EP0555182B1 - Process for dyeing of natural or synthetic polyamide fibers - Google Patents

Description

The present invention relates to a method for dyeing textile materials natural and synthetic polyamide fibers, whereby one during a short and so that the dyeing time is gentle on the fibers and dyes and levels at the boiling temperature of the dye bath Dyeings with good fastness properties are obtained (high-temperature rapid dyeing process).

Customary dyeing processes for the textile materials mentioned require dyeing times that for example in the range of 30 to 90 minutes. It is known that in particular Wool fibers can be damaged during such long dyeing times, resulting in a loss of quality leads to colored material. In addition, the degree of exhaustion of the dye liquors not completely.

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

It has now been found that the task at hand can be achieved surprisingly well by the Using special aids in the dye baths can dissolve.

(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 eine Temperatur von 95 bis 105° C aufheizt,

(b) das Textilmaterial während 5 bis 25 Minuten bei dieser Temperatur färbt,

(c) die an Farbstoff erschöpften Färbebäder auf Temperaturen von 50 bis 90°C abkühlt und das gefärbte Textilmaterial dann aus den Färbebädern entfernt und fertigstellt, wobei das Tensid eine der Komponenten (I) der allgemeinen Formel R-U-(R₁-O)_m-W

worin

R ein aliphatischer Rest von 4 bis 24 Kohlenstoffatomen,
U -O-;

oder

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,

W Wasserstoff, 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 R₂ Alkyl mit 1 bis 8 Kohlenstoffatomen ist,

m eine Zahl von 1 bis 80 ist und

(R₁-O)_m für m gleiche oder verschiedene Reste (R₁-O) steht,

oder (III) der allgemeinen Formel R-U₁-N(R₃₀)-R₃₂-P₁ worin

R ein aliphatischer Rest mit 4 bis 24 Kohlenstoffatomen,

U₁ eine direkte Bindung oder ein Rest CO-NH-(CH₂)_1-3,

R₃₀ C₁-C₄-Alkyl das gegebenenfalls mit Hydroxy substituiert ist,

R₃₂ C₁-C₄-Alkylen das gegebenenfalls mit Hydroxy substituiert ist, und

P₁ 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 bedeutet,

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

(a) The textile materials are placed in aqueous dye baths which, in addition to the dye, contain at least one surfactant and, if appropriate, further auxiliaries and acids, and these dye baths are heated to a temperature of 95 to 105 ° C,

(b) dyes the textile material for 5 to 25 minutes at this temperature,

(c) the dyebaths, which are exhausted of dyestuff, are cooled to temperatures of 50 to 90 ° C. and the dyed textile material is then removed from the dyebaths and finished, the surfactant being one of the components (I) of the general formula RU- (R ₁ -O) _m -W

wherein

R is an aliphatic radical of 4 to 24 carbon atoms,
U -O-;

or

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 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 with 1 to 8 Carbon atoms is

m is a number from 1 to 80 and

(R ₁ -O) _{m represents} m identical or different radicals (R ₁ -O),

or (III) of the general formula RU ₁ -N (R ₃₀ ) -R ₃₂ -P ₁ wherein

R is an aliphatic radical with 4 to 24 carbon atoms,

U _{1 is} a direct bond or a radical CO-NH- (CH ₂ ) _1-3 ,

R ₃₀ C ₁ -C ₄ -alkyl which is optionally substituted by hydroxy,

R ₃₂ C ₁ -C ₄ alkylene which is optionally substituted by hydroxy, and

P _{1 is} COOM or SO ₃ M, where

M is hydrogen, alkali metal or ammonium,

or (IV) of the general formula

wherein

R is an aliphatic radical with 4 to 24 carbon atoms,

R _{1 is} 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,

is.

From EP-A-0 089 004 a method for dyeing natural polyamide fibers in Temperature range from 95 to 105 ° C when using a mixture of auxiliaries, which, in contrast to the mixture of auxiliaries according to the invention, is a quaternary one and contains various nonionic and anionic compounds.

The compounds of component (I) are in particular fatty alcohol polyalkylene glycol ethers of the formula RO- (R ₁ -O) _m -H wherein R is an aliphatic radical of 4 to 24 carbon atoms, in particular 6 to 24 carbon atoms,
R _{1 is} alkylene with 2 to 4 carbon atoms and m is a number from 2 to 50 and (R ₁ -O) _{m stands} for m identical or different radicals (R ₁ -O).

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

As aliphatically saturated alcohols, natural alcohols such as hexyl alcohol, octyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol or behenyl alcohol, as well as synthetic alcohols, e.g. oxo alcohols such as, in particular, 2-ethylbutanol, 2-methylheptanol, 5-methylheptanol, can be used. ol, 2-ethylhexanol, 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 (alfole) with 8 to 18 carbon atoms come into consideration. Some representatives of the 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 and hexadecenyl alcohol or oleyl alcohol.

