EP0581736A1 - Process for printing fibrous material by direct printing - Google Patents

Abstract

Described is a process for printing preferably cellulose-containing fibre material by direct printing. The process is characterised in that the printing paste used contains in addition to at least one water-soluble reactive dye (a) a water-soluble sulpho-containing polymer, (b) fixing alkali and optionally (c) a deaerating agent. The present process makes it possible to produce strong, patterned prints on white ground with good levelness, good fastness properties and crisp outlines (sharp contours). The print pastes are notable for homogeneity, storage stability and simplicity of handling.

Description

The present invention relates to a method for printing fiber material, such as cellulose-containing textile material, wool and silk with reactive dyes in direct printing, and the printing paste used for this printing.

It's been a long time, e.g. from US-A-4,604,099, known to preferably print cellulose-containing fiber materials with reactive dyes.

The printing pastes used for this must meet high requirements with regard to their viscosity behavior, storage and electrolyte stability, etc. In current practice, printing pastes are used which contain at least one thickener, e.g. B. contain sodium alginate. However, a printing paste that contains this component has insufficient storage stability and often also uneven homogeneity, which has a negative impact on the loss of pressure.

Synthetic thickeners are an alternative to natural alginates. However, these in turn prove to be sensitive to electrolytes and are therefore only of limited suitability for printing with powder and granule dyes.

The printing pastes formulated on the basis of these thickeners are often extremely viscous, i.e. their viscosity changes as a function of the shear forces, which causes problems in their handling. Another negative aspect is their sometimes poor washability and sensitivity to Ca and Mg ions.

The present invention was therefore based on the object of providing a printing paste which is free from alginate compounds and at the same time insensitive to electrolytes, is homogeneous, has a long shelf life and is easy to wash out. Surprisingly, it has now been found that the use of certain water-soluble polymers in printing pastes fulfills these conditions.

• (a) ein wasserlösliches sulfogruppenhaltiges Polymer,
• (b) Fixieralkali,

sowie gegebenenfalls

• (c) ein Entlüftungsmittel

enthält.The present invention thus relates to a method for printing fiber material with reactive dyes in direct printing, which is characterized in that the fiber materials are printed with a printing paste which, in addition to at least one water-soluble reactive dye

• (a) a water-soluble polymer containing sulfo groups,
• (b) fixative alkali,

and if necessary

• (c) a deaerating agent

contains.

The printing paste can also other common additives such. B. contain urea and reducing agents. Furthermore, other additives, such as. B. thickeners or preservatives can be used for the production of the printing paste.

The prints produced according to the method according to the invention are vivid in color, lightfast, washable and rub resistant.

As water-soluble sulfo-containing polymer (a) there are e.g. Homo-co- or graft polymers containing 20 mol% units of a sulfo-containing monomer.

• (Meth)acrylamidomethansulfonsäure,
• Vinylsulfonsäure,
• (Meth)allylsulfonsäure,
• 2-Acrylamido-2-methylpropansulfonsäure,
• 3-(Meth)acrylamidopropansulfonsäure,
• 3-Sulfopropyl(meth)acrylat,
• Bis-(3-suifopropyiitaconat),
• 4-Styrolsulfonsäure und
• 3-Allyloxy-2-hydroxypropylsulfonsäure.

Suitable monomers containing sulfo groups are, for example:

• (Meth) acrylamidomethanesulfonic acid,
• Vinyl sulfonic acid,
• (Meth) allylsulfonic acid,
• 2-acrylamido-2-methylpropanesulfonic acid,
• 3- (meth) acrylamidopropanesulfonic acid,
• 3-sulfopropyl (meth) acrylate,
• Bis- (3-suifopropyiitaconate),
• 4-styrene sulfonic acid and
• 3-allyloxy-2-hydroxypropylsulfonic acid.

The polymeric compounds (a) are preferably homopolymers of monomers containing sulfo groups or copolymers which contain more than 50 mol%, in particular more than 75 mol%, of monomer units containing sulfo groups.

Homo- and copolymers are particularly preferred which contain - 50 mol%, in particular 75 mol% of 2-acrylamido-2-methylpropanesulfonic acid units.

The polymers (a) can each be present as free acid or as ammonium, alkali metal (Na, K, Li) or alkaline earth metal salt (e.g. Ca); mixtures of different cations are also possible.

If the polymer (a) is a copolymer, the following are used as sulfo-free comonomers, e.g. monomers containing carboxyl groups, monomers containing phosphoric acid groups or other comonomers.

Suitable comonomers with a carboxyl function are (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, vinyl acetic acid, Vi nyloxyacetic acid, vinyl propionic acid, crotonic acid, aconitic acid, allylacetic acid, allyloxyacetic acid, a, β-dimethylacrylic acid, allylmalonic acid, allyloxymalonic acid, methylenmalonic acid, 2-hydroxy (meth) acrylic acid, 2-halogeno (meth) acrylic acid, a-ethylacrylic acid, acrylamide, acrylamide Carboxyethyl acrylate, allyloxy-3-hydroxybutanoic acid and allylsuccinic acid.

Suitable comonomers with a phosphoric acid group are e.g. Vinylphosphonic acid, (meth) allylphosphonic acid and acrylamidomethylpropanephosphonic acid.

• N-Vinylpyrrolidon, N-Vinylformamid, N-Vinyl-N-methyl-formamid, N-Vinylacetamid, N-Vinyl-N-methyl-acetamid, N-Vinyl-N-ethyl-acetamid, N-Vinylimidazol, N-Vinyl-N-methyl-imidazol, N-Vinylimidazolin, N-Vinyl-2-me- thylimidazolin, N-Vinylcaprolactam, Vinylacetat, Vinylpropionat, Vinylbutyrat, C₁-C₂₂-Alkylvinylketon, C₁-C₂₂-Alkylvinylether, Olefine (Ethylen, Propylen, Isobuten), 1,2-Dimethoxyethylen, Styrolderivate, Hydroxy-ethyl/propyl/bu- tyl/-(meth)acrylat, (Meth)acrylsäurealkylester-C_i-C₂₂, (Meth)acrolein, (Meth)acrylnitril, (Meth)acrylamid, Ester/(subst.) Amide/Nitrile der Monomeren mit Carboxylfunktion, N-Mono/N-Disubstituiertes (Meth)acrylamid (C_i-C₂₂), Alkoxy-(meth)acrylate, EO_x-POy-ButO_z mit x,y,z = 0-250, Dimethyl/Diethyl-aminoethyl/propyl/butyl-(meth)acrylate in Form der Salze oder in quaternierter Form, wobei geeignete Quaternierungsmittel z.B. Dimethyl/ethyl-sulfat, Methyl/ethyl-chlorid oder Benzylchlorid sind.

The following monomers are also suitable as comonomers:

• N-vinylpyrrolidone, N-vinylformamide, N-vinyl-N-methyl-formamide, N-vinyl acetamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl-acetamide, N-vinylimidazole, N-vinyl N-methyl-imidazole, N-vinylimidazoline, N-vinyl-2-methylimidazoline, N-vinylcaprolactam, vinyl acetate, vinyl propionate, vinyl butyrate, C ₁ -C ₂₂ alkyl vinyl ketone, C ₁ -C ₂₂ alkyl vinyl ether, olefins (ethylene, Propylene, isobutene), 1,2-dimethoxyethylene, styrene derivatives, hydroxyethyl / propyl / butyl / - (meth) acrylate, (meth) alkyl acrylate (C _i -C ₂₂₎ , (meth) acrolein, (meth) acrylonitrile, (Meth) acrylamide, esters / (subst.) Amides / nitriles of the monomers with carboxyl function, N-mono / N-disubstituted (meth) acrylamide (C _i -C ₂₂ ), alkoxy- (meth) acrylates, EO _x- POy- ButO _z with x, y, z = 0-250, dimethyl / diethylaminoethyl / propyl / butyl (meth) acrylates in the form of the salts or in quaternized form, suitable quaternizing agents, for example dimethyl / ethyl sulfate, methyl / ethyl are chloride or benzyl chloride.

Homopolymers of alkali metal salts of 2-acrylamido-2-methylpropanesulfonic acid as component (a) have proven to be particularly suitable.

The polymers or copolymers used and their preparation are known per se. The water-soluble polymers used according to the invention are preferably prepared in aqueous solution. Peroxidic compounds which are capable of forming free radicals are suitable as initiators, such as hydrogen peroxide, di-tertiary butyl oxide, benzoyl peroxide, lauryl peroxide or cumene hydroperoxide. The polymerization can also be initiated with aliphatic azo compounds. In addition, the usual redox catalyst systems, such as hydrogen peroxide / iron (II) sulfate, are of course very suitable for initiating the polymerization.

The polymerization is usually carried out in the acidic to neutral range. The temperature during the polymerization is generally 20 to 100 ° C., preferably 40 to 80 ° C. The polymer solutions obtained are e.g. 15 to 30% and have a molecular weight of e.g. 1000 to 3000000 and preferably 5000 to 500000.

The printing pastes contain fixing alkalis to fix the reactive dyes. Examples of alkaline compounds are sodium carbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, sodium acetate, sodium propionate, sodium hydrogen carbonate, borax, aqueous ammonia or alkali donors, such as sodium trichloroacetate or sodium formate. A mixture of water glass and a 25% aqueous sodium carbonate solution can also be used as the fixing alkali. The pH of the additives containing fixative alkali is generally 7.5 to 13.2, preferably 8.5 to 12.5. When producing the printing paste, the amount of fixing alkali is chosen so that the pH of the ready-to-use printing paste is in the alkaline range, preferably between pH 7.5 and 12.

All commercially available deaerating agents can be used as component (c), provided that the rheological properties of the printing paste according to the invention are not adversely affected. Because of their good defoaming properties, low-silicone oil-free to silicone-oil-free deaerating agents are preferred, which generally contain 0 to about 5, in particular 0.1 to 1, percent by weight of a conventional silicone oil.

Preferred venting agents contain e.g. as active substance high-boiling hydrocarbons, hydrogenated naphthalenes, mineral oils, fatty oils or insoluble metal soaps or mixtures thereof and optionally have the silicone oil content indicated above. However, they can also be present as aqueous solutions which, in addition to the active substances of the type mentioned, generally contain a nonionic surfactant, e.g. Contain ethylene adducts of an alkylphenol. Higher alcohols with boiling points above about 100 ° C., turpentine oils, mineral oils or mixtures thereof may be mentioned as preferred ingredients or active substances of the deaerating agents. Hydrocarbon mixtures which generally have a flash point above approximately 120 ° C., preferably from approximately 150 to 220 ° C. and a boiling range from approximately 250 to 500 ° C. under normal conditions are preferably used.

In the foreground of interest are deaerating agents which contain an octanol as active substance, e.g. Contain 2-ethyl-n-hexanol or its mixture with high-boiling hydrocarbon mixtures which have the above-mentioned content of silicone oils and are optionally present as an aqueous preparation, these preparations in addition to the active substances ethylene oxide adducts of an alkylphenol with 6 to 12 carbon atoms in the alkyl radical as a surfactant contain.

As a reducing agent such. B. aromatic nitro compounds, especially salts of aromatic mono- or dinitrocarboxylic acids or sulfonic acids, which are optionally present as alkylene oxides, especially alkali salts of a nitrobenzenesulfonic acid, such as e.g. 2-nitrobenzenesulfonic acid Na salt.

• 2-Acrylamido-2-methylpropansulfonsäure,
• als Komponente (b) Fixieralkali
• und gegebenenfalls
• als Komponente (c) ein Entlüftungsmittel auf Basis von Octanol, oder dessen Gemisch mit hochsiedenden Kohlenwasserstoffgemischen,welches 0 bis 5 Gewichtsprozent Silikonöl
• aufweist,
• enthalten.

For the process according to the invention, preference is given to printing pastes which, as component (a), are a homopolymer of an alkali metal salt of

• 2-acrylamido-2-methylpropanesulfonic acid,
• as component (b) fixing alkali
• and if necessary
• as component (c) a deaerating agent based on octanol, or its mixture with high-boiling hydrocarbon mixtures, which contains 0 to 5 percent by weight silicone oil
• having,
• contain.

Reducing agents, in particular alkali salts of nitrobenzenesulfonic acids, and urea are advantageously added to the printing pastes.

• 0,5 bis 20, vorzugsweise 1,5 bis 5 Gewichtsprozent der Komponente (a)
• 1 bis 10 Gewichtsprozent der Komponente (b),
• 0,1 bis 5, vorzugsweise 0,1 bis 1 Gewichtsprozent der Komponente (c)
• 0,1 bis 4, vorzugsweise 1 bis 2 Gewichtsprozent eines Reduktionsschutzmittels und
• 0,1 bis 20, vorzugsweise 0,1 bis 10 Gewichtsprozent Harnstoff.

In its preferred embodiment, the printing paste contains

• 0.5 to 20, preferably 1.5 to 5 percent by weight of component (a)
• 1 to 10 percent by weight of component (b),
• 0.1 to 5, preferably 0.1 to 1 percent by weight of component (c)
• 0.1 to 4, preferably 1 to 2 percent by weight of a reducing agent and
• 0.1 to 20, preferably 0.1 to 10 weight percent urea.

