KR19990062913A - Aqueous dye solution and uses thereof - Google Patents

Abstract

Concentrated aqueous dye solutions comprising 5 to 50% by weight of one or more dyes of formula (1) provide dyeing with good storage stability and good fastness on hydroxyl group-containing or nitrogen-containing fiber materials.

Formula 1

In the above formula,

X and Y are each independently of the other hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy,

Z is C ₂ -C ₆ alkanoylamino or C ₂ -C ₄ hydroxyalkylsulfamoyl,

M ⁺ is an ammonium cation of an amine of formula ego,

Formula 2

Wherein R ₁ and R ₂ are each independently of one another hydrogen, C _1-6 alkyl, or hydroxy- or amino-substituted C _2-6 alkyl which may be interrupted by an oxygen atom, and R ₃ is an oxygen atom; Hydroxy- or amino-substituted C ₂ -C ₆ alkyl which may be blocked by the proviso that X and Y are methyl and Z is 2-hydroxyethylsulfamoyl, or X and Y are hydrogen and Z is In the case of propionylamino, R ₁ , R ₂ and R ₃ are not radicals of the formula —CH ₂ —CH (OH) —CH ₃ .

Description

Aqueous dye solution and uses thereof

The present invention relates to concentrated aqueous solutions of blue-dyed anthraquinone dyes, methods for their preparation and their use for dyeing or printing hydroxyl group-containing or nitrogen-containing fiber materials.

The dye solution, for example, when producing a dye solution or a printing paste, does not form dust, does not cause wetting problems caused by the formation of agglomerates, and is mottled due to insufficiently dissolved dye particles. It has many advantages over commercially available solid forms, such as powders or particulates, including no dyeing. Due to these advantages, combined with the good metering of liquid commercial forms, more and more liquid formulations are commercially available, and they are moving towards more concentrated solutions as they are substantially saved in transportation and storage costs.

However, in general, the shelf life in solutions and especially concentrated formulations is often questionable. The more concentrated the dye solution, the more easily crystallization occurs during storage and, for example, when the formulation is used for textile printing, it is extremely closely involved in the formation of stains, or used for example transport, metering or dyeing. It creates rather large aggregates that block or contaminate the pipeline, pump or valve of the device. In addition, a solid precipitate is formed which is difficult to mix easily. In such cases, it is often difficult to dissolve the dye again.

It is therefore an object of the present invention to provide a concentrated aqueous solution of a blue-dyed anthraquinone dye which can solve most of the above problems.

Accordingly, the present invention relates to a concentrated aqueous dye solution comprising 5 to 50% by weight of at least one dye of the formula (1) based on the total weight of the solution.

In the above formula,

X and Y are each independently of the other hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy,

Z is C ₂ -C ₆ alkanoylamino or C ₂ -C ₄ hydroxyalkylsulfamoyl,

M ⁺ is an ammonium cation of an amine of formula ego,

Wherein R ₁ and R ₂ are each independently of one another hydrogen, C _1-6 alkyl, or hydroxy- or amino-substituted C _2-6 alkyl which may be interrupted by an oxygen atom, and R ₃ is an oxygen atom; Hydroxy- or amino-substituted C ₂ -C ₆ alkyl which may be blocked by the proviso that X and Y are methyl and Z is 2-hydroxyethylsulfamoyl, or X and Y are hydrogen and Z is In the case of propionylamino, R ₁ , R ₂ and R ₃ are not radicals of the formula —CH ₂ —CH (OH) —CH ₃ .

X and Y, defined as C ₁ -C ₄ alkyl, are suitably each independently of one another, for example methyl, ethyl, propyl, isopropyl, butyl, secondary-butyl, tert-butyl or isobutyl, in particular Methyl or ethyl, preferably methyl.

X and Y, defined as C ₁ -C ₄ alkoxy, are suitably each independently of one another, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, in particular methoxy or ethoxy And preferably methoxy.

Z, defined as C ₂ -C ₆ alkanoylamino, is typically acetylamino, propionylamino, butyrylamino, pentanoylamino or hexanoylamino, preferably with acetylamino, propionylamino or butyrylamino Same C ₂ -C ₄ alkanoylamino, in particular acetylamino or propionylamino.

