EP0178255B1 - Process for fixing dyeings or printings - Google Patents

Description

The present invention relates to a new method for the nuance-stable fixing of azo, metal complex azo and metallized formazan dyes on textile materials with hot steam.

One of the best known and most common methods of dye fixation on colored or printed goods is steam fixation. Steaming dyed or printed goods with water vapor is one of the most important steps in textile dyeing and especially textile printing. The fixation or degree of fixation and thus the extensiveness and the fastness of the dyeings or prints depend on it. The steaming process therefore requires special attention and careful monitoring.

• 1. Lieferant von Wasser durch Kondensation bei allen einstufigen Verfahren (es wird mit trockener Ware in den Dämpfer eingefahren).
• 2. Energiezufuhr zur Beschleunigung der Farbstoffdiffusion.
• 3. EnergiezufuhrzurAuslösung von chemischen Reaktionen für den Fixierprozess (z. B. Na-Formaldehyd-sulfoxylat-Zerfall bei Küpenfarbstoffen).
• 4. Energieabführung zur Vermeidung von Überhitzungen bei exothermen Vorgängen wie chem. Reaktionen, Adsorption von H₂0, etc.
• 5. Schutzgasfunktion gegen Einflüsse von Luftsauerstoff auf Redoxvorgänge in Farbstoffen und Verdickungsmitteln;
• 6. Transportmittel für flüchtige Reaktionsprodukte aus Fixierprozessen.

If water vapor is used for dye fixation, especially of textile prints, it has to perform several functions, such as B .:

• 1. Supplier of water by condensation in all one-step processes (it is run into the damper with dry goods).
• 2. Energy supply to accelerate dye diffusion.
• 3. Energy supply to trigger chemical reactions for the fixing process (e.g. Na formaldehyde sulfoxylate decay in vat dyes).
• 4. Energy dissipation to avoid overheating in exothermic processes such as chem. Reactions, adsorption of H ₂ 0, etc.
• 5. Protective gas function against the effects of atmospheric oxygen on redox processes in dyes and thickeners;
• 6. Means of transport for volatile reaction products from fixing processes.

While all steam functions from positions 1 to 6 are claimed when fixing cage prints using the one-step process, when fixing stains or printing with dyes of other classes (nouns, leucocubes esters, reactive, acid, metal complex, dispersions - and cationic dyes) not all positions of equal importance.

One in many publications, such as B. in Textile Printing by L.W.C. Miles, Deyers Company Publications Trust, 1981, repeatedly asked for steam quality is the absence of steam. The air content should be less than 0.3 percent by volume. This requirement is usually exceeded by today's dampers; the air content is often less than 0.1 percent by volume.

Another phenomenon that occurs repeatedly in steam fixation is the fluctuation in the nuance when fixing, in particular, light shades of dyes that are sensitive to reduction.

All azo, metal complex azo and formazan dyes are considered to be more or less sensitive to reduction.

The fluctuations in nuance when fixing are generally due to the reducing effect of water vapor through boiler water additives such as Hydrazine recycled. However, printing pastes that contain, for example, a sodium alginate thickener and fixing alkali also have a clearly reducing effect.

It was an object of the present invention to find a steam-fixing method which, even when using reduction-sensitive dyes, provides shade-stable dyeings or, in particular, prints.

This object is achieved with the method according to the invention.

The present invention thus relates to a process for the nuance-stable fixing of azo, metal complex azo and metallized formazan dyes on textile materials with hot water vapor, which is characterized in that textile materials dyed or printed with these dyes are dried and then fixed in a hot water vapor atmosphere , which contains 0.5 to 5 volume percent air.

Surprisingly, the steam-fixing method according to the invention gives shades or prints with stable shades; Thus, contrary to the general requirement for the damper to be as free from air as possible, an air content of at least 0.5% by volume is necessary for certain dye classes in order to avoid shade fluctuations in the colors or prints due to steam fixation.

In the process according to the invention, the intermediate drying of the dyed or printed textile materials before the steaming fixation is mandatory.

A preferred embodiment of the method according to the invention is characterized in that textile materials dyed or printed with reduction-sensitive dyes, in particular textile materials dyed or printed with water-insoluble and / or water-soluble dyes, and especially textile materials dyed or printed with water-soluble reactive dyes.

An embodiment of the method according to the invention is characterized in that fixation is carried out in a water vapor atmosphere which contains 0.5 to 5 volume percent air, in particular 1.5 to 5 volume percent air and especially 1.5 to 3.5 volume percent air. In the process according to the invention, an air content of at least 1 percent by volume has proven to be particularly advantageous.

Another preferred embodiment of the method according to the invention is characterized in that it is fixed under normal pressure.

In the method according to the invention, a temperature between 100 ° and 220 ° C., in particular 100 ° to 105 ° C. or 150 ° to 190 ° C., based on a pressure of 1 bar, has been found to be particularly advantageous for fixing in a hot steam atmosphere proven.

A particularly preferred embodiment of the method according to the invention is characterized in that printed textile materials are used, in particular those which are printed with printing pastes containing a thickener that promotes reduction.

