EP0702107A2 - Process for dyeing melamine-formaldehyde condensation products - Google Patents

Abstract

A process for dyeing condensation prods. (I) comprises treating (I), in the form of fibre, yarn, thread, mesh or web goods or non-wovens, with azo, anthraquinone, coumarin, methine, azamethine, quinophthalone and/or nitro dye(s) in an aq. dyebath at pH 1-12 and 20-250 degrees C. (I) are obtd. by condensing a mixt. of: (A) 90-99.9 mole-% mixt. (a) 30-99 mole-% melamine and (b) 1-70 mole-% substd. melamine(s) of formula (II); and (B) 0.1-10 mole-% phenol (opt. substd. by 1-9C alkyl or OH, 1-4C alkanes substd. by hydroxyphenyl and/or bis(hydroxyphenyl)sulphone; with (C) HCHO (precursor) in a ratio of melamines to HCHO of 1:(1.15-4.5). Y = hydroxy-(2-10C)-alkyl, hydroxy-(2-4C)-alkyl-(oxa-(2-4C)-alkyl)n (n=1-5) or amino(2-12C)-alkyl and some but not all Y may = H.

Description

The present application relates to a new process for dyeing condensation products in textile form, which can be obtained by condensing a mixture containing unsubstituted melamine, substituted melamine and hydroxyphenyl compounds, with formaldehyde or formaldehyde-providing compounds, in an aqueous liquor with a dye from the class of the azo , Anthraquinone, coumarin, methine or azamethine, quinophthalone or nitro dyes.

Special condensation products based on melamine and formaldehyde are known from US Pat. No. 5,322,915. These condensation products can be used to produce refractory fibers, fabrics, knitted fabrics or nonwovens, for example refractory suits.

The object of the present invention was to provide a method by means of which such condensation products can be dyed in an aqueous liquor with disperse or acid dyes in an advantageous manner. The condensation products should be in textile form, i.e. in the form of fibers, yarns, threads, knitwear, woven goods or non-wovens.

• (A) 90 bis 99,9 Mol-% eines Gemisches, bestehend im wesentlichen aus
  • (a) 30 bis 99 Mol-% Melamin und
  • (b) 1 bis 70 Mol-% eines substituierten Melamins der Formel I
    
    in der die Reste Y unabhängig voneinander jeweils Wasserstoff, Hydroxy-C₂-C₁₀-alkyl, Hydroxy-C₂-C₄-alkyl-(oxa-C₂-C₄-alkyl)_n, worin n für 1 bis 5 steht, oder Amino-C₂-C₁₂-alkyl bedeuten, mit der Maßgabe, daß mindestens ein Rest Y von Wasserstoff verschieden ist, oder Mischungen von Melaminen der Formel I sowie
• (B) 0,1 bis 10 Mol-%, bezogen auf (A) und (B), Phenol, das gegebenenfalls durch C₁-C₉-Alkyl oder Hydroxy substituiert ist, C₁-C₄-Alkane, die durch Hydroxyphenyl substituiert sind, Bis(hydroxyphenyl)sulfone oder Mischungen dieser Verbindungen,

mit Formaldehyd oder formaldehydliefernden Verbindungen, wobei das Molverhältnis von Melaminen zu Formaldehyd im Bereich von 1:1,15 bis 1:4,5 liegt,
vorteilhaft gelingt, wenn man die Kondensationsprodukte in Form von Fasern, Garnen, Zwirnen, Maschenware, Webware oder Non-wovens in einer wäßrigen Flotte, die einen pH-Wert von 1 bis 12 aufweist, bei einer Temperatur von 20 bis 250°C mit einem oder mehreren Farbstoffen aus der Klasse der Azofarbstoffe, Anthrachinonfarbstoffe, Cumarinfarbstoffe oder Methin- oder Azamethinfarbstoffe, Chinophthalonfarbstoffe oder Nitrofarbstoffe behandelt.It has now been found that the dyeing of condensation products which can be obtained by condensing a mixture containing as essential components

• (A) 90 to 99.9 mol% of a mixture consisting essentially of
  • (a) 30 to 99 mole% melamine and
  • (b) 1 to 70 mol% of a substituted melamine of the formula I.
    
    in which the radicals Y are each independently hydrogen, hydroxy-C₂-C₁₀-alkyl, hydroxy-C₂-C₄-alkyl- (oxa-C₂-C₄-alkyl) _n , where n is 1 to 5, or amino-C₂- C₁₂-alkyl, with the proviso that at least one radical Y is different from hydrogen, or mixtures of melamines of the formula I and
• (B) 0.1 to 10 mol%, based on (A) and (B), phenol which is optionally substituted by C₁-C₉-alkyl or hydroxy, C₁-C₄-alkanes which are substituted by hydroxyphenyl, bis (hydroxyphenyl) sulfones or mixtures of these compounds,

with formaldehyde or compounds providing formaldehyde, the molar ratio of melamines to formaldehyde being in the range from 1: 1.15 to 1: 4.5,
is advantageous if the condensation products in the form of fibers, yarns, twists, knitwear, woven goods or non-wovens in an aqueous liquor which has a pH of 1 to 12 at a temperature of 20 to 250 ° C with a or several dyes from the class of azo dyes, anthraquinone dyes, coumarin dyes or methine or azamethine dyes, quinophthalone dyes or nitro dyes.

As already mentioned at the beginning, the production of the condensation products is described in US Pat. No. 5,322,915, to which express reference is made.

In the process according to the invention, preference is given to using condensation products in which component (A) consists essentially of 50 to 99 mol%, in particular 85 to 95 mol%, melamine and 1 to 50 mol%, in particular 5 to 15 mol% %, Melamine of formula I.

Those condensation products which can be obtained by reacting components (A) and (B) with formaldehyde or formaldehyde-providing compounds are furthermore preferably used, the molar ratio of melamines to formaldehyde being in the range from 1: 1.8 to 1: 3.0 .

Y is e.g. Hydroxy-C₂-C₁₀-alkyl, such as 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxyisopropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl or 3-hydroxy-2,2-dimethylpropyl. Y is preferably hydroxy-C₂-C₆-alkyl, in particular hydroxy-C₂-C₄-alkyl and very particularly preferably 2-hydroxyethyl or 2-hydroxyisopropyl.

Y is furthermore, for example, hydroxy-C₂-C₄-alkyl- (oxa-C₂-C₄-alkyl) _n , such as 5-hydroxy-3-oxapentyl, 5-hydroxy-3-oxa-2,5-dimethylpentyl, 5-hydroxy- 3-oxa-1,4-dimethylpentyl, 5-hydroxy-3-oxa-1,2,4,5-tetramethylpentyl or 8-hydroxy-3,6-dioxaoctyl. N is preferably 1 to 4, in particular 1 or 2.

Y is still e.g. Amino-C₂-C₁₂-alkyl, such as 2-aminoethyl, 3-aminopropyl, 4-aminobutyl, 5-aminopentyl, 6-aminohexyl, 7-aminoheptyl or 8-aminooctyl. Y is preferably amino-C₂-C₈-alkyl, particularly preferably 2-aminoethyl or 6-aminohexyl and very particularly preferably 6-aminohexyl.

Suitable substituted melamines of the formula I are, for example, the following compounds:
2-hydroxyethylamino-1,3,5-triazines, such as 2-hydroxyethylamino-1,3,5-triazine, 2,4-bis (2-hydroxyethylamino) -1,3,5-triazine or 2,4,6- Tris (2-hydroxyethylamino) -1,3,5-triazine, 2-hydroxyisopropylamino-1,3,5-triazines, such as 2- (2-hydroxyisopropylamino) -1,3,5-triazine, 2,4-bis ( 2-hydroxyisopropylamino) -1,3,5-triazine or 2,4,6-tris (2-hydroxyisopropylamino) -1,3,5-triazine, 5-hydroxy-3-oxapentylamino-1,3,5-triazine, such as 2- (5-hydroxy-3-oxapentylamino) -1,3,5-triazine, 2,4-bis (5-hydroxy-3-oxapentylamino) -1,3,5-triazine or 2,4,6- Tris (5-hydroxy-3-oxapentylamino) -1,3,5-triazine, or 6-aminohexylamino-1,3,5-triazines, such as 2- (6-aminohexylamino) -1,3,5-triazine, 2 , 4-bis (6-aminohexylamino) -1,3,5-triazine or 2,4,6-tris (6-aminohexylamino) -1,3,5-triazine or mixtures of these compounds, for example a mixture of 10 mol % 2- (5-hydroxy-3-oxapentylamino) -1,3,5-triazine, 50 mol% 2,4-bis (5-hydroxy-3-oxapentylamino) -1,3,5-triazine and 40 mol -% 2,4,6-tris (5-hydroxy-3-oxapentylamino) -1,3,5-triazine.

Suitable compounds (B) are, for example, phenol, 4-methylphenol, 4-tert-butylphenol, 4-octylphenol, 4-nonylphenol, pyrocatechol, resorcinol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane or 4,4'-dihydroxydiphenyl sulfone. Phenol, resorcinol or 2,2-bis (4-hydroxyhenyl) propane are preferred.

Formaldehyde is generally used as an aqueous solution with a concentration of e.g. 40 to 50% by weight or in the form of compounds providing formaldehyde during the reaction with (A) and (B), for example as oligomeric or polymeric formaldehyde in solid form, such as paraformaldehyde, 1,3,5-trioxane or 1,3 , 5,7-tetroxocan.

Fibers can be produced in a manner known per se from the condensation products described above (e.g. EP-A-408 947).

Of course, the method according to the invention can also be used to dye mixed fabrics of the condensation products described in more detail above with cellulose or aramid fibers, if appropriate using other classes of dyes, such as reactive, vat, direct or sulfur dyes. Particularly suitable aramids consist essentially of a polycondensation product of iso- or terephthalic acid with a meta- or para-phenylenediamine. Such products are known and e.g. commercially available under the name Nomex® or Kevlar® (DuPont).

The dyes used in the process according to the invention come from the class of azo, anthraquinone, coumarin, methine or azamethine, quinophthalone or nitro dyes. They are either free of ionic groups or carry carboxyl and / or sulfonic acid groups.

Suitable dyes that are free of ionic groups are described in more detail below.

Suitable azo dyes are especially mono- or disazo dyes, e.g. those with a diazo component derived from an aniline or from a five-membered aromatic heterocyclic amine, which has one to three heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, in the heterocyclic ring and by a benzene, thiophene , Pyridine or pyrimidine ring can be fused.

Important mono- or disazo dyes are, for example, those whose diazo component is derived, for example, from an aniline or from a heterocyclic amine from the pyrrole, furan, thiophene, pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, Triazole, oxadiazole, thiadiazole, benzofuran, benzthiophene, benzthiophene, Pyrimidothiophene, thienothiophene or thienothiazole series.

Particular mention should be made of those diazo components which are derived from an aniline or from a heterocyclic amine from pyrrole, thiophene, pyrazole, thiazole, isothiazole, triazole, thiadiazole, benzothiophene, benzothiazole, benzisothiazole, pyridothiophene , Pyrimidothiophene, thienothiophene or thienothiazole series.

Of further importance are azo dyes with a coupling component from the aniline, aminonaphthalene, aminothiazole, diaminopyridine or hydroxypyridone series.