Z, defined as C ₂ -C ₄ hydroxyalkylsulfamoyl, is typically 2-hydroxyethylsulfamoyl, 2- or 3-hydroxypropylsulfamoyl or 2-, 3-, or 4-hydroxybutylsulfa Moyl, preferably 2-hydroxyethylsulfamoyl.

R ₁ and R ₂ , defined as C ₁ -C ₆ alkyl, are suitably each independently of one another typically methyl, ethyl, propyl, isopropyl, butyl, secondary-butyl, tert-butyl, isobutyl, pentyl or Hexyl, preferably C ₁ -C ₄ alkyl such as methyl or ethyl.

R ₁ , R ₂ and R ₃ , defined as hydroxy- or amino-substituted C ₂ -C ₆ alkyl which may be interrupted by an oxygen atom, are suitably each independently of each other typically represented by the formula -CH ₂ CH ₂ OH , -CH ₂ -CH (OH) -CH ₃ , -CH ₂ CH ₂ NH ₂ ,-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -OH,-(CH ₂ ) ₂ -O-CH _2- CH ₂ —OH or — (CH ₂ ) ₂ —O—CH ₂ —CH (CH ₃ ) —OH, preferably —CH ₂ CH ₂ OH, —CH ₂ —CH (OH) —CH ₃ or — ( CH ₂ ) ₂ —O—CH ₂ —CH (CH ₃ ) —OH.

The novel concentrated aqueous dye solution may comprise other additives such as urea, caprolactam, N-methylpyrrolidone or polyethylene glycol.

In a preferred embodiment of the invention, the novel dye solution comprises caprolactam or N-methyllipolydone, preferably caprolactam.

In the novel dye solutions, the additives mentioned are present in amounts of 0.01 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 1 to 20% by weight, based on the total weight of the dye solution.

In addition, the novel concentrated aqueous solution may comprise fungal and / or bacteriostatic materials.

Preferred dye solutions are those in which X and Y are each independently hydrogen or methyl, Z is C ₂ -C ₄ alkanoylamino or C ₂ -C ₄ hydroxyalkylsulfamoyl, preferably acetylamino, propionylamino or 2-hydroxyethylsulfamoyl.

In a preferred embodiment of the novel dye solution, R ₁ is hydrogen, methyl, ethyl, hydroxy-substituted C ₂ -C ₃ alkyl or the formula-(CH ₂ ) ₂ -O-CH ₂ -CHR-OH, wherein R Is hydrogen or methyl).

In a particularly preferred embodiment of the novel dye solution, R ₁ is hydroxy-substituted C ₂ -C ₃ alkyl or a formula — (CH ₂ ) ₂ —O—CH ₂ —CHR-OH, wherein R is hydrogen or methyl, Preferably methyl).

In a very particularly preferred embodiment of the novel dye solution, R ₁ is a hydroxy-substituted propyl, in particular a radical of the formula -CH ₂ -CH (OH) -CH ₃ .

R ₂ is preferably hydrogen, methyl, ethyl, hydroxy-substituted C ₂ -C ₃ alkyl or a formula — (CH ₂ ) ₂ —O—CH ₂ —CHR—OH, wherein R is hydrogen or methyl Is a radical.

R ₂ is particularly preferably hydroxy-substituted C ₂ -C ₃ alkyl or a formula — (CH ₂ ) ₂ —O—CH ₂ —CHR—OH, wherein R is hydrogen or methyl, preferably methyl Is a radical.

R ₂ is very particularly preferably a hydroxy-substituted propyl, in particular a radical of the formula -CH ₂ -CH (OH) -CH ₃ .

R ₃ is preferably hydroxy-substituted C ₂ -C ₃ alkyl or the formula R ₂ is a formula-(CH ₂ ) ₂ -O-CH ₂ -CHR-OH, wherein R is hydrogen or methyl, preferably Methyl).

R ₃ is particularly preferably hydroxy-substituted propyl, in particular a radical of the formula -CH ₂ -CH (OH) -CH ₃ .