The alcohol radicals can be used individually or in the form of mixtures of two or more Components are present, such as mixtures of alkyl and / or alkenyl groups, derived e.g. 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 the 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 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 4 bis 50 ist, oder um Verbindungen der Formel R-O-(R₁-O)_n-CONH-R₂ 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 4 bis 20 ist.The compounds of component (I) are also, in particular, compounds of the formula

where R is an aliphatic radical with 4 to 24 carbon atoms, in particular 6 to 24 carbon atoms, R _{1 is} 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 4 to 50, or 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 is} alkylene having 2 to 4 carbon atoms, one of the radicals Y ₁ or Y _{2 is} benzyloxymethylene or phenethyloxymethylene and the other is hydrogen, and m _{1 is} a number from 4 to 50, or compounds of the formula RO- (R ₁ -O) _n -CONH-R ₂ where R is an aliphatic radical with 4 to 24 carbon atoms, in particular 6 to 24 carbon atoms, R _{1 is} alkylene with 2 to 4 carbon atoms, R _{2 is} alkyl with 1 to 8 carbon atoms, in particular 3 to 5 and n is a number from 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 from EP-A-378048 and EP-A-406168 known.

Preferred compounds of the formula (1d) are, for example, the reaction products of the addition products 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 C₉ bis C₁₄-Alkyl,

R₄ Wasserstoff oder ein C₁-C₄-Alkylisocyanatrest,

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 particular interest

wherein

R ₃ 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 from 4 to 10.

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

Compounds in which the C ₁ -C ₄ -alkyl isocyanate radical is the n-butyl isocyanate or isopropyl isocyanate radical are very particularly preferred.

The C ₁ -C ₄ -alkyl isocyanate end-capped nonionic surfactants of the formula (1e) are prepared by reacting the alkyl polyalkylene glycol ethers _{with C 1} -C _{4 -alkyl isocyanate using a catalyst or catalyst mixture.}

The compounds of the formula are also of very particular interest RO- (R ₁ -O) _n -W ₁ where R is an aliphatic radical having 4 to 24 carbon atoms, R _{1 is} alkylene having 2 to 4 carbon atoms, W _{1 is} C ₁ -C ₄ -alkyl, n is a number from 4 to 20 and (R ₁ -O) _{n is} n the same or different radicals (R ₁ -O).

The compounds of component (I) are also, in particular, compounds of the formula RO- (R ₁ -O) _{n 1} -CH ₂ -COOH where R is an aliphatic radical having 4 to 24 carbon atoms, R _{1 is} alkylene having 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 R-COO- (R ₁ - O) _{n 6th} - W ₂ where R is an aliphatic radical with 4 to 24 carbon atoms, R _{1 is} 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 (1h), 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

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

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

where R 'is an aliphatic radical having 8 to 24 carbon atoms, R _{1 is} 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 is} 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, 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

where R 'is an aliphatic radical having 8 to 24 carbon atoms, R _{1 is} 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.

In the compounds of the formulas (1i) 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 inventive dyeing process is carried out in dye baths, in addition to at least one of components (I) to (IV) and the dye, if appropriate, others Contain common auxiliaries, such as leveling agents, defoamers, other wetting agents, Solvents and / or emulsifiers; also inorganic salts, especially ammonium or alkali metal salts such as ammonium sulfate, ammonium or sodium acetate or preferably contain sodium sulfate. Preferably 0.1 to 10 wt .-% Ammonium or alkali sulfate, based on the fiber material used. Suitable Acids used in the dye baths are, for example, mineral acids such as Sulfuric or phosphoric acid, and also organic acids, advantageously low molecular ones organic acids, especially aliphatic carboxylic acids, such as formic, acetic or Oxalic acid. The acids are mainly used to adjust the pH value of the dyebaths, the is usually in the range from 4 to 6.5, with a pH of about 4.2 to 4.7 and, when dyeing polyamide fibers, from 5 to 6.5, especially 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.Usually, in the dye baths used according to the invention, leveling agents, for example compounds based on fatty amines as indicated in the formulas (6) to (8) below, are additionally used, mixtures of an anionic compound of the formula

where 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 being} 2 is up 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 formula

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

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

These dyeing auxiliaries according to the invention therefore preferably consist of a mixture of the compounds of the formulas (6), (7) and (8) (hereinafter referred to as M ₁ ) combined with at least one compound, preferably 2 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 ₂ 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 butyl triglycol) with an active substance content of 25 to 70 percent by weight.

