EP0555182A1 - Process for dyeing of natural or synthetic polyamide fibers - Google Patents

Abstract

Process for dyeing textile materials made of natural and synthetic polyamide fibres, in which dyeing is carried out for a short and thus fibre-sparing dyeing time at the boiling point of the dyeing bath and even dyeings having good fastnesses are obtained (high-temperature rapid dyeing process). The dyeing process is carried out using dyeing baths which contain special surfactants. A high degree of exhaustion of the dyeing liquors is achieved and dyeing from standing baths is thus made possible.

Description

The present invention relates to a process for dyeing textile materials made of natural and synthetic polyamide fibers, dyeing being carried out for a short and therefore gentle dyeing time at the boiling temperature of the dye bath and leveling dyeings with good fastness properties (high-temperature rapid dyeing process).

Usual dyeing processes for the textile materials mentioned require dyeing times which are, for example, in the range from 30 to 90 minutes. It is known that wool fibers in particular can be damaged during such long dyeing times, which leads to a loss of quality in the dyed material. In addition, the degree of exhaustion of the dye liquors is not complete.

The object of the present invention is therefore to provide a dyeing process for dyeing textile materials made of natural and synthetic polyamide fibers which does not have the disadvantages of the known dyeing processes.

It has now been found that the problem can be solved surprisingly well by using special aids in the dye baths.

• (a) die Textilmaterialien in wässrige Färbebäder, die neben dem Farbstoff mindestens ein Tensid sowie gegebenenfalls weitere Hilfsmittel und Säuren enthalten, einbringt und diese Färbebäder auf Kochtemperatur aufheizt,
• (b) das Textilmaterial kurzzeitig bei dieser Temperatur färbt,
• (c) die an Farbstoff erschöpften Bäder auf Temperaturen von 50 bis 90°C abkühlt und
• (d) das gefärbte Textilmaterial dann aus den Färbebädern entfernt und fertigstellt.

The present invention therefore relates to a process for dyeing textile materials made from natural or synthetic polyamide fibers in aqueous dye baths which contain at least one surfactant, in particular from the group consisting of alcohol-polyalkylene glycol ethers or alcohol-polyalkylene glycol ethers blocked with end groups, and optionally further auxiliaries , that he

• (a) introducing the textile materials into aqueous dyebaths which, in addition to the dye, contain at least one surfactant and, if appropriate, other auxiliaries and acids and which heat these dyebaths to boiling temperature,
• (b) briefly dyes the textile material at this temperature,
• (c) cooling the dye-depleted baths to temperatures of 50 to 90 ° C and
• (d) the dyed textile material is then removed from the dyebaths and finished.

worin

• R ein aliphatischer Rest von 4 bis 24 Kohlenstoffatomen,
  
  
• ist, worin Z eine direkte Bindung oder (R₁- O)_r und r eine Zahl von 1 bis 80 ist,
• R₁ Alkylen mit 2 bis 4 Kohlenstoffatomen,
• WWasserstoff, C₁-C₄Alkyl gegebenenfalls substituiert mit einem oder mehreren Substituenten aus der Gruppe Carboxy, Hydroxy, Isocyanato, Phenyl, Benzyloxymethylen und Phenethyloxymethylen; Carboxy oder ein Rest - CONH - R₂ ist, worin R₂Alkyl mit 1 bis 8 Kohlenstoffatomen ist, wobei wenn U ein quaternäres Stickstoffatom enthält, W Sulfat, CH₃SO₄ oder ein Halogenanion, vorzugsweise Cl- ist und
• m eine Zahl von 1 bis 80 ist und
• (R₁-O)m für m gleiche oder verschiedene Reste (R₁-O) steht,
• oder (11) der allaemeinen Formel
  
  worin
• R ein aliphatischer Rest mit 4 bis 24 Kohlenstoffatomen;
• U₁ eine direkte Bindung oder ein Rest CO - NH - (CH₂)_1-3 ;
• R₃₀, R₃₁ und R₃₂ voneinander unabhängig C₁-C₄Alkyl das gegebenenfalls mit Hydroxy substituiert ist und P COO oder SO₃ ist,
• oder (III) der allgemeinen Formel
  
• worin R, U₁, R₃₀, R₃₂ die für die Formel (2) angegebene Bedeutung haben und P_i COOM oder SO₃M ist, wobei M Wasserstoff, Alkalimetal oder Ammonium bedeutet,
• oder (IV) der allgemeinen Formel
  
  worin
• R ein aliphatischer Rest mit 4 bis 24 Kohlenstoffatomen, R₁ Alkylen mit 2 bis 4 Kohlenstoffatomen,
• die Summe k + k' = 4, wobei k = 1, 2 oder 3 und
• m eine Zahl von 1 bis 80 ist,
• verwendet.

Components (I) of the general formula are advantageously used as suitable surfactants

wherein

• R is an aliphatic radical of 4 to 24 carbon atoms,
  
  
• where Z is a direct bond or (R ₁ - O) _r and r is a number from 1 to 80,
• R ₁ alkylene with 2 to 4 carbon atoms,
• W hydrogen, C ₁ -C ₄ alkyl optionally substituted with one or more substituents from the group consisting of carboxy, hydroxy, isocyanato, phenyl, benzyloxymethylene and phenethyloxymethylene; Carboxy or a radical - CONH - R ₂ , wherein R _{2 is} alkyl having 1 to 8 carbon atoms, where if U contains a quaternary nitrogen atom, W is sulfate, CH ₃ SO ₄ or a halogen anion, preferably Cl- and
• m is a number from 1 to 80 and
• (R ₁ -O) m represents m identical or different radicals (R ₁ -O),
• or (11) the general formula
  
  wherein
• R is an aliphatic radical having 4 to 24 carbon atoms;
• U _{1 is} a direct bond or a residue CO - NH - (CH ₂ ) _1-3 ;
• R ₃₀ , R ₃₁ and R ₃₂ independently of one another are C ₁ -C ₄ alkyl which is optionally substituted by hydroxy and P is COO or SO ₃ ,
• or (III) the general formula
  
• wherein R, U ₁ , R ₃₀ , R _{32 have} the meaning given for the formula (2) and P _{i is} COOM or SO ₃ M, where M is hydrogen, alkali metal or ammonium,
• or (IV) the general formula
  
  wherein
• R is an aliphatic radical with 4 to 24 carbon atoms, R ₁ alkylene with 2 to 4 carbon atoms,
• the sum k + k '= 4, where k = 1, 2 or 3 and
• m is a number from 1 to 80,
• used.

Further objects of the invention relate to dyeing aids for carrying out the method and the textile materials dyed according to the invention.

worin R ein aliphatischer Rest von 4 bis 24 Kohlenstoffatomen, insbesondere 6 bis 24 Kohlenstoffatomen, R₁ Alkylen mit 2 bis 4 Kohlenstoffatomen und m eine Zahl von 1 bis 80, vorzugsweise 2 bis 50 ist und (R₁-O)_m für m gleiche oder verschiedene Reste (R₁-0) steht.The compounds of component (I) are, in particular, fatty alcohol-polyalkylene glycol ethers of the formula

wherein R is an aliphatic residue of 4 to 24 carbon atoms, in particular 6 to 24 carbon atoms, R ₁ is alkylene having 2 to 4 carbon atoms and m is a number from 1 to 80, preferably 2 to 50, and (R ₁ -O) _{m are} identical for m or different radicals (R ₁ -0).

The substituent R advantageously represents the hydrocarbon radical of a saturated or unsaturated aliphatic monoalcohol with 4 to 24 carbon atoms. The hydrocarbon radical can be straight-chain or branched. R is preferably alkyl or alkenyl having 8 to 22 and in particular having 8 to 18 carbon atoms.

Natural alcohols such as, for example, hexyl alcohol, octyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol or behenyl alcohol, and synthetic alcohols, for example oxo alcohols such as, in particular, 2-ethylbutanol, 2-methyl-pentanol, 5-methyl-pentanol-5-methyl-5-methyl-3-methylpentanol, can be used as the aliphatically saturated alcohols. ol, 2-ethyl-hexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol, decanol, C ₉ -C ₁₁ oxo alcohol, tridecyl alcohol, isotridecanol or linear primary alcohols (alfoles) with 8 to 18 carbon atoms. Some representatives of Alfole are Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) or Alfol (16-18), ("Alfol" is a registered trademark).

Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol, hexadecenyl alcohol or oleyl alcohol.

The alcohol residues can be present individually or in the form of mixtures of two or more components, e.g. Mixtures of alkyl and / or alkenyl groups, e.g. derived from the corresponding fatty acids.