In particular, printed textile materials with dye mixtures containing at least one water-soluble reactive dye and at least one disperse dye are used in the process according to the invention as printed textile materials from blended fabrics, in particular printed polyester / cellulose blended fabrics and, above all, printed cellulose fibers.

In the method according to the invention, a polyester / cellulose blend fabric which is printed with a printing paste containing at least one water-soluble reactive dye, at least one disperse dye, alginate and fixing alkali is very particularly preferably used as the printed textile material made of polyester / cellulose blend fabric. and above all a polyester / cellulose blended fabric is used which is printed with a printing paste containing at least one fiber-reactive, sulfo-containing azo or metal complex azo dye, at least one azo dispersion dye, alginate and a fixing alkali and in a water vapor atmosphere under normal pressure at 150 ° to 220 ° is fixed, which contains 1.5 to 3.5 percent by volume of air.

Textile materials are those made from natural and synthetic fibers and mixtures thereof. Examples include: cotton, linen (bleached), viscose, polynosic, copper synthetic silk, wool, silk, synthetic polyamide, polyester and polyurethane fibers, wool / polyamide, wool / polyester, wool / cellulose, wool / Polyacrylonitrile and polyester / cellulose blended fabrics.

Synthetic polyamide, polyester, cellulose fibers and polyester / cellulose blended fabrics are preferably used as textile materials.

The textile materials are dyed or printed by methods known per se, dried and then fixed in accordance with the method according to the invention.

The fixation takes place in one of the conventional continuous or discontinuous dampers known per se, which must have a device for the targeted addition of air. The air inlet can be regulated, for example, via a valve.

The water vapor state in the process according to the invention corresponds to the steam state customary in industrial dampers, such as Saturated steam and superheated steam.

Steaming time and steam temperature depend on the dyes and textile material used.

In the process according to the invention, textile materials are used which are dyed or printed with azo, metal complex azo and metallized formazan dyes.

These dyes can be water-soluble or water-insoluble.

Suitable disperse dyes come e.g. B. the dyes known from the Color Index as Disperse Dyes.

• 1. Monoazoverbindungen der Formel
  
  • worin D, einen Rest der Benzol- oder Naphtalinreihe bedeutet, wie z. B. den Phenyl-, Naphthyl-, Stilben-, Diphenyl-, Benzthiazolylphenyl- oder Diphenylaminrest, der durch Sulfogruppen, Halogen, wie z. B. Chlor, Äthylaminogruppen, wie z. B. Athylamino oder Benzolyamino, Aminogruppen, wie z. B. -NH₂ und Methylamino, Alkoxy, wie z. B. Methoxy, Hydroxy und Carboxy sowie faserreaktive Reste X substituiert sein kann.
• 2. Disazoverbindungen der Formel (1), worin D, einen Rest der Azobenzol-, Azonaphthalin- oder Phenylazonaphthalinreihe bedeutet und D, und der Naphthalinkern, wie in Klasse 1 angegeben, substituiert sein können.
• 3. Disazoverbindungen der Formel
  
  • worin X, D, und D₂ unabhängig voneinander die für D₁ unter Formel (1) angegebenen Bedeutung haben. 4. Monoazoverbindungen der Formel
    
  • worin D₁ einen unter Formel (1) angegebenen Rest, insbesondere einen Disulfonaphthyl- oder Stilbenrest bedeutet und X die unter Formel (1) angegebene Bedeutung hat und der Benzolkern weitere Substituenten wie z.B. Halogenatome oder Alkyl-, Alkoxy-, Carbonsäure-, Ureido- und Acylaminogruppen enthalten kann.
• 5. Mono- oder Disazoverbindungen der Formel
  
  • worin D, einen Rest der Azobenzol-, Azonaphthalin- oder Phenylazonaphthalinreihe doer vorzugsweise einen Rest der Benzol- oder Naphthalinreihe, der durch die für D, unter Formel (1) angegebenen Substituenten substituiert sein kann, bedeutet und K, den Rest einer Naphtholsulfonsäure oder den Rest einer Ketomethylenverbindung, wie z. B. ein Acetoacetarylid insbesondere Acetoacetanilid oder ein 5-Pyrazolon insbesondere ein 1-Phenyl-3-methyl-5-pyrazolon, mit der OH-Gruppe in Nachbarstellung zur Azogruppe bedeutet und X die unter Formel (1) angegebene Bedeutung hat. Vorzugsweise bedeutet D, einen Rest der Benzolreihe, der eine Sulfonsäuregruppe enthält.
• 6. Mono- oder Disazoverbindungen der Formel
  