The printing pastes according to the invention are preferably free of alginate-containing compounds.

The dyes used in the process according to the invention are the reactive dyes usually used for dyeing or printing cellulose textile materials.

Reactive dyes are understood to be the usual dyes which form a chemical bond with the cellulose, e.g. the "Reactive Dyes" listed in Color Index in Volume 3 (* edition, 1971) on pages 3391-3560 and in Volume 6 (revised 3rd edition, 1975) on pages 6238-6345.

These dyes are dyes of different classes, for example those from the monoazo or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, nitroaryl, dioxazine, phenazine, stilbene, triphenylmethane -, Xanthene, thioxanthone, napthoquinone, pyrenchinone or perylene tetracarbimide series, which contain at least one reactive group.

Reactive groups are fiber-reactive radicals which are able to react with the hydroxyl groups of cellulose, the amino, carboxy, hydroxyl and thiol groups in wool and silk, or with the amino and possibly carboxy groups of synthetic polyamides to form covalent chemical bonds . The reactive groups are usually bound to the dye residue directly or via a bridge link. Suitable reactive groups are, for example, those which contain at least one removable substituent on an aliphatic, aromatic or heterocyclic radical or in which the radicals mentioned are a radical suitable for reaction with the fiber material, such as e.g. contain a vinyl residue.

A reactive group is, for example, an alkanoyl or alkylsulfonyl radical substituted by a removable atom or a removable group, an alkenoyl or alkenesulfonyl radical optionally substituted by a removable atom or a removable group or an alkenoyl or alkenesulfonyl radical containing a vinyl group. The alkanoyl, alkylsulfonyl and alkenesulfonyl radicals mentioned generally contain 2 to 8 carbon atoms and the alkenoyl radicals generally contain 3 to 8 carbon atoms. Furthermore, carbo- or heterocyclic 4-, 5- or 6-ring radicals substituted by a cleavable atom or a cleavable group may be mentioned. As heterocyclic radicals come e.g. those which contain at least one removable substituent bound to a heterocyclic radical; inter alia those which contain at least one reactive substituent bound to a 5- or 6-membered heterocyclic ring, such as to a monoazine, diazine, triazine, pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine - Or asymmetrical or symmetrical triazine ring, or to such a ring system which has one or more fused aromatic rings, such as a quinoline, phthalazine, chinnoline, quinazoline, quinoxaline, acridine, phenazine and phenanthridine ring system . Furthermore, the heterocyclic fiber-reactive radicals mentioned can contain further fiber-reactive radicals, e.g. the radicals listed above.

Cleavable atoms or cleavable groups include, for example, halogen, such as fluorine, chlorine or bromine, ammonium including hydrazinium, sulfato, thiosulfato, phosphato, acetoxy, propionoxy, azido, carboxypyridinium or rhodanido.

In addition to direct bonding, a wide variety of residues can be considered as a bridge link between the dye residue and the fiber-reactive residue or as a bridge link between two fiber-reactive residues. The bridge member is, for example, an aliphatic, aromatic or heterocyclic radical; Furthermore, the bridge member can also be composed of various such residues. The bridge member generally contains at least one functional group, for example the carbonyl group or the amino group, the amino group being optionally substituted by halogen, hydroxy, cyano, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkoxycarbonyl, carboxy, Sulfamoyl, sulfo or sulfato substituted C ₁ -C ₄ alkyl may be further substituted. An aliphatic radical, for example, is an alkylene radical with 1 to 7 carbon atoms or its branched isomers. The carbon chain of the alkylene radical can be interrupted by a hetero atom, such as an oxygen atom. The aromatic radical is, for example, a phenyl radical which is substituted by C ₁ -C ₄ -alkyl, such as methyl or ethyl, C ₁ -C ₄ -alkoxy, such as methoxy or ethoxy, halogen, such as fluorine, bromine or in particular chlorine, carboxy or Sulfo can be substituted, and a heterocyclic radical, for example a piperazine radical. Examples of such bridge members are the following residues:

In the formulas given above, R _{1 is} hydrogen or C ₁ -C ₄ alkyl, which is substituted by halogen, hydroxy, cyano, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl, carboxy, sulfamoyl, sulfo or sulfato can be.

• Vinylsulfonyl, β-Chloräthylsulfonyl, β-Sulfatoäthylsulfonyl, β-Acetoxy-äthylsulfonyl, Phosphatoäthylsulfonyl, ß-Thiosulfatoäthylsulfonyl, N-Methyl-N-(ß-sulfoäthyl-sulfonyl)-amino, Acryloyl, Mono-, Di- oder Trichloracryloyl wie -CO-CCI=CH₂, -CO-CH=CH-CI, -CO-CCI=CH-CH₃; Mono-, Di- oder Tribromacryloyl wie -CO-CBr=CH₂, -CO-CH=CH-Br, -CO-CBr=CH-CH₃; sowie -CO-CCI=CH-COOH, -CO-CH=CCI-COOH, -CO-CBr=CH-COOH, -CO-CH=CBr-COOH, -CO-CCI=CCI-COOH, -CO-CBr=CBr-COOH; Vorstufen des Acryloylrestes und der Derivate des Acryloylrestes wie ß-Chlor- oder β-Brompropionyl, 3-Phenylsulfonylpropionyl, 3-Methylsulfonylpropionyl, 2-Chlor-3-phenylsulfonylpropionyl, 2,3-Dichlorpropionyl, 2,3-Dibrompropionyl; sowie 2-Fluor-2-chlor-3,3-diflu- orcyclobutan-1-carbonyl, 2,2,3,3-Tetrafluorcyclobutancarbonyl-l- oder sulfonyl-1-, β-(2,2,3,3-Tetrafluorcyclobutyl-1)-acryloyl, a- oder ß-Alkenyl- oder Arylsulfonylacryloylgruppen, wie a- oder β-Methylsulfonylacryloyl, Chloracetyl, Bromacetyl, 4-(ß-Chloräthylsulfonyl)-butyryl, 4-Vinylsulfonyl-butyryl, 5-(ß-Chloräthylsulfonyl)-caproyl, 6-Vinylsulfonylcaproyl; sowie 4-Fluor-3-nitro-benzoyl, 4-Fluor-3-nitrophenylsulfonyl, 4-Fluor-3-me- thylsulfonylbenzoyl, 4-Fluor-3-cyanbenzoyl, 2-Fluor-5-methylsulfonylbenzoyl.

The following radicals may be mentioned as examples of fiber-reactive radicals:

• Vinylsulfonyl, β-chloroethylsulfonyl, β-sulfatoethylsulfonyl, β-acetoxy-ethylsulfonyl, phosphatoethylsulfonyl, ß-thiosulfatoethylsulfonyl, N-methyl-N- (ß-sulfoethylsulfonyl) -amino, acryloyl, mono-chloro or di- -CCI = CH ₂ , -CO-CH = CH-CI, -CO-CCI = CH-CH ₃ ; Mono-, di- or tribromoacryloyl such as -CO-CBr = CH ₂ , -CO-CH = CH-Br, -CO-CBr = CH-CH ₃ ; and -CO-CCI = CH-COOH, -CO-CH = CCI-COOH, -CO-CBr = CH-COOH, -CO-CH = CBr-COOH, -CO-CCI = CCI-COOH, -CO-CBr = CBr-COOH; Precursors of the acryloyl radical and the derivatives of the acryloyl radical such as β-chloro- or β-bromopropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl, 2-chloro-3-phenylsulfonylpropionyl, 2,3-dichloropropionyl, 2,3-dibromopropionyl; and 2-fluoro-2-chloro-3,3-difluorocyclobutane-1-carbonyl, 2,2,3,3-tetrafluorocyclobutanecarbonyl-l- or sulfonyl-1-, β- (2,2,3,3- Tetrafluorocyclobutyl-1) -acryloyl, a- or ß-alkenyl or arylsulfonylacryloyl groups, such as a- or β-methylsulfonylacryloyl, chloroacetyl, bromoacetyl, 4- (ß-chloroethylsulfonyl) butyryl, 4-vinylsulfonyl-butyryl, 5- Chloroethylsulfonyl) caproyl, 6-vinylsulfonylcaproyl; as well as 4-fluoro-3-nitro-benzoyl, 4-fluoro-3-nitrophenylsulfonyl, 4-fluoro-3-methylsulfonylbenzoyl, 4-fluoro-3-cyanobenzoyl, 2-fluoro-5-methylsulfonylbenzoyl.