The quantities of these aqueous or aqueous / organic preparations used 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 which can be used can be from the most varied classes of dyes belong and optionally one or more sulfonic acid groups and possibly contain one or more fiber-reactive groups. In particular, it is Triphenylmethane dyes with at least two sulfonic acid groups, free of heavy metals Monoazo and disazo dyes each with one or more sulfonic acid groups and optionally one or more fiber-reactive groups and those containing heavy metals, namely copper, chromium, nickel or cobalt containing monoazo, disazo, azomethine and Formazan dyes, especially metallized dyes attached to one metal atom Molecules of azo dye or one molecule of azo dye and one molecule of azomethine dye contain bound, especially those with mono- and / or disazo dyes as ligands and / or azomethine dyes and, as the central metal ion, a chromium or Contain cobalt ion, as do anthraquinone dyes, in particular 1-amino-4-arylamino-anthraquinone-2-sulfonic acids or 1,4-diarylamino- or 1-cycloalkylamino-4-arylaminoanthraquinone sulfonic acids. Among fiber-reactive groups are to understand such groups that are covalent with the polyamide material to be dyed Enter into a bond.

Dyes that contain one or more fiber-reactive groups are used in the processes according to the invention, preferably in combination with non-fiber-reactive Dyes used.

The amounts in which the dyes are used in the dye baths can vary vary within wide limits according to the desired depth of color, in general have themselves Amounts from 0.001 to 10 percent by weight, based on the dyed material, of one or more Dyes proven to be beneficial.

(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 R₉ 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-Alkylaminosulfonyl 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 der Azofarbstoffe 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 L einen 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-R₉ substituiert sein kann, bedeuten, wobei R₉ die unter Formel (11) angegebene Bedeutung hat; und

worin R₉ 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 ' independently of one another are 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 optionally bonded via aminobenzoyl and the substituents R _{8 are} independently hydrogen or a phenylamino- or N-phenyl-N-methyl-amino -sulfonyl radical, a = 0 or 1 and b = 0, 1 or 2;

wherein R _{9 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 can contain the substituents given 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 can contain the substituents given under formula (11) and R ₁₂ and R _{13 are} independently 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 is} C _1-4 -alkylsulphonyl, C _1-4 -alkylaminosulphonyl, phenylazo, sulpho or -SO ₂ N ₂ , the hydroxy group in the benz ring D being bonded to the benz ring D in the o-position to the azo bridge and the benzene ring E may contain a nitrobenzene ring fused on in the 5- and 6-positions;
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 alkylaminosulfonyl and R _{19 is} nitro or C _1-4 alkoxy-C _1-4 alkylene aminosulfonyl;

wherein G is -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;

where 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, can contain the substituents given under formula (11), and the phenyl ring L has a 2- and 3- May contain a fused-on benzene ring or, instead of the sulpho group, a sulphobenzene ring fused-on in the 2- and 3-position;

wherein the phenyl ring B in the formulas (21), (22) and (24) can contain the substituents given 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

where 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 ;

in which the substituents R _{24 are,} independently of one another, cyclohexyl and the diphenyl ether radical, which can be substituted _{by sulfo and the radical -CH 2} NH-R _{9 , where R 9 has} the meaning given under formula (11); and

wherein R _{9 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-Cl, -CO-CCl = CH ₂ , -CO-CH = CHBr, -COCBr = CH ₂ , -CO-CBr = CHBr, -CO-CCl = CH-CH ₃ , furthermore -CO-CCl = CH-COOH, -CO-CH = CCl -COOH, 4-chloropropionyl, 3-phenylsulphonylpropionyl, 3-methylsulphonylpropionyl, β-sulphatoethylaminosulphonyl, vinylsulphonyl, β-chloroethylsulphonyl, β-sulphatoethylsulphonyl, β-methylsulphonylethylsulphonyl, β-methylsulphonylethylsulphonyl, β-methylsulphonylethylsulphonyl, β-methylsulphonylethylsulphonyl -1-carbonyl, 2,2,3,3-tetrafluorocyclobutane-carbonyl-1 or sulfonyl-1, β- (2,2,3,3-tetrafluorocyclobutyl-1) acryloyl, α- or β-alkyl or - Arylsulfonyl-acryloyl, such as α- 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- oder disubstituierte 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 radicals particularly suitable for wool are: chloroacetyl, bromoacetyl, α, β-dichloro or α, β-dibromopropionyl, α-chloro- or α-bromoacryloyl, 2,4-difluoro-5-chloropyrimidyl-6, 2,4,6-trifluoropyrimidyl -5, 2,4-dichloro-5-methylsulfonylpyrimidinyl-6, 2-fluoro-4-methyl-5-chloropyrimidyl-6, 2,4-difluoro-5-methylsulfonylpyrimidyl-6, 2,4-difluorotriazinyl-6, and Fluorotriazinyl radicals of the formula

wherein R ₂₆ denotes an optionally substituted amino group or an optionally etherified oxy or thio group, such as, for example, 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 phenylamino substituted with methyl, methoxy, chlorine and especially sulfo, phenoxy, mono- or disulfophenoxy, etc., and the corresponding chlorotriazinyl radicals.

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

The salts are, for example, the alkali, alkaline earth or ammonium salts or the Salts of an organic amine into consideration. Examples are the sodium, lithium, Called potassium or ammonium salts or the salt of triethanolamine.