-OR ₁ O-is derived from 1,2- or 1,3-propylene glycol, 1,4-butylene glycol and preferably ethylene glycol. m is preferably a number from 2 to 50 and particularly preferably from 4 to 20.

The compounds of formula (1a) are known for example from EP-A-312493.

worin R ein aliphatischer Rest mit 4 bis 24 Kohlenstoffatomen, insbesondere 6 bis 24 Kohlenstoffatomen, R₁ Alkylen mit 2 bis 4 Kohlenstoffatomen, X₁ Wasserstoff oder Phenyl, X₂ Wasserstoff oder Phenyl, wobei X₁ und X₂ voneinander verschieden sind und m₁ eine Zahl von 2 bis 80, vorzugsweise von 4 bis 50 ist, oder um Verbindungen der Formel

worin R ein aliphatischer Rest mit 4 bis 24 Kohlenstoffatomen, insbesondere 6 bis 24 Kohlenstoffatomen, R₁ Alkylen mit 2 bis 4 Kohlenstoffatomen, einer der Reste Y₁ oder Y₂ Benzyloxymethylen oder Phenethyloxymethylen und der andere Wasserstoff, und m₁ eine Zahl von 2 bis 80, vorzugsweise von 4 bis 50 ist, oder um Verbindungen der Formel

worin R ein aliphatischer Rest mit 4 bis 24 Kohlenstoffatomen, insbesondere 6 bis 24 Kohlenstoffatomen, R₁ Alkylen mit 2 bis 4 Kohlenstoffatomen, R₂ Alkyl mit 1 bis 8 Kohlenstoffatomen, insbesondere 3 bis 5 und n eine Zahl von 2 bis 60, vorzugsweise von 4 bis 20 ist.The compounds of component (I) are furthermore in particular compounds of the formula

wherein R is an aliphatic radical having 4 to 24 carbon atoms, in particular 6 to 24 carbon atoms, R ₁ Alkylene with 2 to 4 carbon atoms, X _{1 is} hydrogen or phenyl, X _{2 is} hydrogen or phenyl, where X ₁ and X ₂ are different from one another and m _{1 is} a number from 2 to 80, preferably from 4 to 50, or compounds of the formula

wherein R is an aliphatic radical with 4 to 24 carbon atoms, in particular 6 to 24 carbon atoms, R ₁ alkylene with 2 to 4 carbon atoms, one of the radicals Y ₁ or Y ₂ benzyloxymethylene or phenethyloxymethylene and the other hydrogen, and m _{1 is} a number from 2 to 80, preferably from 4 to 50, or compounds of the formula

wherein R is an aliphatic radical with 4 to 24 carbon atoms, in particular 6 to 24 carbon atoms, R ₁ alkylene with 2 to 4 carbon atoms, R ₂ alkyl with 1 to 8 carbon atoms, in particular 3 to 5 and n is a number from 2 to 60, preferably from Is 4 to 20.

In the compounds of the formulas (1b) to (1d), the preferred meanings for R and -OR ₁ O- are the same as those given for the compounds of the formula (1a).

The compounds of the formulas (1b) and (1c) are known from EP-A-378048 and EP-A-406168.

Preferred compounds of the formula (1d) are, for example, the reaction products from the adducts of preferably 2 to 60 mol of alkylene oxides, in particular ethylene oxide, and higher unsaturated or saturated C ₈ -C ₁₈ fatty alcohols with C ₁ -C ₅ alkyl isocyanates.

worin

• R₃ Cg bis C₁₄-Alkyl,
• R₄ Wasserstoff oder ein Niederalkylisocyanatrest,
• einer der Reste Y₃ oder Y₄ Methyl und der andere Wasserstoff,
• m₂ eine ganze Zahl von 0 bis 8 und
• n₂ eine ganze Zahl von 4 bis 10 bedeuten.

The compounds of the formula are of very special interest

wherein

• R ₃ Cg to C ₁₄ alkyl,
• R _{4 is} hydrogen or a lower alkyl isocyanate radical,
• one of the radicals Y ₃ or Y _{4 is} methyl and the other is hydrogen,
• m _{2 is} an integer from 0 to 8 and
• n _{2 is} an integer from 4 to 10.

Of particular interest are the compounds of the formula (1e) in which R _{4 is} a lower alkyl isocyanate radical and m ₂ = 0.

Compounds in which the lower alkyl isocyanate radical is the n-butyl isocyanate or isopropyl isocyanate radical are very particularly preferred.

The lower alkyl isocyanate end-capped nonionic surfactants of the formula (1e) are prepared by reacting the alkyl polyalkylene glycol ethers with lower alkyl isocyanate using a catalyst or catalyst mixture.

worin R ein aliphatischer Rest mit 4 bis 24 Kohlenstoffatomen, R₁ Alkylen mit 2 bis 4 Kohlenstoffatomen, W₁ ein aliphatischer Rest mit 1 bis 6 Kohlenstoffatomen, n eine Zahl von 2 bis 60, vorzugsweise von 4 bis 20 ist und (R₁- O)_n für n gleiche oder verschiedene Reste (R₁- O) steht.Also of special interest are the compounds of the formula

wherein R is an aliphatic radical with 4 to 24 carbon atoms, R ₁ alkylene with 2 to 4 carbon atoms, W _{1 is} an aliphatic radical with 1 to 6 carbon atoms, n is a number from 2 to 60, preferably from 4 to 20 and (R ₁ - O) _{n represents} n identical or different radicals (R ₁ - O).

The compounds of component (I) are furthermore in particular compounds of the formula

wherein R is an aliphatic radical with 4 to 24 carbon atoms, R ₁ alkylene with 2 to 4 carbon atoms and n _{1 is} a number from 2 to 20.

Compounds of component (I) of the general formula are also preferred

in which R is an aliphatic radical with 4 to 24 carbon atoms, R ₁ alkylene with 2 to 4 carbon atoms, W _{2 is} hydrogen or the radical OC-R and n _{6 is} a number from 6 to 30.

In the compounds of the formulas (1e) to (1 h), the preferred meanings for R and -OR ₁ -O- are the same as those given for the compounds of the formula (1a).

worin R'ein aliphatischer Rest mit 8 bis 24 Kohlenstoffatomen, Z eine direkte Bindung oder (R₁-O)_r1 , R₁ Alkylen mit 2 bis 4 Kohlenstoffatomen, n₅ eine Zahl von 4 bis 20 und r₁ eine Zahl von 4 bis 20 ist.Compounds of component (I) of the general formula are also preferred

wherein R 'is an aliphatic radical having 8 to 24 carbon atoms, Z is a direct bond or (R ₁ -O) _r1, R ₁ is alkylene having 2 to 4 carbon atoms, n ₅ is a number from 4 to 20 and r ₁ is a number from 4 to 20 is.

worin R' ein aliphatischer Rest mit 8 bis 24 Kohlenstoffatomen, R₁ Alkylen mit 2 bis 4 Kohlenstoffatomen, m₃ eine Zahl von 1 bis 20, n₃ eine Zahl von 1 bis 20 und die Summe m₃ + n₃ 2 bis 21 ist.Compounds of component (I) of the general formula are also preferred

wherein R 'is an aliphatic radical having 8 to 24 carbon atoms, R ₁ alkylene having 2 to 4 carbon atoms, m _{3 is} a number from 1 to 20, n _{3 is} a number from 1 to 20 and the sum m ₃ + n ₃ 2 to 21 .

worin R' ein aliphatischer Rest mit 8 bis 24 Kohlenstoffatomen, R₁ Alkylen mit 2 bis 4 Kohlenstoffatomen, m₃ eine Zahl von 1 bis 20, n₃ eine Zahl von 1 bis 20 und die Summe m₃ + n₃ 2 bis 21 ist und X ein Anion aus der Gruppe Halogenide, Sulfate oder Alkylsulfate ist.Compounds of component (I) of the general formula are also preferred

wherein R 'is an aliphatic radical having 8 to 24 carbon atoms, R ₁ alkylene having 2 to 4 carbon atoms, m _{3 is} a number from 1 to 20, n _{3 is} a number from 1 to 20 and the sum m ₃ + n ₃ 2 to 21 and X is an anion from the group consisting of halides, sulfates or alkyl sulfates.

worin R' ein aliphatischer Rest mit 8 bis 24 Kohlenstoffatomen, R₁ Alkylen mit 2 bis 4 Kohlenstoffatomen, m₃ eine Zahl von 1 bis 20, n₃ eine Zahl von 1 bis 20, p₁ eine Zahl von 1 bis 20 und die Summe m₃ + n₃ + p₁ 3 bis 22 und t eine Zahl von 2 bis 4 ist.Compounds of component (I) of the general formula are also preferred

wherein R 'is an aliphatic radical with 8 to 24 carbon atoms, R ₁ alkylene with 2 to 4 carbon atoms, m ₃ a number from 1 to 20, n ₃ a number from 1 to 20, p ₁ a number from 1 to 20 and the sum m ₃ + n ₃ + p ₁ 3 to 22 and t is a number from 2 to 4.