Preferred dye solutions are C ₂ -C ₃ alkyl wherein R ₂ and R ₃ are each independently hydroxy-substituted or a formula-(CH ₂ ) ₂ -O-CH ₂ -CHR-OH, wherein R is hydrogen or Methyl, preferably methyl).

R ₁ , R ₂ and R ₃ , defined as hydroxy-substituted C ₂ -C ₃ alkyl radicals, are preferably radicals of 2-hydroxyethyl or of the formula —CH ₂ —CH (OH) —CH ₃ .

In a preferred embodiment of the novel dye solution, R ₁ , R ₂ and R ₃ are each independently of each other hydroxy-substituted C ₂ -C ₃ alkyl, preferably 2-hydroxyethyl or a formula —CH ₂ —CH ( OH) —CH ₃ or a radical of the formula — (CH ₂ ) ₂ —O—CH ₂ —CH (CH ₃ ) —OH.

In a very particularly preferred embodiment of the novel dye solution, R ₁ , R ₂ and R ₃ are radicals of the formula —CH ₂ —CH (OH) —CH ₃ .

The novel dye solution preferably comprises 10 to 50% by weight, more preferably 20 to 50% by weight, of one or more dyes of formula (1) based on the total weight of the solution.

Preferred dye solutions are those comprising two dyes of formula (1).

The novel dye solutions particularly preferably comprise two dyes of the formulas 3, 4 or 5.

In the above formula,

M ⁺ has the meanings given above and preferred meanings.

As such, the novel dye solution is, for example,

(i) a dye of formula 3 and a dye of formula 5,

(ii) a dye of formula 4 and a dye of formula 5, or

(iii) dyes of formula 3 and dyes of formula 4.

Very particularly preferred dye solutions according to (i) or (ii) comprise at least 5% by weight, preferably 10% by weight of the dye of formula 5, based on the total amount of the dyes of formulas 3 and 5 or the dyes of formulas 4 and 5. % Or more, More preferably, it contains 15 weight% or more.

Very particularly preferred dye solutions other than according to (iii) comprise at least 5%, preferably at least 10%, more preferably 20% by weight of the dye of formula 3, based on the total amount of the dyes of formulas 3 and 4. It will contain more than%.

The present invention also relates to dissolving at least one dye of formula (1) wherein M ⁺ is a hydrogen ion in water with an amine of formula (2), or ammonium cation of M ⁺ is an amine of formula (2) Preparation of a novel dye solution, comprising dissolving at least one dye of formula (I) in which X, Y, Z, R ₁ , R _2, and R ₃ each independently have the above meaning in water It is about a method.

The dye of formula (1), wherein M ⁺ is a hydrogen ion, can be prepared in a known or analogous manner to a known manner.

The preparation typically slurries the free acid of the anthraquinone of formula (1), wherein M ⁺ is hydrogen ions in water in anhydrous or wet form, for example in the form of a filter press cake obtained after synthesis, and then the slurry is For example, in the aqueous amine solution of formula (2), a homogeneous solution form, for example, at a pH of 6-8, preferably 6.5-7.5, room temperature or slightly elevated temperature, for example 35-50 ° C. By neutralization until Of course, the preparation can also be carried out at higher temperatures. If necessary, the dye solution thus obtained is clarified by filtration.

In some cases, when using an aqueous solution of an amine, the water used to slurry the dye may contain the additive in advance when the additive mentioned for convenience is in solid form at room temperature. In addition, the additives mentioned may be added in the desired amount after the dye acid is slurried or neutralized. If the additives mentioned are in solid form at room temperature, they are usually dissolved in the required amount of water before addition.

The amount of additives mentioned can vary widely and depends on the solubility of the dye, the amount of dye to be dissolved and the structure of the amine used.

The novel dye solutions comprising two dyes of formula (1) may be, for example, (i) mixing two dye acids in a preferred mixing ratio, or (ii) 1-amino-4-bromo-anthraquinone-2- A mixture of two dye acids is prepared by reaction of sulfonic acid with two aromatic amines of formula 6, and then the anhydrous dye mixture according to (i) or the wet filter cake according to (ii) is treated using the above described method. It can be obtained by.

