-C₆ alkylene radical which is optionally monosubstituted to 2-fold identical or differently substituted by C₁-C₄-alkyl, halogen, carboxy or sulfo and
k represents a number from 1 to 3.
E is preferably an optionally 1 to 2 times the same or different phenylene radical substituted by C₁-C₄-alkyl, halogen, carboxy or sulfo. Pc is preferably the rest of a copper phthalocyanine.

Particularly preferred residues D are also residues of dioxazine dyes formula

wherein
E¹ is a direct bond, an optionally 1 to 2 times the same or different C₁-C₄-alkyl, halogen, carboxy or sulfo substituted phenylene radical or a C₂-C₆-alkylene radical and
the outer benzene rings in formula (26) are optionally 1 to 2 times the same or different substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, carboxy, sulfo.

Particularly preferred residues D are residues of anthraquinone dyes of the formula

wherein
G represents a phenylene radical which is optionally 1 to 2 times the same or different and is substituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen, carboxy or sulfo or represents cyclohexylene, phenylene methylene or a C₂-C₆ alkylene radical,
the anthraquinone nucleus can be substituted by a further sulfo group.

G is preferably 1 to 2 times the same or differently substituted by C₁-C₄ alkyl, halogen, carboxy or sulfo Phenylene radical.

Also preferred are dyes of the formula (1), in which
B for C₂-C₆ alkylene,
R¹ is hydrogen, methyl, ethyl or R² and
R² is C₂-C₄-alkyl which is substituted by a substituent from the series carboxy, sulfo or sulfato.

Dyes of the formula (1) in which

for a rest of the formulas

stands.

In the context of formula (1), dyes are particularly preferred in which D is is a dye residue of formulas (2) to (27) and the rest of a diamine Formula (28) for a radical of formula (28a), (28b), (28c), (28d), (28e), (28f) or (28g) and X represents fluorine. Dyes of the formula are particularly preferred (1) wherein the residue of a diamine of formula (28) is for a residue of formula (28a) stands.

The present invention further relates to methods for producing the inventions reactive dyes of the formula (1) according to the invention. So are the reactive dyes of formula (1) obtained by mixing 1 mole of a dye amine of formula

D-NHR (29)

with 1 mole of a halotriazine compound of the formula

and 0.5 mol of a diamine of the formula

acylated with each other in any order, wherein D, R, R¹, R² and B are the above have the meaning given and Y¹ is chlorine or fluorine.

Corresponding precursors can also be used instead of dyes of the formula (29) are used, the intermediates obtained in the desired Dyes are transferred. In the manufacture of the final dyes from Vor products are mainly couplings that lead to azo dyes. The reaction conditions correspond to those in the field of acylation and clutch usual conditions. This is how the dyes are produced preferably in an aqueous medium.  

In general, the implementation is carried out step by step, the Sequence of simple reactions between the individual reaction compos nente advantageously depends on the special conditions.

So, when using trifluortrazine, it is useful to start with Acylate dye amine of formula (29) with trifluorotriazine and then the obtained Intermediate dye of the formula

where D and R have the meaning given above,
with a diamine of formula (31) to a dye of formula (1) with X = fluorine.

Isolation of the reak obtained by the methods described above tiv dyes in the usual way by salting out, for example with Na trium or potassium chloride, or by evaporating the neutral aqueous paint substance solution, preferably at moderately elevated temperature and reduced pressure or by spray drying. The dyes can be used as solid formations can also be used as concentrated solutions.

In a preferred embodiment, the dyes of the invention used as granules. The granules of the dyes according to the invention can can be obtained, for example, in the following steps.

Mixed granulation

The dye powder with 15 to 55% water - based on the Weight of the powder - moistened, then the gra in a mixing granulator nulate formed under drying conditions and optionally dedusted, whereby the dedusting agent preferably as an aerosol mixture on the granules is sprayed.  

Spray granulation

The synthesis solution or suspension is fluidized in a Spray dryer dried and granulated at the same time.

The invention further relates to solid dye preparations, in particular color Powder or dye granules, the 30 - 95 wt .-% of an inventive Reactive dye of the formula (1), 5-15% by weight of water (residual moisture), each based on the preparation. You can also add other additives such as inorganic salts such as alkali chlorides or alkali sulfates, dispersants, Contain wetting agents, dedusting agents and other common adjusting agents.