In the compounds of the formulas (1 i) to (11), the preferred meanings for R 'and -OR ₁ -O- are the same as those given for R and -OR ₁ -O- in the formula (1a).

The dyeing process according to the invention is carried out in dye baths which, in addition to at least one of components (I) to (IV) and the dye, optionally contain other conventional auxiliaries, such as, for example, leveling agents, defoamers, further wetting agents, solvents and / or emulsifiers; also contain inorganic salts, especially ammonium or alkali metal salts, such as ammonium sulfate, ammonium or sodium acetate or preferably sodium sulfate. Preferably 0.1 to 10 wt .-% ammonium or alkali sulfate, based on the fiber material is used. Suitable acids that are used in the dye baths are, for example, mineral acids, such as sulfuric or phosphoric acid, and also organic acids moderately low molecular weight organic acids, especially aliphatic carboxylic acids, such as formic, acetic or oxalic acid. The acids are used primarily to adjust the pH of the dyebaths, which is generally in the range from 4 to 6.5, with a pH of about 4.2 to 4.7 for wool dyeing and for dyeing polyamide fibers that of 5 to 6.5, in particular 5.5 to 6.0, is suitable.

worin R₅ einen Alkyl- oder Alkenylrest mit 12 bis 22 Kohlenstoffatomen, M Wasserstoff, Alkalimetall oder Ammonium, L₁ Wasserstoff oder ein Rest SO₃M und m₄ und n₄ ganze Zahlen bedeuten, wobei die Summe von m₄ und n₄ 2 bis 14 ist, einer quaternären Verbindung der Formel

worin R" unabhängig von R₅ die für R₅ angegebene Bedeutung hat, A ein Anion, Q einen gegebenenfalls substituierten Alkylrest und p und q ganze Zahlen bedeuten, wobei die Summe von p und q 20 bis 50 ist, und einer nichtionogenen Verbindung der Formel

worin R" unabhängig von R₅ die für R₅ angegebene Bedeutung hat und x und y ganze Zahlen bedeuten, wobei die Summe von x und y 80 bis 140 ist, besonders bevorzugt sind. Dieses Egalisiermittel ist z.B. aus der EP-A-89004 bekannt.In the dye baths used according to the invention, leveling agents, for example compounds based on fatty amines as specified in the following formulas (6) to (8), are usually also used, mixtures of an anionic compound of the formula

wherein R _{5 is} an alkyl or alkenyl radical having 12 to 22 carbon atoms, M is hydrogen, alkali metal or ammonium, L _{1 is} hydrogen or a radical SO ₃ M and m ₄ and n _{4 are} integers, the sum of m ₄ and n ₄ 2 to 14, a quaternary compound of the formula

wherein R "independently of R _{5 has} the meaning given for R ₅ , A is an anion, Q is an optionally substituted alkyl radical and p and q are integers, the sum of p and q being 20 to 50, and a nonionic compound of the formula

in which R ", independently of R _{5, has} the meaning given for R ₅ and x and y are integers, the sum of x and y being 80 to 140, are particularly preferred. This leveling agent is known, for example, from EP-A-89004 .

The said leveling agent mixture can be combined with at least one of components (I) to (IV), i.e. are mixed with at least one of the compounds of the formulas (1a) to (1d) and then forms a dyeing aid which is suitable for the dyeing process according to the invention and which is a further subject of the present invention.

These dyeing auxiliaries according to the invention thus preferably consist of the mixture of the compounds of the formulas (6), (7) and (8) (hereinafter referred to as M ₁ ) combined with at least one compound, preferably two compounds of the formulas (1a) to (1d) (hereinafter Called M ₂ ).

In the mixture M ₁ , the proportions of the individual components can be about 5 to 70 parts of the compound of the formula (6), 15 to 60 parts of the compound of the formula (7) and 5 to 60 parts of the compound of the formula (8), based on 100 Parts M ₁ amount.

If two compounds are used in M ₂ , the weight ratios are in the range from 20:80 to 80:20. M ₂ preferably contains the compounds of the formulas (1a) and (1b), (1a) and (1c) or (1a) and (1d).

The dyeing auxiliary mixture of M ₁ and M _Z according to the invention contains these two components in a weight ratio of (0.1-1): 1. These mixtures are in the form of aqueous or aqueous-organic preparations, in particular solutions (suitable solvents are, for example, glycols and glycol ethers, such as butyltriglycol) with an active substance content of 25 to 70 percent by weight.

The amounts used of these aqueous or aqueous / organic preparations are in the range from 0.3 to 3 percent by weight, preferably 0.5 to 2 percent by weight, based on the fiber material to be dyed.

The anionic dyes that can be used can belong to the most diverse classes of dyes and can optionally contain one or more sulfonic acid groups and, if appropriate, one or more fiber-reactive groups. In particular, these are triphenylmethane dyes with at least two sulfonic acid groups, heavy metal-free monoazo and disazo dyes each with one or more sulfonic acid groups and optionally one or more fiber-reactive groups and heavy metal-containing monoazo, disazo, azomethine, especially those containing copper, chromium, nickel or cobalt and formazan dyes, in particular metallized dyes, which contain two molecules of azo dye or one molecule of azo dye and one molecule of azomethine dye bonded to a metal atom, especially those containing mono- and / or disazo dyes and / or azomethine dyes as ligands and a chromium as the central metal ion. or cobalt ion, as well as anthraquinone dyes, in particular 1-amino-4-alkylamino-anthraquinone-2-sulfonic acids or 1,4-diarylamino or 1-cycloalkylamino-4-arylaminoanthraquinone sulfonic acids. Fiber-reactive groups are understood to be those groups which form a covalent bond with the polyamide material to be colored.

Dyes which contain one or more fiber-reactive groups are preferably used in the process according to the invention in combination with non-fiber-reactive dyes.

The amounts in which the dyes are used in the dyebaths can vary within wide limits depending on the desired depth of color. In general, amounts of 0.001 to 10 percent by weight, based on the material to be dyed, of one or more dyes have proven to be advantageous.

• (a) Triphenylmethanfarbstoffe mit mindestens zwei Sulfonsäuregruppen der Formel
  
  worin R₁' und R₂' unabhängig voneinander C_1-4-Alkyl,
  • R₃' und R₄' unabhängig voneinander Wasserstoff oder C_1-4-Alkyl und R₅'C_1-4-Alkyl, C_1-4-Alkoxy oder Wasserstoff ist;
• (b) Mono- und Disazofarbstoffe der Formeln
  
  
  worin R₆ eine über die -NH-Gruppe gebundene faserreaktive Gruppe, Benzoylamino, Phenoxy, Chlorphenoxy oder Methylphenoxy,
  • R₇ Wasserstoff, Benzoyl, Dichlorphenoxy, Phenyl, C_1-4-Alkyl, Phenylsulfonyl, Methylphenylsulfonyl oder eine gegebenenfalls über Aminobenzoyl gebundene faserreaktive Gruppe und die Substituenten R₈ unabhängig voneinander Wasserstoff oder einen Phenylamino- oder N-Phenyl-N-methyl-amino-sulfonylrest, a = 0 oder 1 und b = 0, 1 oder 2 bedeuten;
    
  
  worin Rg eine faserreaktive Gruppe ist und der Phenylring B durch Halogen, C_1-4-Alkyl und Sulfo substituiert sein kann;
  
  
  worin R₆ die unter Formel (10) angegebene Bedeutung hat;
  
  
  worin c = 0 oder 1 ist;
  