  worin D, einen der für D, in den Klassen 1 und 2 oben definierten Rest und K₂ den Rest einer enolisierbaren Ketomethylenverbindung, wie z.B. ein Acetoacetarylid insbesondere Acetoacetanilid oder ein 5-Pyrazolon insbesondere ein 1-Phenyl-3-methyl-5-pyrazolon, mit der OH-Gruppe in Nachbarstellung zur Azogruppe bedeuten und X die in Klasse 1 angegebene Bedeutung hat.
• 7. Metallkomplexverbindungen, wie z.B. Kupfer-, Chrom- und Kobaltkomplexe, der Farbstoffe der Formeln (1) bis (5), worin D₁, K, und K₂ die angegebenen Bedeutungen haben und ferner eine metallisierbare Gruppe, wie z. B. eine Hydroxyl, Methoxy- oder Carbonsäuregruppe, in Nachbarstellung zur Azogruppe enthalten.
• 8. Metallkomplexe von Formazanfarbstoffen der Formel
  
  worin Q₁ ein organischer Rest, eine Nitro- oder Cyanogruppe ist, A und B Reste von Diazokomponenten der Benzol-, Naphthalin- oder heterocyclischen Reihe und Y, und Y₂ je einen in o-Stellung zur Azogruppe gebundenen, zur Komplexbildung mit einem Schwermetall befähigten Substituenten bedeuten und X die unter Formel (1) angegebene Bedeutung hat und n = 0, oder 2 ist.

Suitable water-soluble dyes which contain, for example, one or more sulfonic acid groups as the water-solubilizing group, are non-reactive or fiber-reactive dyes, such as, for example, the dyes known in the Color Index as acid, direct and reactive dyes. In particular, the water-soluble dyes are derived from the following dyes:

• 1. Monoazo compounds of the formula
  
  • wherein D represents a residue of the benzene or naphthalene series, such as. B. the phenyl, naphthyl, stilbene, diphenyl, benzthiazolylphenyl or diphenylamine residue, which by sulfo groups, halogen, such as. B. chlorine, ethylamino groups, such as. B. Athylamino or benzolyamino, amino groups, such as. B. -NH ₂ and methylamino, alkoxy, such as. B. methoxy, hydroxy and carboxy and fiber-reactive radicals X may be substituted.
• 2. Disazo compounds of the formula (1), in which D is a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series and D, and the naphthalene nucleus, as indicated in class 1, can be substituted.
• 3. Disazo compounds of the formula
  
  • wherein X, D, and D ₂ independently of one another have the meaning given for D ₁ under formula (1). 4. Monoazo compounds of the formula
    
  • in which D ₁ denotes a radical specified under formula (1), in particular a disulfonaphthyl or stilbene radical and X has the meaning given under formula (1) and the benzene nucleus has further substituents such as halogen atoms or alkyl, alkoxy, carboxylic acid, ureido or and may contain acylamino groups.
• 5. Mono- or disazo compounds of the formula
  
  • wherein D, a residue of the azobenzene, azonaphthalene or phenylazonaphthalene series or preferably a residue of the benzene or naphthalene series, which is represented by the formula for D, under formula (1) indicated substituent may be substituted, and K, the residue of a naphtholsulfonic acid or the residue of a ketomethylene compound, such as. B. an acetoacetarylide, especially acetoacetanilide or a 5-pyrazolone, in particular a 1-phenyl-3-methyl-5-pyrazolone, with the OH group adjacent to the azo group and X has the meaning given under formula (1). D is preferably a residue of the benzene series which contains a sulfonic acid group.
• 6. Mono- or disazo compounds of the formula
  
  wherein D, one of the radicals defined for D in classes 1 and 2 above and K ₂ the radical of an enolizable ketomethylene compound, such as, for example, an acetoacetarylide, in particular acetoacetanilide, or a 5-pyrazolone, in particular a 1-phenyl-3-methyl-5-pyrazolone , with the OH group adjacent to the azo group and X has the meaning given in class 1.
• 7. Metal complex compounds, such as copper, chromium and cobalt complexes, of the dyes of the formulas (1) to (5), in which D ₁ , K, and K _{2 have} the meanings given and also a metallizable group, such as. B. contain a hydroxyl, methoxy or carboxylic acid group, adjacent to the azo group.
• 8. Metal complexes of formazan dyes of the formula
  
  wherein Q _{1 is} an organic radical, a nitro or cyano group, A and B are residues of diazo components of the benzene, naphthalene or heterocyclic series and Y, and Y ₂ each have a bond in the o-position to the azo group, for complex formation with a heavy metal qualified substituents and X has the meaning given under formula (1) and n = 0 or 2.

The radical Q ₁ is especially a radical of the benzene series, such as phenyl or sulfophenyl, or an alkyl radical, such as. B. methyl, a low molecular weight alkanoyl group, such as. B. Actyl, a carbalkoxy group having up to 4 carbon atoms, a benzoyl group or a heterocyclic radical, and A and B are preferably phenyl radicals substituted by sulfo, sulfonamido or alkylsulfonyl groups. Y ₁ and Y ₂ are mainly OH and COOH groups. Suitable heavy metals are copper, chromium, cobalt and nickel.

Cellulose fibers printed with fiber-reactive azo dyes are preferably fixed according to the inventive method; printed polyester / cellulose blended fabrics are also preferably fixed with dye mixtures containing at least one fiber-reactive azo dye and at least one dispersion azo dye.