• Mono- oder Dihalogen-symmetrische-triazinylreste, z.B. 2,4-Dichlortriazinyl-6-, 2-Amino-4-chlortriazinyl-6-, 2-Alkyl-amino-4-chlortriazinyl-6-, wie 2-Methylamino-4-chlortriazinyl-6-, 2-Ethylamino- oder 3-Propylamino-4- chlortriazinyl-6-, 2-ß-Oxethylamino-4-chlortriazinyl-6-, 2-Di-ß-oxethylamino-4-chlortriazinyl-6- und die entsprechenden Schwefelsäurehalbester, 2-Diethylamino-4-chlortriazinyl-6-, 2-Morpholino- oder 2-Piperidino-4-chlor-triazinyl-6-, 2-Cyclohexylamino-4-chlortriazinyl-6-, 2-Arylamino- und substituiertes Arylamino-4- chlortriazinyl-6-, wie 2-Phenylamino-4-chlortriazinyl-6-, 2-(o-, m- oder p-Carboxy- oder Sulfophenyl)-amino-4-chlortriazinyl-6-, 2-Alkoxy-4-chlortriazinyl-6-, wie 2-Methoxy- oder Ethoxy-4-chlortriazinyl-6-, 2-(Phenylsulfonylmethoxy)-4-chlortriazinyl-6-, 2-Aryloxy und substituieres Aryloxy-4-chlortriazinyl-6-, wie 2-Phenoxy-4-chlortriazinyl-6-, 2-(p-Sulfophenyl)-oxi-4-chlortriazinyl-6-, 2-(o-, m- oder p-Methyl- oder Methoxyphenyl)-oxi-4-chlortriazinyl-6-, 2-Alkylmercapto- oder 2-Arylmercapto- oder 2-(substituiertes Aryl)-mercapto-4-chlortriazinyl-6-, wie 2-ß-Hydroxyethyl-mercapto-4-chlortriazinyl-6-, 2-Phenylmercapto-4-chlor- triazinyl-6-, 3-(4'-Methylphenyl)-mercapto-4-chlortriazinyl-6-, 2-(2',4'-Dinitro)-Phenylmercapto-4-chlortriazi- nyl-6-, 2-Methyl-4-chlortriazinyl-6-, 2-Phenyl-4-chlor-triazinyl-6-, 2,4-Difluor-triazinyl-6-, Monofluortriazinylreste, die durch Amino-, Alkylamino-, Aralkylamino- oder Acylaminogruppen substituiert sind, wobei Alkyl insbesondere gegebenenfalls substituiertes C₁-C₄-Alkyl, Aralkyl insbesondere gegebenenfalls substituiertes Phenyl-C₁-C₄-Alkyl und Aryl insbesondere gegebenenfalls durch Sulfo, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Carbonsäure-, Acylaminogruppen und Halogenatome wie Fluor, Chlor oder Brom substituiertes Phenyl oder Naphthyl bedeutet, beispielsweise 2-Amino-4-fluor-triazinyl-6, 2-Methylamino-4-fluor-triazinyl-6, 2-Ethyl-amino-4-fluor-triazinyl-6, 2-iso-Propylamino-4-fluor-triazinyl-6, 2-Dimethylamino-4-fluor-triazinyl-6, 2-Diethylamino-4-fluor-triazinyl-6, 2-ß-Methoxy-ethylamino-4-fluortriazinyl-6,2-ß-Hydroxyethylamino-4-fluor-triazinyl-6, 2-Di-(ß-hydroxyethylamino)-4-fluortriazinyl-6-, 2-β-Sulfoethylamino-4-fluor-triazinyl-6, 2-ß-Sulfoethyl-methylamino-4-fluor-triazinyl-6, 2-Carboxymethylamino-4-fluortriazinyl-6, 2-ß-Cyanethyl-amino-4-fluor-triazinyl-6, 2-Benzolamino-4-fluor-triazinyl-6, 2-ß-Phenylethylamino-4-fluor-triazinyl-6, 2-Benzyl-methylamino-4-fluor-triazinyl-6, 2-(2'-, 3'-oder 4'-Sulfobenzyl)-amino-4-fluor-triazinyl-6, 2-Cyclohexylamino-4-fluortriazinyl-6, 2-(o-, m-, p-Methylphenyl)-amino-4-fluor-triazinyl-6, 2-(o-, m-, p-Sulfophenyl)-amino-4-fluor-triazinyl-6, 2-(2',5'-Disulfophenyl)-amino-4-fluortriazinyl-6, 2-(o-, m-, p-Chlorphenyl)-amino-4-fluor-triazinyl-6, 2-(o-, m-, p-Methoxyphenyl)-4-fluor- triazinyl-6, 2-(2'-Methyl-4'-sulfophenyl)-amino-4-fluortriazinyl-6, 2-(2'-Methyl-5'-sulfophenyl)-amino-4-fluor- triazinyl-6, 2-(2'-Chlor4'-sulfophenyl)-amino-4-fluor-triazinyl-6, 2-(2'-Chlor-5'-sulfophenyl)-amino-4-fluor-triazinyl-6, 2-(2'-Methoxy-4'-sulfophenyl)-amino-4-fluor-triazinyl-6, 2-(o-, m-, p-Carboxyphenyl)-amino-4-fluor- triazinyl-6, 2-(2',4'-Disulfophenyl)-amino-4-fluor-triazinyl-6, 2-(3',5'-Disulfophenyl)-amino-4-fluor-triazinyl-6, 2-(2'-Carboxy-4-sulfophenyl)-amino-4-fluor-triazinyl-6, 2-(2'-Carboxy-4-sulfophenyl)-amino-4-fluor-triazinyl-6, 2-(6'-Sulfonaphthyl-(2')-amino-4-fluor-triazinyl-6, 2-(4',8'-Disulfonaphthyl-(2'))-amino-4-fluor-triazinyl-6, 2-(6',8'-Disulfonaphthyl-(2'))-amino-4-fluor-triazinyl-6, 2-(N-Methylphenyl)-amino-4-fluor-triazinyl-6, 2-(N-Ethylphenyl)-amino-4-fluor-triazinyl-6, 2-(N-ß-Hydroxyethylphenyl)-amino-4-fluor-triazinyl-6, 2-(N-iso-Propylphenyl)-amino-4-fluor-triazinyl-6, 2-Morpholino-4-fluor-triazinyl-6, 2-Piperidino-4-fluor-triazinyl-6, 2-(4',6',8'-Trisulfonaphthyl-(2'))-4-fluor-triazinyl-6, 2-(3',6',8'-Trisulfonaphthyl-(2'))-4-fluor-triazinyl-6, 2-(3',6'-Disulfo- naphthyl-(1'))-4-fluor-triazinyl-6, Mono-, Di- oder Trihalogenpyrimidinylreste, wie 2,4-Dichlorpyrimidinyl-6, 2,4,5-Trichlorpyrimidinyl-6-, 2,4-Dichlor-5-nitro- oder -5-methyl- oder-5-carboxymethyl- oder -5-carboxy- oder -5-cyano- oder-5-vinyl- oder-5-sulfo- oder-5-mono-, -di- oder -trichlormethyl- oder-5-carboalkoxy-pyrimidinyl-6, 2,6-Dichlorpyrimidin-4-carbonyl-, 2,4-Dichlorpyrimidin-5-carbonyl-, 2-Chlor-4-methylpyrimidin-5-carbonyl-, 2-Methyl-4-chlorpyrimidin-5-carbonyl-, 2-Methyl-thio-4-fluorpyrimidin-5-carbonyl-, 6-Methyl-2,4-dichlorpyrimidin-5-carbonyl-, 2,4,6-Trichlorpyrimidin-5-carbonyl-, 2,4-Dichlorpyrimidin-5-sulfonyl-, 2-Chlorchi- noxalin-3-carbonyl-, 2- oder 3-Mono-chlorchinoxalin-6-carbonyl-, 2- oder 3-Monochlorchinoxalin-6-sulfonyl-, 2,3-Dichlorchinoxalin-6-carbonyl-, 2,3-Dichlorchinoxalin-6-sulfonyl-, 1,4-Dichlorphthalazin-6-sulfonyl- oder - 6-carbonyl-, 2,4-Dichlorchinazolin-7- oder -6-sulfonyl- oder -carbonyl-, 2- oder 3- oder 4-(4',5'-Dichlorpyrida- zin-6'-yl-1')-phenylsulfonyl- oder -carbonyl-, β-(4',5'-Dichlorpyridazon-6'-yl-1')-ethyl-carbonyl, N-Methyl-N-(2,4-dichlortriazinyl-6)-carbamyl-, N-Methyl-N-(2-methyl-amino-4-chlortriazinyl-6)-carbamyl-, N-Methyl-N-(2-dimethylamino-4-chlortriazinyl-6)-carbamyl, N-Methyl- oder N-Ethyl-N-(2,4-dichlortriazinyl-6)-amino-acetyl-, N-Methyl-N-(2,3-dichlorchinoxalin-6-sulfonyl)-aminoacetyl-, N-Methyl-N-(2,3-dichlorchinoxalin-6-carbonyl)-aminoacetyl-, sowie die entsprechenden Brom- und Fluor-Derivate der oben erwähnten chlorsubstituierten heterocyclischen Reste, unter diesen beispielsweise 2-Fluor-4-pyrimidinyl-, 2,6-Difluor-4-pyrimidinyl-, 2,6-Difluor-5-chlor-4-pyrimidinyl-, 2-Fluor-5,6-dichlor-4-pyrimidinyl-, 2,6-Difluor-5-methyl-4-pyrimidinyl-, 2,5-Difluor-6-methyl-4-pyrimidinyl-, 2-Fluor-5-methyl-6-chlor-4-pyrimidinyl-, 2-Fluor-5-nitro-6-chlor-4-pyrimidinyl-, 5-Brom-2-fluor-4-pyrimidinyl-, 2-Fluor-5-cyan-4-pyrimidinyl-, 2-Fluor-5-methyl-4-pyrimidinyl-, 2,5,6-Trifluor-4-pyrimidinyl-, 5-Chlor-6-chlormethyl-2-fluor-4-pyrimidinyl-, 2,6-Difluor-5-brom-4-pyrimidinyl-, 2-Fluor-5-brom-6-methyl-4-pyrimidinyl-, 2-Fluor-5-brom-6-chlormethyl-4-pyrimidinyl-, 2,6-Difluor-5-chlormethyl-4-pyrimidinyl-, 2,6-Difluor-5-nitro-4-pyrimidinyl-, 2-Fluor-6-methyl-4-pyrimidinyl-, 2-Fluor-5-chlor-6-methyl-4-pyrimidinyl-, 2-Fluor-5-chlor-4-pyrimidinyl-, 2-Fluor-6-chlor-4-pyrimidinyl- , 6-Trifluormethyl-5-chlor-2-fluor-4-pyrimidinyl-, 6-Trifluormethyl-2-fluor-4-pyrimidinyl-, 2-Fluor-5-nitro-4-pyrimidinyl-, 2-Fluor-5-trifluormethyl-4-pyrimidinyl-, 2-Fluor-5-phenyl- oder -5-methylsulfonyl-4-pyrimidinyl-, 2-Fluor-5-carbonamido-4-pyrimidinyl-, 2-Fluor-5-carbomethoxy-4-pyrimidinyl-, 2-Fluor-5-brom-6-trifluormethyl-4-pyrimidinyl-, 2-Fluor-6-carbonami- do-4-pyrimidinyl-, 2-Fluor-6-carbomethoxy-4-pyrimidinyl, 2-Fluor-6-phenyl-4-pyrimidinyl-, 2-Fluor-6-cyan-4-pyrimidinyl-, 2,6-Difluor-5-methylsulfonyl-4-pyrimidinyl-, 2-Fluor-5-sulfonamido-4-pyrimidinyl-, 2-Fluor-5-chlor-6-carbomethoxy-4-pyrimidinyl-, 2,6-Difluor-5-trifluormethyl-4-pyrimidinyl-, 6-Fluor-5-chlor-pyrimidinyl-4, 6-Fluor-5-trifluormethyl-pyrimidinyl-4, 6-Fluor-2-methylpyrimidinyl-4, 6-Fluor-5-chlor-2-methylpyrimidinyl-4, 5,6-Difluor-pyrimidinyl-4, 6-Fluor-5-chlor-2-trifluormethylpyrimidinyl-4, 6-Fluor-2-phenylpyrimidinyl-4, 6-Fluor-5-cyan-pyrimidinyl-4, 6-Fluor-5-nitropyrimidinyl-4, 6-Fluor-5-methyl-sulfonyl-pyrimidinyl-4, 6-Fluor-5-phenylsulfonylpyrimidinyl-4, sulfonylgruppenhaltige Triazinreste, wie 2,4-Bis-(phenylsulfonyl)-triazinyl-6, 2-(3'-Carboxyphenyl)-sulfonyl-4-chlortriazinyl-6, 2-(3'-Sulfophenyl)-sulfonyl-4-chlortriazinyl-6, 2,4-Bis-(3'-car- boxyphenylsulfonyl)-triazinyl-6; sulfonylgruppenhaltige Pyrimidinringen, wie 2-Carboxymethylsulfonyl- pyrimidinyl-4-, 2-Methylsulfonyl-6-methylpyrimidinyl-4, 2-Methylsulfonyl-6-ethyl- pyrimidinyl-4-, 2-Phenylsulfonyl-5-chlor-6-methyl-pyrimidinyl-, 2,6-Bis-methylsulfonyl-pyrimidinyl-4-, 2,6-Bis-methyl-sulfonyl-5-chlor-pyrimidinyl-4-, 2,4-Bis-methylsulfonyl-pyrimidin-5-sulfonyl-, 2-Methylsulfonylpyrimidinyl-4, 2-Phenyl-sulfonyl-pyrimidinyl-4-, 2-Trichlormethylsulfonyl-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-chlor-6-methyl- pyrimidinyl-4-, 2-Methylsulfonyl-5-brom-6-methyl-pyrimidinyl-4-, 2-Methyl-sulfonyl-5-chlor-6-ethyl-pyrimidinyl-4-, 2-Methyl- sulfonyl-5-chlor-6-chlormethyl-pyrimidinyl-4-, 2-Methyl-sulfonyl-4-chlor-6-methylpyrimidin-5-sulfonyl, 2-Methylsulfonyl-5-nitro-6-methyl-pyrimidinyl-4-, 2,5,6-Tris-methylsulfonyl-pyrimidinyl-4-, 2-Methylsulfonyl-5,6-di- methylpyridinyl-4-, 2-Ethylsulfonyl-5-chlor-6-methyl-pyrimidinyl-4-, 2-Methylsulfonyl-6-chlor-pyrimidinyl-4-, 2,6-Bis-methylsulfonyl-5-chlor-pyrimidinyl-4-, 2-Methylsulfonyl-6-carbonyl-pyrimidinyl-4-, 2-Methylsulfonyl-5-sulfopyrimidinyl-4-, 2-Methylsulfonyl-6-carbomethoxy-pyrimidinyl-4-, 2-Methylsulfonyl-5-carboxypyrimidinyl-4-, 2-Methylsulfonyl-5-cyan-6-methoxypyrimidinyl-4-, 2-Methylsulfonyl-5-chlorpyrimidinyl-4-, 2-Sulfoethylsul- fonyl-6-methyl-pyrimidinyl-4-, 2-Methyl-sulfonyl-5-brom-pyrimidinyl-4-, 2-Phenyl-sulfonyl-5-chlor-pyrimidinyl-4-, 2-Carboxymethylsulfonyl-5-chlor-6-methyl-pyrimidinyl-4-, 2-Methylsulfonyl-6-chlorpyrimidin-4- und -5-carbonyl, 2,6-Bis(methyl-sulfonyl)-pyrimidin-4- oder -5-carbonyl-, 2-Ethylsulfonyl-6-chlorpyrimidin-5-carbonyl-, 2,4-Bis-(methylsulfonyl)-pyrimidin-5-sulfonyl-, 2-Methylsulfonyl-4-chlor-6-methyl-pyrimidin-5-sulfonyl-oder -carbonyl-, ammoniumgruppenhaltige Triazinringe, wie Trimethylammonium-4-phenylamino- oder -4-(o-, m-oder p-sulfophenyl)-aminotriazinyl-6-,2-(1,1-Dimethylhydrazinium)-4-phenylamino-oder-4-(o-, m- oder p-sulfophenyl)-aminotriazinyl-6,2-(2-Isopropyliden-1,1-dimethyl)-hydrazinium-4-phenylamino-oder-4-(o-, m- oder p-sulfophenyl)-amino-_- . triazinyl-6-, 2-N-Aminopyrrolidinium- oder 2-Amino-piperidinium-4-phenylamino-oder -4-(o-, m- oder p-sulfophenyl)-aminotriazinyl-6-, 2-N-Aminopyrrolidinium- oder 2-N-Aminopiperidinium-4-phenylamino-oder -4-(o-, m- oder p-Sulfophenyl)-aminotriazinyl-6-, ferner 4-Phenylamino- oder -4-(sulfo- phenylamino)-triazinyl-6-Reste, die in 2-Stellung über eine Stickstoffbindung das 1,4-Bis-azabicyclo-[2,2,2]-octan oder das 1,2-Bis-aza-bicyclo-[0,3,3]-octan quartar gebunden enthalten, 2-Pyridinium-4-phenylamino-oder 4-(o-, m- oder p-Sulfophenyl)-aminotriazinyl-6- sowie entsprechende 2-Oniumtriazinyl-6-Reste, die in 4-Stellung durch Alkylamino-, wie Methylamino-, Ethylamino- oder ß-Hydroxyethylamino- oder Alkoxy-, wie Methoxy- oder Alkoxy-, oder Aroxy-, wie Phenoxy- oder Sulfophenoxy-Gruppen substituiert sind: 2-Chlorbenzthiazol-5- oder -6-carbonyl- oder -5- oder -6-sulfonyl-, 2-Arylsulfonyl- oder -Alkylsulfonylbenzthia- zol-5- oder -6-carbonyl- oder -5- oder -6-sulfonyl-, wie 2-Methyl-sulfonyl- oder 2-Ethoxysulfonylbenzthiazol-5- oder 6-sulfonyl- oder -carbonyl-, 2-Phenylsulfonyl-benzthiazol-5- oder -6-sulfonyl- oder carbonyl- und die entsprechenden im ankondensierten Benzolring Sulfogruppen enthaltenden 2-Sulfonylbenzthiazol-5- oder 6-carbonyl- oder -sulfonyl-Derivate, 2-Chlorbenzoxazol-5- oder -6-carbonyl- oder -sulfonyl-, 2-Chlor- benzimidazol-5- oder-6-carbonyl- oder sulfonyl-, 2-Chlor-1-methylbenzimidazol-5- oder 6-carbonyl- oder sulfonyl-, 2-Chlor-4-methylthiazol-(1,3)-5-carbonyl- oder -4- oder -5-sulfonyl-, N-Oxid des 4-Chlor- oder 4-Nitro- chinolin-5-carbonyl oder auch die Reste 5-Chlor-2,6-difluor-1,3-dicyanphenyl, 2,4-Difluor-1,3,5-tricyanphenyl, 2,4,5-Trifluor-1,3-dicyan-phenyl, 2,4-Dichlor-5-methylsulfonyl-pyrimidinyl-6, 2,4-Trichlor-5-ethylsulfonyl-pyrimidinyl-6, 2-Fluor-5-methylsulfonyl-6'-(2'-sulfophenylamino)-pyrimidinyl-4,2,5-Dichlor-6-methylsulfonyl-pyrimidinyl-4.