• (c) 1:2-Metallkomplexfarbstoffe, wie die 1:2-Chromkomplexfarbstoffe der Azo- und Azomethinfarbstoffe der Formel
  
  worin R₁₀ Wasserstoff, Sulfo oder Phenylazo und R₁₁ Wasserstoff oder Nitro ist, und der Phenylring B die unter Formel (11) angegebenen Substituenten enthalten kann;
• (d) 1:2-Metallkomplexfarbstoffe, wie die symmetrischen 1:2-Chromkomplexfarbstoffe der Azofarbstoffe der Formeln
  
  worin der Phenylring B die unter Formel (11) angegebenen Substituenten enthalten kann und R₁₂ und R₁₃ unabhängig voneinander Wasserstoff, Nitro, Sulfo, Halogen, C_1-4-Alkylsulfonyl, C_1-4-Alkylaminosulfonyl und -SO₂NH₂ bedeuten und d = 0 oder 1 ist;
  
  worin R₁₄ Wasserstoff, C_1-4-Alkoxy-carbonylamino, Benzoylamino, C_1-4-Alkylsulfonylamino, Phenylsulfonylamino, Methylphenylsulfonylamino oder Halogen, R₁₅ Wasserstoff oder Halogen und R₁₆ C_1-4-Alkylsulfonyl, C_1-4-Alkylaminosulfonyl, Phenylazo, Sulfo oder -SO₂N₂ ist, wobei die Hydroxygruppe im Benzring D in o-Stellung zur Azobrücke an den Benzring D gebunden ist, und der Benzring E einen in 5- und 6-Stellung ankondensierten Nitrobenzolring enthalten kann; die symmetrischen 1:2-Kobaltkomplexe der Azofarbstoffe der Formeln
  
  worin R₁₇ die -OH oder NH₂ Gruppe, R₁₈ Wasserstoff oder C_1-4-Akylaminosulfonyl und R₁₉ Nitro oder C_1-4-Alkoxy-C_1-4-alkylenaminosulfonyl ist;
  
  worin G -COOH oder -SO₃H bedeutet; die unsymmetrischen 1:2-Metallkomplexfarbstoffe, wie die 1:2-Chromkomplexfarbstoffe derAzofarbstoffe der Formeln
  
  worin ein Substituent R₂₀ Wasserstoff und der andere Sulfo ist;
  
  worin R₁₁ die unter Formel (14) und R₁₅ die unter Formel (16) angegebene Bedeutung haben und die Phenylringe B unabhänig voneinander, die unter Formel (11) angegebenen Substituenten enthalten können, und der Phenylring Leinen in 2- und 3-Stellung ankondensierten Benzolring oder anstelle der Sulfogruppe einen in 2- und 3-Stellung ankondensierten Sulfobenzolring enthalten kann;
  
  
  worin der Phenylring B in den Formeln (21), (22) und (24) die unter Formel (11) angegebenen Substituenten enthalten kann, R₁₁ die unter Formel (19) angegebene Bedeutung hat, R₂₁ Wasserstoff, Methoxycarbonylamino oder Acetylamino ist und R₁₆ die unter Formel (16) angegebenen Bedeutung hat; 1:2-Chromkomplexfarbstoffe der Azofarbstoffe der Formeln (15) und (16); 1:2-Chrom-Mischkomplexe der Azofarbstoffe der Formeln (15) und (16); (e) Anthrachinonfarbstoffe der Formeln
  
  worin T Wasserstoff oder C_1-4-Alkyl, e = 0 oder 1 ist, und R₉ die unter Formel (11) angegebene Bedeutung hat, R₂₂ unabhängig voneinander Wasserstoff oder C_1-4-Alkyl und R₂₃ Wasserstoff oder Sulfo bedeutet;
  
  worin die Substituenten R₂₄ unabhängig voneinander Cyclohexyl und den Diphenylätherrest, der durch Sulfo und den Rest -CH₂NH-Rg substituiert sein kann, bedeuten, wobei Rg die unter Formel (11) angegebene Bedeutung hat; und
  
  worin Rg die unter Formel (11) und R₂₂ die unter Formel (25) angegebenen Bedeutungen haben und R₂₅ C_4-8-Alkyl ist.

Particularly suitable anionic dyes are those of the following classes of dyes:

• (a) Triphenylmethane dyes with at least two sulfonic acid groups of the formula
  
  wherein R ₁ 'and R ₂ ' independently of one another are C _1-4 alkyl,
  • R ₃ 'and R ₄ ' are independently hydrogen or C _1-4 alkyl and R ₅ 'is C _1-4 alkyl, C _1-4 alkoxy or hydrogen;
• (b) Mono- and disazo dyes of the formulas
  
  
  wherein R _{6 is} a fiber-reactive group bonded via the -NH group, benzoylamino, phenoxy, chlorophenoxy or methylphenoxy,
  • R _{7 is} hydrogen, benzoyl, dichlorophenoxy, phenyl, C _1-4 alkyl, phenylsulfonyl, methylphenylsulfonyl or a fiber-reactive group which may be bonded via aminobenzoyl and the substituents R _{8 are} independently hydrogen or a phenylamino or N-phenyl-N-methylamino -sulfonyl radical, a = 0 or 1 and b = 0, 1 or 2;
    
  
  wherein Rg is a fiber reactive group and the phenyl ring B can be substituted by halogen, C _1-4 alkyl and sulfo;
  
  
  wherein R _{6 has} the meaning given under formula (10);
  
  
  wherein c = 0 or 1;
  
• (c) 1: 2 metal complex dyes, such as the 1: 2 chromium complex dyes of the azo and azomethine dyes of the formula
  
  wherein R _{10 is} hydrogen, sulfo or phenylazo and R _{11 is} hydrogen or nitro, and the phenyl ring B may contain the substituents indicated under formula (11);
• (d) 1: 2 metal complex dyes, such as the symmetrical 1: 2 chromium complex dyes of the azo dyes of the formulas
  
  wherein the phenyl ring B may contain the substituents indicated under formula (11) and R ₁₂ and R ₁₃ independently of one another are hydrogen, nitro, sulfo, halogen, C _1-4 -alkylsulfonyl, C _1-4 -alkylaminosulfonyl and -SO ₂ NH ₂ and d = 0 or 1;
  
  wherein R _{14 is} hydrogen, C _1-4 alkoxycarbonylamino, benzoylamino, C _1-4 alkylsulfonylamino, phenylsulfonylamino, methylphenylsulfonylamino or halogen, R _{15 is} hydrogen or halogen and R ₁₆ C _1-4 alkylsulfonyl, C _1-4 alkylaminosulfonyl , Phenylazo, sulfo or -SO ₂ N ₂ , the hydroxyl group in the benzo ring D being bonded to the benzo ring D in the o position to the azo bridge, and the benzo ring E can contain a nitrobenzene ring fused in the 5- and 6-position; the symmetrical 1: 2 cobalt complexes of the azo dyes of the formulas
  
  wherein R _{17 is} the -OH or NH ₂ group, R _{18 is} hydrogen or C _1-4 alkylamino sulfonyl and R _{19 is} nitro or C _1-4 alkoxy-C _1-4 alkylene aminosulfonyl;
  
  wherein G represents -COOH or -SO ₃ H; the asymmetrical 1: 2 metal complex dyes, such as the 1: 2 chromium complex dyes of the azo dyes of the formulas
  
  wherein one substituent R _{20 is} hydrogen and the other is sulfo;
  
  in which R _{11 has} the meaning given under formula (14) and R _{15 has} the meaning given under formula (16) and the phenyl rings B independently of one another which may contain substituents given under formula (11), and the phenyl ring can contain linen in the 2- and 3-position fused benzene ring or instead of the sulfo group a sulfobenzene ring fused in the 2- and 3-position;
  
  
  wherein the phenyl ring B in the formulas (21), (22) and (24) may contain the substituents indicated under formula (11), R _{11 has} the meaning given under formula (19), R _{21 is} hydrogen, methoxycarbonylamino or acetylamino and R _{16 has} the meaning given under formula (16); 1: 2 chromium complex dyes of the azo dyes of the formulas (15) and (16); 1: 2 chromium mixed complexes of the azo dyes of the formulas (15) and (16); (e) Anthraquinone dyes of the formulas
  
  wherein T is hydrogen or C _1-4 alkyl, e = 0 or 1, and R _{9 has} the meaning given under formula (11), R _{22 is} independently hydrogen or C _1-4 alkyl and R _{23 is} hydrogen or sulfo ;
  
  wherein the substituents R ₂₄ independently of one another mean cyclohexyl and the diphenyl ether radical, which can be substituted by sulfo and the radical -CH ₂ NH-Rg, where Rg has the meaning given under formula (11); and
  
  where Rg has the meanings given under formula (11) and R _{22 has} the meanings given under formula (25) and R _{25 is} C _4-8 alkyl.