If dye mixtures are used in the process according to the invention, then these are produced 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.

The dye mixtures can also be prepared by spray drying the aqueous dye mixtures getting produced.

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

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

The auxiliary mixture according to the invention is expediently the aqueous dye liquor mixed in and applied at the same time as the dye. One can also proceed like this that you first treat the material to be dyed with the auxiliary mixture and in colors the same bath after adding the dye. It is preferable to go with the fiber material in a liquor containing the acid and the auxiliary mixture and a Temperature of 20 to 70 ° C, preferably 40 to 50 ° C. Then the Dyestuff or a dyestuff mixture added and the temperature of the dyebath with a heating rate of 1 to 4 ° C per minute increased to im specified Temperature range from 95 to 105 °, preferably 10 to 20 minutes to dye. At the end the bath is cooled to 70 to 90 ° C and the colored material rinsed and rinsed as usual dried, the dyed fiber material can preferably also be used without rinsing (centrifuged and) dried.

Special devices are not required in the method according to the invention. It the usual dyeing apparatus and machines, e.g. for flake, sliver, Hank yarn, bobbins, woven fabrics, knitted fabrics, piece goods and carpets are used will.

As polyamide fiber materials that are dyed according to the invention, such come from natural polyamides, especially wool, but also mixtures of wool / polyamide, Wool / polyester, wool / cellulose or wool / polyacrylonitrile, as well as silk and made of synthetic polyamides, such as polyamide 6 or 6.6, into consideration. The fiber material can are available in a wide variety of forms, such as loose material, Sliver, yarn, woven, knitted and piece goods or as carpets.

The dyeing process according to the invention leads to textile materials which are dyed with the same fiber and surface area made of natural or synthetic polyamide fibers. Main advantages of the procedure are the short (and therefore gentle on the fibers) dyeing time and the complete The dye is absorbed onto the fiber, i.e. the dye bath is completely drawn out (exhausted) and can be used for further staining after appropriate adjustment will. This setting affects the required dye, auxiliary and Salinity, as well as the pH and volume of the dye bath.

This reuse of dye liquors (dyeing from standing baths) is for Dyeing with identical dyes or dyes that differ from dye bath to dye bath possible without hue shifts and in the respective subsequent coloring Loss of yield occur.

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

An alternative dyeing process to the process according to the invention is at temperatures carried out below the boiling temperature and requires slightly 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 one

(a) The textile materials are placed in aqueous dyebaths which, in addition to the dyestuff, contain at least one of components (I) to (IV) and optionally other auxiliaries and acids, and these dyebaths are heated to temperatures of 75 to 90 ° C,

(b) dyes the textile material for 30 to 90 minutes at these temperatures,

(c) the dyebaths, which are exhausted of dyestuff, are cooled to 50 to 70.degree. C. and the dyed textile material is then removed from the dyebaths and completed.

Preparation instructions (compounds of formula (1d)):

(A) 51 g (approx. 0.1 mol) of the adduct of 1 mol of decyl alcohol and 8 mol Ethylene oxide is dissolved in 25 ml of dry tetrahydrofuran and 8.9 g (0.105 mol) Isopropyl isocyanate added. After adding a catalyst mixture of 100 µl each Dibutyltin laurate and triethylamine are heated to 60 ° with stirring in a stream of inert gas. After 90 minutes, the reaction is ended by adding the batch to 100 ml of petroleum ether poured and the almost colorless precipitated product is separated. After drying at a temperature of 50 ° in vacuo, the slightly oily product in a yield of 56.8 g obtained.

(B) 153 g (approx. 0.3 mol) of the adduct of 1 mol of decyl alcohol and 8 mol Ethylene oxide are placed in a protective gas without solvent and add 30.9 g (0.105 mol) of n-butyl isocyanate was added dropwise with stirring. After adding a catalyst mixture from 100 µl each of dibutyltin laurate and triethylamine, a slight initially emerges The reaction mixture is heated to about 40 °. At an internal temperature of 60 ° the implementation is completely finished after 60 minutes. Finally, in 100 ml Poured petroleum ether (40-80). After drying the precipitated, isolated liquid A yield of 167 g of product is achieved in vacuo at 50 °.

The following examples serve to illustrate the invention. There are those Parts are parts by weight and the percentages are percentages by weight. The temperatures are in Degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimeters.