The following fiber-reactive residues may also be mentioned, for example:

• Mono- or dihalo-symmetrical-triazinyl residues, for example 2,4-dichlorotriazinyl-6-, 2-amino-4-chlorotriazinyl-6-, 2-alkylamino-4-chlorotriazinyl-6-, such as 2-methylamino-4- chlorotriazinyl-6-, 2-ethylamino- or 3-propylamino-4-chlorotriazinyl-6-, 2-ß-oxethylamino-4-chlorotriazinyl-6-, 2-di-ß-oxethylamino-4-chlorotriazinyl-6- and the corresponding sulfuric acid semiesters, 2-diethylamino-4-chlorotriazinyl-6-, 2-morpholino- or 2-piperidino-4-chlorotriazinyl-6-, 2-cyclohexylamino-4-chlorotriazinyl-6-, 2-arylamino and substituted arylamino -4-chlorotriazinyl-6-, such as 2-phenylamino-4-chlorotriazinyl-6-, 2- (o-, m- or p-carboxy- or sulfophenyl) -amino-4-chlorotriazinyl-6-, 2-alkoxy- 4-chlorotriazinyl-6, such as 2-methoxy or ethoxy-4-chlorotriazinyl-6-, 2- (phenylsulfonylmethoxy) -4-chlorotriazinyl-6-, 2-aryloxy and substituted aryloxy-4-chlorotriazinyl-6-, such as 2-phenoxy-4-chlorotriazinyl-6-, 2- (p-sulfophenyl) oxi-4-chlorotriazinyl-6-, 2- (o-, m- or p-methyl or methoxyphenyl) oxi-4-chlorotriazinyl -6-, 2-A alkylmercapto or 2-arylmercapto or 2- (substituted aryl) mercapto-4-chlorotriazinyl-6, such as 2-ß-hydroxyethyl-mercapto-4-chlorotriazinyl-6-, 2-phenylmercapto-4-chlorotriazinyl- 6-, 3- (4'-methylphenyl) mercapto-4-chlorotriazinyl-6-, 2- (2 ', 4'-dinitro) phenylmercapto-4-chlorotriazinyl-6-, 2-methyl-4- chlorotriazinyl-6-, 2-phenyl-4-chlorotriazinyl-6-, 2,4-difluorotriazinyl-6-, monofluorotriazinyl radicals which are substituted by amino, alkylamino, aralkylamino or acylamino groups, alkyl in particular special optionally substituted C ₁ -C ₄ alkyl, aralkyl especially optionally substituted phenyl-C ₁ -C ₄ alkyl and aryl especially optionally substituted by sulfo, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, carboxylic acid, Acylamino groups and halogen atoms such as fluorine, chlorine or bromine are substituted phenyl or naphthyl, for example 2-amino-4-fluorotriazinyl-6, 2-methylamino-4-fluorotriazinyl-6, 2-ethylamino-4-fluoro- triazinyl-6, 2-iso-propylamino-4-fluoro-triazinyl-6, 2-dimethylamino-4-fluoro-triazinyl-6, 2-diethylamino-4-fluoro-triazinyl-6, 2-ß-methoxy-ethylamino- 4-fluorotriazinyl-6,2-ß-hydroxyethylamino-4-fluorotriazinyl-6, 2-di- (ß-hydroxyethylamino) -4-fluorotriazinyl-6-, 2-β-sulfoethylamino-4-fluorotriazinyl-6 , 2-ß-sulfoethyl-methylamino-4-fluorotriazinyl-6, 2-carboxymethylamino-4-fluorotriazinyl-6, 2-ß-cyanoethyl-amino-4-fluorotriazinyl-6, 2-benzolamino-4-fluor -triazinyl-6, 2-ß-phenylethylamino-4-fluoro-triazinyl-6, 2-benzyl-methylamino-4-fluoro-triazinyl-6, 2- (2'-, 3'- or 4'-sulfobenzyl) amino-4-fluoro-triazinyl-6, 2-cyclohexylamino-4-fluoro-triazinyl-6, 2- (o-, m-, p-methylphenyl) amino-4-fluoro triazinyl-6, 2- (o-, m-, p-sulfophenyl) amino-4-fluoro-triazinyl-6, 2- (2 ', 5'-disulfophenyl) amino-4-fluorotriazinyl-6, 2- (o-, m-, p-chlorophenyl) amino-4-fluoro-triazinyl-6, 2- (o-, m-, p-methoxyphenyl) -4-fluoro-triazinyl-6, 2- (2'- Methyl-4'-sulfophenyl) amino-4-fluorotriazinyl-6, 2- (2'-methyl-5'-sulfophenyl) amino-4-fluorotriazinyl-6, 2- (2'-chloro4'-sulfophenyl ) -amino-4-fluoro-triazinyl-6, 2- (2'-chloro-5'-sulfophenyl) -amino-4-fluoro-triazinyl-6, 2- (2'-methoxy-4'-sulfophenyl) - amino-4-fluoro-triazinyl-6, 2- (o-, m-, p-carboxyphenyl) amino-4-fluoro-triazinyl-6, 2- (2 ', 4'-disulfophenyl) amino-4- fluoro-triazinyl-6, 2- (3 ', 5'-disulfophenyl) amino-4-fluoro-triazinyl-6, 2- (2'-carboxy-4-sulfophenyl) amino-4-fluoro-triazinyl-6 , 2- (2'-Carboxy-4-sulfophenyl) amino-4-fluoro-triazinyl-6, 2- (6'-sulfonaphthyl- (2 ') - amino-4-fluoro-triazinyl-6, 2- ( 4 ', 8'-disulfonaphthyl- (2')) - amino-4-fluoro-triazi nyl-6, 2- (6 ', 8'-disulfonaphthyl- (2')) - amino-4-fluoro-triazinyl-6, 2- (N-methylphenyl) amino-4-fluoro-triazinyl-6, 2 - (N-Ethylphenyl) amino-4-fluoro-triazinyl-6, 2- (N-ß-hydroxyethylphenyl) amino-4-fluoro-triazinyl-6, 2- (N-iso-propylphenyl) amino-4 -fluoro-triazinyl-6, 2-morpholino-4-fluoro-triazinyl-6, 2-piperidino-4-fluoro-triazinyl-6, 2- (4 ', 6', 8'-trisulfonaphthyl- (2 ')) -4-fluoro-triazinyl-6, 2- (3 ', 6', 8'-trisulfonaphthyl- (2 ')) - 4-fluoro-triazinyl-6, 2- (3', 6'-disulfonaphthyl- (1 ')) - 4-fluorotriazinyl-6, mono-, di- or trihalopyrimidinyl radicals, such as 2,4-dichloropyrimidinyl-6, 2,4,5-trichloropyrimidinyl-6-, 2,4-dichloro-5- nitro- or -5-methyl- or-5-carboxymethyl- or -5-carboxy- or -5-cyano- or-5-vinyl- or-5-sulfo- or-5-mono-, -di or - trichloromethyl- or 5-carboalkoxypyrimidinyl-6, 2,6-dichloropyrimidine-4-carbonyl-, 2,4-dichloropyrimidine-5-carbonyl-, 2-chloro-4-methylpyrimidine-5-carbonyl-, 2-methyl -4-chloropyrimidine-5-carbonyl-, 2-methylthio-4-fluoropyrimidine-5-carbonyl-, 6-methyl-2,4-dich lorpyrimidine-5-carbonyl-, 2,4,6-trichloropyrimidine-5-carbonyl-, 2,4-dichloropyrimidine-5-sulfonyl-, 2-chloroquinoxaline-3-carbonyl-, 2- or 3-mono-chloroquinoxaline -6-carbonyl-, 2- or 3-monochloroquinoxaline-6-sulfonyl-, 2,3-dichloroquinoxaline-6-carbonyl-, 2,3-dichloroquinoxaline-6-sulfonyl-, 1,4-dichlorophthalazine-6-sulfonyl- or - 6-carbonyl-, 2,4-dichloroquinazolin-7- or -6-sulfonyl- or -carbonyl-, 2- or 3- or 4- (4 ', 5'-dichloropyridazin-6'-yl- 1 ') - phenylsulfonyl- or -carbonyl-, β- (4', 5'-dichloropyridazon-6'-yl-1 ') - ethyl-carbonyl, N-methyl-N- (2,4-dichlorotriazinyl-6) -carbamyl-, N-methyl-N- (2-methylamino-4-chlorotriazinyl-6) -carbamyl-, N-methyl-N- (2-dimethylamino-4-chlorotriazinyl-6) -carbamyl, N-methyl - or N-ethyl-N- (2,4-dichlorotriazinyl-6) -amino-acetyl-, N-methyl-N- (2,3-dichloroquinoxaline-6-sulfonyl) -aminoacetyl-, N-methyl-N- (2,3-dichloroquinoxaline-6-carbonyl) aminoacetyl, as well as the corresponding bromine and fluorine derivatives of the above-mentioned chlorine-substituted heterocyclic radical e, among these for example 2-fluoro-4-pyrimidinyl-, 2,6-difluoro-4-pyrimidinyl-, 2,6-difluoro-5-chloro-4-pyrimidinyl-, 2-fluoro-5,6-dichloro- 4-pyrimidinyl, 2,6-difluoro-5-methyl-4-pyrimidinyl, 2,5-difluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl -, 2-Fluoro-5-nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidinyl, 2-fluoro-5-cyan-4-pyrimidinyl, 2-fluoro-5 -methyl-4-pyrimidinyl-, 2,5,6-trifluoro-4-pyrimidinyl-, 5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl-, 2,6-difluoro-5-bromo-4- pyrimidinyl, 2-fluoro-5-bromo-6-methyl-4-pyrimidinyl, 2-fluoro-5-bromo-6-chloromethyl-4-pyrimidinyl, 2,6-difluoro-5-chloromethyl-4-pyrimidinyl -, 2,6-difluoro-5-nitro-4-pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-6-methyl-4-pyrimidinyl, 2-fluoro -5-chloro-4-pyrimidinyl-, 2-fluoro-6-chloro-4-pyrimidinyl-, 6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl-, 6-trifluoromethyl-2-fluoro-4- pyrimidinyl, 2-fluoro-5-nitro-4-pyrimidinyl, 2-fluoro-5-trifluoromethyl-4-pyrimidinyl, 2-fluoro-5-phenyl or -5-methylsulfonyl-4-pyrimidinyl-, 2-fluoro-5-carbonamido-4-pyrimidinyl-, 2-fluoro-5-carbomethoxy-4-pyrimidinyl-, 2-fluoro-5-bromo-6-trifluoromethyl-4 -pyrimidinyl-, 2-fluoro-6-carbonamido-4-pyrimidinyl-, 2-fluoro-6-carbomethoxy-4-pyrimidinyl, 2-fluoro-6-phenyl-4-pyrimidinyl-, 2-fluoro-6- cyan-4-pyrimidinyl, 2,6-difluoro-5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-sulfonamido-4-pyrimidinyl, 2-fluoro-5-chloro-6-carbomethoxy-4-pyrimidinyl -, 2,6-difluoro-5-trifluoromethyl-4-pyrimidinyl-, 6-fluoro-5-chloro-pyrimidinyl-4, 6-fluoro-5-trifluoromethyl-pyrimidinyl-4, 6-fluoro-2-methylpyrimidinyl-4 , 6-fluoro-5-chloro-2-methylpyrimidinyl-4, 5,6-difluoropyrimidinyl-4, 6-fluoro-5-chloro-2-trifluoromethylpyrimidinyl-4, 6-fluoro-2-phenylpyrimidinyl-4, 6 -Fluoro-5-cyanopyrimidinyl-4, 6-fluoro-5-nitropyrimidinyl-4, 6-fluoro-5-methyl-sulfonyl-pyrimidinyl-4, 6-fluoro-5-phenylsulfonylpyrimidinyl-4, sulfonyl group-containing triazine radicals, such as 2 , 4-bis (phenylsulfonyl) triazinyl-6, 2- (3'-carboxyphenyl) sulfonyl-4-chlorotriazinyl-6, 2- (3rd '-Sulfophenyl) -sulfonyl-4-chlorotriazinyl-6, 2,4-bis (3'-car-boxyphenylsulfonyl) -triazinyl-6; pyrimidine rings containing sulfonyl groups, such as 2-carboxymethylsulfonyl-pyrimidinyl-4-, 2-methylsulfonyl-6-methylpyrimidinyl-4, 2-methylsulfonyl-6-ethyl-pyrimidinyl-4-, 2-phenylsulfonyl-5-chloro-6-methyl-pyrimidinyl- , 2,6-bis-methylsulfonyl-pyrimidinyl-4-, 2,6-bis-methyl-sulfonyl-5-chloropy rimidinyl-4-, 2,4-bis-methylsulfonyl-pyrimidine-5-sulfonyl-, 2-methylsulfonyl-pyrimidinyl-4, 2-phenyl-sulfonyl-pyrimidinyl-4-, 2-trichloromethylsulfonyl-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-bromo-6-methyl-pyrimidinyl-4-, 2-methyl-sulfonyl-5-chloro-6-ethyl-pyrimidinyl- 4-, 2-methylsulfonyl-5-chloro-6-chloromethyl-pyrimidinyl-4-, 2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-sulfonyl, 2-methylsulfonyl-5-nitro-6- methyl-pyrimidinyl-4-, 2,5,6-tris-methylsulfonyl-pyrimidinyl-4-, 2-methylsulfonyl-5,6-dimethylpyridinyl-4-, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidinyl -4-, 2-Methylsulfonyl-6-chloropyrimidinyl-4-, 2,6-bis-methylsulfonyl-5-chloropyrimidinyl-4-, 2-methylsulfonyl-6-carbonyl-pyrimidinyl-4-, 2-methylsulfonyl -5-sulfopyrimidinyl-4-, 2-methylsulfonyl-6-carbomethoxy-pyrimidinyl-4-, 2-methylsulfonyl-5-carboxypyrimidinyl-4-, 2-methylsulfonyl-5-cyan-6-methoxypyrimidinyl-4-, 2-methylsulfonyl -5-chloropyrimidinyl-4-, 2-sulfoethylsulfonyl-6- methyl-pyrimidinyl-4-, 2-methyl-sulfonyl-5-bromo-pyrimidinyl-4-, 2-phenyl-sulfonyl-5-chloropyrimidinyl-4-, 2-carboxymethylsulfonyl-5-chloro-6-methyl-pyrimidinyl -4-, 2-methylsulfonyl-6-chloropyrimidine-4- and -5-carbonyl, 2,6-bis (methyl-sulfonyl) -pyrimidine-4- or -5-carbonyl-, 2-ethylsulfonyl-6-chloropyrimidine- 5-carbonyl-, 2,4-bis- (methylsulfonyl) pyrimidine-5-sulfonyl-, 2-methylsulfonyl-4-chloro-6-methyl-pyrimidine-5-sulfonyl- or -carbonyl-, ammonium group-containing triazine rings, such as trimethylammonium -4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6-, 2- (1,1-dimethylhydrazinium) -4-phenylamino-or-4- (o-, m- or p-sulfophenyl) aminotriazinyl-6,2- (2-isopropylidene-1,1-dimethyl) hydrazinium-4-phenylamino-or-4- (o-, m- or p-sulfophenyl) -amino- _- . triazinyl-6-, 2-N-aminopyrrolidinium- or 2-amino-piperidinium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6-, 2-N-aminopyrrolidinium- or 2-N-aminopiperidinium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6-, furthermore 4-phenylamino- or -4- (sulfophenylamino) -triazinyl-6- Residues in the 2-position via a nitrogen bond the 1,4-bis-azabicyclo- [2,2,2] -octane or the 1,2-bis-aza-bicyclo- [0,3,3] -octane quartar contain bound, 2-pyridinium-4-phenylamino or 4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6 as well as corresponding 2-oniumtriazinyl-6 radicals, which are in the 4-position by alkylamino, such as Methylamino, ethylamino or ß-hydroxyethylamino or alkoxy, such as methoxy or alkoxy, or aroxy, such as phenoxy or sulfophenoxy groups, are substituted: 2-chlorobenzthiazole-5- or -6-carbonyl- or -5 - or -6-sulfonyl-, 2-arylsulfonyl- or -alkylsulfonylbenzthiazole-5- or -6-carbonyl- or -5- or -6-sulfonyl-, such as 2-methyl-sulfonyl- o the 2-ethoxysulfonylbenzothiazole-5- or 6-sulfonyl- or -carbonyl-, 2-phenylsulfonyl-benzothiazole-5- or -6-sulfonyl- or carbonyl- and the corresponding 2-sulfonylbenzothiazole-5- or 6 containing sulfo groups in the fused-on benzene ring -carbonyl- or -sulfonyl-derivatives, 2-chlorobenzoxazole-5- or -6-carbonyl- or -sulfonyl-, 2-chloro-benzimidazole-5- or -6-carbonyl- or sulfonyl-, 2-chloro-1- methylbenzimidazole-5- or 6-carbonyl- or sulfonyl-, 2-chloro-4-methylthiazole- (1,3) -5-carbonyl- or -4- or -5-sulfonyl-, N-oxide of 4-chloro- or 4-nitroquinoline-5-carbonyl or the residues 5-chloro-2,6-difluoro-1,3-dicyanophenyl, 2,4-difluoro-1,3,5-tricyanophenyl, 2,4,5- Trifluoro-1,3-dicyanophenyl, 2,4-dichloro-5-methylsulfonyl-pyrimidinyl-6, 2,4-trichloro-5-ethylsulfonyl-pyrimidinyl-6, 2-fluoro-5-methylsulfonyl-6 '- ( 2'-sulfophenylamino) pyrimidinyl-4,2,5-dichloro-6-methylsulfonyl-pyrimidinyl-4.