In the above formula,

X, Y and Z have the meanings given above.

In another aspect, the invention provides that X, Y, Z, R ₁ , R ₂ and R ₃ have the meanings and preferred meanings given above, provided that X and Y are methyl and Z is 2-hydroxyethylsulfamoyl Or X and Y are hydrogen and Z is propionylamino, R ₁ , R ₂ and R ₃ are not related to the radical of the formula -CH ₂ -CH (OH) -CH ₃ .

The dye of formula 1 can be obtained, for example, by reacting 1-amino-4-bromo-anthraquinone-2-sulfonic acid with an aromatic amine of formula 6 followed by an amine of formula 2. The first reaction is preferably carried out in an aqueous solution, for example at a temperature in the range of 50 to 100 ° C., preferably 65 to 85 ° C., for example in the presence of copper chloride or copper sulfate. The reaction with the amine of formula (2) is carried out, for example, by neutralizing the aqueous dye solution with the corresponding amine.

The novel dyes and novel dye solutions comprising the dyes can be used in conventional dyeing and printing processes. In addition to water and dyes, dye solutions or printing pastes may be further additives, for example wetting agents, antifoams, leveling agents or agents which affect the properties of the fiber material, for example softeners, flame retardant additives, or antifouling, waterproof Or oil preservatives, water softeners and natural or synthetic thickeners such as alginate and cellulose ethers.

In addition, the novel dyes and the novel dye solutions containing these dyes are suitable for dyeing from short solutions, for example in a continuous dyeing process, or in batch and continuous foam dyeing processes.

The novel dyes are particularly characterized by good extraction action, good solubility and good stability of the printing paste as well as good miscibility.

The dye solution of the present invention has excellent storage stability. These are, for example, storage-stable for months in the temperature range of -5 to + 40 ° C. and are substantially insensitive to changes in temperature.

In addition, the novel dye solutions have good resistance to hard water and can be diluted in any proportion, for example, without precipitation of dissolved dye during the preparation of the dye solution.

It is possible to obtain leveling salts with good complete fastness, in particular rubbing, wetting, wetting-wetting and light fastness.

The novel dyes and the novel dye solutions comprising the dyes are suitable for dyeing or printing hydroxyl group-containing or nitrogen-containing fiber materials. They are particularly suitable for dyeing or printing natural polyamide materials, for example wool, or in particular synthetic polyamide materials, for example polyamide 6 or polyamide 6.6, or silk, and they are also used for wool and synthetic polyamides. It is suitable for dyeing or printing blended fabrics and blended yarns.

The materials mentioned, in particular the fibrous materials, may be in any of the forms presented, for example in the form of fibers, yarns, wovens or knits, in particular carpets.

In the following examples, parts are based on weight and temperatures are given in degrees Celsius.

Example 1 :

The sulfonated flask was charged with 880 parts of water, followed by 382 parts of 1-amino-4-bromo-anthraquinone-2-sulfonic acid, 82 parts of 3-propionamidoaniline and 75 parts of 3-acetamidoaniline. After adding 201 parts of sodium bicarbonate, the mixture is heated to 75 deg. While continuing stirring, 1 part of copper and 1 part of copper chloride are added. After about 6 hours the reaction is complete. After adding 2180 parts of water and 345 parts of 32% HCl, the mixture is stirred at 80 ° C. for 30 minutes and the product obtained is collected by suction filtration and then washed with a warm solution of 25 parts of HCl in 800 parts of water. This expression 101 and 780 parts of still wettable product comprising the dye of (102) in a 50:50 weight ratio. 28.5 parts of the wet product are slurried in 31.1 parts of demineralized water and then the resulting paste is neutralized to pH 7-7.2 with triethanolamine. Subsequently, 30.0 parts of epsilon -caprolactam and 0.3 part of commercially available fungicide are added, and then the dye solution is clarified by filtration. The liquid formulation has the following composition:

34.8% by weight of a mixture of the dyes of formulas 3 and 4 in the form of the triethanolamine salt, wherein the weight ratio of the dye is as indicated above

ε-caprolactam 30.0% by weight,

0.3 wt% of a commercial fungicide and

34.9 weight% of water.