Fiber-reactive radicals X are to be understood as those which 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 capital.

X is preferably a fiber-reactive radical of the aliphatic, aromatic or heterocyclic series which is bonded to the radical D directly or via a bridge member.

X is preferably directly or via an optionally monoalkylated amino group, such as, for example, -NH-, -N (CH ₃ ) -, -N (C ₂ H ₅ ) - or -N (C ₃ H ₇ ) - or via a bridge member containing an amino group bound to the radical D, where D is an azo, metal complex azo or metallized formazan dye.

• Vinylsulfonyl-, β-Chloräthylsulfonyl-, β-Sulfatoäthylsulfonyl-, Actoxy-äthylsulfonyl-, Phosphonooxyäthylsulfonyl-, β-Thiosulfatoäthylsulfonyl, N-Methyl-N-(ß-sulfatoäthyl-sulfonyl)-amino, Acryloyl, Mono-, Di- oder Trichloracryloyl wie -CO-CCl=CH₂,-CO-CH=CH-Cl, -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-CO_OH, -CO-CBr=C_H-_COOH, -CO-CH=CBr-COOH; CO-CCL=CCI-COOH, -CO-CBr=CBr-COOH; Vorstufen des Acryloyl-Restes und der Derivate des Acryloyl-Restes wie β-Chlor-oder β-Brompropionyl, 3-Phenylsulfonylpropionyl, 3-Methylsulfonylpropionyl, 3-Chlor-3-phenyl- sulfonylpropionyl, 2,3-Dichlorpropionyl, 2,3-Dibrompropionyl; sowie 2-Fluor-2-chlor-3,3-difluor- cyclobutan-l-carbonyl, 2,2,3,3-Tetrafluorcyclobutan-carbonyl-I- oder sulfonyl-I-, β-(2,2,3,3-Tetrafluorcyclobutyl-I)-acryloyl, a- oder β-Alkenyl- oder Arylsulfonyl-acryloyl-Gruppe wie a- oder β-Methylsulfonylacryloyl, Propiolyl, Chloracetyl, Bromacetyl, 4-(ß-Chloräthyl-sulfonyl)-butyryl, 4-Vinylsulfonyl-butyryl, 5-(ß-Chloräthyl-sulfonyl)-valeryl, 5-Vinylsulfonyl-valeryl, 6-(ß-Chloräthyl-sulfonyl)-caproyl, 6-Vinylsulfonyl-carproyl; sowie 4-Fluor-3-nitro-benzoyl, 4-Fluor-3-nitrophenylsulfonyl, 4-Fluor-3-methyl-sulfonylbenzoyl, 4-Fluor-3-cyan- benzoyl, 2-Fluor-5-methylsulfonylbenzoyl.

As fiber-reactive radicals X in formulas (1) to (6) come, for. B. consider the following aliphatic and aromatic radicals:

• Vinylsulfonyl-, β-chloroethylsulfonyl-, β-sulfatoethylsulfonyl-, actoxy-ethylsulfonyl-, phosphonooxyethylsulfonyl-, β-thiosulfatoethylsulfonyl, N-methyl-N- (ß-sulfatoethylsulfonyl) -amino, acryloyl or mono-acryloyl, mono-acryloyl, mono-chloro such as -CO-CCl = CH ₂ , -CO-CH = CH-Cl, -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-CO _OH, -CO-CBr = C _H - _COOH, -CO-CH = CBr COOH; CO-CCL = 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, 3-chloro-3-phenylsulfonylpropionyl, 2,3-dichloropropionyl, 2,3- Dibromopropionyl; as well as 2-fluoro-2-chloro-3,3-difluoro-cyclobutane-1-carbonyl, 2,2,3,3-tetrafluorocyclobutane-carbonyl-I- or sulfonyl-I-, β- (2,2,3, 3-tetrafluorocyclobutyl-I) -acryloyl, a- or β-alkenyl or arylsulfonyl-acryloyl group such as a- or β-methylsulfonylacryloyl, propiolyl, chloroacetyl, bromoacetyl, 4- (ß-chloroethylsulfonyl) butyryl, 4- Vinylsulfonyl butyryl, 5- (β-chloroethylsulfonyl) valeryl, 5-vinylsulfonylvaleryl, 6- (β-chloroethylsulfonyl) caproyl, 6-vinylsulfonylcarproyl; as well as 4-fluoro-3-nitro-benzoyl, 4-fluoro-3-nitrophenylsulfonyl, 4-fluoro-3-methyl-sulfonylbenzoyl, 4-fluoro-3-cyano-benzoyl, 2-fluoro-5-methylsulfonylbenzoyl.