worin T₁ Fluor, Chlor oder Carboxypyridinium ist und wobei als Substituenten V₁ am Triazinring insbesondere zu nennen sind:

• Fluor oder Chlor, sowie -NH₂, Alkylamino-, N,N-Dialkylamino-, Cyloalkylamino-, N,N-Dicycloalkylamino-, Aralkylamino-, Arylaminogruppen, gemischt substituierte Aminogruppen, wie N-Alkyl-N-cyclohexylamino- und N-Alkyl-N-arylaminogruppen, ferner Aminogruppen, die heterocyclische Reste enthalten, welche weitere ankondensierte carbocyclische Ringe aufweisen können, und Aminogruppen, worin das Aminostickstoffatom Glied eines N-heterocyclischen Ringes ist, der gegebenenfalls weitere Heteroatome enthält, sowie Hydrazino und Semicarbazido. Die oben genannten Alkylreste können geradkettig oder verzweigt, niedrigmolekular oder höhermolekular sein, bevorzugt sind Alkylreste mit 1 bis 6 Kohlenstoffatomen; als Cycloalkyl-, Aralkyl- und Arylreste kommen insbesondere Cyclohexyl-, Benzyl-, Phenäthyl-, Phenyl- und Naphthylreste in Betracht; heterocyclische Reste sind vor allem Furan-, Thiophen-, Pyrazol-, Pyridin-, Pyrimidin-, Chinolin-, Benzimidazol- , Benzthiazol- und Benzoxazolreste; und als Aminogruppen, worin das Aminostickstoffatom Glied eines N-heterocyclischen Ringes ist, kommen vorzugsweise Reste von sechsgliedrigen N-heterocyclischen Verbindungen in Betracht, die als weitere Heteroatome Stickstoff, Sauerstoff oder Schwefel enthalten können. Die oben genannten Alkyl-, Cycloalkyl-,Aralkyl- und Arylreste, die heterocyclischen Reste sowie die N-heterocyclischen Ringe können weitersubstituiert sein, z.B. durch Halogen, wie Fluor, Chlor oder Brom, Nitro, Cyan, Trifluormethyl, Sulfamoyl, Carbamoyl, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Acylaminogruppen, wie Acetylamino oder Benzoylamino, Ureido, Hydroxy, Carboxy, Sulfomethyl oder Sulfo. Als Beispiele für derartige Aminogruppen seien genannt: -NH₂, Methylamino, Aethylamino, Propylamino, Isopropylamino, Butylamino, Hexylamino, ß-Methoxyäthylamino, y-Methoxyäthylamino, ß-Aethoxyäthylamino, N,N-Dimethylamino, N,N-Diäthylamino, ß-Chloräthylamino, ß-Cyanäthylamino, y-Cyanpropylamino, ß-Carboxyäthylamino, Sulfomethylamino, ß-Sulfoäthylamino, ß-Hydroxyäthylamino, N,N-Di-ß-hydroxyäthylamino, y-Hydroxypropylamino, Benzylamino, Phenäthylamino, Cyclohexylamino, Phenylamino, Toluidino, Xylidino, Chloranilino, Anisidino, Phenethidino, N-Methyl-N-phenylamino, N-Aethyl-N-phenylamino, N-ß-Hydroxyäthyl-N-phenylamino, 2-, 3- oder 4-Sulfoanilino, 2,5-Disulfoanilino, 4-Sulfomethylanilino, N-Sulfomethylanilino, 2-, 3- oder 4-Carboxyphenylamino, 2-Carboxy-5-sulfophenylamino, 2-Carboxy-4-sulfophenylamino, 4-Sulfonaphthyl-(1)-amino, 3,6-Disulfonaphthyl-(1)-amino, 3,6,8-Trisulfonaphthyl-(1)-amino, 4,6,8-Trisulfonaphthyl-(1)-amino, 1-Sulfonaphthyl-(2)-amino, 1,5-Disulfonaphthyl-(2)-amino, 6-Sulfonaphthyl-(2)-amino, Morpholino, Piperidino, Piperazino, Hydrazino und Semicarbazido.

Interesting fiber-reactive residues are 1,3,5-triazine residues of the formula

in which T _{1 is} fluorine, chlorine or carboxypyridinium and where, in particular, the substituents V ₁ on the triazine ring are:

• Fluorine or chlorine, and also -NH ₂ , alkylamino, N, N-dialkylamino, cycloalkylamino, N, N-dicycloalkylamino, aralkylamino, arylamino groups, mixed substituted amino groups, such as N-alkyl-N-cyclohexylamino and N- Alkyl-N-arylamino groups, furthermore amino groups which contain heterocyclic radicals which may have further fused-on carbocyclic rings, and amino groups in which the amino nitrogen atom is a member of an N-heterocyclic ring which optionally contains further heteroatoms, and also hydrazino and semicarbazido. The above-mentioned alkyl radicals can be straight-chain or branched, low molecular weight or higher molecular weight; alkyl radicals having 1 to 6 carbon atoms are preferred; suitable cycloalkyl, aralkyl and aryl radicals are, in particular, cyclohexyl, benzyl, phenethyl, phenyl and naphthyl radicals; heterocyclic radicals are especially furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole and benzoxazole; and as amino groups in which the amino nitrogen atom is a member of an N-heterocyclic ring, there are preferably residues of six-membered N-heterocyclic compounds conditions into consideration, which can contain nitrogen, oxygen or sulfur as further heteroatoms. The abovementioned alkyl, cycloalkyl, aralkyl and aryl radicals, the heterocyclic radicals and the N-heterocyclic rings can be further substituted, for example by halogen, such as fluorine, chlorine or bromine, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, acylamino groups such as acetylamino or benzoylamino, ureido, hydroxy, carboxy, sulfomethyl or sulfo. Examples of such amino groups are: -NH ₂ , methylamino, ethylamino, propylamino, isopropylamino, butylamino, hexylamino, ß-methoxyethylamino, y-methoxyethylamino, ß-ethoxyethylamino, N, N-dimethylamino, N, N-diethylamino, ß- Chloroethylamino, ß-cyanoethylamino, y-cyanopropylamino, ß-carboxyethylamino, sulfomethylamino, ß-sulfoethylamino, ß-hydroxyethylamino, N, N-di-ß-hydroxyethylamino, y-hydroxypropylamino, benzylamino, phenethylamino, tolylhexinoamino, cyclo Chloranilino, anisidino, phenethidino, N-methyl-N-phenylamino, N-ethyl-N-phenylamino, N-ß-hydroxyethyl-N-phenylamino, 2-, 3- or 4-sulfoanilino, 2,5-disulfoanilino, 4- Sulfomethylanilino, N-sulfomethylanilino, 2-, 3- or 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino, 4-sulfonaphthyl- (1) -amino, 3,6-disulfonaphthyl- (1st ) -amino, 3,6,8-trisulfonaphthyl- (1) -amino, 4,6,8-trisulfonaphthyl- (1) -amino, 1-sulfonaphthyl- (2) -amino, 1,5-disulfone aphthyl- (2) -amino, 6-sulfonaphthyl- (2) -amino, morpholino, piperidino, piperazino, hydrazino and semicarbazido.

