EP0013378B1 - Process for the production of reserve effects on polyester-cellulose blended textile materials - Google Patents

Description

worin

• R₁ Wasserstoff, Alkyl mit 1 -6 C-Atomen, Cyan, Trifluormethyl oder einen Phenylrest, der durch einen Substituenten der Gruppe Chlor, Brom, Nitro oder Alkyl mit 1-4 C-Atomen substituiert sein kann;
• X₁ Wasserstoff, Chlor, Brom, ein gegebenenfalls durch einen Substituenten der Gruppe Chlor, Brom, Cyan, Hydroxy substituiertes Alkyl mit 1 -4 C-Atomen, Alkoxy mit 1 -4 C-Atomen, Hydroxyalkoxy mit 2 -4 C-Atomen und Alkoxy-alkoxy mit insgesamt 3-6 C-Atomen;
• Y₁ Wasserstoff, Chlor, Brom, gegebenenfalls durch einen Substituenten der Gruppe Chlor, Brom, Cyan, Hydroxy substituiertes Alkyl mit 1-4 C-Atomen, Alkoxy mit 1 -4 C-Atomen, Hydroxyalkoxy mit 2-4 C-Atomen, Alkoxyalkoxy mit insgesamt 3-6 C-Atomen, -NH-CO-Y₂, -NH-SO₂-Y₂, worin
• Y₂ für Alkyl mit 1-4 C-Atomen, wobei der Alkylrest gegebenenfalls mit einem Substituenten aus der Gruppe Phenyl, Chlor, Brom, Cyan, Hydroxy, Alkoxy mit 1-2 C-Atomen oder Phenoxy substituiert sein kann, Phenyl, Amino, N-Alkylamino mit 1 -4 C-Atomen steht;
• R₂ Wasserstoff, ein gegebenenfalls durch Chlor, Brom, Cyan, Hydroxy, Alkoxy oder Hydroxyalkoxy mit 1-4 C-Atomen, Phenyl, Alkanoyloxy mit 2-4 C-Atomen, Alkylaminocarbonyloxy mit 2-4 C-Atomen oder Phenylaminocarbonyloxy substituiertes Alkyl mit 1-6 C-Atomen, Hydroxyalkyl mit 2-4 C-Atomen oder Alkenyl mit 3-6 C-Atomen;
• R₃ ein gegebenenfalls durch Chlor, Brom, Cyan, Hydroxy, Alkoxy oder Hydroxyalkoxy mit 1 -4 C-Atomen, Phenyl, Alkanoyloxy mit 2-4 C-Atomen oder Alkylaminocarbonyloxy mit 2-4 C-Atomen substituiertes Alkyl mit 1-6 C-Atomen, Hydroxyalkyl mit 2-4 C-Atomen, Alkenyl mit 3-6 C-Atomen oder Phenyl ist, oder solche, die in einer der möglichen tautomeren Formen der Formel entsprechen,
  
  worin
• D für Phenyl steht, das gegebenenfalls mindestens einen Substituenten enthält, der aus Chlor, Brom, Nitro, Cyano, Trifluoromethyl, Thiocyano, Niederalkyl, Niederalkoxy, Niederalkylcarbonyl, Niederalkylsulfonyl, Niederalkylcarbonylamino, Carbamoyl und N-Niederalkyl- und N,N-Dinieder- alkylderivaten davon, Sulfamoyl und N-Niederalkyl- und N,N-Diniederalkylderivaten davon, Sulfamato und N-Niederalkyl- und N,N-Diniederalkylderivaten davon, ausgewählt ist;
• X₂ für Wasserstoff, Niederalkyl, Carbamoyl, Cyano, Chlor, Brom, Nitroso, Nitro, Niederalkylcarbonyl, Sulfamoyl, Niederalkylsulfonyl oder Niederalkylcarbonylamino steht;
• Z für Wasserstoff oder Niederalkyl steht;