Furthermore, fiber-reactive radicals X of the heterocyclic series are to be mentioned, such as. B. 2,4-dichlorotriazinyl-6, mono-, di- or trihalopyrimidinyl residues, 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-methylsulfonylpyrimidinyl-6-, 2,5-dichloro-4-methylsufonyl-pyrimidinyl-6-, 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-py rimidinyl-, 2-fluoro-5-nitro-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-fluorine -4-pyrimidinyl-, 2,6-difluoro-5-bromo-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-5-chloro-6-methyl-4-pyrimidinyl-, 2-fluoro-5-chloro-4-pyrimidinyl-, 2- Fluorine-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; 2,4-bis-methylsulfonyl-pyrimidinyl-4-, 2,5-bis-methylsulfonyl-5-chloro-pyrimidinyl. 4-, 2-methylsulfonyl-pyrimidinyl-4-, 2-phenylsulfonyl-pyrimidinyl-4-, 2- Methylsulfonyl-5-chloro-6-methylpyrimidinyl-4-, 2-methylsulfonyl-5-bromo-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-5-chloro-6-ethyl-pyrimidinyl-4-, 2nd -Methylsulfonyl-5-chloromethyl-pyrimidinyl-4-, 2-methylsulfonyl-5-nitro-6-methyl-pyrimidinyl-4 _- , 2,5,6-tris-methylsulfonylpyrimidinyl-4-, 2-methylsulfonyl-5, 6-dimethyl-pyrimidinyl-4-, 2-ethylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4-, 2-methylsulfonyl-6-chloro-pyrimidinyl-4-, 2,6-bis-methylsulfonyl-5-chloro -pyrimidinyl-4-, 2-methylsulfonyl-6-carboxypyrimidinyl-4-, 2-methylsulfonyl-5-sulfopyrimidinyl-4-, 2-methylsulfonyl-6-carbomethoxypyrimidinyl-4-, 2-methylsulfonyl-5 -carboxy-pyrimidinyl-4-, 2-methylsulfonyl-5-cyan-6-methoxy-pyrimidinyl-4-, 2-methylsulfonyl-5-chloro-pyrimidinyl-4-, 2-sulfo-ethylsulfonyl-6-methyl-pyrimidinyl- 4-, 2-methylsulfonyl-5-bromo-pyrimidinyl-4-, 2-phenylsulfonyl-5-ch lor-pyrimidinyla-4-, 2-carboxymethylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4-, 2,4-dichloropyrimidine-6-carbonyl or 6-sulfonyl, 2,4-dichloropyrimidine-5-carbonyl- or 5 -sulfonyl, 2-chloro-4-methylpyrimidine-5-carbonyl, 2-methyl-4-chloropyrimidine-5-carbonyl, 2-methylthio-4-fluoropyrimidine-5-carbonyl, 6-methyl-2,4 -dichloropyrimidine-5-carbonyl, 2,4,6-trichloropyrimidine-5-carbonyl, 2,4-dichloropyrimidine-5-sulfonyl, 2,4-dichloro-6-methyl-pyrimidine-5-carbonyl or 5-sulfonyl , 2-methylsulfonyl-6-chloropyrimidine-4- and 5-carbonyl, 2,6-bis (methylsulfonyl) pyrimidine-4- or -5-carbonyl, 2-ethylsulfonyl-6-chloropyrimidine-5-carbonyl, 2, 4-bis (methylsulfonyl) pyrimdin-5-sulfonyl, 2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-sulfonyl- or -5-carbonyl, 2-chloroquinoxaline-3-carbonyl, 2- or 3-monochloroquinoxaline- 6-carbonyl, 2- or 3-monochloroquinoxaline-6-sulfonyl, 2,3-dichloroquinoxaline-5- or -6-carbonyl, 2,3-dichloro-quinoxaline-5- or -6-sulfonyl, 1,4 -Dichlorophthalazine-6-sulfonyl- or -6-carbonyl, 2,4-dichloroquinoline-7- or -6-sulfonyl- or carbonyl, 2,4,6-trichloroquinazoline-7- or -8-sulfonyl, 2- or 3- or 4- (4 ', 5 '-Dichloropyridazon-6 -'-yl-I') - phenylsulfonyl- or carbonyl, β- (4 ', 5'-dichloropyridazinon-6'-yl-1') - propionyl, 3,6-dichloropyridazin-4-carbonyl -or 4-sulfonyl, 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-methylsulfonyl- or 2-ethylsulfonylbenzothiazole-5- or -6-sulfonyl- or -carbonyl, 2-phenylsulfonyl-benzothiazole-5- or -6-sulfonyl- or carbonyl and the corresponding sulfo groups containing 2 in the condensed benzene ring -Sulfonylbenzthi- azol-5- or -6-carbonyl- or -sulfonyl-derivatives, 2-chlorobenzoxazole-5- or -6-carbonyl- or -sulfonyl, 2-chlorobenzimidazole-5- or -6-carbonyl-or -sulfonyl , 2-chloro-l-methylbenzimidazole-S-or -6-carbonyl- or -sulfonyl, 2-chloro-4-methylthiazole- (1,3) -5-carbonyl) or -4- or -5-sulfony l; Traium rings containing ammonium groups, such as 2-trimethylammonium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -amino-triazinyl-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) 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 radicals which, in the 2-position, the 1,4-bis-aza-bicyclo [2,2,2] octane or the 1,2- Contain bis-aza-bicyclo- [0,3,3] -octane bound in quaternary form, 2-pyridinium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -amino-triazinyl-6- as well Corresponding 2-oniumtriazinyl-6 radicals which are in the 4-position by alkylamino, such as methylamino, ethylamino or ß-hydroxy-ethylamino, or alkoxy, such as methoxy or ethoxy, or aryloxy, such as phenoxy or Sulfophenoxy group ppen are substituted.