In the remainder of the formula (1), V ₁ is preferably fluorine, chlorine, -NH ₂ , a C ₁ -C ₆ -alkylamino-, N, N-di-C ₁ -C ₆ -alkylamino-, cyclohexylamino-, N, N -Dicyclohexylamino-, Benzylamino-, Phenäthylamino-, Phenylamino-, Naphthylamino-, NC ₁ -C ₆ -Alkyl-N-cyclohexylamino- or NC ₁ -C ₆ -Alkyl-N-phenylamino residue, or Morpholino, Piperidino, Piperazino, Hydrazino or Semicarbazido, or an amino group substituted by a furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole or benzoxazole residue. The alkyl, cycloalkyl, aralkyl and aryl radicals mentioned and the heterocyclic radicals can be further substituted as indicated under formula (1).

V ₁ is particularly preferred in the remainder of the formula (1) fluorine, chlorine, phenylamino or NC ₁ -C ₄ -alkyl-N-phenylamino, the phenyl rings being optionally substituted by halogen, such as fluorine, chlorine or bromine, nitro, cyano, trifluoromethyl, Sulfamoyl, carbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, acylamino groups such as acetylamino or benzoylamino, ureido, hydroxy, carboxy, sulfomethyl or in particular sulfo are substituted.

The triazinyl radicals can also be linked to further fiber-reactive radicals, the further fiber-reactive radicals generally being bonded to the halogenotriazinyl radical via a bridge member. Other fiber-reactive residues and bridge members include for example, the aforementioned.

worin T₂ und T₃ unabhängig voneinander Fluor, Chlor oder Carboxypyridinium sind und B ein Brückenglied ist. Als Brückenglied B kommt beispielsweise ein Rest der Formel

in Betracht, worin R₁ und R₁' unabhängig voneinander Wasserstoff oder gegebenenfalls durch Halogen, Hydroxy, Cyan, C₁-C₄-Alkoxy, C₁-C₄-Alkoxycarbonyl, Carboxy, Sulfamoyl, Sulfo oder Sulfato substituiertes C₁-C₄-Alkyl sind und X ein gegebenenfalls durch Hydroxy, Sulfo, Sulfato, C₁-C₄-Alkoxy, Carboxy oder Halogen substituierter C₂-C₆-Alkylen- oder C₅-C₉-Cycloalkylenrest oder ein gegebenenfalls durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Sulfo, Halogen oder Carboxy substituierter Phenylen-, Biphenylen- oder Naphthylenrest ist.Interesting fiber-reactive radicals are also those of the formula

wherein T ₂ and T _{3 are} independently fluorine, chlorine or carboxypyridinium and B is a bridge member. A bridge of the formula B is, for example, a residue

into consideration, wherein R ₁ and R ₁ 'are independently hydrogen or optionally substituted by halogen, hydroxy, cyano, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato-substituted C ₁ -C Are _4- alkyl and X is a C ₂ -C ₆ alkylene or C ₅ -C ₉ cycloalkylene radical which is optionally substituted by hydroxy, sulfo, sulfato, C ₁ -C ₄ alkoxy, carboxy or halogen or a radical which is optionally substituted by C ₁ - C ₄ alkyl, C ₁ -C ₄ alkoxy, sulfo, halogen or carboxy substituted phenylene, biphenylene or naphthylene.

worin T₄ Fluor, Chlor oder Carboxypyridinium ist und
V₂ ein Rest der Formel

ist, worin R₁ Wasserstoff oder C₁-C₄-Alkyl, das durch Halogen, Hydroxy, Cyan, C₁-C₄-Alkoxy, C₁-C₄-Alkoxycarbonyl, Carboxy, Sulfamoyl, Sulfo oder Sulfato substituiert sein kann; B₁ die direkte Bindung oder ein Rest (̵CH₂

oder -O(̵CH₂

; n = 1, 2, 3, 4, 5 oder 6; und R ein Rest der Formel

oder

ist, worin R' Wasserstoff oder C₁-C₆-Alkyl ist, alk einen Alkylenrest mit 1 bis 7 Kohlenstoffatomen darstellt, T Wasserstoff, Halogen, Hydroxy, Sulfato, Carboxy, Cyano, C₁-C₄-Alkanoyloxy, C₁-C₄-Alkoxycarbonyl, Carbamoyl oder einen Rest -S0₂-Z bedeutet, V Wasserstoff, gegebenenfalls substituiertes C₁-C₄-Alkyl oder ein Rest der Formel

ist, worin (alk) die zuvor angegebene Bedeutung hat, alk' unabhängig voneinander Polymethylenreste mit 2 bis 6 C-Atomen bedeutet, Z ß-Sulfatoethyl, β-Thiosulfatoethyl, ß-Phosphatoethyl, ß-Acyloxyethyl, ß-Halogenethyl oder Vinyl ist, p, q, r und t unabhängig voneinander je die Zahl 1, 2, 3, 4, 5 oder 6 bedeuten und s die Zahl 2, 3, 4, 5 oder 6 ist; und der Benzolring in Formel (4) weitere Substituenten enthalten kann; oder worin V₂ ein direkt an den Triazinring gebundener Rest der Formel (4a), (4b), (4c), (4d), (4e), (4f) oder (4g) ist, worin R', T, alk, V, alk', Z, p, q, r, s und t die angegebenen Bedeutungen haben; oder worin V₂ ein Rest der Formel

ist, worin R₁ und Z die oben angegebenen Bedeutungen haben und der Benzolring weitersubstituiert sein kann.Other interesting reactive groups are those of the formula

wherein T _{4 is} fluorine, chlorine or carboxypyridinium and
V _{2 is} a radical of the formula

is wherein R _{1 is} hydrogen or C ₁ -C ₄ alkyl which may be substituted by halogen, hydroxy, cyano, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl, carboxy, sulfamoyl, sulfo or sulfato; B _{1 is} the direct bond or a residue (̵CH ₂

or -O (̵CH ₂

; n = 1, 2, 3, 4, 5 or 6; and R is a radical of the formula

or

where R 'is hydrogen or C ₁ -C ₆ alkyl, alk represents an alkylene radical having 1 to 7 carbon atoms, T Is hydrogen, halogen, hydroxy, sulfato, carboxy, cyano, C ₁ -C ₄ alkanoyloxy, C ₁ -C ₄ alkoxycarbonyl, carbamoyl or a radical -S0 ₂ -Z, V is hydrogen, optionally substituted C ₁ -C ₄ - Alkyl or a radical of the formula

where (alk) has the meaning given above, alk 'independently of one another means polymethylene radicals having 2 to 6 carbon atoms, Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl, p, q, r and t each independently represent the number 1, 2, 3, 4, 5 or 6 and s is the number 2, 3, 4, 5 or 6; and the benzene ring in formula (4) may contain further substituents; or in which V _{2 is} a radical of the formula (4a), (4b), (4c), (4d), (4e), (4f) or (4g) bonded directly to the triazine ring, in which R ', T, alk, V, alk ', Z, p, q, r, s and t have the meanings given; or wherein V _{2 is} a radical of the formula

is in which R ₁ and Z have the meanings given above and the benzene ring may be further substituted.

Other possible substituents for the benzene rings of the compounds of the formulas (4) and (4 ') are halogen, such as fluorine, chlorine or bromine, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ -alkoxy, acylamino groups, such as acetylamino or benzoylamino, ureido, hydroxy, carboxy, sulfomethyl and sulfo.

darstellt, ist B₁ durch das Sauerstoffatom an den Benzolring gebunden. Vorzugsweise ist B₁ die direkte Bindung.The radical B ₁ contains 1 to 6, preferably 1 to 4, carbon atoms; Examples of B ₁ are: methylene, ethylene, propylene, butylene, methyleneoxy, ethyleneoxy, propyleneoxy and butyleneoxy. If B _{1 has} a residue -O (̵CH ₂

B ₁ is bonded to the benzene ring through the oxygen atom. B ₁ is preferably the direct bond.

As β-haloethyl Z is in particular the β-chloroethyl radical and β-acyloxyethyl in particular the β-acetoxyethyl radical. The alkylene radical alk is preferably methylene, ethylene, methylmethylene, propylene or butylene. The substituent T is in particular acetyloxy, propionyloxy or butyryloxy as the alkanoyloxy radical, and in particular methoxycarbonyl, ethoxycarbonyl or propyloxycarbonyl as the alkoxycarbonyl radical. If V is an alkyl radical, this can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl. The radical R 'is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl or hexyl, or preferably hydrogen. The polymethylene residues alk 'are preferably ethylene, propylene or butylene. The indices p, q and t are preferably 2, 3 or 4 independently of one another. The indices r and s are preferably 2 independently of one another.

Preferred radicals V ₂ are those of the formula (4), in which B _{1 is} the direct bond and R is a radical of the formula (4a), or in which V _{2 is} a radical of the formula (4b), (4c) or which is bonded directly to the triazine ring (4f), or wherein V _{2 is} a radical of formula (4 ').

und

worin Z die oben angegebenen Bedeutungen hat, Z₁ die Bedeutungen von Z hat und zusätzlich a,ß-Dihalo- genethyl oder a-Halogenacryloyl sein kann, bevorzugt.As aliphatic reactive groups are those of the formulas

and

wherein Z has the meanings given above, Z _{1 has} the meanings of Z and can additionally be a, β-dihaloethyl or a-haloacryloyl, is preferred.

For Z ₁ , halogen in the β-haloethyl, a, β-dihaloethyl and a-haloacryloyl groups in particular chlorine and bromine are suitable.

Particularly preferred aliphatic reactive groups are those of the formula (5a) and also those of the formulas (5c) and (5d). For these radicals, Z is in particular β-sulfatoethyl, β-haloethyl or vinyl.

The reactive dyes very particularly preferably contain at least one reactive group of the formulas (1), (2), (3) and (5a) to (5e), where for T ₁ , T ₂ , T ₃ , T ₄ , V ₁ , V ₂ , B, Z and Z ₁ the meanings given above and favors apply.

The reactive dyes are derived in particular from the remainder of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl , Naphthoquinone, pyrenchinone or perylene tetracarbimide dye, preferably the remainder of a monoazo, disazo, metal complex azo, formazan, anthraquinone, phthalocyanine or dioxazine dye. In addition to the reactive group, the reactive dyes can contain, as further substituents, the substituents customary in organic dyes.

• Alkylgruppen mit 1 bis 4 Kohlenstoffatomen, wie Methyl, Ethyl, Propyl, Isopropyl oder Butyl, Alkoxygruppen mit 1 bis 4 Kohlenstoffatomen, wie Methoxy, Ethoxy, Propoxy, Isopropoxy oder Butoxy, Acylaminogruppen mit 1 bis 8 Kohlenstoffatomen, insbesondere Alkanoylaminogruppen und Alkoxycarbonylaminogruppen, wie Acetylamino, Propionylamino, Methoxycarbonylamino, Ethoxycarbonylamino oder Benzoylamino, Phenylamino, N-N-Di-ß-hydroxyethylamino, N,N-Di-ß-sulfatoethylamino, Sulfobenzylamino, N,N-Disulfoben- zylamino, Alkoxycarbonyl mit 1 bis 4 Kohlenstoffatomen im Alkoxyrest, wie Methoxycarbonyl oder Ethoxycarbonyl, Alkylsulfonyl mit 1 bis 4 Kohlenstoffatomen, wie Methylsulfonyl oder Ethylsulfonyl, Trifluormethyl, Nitro, Cyano, Halogen, wie Fluor, Chlor oder Brom, Carbamoyl, N-Alkylcarbamoyl mit 1 bis 4 Kohlenstoffatomen im Alkylrest, wie N-Methylcarbamoyl oder N-Ethylcarbamoyl, Sulfamoyl, N-Alkylsulfamoyl mit 1 bis 4 Kohlenstoffatomen, wie N-Methylsulfamoyl, N-Ethylsulfamoyl, N-Propylsulfamoyl, N-Isopropylsulfamoyl oder N-Butylsulfamoyl, N-(ß-Hydroxyethyl)-sulfamoyl, N,N-Di-(ß-hydroxyethyl)-sulfamoyl, N-Phenylsulfamoyl, Ureido, Hydroxy, Carboxy, Sulfomethyl oder Sulfo sowie weitere faserreaktive Reste. Vorzugsweise enthalten die Reaktivfarbstoffe eine oder mehrere Sulfonsäuregruppen.