Example 2 :

Replace 82 parts of 3-propionamidoaniline with 138 parts of 3-propionamidoaniline and 75 parts of 3-acetamidoaniline with 51.2 parts of 5-amino-1,2-xylene-3-sulfo-2'-hydroxyethylamide The procedure of Example 1 is repeated except that it is substituted, 840 parts of still wettable product are obtained comprising the dye of (103) in a weight ratio of 80:20. 34.0 parts of the wet product is slurried in 50.6 parts of demineralized water, and then the resulting paste is neutralized to pH 7-7.2 using 15.1 parts of aqueous triisopropanolamine (66%). Subsequently, 0.3 part of a commercial fungicide is added, and then the dye solution is clarified by filtration. The liquid formulation has the following composition:

A mixture of the dyes of formulas 4 and 5 in the form of the triisopropanolamine salt, wherein the weight ratio of the dyes is as indicated above 37.7% by weight,

0.3 wt% of a commercial fungicide and

62.0 wt.% Water.

Example 3 :

Replace 82 parts of 3-propionamidoaniline with 43 parts of 3-propionamidoaniline and 75 parts of 3-acetamidoaniline with 192 parts of 5-amino-1,2-xylene-3-sulfo-2'-hydroxyethylamide The procedure of Example 1 was repeated except to replace 880 parts of still wettable product comprising the dyes of formulas (102) and (103) in a weight ratio of 25:75. 35.0 parts of the wet product is slurried in 25.0 parts of demineralized water and then the resulting paste is neutralized to pH 7-7.2 using 15.0 parts of aqueous triisopropanolamine (66%). Subsequently, 20.0 parts of ε-caprolactam and 0.3 part of a commercial fungicide are added, and then the dye solution is clarified by filtration. The liquid formulation has the following composition:

A mixture of the dyes of formulas 4 and 5 in the form of the triisopropanolamine salt, wherein the weight ratio of the dyes is as indicated above 25.1% by weight,

ε-caprolactam 20.0% by weight,

0.3 wt% of a commercial fungicide and

54.6 weight% of water.

Example 4 :

Example 1 was repeated except that 82 parts of 3-propionamidoaniline were replaced with 128 parts of 5-amino-1,2-xylene-3-sulfo-2'-hydroxyethylamide, And 860 parts of still wettable product comprising the dye of (103) in a weight ratio of 50:50. 39.1 parts of the wet product are slurried in 28.3 parts of demineralized water, and then the resulting paste is neutralized to pH 7-7.2 using 7.3 parts of triethanolamine. Subsequently, 25.0 parts of ε-caprolactam and 0.3 part of a commercial fungicide are added, and then the dye solution is clarified by filtration. The liquid formulation has the following composition:

A mixture of the dyes of formulas 3 and 5 in the form of the triethanolamine salt, wherein the weight ratio of the dyes is as indicated above 25.8% by weight,

ε-caprolactam 25.0 wt%

0.3 wt% of a commercial fungicide and

48.9 weight% of water.

Example 5 :

37.0 parts of the wet product of the dyes of formulas (101) and (103) of Example 4 were slurried in 28.4 parts of demineralized water, and then the resulting paste was neutralized to pH 7 to 7.2 using 14.3 parts of aqueous triisopropanolamine (66%). Let's do it. 20.0 parts of epsilon -caprolactam and 0.3 part of commercially available fungicide are added, and then the dye solution is clarified by filtration. The liquid formulation has the following composition:

A mixture of the dyes of formulas 3 and 5 in the form of the triethanolamine salt, wherein the weight ratio of the dyes is as indicated above 27.5% by weight,

ε-caprolactam 20.0% by weight,

0.3 wt% of a commercial fungicide and

52.2% by weight of water.

The formulations obtained according to Examples 1 to 5 are storage-stable at temperatures ranging from -5 to + 40 ° C. and dyeing polyamide fabrics in a blue tint.