D¹

für einen Rest der Formel

und

K

für Hydroxyphenyl oder einen Rest der Formel

stehen, worin

L¹

Nitro, Cyano, C₁-C₆-Alkanoyl, Benzoyl, C₁-C₆-Alkylsulfonyl, gegebenenfalls substituiertes Phenylsulfonyl oder einen Rest der Formel -CH=T, worin T die Bedeutung von Hydroxyimino, C₁-C₄-Alkoxyimino oder eines Restes einer CH-aciden Verbindung H₂T besitzt,

L²

Wasserstoff, C₁-C₆-Alkyl, Halogen, Hydroxy, Mercapto, gegebenenfalls durch Phenyl oder C₁-C₄-Alkoxy substituiertes C₁-C₆-Alkoxy, gegebenenfalls substituiertes Phenoxy, gegebenenfalls durch Phenyl substituiertes C₁-C₆-Alkylthio, gegebenenfalls substituiertes Phenylthio, C₁-C₆-Alkylsulfonyl oder gegebenenfalls substituiertes Phenylsulfonyl,

L³

Cyano, C₁-C₄-Alkoxycarbonyl oder Nitro,

L⁴

Wasserstoff, C₁-C₆-Alkyl oder Phenyl,

L⁵

C₁-C₆-Alkyl oder Phenyl,

L⁶

Wasserstoff, Cyano, C₁-C₄-Alkoxycarbonyl, C₁-C₆-Alkanoyl, Thiocyanato oder Halogen,

L⁷

Nitro, Cyano, C₁-C₆-Alkanoyl, Benzoyl, C₁-C₄-Alkoxycarbonyl, C₁-C₆-Alkylsulfonyl, gegebenenfalls substituiertes Phenylsulfonyl oder einen Rest der Formel -CH=T, worin T die obengenannte Bedeutung besitzt,

L⁸

Wasserstoff, C₁-C₆-Alkyl, Cyano, Halogen, gegebenenfalls durch Phenyl oder C₁-C₄-Alkoxy substituiertes C₁-C₆-Alkoxy, gegebenenfalls durch Phenyl substituiertes C₁-C₆-Alkylthio, gegebenenfalls substituiertes Phenylthio, C₁-C₆-Alkylsulfonyl, gegebenenfalls substituiertes Phenylsulfonyl oder C₁-C₄-Alkoxycarbonyl,

L⁹

Cyano, gegebenenfalls durch Phenyl substituiertes C₁-C₆-Alkyl, gegebenenfalls durch Phenyl substituiertes C₁-C₆-Alkylthio, gegebenenfalls substituiertes Phenyl, Thienyl, C₁-C₄-Alkylthienyl, Pyridyl oder C₁-C₄-Alkylpyridyl,

L¹⁰

Phenyl oder Pyridyl,

L¹¹

Trifluormethyl, Nitro, C₁-C₆-Alkyl, Phenyl, gegebenenfalls durch Phenyl substituiertes C₁-C₆-Alkylthio oder C₁-C₆-Dialkylamino,

L¹²

C₁-C₆-Alkyl, Phenyl, 2-Cyanoethylthio oder 2-(C₁-C₄-Alkoxycarbonyl)ethylthio,

L¹³

Wasserstoff, Nitro oder Halogen,

L¹⁴

Wasserstoff, Cyano, C₁-C₄-Alkoxycarbonyl, Nitro oder Halogen,

L¹⁵, L¹⁶ und L¹⁷

gleich oder verschieden sind und unabhängig voneinander jeweils Wasserstoff, C₁-C₆-Alkyl, C₁-C₆-Alkoxy, Halogen, Nitro, Cyano, gegebenenfalls substituiertes C₁-C₄-Alkoxycarbonyl, C₁-C₆-Alkylsulfonyl, gegebenenfalls substituiertes Phenylsulfonyl oder gegebenenfalls substituiertes Phenylazo,

R¹ und R²

unabhängig voneinander jeweils Wasserstoff, gegebenenfalls substituiertes C₁-C₆-Alkyl, das durch 1 oder 2 Sauerstoffatome in Etherfunktion unterbrochen sein kann, C₅-C₇-Cycloalkyl oder C₃-C₆-Alkenyl,

R³

Wasserstoff, C₁-C₆-Alkyl oder C₁-C₆-Alkoxy,

R⁴

Wasserstoff, C₁-C₆-Alkyl, C₁-C₆-Alkoxy, C₁-C₆-Alkylsulfonylamino, gegebenenfalls substituiertes C₁-C₆-Alkanoylamino oder Benzoylamino,

R⁵ und R⁶

unabhängig voneinander jeweils Wasserstoff oder C₁-C₆-Alkyl,

R⁷

Wasserstoff, gegebenenfalls substituiertes Phenyl oder Thienyl,

R⁸

Wasserstoff oder C₁-C₆-Alkyl,

R⁹

Cyano, Carbamoyl oder Acetyl,

R¹⁰, R¹¹ und R¹²

unabhängig voneinander jeweils gegebenenfalls substituiertes C₁-C₁₂-Alkyl, das durch 1 bis 3 Sauerstoffatome in Etherfunktion unterbrochen sein kann, C₅-C₇-Cycloalkyl, gegebenenfalls substituiertes Phenyl, C₃-C₆-Alkenyl, gegebenenfalls substituiertes Benzoyl, C₁-C₈-Alkanoyl, C₁-C₆-Alkylsulfonyl oder gegebenenfalls substituiertes Phenylsulfonyl oder R¹¹ und R¹² zusammen mit dem sie verbindenden Stickstoffatom einen 5- oder 6-gliedrigen gesättigten heterocyclischen Rest, der gegebenenfalls weitere Heteroatome enthält, und

R¹³

Wasserstoff oder C₁-C₆-Alkyl bedeuten.

Azo dyes of the formula IIa are of particular importance

D¹-N = N-K¹ (IIa),

in the

D¹

for a rest of the formula

and

K

for hydroxyphenyl or a radical of the formula

stand in what

L¹

Nitro, cyano, C₁-C₆-alkanoyl, benzoyl, C₁-C₆-alkylsulfonyl, optionally substituted phenylsulfonyl or a radical of the formula -CH = T, where T is hydroxyimino, C₁-C₄-alkoxyimino or a radical of a CH-acidic Has H₂T compound,

L²

Hydrogen, C₁-C₆-alkyl, halogen, hydroxy, mercapto, optionally substituted by phenyl or C₁-C₄-alkoxy, C₁-C₆-alkoxy, optionally substituted phenoxy, optionally substituted by phenyl, C₁-C₆-alkylthio, optionally substituted phenylthio, C₁-C₆ alkylsulfonyl or optionally substituted phenylsulfonyl,

L³

Cyano, C₁-C₄ alkoxycarbonyl or nitro,

L⁴

Hydrogen, C₁-C₆ alkyl or phenyl,

L⁵

C₁-C₆ alkyl or phenyl,

L⁶

Hydrogen, cyano, C₁-C₄-alkoxycarbonyl, C₁-C₆-alkanoyl, thiocyanato or halogen,

L⁷

Nitro, cyano, C₁-C₆-alkanoyl, benzoyl, C₁-C₄-alkoxycarbonyl, C₁-C₆-alkylsulfonyl, optionally substituted phenylsulfonyl or a radical of the formula -CH = T, in which T has the meaning given above,

L⁸

Hydrogen, C₁-C₆-alkyl, cyano, halogen, optionally substituted by phenyl or C₁-C₄-alkoxy, C₁-C₆-alkoxy, optionally substituted by phenyl, C₁-C₆-alkylthio, optionally substituted phenylthio, C₁-C₆-alkylsulfonyl, optionally substituted Phenylsulfonyl or C₁-C₄ alkoxycarbonyl,

L⁹

Cyano, optionally substituted by phenyl C₁-C₆-alkyl, optionally substituted by phenyl C₁-C₆-alkylthio, optionally substituted phenyl, thienyl, C₁-C₄-alkylthienyl, pyridyl or C₁-C₄-alkylpyridyl,

L¹⁰

Phenyl or pyridyl,

L¹¹

Trifluoromethyl, nitro, C₁-C₆ alkyl, phenyl, optionally substituted by phenyl C₁-C₁ alkylthio or C₁-C₆ dialkylamino,

L¹²

C₁-C₆-alkyl, phenyl, 2-cyanoethylthio or 2- (C₁-C₄-alkoxycarbonyl) ethylthio,

L¹³

Hydrogen, nitro or halogen,

L¹⁴

Hydrogen, cyano, C₁-C₄ alkoxycarbonyl, nitro or halogen,

L¹⁵, L¹⁶ and L¹⁷

are identical or different and are each independently hydrogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, halogen, nitro, cyano, optionally substituted C₁-C₄-alkoxycarbonyl, C₁-C₆-alkylsulfonyl, optionally substituted Phenylsulfonyl or optionally substituted phenylazo,

R1 and R2

independently of one another each hydrogen, optionally substituted C₁-C--alkyl which can be interrupted by 1 or 2 oxygen atoms in ether function, C₅-C₇-cycloalkyl or C₃-C₆-alkenyl,

R³

Hydrogen, C₁-C₆-alkyl or C₁-C₆-alkoxy,

R⁴

Hydrogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylsulfonylamino, optionally substituted C₁-C₆-alkanoylamino or benzoylamino,

R⁵ and R⁶

independently of one another in each case hydrogen or C₁-C₆-alkyl,

R⁷

Hydrogen, optionally substituted phenyl or thienyl,

R⁸

Hydrogen or C₁-C₆ alkyl,

R⁹

Cyano, carbamoyl or acetyl,

R¹⁰, R¹¹ and R¹²

independently of one another each optionally substituted C₁-C₁₂ alkyl, which can be interrupted by 1 to 3 oxygen atoms in ether function, C₅-C₇-cycloalkyl, optionally substituted phenyl, C₃-C₆-alkenyl, optionally substituted benzoyl, C₁-C₈-alkanoyl, C₁ -C₆-alkylsulfonyl or optionally substituted phenylsulfonyl or R¹¹ and R¹² together with the nitrogen atom connecting them a 5- or 6-membered saturated heterocyclic radical which optionally contains further heteroatoms, and

R¹³

Is hydrogen or C₁-C₆ alkyl.

worin

A¹

Wasserstoff, C₁-C₈-Alkyl oder gegebenenfalls substituiertes Phenyl,

A²

Hydroxy oder den Rest NH-A¹,

A³

Wasserstoff oder Nitro,

A⁴

Halogen, Hydroxyphenyl, C₁-C₄-Alkoxyphenyl oder ein Rest der Formel

worin G¹ für Sauerstoff oder Schwefel und G² für Wasserstoff oder C₁-C₈-Monoalkylsulfamoyl, dessen Alkylkette durch 1 oder 2 Sauerstoffatome in Etherfunktion unterbrochen sein kann, stehen,

einer der beiden Reste A⁵ und A⁶ Hydroxy und der andere den Rest NH-A¹ oder A⁵ und A⁶ jeweils Wasserstoff,

A⁷

Wasserstoff oder C₁-C₈-Alkyl, das gegebenenfalls durch 1 bis 3 Sauerstoffatome in Etherfunktion unterbrochen ist,

einer der beiden Reste A⁸ und A⁹ Hydroxy und der andere Anilino und

G³

Sauerstoff oder Imino bedeuten.

Suitable anthraquinone dyes come, for example, from the class of 1-aminoanthraquinones. They obey, for example, the formula Va, Vb, Vc or Vd

wherein

A¹

Hydrogen, C₁-C₈-alkyl or optionally substituted phenyl,

A²

Hydroxy or the radical NH-A¹,

A³

Hydrogen or nitro,

A⁴

Halogen, hydroxyphenyl, C₁-C₄ alkoxyphenyl or a radical of the formula

where G¹ is oxygen or sulfur and G² is hydrogen or C₁-C₈ monoalkylsulfamoyl, the alkyl chain of which can be interrupted by 1 or 2 oxygen atoms in ether function,

one of the two residues A⁵ and A⁶ hydroxy and the other the rest NH-A¹ or A⁵ and A⁶ are each hydrogen,

A⁷

Hydrogen or C₁-C₈-alkyl, which is optionally interrupted by 1 to 3 oxygen atoms in ether function,

one of the two residues A⁸ and A⁹ hydroxy and the other anilino and

G³

Mean oxygen or imino.

worin

W¹ und W²

unabhängig voneinander jeweils C₁-C₄-Alkyl,

W³

Benzimidazol-2-yl, 5-Chlorbenzoxazol-2-yl, Benzthiazol-2-yl, 4-Hydroxychinazolin-2-yl oder 5-Phenyl-1,3,4-thiadiazol-2-yl und

W⁴

C₁-C₈-Alkyl bedeuten.

