EP0264346A1 - Process for dyeing a natural or synthetic fibrous polyamide material with 1:1 metallic complex dyes - Google Patents

Abstract

The invention relates to a process for dyeing fiber materials from natural or synthetic polyamides from an aqueous liquor with dyes in the presence of alkali or ammonium salt and in the presence of auxiliaries, which is characterized in that these fiber materials are treated with at least one 1: 1 metal complex dye containing sulfo groups or with a mixture containing at least one 1: 1 metal complex dye containing sulfo groups and at least one metal-free dye containing sulfo groups in the presence of 10 to 45% by weight of an alkali metal and / or ammonium fluorosilicate, based on the weight of the 1: 1 metal complex dye, at a pH from 3 to 5 colors. The process according to the invention is suitable for dyeing natural or synthetic polyamide materials, fiber and flat dyeings having good fastness properties being achieved.

Description

The present invention relates to a new process for fiber and flat level dyeing of natural and synthetic polyamide fiber materials with sulfo group-containing 1: 1 metal complex dyes or with dye mixtures containing sulfo group-containing 1: 1 metal complex dyes and metal-free sulfonic acid group-containing dyes in the presence of 10 to 45 percent by weight an alkali and / or ammonium fluorosilicate, based on the amount by weight of the 1: 1 metal complex dye used in the presence of an auxiliary, dyeing being carried out at a pH value of 3 to 5 which is gentle on the fibers, the dye bath being virtually completely drawn off, the dyeing being thoroughly colored and shows good overall fastness properties, in particular good wet fastness properties and good light fastness properties, as well as the material dyed by the new process and means for carrying out the process.

A disadvantage of the dyeing processes used hitherto for natural or synthetic polyamide materials with 1: 1 metal complex dyes or mixtures of 1: 1 metal complex dyes with metal-free acid dyes is that these dyes or mixtures are dyed at a pH of approximately 1.9 to 2.8 must be in order to obtain level coloring. In addition to the dyeing time, the pH value of the dyebath is crucial when dyeing natural and synthetic polyamide materials, especially when dyeing wool Significance because natural and synthetic polyamide materials, especially wool, are strongly attacked both in the strongly acidic and in the alkaline pH range.

Surprisingly, a new process has now been found which does not have the disadvantages mentioned and which allows natural or synthetic textile polyamide fiber materials in the fiber-protecting pH range from 3 to 5, in particular 3.5 to 4.5, preferably 3, to be carried out in a simple manner. 7 to 4.2 to color.

The present invention thus relates to a process for dyeing fiber material from natural or synthetic polyamides from an aqueous liquor with dyes in the presence of alkali or ammonium salts and in the presence of auxiliaries, which is characterized in that these fiber materials are treated with at least one sulfo group-containing 1: 1-metal complex dye or with a mixture containing at least one 1: 1 metal complex dye containing sulfo groups and at least one metal-free dye containing sulfo groups in the presence of 10 to 45 percent by weight of an alkali metal and / or ammonium fluorosilicate, based on the amount by weight of the 1: 1 metal complex dye used Presence of an auxiliary at pH 3 to 5 colors.

The usable 1: 1 metal complex dyes containing sulfo groups are preferably monoazo or disazo dyes which contain a chromium ion as the metal ion. 1: 1 metal complex azomethine dyes, which preferably contain a chromium ion, can also be used.

The usable sulfo group-containing metal-free dyes are preferably acidic to strongly acidic acid dyes from the series of monoazo or polyazo, anthraquinone, triphenylmethane or xanthene dyes, which are the usual for acid dyes May contain substituents. The sulfo-containing metal-free dyes can be substituted by fiber-reactive radicals.

The amounts in which the defined dyes or dye mixtures are used in the dyebaths can vary within wide limits depending on the desired depth of color, in general amounts of from 0.01 to 10 percent by weight, based on the material to be dyed, of one or more dyes proven advantageous.

The dyeing of natural or synthetic polyamide fiber materials with 1: 1 metal complex dyes or their mixture with metal-free dyes in the presence of alkali sulfate or chloride, e.g. Sodium sulfate and sodium chloride, and optionally an auxiliary have been known for a long time. Surprisingly, the use of alkali and / or ammonium fluorosilicate already in an amount of 10 to 45 percent by weight, based on the amount by weight of the 1: 1 metal complex dye, in the presence of an auxiliary, enables the dyeing of these fiber materials in the fiber-protecting pH range, good and no matter what the color is.

Alkali or ammonium salts of hexafluorosilicic acid or mixtures thereof are used as alkali or ammonium fluorosilicates in the process according to the invention. Na₂SiF₆ or (NH₄) ₂SiF₆ or a mixture of Na₂SiF₆ and (NH₄) ₂SiF₆ is preferably used.

• a) die Fasermaterialien mit einer Mischung enthaltend mindestens einen sulfogruppenhaltigen 1:1-Metallkomplexfarbstoff und mindestens einen sulfogruppenhaltigen metallfreien Farbstoff in Gegenwart von 10 bis 45 Gewichtsprozent eines Alkali- oder Ammoniumfluorosilikats bezogen auf die eingesetzte Menge des 1:1-Metallkomplexfarbstoffs und in Gegenwart eines Hilfsmittels bei einem pH-Wert von 3 bis 5 färbt;
• b) in Gegenwart von Natrium- oder insbesondere Ammoniumfluorosilikat färbt;
• c) in Gegenwart einer Mischung aus Na₂SiF₆ und (NH₄)₂SiF₆ färbt, wobei das Verhältnis Na₂SiF₆:(NH₄)₂SiF₆ 20:80 bis 80:20 ist.

Preferred embodiments of the method according to the invention are characterized in that

• a) the fiber materials with a mixture containing at least one sulfo-containing 1: 1 metal complex dye and at least one sulfo-containing metal-free dye in the presence of 10 to 45 percent by weight of an alkali metal or ammonium fluorosilicate based on the amount of 1: 1 metal complex dye used and in the presence of an auxiliary at a pH of 3 to 5;
• b) colors in the presence of sodium or in particular ammonium fluorosilicate;
• c) colors in the presence of a mixture of Na₂SiF₆ and (NH₄) ₂SiF₆, the ratio Na₂SiF₆: (NH₄) ₂SiF₆ being 20:80 to 80:20.

The amount in which the alkali and / or ammonium fluorosilicate is used in the dyebaths is 10 to 45 percent by weight, preferably 15 to 45 percent by weight, in particular 20 to 35 percent by weight, based on the amount by weight of the 1: 1 metal complex dye.

The term "amount by weight of the 1: 1 metal complex dye" refers to the raw dye, i.e. to the amount by weight of a dye isolated by customary methods (e.g. salting out), which contains about 20 to 40 percent by weight of salt.

The auxiliaries which can be used in the process according to the invention are known per se and are produced by known methods. They are preferably leveling aids or mixtures of different leveling aids; anionic agents, cationic agents, nonionic agents and amphoteric agents or mixtures thereof can be considered.