Further, the triethanolamines of Examples 1 and 4 and the respective aqueous triisopropanolamines of Examples 2, 3, and 5 were added in equimolar amounts of formula N-[(CH ₂ ) ₂ -O-CH ₂ -CH (CH ₃ )- OH] ₃ and the polyamide fabric in storage-stable and blue tones in the temperature range of -5 to + 40 ° C. by not adding the ε-caprolactam used in Examples 1, 3, 4 and 5 Obtain a formulation to dye.

Example 6 :

The sulfonated flask was charged with 880 parts of water, then 382 parts of 1-amino-4-bromo-anthraquinone-2-sulfonic acid and 158 parts of 3-propionamidoaniline were added. After adding 200 parts of sodium hydrogen carbonate, the mixture is heated to 75 deg. While continuing stirring, 1 part of copper and 1 part of copper chloride are added. After about 6 hours the reaction is complete. Subsequently, after adding 2180 parts of water and 345 parts of 32% HCl, the mixture was stirred at 80 ° C. for 30 minutes, and the obtained product was collected by suction filtration, followed by a warm solution of 25 parts of HCl in 800 parts of water. Wash. This gives 750 parts of still wettable product comprising 36.5% by weight of the dye of formula (101).

67.2 parts of the wet product is slurried in 4.2 parts of demineralized water, and then the resulting paste is neutralized to pH 7.0 using an amine of the formula N-[(CH ₂ ) ₂ -O-CH (CH ₃ ) CH ₂ -OH] ₃ . . Subsequently, 0.3 parts of a commercial fungicide ( ^R Proxel GXL from Zenca) and 1 part of a commercial penetration accelerator ( ^R Albegal from Ciba Specialty Chemicals AG) are added, and then the dye solution is clarified by filtration. The liquid formulation has the following composition:

51.2% by weight of the dye of formula (101) in the form of the tri (hydroxyisopropoxyethyl) amine salt,

0.3 wt% of commercially available fungicides,

1.0 wt% of commercial penetration accelerator and

47.5% by weight of water.

The formulations obtained are storage-stable in the temperature range of -5 to + 40 ° C. and dye the polyamide fabrics in a blue tint.

Dyeing Example I

Ten parts of the polyamide 6.6 fabric are dyed with 500 parts of an aqueous solution containing 2 g / L ammonium acetate and adjusted to pH 5 with disodium phosphate. The amount of liquid formulation of Example 1 is 2% based on the weight of the fiber. Dyeing time is 30 to 90 minutes at 98 ° C. The dyed polyamide 6.6 fabric is removed from the liquid, washed and dried as usual.

Dyeing Example II

Ten parts of the polyamide 6.6 fabric are dyed with 500 parts of an aqueous solution containing 1 g / L monosodium phosphate and adjusted to pH 5 with disodium phosphate. The amount of liquid formulation of Example 1 is 2% based on the weight of the fiber. Dyeing time is 30 to 90 minutes at 98 ° C. The dyed polyamide 6.6 fabric is removed from the liquid, washed and dried as usual.

Dyeing Example III

10 parts of wool piece products are dyed with 500 parts of aqueous solution. The solution contains 2% of the liquid formulation according to Example 1, 5% of the calcined Glauber salt and 80% of acetic acid, based on the weight of the fiber. Dyeing time is 30 to 60 minutes at 98 ° C.

Concentrated aqueous dye solutions comprising 5 to 50% by weight of one or more dyes of Formula 1 of the present invention have excellent storage stability and provide dyeing with good fastness on hydroxyl group-containing or nitrogen-containing fiber materials.