Suitable coumarin dyes come, for example, from the class of 7-dialkylaminocoumarins. They obey, for example, the formula VI, VIb or VIc

wherein

W¹ and W²

independently of one another each C₁-C₄-alkyl,

W³

Benzimidazol-2-yl, 5-chlorobenzoxazol-2-yl, benzthiazol-2-yl, 4-hydroxyquinazolin-2-yl or 5-phenyl-1,3,4-thiadiazol-2-yl and

W⁴

C₁-C₈ alkyl mean.

worin

X

Stickstoff oder CH,

Q¹

C₁-C₂₀-Alkyl, das gegebenenfalls substituiert ist und durch ein oder mehrere Sauerstoffatome in Etherfunktion unterbrochen sein kann, gegebenenfalls substituiertes Phenyl oder Hydroxy,

Q²

einen 5-gliedrigen aromatischen heterocyclischen Rest,

Q³

Wasserstoff, Cyano, Carbamoyl, Carboxyl oder C₁-C₄-Alkoxycarbonyl,

Q⁴

Sauerstoff oder einen Rest der Formel C(CN)₂, C(CN)COOE¹ oder C(COOE¹)₂, wobei E¹ jeweils für C₁-C₈-Alkyl, das gegebenenfalls durch 1 oder 2 Sauerstoffatome in Etherfunktion unterbrochen ist, steht,

Q⁵

Wasserstoff oder C₁-C₄-Alkyl,

Q⁶

C₁-C₂₀-Alkyl, das gegebenenfalls substituiert ist und durch ein oder mehrere Sauerstoffatome in Etherfunktion unterbrochen sein kann, gegebenenfalls substituiertes Phenyl, Hydroxy oder einen Rest der Formel NE²E³, wobei E² und E³ unabhängig voneinander jeweils für Wasserstoff, gegebenenfalls substituiertes C₁-C₁₂-Alkyl, C₅-C₇-Cycloalkyl, gegebenenfalls substituiertes Phenyl, gegebenenfalls substituiertes Pyridyl, gegebenenfalls substituiertes C₁-C₁₂-Alkanoyl, C₁-C₁₂-Alkoxycarbonyl, gegebenenfalls substituiertes C₁-C₁₂-Alkylsulfonyl, C₅-C₇-Cycloalkylsulfonyl, gegebenenfalls substituiertes Phenylsulfonyl, gegebenenfalls substituiertes Pyridylsulfonyl, gegebenenfalls substituiertes Benzoyl, Pyridylcarbonyl oder Thienylcarbonyl oder E² und E³ zusammen mit dem sie verbindenden Stickstoffatom gegebenenfalls durch C₁-C₄-Alkyl substituiertes Succinimido, gegebenenfalls durch C₁-C₄-Alkyl substituiertes Phthalimido oder einen 5- oder 6-gliedrigen gesättigten heterocyclischen Rest, der gegebenenfalls weitere Heteroatome enthält, stehen, bedeuten.

Suitable methine or azamethine dyes come, for example, from the class of the triazolopyridines or pyridines. They obey, for example, Formula VIIa or VIIb

wherein

X

Nitrogen or CH,

Q¹

C₁-C₂₀-alkyl, which is optionally substituted and can be interrupted by one or more oxygen atoms in ether function, optionally substituted phenyl or hydroxy,

Q²

a 5-membered aromatic heterocyclic radical,

Q³

Hydrogen, cyano, carbamoyl, carboxyl or C₁-C₄ alkoxycarbonyl,

Q⁴

Oxygen or a radical of the formula C (CN) ₂, C (CN) COOE¹ or C (COOE¹) ₂, where E¹ each represents C₁-C₈-alkyl, which is optionally interrupted by 1 or 2 oxygen atoms in ether function,

Q⁵

Hydrogen or C₁-C₄ alkyl,

Q⁶

C₁-C₂₀-alkyl, which is optionally substituted and can be interrupted by one or more oxygen atoms in ether function, optionally substituted phenyl, hydroxy or a radical of the formula NE²E³, where E² and E³ each independently represent hydrogen, optionally substituted C₁-C₁₂- Alkyl, C₅-C₇-cycloalkyl, optionally substituted phenyl, optionally substituted pyridyl, optionally substituted C₁-C₁₂ alkanoyl, C₁-C₁₂-alkoxycarbonyl, optionally substituted C₁-C₁₂-alkylsulfonyl, C₅-C₇-cycloalkylsulfonyl, optionally substituted phenylsulfonyl, optionally substituted Pyridylsulfonyl, optionally substituted benzoyl, pyridylcarbonyl or thienylcarbonyl or E² and E³ together with the nitrogen atom connecting them optionally substituted by C₁-C₄-alkyl succinimido, optionally substituted by C₁-C₄-alkyl or a 5- or 6-membered phthalimido ige saturated heterocyclic radical, which optionally contains further heteroatoms, mean.

Reste Q² können sich z.B. von Komponenten aus der Pyrrol-, Thiazol-, Thiophen- oder Indolreihe ableiten.The dyes of formula VIIa or VIIb can occur in several tautomeric forms, all of which are encompassed by the claims. For example, the connections of the Formula VIIa (with Q⁴ = oxygen and Q⁵ = methyl) occur inter alia in the following tautomeric forms:

Residues Q² can be derived, for example, from components from the pyrrole, thiazole, thiophene or indole series.

worin

m

0 oder 1,

E⁴ und E⁵

unabhängig voneinander jeweils Wasserstoff oder mit Ausnahme von Hydroxy auch den obengenannten Rest R¹ oder zusammen mit dem sie verbindenden Stickstoffatom einen 5- oder 6-gliedrigen gesättigten heterocyclischen Rest, der gegebenenfalls weitere Heteroatome enthält,

E⁶

Wasserstoff, Halogen, C₁-C₈-Alkyl, gegebenenfalls durch C₁-C₄-Alkyl oder C₁-C₄-Alkoxy substituiertes Phenyl, gegebenenfalls durch C₁-C₄-Alkyl oder C₁-C₄-Alkoxy substituiertes Benzyl, Cyclohexyl, Thienyl, Hydroxy oder C₁-C₈-Monoalkylamino,

E⁷ und E⁸

unabhängig voneinander jeweils Wasserstoff, Hydroxy, gegebenenfalls durch Phenyl oder C₁-C₄-Alkylphenyl substituiertes C₁-C₈-Alkyl, gegebenenfalls durch Phenyl oder C₁-C₄-Alkylphenyl substituiertes C₁-C₈-Alkoxy, C₁-C₈-Alkanoylamino, C₁-C₈-Alkylsulfonylamino oder C₁-C₈-Mono- oder Dialkylaminosulfonylamino,

E⁹

Cyano, Carbamoyl, C₁-C₈-Mono- oder Dialkylcarbamoyl, C₁-C₈-Alkoxycarbonyl oder gegebenenfalls substituiertes Phenyl und

E¹⁰

Halogen, Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₁-C₄-Alkylthio, gegebenenfalls durch C₁-C₄-Alkyl oder C₁-C₄-Alkoxy substituiertes Phenyl oder Thienyl bedeuten.

Important residues Q² are, for example, those of the formulas VIIIa to VIIId

wherein

m

0 or 1,

E⁴ and E⁵

independently of one another in each case hydrogen or with the exception of hydroxy also the abovementioned radical R 1 or together with the nitrogen atom connecting them a 5- or 6-membered saturated heterocyclic radical which optionally contains further heteroatoms,

E⁶

Hydrogen, halogen, C₁-C₈-alkyl, phenyl optionally substituted by C₁-C₄-alkyl or C₁-C₄-alkoxy, optionally benzyl, cyclohexyl, thienyl, hydroxy or C₁- substituted by C₁-C₄-alkyl or C₁-C₄-alkoxy C₈-monoalkylamino,

E⁷ and E⁸

independently of one another in each case hydrogen, hydroxy, optionally substituted by phenyl or C₁-C₄-alkylphenyl C₁-C₈-alkyl, optionally by phenyl or C₁-C₄-alkylphenyl-substituted C₁-C₈-alkoxy, C₁-C₈-alkanoylamino, C₁-C₈-alkylsulfonylamino or C₁-C₈-mono- or dialkylaminosulfonylamino,

E⁹

Cyano, carbamoyl, C₁-C₈-mono- or dialkylcarbamoyl, C₁-C₈-alkoxycarbonyl or optionally substituted phenyl and

E¹⁰

Halogen, hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, optionally substituted by C₁-C₄-alkyl or C₁-C₄-alkoxy, phenyl or thienyl.

in der G⁴ Wasserstoff, Chlor oder Brom bedeutet.Particularly suitable quinophthalone dyes have a quinoline ring on which ring position 4 is either unsubstituted or substituted by halogen. For example, they obey Formula IX

in which G⁴ means hydrogen, chlorine or bromine.

Alle in den obengenannten Formeln auftretenden Alkyl- oder Alkenylgruppen können sowohl geradkettig als auch verzweigt sein.A suitable nitro dye obeys formula X, for example

All alkyl or alkenyl groups occurring in the above formulas can be both straight-chain and branched.

If substituted alkyl radicals occur in the abovementioned formulas, unless otherwise stated, substituents such as cyclohexyl, phenyl, C₁-C₄-alkylphenyl, C₁-C₄-alkoxyphenyl, halophenyl, C₁-C₈-alkanoyloxy, C₁-C₈-alkylaminocarbonyloxy, C₁-C₂₀-alkoxycarbonyl, C₁-C₂₀-alkoxycarbonyloxy, where the alkyl chain of the last three radicals optionally interrupted by 1 to 4 oxygen atoms in ether function and / or substituted by phenyl or phenoxy, cyclohexyloxy, phenoxy, halogen, hydroxy or cyano come into consideration . The alkyl radicals generally have 1 or 2 substituents.

If alkyl radicals which are interrupted by oxygen atoms in ether function occur in the above formulas, unless otherwise noted, preference is given to those alkyl radicals which are interrupted by 1 to 4 oxygen atoms, in particular 1 to 2 oxygen atoms, in ether function.

If substituted phenyl or pyridyl radicals occur in the above formulas, unless otherwise noted, the substituents can be e.g. C₁-C₈-alkyl, C₁-C₈-alkoxy, halogen, in particular chlorine or bromine, nitro or carboxyl. The phenyl or pyridyl radicals generally have 1 to 3 substituents.

The following are exemplary lists for the radicals in the formulas II to IV.

L², L⁴, L⁵, L⁸, L⁹, L¹¹, L¹², L¹⁵, L¹⁶, L¹⁷, R¹, R², R³, R⁴, R⁵, R⁵, R⁶, R⁸, R¹⁰, R¹¹, R¹² and R¹³ are e.g. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl or 2-methylpentyl.

Residues L⁹ are still e.g. Benzyl or 1- or 2-phenylethyl.

L², L⁸, L⁹ and L¹¹ are also e.g. Methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, pentylthio, hexylthio, benzylthio or 1- or 2-phenylethylthio.

L² and L⁸ are still e.g. Phenylthio, 2-methylphenylthio, 2-methoxyphenylthio or 2-chlorophenylthio.

L², L⁸, L¹⁵, L¹⁶, L¹⁷, R³ and R⁴ are also e.g. Methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, neopentyloxy, tert-pentyloxy, hexyloxy or 2-methylpentyloxy.

L⁶ radicals, as are also L², L⁸, L¹³, L¹⁴, L¹⁵, L¹⁶ and L¹⁷ radicals, e.g. Fluorine, chlorine or bromine.

Radicals L⁷, as further also radicals L¹, L², L⁸, L¹⁵, L¹⁶, L¹⁷, R¹⁰, R¹¹ and R¹², for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl sec-butylsulfonyl, pentylsulfonyl, Isopentylsulfonyl, Neopentylsulfonyl, hexylsulfonyl, Phenylsulfonyl, 2-methylphenylsulfonyl, 2-methoxyphenylsulfonyl or 2-chlorophenylsulfonyl.

L³ residues, like L weiterhin, L⁷, L⁸, L¹⁴, L¹⁵, L¹⁶ and L¹⁷ residues, e.g. Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl or sec-butoxycarbonyl.