Examples of anionic agents which may be mentioned are: substituted naphthalenesulfonic acids, sulfuric acid semiesters of ethoxylation products, salts of longer-chain alkanesulfonic acids, salts of alkylarylsulfonic acids, in particular dodecylbenzenesulfonic acids, fatty acid amidesulfonic acids, sulfuric acid semiesters of fatty amine polyglycol ethers. Examples of cationic agents which may be mentioned are: polyglycol ethers of fatty amines, polyglycol ethers of fatty acid amidamines, quaternary ammonium compounds bonds. Examples of nonionic agents which may be mentioned are: polyglycol ethers of fatty alcohols, of alkylphenols, of resin acids, of fatty acid alkylolamides. Examples of amphoteric agents are: reaction products of ethoxylated fatty amines and hydroxyethanesulfonic acids, reaction products of phenol and styrene, polyethylene glycol difatty acid esters.

worin R einen Alkyl- oder Alkenylrest mit 12 bis 22 Kohlenstoffatomen, M Wasserstoff, Alkalimetall oder Ammonium und m und n ganze Zahlen bedeuten, wobei die Summe von m und n 2 bis 14 ist, oder der Formel

worin Rʹ unabhängig von R die für R angegebene Bedeutung hat, A ein Anion, Q einen gegebenenfalls substituierten Al kylrest und p und q ganze Zahlen bedeuten, wobei die Summe von p und q 2 bis 50 ist, oder der Formel

worin Rʺ unabhängig von R die für R angegebene Bedeutung hat und x und y ganze Zahlen bedeuten, wobei die Summe von x und y 80 bis 140 ist, eine Mischung enthaltend Verbindungen der Formel (1) und (2) oder eine Mischung enthaltend Verbindungen der Formeln (1), (2) und (3) oder eine Mischung enthaltend Verbindungen der Formeln (1a), (2) und (3).Leveling aids containing compounds of the formula are preferably used

wherein R is an alkyl or alkenyl radical having 12 to 22 carbon atoms, M is hydrogen, alkali metal or ammonium and m and n are integers, the sum of m and n being 2 to 14, or of the formula

wherein Rʹ independently of R has the meaning given for R, A is an anion, Q is an optionally substituted alkyl radical and p and q are integers, the sum of p and q being 2 to 50, or of the formula

wherein Rʺ independently of R has the meaning given for R and x and y are integers, the sum of x and y being 80 to 140, a mixture containing compounds of the formula (1) and (2) or a mixture containing compounds of Formulas (1), (2) and (3) or a mixture containing compounds of the formulas (1a), (2) and (3).

In particular, leveling aid mixtures containing 5 to 70 parts by weight of the compound of the formula (1) or (1a), 15 to 60 parts by weight of the compound of the formula (2) and 5 to 60 parts by weight of the compounds of the formula (3), based on 100, are used Parts by weight of the leveling agent mixture, where in the formulas (1), (1a), (2) and (3) R, Rʹ and Rʺ independently of one another denote an alkyl or alkenyl radical having 16 to 22 carbon atoms.

It is advantageous to use a compound of the formula (2) in which A and Q are derived from the quaternizing agents chloroacetamide, ethylene chlorohydrin, ethylene bromohydrin, epichlorohydrin, epibromohydrin or preferably dimethyl sulfate.

In the process according to the invention, in particular a leveling aid mixture is used which, in addition to compounds of the formulas (1) or (1a), (2) and (3), where the sum of p and q in formula (2) is preferably 20 to 50 contains an adduct of 60 to 100 moles of ethylene oxide with one mole of C₁₅-C₂₀ alkenyl alcohol.

Also preferred is the use of a leveling agent mixture which contains the compounds of the formulas (1) and (2) or (1a) and (2), in which the sum of the symbols p and q in formula (2) is 4 to 10.

Also preferred is the use of a leveling agent mixture of compounds of the formula (2), in which the sum of the symbols p and q in formula (2) is 30 to 40 and Rʹ is an alkyl radical having 15 to 22 carbon atoms.

It is very particularly preferred to use a leveling aid mixture containing the compound of the formula (1a), in which R is a C₁₆-C₁ Alkyl alkyl radical and m + n = 7 or 8, in the process of the invention, the compound of the formula (2), in which Rʹ is a C₂₀-C₂₂-alkyl radical, A and Q are derived from the quaternizing agent dimethyl sulfate, and p + q = 7 to 8, the compound of formula (2), wherein Rʹ is a C₂₀-C₂₂-alkyl radical, A and Q are from the quaternizing agent Derive dimethyl sulfate, and p + q = 34, and the compound of formula (3), wherein Rʺ is a C₂₀-C₂₂ alkyl radical and x + y = 106. The very particularly preferred leveling aid mixture can, in addition to water, e.g. still contain an adduct of 60 to 100 moles of ethylene oxide with one mole of C₁₅-C₂₀ alkenyl alcohol, preferably 80 moles of ethylene oxide with one mole of oley alcohol.

In particular, the very particularly preferred leveling aid mixture contains 20 to 40 parts by weight of the compound of the formula (1a), 20 to 40 parts by weight of the compound of the formula (2), in which p + q = 7 or 8, 10 to 25 parts by weight of the compound of the formula ( 2), wherein p + q = 34, 3 to 9 parts by weight of the compound of formula (3) and optionally up to 8 parts by weight of the adduct of ethylene oxide with an alkenyl alcohol based on 100 parts of the anhydrous leveling agent mixture.

The amount in which the leveling aid or the leveling aid mixture is used in the dyebaths can vary within wide limits, in general an amount of 0.3 to 3 percent by weight, preferably 1 to 2 percent by weight, based on the fiber material, of leveling aid or Leveling agent mixture proved to be advantageous.

As further auxiliaries, the dyebaths can contain mineral acids, such as sulfuric acid, sulfamic acid or phosphoric acid, organic acids, expediently lower, aliphatic carboxylic acids, such as formic, acetic or maleic acid. The acids are used primarily to adjust the pH of the liquors used according to the invention. The pH is preferably adjusted from 3 to 5 using an organic acid, in particular formic acid or acetic acid.

It is preferred to dye at a pH of 3.5 to 4.5, in particular 3.7 to 4.2.

Furthermore, the dye liquor of alkali or ammonium fluorosilicate can be various salts, in particular ammonium or alkali salts such as e.g. Contain ammonium sulfate or preferably sodium sulfate as an auxiliary. 1 to 10 percent by weight of ammonium or alkali metal salts, based on the fiber material, are preferably used.

The 1: 1 metal complex dyes which can be used in the process according to the invention are preferably those which have at least one 1: 1 chromium complex azo or azomethine dye with 1 to 3 sulfonic acid groups, in particular 1 to 2 sulfonic acid groups, and in the case of dye mixtures, at least one metal-free one Contain dye with 1 to 2 sulfonic acid groups.

In particular, metal-free sulfo-containing dyes are used in the process according to the invention with good migration properties. The migrating ability of these dyes should correspond to the migrating ability of the 1: 1 chromium complex azo or azomethine dyes.

The migratory capacity on wool is determined by treating a sample dyed to 1/1 standard depth together with an uncolored sample of the same weight in a blind bath.

The treatment conditions for determining the migratory capacity correspond to the conditions given in Example 1 with regard to liquor ratio, pH and treatment duration. The evaluation is carried out by spectrophotometric determination of the amount of dye on the originally undyed wool as a percentage of the originally colored wool.

A range of 25 to 50% has proven to be advantageous as good migratory power, colored at pH 4 to 5 and measured as a difference in strength.

Suitable metal-free dyes containing sulfo groups are, for example, C.I. Acid Blue 1, 7, 13, 23, 40, 40: 1, 43, 45, 47, 72, 147, 258 and 277; C.I. Acid Red 1, 5, 37, 42, 52, 57 and 361; C.I. Acid Yellow 10, 17, 25, 27, 99 and 219; C.I. Acid Orange 1, 3 and 156; C.I. Acid Green 3, 9 and 16; C.I. Acid Violet 9 and 36; C.I. Acid Brown 10, 11 and 248.

Mixtures of several dyes or dye mixtures according to the definition can optionally also be used in the process according to the invention.

• a) mindestens zwei 1:1-Chromkomplexazo- oder -azomethinfarbstoffe und gegebenenfalls mindestens einen sulfogruppenhaltigen metallfreien Farbstoff enthält; und
• b) mindestens drei 1:1-Chromkomplexazo- oder -azomethinfarbstoffe und gegebenenfalls mindestens einen sulfogruppenhaltigen metallfreien Farbstoff enthält; oder
• c) zum Trichromiefärben mindestens drei 1:1-Chromkomplexazo- oder -azomethinfarbstoffe aus gelb- bzw. orange-, rot- und blaufärbenden Farbstoffen und gegebenenfalls mindestens einen sulfogruppenhaltigen metallfreien Farbstoff aus gelb- bzw. orange- und/oder rot- und/oder blaufärbenden Farbstoffen enthält.