A-1:

C₉-C₁₁-Alkyl-O-(CH₂CH₂O)₄-H

A-2:

Gemisch aus

• 35 Teilen C₉-C₁₁-Alkyl-O-(CH₂CH₂O)₈-CONH(CH₂)₃CH₃
• 10 Teilen eines Gemisches aus 12,6 Teilen der anionischen Verbindung der Formel
  

21,3 Teilen der quaternären Verbindung der Formel

7,7 Teilen des Umsetzungsproduktes von Oleylalkohol mit 80 Mol Aethylenoxid;

7,0 Teilen der Verbindung der Formel

sowie 51,4 Teilen Wasser,

• 20 Teilen Butyltriglykol
• 35 Teilen Wasser

A-3:

C₁₀-Alkyl-O-(CH₂CH₂O)₈-CONHCH(CH₃)₂

A-4:

C₁₀-Alkyl-O-(CH₂CH₂O)₈-CONH(CH₂)₃CH₃

A-5:

A-6:

A-7:

C₁₂-C₁₄-Alkyl-O-(CH₂CH₂O)_2,5CH₂-COOH

A-8

C₁₆-C₁₈-Alkyl-O-(CH₂CH₂O)₉CH₂-COOH

A-9:

A-10:

A-11:

A-12:

A-13:

A-14:

A-15:

A-16:

A-17:

C₉-C₁₁-Alkyl-O-(CH₂CH₂O)₄-(CH(CH₃)CH₂O)₂-H

A-18:

A-19:

Gemisch aus

• 34 Teilen C₉-C₁₁-Alkyl-O-(CH₂CH₂O)₄-H und C₉-C₁₁-Alkyl-O-(CH₂CH₂O)₄-H umgesetzt mit Styroloxyd (Gewichtsverhältnis: 2:1)
• 10 Teilen eines Gemisches aus 12,6 Teilen der anionischen Verbindung der Formel
  

21,3 Teilen der quaternären Verbindung der Formel

7,7 Teilen des Umsetzungsproduktes von Oleylalkohol mit 80 Mol Aethylenoxid;

7,0 Teilen der Verbindung der Formel

sowie 51,4 Teilen Wasser,

• 20 Teilen Butyltriglykol
• 36 Teilen Wasser

A-20:

Gemisch aus

• 35 Teilen
  
• 10 Teilen
  
• 5 Teilen der Verbindung der Formel
  
• 3 Teilen C₁₈H₃₅-O-(CH₂CH₂O)₈₀-H
• 25 Teilen Butyltriglykol
• 22 Teilen Wasser

A-21:

Gemisch aus

• 34 Teilen C₁₃-Alkyl-O(CH₂CH₂O)₅H
• 10 Teilen eines Gemisches aus 12,6 Teilen der anionischen Verbindung der Formel
  

21,3 Teilen der quaternären Verbindung der Formel

7,7 Teilen des Umsetzungsproduktes von Oleylalkohol mit 80 Mol Aethylenoxid;

7,0 Teilen der Verbindung der Formel

sowie 51,4 Teilen Wasser,

• 20 Teilen Butyltriglykol
• 36 Teilen Wasser

The auxiliaries used in the following examples have the following compositions:

A-1:

C ₉ -C ₁₁ alkyl-O- (CH ₂ CH ₂ O) ₄ -H

A-2:

Mixture of

• 35 parts 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
  

21.3 parts of the quaternary compound of formula

7.7 parts of the reaction product of oleyl alcohol with 80 moles of ethylene oxide;

7.0 parts of the compound of formula

and 51.4 parts of 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:

A-14:

A-15:

A-16:

A-17:

C ₉ -C ₁₁ alkyl- O- (CH ₂ CH ₂ O) ₄ - (CH (CH ₃ ) CH ₂ O) ₂ -H

A-18:

A-19:

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
  

21.3 parts of the quaternary compound of formula

7.7 parts of the reaction product of oleyl alcohol with 80 moles of ethylene oxide;

7.0 parts of the compound of formula

and 51.4 parts of water,

• 20 parts of butyl triglycol
• 36 parts of water

A-20:

Mixture of

• 35 parts
  
• 10 parts
  
• 5 parts of the compound of 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-21:

Mixture of

• 34 parts C ₁₃ alkyl-O (CH ₂ CH ₂ O) ₅ H
• 10 parts of a mixture of 12.6 parts of the anionic compound of the formula
  

21.3 parts of the quaternary compound of formula

7.7 parts of the reaction product of oleyl alcohol with 80 moles of ethylene oxide;

7.0 parts of the compound of formula

and 51.4 parts of water,

• 20 parts of butyl triglycol
• 36 parts of water

0,1 g eines Netzmittels (Alkylphenylethoxilat)

75 mg Hilfsmittel A-1

0,1 g Ameisensäure (85 %)

165 ml Wasser

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

0.1 g of a wetting agent (alkylphenyl ethoxylate)

75 mg of auxiliary A-1

0.1 g formic acid (85%)

165 ml of 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/Minute 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. There is then 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 liquor is then practically clear as water. After the liquor has cooled to 70 ° C., the dyed wool material is removed from the dyeing apparatus and then finished as usual, for example by rinsing and drying. Because of the good bath extract, the rinsing process can be shortened considerably.

A level red dyeing with good fastness properties and very good depth of color is obtained.

Instead of the auxiliary A-1 you can also use the same amount of the auxiliary A-7 bis Insert A-18.