• wobei als Substituenten V am Triazinring insbesondere zu nennen sind:
  • -NH₂, Alkylamino-, N,N-Dialkylamino-, Cycloalkylamino-, 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 Cycloaklyl-, Aralkyl- und Arylreste kommen insbesondere Cyclohexyl-, Benzyl-, Phenäthyl-, Phenyl- und Naphthylreste in Frage; 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 Resten sowie die N-heterocyclischen Ringe können weitersubstituiert sein, z. B. durch: Halogen, wie Fluor, Chlor und Brom, Nitro, Cyn, Trifluormethyl, Sulfamoyl, Carbamoyl, C_1-4-Alkyl, Cl-4-Alkoxy, Acylaminogruppen, wie Acetylamino oder Benzoylamino, Ureido, Hydroxy, Carboxy, Sulfomethyl oder Sulfo. Als Beispiele für derartige Aminogruppen seien genannt: -NH₂, Methylamino, Athylamino, Propylamino, Isopropylamino, Butylamino, Hexylamino, β-Methoxyäthilamino, y-Methoxypropylamino, β-Äthoxyäthylamino, N,N-Di- methylamino, N,N-Diäthylamino, β-Chloräthylamino, ß-Cyanäthylamino, y-Cyanpropylamino, β-Carboxyäthylamino, Sulfomethylamino, β-Sulfo- äthylamino, β-Hydorxyäthylamino, N,N-Di-ß-hy- droxyäthylamino, y-Hydroxypropylamino, Benzylamino, Phenäthylamino, Cyclohexylamino, Phenylamino, Toluidino, Xylidino, Chloranilino, Anisidino, Phenetidino, N-Methyl-N-phenylamino, N-Äthyl-N-phenylamino, N-ß-Hydroxyäthyl-N-phenylamino, 2-, 3- oder 4-Sulfoanilino, 2,5-Disulfinoanilino, 4-Sulfomethylanilino, N-Sulfomethylanilino, 2-, 3- oder 4-Carboxyphenylamino, 2-Carboxy-5-sulfophenylamino, 2-Carboxy-4-sulfophe- nylamino, 4-Sulfonaphthyl-(1)-amino, 3,6-Disulfonaphthyl-(1)-amino, 3,6,8-Trisulfonaphtyl-(1)-amino, 4,6,8-Trisulfonaphthyl-(1)-amino, 1-Sulfo- naphthyl-(2)-amino, 1,5-Disulfonaphthyl-(2)-amino, 6-Sulfonaphthyl-(2)-amino, Morpholino, Piperidino, Piperazino, Hydrazino und Semicarbazido. Die Reaktivfarbstoffe der Formeln (1) bis (6) können bis zu sechs gleichartige oder verschiedenartige Reaktivgruppen enthalten.

Particularly interesting fiber-reactive residues are fluoro-1,3,5-triazine residues of the formula

• where the substituents V on the triazine ring are in particular:
  • -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 may be further hetero contains roatome, as well as hydrazino and semicarbazido. The abovementioned 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 cycloaklyl, 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, preference is given to residues of six-membered N-heterocyclic compounds which may contain nitrogen, oxygen or sulfur as further heteroatoms. The above-mentioned alkyl, cycloalkyl, aralkyl and aryl radicals, the heterocyclic radicals and the N-heterocyclic rings can be further substituted, e.g. B. by: halogen, such as fluorine, chlorine and bromine, nitro, cyn, trifluoromethyl, sulfamoyl, carbamoyl, C _1-4 alkyl, Cl-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, β-methoxyäthilamino, y-methoxypropylamino, β-ethoxyethylamino, N, N-dimethylamino, N, N-diethylamino, β-chloroethylamino, ß-cyanoethylamino, y-cyanopropylamino, β-carboxyethylamino, sulfomethylamino, β-sulfoethylamino, β-hydroxyethylamino, N, N-di-ß-hydroxyethylamino, y-hydroxypropylamino, benzylamino, phenylamino Phenylamino, toluidino, xylidino, chloranilino, anisidino, phenetidino, N-methyl-N-phenylamino, N-ethyl-N-phenylamino, N-ß-hydroxyethyl-N-phenylamino, 2-, 3- or 4-sulfoanilino, 2, 5-disulfinoanilino, 4-sulfomethylanilino, N-sulfomethylanilino, 2-, 3- or 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino, 4-sulfonaphthyl- (1) -amino, 3,6-disulfonaphthyl- (1) -amino, 3,6,8-trisulfonaphtyl- (1) -amino, 4,6,8-trisulfonaphthyl- (1) -amino, 1-sulfonaphthyl- (2) - amino, 1,5-disulfonaphthyl- (2) -am ino, 6-sulfonaphthyl- (2) -amino, morpholino, piperidino, piperazino, hydrazino and semicarbazido. The reactive dyes of the formulas (1) to (6) can contain up to six identical or different types of reactive groups.