als ätzbare Reaktivfarbstoffe solche, die reaktive Reste der Formeln 111 bis VI

worin

• M Wasserstoff oder ein Metallkation und
• hal Halogen bedeuten,

enthalten, und eine Reservepaste, die als Reservierungsmittel

• a) ein Alkalisulfit oder aber ein Alkalihydrogensulfit in Kombination mit Alkalicarbonat oder Alkalihydrogencarbonat und gegebenenfalls einem Aldehyd und
• b) gegebenenfalls ein nichtionogenes Detergens enthält,

eingesetzt werden.The present invention relates to a process for the production of reserve effects on textile materials based on mixed fibers of polyester and cellulose, in particular polyester-cotton fibers, by impregnating the materials with dye liquors which, in addition to conventional dyeing and padding aids, contain disperse and reactive dyes which contain the reservation agents react and optionally contain further dispersing and reactive dyes that are resistant to the reservation agents, drying or drying the padded materials and then printing on a reserve paste, which optionally contains, in addition to the reservation agent, dispersing and reactive dyes that are resistant to the reservation agent, heat treatment at temperatures of 100 to 190 ° C and subsequent alkaline fixation of the reactive dye in a manner known per se, which is characterized in that the etchable disperse dyes are those of the formula

wherein

• R _{1 is} hydrogen, alkyl having 1 -6 C atoms, cyano, trifluoromethyl or a phenyl radical which can be substituted by a substituent from the group chlorine, bromine, nitro or alkyl having 1-4 C atoms;
• X _{1 is} hydrogen, chlorine, bromine, an alkyl which is optionally substituted by a substituent from the group of chlorine, bromine, cyano, hydroxyl and has 1-4 carbon atoms, alkoxy with 1-4 carbon atoms, hydroxyalkoxy with 2-4 carbon atoms and Alkoxy-alkoxy with a total of 3-6 carbon atoms;
• Y _{1 is} hydrogen, chlorine, bromine, optionally substituted by a substituent from the group chlorine, bromine, cyano, hydroxy-alkyl with 1-4 C-atoms, alkoxy with 1 -4 C-atoms, hydroxyalkoxy with 2-4 C-atoms, alkoxyalkoxy with a total of 3-6 C atoms, -NH-CO-Y ₂ , -NH-SO ₂ -Y ₂ , wherein
• Y ₂ for alkyl with 1-4 C atoms, where the alkyl radical can optionally be substituted with a substituent from the group phenyl, chlorine, bromine, cyano, hydroxy, alkoxy with 1-2 C atoms or phenoxy, phenyl, amino, N-alkylamino with 1 -4 C atoms;
• R _{2 is} hydrogen, an alkyl optionally substituted by chlorine, bromine, cyano, hydroxy, alkoxy or hydroxyalkoxy with 1-4 C atoms, phenyl, alkanoyloxy with 2-4 C atoms, alkylaminocarbonyloxy with 2-4 C atoms or phenylaminocarbonyloxy 1-6 C atoms, hydroxyalkyl with 2-4 C atoms or alkenyl with 3-6 C atoms;
• R _{3 is} an alkyl with 1-6 C which is optionally substituted by chlorine, bromine, cyano, hydroxy, alkoxy or hydroxyalkoxy with 1 -4 C atoms, phenyl, alkanoyloxy with 2-4 C atoms or alkylaminocarbonyloxy with 2-4 C atoms -Atoms, hydroxyalkyl having 2-4 C atoms, alkenyl having 3-6 C atoms or phenyl, or those which correspond to the formula in one of the possible tautomeric forms,
  
  wherein
• D represents phenyl, which optionally contains at least one substituent consisting of chlorine, bromine, nitro, cyano, trifluoromethyl, thiocyano, lower alkyl, lower alkoxy, lower alkylcarbonyl, lower alkylsulfonyl, lower alkylcarbonylamino, carbamoyl and N-lower alkyl and N, N-di-lower alkyl derivatives thereof, sulfamoyl and N-lower alkyl and N, N-lower alkyl derivatives thereof, sulfamato and N-lower alkyl and N, N-lower alkyl derivatives thereof;
• X _{2 represents} hydrogen, lower alkyl, carbamoyl, cyano, chlorine, bromine, nitroso, nitro, lower alkylcarbonyl, sulfamoyl, lower alkylsulfonyl or lower alkylcarbonylamino;
• Z represents hydrogen or lower alkyl;

as etchable reactive dyes are those which contain reactive radicals of the formulas 111 to VI

wherein

• M is hydrogen or a metal cation and
• hal is halogen,

included, and a reserve paste that acts as a reservation agent

• a) an alkali sulfite or an alkali hydrogen sulfite in combination with alkali carbonate or alkali hydrogen carbonate and optionally an aldehyde and
• b) optionally contains a nonionic detergent,

be used.