A mixture of dyes or dye mixtures according to the definition is preferred

• a) contains at least two 1: 1 chromium complex azo or azomethine dyes and optionally at least one metal group-free dye containing sulfo groups; and
• b) contains at least three 1: 1 chromium complex azo or azomethine dyes and optionally at least one metal group-free dye containing sulfo groups; or
• c) for trichromatic dyeing at least three 1: 1 chromium complex azo or azomethine dyes from yellow or orange, red and blue coloring dyes and optionally at least one sulfo-containing metal-free dye from yellow or orange and / or red and / or contains blue-coloring dyes.

The color mixture of suitably selected yellow or understand orange, red and blue coloring dyes, with which any desired shade of the visible color spectrum can be adjusted by a suitable choice of the proportions of the dyes.

verwendet, worin -(CO) _0-1-O- und (O oder NR₁) in Nachbarstellung zur Azobrücke an D und K gebunden sind, D der Rest einer Diazokomponente der Benzol- o der Naphthalinreihe, K der Rest einer Kupplungskomponente der Benzol-, Naphthalin- oder heterocyclischen Reihe oder der Acetessigsäurearylidreihe, R₁ Wasserstoff, oder ein gegebenenfalls substituierter Alkyl- oder Phenylrest, M ein Kation und An ein Anion ist, und Y das Stickstoffatom oder die CH-Gruppe bedeutet.In particular, in the process according to the invention, 1: 1 chromium complex azo or azomethine dyes are those of the formula

used, in which - (CO) _0-1 -O- and (O or NR₁) in the vicinity of the azo bridge are bonded to D and K, D the rest of a diazo component of the benzene or naphthalene series, K the rest of a coupling component of the benzene , Naphthalene or heterocyclic series or the acetoacetic acid arylide series, R₁ hydrogen, or an optionally substituted alkyl or phenyl radical, M is a cation and An is an anion, and Y represents the nitrogen atom or the CH group.

In the process according to the invention, sulfo group-containing 1: 1 chromium complex azo or azomethine dyes of the formula (4) are preferably used, in which D is a benzene or naphthalene residue optionally substituted by halogen, C₁-C--alkyl, C₁-C₄-alkoxy, nitro or sulfamoyl , K a optionally substituted by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₂-C₄-alkanoylamino, sulfamoyl or hydroxy-phenyl-, naphthyl-, 1-phenyl-3-methylpyrazolen- (5) -, acetoacetamide- , in particular acetoacetoanilide or quinoline, R₁ is hydrogen and M is an alkaline application.

Y in formula (4) preferably denotes the nitrogen atom.

In particular, the metal-free dyes containing sulfonic acid groups used in the process according to the invention are those of the dye series mentioned above which, for example, can be substituted by alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl and butyl, alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy and butoxy, acylamino groups having 1 to 6 carbon atoms, such as acetylamino and Propionylamino, benzoylamino, amino, alkylamino with 1 to 4 carbon atoms, phenylamino, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy radical, nitro, acetyl, cyano, trifluoromethyl, halogen, such as fluorine, chlorine and bromine, sulfamoyl, carbamoyl, ureido, hydroxy, carboxy and sulfomethyl.

Furthermore, the metal-free dyes containing sulfonic acid groups can be substituted by one or more fiber-reactive radicals. Suitable fiber-reactive radicals are, for example, the radicals mentioned in DE-OS 29 13 102.

Mixtures of 1: 1 metal complex dyes containing sulfo groups and metal-free dyes containing sulfo groups are preferably used in the process according to the invention in a weight ratio of 40:60 to 95: 5.

The sulfo-containing dyes used in the process according to the invention are present either in the form of their free sulfonic acid or preferably as their salts.

Examples of suitable salts are the alkali metal, alkaline earth metal or ammonium salts or the salts of an organic amine. Examples include the sodium, lithium, potassium or ammonium salts or the salt of triethanolamine.

The 1: 1 metal complex dyes containing sulfo groups used in the process according to the invention and the metal-free dyes containing sulfo groups are known per se and are obtained by known methods.

The dye mixtures used in the process according to the invention can be prepared by mixing the individual dyes. This mixing process takes place, for example, in suitable mills, e.g. Ball or pin mills, as well as in kneaders or mixers.

Furthermore, the dye mixtures can be prepared by spray drying the aqueous dye mixtures.

In addition to the dye and the auxiliaries mentioned, the dyebaths can also contain other customary additives, such as Wool protection, wetting and defoaming agents included.

The liquor ratio can be selected within a wide range, from 1: 6 to 1:80, preferably 1:10 to 1:30.

Dyeing is carried out from an aqueous liquor using the exhaust process, e.g. at temperatures between 80 and 105 ° C or 110 ° C when using a formaldehyde-releasing wool protection agent, preferably between 98 and 103 ° C.

The dyeing time is usually 30 to 120 minutes.

Special devices are not required in the method according to the invention. It is possible to use the customary dyeing apparatus and machines, for example for flake, sliver, strand yarn, bobbins, piece goods and carpets.

The leveling aid and the alkali metal or ammonium fluorosilicate are expediently mixed into the aqueous dye liquor and applied simultaneously with the dye mixture. One can also proceed in such a way that the material to be dyed is first dealt with by the leveling aid and dyed in the same bath after adding the dye mixture and the alkali metal or ammonium fluorosilicate. The fiber material is preferably added to a liquor which contains acid and auxiliaries and a temperature of 30 to 70 ° C having. The dye mixture and the alkali metal or ammonium fluorosilicate are then added and the temperature of the dyebath is increased at a heating rate of 0.75 to 3 ° C. per minute, if necessary with a temperature stop during the heating, in the specified temperature range of 80 ° C. to 105 ° ° C preferably 30 to 120 minutes to color. Finally, the bath is cooled and the colored material rinsed and dried as usual.

A particularly preferred procedure is characterized in that the fiber material is added to a liquor which contains acid and a leveling agent containing alkali and / or ammonium hexafluorosilicate and Na₂SO₄ and has a temperature of 30 to 70 ° C. Subsequently, the dyes or dye mixtures which contain alkali and / or ammonium hexafluorosilicate are added, and the temperature of the dyebath is increased at a heating rate of 0.75 to 3 ° C. per minute, optionally with a temperature stop during heating, in order to to color the specified temperature range from 80 ° C to 105 ° C. The bath is then cooled and the colored material rinsed and dried as usual.

As a textile fiber material made of natural polyamides, which can be dyed according to the invention, above all wool, but also mixtures of wool / polyamide, wool / polyester, wool / cellulose or wool / polyacrylonitrile and silk should be mentioned. The fiber material can be in a wide variety of forms, e.g. as loose material, sliver, yarn and piece goods or as carpet.

Suitable fiber material made of synthetic polyamides, which can be dyed according to the invention, is that of all known, suitable synthetic polyamides. The fiber material can be in a wide variety of forms, such as loose material, sliver, yarn and piece goods or as a carpet.

A particularly preferred embodiment of the process according to the invention is characterized in that natural or synthetic polyamide fiber materials, in particular wool, with at least one dye mixture as defined above in the presence of ammonium fluorosilicate or sodium fluorosilicate, preferably in a 15 to 45% by weight amount, based on the weight amount 1: 1 chromium complex dye used, and in the presence of a leveling agent, containing compounds of the formula (1) and (2) or (1), (2) and (3) or (1a), (2) and (3), and colors in the presence of sodium sulfate at a pH of 3.7 to 4.2.