L¹⁵, L¹⁶ and L¹⁷ are also e.g. 2-phenoxyethoxycarbonyl, 2- or 3-phenoxypropoxycarbonyl, 2- or 4-phenoxybutoxycarbonyl, phenylazo, 4-nitrophenylazo or 2,4-dinitro-6-bromophenylazo.

L² and L⁸ are still e.g. 2-methoxyethoxy, 2-ethoxyethoxy, 2- or 3-methoxypropoxy, 2- or 3-ethoxypropoxy, 2- or 4-methoxybutoxy, 2- or 4-ethoxybutoxy, 5-methoxypentyloxy, 5-ethoxypentyloxy, 6-methoxyhexyloxy, 6- Ethoxyhexyloxy, benzyloxy or 1- or 2-phenylethoxy.

Residues L¹¹ are further e.g. Dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, dipentylamino, dihexylamino or N-methyl-N-ethylamino.

Residues L¹² are further e.g. 2-methoxycarbonylethylthio or 2-ethoxycarbonylethylthio.

R¹, R², R¹¹, R¹² and R¹³ are also e.g. Cyclopentyl, cyclohexyl or cycloheptyl.

Residues L⁹ are still e.g. Phenyl, 2-, 3- or 4-methylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-chlorophenyl, 2- or 3-methylthienyl or 2-, 3- or 4-methylpyridyl.

L¹, L⁶ and L⁷ are further e.g. Formyl, acetyl, propionyl, butyryl, pentanoyl or hexanoyl.

in Betracht kommen, wobei

Z¹

Cyano, Nitro, C₁-C₄-Alkanoyl, gegebenenfalls substituiertes Benzoyl, C₁-C₄-Alkylsulfonyl, gegebenenfalls substituiertes Phenylsulfonyl, C₁-C₄-Alkoxycarbonyl, C₃-C₄-Alkenyloxycarbonyl, Phenoxycarbonyl, Carbamoyl, C₁-C₄-Mono- oder Dialkylcarbamoyl, gegebenenfalls substituiertes Phenylcarbamoyl, gegebenenfalls substituiertes Phenyl, Benzthiazol-2-yl, Benzimidazol-2-yl, 5-Phenyl-1,3,4-thiadiazol-2-yl oder 2-Hydroxychinoxalin-3-yl,

Z²

C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder C₃-C₄-Alkenyloxy,

Z³

C₁-C₄-Alkoxycarbonyl, C₃-C₄-Alkenyloxycarbonyl, Phenylcarbamoyl oder Benzimidazol-2-yl,

Z⁴

Cyano, C₁-C₄-Alkoxycarbonyl oder C₃-C₄-Alkenyloxycarbonyl,

Z⁵

Wasserstoff oder C₁-C₆-Alkyl,

Z⁶

Wasserstoff, C₁-C₄-Alkyl oder Phenyl und

Z⁷

C₁-C₄-Alkyl bedeuten.

If L¹ or L⁷ represent the radical -CH = T, in which T is derived from a CH-acidic compound H₂T, as CH-acidic compounds H₂T, for example, compounds of the formula

come into consideration, whereby

Z¹

Cyano, nitro, C₁-C₄-alkanoyl, optionally substituted benzoyl, C₁-C₄-alkylsulfonyl, optionally substituted phenylsulfonyl, C₁-C₄-alkoxycarbonyl, C₃-C₄-alkenyloxycarbonyl, phenoxycarbonyl, carbamoyl, C₁-C₄-mono- or dialkylcarbamoyl substituted phenylcarbamoyl, optionally substituted phenyl, benzthiazol-2-yl, benzimidazol-2-yl, 5-phenyl-1,3,4-thiadiazol-2-yl or 2-hydroxyquinoxalin-3-yl,

Z²

C₁-C₄-alkyl, C₁-C₄-alkoxy or C₃-C₄-alkenyloxy,

Z³

C₁-C₄-alkoxycarbonyl, C₃-C₄-alkenyloxycarbonyl, phenylcarbamoyl or benzimidazol-2-yl,

Z⁴

Cyano, C₁-C₄-alkoxycarbonyl or C₃-C Al-alkenyloxycarbonyl,

Z⁵

Hydrogen or C₁-C₆ alkyl,

Z⁶

Hydrogen, C₁-C Alkyl alkyl or phenyl and

Z⁷

C₁-C₄ alkyl mean.

The radical which is derived from compounds of the formula XIa, XIb or XIc, in which Z¹ is cyano, C₁-C₄-alkanoyl, C₁-C₄-alkoxycarbonyl or C₃-C₄-alkenyloxycarbonyl, Z² is C₁-C₄-alkyl, C₁-C₄ -Alkoxy or C₃-C₄-alkenyloxy, Z³ C₁-C₄-alkoxycarbonyl or C₃-C₄-alkenyloxycarbonyl and Z⁴ cyano mean to emphasize.

Particularly noteworthy is the rest of the compounds derived from the formula XIa, XIb or XIc, wherein Z¹ is cyano, C₁-C Alk-alkoxycarbonyl or C₃-C₄-alkenyloxycarbonyl, Z² C₁-C₄-alkoxy or C₂-C₄-alkenyloxy, Z³ C₁ -C₄-alkoxycarbonyl or C₃-C₄-alkenyloxycarbonyl and Z⁴ mean cyano.

R¹⁰, R¹¹ and R¹² are also e.g. Heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, 4,7-dioxanonyl, 4,8-dioxadecyl, 4,6-dioxaundecyl, 3,6,9-trioxaundecyl, 4,7,10-trioxaundecyl or 4,7,10-trioxadodecyl.

R¹, R², R¹⁰, R¹¹ and R¹² are also e.g. 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-isobutoxyethyl, 2- or 3-methoxypropyl, 1-methoxyprop-2-yl, 2- or 3-ethoxypropyl or 2- or 3-propoxypropyl, 3 , 6-dioxaheptyl, 3,6-dioxaoctyl, 4,7-dioxaoctyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-cyclohexyloxyethyl, 2- or 3-cyclohexyloxypropyl, 2- or 4-cyclohexyloxybutyl, 2-phenoxyethyl , 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2- or 3-methoxycarbonylpropyl, 2- or 3-ethoxycarbonylpropyl, 2- or 3-butoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, 2-cyanoethyl, 2- or 3-cyanopropyl, 4-cyanobutyl, 2-cyclohexylethyl, 2- or 3-cyclohexylpropyl, benzyl, 1- or 2-phenylethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2- or 3-acetyloxypropyl, Prop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl or but-3-en-1-yl.

If the radicals R¹¹ and R¹² together with the nitrogen atom connecting them represent a 5- or 6-membered saturated heterocyclic radical which optionally contains further heteroatoms, then e.g. Pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl, thiomorpholinyl-S, S-dioxide, piperazinyl or N- (C₁-C₄-alkyl) piperazinyl, such as N-methyl- or N-ethylpiperazinyl, into consideration.

R¹⁰, R¹¹ and R¹² are also e.g. Formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, 2-ethylhexanoyl, benzoyl, 2-, 3- or 4-methylbenzoyl, 2-, 3- or 4-methoxybenzoyl or 2-, 3- or 4-chlorobenzoyl.

The following are exemplary lists for the residues in the formulas Va to Vd.

Suitable radicals A¹ and A⁷ are e.g. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl or isooctyl.

Residues A⁷ are still e.g. 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxyropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4 , 7-dioxaoctyl, 4,7-dioxanonyl, 2- or 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl or 3,6,9-trioxaundecyl.

Residues A¹ are further e.g. Phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-propylphenyl, 2-, 3- or 4-isopropylphenyl, 2-, 3- or 4- Butylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-isobutoxyphenyl or 2,4-dimethoxyphenyl.

Residues A⁴ are e.g. Fluorine, chlorine, bromine, 2-, 3- or 4-methoxyphenyl or 2-, 3- or 4-ethoxyphenyl.

Residues G² are e.g. Methylsulfamoyl, ethylsulfamoyl, propylsulfamoyl, isopropylsulfamoyl, butylsulfamoyl, pentylsulfamoyl, hexylsulfamoyl, heptylsulfamoyl, octylsulfamoyl or 4-oxahexylsulfamoyl.

The following are examples of the residues in the formulas VIa to VIc.

Suitable residues W¹, W² and W⁴ e.g. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.

Residues W⁴ are still e.g. Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl or isooctyl.

The following are exemplary lists for the radicals in the formulas VIIa and VIIb.

Suitable radicals Q¹, Q⁵, Q⁶, E¹, E², E³, E⁴, E⁵, E⁶, E⁷, E⁸ and E¹⁰ are, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.

Residues Q¹, Q⁶, E¹, E², E³, E⁴, E⁵, E⁶, E⁷ and E⁸ are further e.g. Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl or isooctyl.

Residues Q¹, E² and E³ are further e.g. Nonyl, isononyl, decyl, isodecyl, undecyl or dodecyl.

Residues Q¹ are further e.g. Tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl (the above designations isooctyl, isononyl, isodecyl and isotridecyl are trivial designations and come from the alcohols obtained after oxosynthesis - see Encyclopedia Ullmanns Eniechemie, see also Ullmanns Enieklie Edition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436.), 2-methoxycarbonylethyl, benzyl, 1- or 2-phenylethyl, 3-benzyloxypropyl, phenoxymethyl, 6-phenoxy-4-oxahexyl, 8 -Phenoxy-4-oxaoctyl, 2-, 3- or 4-chlorophenyl or 2-, 3- or 4-carboxylphenyl.

Q¹ and E¹ are further e.g. 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4 , 7-dioxaoctyl, 4,7-dioxanonyl, 2- or 4-butoxybutyl or 4,8-dioxadecyl.

Residues Q¹ are further e.g. 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9-trioxadodecyl, 3,6,9,12-tetraoxatridecyl, 3,6,9,12-tetraoxatetradecyl, 11-oxahexadecyl, 13- Butyl-11-oxaheptadecyl or 4,11-dioxapentadecyl.

Residues Q³, E², E³ and E⁹ are e.g. Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl or sec-butoxycarbonyl.

Residues E⁹ are still e.g. Mono- or dimethylcarbamoyl, mono- or diethylcarbonyl, mono- or dipropylcarbamoyl, mono- or diisopropylcarbonyl, mono- or dibutylcarbamoyl or N-methyl-N-butylcarbamoyl.

Residues E⁷, E⁸ and E¹⁰ are further e.g. Methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.

Residues E¹⁰ are also, for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio or sec-butylthio.

Residues Q¹, E², E³ and E¹⁰ are further e.g. Phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-propylphenyl, 2-, 3- or 4-isopropylphenyl, 2-, 3- or 4- Butylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-isobutoxyphenyl or 2,4-dimethoxyphenyl.

Residues Q¹, E² and E³ are further e.g. 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2-cyanoethyl, 2- or 3-cyanopropyl, 2-acetyloxyethyl, 2- or 3-acetyloxypropyl, 2-isobutyryloxyethyl, 2- or 3-isobutyryloxypropyl, 2-methoxycarbonylethyl, 2- or 3-methoxycarbonylpropyl, 2-ethoxycarbonylethyl, 2- or 3-ethoxycarbonylpropyl, 2-methoxycarbonyloxyethyl, 2- or 3-methoxycarbonyloxypropyl, 2-ethoxycarbonyloxyethyl, 2- or 3-ethoxycarbonyloxypropyl, 2-butoxycarbonyloxyethyl, 2- or 3-butoxycarbonyloxypropyl, 2 - (2-Phenylethoxycarbonyloxy) ethyl, 2- or 3- (2-phenylethoxycarbonyloxy) propyl, 2- (2-ethoxyethoxycarbonyloxy) ethyl or 2- or 3- (2-ethoxyethoxycarbonyloxy) propyl.