In the field of textile printing, it has always been a problem to produce white or colored sharply delimited patterns on a deep-colored background. In particular, if the production of filigree-like patterns on a dark background is desired, the direct printing of the textile material fails completely. In order to produce such designs, it has long been known to print an etching paste in the desired pattern on a deep background color produced with a white-etchable dye and then to destroy the dye at the locations printed with the etching paste by means of a dry or wet heat treatment. After washing out the prints obtained in this way, the desired pattern is obtained in white on a dark background. It is also known to add dyes that are resistant to the etchant to the etching printing pastes. In this case, at the same time as the background color is destroyed, the textile material is colored at the printed areas by the indestructible dye. In this case you get colored prints on a dark background. Colored prints on a dark background can also be obtained if the dark background is made with a mixture of an etchable and a differently colored non-etchable dye by introducing both types of dye into the padding liquor.

German Patent Specification 2,326,522 describes a process for producing reserve effects with reactive dyes on native or regenerated cellulose fiber materials. In this process, the textile material is printed with sulfites, thiosulfates or thioureas as a reservation agent, alkalis as a fixing agent and reactive dyes, which a) react with the reservation agent and have the ß-sulfatoethylsulfonyl or ß-sulfatoethylsulfonamide group as reactive group and b) do not have on fixing react with the reservation agents and have as a reactive group the chloraminotriazine, dichloropyrimidine, trichloropyrimidine, dichlorotriazine, monochlorotriazine, quaternized chlorotriazine or the dichloropyridazine group, in the form or overpressure process, then dries and fixes the dyes by steaming or Hot air treatment.

It is also already known to dye mixtures of aromatic polyester fibers and cellulose fibers with mixtures of disperse and reactive dyes. In this known method, the cellulose fibers are also slightly colored by the disperse dyes. It is extremely difficult to remove the disperse dye from the cellulose fiber by reduction without at the same time destroying the reactive dye.

When the known etching reserve printing methods are transferred to textile materials which consist of mixtures of aromatic polyester fibers and cellulose fibers, a problem arises in that the etching of polyester fibers dyed with disperse dyes, for example, is very difficult. Disperse dyes, which are once fixed, ie dissolved, in the polyester fiber are largely removed from the access of aqueous agents and thus also from the attack of aqueous etching pastes. In the production of etching prints on textile materials containing hydrophobic fibers or consisting of hydrophobic fibers, the known etching printing process is therefore modified in such a way that the textile material is first padded with a dye liquor containing disperse dye and reactive dye and dried or dried, but no fixation of the Dye, that is, solution of the disperse dye in the hydrophobic fiber, may take place. The desired pattern is then printed on the dried or dried-on padded fabric with the etching paste, and the padded and printed fabric is then subjected to a heat treatment, at the same time the base dye immersed in the non-printed areas in the polyester and the reactive dye is fixed on the cellulose and the dye is destroyed at the printed areas, ie no coloring takes place. With regard to this mechanism, this method is also referred to as etching reserve pressure.

The process of etching reserve printing, which is simple in itself, involves a number of technical difficulties which often make its use more difficult. It is usually not easy to completely destroy the base dye with the etchant. If this does not succeed, a colored residue remains on the etched areas, the shade of which can fluctuate between yellow-brown and dull violet or reddish gray tones and which soils the white background at the etched areas. This leads to white etchings which appear to be unclean or, in the event that a colored etch is to be produced, to a falsification of the shade of the etchant-resistant dye. To overcome this difficulty, etching pastes are used which contain relatively strong reducing or oxidizing agents, such as. B. sodium dithionite in conjunction with alkali, alkali formaldehyde sulfoxylates or even heavy metal salts such as tin (II) chloride (see. DE-A-2 314 541). With such strong etching agents, it is generally possible to achieve a perfect white etching print, but damage to the fiber material often occurs, especially if the polyester fiber also contains accompanying fibers, such as cellulose fibers. Furthermore, these etchants are generally not cheap, and in the case of heavy metal etchants they represent an additional ecological burden or cause additional expenditure in the purification of the waste water. In addition, there are relatively few types of dispersions and reactive dyes that are resistant to such etchants, and so the selection of etch-resistant dyes that can be used to produce colored etchings is relatively small.