The sulfo-containing, metal-free dyes used in the process according to the invention can contain one or more fiber-reactive groups. Such dye mixtures of the 1: 1 metal complex dyes defined according to the invention and the metal-free dyes containing sulfo groups are preferably used in the process according to the invention, in which the metal-free dyes used are either all reactive dyes or all are free from fiber-reactive groups; metal-free dyes containing sulfo groups are very particularly preferably used.

A very particularly preferred embodiment of the method according to the invention is characterized in that the dye mixtures used according to the invention consist of metal-containing and metal-free dyes defined according to the invention which give colorations of the same nuances, i.e. For example, the use of a mixture of at least one blue-coloring, 1: 1 metal complex dye containing sulfo groups and at least one blue-coloring, metal-free dye containing sulfo groups.

The method according to the invention has the following advantages over the known methods for fiber material made of natural or synthetic polyamides in addition to the ones already mentioned. The material dyed under the mentioned dyeing conditions is characterized by better overall fastness properties, in particular better wet fastness properties. Another important advantage is that the dyes are almost completely absorbed.

The method according to the invention is preferably used for dyeing wool.

When dyeing is complete, the dye baths are almost completely drawn out.

Compared to the process known from EP-A-0 163 608, the process according to the invention surprisingly manages with a significantly smaller amount of alkali metal or ammonium hexafluorosilicate.

The invention further relates to a means for carrying out the method according to the invention. The agent is a solid mixture containing at least one sulfo group-containing 1: 1 metal complex dye, in particular a 1: 1 chromium complex dye, and optionally at least one sulfo group-containing metal-free dye and 10 to 45 percent by weight of an alkali metal or ammonium fluorosilicate based on the 1: 1 metal complex weight amount.

The mixture according to the invention is prepared by mixing at least one 1: 1 chromium complex dye containing sulfo groups and optionally at least one metal-free dye containing sulfo groups with 10 to 45 percent by weight (based on the weight of the 1: 1 metal complex dye) alkali metal and / or ammonium fluorosilicate. The mixing process takes place, for example, in suitable mills, e.g. Ball or pin mills, as well as in kneaders or mixers.

Mixtures which contain sodium or ammonium fluorosilicate in addition to the dye mixture as defined are preferred.

The solid mixtures can be used for dyeing natural or synthetic textile polyamide fiber materials. The same preferences apply to the solid mixtures as stated for the process.

The invention further relates to a further means for carrying out the method according to the invention. The agent is a mixture containing a leveling aid consisting of one or more compounds of the formula (1), (1a), (2) or (3), in particular a leveling agent mixture consisting of compounds of the formulas (1a), (2) and (3), and 5 to 25 percent by weight of alkali and / or ammonium hexafluorosilicate, preferably (NH₄) ₂SiF₆, based on the amount by weight of the compounds of the formulas (1), (1a), (2) and / or (3).

The mixture according to the invention is produced by mixing at least one compound of the formulas (1), (1a), (2) or (3) with 5 to 25 percent by weight of alkali metal and / or ammonium hexafluorosilicate. The mixing process takes place, for example, in suitable mixers.

The mixture can be used together with the dye mixture containing alkali and / or ammonium hexafluorosilicate for dyeing natural or synthetic polyamide fiber materials. The same preferences apply to the mixture as apply to the process.

The following examples serve to illustrate the invention. The parts are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between grams and cubic meters timeter. The indicated amounts of dye refer to raw dye.

R₂ = C₁₆-C₁₈-Kohlenwasserstoffrest; m + n = 7;
24 Teilen der quaternären Verbindung der Formel

R₃ = C₂₀-C₂₂-Kohlenwasserstoffrest;
5 Teilen Ammoniumchlorid
3 Teilen Oxalsäure und
44 Teilen Wasser, bezogen auf 100 Teile Egalisierhilfsmittel, während 15 Minuten bei 50° vorbehandelt. Nach Zugabe einer Lösung von
1,1 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

0,5 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

0,23 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

0,23 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

0,64 Teilen des Farbstoffes der Formel

0,97 Teilen des Farbstoffes der Formel

und 0,4 Teilen des Farbstoffes der Formel

wird die Färbeflotte noch 10 Minuten bei 50° gehalten und anschliessend mit einer Aufheizrate von 0,8°/Minute auf 98° erwärmt. Der pH beträgt zu Anfang des Färbens 3,8. Nach 90 Minuten bei 98° wird auf 50° abgekühlt und die Färbeflotte abgelassen. Das braun gefärbte Wollgarn wird je 10 Minuten erst bei 50°, dann bei Raumtemperatur gespült und wie üblich getrocknet. Die erhaltene mittelbraune Färbung ist ausgezeichnet faseregal und weist gute Echtheiten auf. Example 1: 800 parts of worsted wool are in a dyebath containing 20,000 parts of water at 50 °, 64 parts of sodium sulfate, 0.55 parts of (NH₄) ₂SiF₆, 20 parts of 85% formic acid and 12 parts of a leveling agent consisting of 24 parts the anionic compound of the formula

R₂ = C₁₆-C₁₈ hydrocarbon residue; m + n = 7;
24 parts of the quaternary compound of the formula

R₃ = C₂₀-C₂₂ hydrocarbon residue;
5 parts of ammonium chloride
3 parts of oxalic acid and
44 parts of water, based on 100 parts of leveling agent, pretreated at 50 ° for 15 minutes. After adding a solution of
1.1 parts of the 1: 1 chromium complex of the dye of the formula

0.5 parts of the 1: 1 chromium complex of the dye of the formula

0.23 parts of the 1: 1 chromium complex of the dye of the formula

0.23 parts of the 1: 1 chromium complex of the dye of the formula

0.64 parts of the dye of the formula

0.97 parts of the dye of the formula

and 0.4 parts of the dye of the formula

the dye liquor is kept at 50 ° for a further 10 minutes and then heated to 98 ° at a heating rate of 0.8 ° / minute. The pH at the beginning of dyeing is 3.8. After 90 minutes at 98 °, the mixture is cooled to 50 ° and the dye liquor is drained off. That brown dyed wool yarn is rinsed at 50 ° for 10 minutes, then at room temperature and dried as usual. The medium brown coloration obtained is excellent fiber-level and has good fastness properties.

Example 2: 100 parts of wool fabric are in a dyebath which contains 8 parts of sodium sulfate, 1.2 parts of the leveling aid given in Example 1 and 2.3 parts of 85% strength formic acid in 2000 parts of water at 40 ° for 15 minutes at 40 ° pretreated. The pH is 3.7.

0,26 Teilen des Farbstoffes der Formel

0,11 Teilen des Farbstoffes der Formel

0,11 Teilen des Farbstoffes der Formel

0,13 Teilen des Farbstoffes der Formel

0,11 Teilen des Farbstoffes der Formel

und 0,12 Teilen des Farbstoffes der Formel

wird die Färbeflotte noch 10 Minuten bei 40° gehalten und anschliessend mit einer Aufheizrate von 1° per Minute auf 70° erwärmt. Nach 20 Minuten Färbezeit bei 70° wird die Färbeflotte auf 100° erwärmt. Nach 90 Minuten Färbezeit bei 100° wird auf 60° abgekühlt und die Färbeflotte abgelassen. Das braungefärbte Wollgewebe wird je 5 Minuten erst bei 50°, dann bei Raumtemperatur gespült und wie üblich getrocknet. Die erhaltene Färbung ist ausgezeichnet faseregal und weist gute Echtheiten auf.After adding a solution of 0.18 parts Na₂SiF₆ and 0.21 parts of the dye of the formula

0.26 parts of the dye of the formula

0.11 parts of the dye of the formula

0.11 parts of the dye of the formula

0.13 parts of the dye of the formula

0.11 parts of the dye of the formula

and 0.12 parts of the dye of the formula

the dye liquor is kept at 40 ° for a further 10 minutes and then heated to 70 ° at a rate of 1 ° per minute. After 20 minutes of dyeing at 70 °, the dye liquor is heated to 100 °. After 90 minutes of dyeing at 100 °, the mixture is cooled to 60 ° and the dye liquor is drained off. The brown-colored wool fabric is rinsed for 5 minutes at 50 °, then at room temperature and dried as usual. The dyeing obtained has excellent fiber shelf properties and good fastness properties.