Suitable fiber reactive groups in the formulas given are, for example, those of the aliphatic series, such as acryloyl, mono-, di- or trichloro- or mono-, di- or tribromoacryloyl or -methacryloyl, such as -CO-CH = CH-CI, -CO-CCI = CH ₂ , -CO-CH = CHBr, -COCBr = CH ₂ , -CO-CBr = CHBr, -CO-CCI = CH-CH ₃ , also -CO-CCI = CH-COOH, -CO-CH = CCI -COOH, 4-chloropropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl, β-sulfatoethylaminosulfonyl, vinylsulfonyl, β-chloroethylsulfonyl, β-sulfatoethylsulfonyl, β-methylsulfonylethylsulfonyl, β-phenylsulfonyl 2-phenylsulfonyl -1-carbonyl, 2,2,3,3-tetrafluorocyclobutane-carbonyl-1 or sulfonyl-1, ß- (2,2,3,3-tetrafluorocyclobutyl-1) -acryloyl, a- or β-alkyl-or - Arylsulfonyl-acryloyl, such as a- or β-methylsulfonylacryloyl.

worin R₂₆ eine gegebenenfalls substituierte Aminogruppe oder eine gegebenenfalls verätherte Oxy- oder Thiogruppe bedeutet, wie z.B. die NH₂-Gruppe, eine mit C₁-C₄-Alkylresten mono- oderdisubstituierte Aminogruppe, eine C₁-C₄-Alkoxygruppe, eine C₁-C₄-Alkylmercaptogruppe, Arylamino, insbesondere Phenylamino, oder mit Methyl, Methoxy, Chlor und vor allem Sulfo substituiertes Phenylamino, Phenoxy, Mono- oder Disulfophenoxy etc., sowie die entsprechenden Chlortriazinylreste.Reactive residues particularly suitable for wool are: chloroacetyl, bromoacetyl, a, ß-dichloro- or a, ß-dibromo propionyl, a-chloro- or a-bromoacryloyl, 2,4-difluoro-5-chloropyrimidyl-6, 2,4,6-Tr! f! uoropyr! m! dy! -5, 2,4-dichloro-5- methylsulfonylpyrimidinyl-6, 2-fluoro-4-methyl-5-chloropyrimidyl-6, 2,4-difluoro-5-methylsulfonylpyrimidyl-6, 2,4-difluorotriazinyl-6, as well as fluotriazinyl residues of the formula

wherein R _{26 represents} an optionally substituted amino group or an optionally etherified oxy or thio group, such as the NH ₂ group, an amino group mono- or disubstituted with C ₁ -C ₄ alkyl radicals, a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl mercapto group, arylamino, especially phenylamino, or with methyl, methoxy, chlorine and especially sulfo substituted phenylamino, phenoxy, mono- or disulfophenoxy etc., and the corresponding chlorotriazinyl residues.

The sulfo-containing dyes used in the process according to the invention are 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.

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

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

The dyeing is carried out from an aqueous liquor by the exhaust process at temperatures which are in the cooking area of the liquor, i.e. between 95 and 105 ° C, in particular between 98 and 103 ° C. The dyeing time is usually 5 to 25, and in particular 10 to 20 minutes.

The liquor ratio can be selected within a wide range, e.g. from 1: 5 to 1:40, preferably from 1: 8 to 1:25.

The mixture of auxiliaries according to the invention is expediently admixed with the aqueous dye liquor and applied simultaneously with the dye. One can also proceed by first treating the material to be dyed with the auxiliary mixture and dyeing in the same bath after adding the dye. The fiber material is preferably added to a liquor which contains acid and the auxiliary mixture and has a temperature of 20 to 70 ° C., preferably 40 to 50 ° C. The dye or a dye mixture is then added and the temperature of the dyebath is increased at a rate of 1 to 4 ° C. per minute in order to dye in the stated temperature range from 95 to 105 ° C. for preferably 10 to 20 minutes. Finally, the bath is cooled to 70 to 90 ° C. and the dyed material is rinsed and dried as usual, preferably the dyed fiber material can also be dried (rinsed and) without rinsing.

Special devices are not required in the method according to the invention. The usual dyeing apparatus and machines can be used, for example for flake, sliver, strand yarn, wound packages, woven fabrics, knitted fabrics, piece goods and carpets.

The polyamide fiber materials that are dyed according to the invention are those made from natural polyamides, especially wool, but also mixtures of wool / polyamide, wool / polyester, wool / cellulose or wool / polyacrylonitrile, as well as silk and synthetic polyamides, such as polyamide 6 or 6.6 , into consideration. The fiber material can be in a wide variety of forms, e.g. as loose material, sliver, yarn, fabric, knitted fabric and piece goods or as carpet.

The dyeing process according to the invention results in textile materials made of natural or synthetic polyamide fibers that are dyed in a manner that is equal to fibers and flat. The main advantages of the process are the short (and therefore gentle on the fibers) dyeing time and the complete absorption of the dye on the fiber, i.e. the dye bath is completely pulled out (exhausted) and can be used for further dyeings after appropriate setting. This setting affects the required dye, auxiliary and salt content, as well as the pH value and the volume of the dyebath.

This reuse of dyeing liquors (dyeing from standing baths) is possible for dyeing with identical or different dyes from dye bath to dye bath, without any color shifts and losses in yield occurring in the subsequent dyeing.

Dyeing from standing baths (reuse of the already heated aqueous liquors) leads to considerable time and energy savings.

An alternative dyeing method to the method according to the invention is carried out at temperatures below the boiling temperature and requires somewhat longer dyeing times

• (a) die Textilmaterialien in wässrige Färbebäder, die neben dem Farbstoff mindestens eine der Komponenten (I) bis (IV) sowie gegebenenfalls weitere Hilfsmittel und Säuren enthalten, einbringt und diese Färbebäder auf Temperaturen von 75 bis 90°C aufheizt,
• (b) das Textilmaterial während 30 bis 90 Minuten bei diesen Temperaturen färbt,
• (c) die an Farbstoff erschöpften Färbebäder auf 50 bis 70°C abkühlt und das gefärbte Textilmaterial dann aus den Färbebädern entfernt und fertigstellt.

It is a process for dyeing textile materials made from natural or synthetic polyamide fibers in aqueous dye baths which contain at least one of components (I) to (IV) (see above) and, if appropriate, further auxiliaries, characterized in that

• (a) introducing the textile materials into aqueous dyebaths which, in addition to the dyestuff, contain at least one of components (I) to (IV) and, if appropriate, other auxiliaries and acids and which heat these dyebaths to from 75 to 90 ° C.,
• (b) dyeing the textile material at these temperatures for 30 to 90 minutes,
• (c) cooling the dye baths depleted of dye to 50 to 70 ° C and then removing the dyed textile material from the dye baths and finishing.

• (A) 51 g (ca. 0,1 Mol) des Anlagerungsproduktes aus 1 Mol Decylalkohol und 8 Mol Ethylenoxid werden in 25 ml trockenem Tetrahydrofuran gelöst und mit 8,9 g (0,105 Mol) Isopropylisocyanat versetzt. Nach Zugabe eines Katalysatorgemisches aus jeweils 100 µl Dibutylzinnlaurat und Triethylamin wird im Inertgasstrom unter Rühren auf 60° erwärmt. Nach 90 Minuten wird die Umsetzung beendet, indem der Ansatz in 100 ml Petrolether gegossen und das fast farblos ausfallende Produkt abgetrennt wird. Nach Trocknung bei einerTemperaturvon 50° im Vakuum wird das leicht ölige Produkt in einerAusbeute von 56,8 g erhalten.
• (B) 153 g (ca. 0,3 Mol) des Anlagerungsproduktes aus 1 Mol Decylalkohol und 8 Mol Ethylenoxid werden ohne Lösungsmittel unter Schutzgas vorgelegt und hierzu 30,9 g (0,105 Mol) n-Butylisocyanat unter Rühren zugetropft. Nach Zugabe eines Kataysatorgemisches aus je 100 µl Dibutylzinnlaurat und Triethylamin tritt zunächst eine leichte Erwärmung des Reaktionsgemisches auf etwa 40° auf. Bei einer Innentemperatur von 60° ist die Umsetzung nach 60 Minuten vollständig abgeschlossen. Schliesslich wird in 100 ml Petrolether (40-80) eingegossen. Nach Trocknen des ausgefallenen, isolierten flüssigen Produktes im Vakuum bei 50° wird eine Ausbeute von 167 g erzielt.

Production instructions (compounds of the formula (1d)):

• (A) 51 g (approx. 0.1 mol) of the adduct of 1 mol of decyl alcohol and 8 mol of ethylene oxide are dissolved in 25 ml of dry tetrahydrofuran, and 8.9 g (0.105 mol) of isopropyl isocyanate are added. After adding a catalyst mixture of 100 ul dibutyltin laurate and triethylamine, the mixture is heated to 60 ° in the inert gas stream with stirring. After 90 minutes, the reaction is ended by pouring the mixture into 100 ml of petroleum ether and separating off the almost colorless product. After drying at a temperature of 50 ° in vacuo, the slightly oily product is obtained in a yield of 56.8 g.
• (B) 153 g (approx. 0.3 mol) of the adduct of 1 mol of decyl alcohol and 8 mol of ethylene oxide are initially introduced under a protective gas without solvent, and 30.9 g (0.105 mol) of n-butyl isocyanate are added dropwise with stirring. After adding a catalyst mixture of 100 μl dibutyltin laurate and triethylamine, the reaction mixture is warmed slightly to about 40 °. At an internal temperature of 60 °, the reaction is complete after 60 minutes. Finally it is poured into 100 ml of petroleum ether (40-80). After drying the precipitated, isolated liquid product in vacuo at 50 °, a yield of 167 g is achieved.