Examples of such further substituents for the reactive dyes are:

• Alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl or butyl, alkoxy groups with 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, acylamino groups with 1 to 8 carbon atoms, in particular alkanoylamino groups and alkoxycarbonylamino groups, such as acetylamino , Propionylamino, methoxycarbonylamino, ethoxycarbonylamino or benzoylamino, phenylamino, NN-di-ß-hydroxyethylamino, N, N-di-ß-sulfatoethylamino, sulfobenzylamino, N, N-disulfobenzylamino, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy radical, such as methoxy or ethoxycarbonyl, alkylsulfonyl with 1 to 4 carbon atoms, such as methylsulfonyl or ethylsulfonyl, trifluoromethyl, nitro, cyano, halogen, such as fluorine, chlorine or bromine, carbamoyl, N-alkylcarbamoyl with 1 to 4 carbon atoms in the alkyl radical, such as N-methylcarbamoyl or N- Ethyl carbamoyl, sulfamoyl, N-alkylsulfamoyl having 1 to 4 carbon atoms, such as N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl , N-isopropylsulfamoyl or N-butylsulfamoyl, N- (ß-hydroxyethyl) -sulfamoyl, N, N-di- (ß-hydroxyethyl) -sulfamoyl, N-phenylsulfamoyl, ureido, hydroxy, carboxy, sulfomethyl or sulfo and other fiber-reactive radicals . The reactive dyes preferably contain one or more sulfonic acid groups.

The reactive dyes are preferably derived from the following dye residues:

• a) dye residues of a 1: 1 copper complex azo dye of the benzene or naphthalene series, in which the copper atom is bonded to a metallizable group on both sides in the ortho position to the azo bridge.
• b) Very particularly preferred for the reactive dyes of the dye mixtures according to the invention are dye residues of a mono- or disazo dye, of the formula
  
  
  
  or
  
  
  or a metal complex derived therefrom; D ₁ is the residue of a diazo component of the benzene or naphthalene series, M the residue of a middle component of the benzene or naphthalene series, and K the residue of a coupling component of the benzene, naphthalene, pyrazolone, 6-hydroxypyridone (2) or acetoacetic acid arylamide Series, where D ₁ , M and K can carry customary substituents in azo dyes, in particular hydroxyl, amino, methyl, ethyl, methoxy or ethoxy groups, optionally substituted alkanoylamino groups with 2 to 4 carbon atoms, optionally substituted benzoylamino groups, halogen atoms or a fiber-reactive radical, in particular a radical -SO ₂ -Z, where Z is ß-sulfatoethyl, ß-thiosulfatoethyl, ß-phosphatoethyl, ß-acyloxyethyl, ß-haloethyl or vinyl; u = 0 or 1; and D ₁ , M and K together contain at least two sulfo groups, preferably three or four sulfo groups.
• c) Likewise very particularly preferred for the reactive dyes of the dye mixtures according to the invention are the dye residues of a disazo dye, of the formula
  
  
  or
  
  
  wherein D ₁ and D _{2 are} independently the residue of a diazo component of the benzene or naphthalene series, and K is the residue of a coupling component of the naphthalene series; where D ₁ , D ₂ and K can carry usual substituents in azo dyes, in particular hydroxyl, amino, methyl, ethyl, methoxy or ethoxy groups, optionally substituted alkanoylamino groups with 2 to 4 carbon atoms, optionally substituted benzoylamino groups, halogen atoms or a fiber-reactive Residue, in particular a residue -S0 ₂ -Z, where Z has the meaning given, and D ₁ , D ₂ and K together contain at least two sulfo groups, preferably three or four sulfo groups. Are important
• d) dye residues of a formazan dye, the formula
  
  
  
  in which the benzene nuclei can further be substituted by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylsulfonyl having 1 to 4 carbon atoms, halogen or carboxy.
• e) dye residues of an anthraquinone dye, the formula
  
  
  wherein G is a phenylene, cyclohexylene, phenylene methylene or C ₂ -C ₆ alkylene radical; wherein the anthraquinone nucleus can be substituted by a further sulfo group, and G as a phenyl radical by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogen, carboxy or sulfo, and the dye preferably contains at least 2 sulfo groups.
• f) dye residues of a phthalocyanine dye, the formula
  
  
  wherein Pc is the balance of a copper or nickel phthalocyanine; W -OH and / or -NR ₅ R ₅ -; R ₅ and R ₅ , independently of one another, are hydrogen or alkyl having 1 to 4 carbon atoms, which may be substituted by hydroxy or sulfo; R _{4 is} hydrogen or alkyl of 1 to 4 carbon atoms; E is a phenylene radical which can be substituted by alkyl having 1 to 4 carbon atoms, halogen, carboxy or sulfo; or an alkylene radical having 2 to 6 carbon atoms, preferably a sulfophenylene or ethylene radical; and k = 1, 2 or 3.
• g) dye residues of a dioxazine dye, the formula
  
  
  or
  
  
  or
  
  
  in which E is a phenylene radical which can be substituted by alkyl having 1 to 4 carbon atoms, halogen, carboxy or sulfo; or is an alkylene radical having 2 to 6 carbon atoms; and the outer benzene rings in the formulas (11a), (11b) and (11c) by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, acetylamino, nitro, halogen, carboxy, sulfo or -SO ₂ -Z may be further substituted, where Z is ß-sulfatoethyl, β-thiosulfatoethyl, ß-phosphatoethyl, ß-acyloxyethyl, ß-haloethyl or vinyl.

oder

worin R₆ für C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, -SO₂-Z, Carboxy und Sulfo steht; und Z β-Sulfatoethyl, β-Thiosulfatoethyl, β-Phosphatoethyl, β-Acyloxyethyl, β-Halogenethyl oder Vinyl ist, und R die unter Formel (4) angegebene Bedeutung hat.

oder

worin R₁₃ für C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, -SO₂-Z, Carboxy, Sulfo und C₁-C₄-Alkoxyanilino steht; und Z β-Sulfatoethyl, β-Thiosulfatoethyl, β-Phosphatoethyl, β-Acyloxyethyl, β-Halogenethyl oder Vinyl ist, und R die unter Formel (4) angegebene Bedeutung hat.

worin R₆ für C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, -SO₂-Z, Carboxy und Sulfo steht; und Z β-Sulfatoethyl, β-Thiosulfatoethyl, β-Phosphatoethyl, β-Acyloxyethyl, β-Halogenethyl oder Vinyl ist.

• oder
  
• oder
  
• oder
  
  
  worin R₇ für Halogen, Nitro, Cyan, Trifluormethyl, Sulfamoyl, Carbamoyl, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Amino, Acetylamino, Ureido, Hydroxy, Carboxy, Sulfomethyl und Sulfo steht; und Z β-Sulfatoethyl, β-Thiosulfatoethyl, β-Phosphatoethyl, β-Acyloxyethyl, β-Halogenethyl oder Vinyl ist.
  
  
  
  oder
  
  
  worin R₈ C₁-C₄-Alkanoyl oder Benzoyl ist; und Z β-Sulfatoethyl, β-Thiosulfatoethyl, β-Phosphatoethyl, β-Acyloxyethyl, β-Halogenethyl oder Vinyl ist.
  
  
  worin R₈ C₁-C₄-Alkanoyl oder Benzoyl ist.
  
• worin R₉ für C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, -SO₂-Z, Carboxy und Sulfo steht; und z β-Sulfatoethyl, β-Thiosulfatoethyl, β-Phosphatoethyl, β-Acyloxyethyl, β-Halogenethyl oder Vinyl ist.
  
• worin R₁₂ und R₁₀ unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl oder Phenyl, und R₁₁ Wasserstoff, Cyano, Carbamoyl oder Sulfomethyl ist.
  
• worin R₉ für C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, -SO₂-Z, Carboxy und Sulfo steht; und Z β-Sulfatoethyl, β-Thiosulfatoethyl, β-Phosphatoethyl, β-Acyloxyethyl, β-Halogenethyl oder Vinyl ist.
  
  
• worin R₁₄ für C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, Carboxy und Sulfo steht; und Z β-Sulfatoethyl, β-Thiosulfatoethyl, β-Phosphatoethyl, β-Acyloxyethyl, β-Halogenethyl oder Vinyl ist,
  
  
  
  
  
  
• worin R₆ und Z die unter Formel (14) angegebenen Bedeutungen haben, und R die unter Formel (4) angegebene Bedeutung hat.

The following dye residues of the formulas (12) to (23) below are particularly important as monoazo and polyazo dye residues:

or

wherein R _{6 is} C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, -SO ₂ -Z, carboxy and sulfo; and Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl, and R has the meaning given under formula (4).

or

wherein R _{13 is} C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, -SO ₂ -Z, carboxy, sulfo and C ₁ -C ₄ alkoxyanilino; and Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl, and R has the meaning given under formula (4).

wherein R _{6 is} C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, -SO ₂ -Z, carboxy and sulfo; and Z β-sulfatoethyl, β-thio is sulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl.

• or
  
• or
  
• or
  
  
  wherein R _{7 represents} halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, amino, acetylamino, ureido, hydroxy, carboxy, sulfomethyl and sulfo; and Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl.
  
  
  
  or
  
  
  wherein R _{8 is} C ₁ -C ₄ alkanoyl or benzoyl; and Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl.
  
  
  wherein R _{8 is} C ₁ -C ₄ alkanoyl or benzoyl.
  
• wherein R _{9 is} C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, -SO ₂ -Z, carboxy and sulfo; and z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl.
  
• wherein R ₁₂ and R _{10 are} independently hydrogen, C ₁ -C ₄ alkyl or phenyl, and R _{11 is} hydrogen, cyano, carbamoyl or sulfomethyl.
  
• wherein R _{9 is} C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, -SO ₂ -Z, carboxy and sulfo; and Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl.
  
  
• wherein R _{14 is} C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxy and sulfo; and Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl,
  
  
  
  
  
  
• wherein R ₆ and Z have the meanings given under formula (14), and R has the meaning given under formula (4).

Heavy metal complexes of reactive dyes are also particularly important; copper, nickel, cobalt or chromium are particularly suitable as complex-forming heavy metals. Copper complex azo dyes are preferred, in particular those of the formulas (12) to (23) which contain the copper atom bonded via an oxygen atom each in the ortho position to the azo bridge.

Examples of azo dyes that are suitable as metal complexes:

Cu (1: 1 complex) or Cr and Co (1: 2 complex) are preferred as metal atoms. Cr and Co complexes may contain the azo compound of the formula given above once or twice, i.e. they can be symmetrical or asymmetrical with any other ligand.

worin R₆ die unter Formel (14) angegebenen Bedeutungen hat.Copper complexes such as, for example, are preferred

wherein R _{6 has} the meanings given under formula (14).

The aromatic rings in the above dyes can be further substituted, the benzene rings especially by methyl, ethyl, methoxy, ethoxy, methylsulfonyl, ethylsulfonyl, carboxy, acetylamino or chlorine, and the naphthalene rings in particular by methoxy, carboxy, acetylamino, nitro or chlorine. The benzene rings are preferably not further substituted.

dar, worin A₁ und A₂ unabhängig voneinander z.B. je einen Rest der zuvor angegebenen Formel (6a) - (31c) bedeuten, T₁ und T₁' unabhängig voneinander je die zuvor für T₁ angegebenen Bedeutung haben und bevorzugt je für Chlor stehen, R₁, R_i', R₁" und R₁'" unabhängig voneinander je die zuvor für R₁ angegebene Bedeutung haben und bevorzugt je für Wasserstoff stehen und A einen bivalenten aromatischen oder aliphatischen Rest, z.B. gegebenenfalls durch 1 bis 2 Sulfogruppen substituiertes 1,3- oder 1,4-Phenylen oder C₂-C₆-Alkylen, bedeutet.Another group of reactive dyes suitable for the process according to the invention are compounds of the formula

in which A ₁ and A ₂ independently, for example, each represent a radical of the formulas (6a) - (31c) given above, T ₁ and T ₁ 'independently of one another each have the meaning given previously for T ₁ and preferably each represent chlorine , R ₁ , R _i ', R ₁ "and R ₁ '" independently of one another each have the meaning previously given for R ₁ and preferably each represent hydrogen and A is a bivalent aromatic or aliphatic radical, for example optionally substituted by 1 to 2 sulfo groups 1,3- or 1,4-phenylene or C ₂ -C ₆ alkylene.

For the process according to the invention, reactive dyes are preferred which contain at least one monohalotriazine group, preferably a monochlorotriazine group.

Dyes with two or more identical or different reactive groups can also be used.

Due to the electrolyte resistance of component (a), the dyes used according to the invention can be either liquid or formulated as powder or granules.

The amount of the dyes used is generally dependent on the desired color strength and is advantageously from 0.01 to 400 g, advantageously from 0.5 to 300 and preferably from 1 to 200 g per kg of printing paste.

The printing paste according to the invention is produced in a simple manner by mixing components (a) and (b) and, if appropriate, (c), and urea and reducing agent with the desired dye formulation, the amount of water required being added at the end, so that a sets a suitable viscosity for direct printing, which is between 1,500 and 7,000 mPa · s.