0,13 Teile des Farbstoffes der Formel

und 0,12 Teile (NH₄)₂SiF₆ wird die Färbeflotte noch 10 Minuten bei 40° gehalten und anschliessend mit einer Aufheizrate von 0,8° pro Minute auf 100° erwärmit. Nach 90 Minuten Färbezeit bei 100° wird auf 60° abgekühlt und die Färbeflotte abgelassen. Das blaugefärbte Wollgewebe wird wie üblich gespült und getrocknet. Die erhaltene mittelblaue Färbung ist ausgezeichnet faseregal und weist gute Echtheitseigenschaften auf. Example 3: 100 parts of woolen fabric are placed in a dyebath containing 1000 parts of water at 40 °, 8 parts of sodium sulfate, 1.5 parts of the leveling aid given in Example 1 and 2 parts of 85% strength Contains formic acid, pretreated at 40 ° for 10 minutes. The pH is 3.8. After adding a solution containing 0.49 parts of the dye of the formula

0.13 parts of the dye of the formula

and 0.12 parts (NH₄) ₂SiF₆, the dye liquor is kept at 40 ° for 10 minutes and then heated to 100 ° with a heating rate of 0.8 ° per minute. After 90 minutes of dyeing at 100 °, the mixture is cooled to 60 ° and the dye liquor is drained off. The blue-colored wool fabric is rinsed and dried as usual. The medium blue color obtained is excellent fiber-level and has good fastness properties.

R₂ = Kohlenwasserstoffrest des Talgfettamins, m + n =

;
21 Teile der quaternären Verbindung der Formel

R₃ = C₂₀-C₂₂-Kohlenwasserstoffrest;
7,7 Teile des Umsetzungsproduktes von Oleylalkohol mit 80 Mol Aethylenoxid; und
7 Teile der Verbindung der Formel

sowie 49,7 Teile Wasser, bezogen auf 100 Teile des Egalisierhilfsmittelgemisches;
und 2,6 Teile 85%ige Ameisensäure enthält, während 15 Minuten bei 40° vorbehandelt. Der pH-Wert beträgt 3,8. Nach Zugabe einer Lösung enthaltend 0,30 Teile Na₂ SiF₆, 0,72 Teile des Farbstoffes der Formel

und 0,55 Teile des Farbstoffes der Formel

wird die Färbeflotte noch 10 Minuten bei 40° gehalten und anschliessend mit einer Aufheizrate von 0,8° pro Minute auf 100° erwärmt. Nach 90 Minuten Färbezeit bei 100° wird auf 50° abgekühlt und die Färbeflotte abgelassen. Das rotgefärbte Wollgewebe wird wie üblich gespült und getrocknet. Die erhaltene tiefrote Färbung ist ausgezeichnet faseregal und weist gute Echtheitseigenschaften auf. Example 4: 100 parts of woolen fabric are placed in a dyebath, which is based on 1500 parts of water at 40 °, 8 parts of sodium sulfate, 1.5 parts of the leveling aid of the following composition:
14.6 parts of the anionic compound of the formula

R₂ = hydrocarbon residue of tallow fatty amine, m + n =

;
21 parts of the quaternary compound of the formula

R₃ = C₂₀-C₂₂ hydrocarbon residue;
7.7 parts of the reaction product of oleyl alcohol with 80 moles of ethylene oxide; and
7 parts of the compound of the formula

and 49.7 parts of water, based on 100 parts of the leveling agent mixture;
and contains 2.6 parts of 85% formic acid, pretreated at 40 ° for 15 minutes. The pH is 3.8. After adding a solution containing 0.30 parts Na₂ SiF₆, 0.72 parts of the dye of the formula

and 0.55 part of the dye of the formula

the dye liquor is kept at 40 ° for a further 10 minutes and then heated to 100 ° at a heating rate of 0.8 ° per minute. After 90 minutes of dyeing at 100 °, the mixture is cooled to 50 ° and drained the dye liquor. The red-colored wool fabric is rinsed and dried as usual. The deep red color obtained is excellently fibrous and has good fastness properties.

und 0,21 Teilen des Farbstoffes der Formel

0,45 Teile einer festen Mischung bestehend aus
0,08 Teilen (NH₄)₂SiF₆,
0,26 Teilen des Farbstoffes

und 0,11 Teile des Farbstoffes der Formel

und 0,38 Teile einer festen Mischung bestehend aus
0,04 Teilen Na₂SiF₆,
0,11 Teilen des Farbstoffes der Formel

0,11 Teilen des Farbstoffes der Formel

und 0,12 Teilen des Farbstoffes der Formel

Dann wird die Färbeflotte noch 10 Minuten bei 40° gehalten und anschliessend mit einer Aufheizrate von 1° pro Minute auf 70° erwärmt. Nach 20 Minuten Färbezeit bei 70° wird die Färbeflotte auf 100° erwärmt. Nach 90 Minuten Färbezeit bei 100° wird auf 60° abgekühlt und die Färbeflotte abgelassen. Das braungefärbte Woll gewebe wird je 5 Minuten erst bei 50°, dann bei Raumtemperatur gespült und wie üblich getrocknet. Die erhaltene Färbung ist ausgezeichnet faseregal und weist gute Echtheiten auf. EXAMPLE 5 100 parts of woolen fabric are placed in a dyebath which contains 8 parts of sodium sulfate, 1.2 parts of the leveling aid given in Example 1 and 2.3 parts of 85% formic acid in 2000 parts of water at 40 ° for 15 minutes at 40 ° pretreated. The pH is 3.7. Subsequently, 0.43 parts of a solid mixture consisting of are added to the dye liquor
0.09 parts (NH₄) ₂SiF₆,
0.13 parts of the dye of the formula

and 0.21 parts of the dye of the formula

0.45 part of a solid mixture consisting of
0.08 parts (NH₄) ₂SiF₆,
0.26 parts of the dye

and 0.11 parts of the dye of the formula

and 0.38 part of a solid mixture consisting of
0.04 parts Na₂SiF₆,
0.11 parts of the dye of the formula

0.11 parts of the dye of the formula

and 0.12 parts of the dye of the formula

The dye liquor is then kept at 40 ° for 10 minutes and then heated to 70 ° at a rate of 1 ° per minute. After 20 minutes of dyeing at 70 °, the dye liquor is heated to 100 °. After 90 minutes of dyeing at 100 °, the mixture is cooled to 60 ° and the dye liquor is drained off. The brown colored wool tissue is rinsed for 5 minutes at 50 °, then at room temperature and dried as usual. The dyeing obtained has excellent fiber shelf properties and good fastness properties.