120 g eines Netzmittels (Alkylphenylethoxilat)

600 g des Hilfsmittels A-2

400 g Ameisensäure (85 %)

500 l Wasser

Example 2 : 40 kg of wool tops are prewetted in a top dyeing machine for 10 minutes at 50 ° C. with the following liquor:

120 g of a wetting agent (alkylphenyl ethoxylate)

600 g of A-2

400 g formic acid (85%)

500 liters of water

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

eingerührt werden.Part 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 fed

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

be stirred in.

After the dyes have completely dissolved, the two parts of the liquor are combined. The pH of the liquor is 4.2. The fleet is then at a speed of 2 ° C / minute heated to 98 ° C; the wool top is 10 minutes at this temperature colored. After the liquor has cooled to 80 ° C., the material to be dyed is removed from the dyeing machine removed and allowed to drain for 5 minutes. The top pull is then without rinse directly centrifuged and dried. The ridge is colored yellow regardless. The fleet is fully extended and its pH is 4.7.

The drawn liquor can be used for dyeing further batches of woolen tops will. To do this, the water loss is compensated for by adding cold water. After cooling to 50 ° C., new material to be dyed is run in, the pH of the liquor adjusted to 4.2 with formic acid and the necessary auxiliaries and dyes admitted. The second staining is then carried out like the first.

Further colorations can be carried out in the same way.

480 g eines Netzmittels (Alkylphenylethoxilat)

2700 g des Hilfsmittels A-2

2700 g Ameisensäure (85 %)

1600 l Wasser

Der pH-Wert der Flotte beträgt 4,5. Example 3 : 180 kg of woolen tops are pretreated in a circulation dyeing machine for 10 minutes at 50 ° C. with the following liquor:

480 g of a wetting agent (alkylphenyl ethoxylate)

2700 g of A-2

2700 g formic acid (85%)

1600 l of 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 Aufheizrate 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 held at 50 ° C for a further 5 minutes and then heated to 95 ° C at a rate of 1.5 ° C / minute. The woolen sliver is dyed for 10 minutes at this temperature.
After the liquor has cooled down, the woolen sliver is centrifuged and dried without rinsing.

An orange dyeing which is level across the fibers and has good all-round fastness properties is obtained. The bath extract is significantly better compared to a comparable one Coloring with the usual aids for 45 minutes.

Dyes of comparable quality are also obtained if formic acid is used instead 4500 g of acetic acid (80%) are used.

Instead of the aid A-2, you can also use the auxiliaries A-3 to A-6 or A-19 to Insert A-21.

0,18 g eines Netzmittels (Alkylphenylethoxilat)

0,6 g des Hilfsmittels A-2

0,6 g Ameisensäure (85 %)

600 ml Wasser

Der pH-Wert der Flotte beträgt 4,5. Example 4 : 40 g of woolen fabric are pre-wetted in a circulation dyeing machine using the tree dyeing method for 10 minutes at 50 ° C. with the following liquor:

0.18 g of a wetting agent (alkylphenyl ethoxylate)

0.6 g of 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 1: 2 chromium complex dyes according to Example 2, the dye liquor is about 5 minutes held at 50 ° C. The liquor is then heated up at a rate of 1 ° C./minute heated to 98 ° C and dyed the wool fabric for 10 minutes at this temperature. the The liquor is then cooled to 70 ° C .; the yellow colored material is removed from the liquor removed and dried without rinsing.

The withdrawn liquor are then again the above-specified amounts of network and Leveling agent is added and 40 g of woolen fabric are again introduced into the liquor; the pH of the liquor is after making up to 600 ml with water and after cooling to 50 ° C. 4.5.

und

(Gewichtsverhältnis 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 erhält ein egal braun gefärbtes Wollgewebe.After adding 50 ml of an aqueous solution containing 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. This is followed by heating to 98 ° C. at a rate of 1 ° C./minute and dyeing at this temperature for 10 minutes. The further processing takes place as indicated above. A woolen fabric dyed evenly brown is obtained.

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 colorations, in each case starting from an exhausted bath as described, are carried out with a dyebath containing 0.68 g of the 1: 2 chromium complex dye of the formula

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

In all cases the dyeings obtained are level with fibers and surfaces and have good fastness properties. Comparable staining with conventional aids cannot be carried out because the bath is not fully drawn out.

The bath pull-out in the above-mentioned colorations leads to water-clear baths; it will thus possible, not only with the same dye, but also with dyes other color nuances to carry out colorings from the same (drawn out) bath in each case. Color deviations of the colored material compared to corresponding colors from each new dye bath are not observed.

0,1 g Natriumacetat

0,5 g Natriumsulfat (wasserfrei)

0,25 g Essigssäure (80 %)

0,15 g des Hilfsmittels A-1

100 ml Wasser

Der pH-Wert der Flotte beträgt 4,5. Example 5 : 10 g of woolen 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 A-1

100 ml of 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 contains, the liquor held at 50 ° C for a further 10 minutes and then heated up at a rate of 1 ° C / minute 90 ° C heated. The fabric is then dyed at this temperature for 45 minutes. To the dyed woolen fabric is removed from the liquor after the liquor has cooled to 70 ° C and completed by rinsing, centrifuging and drying.