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 centimeters.

The auxiliaries used in the examples below have the following compositions: A-1: Cg-C ₁ , -alkyl-0- (CH ₂ CH ₂ 0) ₄ -H

A-2: mixture of

• - 35 parts of C ₉ -C ₁₁ alkyl-O- (CH ₂ CH ₂ O) ₈ -CONH (CH ₂ ) ₃ CH ₃
• - 10 parts of a mixture of 12.6 parts of the anionic compound of the formula
  
  (R ₂₇ = hydrocarbon residue of tallow fatty amine, m + n = 8); 21.3 parts of the quaternary compound of the formula
  
  (R ₂₈ ⁼ C _20-22 hydrocarbon residue); 7.7 parts of the reaction product of oleyl alcohol with 80 moles of ethylene oxide; 7.0 parts of the compound of the formula
  
  and 51.4 parts water,
  • - 20 parts of butyl triglycol
  • - 35 parts of water
  • A-3: C ₁₀ alkyl-O- (CH ₂ CH ₂ O) ₈ -CONHCH (CH ₃ ) ₂ A-4: C ₁₀ alkyl-O- (CH ₂ CH ₂ O) ₈ -CONH (CH ₂ ) ₃ CH ₃ A-5:
    
    A-6:
    
  • A-7: C ₁₂ -C ₁₄ alkyl-O- (CH ₂ CH ₂ O) _2.5 CH ₂ -COOH
  • A-8 C ₁₆ -C ₁₈ alkyl-O- (CH ₂ CH ₂ O) ₉ CH ₂ -COOH
  • A-9:
    
  • A-10:
    
  • A-11:
    
  • A-12:
    
  • A-13: R ₃₄ -CONH- (CH ₂ ) ₃ -N + (CH ₃ ) ₂ -CH ₂ -COO- (R ₃₄ = hydrocarbon residue of coconut fatty amine)
  • A-14: R ₃₄ -CONH- (CH ₂ ) ₃ -N + (CH ₃ ) ₂ -CH ₂ CHOHCH ₂ -SO ₃ (R ₃₄ = hydrocarbon residue of the coconut fatty amine)
  • A-15: R ₂₇ -N + (CH ₂ CH ₂ OH) ₂ -CH ₂ -COO- (R ₂₇ = hydrocarbon residue of the tallow fatty amine)
  • A-16: R ₃₄ -N + (CH ₃ ) (CH ₂ CH ₂ O) fH (CH ₂ CH ₂ O) ₉ H / Cl- (R ₃₄ = hydrocarbon residue of coconut fatty amine, f + g = 15)
  • A-17:
    
  • (R ₃₄ = hydrocarbon residue of coconut fatty amine)
  • A-18:
    
  • (R ₂₇ = hydrocarbon residue of tallow fatty amine)
  • A-19:
    
  • (a + b + c = 4)
  • A-20:
    
  • A-21:
    
  • (R ₃₄ = hydrocarbon residue of coconut fatty amine)
  • A-22: C ₉ -C ₁₁ alkyl-O- (CH ₂ CH ₂ O) ₄ - (CH (CH ₃ ) CH ₂ O) ₂ -H A-23:
    
  • A-24: Mixture of
    • - 34 parts of C ₉ -C ₁₁ alkyl-O- (CH ₂ CH ₂ O) ₄ -H and C ₉ -C ₁₁ -alkyl-O- (CH ₂ CH ₂ O) ₄ -H reacted with styrene oxide (weight ratio: 2: 1)
    • - 10 parts of a mixture of 12.6 parts of the anionic compound of the formula
      
  • (R ₂₇ = hydrocarbon residue of tallow fatty amine, m + n = 8);
  • 21.3 parts of the quaternary compound of the formula
    
  • (R ₂₈ ⁼ C _2o - ₂₂ hydrocarbon residue);
  • 7.7 parts of the reaction product of oleyl alcohol with 80 moles of ethylene oxide;
  • 7.0 parts of the compound of the formula
    
  • and 51.4 parts water,
    • - 20 parts of butyl triglycol
    • - 36 parts of water
  • A-25: Mixture of
    • - 35 parts
      
      (R ₃₄ = hydrocarbon residue of coconut fatty amine)
    • - 10 parts
      
      (R ₂₇ = hydrocarbon residue of tallow fatty amine, m + n = 8);
    • - 5 parts of the compound of the formula
      
    • - 3 parts C ₁₈ H ₃₅ -O- (CH ₂ CH ₂ O) ₈₀ -H
    • - 25 parts of butyl triglycol
    • - 22 parts of water
  • A-26: Mixture of
    • - 34 parts of C ₁₃ alkyl-O (CH ₂ CH ₂ 0) ₅ H
    • - 10 parts of a mixture of 12.6 parts of the anionic compound of the formula
      
  • (R ₂₇ = hydrocarbon residue of tallow fatty amine, m + n = 8);
  • 21.3 parts of the quaternary compound of the formula
    
  • (R ₂₈ ⁼ C _2o - ₂₂ hydrocarbon residue);
  • 7.7 parts of the reaction product of oleyl alcohol with 80 moles of ethylene oxide; 7.0 parts of the compound of the formula
    
  • and 51.4 parts water,
    • - 20 parts of butyl triglycol
    • - 36 parts of water

Example 1: 15 g of wool serge are pre-wetted in a laboratory dyeing machine for 10 minutes at 40 ° C. using the following liquor:

• 0.1 g of a wetting agent (alkylphenyl ethoxylate)
• 75 mg auxiliary A-1
• 0.1 g formic acid (85%)
• 165 ml water

und 41 mg des 1:2-Chromkomplexes des Azofarbstoffs der Formel

die in 10 ml Wasser gelöst ist, in die Flotte gegeben. Nach weiteren 5 Minuten bei 40°C wird die Flotte mit einer Geschwindigkeit von 1 °C/M inute auf Kochtemperatur aufgeheizt und 10 Minuten bei dieser Temperatur gefärbt. Die Flotte ist dann praktisch wasserklar ausgezogen. Nach dem Abkühlen der Flotte auf 70°C wird das gefärbte Wollmaterial aus dem Färbeapparat entnommen und dann wie üblich, z.B. durch Spülen und Trocknen fertiggestellt. Wegen des guten Badeauszugs kann der Spülprozess erheblich verkürzt werden.After this lead time, the pH of the liquor is checked and, if necessary, adjusted to a value of 4.5 by adding further formic acid. It then becomes a mixture of 184 mg of the 1: 2 chromium complex of the azo dyes of the formulas

and 41 mg of the 1: 2 chromium complex of the azo dye of the formula

which is dissolved in 10 ml of water, added to the liquor. After a further 5 minutes at 40 ° C, the liquor is heated to boiling temperature at a rate of 1 ° C / minute and dyed at this temperature for 10 minutes. The fleet is then practically water-clear. After the liquor has cooled to 70 ° C., the dyed wool material is removed from the dyeing machine and then finished as usual, for example by rinsing and drying. Because of the good bath pull-out, the rinsing process can be shortened considerably.

You get a level red color with good fastness properties and a very good color depth.

Instead of auxiliary A-1, the same amount of auxiliary A-7 to A-23 can also be used.

• 120 g eines Netzmittels (Alkylphenylethoxilat)
• 600 g des Hilfsmittels A-2
• 400 g Ameisensäure (85 %)
• 500 I Wasser

Example 2: 40 kg of wool sliver are pre-wetted in a sliver dyeing machine for 10 minutes at 50 ° C. using the following liquor:

• 120 g of a wetting agent (alkylphenyl ethoxylate)
• 600 g of aid A-2
• 400 g formic acid (85%)
• 500 l water

630 g des 1:2-Chromkomplexes des Farbstoffs der Formel

eingerührtwerden.A portion of the liquor is then pumped into a batch container, into which 290 g of the 1: 2 cobalt complex of the dye of the formula are then placed

630 g of the 1: 2 chromium complex of the dye of the formula

be stirred in.

After the dyes are completely dissolved, the two parts of the liquor are combined. The pH of the liquor is 4.2. The liquor is then heated to 98 ° C. at a rate of 2 ° C./minute; the wool sliver is dyed at this temperature for 10 minutes.

After the liquor has cooled to 80 ° C., the material to be dyed is removed from the dyeing apparatus and left for 5 minutes drained. The comb is then centrifuged and rinsed directly without rinsing. The ridge is colored yellow no matter what. The fleet is fully drawn out and its pH is 4.7.