Preferred solid preparations additionally contain buffer substances which are used in Dissolve in 20 times the amount of water (based on the weight of the feast preparation) give a pH of 4.5 to 8.5, especially 6 to 8. These buffer substances are preferably in amounts of 3 to 50, ins particularly 5 to 15 wt .-%, based on the total weight, added.

Aqueous reactive dye solutions generally contain 5 to 50% by weight a dye of formula (1) (based on the total weight of the solution). Preferred aqueous reactive dye solutions additionally contain buffer substances and have a pH of 4.5 to 8.5, in particular 6 to 8. This Buffer substances are preferably added to the solution in amounts of 0.1 to 50 in particular 1 to 20 wt .-%, based on the total mixture, added.

The buffers used are inert to the reactive groups. examples for Buffers are: sodium dihydrogen phosphate, sodium acetate, potassium acetate, sodium borate, potassium borate, sodium oxalate, potassium oxalate and sodium hydrogen phthalate. These buffers can be used alone or as a mixture.

The reactive dyes of the formula (1) according to the invention have valuable ones Dye properties. As a result of the fiber-reactive groups X, they show fiber reactive properties.

The reactive dyes of the formula (1) according to the invention also give colorations good wet and light fastness. It is particularly noteworthy that the color substances have good solubility and electrolyte solubility with good extraction properties  shafts and high dye fixation, and that the unfixed Have parts easily removed.

The reactive dyes of the formula (1) according to the invention are suitable for dyeing and printing of materials containing hydroxyl or amide groups, such as Textile fibers, threads and fabrics made of wool, silk, synthetic polyamide and Polyurethane fibers and for washable dyeing and printing of native or regenerated cellulose, the treatment of cellulose materials moderately in the presence of acid-binding agents and optionally by heat effect takes place according to the process known for reactive dyes.

The formulas given are those of the corresponding free acids. The color substances are generally in the form of the alkali salts, especially the Na salts isolated and used for dyeing.

example 1

0.1 mole of the dye of the formula

according to the general formula D-NHR (29), were in 800 ml of ice water solved neutral. 2 g of dipotassium hydrogenphosphate were added and then added dropwise 13.5 g trifluorotriazine. The pH was increased by adding 10% Sodium hydroxide solution kept at pH 6. After the acylation had ended, 8.4 g (0.05 mol) N- (β-sulfoethyl) ethylenediamine, corresponds

added dropwise to a pH of 8.5-9.0. Then the pH in kept in this area by adding 10% sodium hydroxide solution. The temperature was at 4-8 ° C. After the condensation had ended, the dye became clear Salt out the solution by adding 10% by volume of potassium chloride. After this Suction, drying and grinding gave a yellow dye powder, which is easily dissolved in water with yellow color.

The dye corresponds to the following formula

where D in the form of the free acid represents the following radical:

The dye dyes cotton in clear yellow shades.

Alternatively, you can isolate the dye by using the solution of the dye if necessary after concentration by pressure permeation directly spray dried.

Example 2

0.1 mole of the dye of the formula

(obtained by coupling diazotized 2-amino-naphthalene-1,5-disulfonic acid to 1-hydroxy-6-ethoxycarbonylamino-naphthalene-3-sulfonic acid and subsequent Saponification by heating with sodium hydroxide solution) became neutral in 800 ml of ice water solved. 2 g of dipotassium hydrogen phosphate were added, and 13.5 g of tri were then added dropwise fluorotriazine. The pH was adjusted by adding 12% lithium hydroxide solution kept at pH 6. The acylation product precipitated in part. After the condensation had ended, 8.4 g (0.05 mol) of N- (β-sulfoethyl) ethylene diamine

added dropwise to a pH of 8.5-9.0. Then the temperature brought to 15 ° C. The pH was increased by adding 12% Lithium hydroxide solution kept between 8.5 and 9.0. After the condensate has ended The dye solution was clarified and the dye was added by adding 20 Salt out volume% of potassium chloride. After suction, drying at 70 ° C in a vacuum drying cabinet and grinding, a light red dye powder was obtained, which easily dissolved in water, creating an orange solution.