A fiber and surface-level red coloration is obtained, 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 can be reached. Furthermore, the degree of exhaustion of the liquor is at the above 90 ° C coloring significantly better than the aforementioned coloring at 98 ° C.

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

Instead of auxiliaries A-1 and A-2 in Examples 1 to 5, equivalents are used Quantities of auxiliaries A-3 to A-21, excellent dyeings are also obtained.

Claims (28)

1. A process for dyeing textile materials of naturally occurring or synthetic polyamide fibres in aqueous dyebaths comprising at least one surfactant and if appropriate other dyeing assistants, which comprises

   (a) introducing the textile materials into aqueous dyebaths comprising, in addition to the dye, at least one surfactant and if appropriate other dyeing assistants and acids, and heating these dyebaths to a temperature of 95 to 105°C,

   (b) dyeing the textile material for 5 to 25 minutes at this temperature,

   (c) cooling the dyebaths exhausted of dyestuff to temperatures of 50 to 90°C and subsequently removing the dyed textile material from the dyebaths and finishing it, the surfactant being one of the components (1) of the general formula R - U - (R₁-O)_m-W in which R is an aliphatic radical having 4 to 24 carbon atoms,

   U is -O-;

   

   

   in which Z is a direct bond or (R₁-O)_r and r is a number from 1 to 80, R₁ is alkylene having 2 to 4 carbon atoms, W is hydrogen, C₁-C₄alkyl which is unsubstituted or substituted by one or more substituents from the group comprising carboxyl, hydroxyl, isocyanato, phenyl, benzyloxymethylene and phenethyloxymethylene; carboxyl or a radical -CONH-R₂, in which R₂ is alkyl having 1 to 8 carbon atoms, m is a number from 1 to 80, and (R₁-O)_m are m identical or different radicals (R₁-O),
   or (III) of the general formula R - U₁ - N(R₃₀) - R₃₂ - P₁ in which R is an aliphatic radical having 4 to 24 carbon atoms, U₁ is a direct bond or a radical CO-NH-(CH₂)_1-3, R₃₀ is C₁-C₄alkyl which is unsubstituted or substituted by hydroxyl, R₃₂ is C₁-C₄alkylene which is unsubstituted or substituted by hydroxyl, and P₁ is COOM or SO₃M, in which M is hydrogen, an alkali metal or ammonium,
   or (IV) of the general formula

   

   in which R is an aliphatic radical having 4 to 24 carbon atoms, R₁ is alkylene having 2 to 4 carbon atoms, the sum k + k' = 4, in which k = 1, 2 or 3, and m is a number from 1 to 80.
2. A process according to claim 1, wherein component (I) is a compound of the formula R-O-(R₁-O)_m-H in which R is an aliphatic radical having 4 to 24 carbon atoms, R₁ is alkylene having 2 to 4 carbon atoms, and m is a number from 2 to 50, and (R₁-O)_m is m identical or different radicals (R₁-O) .
3. A process according to claim 1, wherein component (I) is a compound of the formula

   

   in which R is an aliphatic radical having 4 to 24 carbon atoms, R₁ is alkylene having 2 to 4 carbon atoms, X₁ is hydrogen or phenyl, X₂ is hydrogen or phenyl, X₁ and X₂ differing from one another, and m₁ is a number from 4 to 50.
4. A process according to claim 1, wherein component (I) is a compound of the formula

   

   in which R is an aliphatic radical having 4 to 24 carbon atoms, R₁ is alkylene having 2 to 4 carbon atoms, one of the radicals Y₁ or Y₂ is benzyloxymethylene or phenethyloxymethylene and the other is hydrogen, and m₁ is a number from 4 to 50.
5. A process according to claim 1, wherein component (I) is a compound of the formula R-O-(R₁-O)_n-CONH-R₂ in which R is an aliphatic radical having 4 to 24 carbon atoms, R₁ is alkylene having 2 to 4 carbon atoms, R₂ is alkyl having 1 to 8 carbon atoms, and n is a number from 4 to 20, and (R₁-O)_n is n identical or different radicals (R₁-O).
6. A process according to claim 1, wherein component (I) is a compound of the formula