Residues E² and E³ are still e.g. Pyridyl, 2-, 3- or 4-methylpyridyl, 2-, 3- or 4-methoxypyridyl, formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, 2-ethylhexanoyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl Isopropylsulfonyl, butylsulfonyl, cyclopentylsulfonyl, cyclohexylsulfonyl, cycloheptylsulfonyl, phenylsulfonyl, tolylsulfonyl, pyridylsulfonyl, benzoyl, 2-, 3- or 4-methylbenzoyl, 2-, 3- or 4-methoxybenzoyl, 3-carbonyl, 3-ynylcarbonyl, thienyl-3-carbonyl Cyclopentyl, cyclohexyl or cycloheptyl.

If E² and E³ or E⁴ and E⁵ together with the nitrogen atom connecting them represent a 5- or 6-membered saturated heterocyclic radical which optionally contains further heteroatoms, e.g. Pyrrolidinyl, piperidinyl, morpholinyl, piperazinyl, thiomorpholinyl, thiomorpholinyl-5,5-dioxide, or N- (C₁-C₄-alkyl) piperazinyl, such as N-methyl- or N-ethylpiperazinyl, are suitable.

Particularly suitable monoazo dyes are those of the formula IIa in which D¹ is a radical of the formula IIIb.

Particularly suitable monoazo dyes are furthermore those of the formula IIa in which K¹ is a radical of the formula IVa or IVd.

in der

L¹

Nitro, Cyano, C₁-C₆-Alkanoyl oder einen Rest der Formel -CH=T, worin T die Bedeutung eines Restes einer CH-aciden Verbindung H₂T besitzt,

L²

C₁-C₆-Alkyl, Halogen, gegebenenfalls durch Phenyl oder C₁-C₄-Alkoxy substituiertes C₁-C₆-Alkoxy,

L³

Cyano, C₁-C₄-Alkoxycarbonyl oder Nitro,

R¹ und R²

unabhängig voneinander jeweils Wasserstoff, gegebenenfalls substituiertes C₁-C₆-Alkyl, das durch 1 oder 2 Sauerstoffatome in Etherfunktion unterbrochen sein kann, oder C₃-C₆-Alkenyl,

R³

Wasserstoff, C₁-C₆-Alkyl oder C₁-C₆-Alkoxy und

R⁴

Wasserstoff, C₁-C₆-Alkyl, C₁-C₆-Alkoxy, C₁-C₆-Alkylsulfonylamino oder gegebenenfalls substituiertes C₁-C₆-Alkanoylamino bedeuten.

Particularly noteworthy are monoazo dyes of the formula IIb

in the

L¹

Nitro, cyano, C₁-C₆ alkanoyl or a radical of the formula -CH = T, where T has the meaning of a radical of a CH-acidic compound H₂T,

L²

C₁-C₆-alkyl, halogen, optionally substituted by phenyl or C₁-C₄-alkoxy, C₁-C₆-alkoxy,

L³

Cyano, C₁-C₄ alkoxycarbonyl or nitro,

R1 and R2

independently of one another in each case hydrogen, optionally substituted C₁-C₆-alkyl which can be interrupted by 1 or 2 oxygen atoms in ether function, or C₃-C₆-alkenyl,

R³

Hydrogen, C₁-C₆ alkyl or C₁-C₆ alkoxy and

R⁴

Are hydrogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylsulfonylamino or optionally substituted C₁-C₆-alkanoylamino.

Particularly suitable methine or azamethine dyes obey the formula VIIa or VIIb, in which R⁵ is methyl.

Particularly suitable methine or azamethine dyes also obey the formula VIIa or VIIb, in which Q⁵ denotes cyano.

Particularly suitable methine or azamethine dyes also obey the formula VIIa or VIIb, in which Q⁴ is oxygen.

Particularly suitable azamethine dyes also obey Formula VII, in which X is nitrogen.

Particularly suitable methine dyes continue to obey the formula VII, in which X is CH.

Particularly suitable methine or azamethine dyes also obey the formula VIIa or VIIb, in which Q² is a radical from the pyrrole, thiazole or thiophene series.

Particularly suitable methine or azamethine dyes also obey the formula VIIa, in which Q¹ is C₁-C₁₂-alkyl, optionally by C₁-C₆-alkanoyloxy, C₁-C₈-alkoxycarbonyl, the alkyl chain of which can be interrupted by 1 or 2 oxygen atoms in ether function, phenyl or C₁-C₄ alkylphenyl is substituted and can be interrupted by 1 or 2 oxygen atoms in ether function means.

Particularly suitable methine or azamethine dyes also obey the formula VIIb, in which Q⁶ is a radical of the formula NE²E³, where E² and E³ independently of one another each represent optionally substituted C₁-C₁₂ alkanoyl or optionally substituted benzoyl or E² also represents hydrogen.

Particularly noteworthy are methine or azamethine dyes of the formula VIIb, in which Q⁶ is a radical of the formula NE²E³, where E² and E³ independently of one another each represent C₁-C₈ alkanoyl or benzoyl or E² also represents hydrogen.

Also particularly noteworthy are methine or azamethine dyes of the formula VIIa in which Q¹ is alkyl, alkoxyalkyl, alkanoyloxyalkyl or alkoxycarbonylalkyl, these radicals each having up to 12 carbon atoms, optionally benzyl substituted by methyl or phenyl optionally substituted by methyl.

E⁴ und E⁵

unabhängig voneinander für Alkyl, Alkoxyalkyl, Alkanoyloxyalkyl oder Alkoxycarbonylalkyl, wobei diese Reste jeweils bis zu 12 Kohlenstoffatome aufweisen, Wasserstoff, gegebenenfalls durch Methyl substituiertes Benzyl oder gegebenenfalls durch Methyl substituiertes Phenyl,

E⁶

für Wasserstoff, C₁-C₄-Alkyl, gegebenenfalls durch C₁-C₄-Alkyl oder C₁-C₄-Alkoxy substituiertes Phenyl, Benzyl oder Thienyl,

E⁹

für Cyano,

E¹⁰

für Halogen, Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, C₁-C₄-Alkylthio, gegebenenfalls durch C₁-C₄-Alkyl substituiertes Phenyl oder Thienyl und

n

für 0 stehen.

Also particularly noteworthy are methine or azamethine dyes of the formula VIIa or VIIb, in which Q² is a radical of the abovementioned formula VIIIa or VIIIc, in particular VIIIa, where

E⁴ and E⁵

independently of one another for alkyl, alkoxyalkyl, alkanoyloxyalkyl or alkoxycarbonylalkyl, where these radicals each have up to 12 carbon atoms, hydrogen, optionally benzyl substituted by methyl or phenyl optionally substituted by methyl,

E⁶

for hydrogen, C₁-C₄-alkyl, optionally substituted by C₁-C₄-alkyl or C₁-C₄-alkoxy phenyl, benzyl or thienyl,

E⁹

for cyano,

E¹⁰

for halogen, hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, optionally substituted by C₁-C₄-alkyl, phenyl or thienyl and

n

stand for 0.

Particularly suitable quinophthalone dyes obey the formula IX in which G⁴ is hydrogen or bromine.

The monoazo dyes of the formula IIa are known per se and are described in large numbers, e.g. in K. Venkataraman "The Chemistry of Synthetic Dyes", Vol. VI, Academic Press, New York, London, 1972, or in EP-A-201 896.

The anthraquinone dyes of the formulas Va to Vc are also known per se and are e.g. in D.R. Waring, G. Hallas "The Chemistry and Application of Dyes", pages 107 to 118, Plenum Press, New York, London, 1990.

The coumarin dyes of formula VIa to VIc are also known per se and e.g. in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 17, page 469.

The methine or azamethine dyes of formula VIIa and VIIb are also known per se and e.g. in US-A-5 079 365 and WO-A-92/19684.

The quinophthalone dyes of formula IX are also known per se and e.g. described in EP-83 553.

The nitro dye of the formula X is known as C.I. Disperse Yellow 42 (10 338) in use.

Suitable dyes which have carboxyl and / or sulfonic acid groups are described in more detail below. These are in particular azo or anthraquinone dyes.

In the case of azo dyes, mono- or disazo dyes, which can also be metallized, are to be emphasized, in particular those which have 1 to 6 carboxyl and / or sulfonic acid groups.

Important azo dyes are e.g. those whose diazo component is derived from an aniline or aminonaphthalene.

Important azo dyes are also, for example, those whose coupling component is derived from aniline, naphthalene, pyrazolone, aminopyrazole, diaminopyridine, pyridone or acylacetarylide.

Examples include metal-free or metallized (metal complexes) azo dyes from phenyl-azo-naphthalene, phenyl-azo-1-phenylpyrazol-5-one, phenyl-azo-benzene, naphthyl-azo-benzene, phenyl-azo -aminonaphthalene, naphthyl-azo-naphthalene, naphthyl-azo-1-phenylpyrazol-5-one, phenyl-azo-pyridone, phenyl-azo-aminopyridine, naphthyl-azo-pyridone, naphthyl-azo-aminopyridine - or Stilbyl-azo-benzene series.

aufweisen, der über eine gegebenenfalls substituierte Aminogruppe entweder an die Diazo- oder Kupplungskomponente geknüpft ist.The azo dyes can additionally also be a reactive group, for example the rest of the formula

have, which is linked via an optionally substituted amino group to either the diazo or coupling component.

und
K² für einen Rest der Formel

stehen, worin

a

0, 1, 2 oder 3,

b

0, 1 oder 2,

c

0 oder 1,

U¹

Wasserstoff, Methyl, Ethyl, Methoxy, Ethoxy, Acetyl, Cyano, Carboxyl, Hydroxysulfonyl, C₁-C₄-Alkoxycarbonyl, Hydroxy, Carbamoyl, C₁-C₄-Mono- oder Dialkylcarbamoyl, Fluor, Chlor, Brom oder Trifluormethyl,

U²

Wasserstoff, Methyl, Ethyl, Methoxy, Ethoxy, Cyano, Carboxyl, Hydroxysulfonyl, Acetylamino, C₁-C₄-Alkoxycarbonyl, Carbamoyl, C₁-C₄-Mono- oder Dialkylcarbamoyl, Fluor, Chlor, Nitro, Sulfamoyl, C₁-C₄-Mono- oder Dialkylsulfamoyl, C₁-C₄-Alkylsulfonyl, Phenylsulfonyl oder Phenoxy,

U³

eine direkte Bindung, Sauerstoff, Schwefel oder die Gruppe -NHCO-, NH-CO-NH-, -CONH-, -CO-, -NHSO₂-, -SO₂NH-, -SO₂-, -CH=CH-, -CH₂-CH₂-, -CH₂-, -NH-, oder -N=N-,

V¹

Wasserstoff oder C₁-C₄-Alkyl,

V²

Wasserstoff, C₁-C₄-Alkyl oder Phenyl, das durch C₁-C₅-Alkyl, C₁-C₄-Alkoxy, Chlor, Brom oder Hydroxysulfonyl substituiert sein kann,

V³

Wasserstoff oder C₁-C₄-Alkyl, das durch Hydroxy, Cyano, Carboxyl, Hydroxysulfonyl, Sulfato, Methoxycarbonyl, Ethoxycarbonyl oder Acetoxy substituiert sein kann,

V⁴

Wasserstoff, C₁-C₄-Alkyl, das durch Hydroxy, Cyano, Carboxyl, Hydroxysulfonyl, Sulfato, Methoxycarbonyl, Ethoxycarbonyl oder Acetoxy substituiert sein kann, Benzyl oder Phenyl, das durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Chlor oder Hydroxysulfonyl substituiert sein kann,

V⁵

C₁-C₆-Alkylureido, Phenylureido, das durch Chlor, Methyl, Methoxy, Nitro, Hydroxysulfonyl oder Carboxyl substituiert sein kann, C₁-C₆-Alkanoylamino, das durch Hydroxysulfonyl oder Chlor substituiert sein kann, Cyclohexanoylamino, Benzoylamino, das durch Chlor, Methyl, Methoxy, Nitro, Hydroxylsulfonyl oder Carboxyl substituiert sein kann, oder Hydroxy,