The dye corresponds to the following formula

where D in the form of the free acid represents the following radical.

The dye dyes cotton according to one of the usual for reactive dyes Process in clear shades of orange.

Table 1 shows a series of amino dyes D-NHR of the formula (29) listed. They are marked with the Roman numerals I to XLIV.  

Table 1

In Table 2 are a number of diamines of the formula

listed. They are identified by the small letters a to i.  

Table 2

Further valuable dyes, which are listed in Table 3, are obtained after the Data of Example 1 or 2, if one of the amino listed in Table 1 dyes (D-NHR) and the diamines of the formula listed in Table 2

starts.

Table 3

Examples 58 through 86

The procedure followed is as described in Examples 1 to 28 and Example 57 however, instead of diamine a, an equivalent amount of diamine c (see table 2), this also results in valuable reactive dyes, the cotton in the color the shade given in the examples.  

Examples 87 to 115

The procedure followed is as described in Examples 1 to 28 and Example 57 however, instead of diamine a, an equivalent amount of diamine d (see table 2), you also get valuable reactive dyes, the cotton in the color the shade given in the examples.

Examples 116 to 144

The procedure followed is as described in Examples 1 to 28 and Example 57 however, instead of diamine a, an equivalent amount of diamine e (see table 2), you also get valuable reactive dyes, the cotton in the color the shade given in the examples.

Examples 145 to 173

The procedure followed is as described in Examples 1 to 28 and Example 57 however, instead of diamine a, an equivalent amount of diamine f (see table 2), you also get valuable reactive dyes, the cotton in the color the shade given in the examples.

Examples 174-202

The procedure followed is as described in Examples 1 to 28 and Example 57 however, instead of diamine a, an equivalent amount of diamine g (see table 2), you also get valuable reactive dyes, the cotton in the color the shade given in the examples.  

Examples 203 to 231

The procedure followed is as described in Examples 1 to 28 and Example 57 however, instead of diamine a, an equivalent amount of diamine h (see table 2), you also get valuable reactive dyes, the cotton in the color the shade given in the examples.

Examples 232 to 260

The procedure followed is as described in Examples 1 to 28 and Example 57 however, instead of diamine a, an equivalent amount of diamine i (see table 2), you also get valuable reactive dyes, the cotton in the color the shade given in the examples.

Example 261

A solution of 0.1 mole of the dye of the formula

(corresponds to D-NHR)
in 400 ml of water to a 5-10 ° C cold suspension of 18.9 g of cyanuric chloride was added dropwise to a pH of 3-4, which is then maintained by adding dilute sodium hydroxide solution. After the acylation had ended, 8.4 g (0.05 mol) of N- (β-sulfoethyl) ethylenediamine (corresponding to

added dropwise to a pH of 8.5-9. Then the pH kept in this area by adding 10% sodium hydroxide solution. The tempe The temperature was raised to 25 ° C. After the condensation had ended, the Dye from the clear solution by adding 10% by volume of potassium chloride salted out. After suction, drying at 70 ° C in a forced air drying cabinet You obtained a yellow dye powder that is easily in water with a yellow color solves.

The dye corresponds to the following formula

where D in the form of the free acid represents the following radical:

The dye dyes cotton in clear yellow tones.

Alternatively, you can isolate the dye by using the solution of the dye if necessary after concentration by pressure permeation directly spray dried.

Examples 262 to 289

Further valuable dyes are obtained according to the information in Example 261, if instead of the amino dye D-NHR used there an equi valent amount of those used in Examples 2 to 28 and Example 57 Uses amino dyes. These dye cotton in the same way as in the examples specified shade.  

The procedure is as described in Examples 261 to 289, but is used instead of diamine a, an equivalent amount of diamines b, c, d, e, f, g, h or i, this also results in valuable reactive dyes that Color cotton as indicated in Examples 261 to 289.