   

   in which R₃ is C₉ to C₁₄alkyl, R₄ is hydrogen or a C₁-C₄alkyl isocyanate radical, one of the radicals Y₃ or Y₄ is methyl and the other is hydrogen, m₂ is an integer from 0 to 8 and n₂ is an integer from 4 to 10.
7. A process according to claim 1, wherein component (I) is a compound of the formula R - O - (R₁ - O)_n - W₁ in which R is an aliphatic radical having 4 to 24 carbon atoms, R₁ is alkylene having 2 to 4 carbon atoms, W₁ is C₁-C₄alkyl and n is a number from 4 to 20.
8. A process according to claim 1, wherein component (I) is a compound of the formula R - O - (R₁ - O)_n1 - CH₂ - COOH in which R is an aliphatic radical having 4 to 24 carbon atoms, R₁ is alkylene having 2 to 4 carbon atoms and n₁ is a number from 2 to 20.
9. A process according to claim 1, wherein component (I) is a compound of the formula R - COO - (R₁ - O)_n6 - W₂ in which R is an aliphatic radical having 4 to 24 carbon atoms, R¹ is alkylene having 2 to 4 carbon atoms, W₂ is hydrogen or the radical OC-R and n₆ is a number from 6 to 30.
10. A process according to claim 1, wherein component (I) is a compound of the formula

    

    in which R' is an aliphatic radical having 8 to 24 carbon atoms, Z is a direct bond or (R₁-O)_r, R₁ is alkylene having 2 to 4 carbon atoms, n₅ is a number from 4 to 20 and r₁ is a number from 4 to 20.
11. A process according to claim 1, wherein component (I) is a compound of the formula

    

    in which R' is an aliphatic radical having 8 to 24 carbon atoms, R₁ is alkylene having 2 to 4 carbon atoms, m₃ is a number from 1 to 20, n₃ is a number from 1 to 20 and the sum m₃ + n₃ is 2 to 21.
12. A process according to claim 1, wherein component (I) is a compound of the formula

    

    in which R' is an aliphatic radical having 8 to 24 carbon atoms, R₁ is alkylene having 2 to 4 carbon atoms, m₃ is a number from 1 to 20, n₃ is a number from 1 to 20, p₁ is a number from 1 to 20 and the sum m₃ + n₃ + p₁ is 3 to 22, and t is a number from 2 to 4.
13. A process according to claim 1, wherein component (III) is a compound of the formula R - U₁ - N(R₃₀) - R₃₂ - P₁ in which R, U₁, R₃₀ and R₃₂ are as defined in claim 1 and P₁ is COOH or SO₃H.
14. A process according to claim 1, wherein component (IV) is a compound of the formula

    

    in which R is an aliphatic radical having 4 to 24 carbon atoms, R₁ is alkylene having 2 to 4 carbon atoms, the sum k + k' = 4, in which k = 1, 2 or 3, and m is a number from 1 to 80.
15. A process according to any one of claims 1 to 14, wherein the other dyeing assistants are levelling agents, defoamers, wetting agents, solvents and/or emulsifiers, as well as inorganic salts, and the acids are mineral acids, in particular sulfuric acid, or low molecular weight organic acids, in particular formic acid.
16. A process according to any one of claims 1 to 15, wherein anionic dyes, in particular dyes containing sulfonic acid groups, are employed.
17. A process according to claim 16, wherein metal-free dyes, reactive dyes or, preferably, metal complex dyes are employed.
18. A process according to any one of claims 1 to 17, wherein the textile materials are introduced into dyebaths at 20 to 70°C, in particular 40 to 50°C, and the dyebaths are then heated up to the boiling point.
19. A process according to any one of claims 1 to 18, wherein the dyebaths are heated up to temperatures of 98 to 103°C.
20. A process according to any one of claims 1 to 19, wherein the dyebaths are heated up with a heating up rate of 1 to 4°C/minute.
21. A process according to any one of claims 1 to 20, wherein the textile materials are dyed for 10 to 20 minutes.
22. A process according to any one of claims 1 to 21, wherein the dyebaths exhausted of dye are cooled to 70 to 90°C.
23. A process according to any one of claims 1 to 22, wherein the dyed textile materials are rinsed and aftertreated after removal from the dyebaths.
24. A process according to any one of claims 1 to 22, wherein, after removal from the dyebaths, the dyed textile materials are dried, without being rinsed.
25. A process according to claim 22, wherein, after appropriate adjustment, the exhausted dyebaths are reused for another dyeing.
26. A process according to claim 25, wherein the exhausted dyebaths are adjusted to the required, dye, dyeing assistant and salt content, and the pH and the volume are adjusted.
27. A process according to any one of claims 1 to 26, wherein textile woollen materials, in particular woollen woven fabric, loose wool or slubbing, are dyed.
28. An aqueous dyeing assistant, which comprises a mixture of an anionic compound of the formula

    

    in which R₅ is an alkyl or alkenyl radical having 12 to 22 carbon atoms, M is hydrogen, an alkali metal or ammonium, L₁ is hydrogen or a radical SO₃M and m₄ and n₄ are integers, the sum of m₄ and n₄ being 2 to 14, a quaternary compound of the formula

    

    in which R", independently of R₅, is as defined for R₅, A is an anion, Q is a substituted or unsubstituted 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 R₅, is as defined for R₅ and x and y are integers, the sum of x and y being 80 to 140, and at least one, preferably two, of the compounds of the formulae (1a) to (1d).