V⁶

Wasserstoff, C₁-C₆-Alkyl, das durch Phenyl, C₁-C₄-Alkoxy, Hydroxy, Phenoxy oder C₁-C₄-Alkanoyloxy substituiert sein kann, C₅-C₇-Cycloalkyl, Hydroxysulfonylphenyl, C₁-C₄-Alkanoyl, Carbamoyl, C₁-C₄-Mono- oder Dialkylcarbamoyl, Phenylcarbamoyl oder Cyclohexylcarbamoyl,

V⁷

Methoxy, Ethoxy, Chlor, Brom, Hydroxysulfonyl, Acetylamino, Amino, Ureido, Methylsulfonylamino, Ethylsulfonylamino, Dimethylaminosulfonylamino, Methylamino, Ethylamino, Dimethylamino oder Diethylamino,

V⁸

Wasserstoff, Methyl, Ethyl, Methoxy, Ethoxy, Hydroxysulfonyl, Chlor oder Brom,

M

den Rest eines Benzol- oder Naphthalinrings,

V⁹

Methyl, Carboxyl, C₁-C₄-Alkoxycarbonyl oder Phenyl,

V¹⁰

C₁-C₄-Alkyl, Cyclohexyl, Benzyl oder Phenyl, das gegebenenfalls durch Fluor, Chlor, Brom, Methyl, Methoxy, Nitro, Hydroxysulfonyl, Carboxyl, Acetyl, Acetylamino, Methylsulfonyl, Sulfamoyl oder Carbamoyl substituiert ist,

V¹¹

Wasserstoff oder C₁-C₄-Alkyl, das durch Methoxy, Ethoxy oder Cyano substituiert sein kann,

V¹²

Wasserstoff, Methyl, Hydroxysulfonylmethyl, Hydroxysulfonyl, Cyano oder Carbamoyl,

V¹³

Wasserstoff, C₁-C₄-Alkyl, das durch Phenyl, Hydroxysulfonylphenyl, Hydroxy, Amino, Methoxy, Ethoxy, Carboxyl, Hydroxysulfonyl, Acetylamino, Benzoylamino oder Cyano substituiert sein kann, Cyclohexyl, Phenyl, das gegebenenfalls durch Carboxyl, Hydroxysulfonyl, Benzoylamino, Acetylamino, Methyl, Methoxy, Cyano oder Chlor substituiert ist, oder Amino, das durch Phenyl, C₁-C₄-Alkyl, Acetyl oder Benzoyl substituiert ist,

V¹⁴

C₁-C₄-Alkyl, Phenyl, Hydroxy, Cyano, Acetyl, Benzoyl, Carboxyl, Methoxycarbonyl, Carbamoyl oder Hydroxysulfonylmethyl und

V¹⁵

Wasserstoff, Chlor, Brom, Acetylamino, Amino, Nitro, Hydroxysulfonyl, Sulfamoyl, Methylsulfonyl, Phenylsulfonyl, Carboxyl, Methoxycarbonyl, Acetyl, Benzoyl, Carbamoyl, Cyano oder Hydroxysulfonylmethyl bedeuten,

mit der Maßgabe, daß mindestens eine Carboxyl- und/oder Sulfonsäuregruppe im Molekül vorhanden ist.Azo dyes of the formula IIc are of particular importance

D²-N = N-K² (IIc),

in the D² for a residue of the formula

and
K² for a residue of the formula

stand in what

a

0, 1, 2 or 3,

b

0, 1 or 2,

c

0 or 1,

U¹

Hydrogen, methyl, ethyl, methoxy, ethoxy, acetyl, cyano, carboxyl, hydroxysulfonyl, C₁-C₄-alkoxycarbonyl, hydroxy, carbamoyl, C₁-C₄-mono- or dialkylcarbamoyl, fluorine, chlorine, bromine or trifluoromethyl,

U²

Hydrogen, methyl, ethyl, methoxy, ethoxy, cyano, carboxyl, hydroxysulfonyl, acetylamino, C₁-C₄-alkoxycarbonyl, carbamoyl, C₁-C₄-mono- or dialkylcarbamoyl, fluorine, chlorine, nitro, sulfamoyl, C₁-C₄-mono- or Dialkylsulfamoyl, C₁-C₄ alkylsulfonyl, phenylsulfonyl or phenoxy,

U³

a direct bond, oxygen, sulfur or the group -NHCO-, NH-CO-NH-, -CONH-, -CO-, -NHSO₂-, -SO₂NH-, -SO₂-, -CH = CH-, -CH₂- CH₂-, -CH₂-, -NH-, or -N = N-,

V¹

Hydrogen or C₁-C₄ alkyl,

V²

Hydrogen, C₁-C₄-alkyl or phenyl, which can be substituted by C₁-C₅-alkyl, C₁-C₄-alkoxy, chlorine, bromine or hydroxysulfonyl,

V³

Hydrogen or C₁-C₄-alkyl, which can be substituted by hydroxy, cyano, carboxyl, hydroxysulfonyl, sulfato, methoxycarbonyl, ethoxycarbonyl or acetoxy,

V⁴

Hydrogen, C₁-C₄-alkyl, which can be substituted by hydroxy, cyano, carboxyl, hydroxysulfonyl, sulfato, methoxycarbonyl, ethoxycarbonyl or acetoxy, benzyl or phenyl, which can be substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, chlorine or hydroxysulfonyl can be substituted

V⁵

C₁-C₆-alkylureido, phenylureido, which may be substituted by chlorine, methyl, methoxy, nitro, hydroxysulfonyl or carboxyl, C₁-C₆-alkanoylamino, which may be substituted by hydroxysulfonyl or chlorine, cyclohexanoylamino, benzoylamino, which may be substituted by chlorine, methyl, Methoxy, nitro, hydroxylsulfonyl or carboxyl can be substituted, or hydroxy,

V⁶

Hydrogen, C₁-C₆-alkyl, which may be substituted by phenyl, C₁-C₄-alkoxy, hydroxy, phenoxy or C₁-C₄-alkanoyloxy, C₅-C₇-cycloalkyl, hydroxysulfonylphenyl, C₁-C₄-alkanoyl, carbamoyl, C₁-C₄ Mono- or dialkylcarbamoyl, phenylcarbamoyl or cyclohexylcarbamoyl,

V⁷

Methoxy, ethoxy, chlorine, bromine, hydroxysulfonyl, acetylamino, amino, ureido, methylsulfonylamino, ethylsulfonylamino, dimethylaminosulfonylamino, methylamino, ethylamino, dimethylamino or diethylamino,

V⁸

Hydrogen, methyl, ethyl, methoxy, ethoxy, hydroxysulfonyl, chlorine or bromine,

M

the rest of a benzene or naphthalene ring,

V⁹

Methyl, carboxyl, C₁-C₄ alkoxycarbonyl or phenyl,

V¹⁰

C₁-C₄-alkyl, cyclohexyl, benzyl or phenyl, which is optionally substituted by fluorine, chlorine, bromine, methyl, methoxy, nitro, hydroxysulfonyl, carboxyl, acetyl, acetylamino, methylsulfonyl, sulfamoyl or carbamoyl,

V¹¹

Hydrogen or C₁-C₄-alkyl, which can be substituted by methoxy, ethoxy or cyano,

V¹²

Hydrogen, methyl, hydroxysulfonylmethyl, hydroxysulfonyl, cyano or carbamoyl,

V¹³

Hydrogen, C₁-C₄-alkyl, which can be substituted by phenyl, hydroxysulfonylphenyl, hydroxy, amino, methoxy, ethoxy, carboxyl, hydroxysulfonyl, acetylamino, benzoylamino or cyano, cyclohexyl, phenyl, which may be substituted by carboxyl, hydroxysulfonyl, benzoylamino, acetylamino, Methyl, methoxy, cyano or chlorine is substituted, or amino which is substituted by phenyl, C₁-C₄-alkyl, acetyl or benzoyl,

V¹⁴

C₁-C₄ alkyl, phenyl, hydroxy, cyano, acetyl, benzoyl, carboxyl, methoxycarbonyl, carbamoyl or hydroxysulfonylmethyl and

V¹⁵

Are hydrogen, chlorine, bromine, acetylamino, amino, nitro, hydroxysulfonyl, sulfamoyl, methylsulfonyl, phenylsulfonyl, carboxyl, methoxycarbonyl, acetyl, benzoyl, carbamoyl, cyano or hydroxysulfonylmethyl,

with the proviso that at least one carboxyl and / or sulfonic acid group is present in the molecule.

Aromatic amines which are suitable as diazo components and are derived from the formula XIIa, XIIb, XIIc or XIId are, for example, aniline, 2-methoxyaniline, 2-methylaniline, 4-chloro-2-aminoanisole, 4-methylaniline, 4-methoxyaniline, 2-methoxy-5-methylaniline, 2,5-dimethoxyaniline, 2,5-dimethylaniline, 2,4-dimethylaniline, 2,5-diethoxyaniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2,5-dichloroaniline, 4-chloro-2-nitroaniline, 4-chloro-2-methylaniline, 3-chloro-2-methylaniline, 4-chloro-2-aminotoluene, 4-phenylsulfonylaniline, 2-ethoxy-1-naphthylamine, 1-naphthylamine, 2- Naphthylamine, 4-methylsulfonylaniline, 2,4-dichloroaniline-5-carboxylic acid, 2-aminobenzoic acid, 4-aminobenzoic acid, 3-aminobenzoic acid, 3-chloroaniline-6-carboxylic acid, aniline-2- or -3- or -4-sulfonic acid, Aniline-2,5-disulfonic acid, aniline-2,4-disulfonic acid, aniline-3,5-disulfonic acid, 2-aminotoluene-4-sulfonic acid, 2-aminoanisole-5-sulfonic acid, 2-ethoxyaniline-5-sulfonic acid, 2- Ethoxyaniline-4-sulfonic acid, 4-hydroxysulfonyl-2-amino benzoic acid, 2,5-dimethoxyaniline-4-sulfonic acid, 2,4-dimethoxyaniline-5-sulfonic acid, 2-methoxy-5-methylaniline-4-sulfonic acid, 4-aminoanisole-3-sulfonic acid, 4-aminotoluene-3-sulfonic acid, 2-aminotoluene-5-sulfonic acid, 2-chloroaniline-4-sulfonic acid, 2-chloroaniline-5-sulfonic acid, 2-bromoaniline-4-sulfonic acid, 2,6-dichloroaniline-4-sulfonic acid, 2,6-dimethylaniline-3- or -4-sulfonic acid, 3-acetylaminoaniline-6-sulfonic acid, 4-acetylaminoaniline-2-sulfonylic acid, 1-aminonaphthalene-3-, -4-, -5-, -6- or -7-sulfonic acid, 1-aminonaphthalene 3,7-disulfonic acid, 1-aminonaphthalene-3,6,8-trisulfonic acid, 1-aminonaphthalene-4,6,8-trisulfonic acid, 2-aminonaphthalene-5-, -6- or -8-sulfonic acid, 2-aminonaphthalene 3,6,8-trisulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid, 2-aminonaphthalene-1,6-disulfonic acid, 2-aminonaphthalene-1-sulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid, 2-aminonaphthalene 3,6-disulfonic acid, 2-aminonaphthalene-4,8-disulfonic acid, 2-aminophenol-4-sulfonic acid, 2-aminophenol-5-sulfo acid, 3-aminophenol-6-sulfonic acid, 1-hydroxy-2-aminonaphthalene-5,8- or -4,6-disulfonic acid, 4-aminodiphenylamine, 4-amino-4'-methoxydiphenylamine, 4-amino-4'- methoxydiphenylamine-3-sulfonic acid, 4- (2'-methylphenylazo) -2-methylaniline, 4-aminoazobenzene, 4'-nitrophenylazo-1-aminonaphthalene, 4- (6'-hydroxysulfonylnaphthylazo) -1-aminonaphthalene, 4- (2 ', 5'-dihydroxysulfonylphenylazo) -1-aminonaphthalene, 4'-amino-3'-methyl-3-nitrobenzophenone, 4-aminobenzophenone, 4- (4'-aminophenylazo) benzenesulfonic acid, 4- (4'-amino-2'- or 3'-methoxyphenylazo) benzenesulfonic acid or 2-ethoxy-1-naphthylamine-6-sulfonic acid.