Azo, metal complex azo or metallized formazan dyes which dyed or printed on textile materials in conventional dampers with an air content of less than 0.3 percent by volume to at least 1% during the fixing process are particularly suitable as strongly reduction-sensitive dyes.

A major advantage of the method according to the invention is that both with continuous and discontinuous steam fixation there are no nuance fluctuations and a consistently high yield of the dyes used is ensured. This advantage is particularly important for light shades, i. H. Textile materials that are dyed or printed with less than 0.5% dye based on the fiber weight.

Another advantage of the method according to the invention is that textile materials can be used which are printed with printing pastes which contain thickeners with a reducing property.

A damping chamber for fixing dyed or printed textile materials in a hot steam atmosphere serves as a means for carrying out the method according to the invention, the damping chamber containing a device for admixing air. A valve, for example, can be used as a device for adding air. The air is preferably added to the water vapor via a valve that can be regulated from the outside by a nozzle system.

DE-A-1 460 356 describes a process which differs in a characteristic manner from the process according to the invention in that the fiber material is first dried in a steam-air mixture and then treated in the presence of pure superheated steam.

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

• 5 g des Reaktivfarbstoffes der Formel
  
  und 100 g Harnstoff werden gelöst in 355 g Wasser und anschliessend mit 500g einer 10%igen Na-Alginat-Verdickung zusammen homogenisiert.

Example 1: A printing paste is made according to the following recipe:

• 5 g of the reactive dye of the formula
  
  and 100 g of urea are dissolved in 355 g of water and then homogenized together with 500 g of a 10% Na alginate thickener.

• 30 g Soda calc. und
• 10 o-Nitrobenzosulfosäure-Na-Salz eingestreut und bis zur Lösung gerührt.

Be under a quick stirrer

• 30 g soda calc. and
• 10 o-nitrobenzosulfonic acid Na salt sprinkled in and stirred until dissolved.

This printing paste is used to print a cotton fabric in a conventional manner (flat or rotary film printing or Rouleaux printing) and then drying it.

For fixation, the printed fabric is steamed for 8 minutes in a water vapor atmosphere without excess pressure (- 1 bar) at 100-102 ° C. This water vapor contains 1.5-2% by volume of air. The resulting prints have a blue-gray shade after their usual post-washing treatment.

If a comparison print is fixed in an analogous manner in a steam atmosphere which contains only 0.05% by volume of air, a pink hue results, instead of the desired gray-blue shade. H. the dye was partially destroyed during the fixation process.

If the procedure is as described in Example 1 and the dyes, textile materials and fixing conditions used are the dyes indicated in column II in the following table and the textile material specified in column III and the prints obtained are fixed in accordance with the conditions indicated in column IV, this also gives nuance-stable prints.

In Examples 2 to 6, saturated steam means a saturated water vapor atmosphere at 100 to 102 ° C, which contains 1.5 to 2 percent by volume of air.

Example 7: A printing paste is prepared according to the following recipe: 1.5 g of the dye of the formula

und 100g Harnstoff werden in 398,5g heissem Wasser gelöst und in 500 einer 4%igen Verdikkung auf der Basis von hydroxyäthyliertem Guar unter dem Schnellrührer eingearbeitet.

and 100 g of urea are dissolved in 398.5 g of hot water and incorporated in 500% of a 4% thickening based on hydroxyethylated guar under the high-speed stirrer.

This printing paste is used to print a knitted fabric made of synthetic polyamide in a conventional manner and then drying it. For fixing, the printed knitted fabric is fixed for 40 minutes in a water vapor atmosphere without excess pressure (- 1 bar) at 100-102 ° C and an air content of 1.5 to 2 percent by volume. The result is a level, level-stable print.

If a reference pressure is fixed in an air-free steam atmosphere, cloudy, nuances that are not reproducible result.

Example 8: A printing paste is prepared according to the following recipe: 1.5 g of the dye of the formula

und 100g Harnstoff werden in 398,5g heissem Wasser gelöst und in 500g einer 4%igen Verdikkung auf der Basis von hydroxyäthyliertem Guar unter dem Schnellrührer eingearbeitet.

and 100 g of urea are dissolved in 398.5 g of hot water and incorporated into 500 g of a 4% thickening based on hydroxyethylated guar under the high-speed stirrer.

This printing paste is used to print a knitted fabric made of synthetic polyamide in a conventional manner and then drying it. To the fixie The printed knitted fabric is fixed for 40 minutes in a water vapor atmosphere without excess pressure (- 1 bar) at 100 -102 ° C and an air content of 1.5 to 2 percent by volume. The result is a level, level-stable print.

If a reference pressure is fixed in an air-free steam atmosphere, cloudy, nuances that are not reproducible result.