R₂ = Kohlenwasserstoffrest des Talgfettamins, m + n = 8;
21 Teilen der quaternären Verbindung der Formel

R₃ = C₂₀-C₂₂-Kohlenwasserstoffrest;
7,7 Teile des Umsetzungsproduktes von Oleyla lkohol mit 80 Mol Aethylenoxid; und
7 Teile der Verbindung der Formel

sowie 49,7 Teile Wasser, bezogen auf 100 Teile des Egalisierhilfsmittelgemisches, enthält, während 15 Minuten bei 50° vorbehandelt. Nach Zugabe einer 50° warmen Lösung von 2,11 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

2,22 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

0,82 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

und 1,05 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

und 1,28 Teilen Na₂SiF₆ in 1000 Teilen Wasser wird die Färbeflotte noch 10 Minuten bei 50° gehalten und anschliessend mit einer Aufheizrate von 1°/Minute auf 98° erwärmt. Der pH-Wert beträgt am Anfang des Färbens 4. Nach 90 Minuten Färbezeit bei 98° wird auf 50° abkühlen gelassen, das braun gefärbte Wollgarn je 10 Minuten erst bei 50° und dann bei Raumtemperatur gespült und wie üblich getrocknet. Der pH-Wert gegen Ende des Färbens beträgt 4,2. Die erhaltene mittelbraune Färbung ist ausgezeichnet faseregal; das gefärbte Kammgarn zeigt einen vollen, weichen Griff. Die Endflotte ist praktisch ungefärbt. Example 6: 800 parts of wool worsted yarn, consisting of 20 parts of softened (deionized) water at 50 °, 40 parts of acetic acid (80%), 20 parts of crystalline sodium acetate and 12 parts of a leveling aid in a dye bath
14.6 parts of the anionic compound of the formula

R₂ = hydrocarbon residue of tallow fatty amine, m + n = 8;
21 parts of the quaternary compound of the formula

R₃ = C₂₀-C₂₂ hydrocarbon residue;
7.7 parts of the reaction product of Oleyla alcohol with 80 moles of ethylene oxide; and
7 parts of the compound of the formula

and 49.7 parts of water, based on 100 parts of the leveling agent mixture, contains pretreated at 50 ° for 15 minutes. After adding a 50 ° warm solution of 2.11 parts of the 1: 1 chromium complex of the dye of the formula

2.22 parts of the 1: 1 chromium complex of the dye of the formula

0.82 parts of the 1: 1 chromium complex of the dye of the formula

and 1.05 parts of the 1: 1 chromium complex of the dye of the formula

and 1.28 parts Na₂SiF₆ in 1000 parts of water, the dye liquor is kept at 50 ° for 10 minutes and then heated to 98 ° at a rate of 1 ° / minute. The pH at the beginning of dyeing is 4. After 90 minutes of dyeing at 98 °, the mixture is allowed to cool to 50 °, the brown-colored wool yarn is rinsed at 50 ° for 10 minutes and then at room temperature and dried as usual. The pH at the end of dyeing is 4.2. The medium brown color obtained is excellently fibrous; the dyed worsted shows a full, soft feel. The final fleet is practically undyed.

A yarn dyeing carried out with the same dyes according to the above procedure, but without the addition of Na₂SiF₆, is strongly fiber-uneven and very much weaker. The final fleet is still clearly colored.

R₂ = C₁₆-C₁₈-Kohlenwasserstoffrest; m + n = 7;
24 Teilen der quaternären Verbindung der Formel

R₃ = C₂₀-C₂₂-Kohlenwasserstoffrest;
5 Teilen Ammoniumchlorid
3 Teilen Oxalsäure und
44 Teilen Wasser, bezogen auf 100 Teile Egalisierhilfsmittel, während 15 Minuten bei 50° vorbehandelt. Nach Zugabe einer Lösung von
2,15 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

0,98 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

0,45 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

und 0,46 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

wird die Färbeflotte noch 10 Minuten bei 50° gehalten und anschliessend mit einer Aufheizrate von 0,8°/Minute auf 98° erwärmt. Der pH beträgt zu Anfang des Färbens 3,8. Nach 90 Minuten Färbezeit bei 98° wird auf 50° abgekühlt und die Färbeflotte abgelassen. Das braungefärbte Wollgarn wird je 10 Minuten erst bei 50°, dann bei Raumtemperatur gespült und wie üblich getrocknet. Die erhaltene mittelbraune Färbung ist ausgezeichnet faseregal und weist gute Echtheiten auf. Example 7: 800 parts of worsted wool are in a dyebath containing 20,000 parts of water at 50 °, 64 parts of sodium sulfate, 0.82 part of (NH₄) ₂SiF₆, 20 parts of 85% formic acid and 12 parts of a leveling agent consisting of 24 parts the anionic compound of the formula

R₂ = C₁₆-C₁₈ hydrocarbon residue; m + n = 7;
24 parts of the quaternary compound of the formula

R₃ = C₂₀-C₂₂ hydrocarbon residue;
5 parts of ammonium chloride
3 parts of oxalic acid and
44 parts of water, based on 100 parts of leveling agent, pretreated at 50 ° for 15 minutes. After adding a solution of
2.15 parts of the 1: 1 chromium complex of the dye of the formula

0.98 parts of the 1: 1 chromium complex of the dye of the formula

0.45 parts of the 1: 1 chromium complex of the dye of the formula

and 0.46 parts of the 1: 1 chromium complex of the dye of the formula

the dye liquor is kept at 50 ° for a further 10 minutes and then heated to 98 ° at a heating rate of 0.8 ° / minute. The pH at the beginning of dyeing is 3.8. After 90 minutes of dyeing at 98 °, the mixture is cooled to 50 ° and the dye liquor is drained off. The brown-colored wool yarn is rinsed at 50 ° for 10 minutes, then at room temperature and dried as usual. The medium brown coloration obtained is excellent fiber-level and has good fastness properties.

1,74 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

0,82 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

und 1,05 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

wird die Färbeflotte noch 10 Minuten bei 50° gehalten und anschliessend mit einer Aufheizrate von 1°/Minute auf 70° erwär mt, noch 20 Minuten bei 70° gehalten und anschliessend mit 1°/Minute auf 85° erwärmt. Der pH-Wert beträgt am Anfang des Färbens 4. Nach 120 Minuten Färbezeit bei 85° wird auf 50° abgekühlt und die Färbeflotte abgelassen. Das braungefärbte Wollgarn wird je 10 Minuten bei 50°, dann bei Raumtemperatur gespült und wie üblich getrocknet. Die erhaltene volle Braunfärbung ist ausgezeichnet faseregal und weist gute Echtheiten auf. Eine mit den gleichen Farbstoffen nach obigem Verfahren, aber ohne Zusatz von Na₂SiF₆ durchgeführte Garnfärbung ist stark faserunegal und ganz bedeutend schwächer. Example 8: 800 parts of worsted wool are in a dyebath containing 20 parts of water at 50 °, 64 parts of sodium sulfate, 1.1 parts of Na₂SiF₆, 32 parts of acetic acid (80%) and 12 parts of the leveling agent used in Example 7, while Pretreated for 15 minutes at 50 °. After adding a solution of 1.88 parts of the 1: 1 chromium complex of the dye of the formula

1.74 parts of the 1: 1 chromium complex of the dye of the formula

0.82 parts of the 1: 1 chromium complex of the dye of the formula

and 1.05 parts of the 1: 1 chromium complex of the dye of the formula

the dye liquor is kept at 50 ° for a further 10 minutes and then heated to 70 ° at a rate of 1 ° / minute, held at 70 ° for a further 20 minutes and then heated to 85 ° at 1 ° / minute. The pH at the beginning of dyeing is 4. After 120 minutes of dyeing at 85 °, the mixture is cooled to 50 ° and the dye liquor is drained off. The brown-colored wool yarn is rinsed at 50 ° for 10 minutes, then at room temperature and dried as usual. The full brown color obtained is excellently fibrous and has good fastness properties. A yarn dyeing with the same dyes according to the above procedure, but without the addition of Na₂SiF₆, is strongly fiber-uneven and significantly weaker.