Aromatic diamines which are suitable as tetrazo components and are derived from the formula XIIe or XIIf are, for example, 1,3-diaminobenzene, 1,3-diaminobenzene-4-sulfonic acid, 1,4-diaminobenzene, 1,4-diaminobenzene-2- sulfonic acid, 1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene, 1,3-diamino-4-methylbenzene, 1,3-diaminobenzene-5-sulfonic acid, 1,3-diamino-5- methylbenzene, 1,6-diaminonaphthalene-4-sulfonic acid, 2,6-diaminonaphthalene-4,8-disulfonic acid, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminostilbene-2,2'- disulfonic acid, 2,7'-diaminodiphenyl sulfone, 2,7'-diaminodiphenyl sulfone-4,5-disulfonic acid, 4,4'-diaminobenzophenone, 4,4'-diamino-3,3'-dinitrobenzophenone, 3,3'-diamino 4,4'-dichlorobenzophenone, 4,4'- or 3,3'-diaminodiphenyl, 4,4'-diamino-3,3'-dichlorodiphenyl, 4,4'-diamino-3,3'-dimethoxy-, - 3,3'-dimethyl-, -2,2'-dimethyl-, -2,2'-dichloro- or -3,3'-diethoxydiphenyl, 4,4'-diamino-3,3'-dimethyl-6, 6'-dinitrodiphenyl, 4,4'-diaminodiphenyl-2,2'- or -3,3'-di sulfonic acid, 4,4'-diamino-3,3'-dimethyl-, -3,3, -dimethoxy or -2,2'-dimethoxydiphenyl-6,6'-disulfonic acid, 4,4'-diamino-2,2 ', 5,5'-tetrachlorodiphenyl, 4,4'-diamino-3,3'-dinitrodiphenyl, 4,4'-diamino-2,2'-dichloro-5,5'-dimethoxydiphenyl, 4,4'-diaminodiphenyl -2,2'- or -3,3'-dicarboxylic acid, 4,4'-diamino-3,3'-dimethyldiphenyl-5,5'-disulfonic acid, 4,4'-diamino-2-nitrodiphenyl, 4,4 '-Diamino-3-ethoxy- or -3-hydroxysulfonyldiphenyl, 4,4'-diamino-3,3'-dimethyldiphenyl-5-sulfonic acid, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3' -dimethyldiphenylmethane, 4,4'-diamino-2,2 ', 3,3'-tetramethyldiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminostilbene or 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid.

Residues K² are e.g. Anilines, such as o- or m-toluidine, o- or m-anisidine, cresidine, 2,5-dimethylaniline, 2,5-dimethoxyaniline, m-aminoacetanilide, 3-amino-4-methoxyacetanilide, 3-amino-4-methylacetanilide , m-aminophenylurea, N-methylaniline, N-methyl-m-toluidine, N-ethylaniline, N-ethyl-m-toluidine, N- (2-hydroxyethyl) aniline or N- (2-hydroxyethyl) -m-toluidine.

Residues K² are furthermore, for example, naphtholsulfonic acids, such as 1-naphthol-3-sulfonic acid, 1-naphthol-4-sulfonic acid, 1-naphthol-5-sulfonic acid, 1-naphthol-8-sulfonic acid, 1-naphthol-3,6-disulfonic acid, 1-naphthol-3,8-disulfonic acid, 2-naphthol-5-sulfonic acid, 2-naphthol-6-sulfonic acid, 2-naphthol-7-sulfonic acid, 2-naphthol-8- sulfonic acid, 2-naphthol-3,6-disulfonic acid, 2-naphthol-6,8-disulfonic acid, 2-naphthol-3,6,8-trisulfonic acid, 1,8-dihydroxynaphthalene-3,6-disulfonic acid, 2,6- Dihydroxynaphthalene-8-sulfonic acid or 2,8-dihydroxynaphthalene-6-sulfonic acid.

Residues K² are further e.g. Naphthylamines or naphthols, such as 1-naphthylamine, N-phenyl-1-naphthylamine, N-ethyl-1-naphthylamine, N-phenyl-2-naphthylamine, 1-naphthol, 2-naphthol, 1,5-dihydroxynaphthalene, 1.6 -Dihydroxynaphthalene, 1,7-dihydroxynaphthalene or 2,7-dihydroxynaphthalene.

Residues K² are further e.g. Aminonaphthalenesulfonic acids, such as 1-naphthylamine-6-sulfonic acid, 1-naphthylamine-7-sulfonic acid, 1-naphthylamine-8-sulfonic acid, 2-naphthylamine-3,6-disulfonic acid, 2-naphthylamine-5,7-disulfonic acid or 2-naphthylamine -6,8-disulfonic acid.

Residues K² are further e.g. Aminonaphtholsulfonic acids such as 1-amino-5-hydroxynaphthalene-7-sulfonic acid, 1-amino-8-hydroxynaphthalene-4-sulfonic acid, 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid, 1-amino-8-hydroxynaphthalene-3 , 6-disulfonic acid, 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid, 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 2-amino-8-hydroxynaphthalene -3,6-disulfonic acid, 2-amino-5-hydroxynaphthalene-1,7-disulfonic acid, 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid, 1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid, 1 -Acetylamino-8-hydroxynaphthalene-4,6-disulfonic acid, 1-benzoylamino-8-hydroxynaphthalene-4,6-disulfonic acid, 1-acetylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-methylamino-8-hydroxynaphthalene-6-sulfonic acid , 2-methylamino-8-hydroxynaphthalene-6-sulfonic acid or 2- (3'- or 4'-hydroxysulfonylphenyl) amino-8-hydroxynaphthalene-6-sulfonic acid.

Residues K² are furthermore, for example, pyrazolones, such as 1-phenyl-, 1- (2'-chlorophenyl) -, 1- (2'-methoxyphenyl) -, 1- (2'-methylphenyl) -, 1- (1 ', 5 '-Dichlorophenyl) -, 1- (2', 6'-dichlorophenyl) -, 1- (2'-methyl-6'-chlorophenyl) -, 1- (2'-methoxy-5'-methylphenyl) -, 1 - (2'-Methoxy-5'-hydroxysulfonylphenyl) -, 1- (2 ', 5'-dihydroxysulfonylphenyl) -, 1- (2'-carboxyphenyl) -, 1- (3-hydroxysulfonylphenyl) -, 1- (4th '-Hydroxysulfonylphenyl) - or 1- (3'-sulfamoylphenyl) -3-carboxylpyrazol-5-one, 1- (3'- or 4'-hydroxysulfonylphenyl) -, 1- (2'-chloro-4'- or - 5'-hydroxysulfonylphenyl) -, 1- (2'-methyl-4'-hydroxysulfonylphenyl) -, 1- (2 ', 5'-dichlorophenyl) -, 1- (4', 8'-dihydroxysulfonyl-l-naphthyl) - or 1- (6'-Hydroxysulfonylnaphth-1-yl) -3-methylpyrazol-5-one, 1-phenylpyrazol-5-one-3-carboxylic acid ethyl ester, pyrazol-5-one-3-carboxylic acid ethyl ester or pyrazol-5-one-3 -carboxylic acid.

Residues K² are further e.g. Aminopyrazoles such as 1-methyl, 1-ethyl, 1-propyl, 1-butyl, 1-cyclohexyl, 1-benzyl or 1-phenyl-5-aminopyrazole, 1- (4-chlorophenyl) - or 1- (4'-methylphenyl) -5-aminopyrazole or 1-phenyl-3-methyl-5-aminopyrazole.

Residues K² are further e.g. Pyridones, such as 1-ethyl-2-hydroxy-4-methyl-5-carbamoylpyrid-6-one, 1- (2'-hydroxyethyl) -2-hydroxy-4-methyl-5-carbamoylpyrid-6-one, 1- Phenyl-2-hydroxy-4-methyl-5-carbamoylpyrid-6-one, 1-ethyl-2-hydroxy-4-methyl-5-cyanopyrid-6-one, 1-ethyl-2-hydroxy-4-methyl 5-hydroxysulfonylmethylpyrid-6-one, 1-methyl-2-hydroxy-4-methyl-5-cyanopyrid-6-one, 1-methyl-2-hydroxy-5-acetylpyrid-6-one, 1,4-dimethyl- 2-hydroxy-5-cyanopyrid-6-one, 1,4-dimethyl-5-carbamoylpyrid-6-one, 2,6-dihydroxy-4-ethyl-5-cyanopyridine, 2,6-dihydroxy-4-ethyl 5-carbamoylpyridine, 1-ethyl-2-hydroxy-4-methyl-5-hydroxysulfonylmethylpyrid-6-one, 1-methyl-2-hydroxy-4-methyl-5-methylsulfonylpyrid-6-one or 1-carboxymethyl-2- hydroxy-4-ethyl-5-phenylsulfonylpyrid-6-one.

Instead of the azo dyes of the formula IIc, the corresponding metal complex dyes can also be used in the process according to the invention.

Copper, cobalt, chromium, nickel or iron are particularly suitable as complexing metals, copper, cobalt or chromium being preferred. Symmetrical or asymmetrical 1: 1 or 1: 2 chromium complexes are particularly worth mentioning. The metallized groups in the azo dyes mentioned above are preferably each ortho to the azo group, e.g. in the form of o, o-dihydroxy, o-hydroxy-o'-carboxy, o-carboxy-o'-amino or o-hydroxy-o'-amino-azo groups.

Preferred are dyes of the formula IIc in which D² is a radical of the formula XIIa, XIIb, XIIc, XIId, XIIe or XIIf, in which U¹ is hydrogen, methyl, methoxy, carboxyl, hydroxysulfonyl, hydroxy or chlorine, U² is hydrogen, methyl, methoxy , Carboxyl, hydroxysulfonyl, acetylamino or chlorine and U³ are the group -CO-, -SO₂-, -CH = CH-, -CH₂-CH₂-, -CH₂- or -N = N-.

Also preferred are dyes of the formula IIc in which the radical K 2 is derived from coupling components which have sulfonic acid and / or carboxyl groups and which couple in the ortho or para position to a hydroxyl and / or amino group.

Examples of such coupling components are 2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid, 2-acetylamino-8-hydroxynaphthalene-6-sulfonic acid, 1-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid, 1-benzoylamino-8- hydroxynaphthalene-3,6-disulfonic acid, 1-acetylamino-8-hydroxynaphthalene-4,6-disulfonic acid or 1-benzoylamino-8-hydroxynaphthalene-4,6-disulfonic acid.

in der B¹ Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Chlor oder Hydroxysulfonyl und K³ den Rest einer Kupplungskomponente der Naphthalin-, Pyrazolon- oder Pyridonreihe bedeuten.Azo dyes of the formula XIV are preferred

in which B¹ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, chlorine or hydroxysulfonyl and K³ are the rest of a coupling component of the naphthalene, pyrazolone or pyridone series.

in der D² die obengenannte Bedeutung besitzt und B² für Hydroxysulfonyl in Ringposition 3 oder 4 steht.Azo dyes of the formula XV are furthermore particularly preferred

in which D² has the abovementioned meaning and B² represents hydroxysulfonyl in ring position 3 or 4.

in der D² die obengenannte Bedeutung besitzt und die Aminogruppe in Ringposition 6 oder 7 steht.Azo dyes of the formula XVI are furthermore particularly preferred

in which D² has the meaning given above and the amino group is in ring position 6 or 7.

in der D² die obengenannte Bedeutung besitzt und d und e unabhängig voneinander jeweils für 0, 1 oder 2 stehen.Furthermore, valuable compounds are those of the formula XVII

in which D² has the meaning given above and d and e each independently represent 0, 1 or 2.

in der B² die obengenannte Bedeutung besitzt und einer der beiden Reste B³ und B⁴ für den Rest D², wobei dieser die obengenannte Bedeutung besitzt und der andere für 3-Amino-6-hydroxysulfonylphenyl oder auch beide Reste B³ und B⁴ für 3-Amino-6-hydroxysulfonylphenyl stehen.Furthermore, valuable compounds are those of the formula XVIII

in which B² has the abovementioned meaning and one of the two radicals B³ and B⁴ for the radical D², this having the abovementioned meaning and the other for 3-amino-6-hydroxysulfonylphenyl or both radicals B³ and B⁴ for 3-amino-6 -hydroxysulfonylphenyl stand.