It is also already known to produce reserve effects on hydrophobic fibers (cf. FR-A-2 321 009) by padding the fiber materials with dye liquors which contain disperse dyes containing carboxylic acid ester groups. After the padded fabric has dried, etching printing pastes are printed on, which contain an alkali as the etchant in combination with polyhydric aliphatic alcohols such as glycol, glycerol or polyglycol. However, such combinations of etchants have a negative influence on the fixing behavior of the dyes, i.e. H. in the case of the production of colored reserves, the color yields of the dyes that are resistant to caustic agents are reduced.

worin R₁ Wasserstoff, Alkyl mit 1 bis 6 C-Atomen, Cyan, Trifluormethyl oder einen Phenylrest, der durch einen Substituenten der Gruppe Chlor, Brom, Nitro oder Alkyl mit 1 bis 4 C-Atomen substituiert sein kann; X₁ Wasserstoff, Chlor, Brom, ein gegebenenfalls durch einen Substituenten der Gruppe Chlor, Brom, Cyan, Hydroxy substituiertes Alkyl mit 1 bis 4 C-Atomen, Alkoxy mit 1 bis 4 C-Atomen, Hydroxyalkoxy mit 2 bis 4 C-Atomen und Alkoxy-alkoxy mit insgesamt 3 bis 6 C-Atomen; Y₁ Wasserstoff, Chlor, Brom, gegebenenfalls durch einen Substituenten der Gruppe Chlor, Brom, Cyan, Hydroxy substituiertes Alkyl mit 1 bis 4 C-Atomen, Alkoxy mit 1 bis 4 C-Atomen, Hydroxyalkoxy mit 2 bis 4 C-Atomen, Alkoxyalkoxy mit insgesamt 3 bis 6 C-Atomen, -NH-CO-Y₂, -NH-SO₂-Y₂, worin Y₂ für Alkyl mit 1 bis 4 C-Atomen, wobei der Alkylrest gegebenenfalls mit einem Substituenten aus der Gruppe Phenyl, Chlor, Brom, Cyan, Hydroxy, Alkoxy mit 1 bis 2 C-Atomen oder Phenoxy substituiert sein kann, Phenyl, Amino, N-Alkylamino mit 1 bis 4 C-Atomen steht; R₂ Wasserstoff, ein gegebenenfalls durch Chlor, Brom, Cyan, Hydroxy, Alkoxy oder Hydroxyalkoxy mit 1 bis 4 C-Atomen, Phenyl, Alkanoyloxy mit 2 bis 4 C-Atomen, Alkylaminocarbonyloxy mit 2 bis 4 C-Atomen oder Phenylaminocarbonyloxy substituiertes Alkyl mit 1 bis 6 C-Atomen, Hydroxyalkyl mit 2 bis 4 C-Atomen oder Alkenyl mit 3 bis 6 C-Atomen; R₃ ein gegebenenfalls durch Chlor, Brom, Cyan, Hydroxy, Alkoxy oder Hydroxyalkoxy mit 1 bis 4 C-Atomen, Phenyl, Alkanoyloxy mit 2 bis 4 C-Atomen oder Alkylaminocarbonyloxy mit 2 bis 4 C-Atomen substituiertes Alkyl mit 1 bis 6 C-Atomen, Hydroxyalkyl mit 2 bis 4 C-Atomen, Alkenyl mit 3 bis 6 C-Atomen oder Phenyl ist, oder solche, die in einer der möglichen tautomeren Formen der Formel II entsprechen,