R₃ = C₁₇-C₂₁-Kohlenwasserstoffrest;
30 Teile N,Nʹ-Dimethyloläthylenharnstoff
0,7 Teile des Adduktes von 5 Mol Aethylenoxid an 1 Mol 2-Aethyl-n-hexanol
2 Teile eines sulfatierten Fettaminpolyglykoläthers und
59,3 Teile Wasser bezogen auf 100 Teile Egalisierhilfsmittel,
während 15 Minuten bei 50° vorbehandelt. Nach Zugabe einer Lösung von
2,7 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

0,43 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

0,45 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

und 1,8 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

wird die Färbeflotte noch 10 Minuten bei 50° gehalten und anschliessend mit einer Aufheizrate von 1°/Minute auf 70° erwärmt, noch 20 Minuten bei 70° gehalten und anschliessend mit 1°/Minute auf 98° erwärmt. Der pH-Wert beträgt am Anfang des Färbens 3,7. Nach 90 Minuten Färbezeit bei 98° wird auf 60° abgekühlt und die Färbeflotte abgelassen. Das marineblau gefärbte Wollgarn wird zweimal 10 Minuten bei 50°, dann 5 Minuten bei Raumtemperatur gespült und wie üblich getrocknet. Die erhaltene Marinefärbung ist ausgezeichnet faseregal und weist gute Echtheiten auf. Example 9: 800 parts of worsted wool are in a dyebath containing 20 parts of water at 50 ° 64 parts of sodium sulfate, 1.55 parts of Na₂SiF₆, 20 parts of formic acid (85%) and 12 parts of the leveling aid

R₃ = C₁₇-C₂₁ hydrocarbon residue;
30 parts of N, Nʹ-dimethylolethylene urea
0.7 parts of the adduct of 5 moles of ethylene oxide and 1 mole of 2-ethyl-n-hexanol
2 parts of a sulfated fatty amine polyglycol ether and
59.3 parts of water based on 100 parts of leveling agent,
pretreated at 50 ° for 15 minutes. After adding a solution of
2.7 parts of the 1: 1 chromium complex of the dye of the formula

0.43 parts of the 1: 1 chromium complex of the dye of the formula

0.45 parts of the 1: 1 chromium complex of the dye of the formula

and 1.8 parts of the 1: 1 chromium complex of the dye of the formula

the dye liquor is kept at 50 ° for a further 10 minutes and then heated to 70 ° at a rate of 1 ° / minute, held at 70 ° for a further 20 minutes and then heated to 98 ° at 1 ° / minute. The pH value at the start of dyeing is 3.7. After 90 minutes of dyeing at 98 °, the mixture is cooled to 60 ° and the dye liquor is drained off. The navy blue colored wool yarn is rinsed twice for 10 minutes at 50 °, then for 5 minutes at room temperature and dried as usual. The marine dyeing obtained is excellently fibrous and has good fastness properties.

0,11 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

und 0,06 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

wird die Färbeflotte innerhalb von 45 Minuten auf 98° erwärmt. Nach 90 Minuten Färbezeit bei 98° wird auf 60° abgekühlt. Der braungefärbte Trikot wird wie üblich gespült und getrocknet. Die erhaltene mittelbraune Färbung ist etwas reiner und voller als eine unter gleichen Bedingungen, ohne Na₂SiF₆, durchgeführte Färbung. Example 10: 100 parts of polyamide 6.6 textured tricot are placed in a dyebath containing 4000 parts of water at 40 °, 0.1 part of Na₂SiF₆, 4 parts of ammonium acetate and sufficient acetic acid to adjust the pH to 4. pre-treated for 10 minutes. After adding a solution of
0.22 parts of the 1: 1 chromium complex of the dye of the formula

0.11 parts of the 1: 1 chromium complex of the dye of the formula

and 0.06 part of the 1: 1 chromium complex of the dye of the formula

the dye liquor is heated to 98 ° within 45 minutes. After 90 minutes of dyeing at 98 °, the mixture is cooled to 60 °. The brown-colored jersey is rinsed and dried as usual. The medium brown coloration obtained is somewhat purer and fuller than a coloration carried out under the same conditions, without Na₂SiF₆.

0,076 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

und 0,4 Teilen des 1:1-Chromkomplexes des Farbstoffes der Formel

wird die Färbeflotte noch 10 Minuten bei 40° gehalten und anschliessend mit einer Aufheizrate von 0,8°/Minute auf 70° erwärmt. Nach 10 Minuten Färbe zeit bei 70° wird die Färbeflotte auf 100° erwärmt. Nach 90 Minuten bei 100° wird auf 60° abgekühlt und die Färbeflotte abgelassen. Das graugefärbte Wollgewebe wird je 5 Minuten erst bei 50°, dann bei Raumtemperatur gespült und wie üblich getrocknet. Example 11: 100 parts of wool fabric are in a dyebath which contains 8 parts of sodium sulfate, 1.5 parts of the leveling aid given in Example 1 and 2.6 parts of 85% strength formic acid in 1500 parts of water at 40 ° for 10 minutes at 40 ° pretreated. The pH is 3.7. After adding a solution of 0.17 parts (NH₄) ₂SiF₆ and 0.09 parts of the 1: 1 chromium complex of the dye

0.076 parts of the 1: 1 chromium complex of the dye of the formula

and 0.4 parts of the 1: 1 chromium complex of the dye of the formula

the dye liquor is kept at 40 ° for a further 10 minutes and then heated to 70 ° at a heating rate of 0.8 ° / minute. After 10 minutes of dyeing at 70 °, the dye liquor is heated to 100 °. After 90 minutes at 100 °, the mixture is cooled to 60 ° and the dye liquor is drained off. The gray-colored wool fabric is rinsed for 5 minutes at 50 °, then at room temperature and dried as usual.

The dyeing obtained has excellent fiber shelf properties and good fastness properties.

mit 0,018 Teilen (NH₄)₂SiF₆;
0,076 Teile des 1:1-Chromkomplexes des Farbstoffes der Formel

mit 0,037 Teilen (NH₄)₂SiF₆;
0,4 Teile des 1:1-Chromkomplexes des Farbstoffes der Formel

mit 0,11 Teilen (NH₄)₂SiF₆.The same color result is obtained if one uses Na₂SiF₆ instead of (NH₄) ₂SiF₆ or if the dyes are mixed individually with Na₂SiF₆ or (NH₄) ₂SiF₆ as a powder, eg
0.09 parts of the 1: 1 chromium complex of the dye of the formula

with 0.018 parts (NH₄) ₂SiF₆;
0.076 parts of the 1: 1 chromium complex of the dye of the formula

with 0.037 parts (NH₄) ₂SiF₆;
0.4 parts of the 1: 1 chromium complex of the dye of the formula

with 0.11 parts (NH₄) ₂SiF₆.

R₂ = Kohlenwasserstoffrest des Talgfettamins, m + n = 7;
10 Teilen der quaternären Verbindung der Formel

R₃ = C₂₀-C₂₂-Kohlenwasserstoffrest;
2 Teilen des Umsetzungsproduktes von Oleylalkohol mit 80 Mol Aethylenoxid;
2 Teilen der Verbindung der Formel

5 Teilen der quaternären Verbindung der Formel; und

5 Teilen (NH₄)₂SiF₆
sowie 66 Teilen Wasser, bezogen auf 100 Teile des Egalisierhilfsmittelgemisches, enthält, während 15 Minuten bei 50° vorbehandelt. Nach Zugabe einer 50° warmen Lösung enthaltend 1,72 Teile der Mischung aus
0,96 Teilen des Farbstoffes der Formel

0,45 Teilen des Farbstoffes der Formel

und 0,31 Teilen (NH₄)₂SiF₆;
1,88 Teile der Mischung aus
1,2 Teilen des Farbstoffes der Formel

0,3 Teilen des Farbstoffes der Formel

und 0,38 Teilen (NH₄)₂SiF₆; und
1,91 Teilen einer Mischung aus
1,5 Teilen des Farbstoffes der Formel

und 0,41 Teilen (NH₄)₂SiF₆ in 1000 Teilen Wasser wird die Färbeflotte noch 10 Minuten bei 50° gehalten und anschliessend mit einer Aufheizrate von 1°/Minute auf 98° erwärmt. Der pH-Wert beträgt am Anfang des Färbens 3,5. Nach 90 Minuten Färbezeit bei 98° wird auf 50° abkühlen gelassen, das hellbraun gefärbte Wollgarn je 10 Minuten erst bei 50° und dann bei Raumtemperatur gespült und wie üblich getrocknet. Der pH-Wert gegen Ende des Färbens beträgt 3,8. Die erhaltene beige Färbung ist ausgezeichnet faseregal; das gefärbte Kammgarn zeigt einen vollen, weichen Griff. Die Endflotte ist ungefärbt. Example 12: 800 parts of wool worsted yarn in a dyebath consisting of 14 400 parts of softened (deionized) water at 50 °, 28 parts of formic acid (85%), 64 parts of sodium sulfate and 12 parts of a leveling aid
10 parts of the anionic compound of the formula