The symmetrical 1: 2-chromium complex dye, which is based on the azo dye 1- (2-hydroxy-4-hydroxysulfonyl-6-nitronaphth-1-ylazo) -2-hydroxynaphthalene, should also be mentioned in particular.

Azo dyes with acidic groups and metal complex dyes are e.g. in K. Venkataraman "The Chemistry of Synthetic Dyes", Vol.III, Academic Press, New York, London, 1970.

Acidic anthraquinone dyes can also be used in the process according to the invention. Such anthraquinones are known per se and are described, for example, in K. Venkataraman "The Chemistry of Synthetic Dyes", Vol. II, Academic Press, New York, 1952.

in der P¹ für Amino oder einen Rest der Formel

worin P² und P³ unabhängig voneinander jeweils Wasserstoff oder Methyl und einer der beiden Reste P⁴ und P⁵ Wasserstoff oder Methyl und der andere Hydroxysulfonyl bedeuten.Acidic anthraquinone dyes from the series of 1,4-diaminoanthraquinones are preferred. For example, they obey Formula XIII

in the P¹ for amino or a radical of the formula

wherein P² and P³ each independently represent hydrogen or methyl and one of the two radicals P Res and P⁵ is hydrogen or methyl and the other hydroxysulfonyl.

The inventive method is carried out in an aqueous liquor at a temperature of 20 to 250 ° C.

When using dyes from the class of azo, anthraquinone, coumarin, methine or azamethine, quinophthalone or nitro dyes which are free of ionic groups, the new process is preferably at a temperature of 60 to 150 ° C, in particular 90 to 140 ° C, 120 to 135 ° C are particularly worth mentioning. The pH is 1 to 12, preferably 2 to 10 and in particular 3 to 5 or 9 to 10, 9 to 10 being particularly worth mentioning. In the preferred pH ranges, all of the nonionic dyes mentioned are generally used in the range 3 to 5. In the range 9 to 10, in particular the dyes from the class of the anthraquinones, quinophthalones or alkali-stable azo dyes can be used.

When using dyes which have carboxyl and / or sulfonic acid groups in the molecule, in particular acidic azo or anthraquinone dyes, the new process is preferably carried out at a temperature of 100 to 140 ° C., in particular 120 to 140 ° C. The pH is 2 to 5, preferably 2 to 3.

Based on the weight of the condensation products to be dyed in the form of fibers, yarns, twists, knitwear, woven goods or non-wovens, 0.05 to 20% by weight, preferably 0.5 to 10% by weight, is generally used. and especially 1 to 5% by weight of dye.

The process according to the invention is expediently carried out in such a way that the material to be dyed is added at room temperature to a dyebath containing the dye or a combination of the abovementioned dyes in the abovementioned amount, and the bath is then left over for a period of 30 to 60 minutes heated above temperature. The mixture is then left at this temperature for 30 to 180 minutes, preferably 60 to 120 minutes, and then cooled again to room temperature. If acidic dyes are used, the dyebath can additionally contain 5 to 10% by weight, based on the weight of the dyed material, of Glauber's salt.

When using dyes that are free of ionic groups, the material to be dyed is then removed, washed, optionally subjected to a reductive aftertreatment known per se (e.g. with sodium dithionite) and dried.

When using dyes which are free from ionic groups, further dyeing auxiliaries known per se can be added during dyeing in the dye bath, e.g. Dispersants based on lignin sulfonates or condensation products of naphthalenesulfonic acid with formaldehyde, or organic solvents such as benzaldehyde, benzyl alcohol or organic halogen compounds, for example chlorobenzene (carrier process).

Based on the liquor ratio, the concentration of these auxiliaries is generally 0 to 100 g / l, preferably 20 to 70 g / l.

With the new method it is possible to easily color the condensation products described in the introduction. This gives dyeings with good fastness properties.

The following examples are intended to explain the invention in more detail.

A1) Dyeing instructions for dyes which are free of ionic groups in the acidic range

10 g of a fabric which was produced from fibers of condensation products, the production of which is described in Example 3b of US Pat. No. 5,322,915, were placed at a temperature of 80.degree. C. in 200 ml of a dyeing liquor containing 3% by weight. , based on the fabric, dye and 0.5 g / l, based on the liquor ratio, contained dispersants and the pH of which was adjusted to 3.5 using acetic acid. Treatment was carried out at 80 ° C. for 5 minutes, the temperature was then raised to 135 ° C. within 30 minutes, held at this temperature for 60 minutes and then allowed to cool to 60 ° C. within 40 minutes. The dyed tissue was then reductively cleaned by placing it in 200 ml of a liquor, 6 ml / l of 32% by weight sodium hydroxide solution, 3 g / l of sodium dithionite and 1 g / l of an ethoxylation product of a vegetable oil (nonionic) for 15 min. treated. Finally the fabric was rinsed and dried.

A2) Regulation analogous to A1, but with the addition of 50 g of benzyl alcohol B1) Dyeing instructions for dyes which are free of ionic groups, in the alkaline range

10 g of a fabric which was produced from fibers of condensation products, the production of which is described in Example 3b of US Pat. No. 5,322,915, were placed at a temperature of 80.degree. C. in 200 ml of a dyeing liquor containing 4% by weight , based on the fabric, contained dye and its pH was adjusted to 10 using sodium hydroxide solution. Treatment was carried out at 80 ° C. for 5 minutes, the temperature was then raised to 135 ° C. within 40 minutes, held at this temperature for 180 minutes and then allowed to cool to 60 ° C. within 30 minutes. The dyed tissue was then reductively cleaned by placing it in 200 ml of a liquor, 6 ml / l of 32% by weight sodium hydroxide solution, 3 g / l of sodium dithionite and 1 g / l of an ethoxylation product of a vegetable oil (nonionic) for 15 min. treated. Finally the fabric was rinsed and dried.

B2) Regulation analogous to B1, but with the addition of 50 g / l benzyl alcohol C1) Dyeing instructions for dyes which carry sulfonic acid and / or carboxylic acid groups

10 g of a fabric which was produced from fibers of condensation products, the production of which is described in Example 3b of US Pat. No. 5,322,915, were placed at a temperature of 80.degree. C. in 150 ml of a dyeing liquor containing 3.3% by weight. -%, based on the fabric, dye 12 ml / l 60 wt .-% aqueous acetic acid and 5 wt .-%, based on the fabric, Glauber's salt. The treatment was carried out at 80 ° C. for 5 minutes, the temperature was then raised to 135 ° C., the temperature was kept at this temperature for 60 minutes and then allowed to cool to 70 ° C. within 40 minutes. The fabric was then rinsed and dried to give a full liquor extract.

C2) Regulation analogous to C1, but with the addition of 50 g / l benzyl alcohol

In the dyeing instructions instead of the woven goods e.g. Fibers, yarns, threads, knitwear or non-wovens are also used.

• Farbstoff 1
  
• Farbstoff 2
  
• Farbstoff 3
  
• Farbstoff 4
  
• Farbstoff 5
  
• Farbstoff 6
  
• Farbstoff 7
  
• Farbstoff 8
  Mischung aus
  
• Farbstoff 9
  
• Farbstoff 10
  1 : 2 Chromkomplex von
  
• Farbstoff 11
  1 : 2 Chrom/Nickelkomplex von
  
• Farbstoff 12
  1 : 2 Chromkomplex von

Zusätzlich sind in der folgenden Tabelle jeweils das Farbeverfahren und der resultierende Farbton angegeben.

The following dyes were used.

• Dye 1
  
• Dye 2
  
• Dye 3
  
• Dye 4
  
• Dye 5
  
• Dye 6
  
• Dye 7
  
• Dye 8
  Mixture of
  
• Dye 9
  
• Dye 10
  1: 2 chromium complex from
  
• Dye 11
  1: 2 chrome / nickel complex from
  
• Dye 12
  1: 2 chromium complex from

In addition, the color process and the resulting shade are given in the following table.

Claims (12)

Process for dyeing condensation products which can be obtained by condensing a mixture containing as essential components (A) 90 to 99.9 mol% of a mixture consisting essentially of (a) 30 to 99 mole% melamine and (b) 1 to 70 mol% of a substituted melamine of the formula I.

in which the radicals Y are each independently hydrogen, hydroxy-C₂-C₁₀-alkyl, hydroxy-C₂-C₄-alkyl- (oxa-C₂-C₄-alkyl) _n , where n is 1 to 5, or amino-C₂- C₁₂-alkyl, with the proviso that at least one radical Y is different from hydrogen, or mixtures of melamines of the formula I and (B) 0.1 to 10 mol%, based on (A) and (B), phenol which is optionally substituted by C₁-C₉-alkyl or hydroxy, C₁-C₄-alkanes which are substituted by hydroxyphenyl, bis (hydroxyphenyl) sulfones or mixtures of these compounds, With
Formaldehyde or compounds providing formaldehyde, the molar ratio of melamines to formaldehyde being in the range from 1: 1.15 to 1: 4.5, characterized in that the condensation products in the form of fibers, yarns, twists, knitwear, woven goods or non-wovens in an aqueous liquor which has a pH of 1 to 12 at a temperature of 20 to 250 ° C with a or several dyes from the class of azo dyes, Anthraquinone dyes, coumarin dyes, methine or azamethine dyes, quinophthalone dyes or nitro dyes are treated. Process according to Claim 1, characterized in that the condensation products are treated with one or more dyes which are free from ionic groups. Process according to Claim 1, characterized in that the condensation products are treated with one or more mono- or disazo dyes which are free from ionic groups and whose diazo component is derived from an aniline or from a five-membered aromatic heterocyclic amine which contains one to three heteroatoms, selected from the group consisting of nitrogen, oxygen and sulfur, in the heterocyclic ring and can be fused by a benzene, thiophene, pyridine or pyrimidine ring. Process according to Claim 1, characterized in that the condensation products are treated with one or more anthraquinone dyes which are free from ionic groups and come from the class of 1-aminoanthraquinones. Process according to Claim 1, characterized in that the condensation products are treated with one or more coumarin dyes which are free from ionic groups and come from the class of 7-dialkylaminocoumarins. Process according to Claim 1, characterized in that the condensation products are treated with one or more methine or azamethine dyes which are free of ionic groups and come from the class of the triazolopyridines or pyridones. Process according to Claim 1, characterized in that the condensation products are treated with one or more quinophthalone dyes which are free from ionic groups and are either unsubstituted or substituted by halogen in the quinoline ring in ring position 4. Process according to Claim 1, characterized in that the condensation products are treated with one or more dyes which have 1 to 6 carboxyl and / or sulfonic acid groups. Process according to Claim 1, characterized in that the condensation products are treated with one or more metal-free or metallized azo dyes which have 1 to 6 carboxyl and / or sulfonic acid groups and from which phenyl-azo-naphthalene, phenyl-azo-1-phenylpyrazole -5-one, phenyl-azo-benzene, naphthyl-azo-benzene, phenyl-azo-aminonaphthalene, naphthyl-azo-naphthalene, naphthyl-azo-1-phenylpyrazol-5-one, phenyl-azo -pyridone, phenyl-azo-aminopyridine, naphthyl-azo-pyridone, naphthyl-azo-aminopyridine or stilbyl-azo-benzene series. Process according to Claim 1, characterized in that the condensation products are treated with one or more acidic anthraquinone dyes from the class of 1,4-diaminoanthraquinones. Process according to Claim 1, characterized in that, based on the weight of the condensation products to be colored, 0.01 to 20% by weight of dye is used. Process according to Claim 1, characterized in that the dyeing is carried out in the presence of 0 to 100 g / l, based on the liquor ratio, of an organic solvent.