Example 290

A solution of 0.1 mole of the dye of the formula

(corresponds to D-NHR; obtainable by coupling diazotized 2-amino-naphthalene-1,5-disulfonic acid to acetyl-H-acid and subsequent saponification of the acetyl group in an alkaline medium)
in 500 ml of water was added dropwise to a 5-10 ° C. slurry of 18.9 g of cyanuric chloride in 400 ml of water to a pH of 3 to 4, which was then maintained by adding sodium bicarbonate. After the acylation had ended, 8.4 g (0.05 mol) of N- (β-sulfoethyl) ethylenediamine (corresponding to

added dropwise to a pH of 7 to 8. Then the pH in kept in this area by adding 10% sodium hydroxide solution. The temperature was raised to 15-20 ° C.

After the condensation had ended, the dye was removed from the clear solution Salted addition of potassium chloride. After suction, drying at 70 ° C in the circulating air drying cabinet, a red dye powder was obtained, which easily turns into Water with red color dissolves.  

The dye corresponds to the following formula

where D in the form of the free acid represents the following radical:

The dye dyes cotton in clear bluish red tones.

According to the information in the example, other valuable dyes are obtained when instead of the amino dye D-NHR used there, the following performed from Table 1 known amino dyes and as diamine

uses the compounds known from Table 2.  

Table 4

Further valuable dyes are obtained according to the information in Example 290 to 299 if, instead of the diamine used there, an equivalent amount of diamines b, c, d, e, f, g, h and i listed in Table 2.

Claims (10)