R₂ = hydrocarbon residue of tallow fatty amine, m + n = 7;
10 parts of the quaternary compound of the formula

R₃ = C₂₀-C₂₂ hydrocarbon residue;
2 parts of the reaction product of oleyl alcohol with 80 moles of ethylene oxide;
2 parts of the compound of the formula

5 parts of the quaternary compound of the formula; and

5 parts (NH₄) ₂SiF₆
and 66 parts of water, based on 100 parts of the leveling agent mixture, pretreated at 50 ° for 15 minutes. After adding a 50 ° warm solution containing 1.72 parts of the mixture
0.96 parts of the dye of the formula

0.45 parts of the dye of the formula

and 0.31 parts (NH₄) ₂SiF₆;
1.88 parts of the mixture
1.2 parts of the dye of the formula

0.3 parts of the dye of the formula

and 0.38 parts (NH₄) ₂SiF₆; and
1.91 parts of a mixture of
1.5 parts of the dye of the formula

and 0.41 parts (NH₄) ₂SiF₆ in 1000 parts of water, the dye liquor is kept at 50 ° for 10 minutes and then heated to 98 ° at a rate of 1 ° / minute. The pH is 3.5 at the start of dyeing. After 90 minutes of dyeing at 98 °, the mixture is allowed to cool to 50 °, the light brown colored wool yarn is rinsed at 50 ° for 10 minutes and then at room temperature and dried as usual. The pH at the end of dyeing is 3.8. The beige color obtained is excellent fiber-level; the dyed worsted shows a full, soft feel. The final fleet is undyed.

A yarn dyeing carried out with the same dyes according to the above process, but without the addition of (NH₄) ₂SiF₆, is strongly fiber-uneven and significantly weaker. The final fleet is still clearly colored.

Claims (20)

1. A process for dyeing fiber material from natural or synthetic polyamides from an aqueous liquor with dyes in the presence of alkali or ammonium salts and in the presence of auxiliaries, characterized in that these fiber materials are treated with at least one 1: 1 metal complex dye containing sulfo groups or with a mixture containing at least one 1: 1 metal complex dye containing sulfo groups and at least one metal-free dye containing sulfo groups in the presence of 10 to 45 percent by weight of an alkali metal and / or ammonium fluorosilicate, based on the amount by weight of the 1: 1 metal complex dye used, in the presence of an auxiliary at a pH -Value from 3 to 5 colors. 2. The method according to claim 1, characterized in that with a mixture containing at least one sulfo-containing 1: 1 metal complex dye and at least one sulfo-containing metal-free dye in the presence of 10 to 45 percent by weight of an alkali metal or ammonium fluorosilicate, based on the weight of the 1st : 1-metal complex dye, in the presence of an auxiliary at a pH of 3 to 5 colors. 3. The method according to claim 1, characterized in that dyeing in the presence of sodium or in particular ammonium fluorosilicate. 4. The method according to claim 1, characterized in that dyeing in the presence of a mixture of Na₂SiF (and (NH₄) ₂SiF₆. 5. The method according to claim 1, characterized in that one uses 15 to 45 percent by weight of an alkali metal or ammonium fluorosilicate. 6. The method according to claim 1, characterized in that one uses 20 to 35 percent by weight of an alkali metal or ammonium fluorosilicate. 7. The method according to claim 1, characterized in that to adjust the pH from 3 to 5, an organic acid, preferably formic or acetic acid, and optionally additionally an ammonium or alkali metal salt other than ammonium or alkali metal fluorosilicate, in particular alkali metal sulfate, preferably sodium sulfate used. 8. The method according to any one of claims 1 to 7, characterized in that dyeing at a pH of 3.5 to 4.5, in particular 3.7 to 4.2. 9. The method according to claim 1, characterized in that dyeing in the presence of a leveling aid or a mixture of leveling aids. 10. The method according to claim 9, characterized in that one uses 0.3 to 3 percent by weight, preferably 1 to 2 percent by weight, based on the fiber material, the leveling aid or the leveling aid mixture. 11. The method according to claim 2, characterized in that dye mixtures are used which contain at least one 1: 1 chromium complex azo or azomethine dye with 1 to 3 sulfonic acid groups, preferably 1 to 2 sulfonic acid groups, and at least one metal-free dye with 1 to 2 Contain sulfonic acid groups. 12. The method according to claim 11 for trichromatic dyeing, characterized in that a mixture of at least three 1: 1 chromium complex azo or azomethine dyes from yellow or orange, red and blue coloring dyes and at least one metal-free dye made of yellow or orange and / or red and / or blue coloring dyes. 13. The method according to any one of claims 1 to 12, characterized in that as 1: 1 chromium complex azo or azomethine dyes those of the formula

used, in which - (CO) _0-1 -O- and (O or NR₁) in the vicinity of the azo bridge are bound to D or K, D an optionally by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, nitro or sulfamoyl substituted benzene or naphthalene radical, K is a phenyl, naphthyl, 1-phenyl-3-methylpyrazolone optionally substituted by halogen, C₁-C₄-alkyl, C₁-C Alk-alkoxy, C₂-C₄-alkanoylamino, sulfamoyl or hydroxy (5) -, Acetoacetamide or quinoline and R₁ is hydrogen, M is an alkali metalation and An is an anion, and Y represents the nitrogen atom or the CH group. 14. The method according to claim 1, characterized in that one uses mixtures or sulfo-containing 1: 1 metal complex azo dyes and sulfo-containing metal-free dyes in a weight ratio of 40:60 to 95: 5. 15. The method according to claim 11, characterized in that the metal-free sulfo-containing dyes are those of the monoazo, polyazo, anthraquinone, xanthene or triphenylmethane series. 16. The method according to claim 1, characterized in that synthetic polyamide materials, silk or in particular wool are used as the fiber material. 17. The method according to claim 16, characterized in that wool is used as the fiber material. 18. Mixture comprising at least one 1: 1 metal complex dye containing sulfo groups, in particular a 1: 1 chromium complex dye, at least one metal-free dye containing sulfo groups and 10 to 45 percent by weight of an alkali metal or ammonium fluorosilicate based on the weight of the 1: 1 metal complex dye. 19. Mixture containing at least one 1: 1 metal complex dye containing sulfo groups, in particular a 1: 1 chromium complex dye, and 10 to 45 percent by weight of an alkali metal or ammonium fluorosilicate based on the weight of the 1: 1 metal complex dye. 20. Mixture containing a compound of the formula

wherein R is an alkyl or alkenyl radical having 12 to 22 carbon atoms, M is hydrogen, alkali metal or ammonium and m and n are integers, the sum of m and n being 2 to 14, or the

wherein Rʹ independently of R has the meaning given for R, A is an anion, Q is an optionally substituted alkyl radical and p and q are integers, the sum of p and q being 2 to 50, or the formula

wherein Rʺ independently of R has the meaning given for R and x and y are integers, the sum of x and y being 80 to 140, a mixture containing compounds of the formula (1) and (2) or a mixture containing compounds of Formulas (1), (2) and (3) or (1a), (2) and (3) and 5 to 25 percent by weight (NH₄) ₂SiF₆ based on the weight of the compounds of the formulas (1), (1a), ( 2) or (3) or a mixture thereof.