Claims (15)

A concentrated dye solution comprising 5 to 50% by weight of at least one dye of the formula (1) based on the total weight of the solution. Formula 1 In the above formula, X and Y are each independently of the other hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, Z is C ₂ -C ₆ alkanoylamino or C ₂ -C ₄ hydroxyalkylsulfamoyl, M ⁺ is an ammonium cation of an amine of formula ego, Formula 2 Wherein R ₁ and R ₂ are each independently of one another hydrogen, C _1-6 alkyl, or hydroxy- or amino-substituted C _2-6 alkyl which may be interrupted by an oxygen atom, and R ₃ is an oxygen atom; Hydroxy- or amino-substituted C ₂ -C ₆ alkyl which may be blocked by the proviso that X and Y are methyl and Z is 2-hydroxyethylsulfamoyl, or X and Y are hydrogen and Z is In the case of propionylamino, R ₁ , R ₂ and R ₃ are not radicals of the formula —CH ₂ —CH (OH) —CH ₃ . The dye solution of claim 1 comprising caprolactam or N-methylpyrrolidone. The dye solution of claim 1 or 2 wherein X and Y are each independently hydrogen or methyl and Z is C ₂ -C ₄ alkanoylamino or C ₂ -C ₄ hydroxyalkylsulfamoyl. The dye solution according to any one of claims 1 to 3, wherein X and Y are each independently hydrogen or methyl, and Z is acetylamino, propionylamino or 2-hydroxyethylsulfamoyl. The formula-(CH ₂ ) ₂ -according to any one of claims 1 to 4, wherein R ₁ is hydrogen, methyl, ethyl, hydroxy-substituted C ₂ -C ₃ alkyl, or R is hydrogen or methyl. Dye solution which is a radical of O-CH ₂ -CHR-OH. The formula-(CH ₂ ) ₂ -O-CH ₂ -CHR according to any one of claims 1 to 5, wherein R ₁ is hydroxy-substituted C ₂ -C ₃ alkyl, or R is hydrogen or methyl. Dye solution which is a radical of -OH. The formula-(CH ₂ ) ₂ according to claim 1, wherein R ₂ and R ₃ are each independently hydroxy-substituted C ₂ -C ₃ alkyl, or R is hydrogen or methyl. Dye solution which is a radical of -O-CH ₂ -CHR-OH. 8. The compound of claim ₁ , wherein R ₁ , R ₂ and R ₃ are each independently hydroxy-substituted C ₂ -C ₃ alkyl or a formula — (CH ₂ ) ₂ —O—CH. Dye solution which is a radical of ₂ -CH (CH ₃ ) -OH. 9. The dye solution according to claim 1, wherein the dye solution comprises from 10 to 50% by weight, preferably from 20 to 50% by weight of at least one dye of formula (I). 10. The dye solution according to any one of claims 1 to 9, comprising two dyes of formula (I). The dye solution according to any one of claims 1 to 10, comprising two dyes of the formula (3), (4) or (5). Formula 3 Formula 4 Formula 5 In the above formula, M ⁺ has the meaning defined in claim 1. At least one dye of formula (1) wherein M ⁺ is a hydrogen ion in water with an amine of formula (2) or ammonium cation of M ⁺ is an amine of formula (2) Wherein each of X, Y, Z, R ₁ , R ₂ and R ₃ independently of one another comprises dissolving in water at least one dye of formula 1 having the meaning defined in claim 1. A method for producing a dye solution according to claim 11. Use of the dye solution according to any one of claims 1 to 12 for dyeing or printing hydroxyl group-containing or nitrogen-containing fiber materials. Use according to claim 13 for dyeing or printing natural or synthetic polyamide fiber materials, in particular synthetic polyamide fiber materials. Dyes of formula (1). Formula 1 In the above formula, X and Y are each independently of the other hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, Z is C ₂ -C ₆ alkanoylamino or C ₂ -C ₄ hydroxyalkylsulfamoyl, M ⁺ is an ammonium cation of an amine of formula ego, Formula 2 Wherein R ₁ and R ₂ are each independently of one another hydrogen, C _1-6 alkyl, or hydroxy- or amino-substituted C _2-6 alkyl which may be interrupted by an oxygen atom, and R ₃ is an oxygen atom; Hydroxy- or amino-substituted C ₂ -C ₆ alkyl which may be blocked by the proviso that X and Y are methyl and Z is 2-hydroxyethylsulfamoyl, or X and Y are hydrogen and Z is In the case of propionylamino, R ₁ , R ₂ and R ₃ are not radicals of the formula —CH ₂ —CH (OH) —CH ₃ .