1. Reactive dyes of the formula wherein
D for the rest of a - monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, dioxazine, phena, zin, stilbene, triphenyl methane, xanthene, thioxanthone, nitro aryl, Naphthoquinone, pyrenequinone or perylene tetracarbimide dye,
R represents hydrogen, methyl, ethyl or hydroxyethyl,
R¹ and R² independently of one another are hydrogen or optionally substituted C₁-C₄-alkyl,
X for halogen or carboxypyridinium and
B represents an aliphatic bridge member,
with the proviso that at least one of the radicals R¹, R² or B contains at least one substituent from the series sulfo, sulfato and carboxy,
except the dyes of the formulas and 2. Dyes according to claim 1, characterized in that the rest D contains one to four sulfo groups. 3. Dyes according to claims 1 and 2, characterized in that D for the rest of a monoazo, disazo, anthraquinone, dioxazin, phthalo cyanine or formazan dye. 4. Dyes according to claims 1 to 3, characterized in that D for a radical of the formula wherein
R³ represents C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, carboxy or sulfo,
R⁴ represents halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, amino, acetylamino, ureido, hydroxy, carboxy, sulfomethyl or sulfo,
R⁵ represents C₁-C₄ alkanoyl, benzoyl or an optionally substituted halotriazinyl radical,
R⁶ and R⁷ independently of one another represent hydrogen, C₁-C₄-alkyl or phenyl,
R⁸ represents hydrogen, cyano, sulfo, chlorine, carbamoyl or sulfomethyl, and
Z represents β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl,
in the event that the above-mentioned substituents occur more than once on the same molecule or part of a molecule, as is indicated by the index behind the parenthesis, these may be the same or different,
or
D for a rest of the formulas wherein the benzene nuclei are optionally 1 to 2 times, identical or different, further substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylsulfonyl, halogen or carboxy,
or D for a rest wherein
Pc represents the rest of a metal phthalocyanine, in particular the rest of a copper or nickel phthalocyanine,
W¹ and W² independently represent OH or -NR¹⁰R¹¹, where R¹⁰ and R¹¹ independently represent hydrogen or C₁-C₄-alkyl optionally substituted by hydroxy or sulfo,
R¹² represents hydrogen or C₁-C₄-alkyl,
E represents a phenylene radical or a C₂-C₆ alkylene radical which is optionally monosubstituted to 2-fold identical or differently substituted by C₁-C₄-alkyl, halogen, carboxy or sulfo, and
k represents a number from 1 to 3,
or D for a rest wherein
E¹ for a direct bond, an optionally 1 to 2 times the same or different C₁-C₄-alkyl, halogen, carboxy or sulfo substituted phenylene radical or a C₂-C₆-alkylene radical and the outer benzene rings optionally 1 to 2 times the same or are differently substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, carboxy, sulfo,
or D for a rest wherein
G represents an optionally 1 to 2-fold identical or different phenylene radical substituted by C₁-C C-alkyl, C₁-C₄-alkoxy, halogen, carboxy or sulfo or cyclohexylene, phenylene methylene or a C₂-C₆-alkylene radical,
the anthraquinone nucleus can be substituted by a further sulfo group,
stands. 5. Dyes according to claims 1 to 4, characterized in that in formula (1) of claim 1
B for C₂-C₆ alkylene,
R¹ for hydrogen is methyl, ethyl or R² and
R² is C₂-C₄-alkyl which is substituted by a substituent from the series carboxy, sulfo or sulfato,
stands. 6. Dyes according to claims 1 to 5, characterized in that in formula (1) of claim 1 for a rest of the formulas stands. 7. Dyes according to claims 1 to 6, characterized in that D for a rest of the formulas wherein
R³ represents C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, carboxy or sulfo,
R⁴ represents halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, amino, acetylamino, ureido, hydroxy, carboxy, sulfomethyl or sulfo,
R⁵ represents C₁-C₄ alkanoyl, benzoyl or an optionally substituted by halotriazinyl,
R⁶ and R⁷ independently of one another represent hydrogen C₁-C₄-alkyl or phenyl,
R⁸ represents hydrogen, cyano, sulfo, chlorine, carbamoyl or sulfomethyl, and
Z represents β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl,
in the event that the above-mentioned substituents occur more than once on the same molecule or part of a molecule, as is indicated by the index behind the parenthesis, these may be the same or different,
or for a rest of the formulas wherein the benzene nuclei are optionally substituted 1 to 2 times, identically or differently by C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylsulfonyl, halogen or carboxy,
or for a residue of the formula wherein
Pc represents the rest of a metal phthalocyanine, in particular the rest of a copper or nickel phthalocyanine,
W¹ and W² independently represent OH or -NR¹⁰R¹¹, where R¹⁰ and R¹¹ independently represent hydrogen or C₁-C₄-alkyl optionally substituted by hydroxy or sulfo,
R¹² represents hydrogen or C₁-C₄-alkyl,
E represents a phenylene radical or a C₂-C₆ alkylene radical which is optionally monosubstituted to 2-fold identical or differently substituted by C₁-C₄-alkyl, halogen, carboxy or sulfo, and
k represents a number from 1 to 3,
or for a residue of the formula wherein
E¹ for a direct bond, an optionally 1- to 2-fold identical or different by C₁-C₄-alkyl, halogen, carboxy or sulfo substituted phenylene radical or a C₂-C₆-alkylene radical and the outer benzene rings optionally 1- to 2-fold , identical or different, are substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, carboxy, sulfo,
or for a residue of the formula wherein
G represents an optionally 1- to 2-fold identical or different phenylene radical substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, carboxy or sulfo or represents cyclohexylene, phenylene methylene or a C₂-C Alk-alkylene radical,
the anthraquinone nucleus can be substituted by a further sulfo group,
stands, and
R for hydrogen
R1 for hydrogen
R² for -CH₂CH₂SO₃H,
X for fluorine and
B stands for -CH₂CH₂-. 8. Process for the preparation of reactive dyes of the formula (1) wherein
D for the remainder of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, pyrenequinone - or perylene tetra carbimide dye,
R for hydrogen is methyl, ethyl or hydroxyethyl,
R¹ and R² independently of one another are hydrogen or optionally substituted C₁-C₄alkyl,
X for halogen or carboxypyridinium and
B represents an aliphatic bridge member,
with the proviso that at least one of the radicals R¹, R² or B contains at least one substituent from the series sulfo, sulfato and carboxy,
characterized in that 1 mole of a dye amine of the formula D-NHR (29) wherein
D and R have the meaning given above,
with 1 mole of a halotriazine compound of the formula and 0.5 mol of a diamine of the formula Acylated with one another in any order, in which D, R, R 1, R 2 and B have the meaning given above and Y 1 is chlorine or fluorine. 9. Solid dye preparations, especially in powder or granule form containing 30 to 95 wt .-% according to at least one reactive dye Claims 1 to 8 and optionally at least one buffer in one Amount of 5 to 15 wt .-%, based on the preparation. 10. Process for dyeing and printing hydroxyl and / or amide materials containing groups, characterized in that at least one reactive dye according to claims 1 to 8 used becomes.