• welche zu 25 Gewichtsprozent aus dem Farbstoff der Formel (I) und zu 75 Gewichtsprozent aus dem Farbstoff der Formel (11) besteht, 2g einer salzarmen flüssigen Formulierung des Kupferkomplexes des Farbstoffes der Formel
  
  • 50 g Harnstoff,
  • 416,5 g Wasser,
  • 20g Na-Bicarbonat,
  • 10g m-nitrobenzolsulfosaures Natrium und 500 einer 10%igen Lösung eines niedrig-viscosen Na-Alginats in Wasser.

Example 9: A fabric consisting of 50% bleached cotton and 50% polyester staple fiber is printed with a printing paste consisting of 1.5 a low-dispersant liquid formulation of the mixture of the dyes of the formulas

• which consists of 25 percent by weight of the dye of formula (I) and 75 percent by weight of the dye of formula (11), 2g of a low-salt liquid formulation of the copper complex of the dye of the formula
  
  • 50 g urea,
  • 416.5 g water,
  • 20g Na bicarbonate,
  • 10 g of sodium m-nitrobenzenesulfonate and 500% of a 10% solution of a low-viscosity Na alginate in water.

• 8 Min. im Sattdampf bei 102°C und 1,5-2 Volumenprozent Luft, anschliessend
• 8 Min. in überhitztem Dampf bei 170°C und 1,5-2 Volumenprozent Luft.

After drying it is fixed as follows:

• 8 minutes in saturated steam at 102 ° C and 1.5-2 volume percent air, then
• 8 minutes in superheated steam at 170 ° C and 1.5-2 volume percent air.

The unfixed portion of the dye is removed by repeated cold and warm rinsing. A level print of gray-blue stable, reproducible shade is obtained.

If the procedure is the same as above, but is fixed without air, the result is uneven, blue-pink shades, which cannot be reproduced if repeated.

• 2,5 g/I des Farbstoffes der Formel
  
  50g/l Harnstoff, 20g/l Soda calc., 5g/1 m-nitrobenzolsulfosaures Natrium, 50g/15%ige Na-Alginatlösung.

Example 10: A bleached, leached cotton calicot fabric with an m weight of 120 g / m ² is impregnated on a foulard with a squeezing effect of 85% with a fleet of the following composition:

• 2.5 g / l of the dye of the formula
  
  50g / l urea, 20g / l soda calc., 5g / 1m-nitrobenzenesulfonic acid sodium, 50g / 15% Na alginate solution.

After drying on the hot flue, it is fixed in a continuous steamer at 101 -103 ° C for 5 minutes. The damper atmosphere contains 3% air. It is then rinsed cold and hot and dried.

A reproducible blue shade is obtained. If fixed in an air-free damper, the nuances are not reproducible.

Claims (16)

1. A process for fixing azo, metal complex azo and metallized formazan dyes on textile materials with hot steam to give stable shades, which process comprises drying textile materials dyed or printed with these dyes and then carrying out fixation in a hot steam atmosphere that contrains 0,5 to 5 per cent by volume of air.

2. A process according to claim 1, wherein textile material dyed or printed with dyes that are sensitive to reduction are used.

3. A process according to claim 1, wherein fixation is carried out in a steam atmosphere that contains at least 1 per cent by volume of air.

4. A process according to claim 1, wherein fixation is carried out in a steam atmosphere that contains 1,5 to 5 per cent by volume of air.

5. A process according to claim 4, wherein fixation is carried out in a steam atmosphere that contains 1,5 to 3,5 per cent by volume of air.

6. A process according to claim 1, wherein textile materials dyed or printed with water-insoluble and/or water-soluble dyes are used.

7. A process according to claim 6, wherein textile materials dyed or printed with water-soluble reactive dyes are used.

8. A process according to any one of claims 1, 6 and 7, wherein printed textile materials are used.

9. A process according to either of claims 1 and 6, wherein textile materials made of blended fabrics and printed with mixtures of dyes contraining at least one water-soluble reactive dye and at least one disperse dye are used.

10. A process according to claim 8, wherein printed cellulose fibres are used.

11. A process according to claim 9, wherein printed polyester/cellulose blended fabric is used.

12. A process according to claim 11, wherein a polyester/cellulose blend fabric that is printed with a printing paste containing at least one water-soluble reactive dye, at least one disperse dye, alginate and fixation alkali is used.

13. A process according to claim 1, wherein fixation is carried out under normal pressure.

14. A process according to claim 1, wherein fixation is carried out at a temperature between 100 and 220°C.

15. A process according to claim 1, wherein textile materials that are printed with printing pastes containing a reduction promoting thickener are used.

16. A process according to claim 1, which comprises fixing polyester/cellulose blend fabric which is printed with a printing paste containing at least one fibre-reactive sulfo group-containing azo or metal complex azo dye, at least one azo disperse dye, alginate and a fixation alkali, in a steam atmosphere that contains 1,5 to 3,5 per cent by volume of air, under normal pressure at 150 to 220 °C.