The extended fleet can be used to dye additional batches of woolen roving. The water loss is compensated for by adding cold water. After cooling to 50 ° C, new dyed material is run in, the pH of the liquor is adjusted to 4.2 with formic acid and the necessary auxiliaries and dyes are added. The second coloring is then carried out like the first.

Further dyeings can be carried out in the same way.

• 480 g eines Netzmittels (Alkylphenylethoxilat)
• 2700 g des Hilfsmittels A-2
• 2700 g Ameisensäure (85 %)
• 1600 I Wasser
• Der pH-Wert der Flotte beträgt 4,5.

Example 3: 180 kg of wool roving are pretreated in a circulation dyeing machine for 10 minutes at 50 ° C. using the following liquor:

• 480 g of a wetting agent (alkylphenyl ethoxylate)
• 2700 g of aid A-2
• 2700 g formic acid (85%)
• 1600 l water
• The pH of the liquor is 4.5.

1720 g des 1:2-Chromkomplexes des Farbstoffs der Formel

1800 g des 1:2-Chromkomplexes der Farbstoffe der Formeln

und 900 g des Farbstoffs der Formel

enthält, wird die Färbeflotte noch 5 Minuten bei 50°C gehalten und dann mit einer Auf heizrate von 1,5°C/Minute auf 95°C aufgeheizt. Der Wollkammzug wird 10 Minuten bei dieser Temperatur gefärbt. Nach dem Abkühlen der Flotte wird der Wollkammzug ohne zu spülen zentrifugiert und getrocknet.After adding 150 l of a dye solution, the 800 g of the 1: 2 cobalt complex of the dye of the formula

1720 g of the 1: 2 chromium complex of the dye of the formula

1800 g of the 1: 2 chromium complex of the dyes of the formulas

and 900 g of the dye of the formula

contains, the dye liquor is kept at 50 ° C for 5 minutes and then heated to 95 ° C at a heating rate of 1.5 ° C / minute. The wool sliver is dyed at this temperature for 10 minutes. After the liquor has cooled, the wool comb is centrifuged and rinsed without rinsing.

An fiber-colored and flat-level orange-colored dyeing with good general fastness properties is increased. The bathing extract is significantly better compared to a comparable coloring with conventional aids for 45 minutes.

Colorings of comparable quality can also be obtained if 4500 g of acetic acid (80%) are used instead of formic acid.

Instead of auxiliary A-2, auxiliary A-3 to A-6 or A-24 to A-26 can also be used.

Example 4: 40 g of wool fabric are pre-wetted in a circulation dyeing machine using the tree dyeing method for 10 minutes at 50 ° C. using the following liquor:

• 0.18 g of a wetting agent (alkylphenyl ethoxylate)
• 0.6 g of aid A-2
• 0.6 g formic acid (85%)
• 600 ml of water

The pH of the liquor is 4.5.

After adding 50 ml of a solution containing 0.5 g of the dye mixture of the 1: 2 chromium complex dyes according to Example 2, the dye liquor is kept at 50 ° C. for about 5 minutes. The liquor is then heated to 98 ° C. at a heating rate of 1 ° C./minute and the wool fabric is dyed at this temperature for 10 minutes. The liquor is then cooled to 70 ° C; The yellow material, regardless of color, is removed from the fleet and dried without rinsing.

The above-mentioned amounts of wetting and leveling agent are then again added to the drawn-out liquor and again 40 g of wool fabric are introduced into the liquor; the pH of the liquor after filling with water to 600 ml and after cooling to 50 ° C is 4.5.

und

(Gewichsverhältnis 2:1) enthält, wird die Färbeflotte noch etwa 5 Minuten bei 50°C gehalten. Anschliessend wird mit einer Aufheizrate von 1 °C/Minute auf 98 °C aufgeheizt und 10 Minuten bei dieser Temperatur gefärbt. Die Weiterbehandlung erfolgt wie oben angegeben. Man erhöht ein egal braun gefärbtes Wollgewebe.After adding 50 ml of an aqueous solution, the 0.56 g of a mixture of the 1: 2 chromium complex dyes of the formulas

and

(Weight ratio 2: 1), the dye liquor is kept at 50 ° C for about 5 minutes. The mixture is then heated to 98 ° C. at a heating rate of 1 ° C./minute and dyed at this temperature for 10 minutes. The further treatment takes place as indicated above. You raise a woolen fabric dyed brown.

enthält und dann wieder mit einem Färbebad, das 0,56 g des Farbstoffgemisches aus den Farbstoffen der Formeln (108) und (109) enthält, durchgeführt. Man erhält marineblaue beziehungsweise braune Färbungen.Further dyeings, each starting from a drawn bath as described, are carried out with a dye bath containing 0.68 g of the 1: 2 chromium complex dye of the formula

contains and then again with a dyebath containing 0.56 g of the dye mixture of the dyes of the formulas (108) and (109). Navy blue or brown colorations are obtained.

The fifth dyeing in the same bath is then carried out again with 0.5 g of the dye mixture of the 1: 2 chromium complex dyes according to Example 2.

In all cases, fiber and flat-level dyeings with good fastness properties are obtained. Comparable staining with conventional aids cannot be carried out because the bath is not completely drawn out.

The bath extract for the above-mentioned colors leads to water-clear baths; it is thus possible to carry out dyeings not only with the same dye, but also with dyes of different shades from the same (pulled out) bath. Color deviations of the dyed material from corresponding dyeings from new dye baths are not observed.

Example 5: 10 g of wool fabric are pretreated in a cup dyeing machine for 10 minutes at 50 ° C. with the following liquor:

• 0.1 g sodium acetate
• 0.5 g sodium sulfate (anhydrous)
• 0.25 g acetic acid (80%)
• 0.15 g of aid A-1
• 100 ml water

The pH of the liquor is 4.5.

After adding 30 ml of a solution containing 0.05 g of the dye mixture according to Example 2 and 0.3 g of the dye mixture according to Example 1, the liquor is kept at 50 ° C. for 10 minutes and then at a heating rate of 1 ° C. / Minute heated to 90 ° C. The fabric is then dyed at this temperature for 45 minutes. After the liquor has cooled to 70 ° C., the dyed wool fabric is removed from the liquor and finished by rinsing, centrifuging and drying.

The result is a fiber and surface-level red coloring, which can only be achieved with conventional aids after a dyeing time of at least 45 minutes and at a dyeing temperature of 98 ° C. Furthermore, the degree of exhaustion of the liquor is significantly better with the above 90 ° C dyeing than with the dyeing mentioned at 98 ° C.

Excellent dyeings are also obtained if a liquor is used which contains 0.15 g of formic acid and 1.5% of the leveling agent A-2 instead of the acetic acid. The pH of this liquor is also 4.5.

If instead of auxiliaries A-1 and A-2 in Examples 1 to 5 equivalent amounts of auxiliaries A-3 to A-26 are used, excellent colorations are also obtained.

Claims (33)

1. A process for dyeing textile materials made from natural or synthetic polyamide fibers in aqueous dye baths which contain at least one surfactant and, if appropriate, further auxiliaries, characterized in that (a) introducing the textile materials into aqueous dyebaths which, in addition to the dye, contain at least one surfactant and, if appropriate, other auxiliaries and acids and which heat these dyebaths to boiling temperature, (b) briefly dyes the textile material at this temperature, (c) cooling the dye baths depleted of dye to temperatures of 50 to 90 ° C. and then removing the dyed textile material from the dye baths and finishing them. 2. The method according to claim 1, characterized in that the surfactant is one of the components (I) of the general formula

wherein R is an aliphatic radical of 4 to 24 carbon atoms,

where Z is a direct bond or (R _i -O) _r and r is a number from 1 to 80, R ₁ alkylene with 2 to 4 carbon atoms, W is hydrogen, C ₁ -C ₄ alkyl optionally substituted with one or more substituents from the group consisting of carboxy, hydroxy, isocyanato, phenyl, benzyloxymethylene and phenethyloxymethylene, carboxy or a radical - CONH - R ₂ , in which R _{2 is} alkyl having 1 to 8 carbon atoms, where if U contains a quaternary nitrogen atom, W is sulfate, CH ₃ SO ₄ or a halogen anion, m is a number from 1 to 80 and (R ₁ - O) _{m represents} m identical or different radicals (R ₁ - O), or (II) the general formula

wherein R is an aliphatic radical having 4 to 24 carbon atoms; U _{1 is} a direct bond or a residue CO - NH - (CH ₂ ) _1-3 ; R ₃₀ , R ₃₁ and R ₃₂ independently of one another are C ₁ -C ₄ alkyl which is optionally substituted by hydroxy and P is COO or SO ₃ , or (III) the general formula