When printing, the printing paste is applied over the entire surface, preferably in a pattern, to the substrate, printing presses of conventional design, e.g. Rotary film printing or flat film printing machines are used expediently.

The method according to the invention is particularly suitable for printing textiles which consist of or contain cellulose. However, wool or silk can also be printed.

Suitable cellulose material is that of regenerated or, in particular, natural cellulose, such as Cellulose, viscose silk, cellulose acetate, hemp, linen, jute or preferably cotton, as well as fiber mixtures, e.g. those made of polyamide / cotton or in particular polyester / cotton, it being possible for the polyester portion to be printed simultaneously with disperse dyes.

As a rule, these are mainly sheet-like textile materials, such as Fleeces, felts, carpets, knitted fabrics and in particular fabrics. The process according to the invention is suitable for fiber materials which may have been pretreated with sodium hydroxide solution, for cellulose material and regenerated cellulose, such as Viscose cellulose.

After the application of the printing paste, the printed textile material is preferably dried and then one Subject to heat treatment process to complete the print or fix the dye.

The heat treatment can be carried out by a warm dwell process, a thermal insulation process or preferably by a steaming process.

In the steaming process, the printed textile materials are subjected to a treatment in a steamer with possibly superheated steam, expediently at a temperature of 98 to 210 ° C., advantageously 100 to 180 ° C. and preferably 100 to 120 ° C.

The completion of the prints by the so-called thermal insulation process can take place after or without intermediate drying, e.g. at a temperature of 100 to 210 ° C. The thermal insulation is preferably carried out at a temperature of 120 to 210 ° C, preferably 140 to 180 ° C and after an intermediate drying at 80 to 140 ° C of the printed goods. Depending on the temperature, the thermal insulation can take 20 seconds to 5 minutes, preferably 30 seconds to 4 minutes.

After the printing process, the cellulose-containing textile material is washed out in the usual way to remove unfixed dye. For this purpose, the substrate is treated, for example, at from 40 ° C. to the cooking temperature in a solution which contains soap or synthetic detergent.

The present process gives strong, pattern-like prints on a white background with good levelness, good fastness properties and with sharp contours.

• (a) ein wasserlösliches sulfogruppenhaltiges Polymer,
• (b) Fixieralkali,

sowie gegebenenfalls

• (c) ein Entlüftungsmittel.

Another subject matter of the invention is the printing paste used for the process according to the invention containing, in addition to at least one water-soluble reactive dye

• (a) a water-soluble polymer containing sulfo groups,
• (b) fixative alkali,

and if necessary

• (c) a deaerating agent.

The printing paste according to the invention advantageously contains urea and reducing agents as further additives.

For the printing paste according to the invention, the same preferences apply as for R and M, components (a) and (b), and optionally added component (c), urea and reducing agents, as stated above for the printing process.

The printing paste according to the invention is characterized by good homogeneity, excellent storage stability and simple handling.

Unless stated otherwise, the percentages given in the examples below are based on weight.

Example 1:

• 100 g/kg einer handelsüblichen, flüssigen Formulierung des Farbstoffes der Formel
  
• 10 g/kg 2-Nitrobenzolsulfonsäure Na-Salz,
• 75 g/kg 20%-ige, wässrige Na₂CO₃ calc. Lösung,
• 100 g/kg Harnstoff,
• 540 g/kg Homopolymerisat von 2-Acrylamido-2-methylpropansulfonsäure K-Salz als 25%-ige wässrige Lösung (Viskosität einer 5%igen wässrigen Lösung gemessen am Viskosimeter Brookfield RVT, Spindel 4, 20 rpm, 20°C 350 mPa.s),
• 2 g/kg Entlüftungsmittel auf Basis von 2-Ethyl-n-hexanol und
• 173 g/kg Wasser

A fabric made of bleached, mercerized cotton is printed on a flat film printing machine with a printing paste of the following composition:

• 100 g / kg of a commercially available, liquid formulation of the dye of the formula
  
• 10 g / kg of 2-nitrobenzenesulfonic acid sodium salt,
• 75 g / kg 20% aqueous Na ₂ CO ₃ calc. Solution,
• 100 g / kg urea,
• 540 g / kg homopolymer of 2-acrylamido-2-methylpropanesulfonic acid K salt as 25% aqueous solution (viscosity of a 5% aqueous solution measured on the Brookfield RVT viscometer, spindle 4, 20 rpm, 20 ° C 350 mPa.s ),
• 2 g / kg deaerating agent based on 2-ethyl-n-hexanol and
• 173 g / kg water

The printing paste has a pH of 11.3. The viscosity is 2,400 mPa.s, measured on the Brookfield RVT viscometer, spindle 6, 20 rpm at 25 ° C. The printed fabric is dried at 90 ° C. and fixed for 8 minutes to fix the dye. treated with saturated steam at 100 ° C. The fabric is then rinsed with cold and boiling water until the unfixed portions of the dye and auxiliary agents have been removed. After the fabric has been dried at 90 to 100 ° C, a color-rich red level print with sharp contours is included. The treated fabric also has a soft feel.

Example 2:

The procedure is as described in Example 1, but 33 g / kg of the granule formulation of the same dye is used instead of the commercially available liquid formulation of the dye of the formula (3) and the amount of water is accordingly increased to 240 g / kg. You also get a bright red, level print with sharp contours and a soft feel. The viscosity of the printing paste is not affected by the use of another commercial form.

Example 3:

• 100 g/kg einer handelsüblichen, flüssigen Formulierung des Farbstoffes der Formel:
  
• 10 g/kg 2-Nitrobenzolsulfonsäure Na-Salz,
• 75 g/kg 20%-ige, wässrige Na₂CO₃ calc. Lösung,
• 100 g/kg Harnstoff,
• 540 g/kg Homopolymerisat von 2-Acrylamido-2-methylpropansulfonsäure Na-Salz als 25%-ige wässrige Lösung,
• 2 g/kg Entlüftungsmittel auf Basis von 2-Ethyl-n-hexanol und
• 173 g/kg Wasser.

The procedure is as described in Example 1, but instead of a bleached, mercerized cotton fabric, a bleached viscose fabric is printed with a printing paste of the following composition:

• 100 g / kg of a commercially available, liquid formulation of the dye of the formula:
  
• 10 g / kg of 2-nitrobenzenesulfonic acid sodium salt,
• 75 g / kg 20% aqueous Na ₂ CO ₃ calc. Solution,
• 100 g / kg urea,
• 540 g / kg homopolymer of 2-acrylamido-2-methylpropanesulfonic acid Na salt as 25% aqueous solution,
• 2 g / kg deaerating agent based on 2-ethyl-n-hexanol and
• 173 g / kg water.

You get a strong blue level print with sharp contours and a soft handle. The viscosity of the printing paste, measured on the Brookfield RVT viscometer, spindle 6, 20 rpm at 25 ° C, is not changed by using a different dye and remains at 2,400 mPa.s.

• - Dämpfen mit Sattdampf: 4-10 min bei 100-102°C
• - Thermofixieren mit Heissluft: 3-5 min bei 130-150° C
• - Hochtemperaturdämpfen mit überhiztem Dampf: 4 min bei 120-150° C

The dye fixation takes place in the above examples under the following conditions:

• - Steaming with saturated steam: 4-10 min at 100-102 ° C
• - Heat setting with hot air: 3-5 min at 130-150 ° C
• - High temperature steaming with superheated steam: 4 min at 120-150 ° C

Examples 4-7:

• 4 Copolymer aus 2-Acrylamido-2-methylpropansulfonsäure-K-Salz und Octylacrylamid (99,5/0,5 Mol-%) mit einer Brookfieldviskosität von 170 mPa·s (5%ige Lösung, Spindel 4, 20 rpm, 20°C).
• 5 Copolymer aus 2-Acrylamido-2-methylpropansulfonsäure-K-Salz und Acrylamid (60/40 Mol-%) mit einer Brookfieldviskosität von 250 mPa·s (5%ige Lösung, Spindel 4, 20 rpm, 20°C).
• 6 Copolymer aus 2-Acrylamido-2-methylpropansulfonsäure-K-Salz und Acrylsäure-K-Salz (80/20 Mol- %) mit einer Brookfieldviskosität von 125 mPa·s (5%ige Lösung, Spindel 4, 20 rpm, 20°C).
• 7 Styrolsulfonat-Na-Salz mit einer Brookfieldviskosität von 100 mPa.s (5%ige Lösung, Spindel 4, 20 rpm, 20°C).

If the procedure described in Example 1 is followed and the equivalent amount of one of the polymers mentioned below is used instead of the 2-acrylamido-2-methylpropanesulfonic acid homopolymer used there, similarly good results are obtained.

• 4 copolymer of 2-acrylamido-2-methylpropanesulfonic acid K salt and octylacrylamide (99.5 / 0.5 mol%) with a Brookfield viscosity of 170 mPa · s (5% solution, spindle 4, 20 rpm, 20 ° C).
• 5 copolymer of 2-acrylamido-2-methylpropanesulfonic acid K salt and acrylamide (60/40 mol%) with a Brookfield viscosity of 250 mPa · s (5% solution, spindle 4, 20 rpm, 20 ° C).
• 6 copolymer of 2-acrylamido-2-methylpropanesulfonic acid K salt and acrylic acid K salt (80/20 mol%) with a Brookfield viscosity of 125 mPa · s (5% solution, spindle 4, 20 rpm, 20 ° C).
• 7 styrene sulfonate Na salt with a Brookfield viscosity of 100 mPa.s (5% solution, spindle 4, 20 rpm, 20 ° C).

Examples 8-13:

If the procedure described in Example 1 is followed and the equivalent amount of one of the reactive dyes mentioned below is used instead of the reactive dye used there, similarly good results are obtained.

Claims (18)

1. A method for printing fiber material with reactive dyes in direct printing, characterized in that the fiber materials are printed with a printing paste which, in addition to at least one water-soluble reactive dye (a) a water-soluble polymer containing sulfo groups, (b) fixative alkali
and if necessary (c) contains a deaerating agent. 2. The method according to claim 1, characterized in that component (a) is homo-co- or graft polymers which - 20 mol% units of a sulfo-containing monomer selected from the group (Meth) acrylamidomethanesulfonic acid, Vinyl sulfonic acid, (Meth) allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3- (meth) acrylamidopropanesulfonic acid, 3-sulfopropyl (meth) acrylate, Bis (3-sulfopropyl itaconate), 4-styrene sulfonic acid and 3-allyloxy-2-hydroxypropylsulfonic acid
included, acts. 3. The method according to claim 1 or 2, characterized in that component (a) is homopolymers or copolymers which contain ≧ 50 mol%, in particular 75 mol% of 2-acrylamido-2-methylpropanesulfonic acid units , acts. 4. Process according to claims 1 to 3, characterized in that a homopolymer of 2-acrylamido-2-methylpropanesulfonic acid in the form of its alkali metal salts is used as component (a) of the printing paste. 5. The method according to any one of claims 1 to 4, characterized in that the polymer (a) has a molecular weight of 1000 to 3000000 and preferably 5000 to 500000. 6. The method according to any one of claims 1 to 5, characterized in that a printing paste is used which contains a deaerating agent, in particular a deaerating agent which is low in silicone oil or free of silicone oil. 7. The method according to claim 6, characterized in that the deaerating agent contains a higher alcohol with a boiling range above 100 ° C, turpentine oils, mineral oils or mixtures thereof. 8. The method according to claim 6 or 7, characterized in that the deaerating agent contains an octanol or its mixture with high-boiling hydrocarbon mixtures, which has 0 to 5% silicone oil. 9. The method according to claims 1 to 8, characterized in that the printing paste contains urea as a further component. 10. The method according to claims 1 to 19, characterized in that the printing paste contains a reducing agent as a further component. 11. The method according to claim 10, characterized in that the reducing protection agent is a 2-nitrobenzenesulfonic acid sodium salt. 12. The method according to claims 1 to 11, characterized in that the printing paste 0.5 to 20, preferably 1.5 to 5 percent by weight of component (a), 1 to 10 percent by weight fixing alkali, 0.1 to 5, preferably 0.1 to 1 percent by weight of a deaerating agent, 0.1 to 20, preferably 0.1 to 10 weight percent urea and Contains 0.1 to 4, preferably 1 to 2 percent by weight of a reducing agent. 13. The method according to claims 1 to 12, characterized in that cellulose-containing fiber material is used as the fiber material. 14. The material printed by the method according to one of claims 1 to 13. 15. Aqueous printing paste containing at least one water-soluble reactive dye (a) a water-soluble polymer containing sulfo groups, (b) fixative alkali and if necessary (c) a deaerating agent. 16. Printing paste according to claim 15, characterized in that component (a) is a homopolymer of 2-acrylamido-2-methylpropanesulfonic acid in the form of an alkali or alkaline earth metal salt. 17. Printing paste according to claim 15 or 16, characterized in that it contains urea as a further component. 18. Printing paste according to one of claims 16 to 18, characterized in that it contains a reducing agent as a further component.