wherein R, U ₁ , R ₃₀ , R _{32 have} the meaning given for the formula (2) and P _{1 is} COOM or SO ₃ M, where M is hydrogen, alkali metal or ammonium, or (IV) the general formula

wherein R is an aliphatic radical with 4 to 24 carbon atoms, R ₁ alkylene with 2 to 4 carbon atoms, the sum k + k '= 4, where k = 1, 2 or 3 and m is a number from 1 to 80. 3. The method according to claim 2, characterized in that component (I) is a compound of the formula

in which purely aliphatic radical having 4 to 24 carbon atoms, R ₁ alkylene having 2 to 4 carbon atoms and m is a number from 1 to 80, preferably from 2 to 50 and (R ₁ -O) _m for m identical or different radicals (R ₁ -O) stands. 4. The method according to claim 2, characterized in that component (I) is a compound of the formula

is where R is an aliphatic radical having 4 to 24 carbon atoms, R ₁ alkylene having 2 to 4 carbon atoms, X _{1 is} hydrogen or phenyl, X _{2 is} hydrogen or phenyl, where X ₁ and X ₂ are different from one another, and m _{1 is} a number of 2 to 80, preferably 4 to 50. 5. The method according to claim 2, characterized in that component (I) is a compound of the formula

is wherein R is an aliphatic radical having 4 to 24 carbon atoms, R ₁ alkylene having 2 to 4 carbon atoms, one of the radicals Y ₁ or Y ₂ benzyloxymethylene or phenethyloxymethylene and the other hydrogen, and m _{1 is} a number from 2 to 80, preferably of Is 4 to 50. 6. The method according to claim 2, characterized in that component (I) is a compound of the formula

is where R is an aliphatic radical with 4 to 24 carbon atoms, R ₁ alkylene with 2 to 4 carbon atoms, R ₂ alkyl with 1 to 8 carbon atoms and n is a number from 2 to 60, preferably from 4 to 20 and (R ₁ - O) _{n represents} n identical or different radicals (R ₁ - O). 7. The method according to claim 2, characterized in that component (I) is a compound of the formula

is what R _{3 is} C ₉ to C ₁₄ alkyl, R _{4 is} hydrogen or a C ₁ -C ₄ alkyl isocyanate radical, one of the radicals Y ₃ or Y ₄ methyl and the other hydrogen, m _{2 is} an integer from 0 to 8 and n _{2 is} an integer Number is from 4 to 10. 8. The method according to claim 2, characterized in that component (I) is a compound of the formula

is where R is an aliphatic radical having 4 to 24 carbon atoms, R ₁ alkylene having 2 to 4 carbon atoms, W ₁ C ₁ -C ₄ alkyl and n is a number from 2 to 60, preferably 4 to 20. 9. The method according to claim 2, characterized in that component (I) is a compound of the formula

in which pure aliphatic radical having 4 to 24 carbon atoms, R ₁ alkylene having 2 to 4 carbon atoms and n _{1 is} a number from 2 to 20. 10. The method according to claim 2, characterized in that component (I) is a compound of the formula

in which R is an aliphatic radical having 4 to 24 carbon atoms, R ₁ alkylene having 2 to 4 carbon atoms, W _{2 is} hydrogen or the radical OC-R and n _{6 is} a number from 6 to 30. 11. The method according to claim 2, characterized in that component (I) is a compound of the formula

wherein R 'is an aliphatic radical having 8 to 24 carbon atoms, Z is a direct bond or (R ₁ -O) _r1, R ₁ is alkylene having 2 to 4 carbon atoms, n ₅ is a number from 4 to 20 and r ₁ is a number from Is 4 to 20. 12. The method according to claim 2, characterized in that component (I) is a compound of For mel

is where R 'is an aliphatic radical having 8 to 24 carbon atoms, R ₁ alkylene having 2 to 4 carbon atoms, m _{3 is} a number from 1 to 20, n _{3 is} a number from 1 to 20 and the sum m ₃ + n ₃ 2 to 21 is. 13. The method according to claim 2, characterized in that component (I) is a compound of the formula

is where R 'is an aliphatic radical having 8 to 24 carbon atoms, R ₁ alkylene having 2 to 4 carbon atoms, m _{3 is} a number from 1 to 20, n _{3 is} a number from 1 to 20 and the sum m ₃ + n ₃ 2 to 21 and X is an anion from the group consisting of halides, sulfates or alkyl sulfates. 14. The method according to claim 2, characterized in that component (I) is a compound of the formula

is where R 'is an aliphatic radical having 8 to 24 carbon atoms, R ₁ alkylene having 2 to 4 carbon atoms, m _{3 is} a number from 1 to 20, n _{3 is} a number from 1 to 20, p _{1 is} a number from 1 to 20 and the sum m ₃ + n ₃ + p ₁ 3 to 22 and t is a number from 2 to 4. 15. The method according to claim 2, characterized in that component (II) is a compound of the formula

is what R is an aliphatic radical having 4 to 24 carbon atoms; U _{1 is} a direct bond or a residue CO - NH - (CH ₂ ) _1-3 ; R ₃₀ , R ₃₁ and R ₃₂ independently of one another are C ₁ -C ₄ alkyl which is optionally substituted by hydroxy and P is COO or SO ₃ . 16. The method according to claim 2, characterized in that component (III) is a compound of the formula

wherein R, U ₁ , R ₃₀ , R _{32 have} the meaning given in claim 15 and P _{1 is} COOH or SO ₃ H. 17. The method according to claim 2, characterized in that component (IV) is a compound of the formula

is what R is an aliphatic radical with 4 to 24 carbon atoms, R ₁ alkylene with 2 to 4 carbon atoms, the sum k + k '= 4, where k = 1, 2 or 3 and m is a number from 1 to 80. 18. The method according to any one of claims 1 to 17, characterized in that the further auxiliaries leveling agents, defoamers, wetting agents, solvents and / or emulsifiers and inorganic salts and the acids are mineral acids, especially sulfuric acid, or low molecular weight organic acids, especially formic acid. 19. The method according to any one of claims 1 to 18, characterized in that one uses anionic dyes, in particular dyes containing sulfonic acid groups. 20. The method according to claim 19, characterized in that one uses metal-free dyes, reactive dyes or preferably metal complex dyes. 21. The method according to any one of claims 1 to 20, characterized in that the textile materials are introduced into dyebaths from 20 to 70 ° C, in particular 40 to 50 ° C and then heated to boiling temperature. 22. The method according to any one of claims 1 to 21, characterized in that the dyebaths are heated to temperatures of 95 to 105 ° C, preferably 98 to 103 ° C. 23. The method according to any one of claims 1 to 22, characterized in that the dyebaths are heated at a heating rate of 1 to 4 ° C / minute. 24. The method according to any one of claims 1 to 23, characterized in that the textile materials are dyed for 5 to 25, preferably for 10 to 20 minutes. 25. The method according to any one of claims 1 to 24, characterized in that the dye baths depleted of dye are cooled to 70 to 90 ° C. 26. The method according to any one of claims 1 to 25, characterized in that the dyed textile materials are rinsed and after-treated after removal from the dyebaths. 27. The method according to any one of claims 1 to 25, characterized in that drying the dyed textile materials after removal from the dyebaths without rinsing. 28. The method according to claim 25, characterized in that the exhausted dye baths are reused for further dyeing after appropriate setting. 29. The method according to claim 28, characterized in that the exhausted dyebaths are adjusted to the required dye, auxiliary and salt content, and the pH and the volume. 30. A process for dyeing textile materials made of natural or synthetic polyamide fibers in aqueous dye baths which contain at least one of components (I), (11), (III) or (IV) and optionally other auxiliaries, characterized in that (a) the textile materials are introduced into aqueous dyebaths which, in addition to the dyestuff, contain at least one of components (I), (11), (111) and (IV) and, if appropriate, other auxiliaries and acids and heats these dye baths to temperatures of 75 to 90 ° C, (b) dyeing the textile material at these temperatures for 30 to 90 minutes, (c) cooling the dye baths depleted of dye to 50 to 70 ° C and then removing the dyed textile material from the dye baths and finishing. 31. The method according to any one of claims 1 to 30, characterized in that textile wool materials, in particular wool fabric, loose wool or sliver are dyed. 32. Aqueous dyeing auxiliaries, characterized in that they contain a mixture of the compounds of the formulas (6), (7) and (8) and at least one, preferably two, of the compounds of the formulas (1a) to (1d). 33. The textile materials dyed by the process according to one of claims 1 to 31 made of natural or synthetic polyamide fibers.