worin D für Phenyl steht, das gegebenenfalls mindestens einen Substituenten enthält, der aus Chlor, Brom, Nitro, Cyano, Trifluoromethyl, Thiocyano, Niederalkyl, Niederalkoxy, Niederalkylcarbonyl, Niederalkylsulfonyl, Niederalkylcarbonylamino, Carbamoyl und N-Niederalkyl- und N,N-Diniederal- kylderivaten davon, Sulfamoyl und N-Niederalkyl- und N,N-Diniederalkylderivaten davon, Sulfamato und N-Niederalkyl- und N,N-Diniederalkylderivaten davon, ausgewählt ist; X₂ für Wasserstoff, Niederalkyl, Carbamoyl, Cyano, Chlor, Brom, Nitroso, Nitro, Niederalkylcarbonyl, Sulfamoyl, Niederalkylsulfonyl oder Niederalkylcarbonylamino steht; Z für Wasserstoff oder Niederalkyl steht; als ätzbare Reaktivfarbstoffe solche, die reaktive Reste der Formeln III bis Vl

worin M Wasserstoff oder ein Metallkation und hal Halogen bedeuten, enthalten, und eine Reservepaste, die als Reservierungsmittel

• a) ein Alkalisulfit oder aber ein Alkalihydrogensulfit in Kombination mit Alkalicarbonat oder Alkalihydrogencarbonat und gegebenenfalls einem Aldehyd und
• b) gegebenenfalls ein nichtionogenes Detergens enthält,

einsetzt.The above-mentioned disadvantages of the known processes for the production of reserve effects on textile materials based on mixed fibers made of polyester and cellulose, in particular polyester-cotton fibers, by impregnating the materials with dye liquors which, in addition to conventional dyeing and padding aids, contain disperse and reactive dyes which are compatible with the Reserving agents react and possibly contain further dispersing and reactive dyes that are resistant to the reserving agents and optionally alkali metal formate, drying or drying the padded materials and then printing on a reserve paste, which optionally contains dispersing and reactive dyes that are resistant to the reserving agent, heat treatment at temperatures of 100 to 190 ° C. and, if appropriate, subsequent alkaline fixing of the reactive dye in a manner known per se can surprisingly be overcome by that 1. as etchable disperse dyes those of the formula

wherein R _{1 is} hydrogen, alkyl having 1 to 6 carbon atoms, cyan, trifluoromethyl or a phenyl radical which can be substituted by a substituent from the group chlorine, bromine, nitro or alkyl having 1 to 4 carbon atoms; X _{1 is} hydrogen, chlorine, bromine, an alkyl which is optionally substituted by a substituent from the group chlorine, bromine, cyano, hydroxyl and has 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxyalkoxy with 2 to 4 carbon atoms and Alkoxy-alkoxy with a total of 3 to 6 carbon atoms; Y _{1 is} hydrogen, chlorine, bromine, optionally substituted by a substituent from the group chlorine, bromine, cyano, hydroxy-alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, hydroxyalkoxy having 2 to 4 carbon atoms, alkoxyalkoxy with a total of 3 to 6 carbon atoms, -NH-CO-Y ₂ , -NH-SO ₂ -Y ₂ , wherein Y _{2 is} alkyl with 1 to 4 carbon atoms, the alkyl radical optionally having a substituent from the group phenyl , Chlorine, bromine, cyano, hydroxyl, alkoxy with 1 to 2 carbon atoms or phenoxy can be substituted, phenyl, amino, N-alkylamino with 1 to 4 carbon atoms; R _{2 is} hydrogen, optionally by chlorine, bromine, cyano, hydroxyl, alkoxy or hydroxyalkoxy having 1 to 4 carbon atoms, Phenyl, alkanoyloxy with 2 to 4 C atoms, alkylaminocarbonyloxy with 2 to 4 C atoms or phenylaminocarbonyloxy substituted alkyl with 1 to 6 C atoms, hydroxyalkyl with 2 to 4 C atoms or alkenyl with 3 to 6 C atoms; R _{3 is} an alkyl of 1 to 6 C which is optionally substituted by chlorine, bromine, cyano, hydroxy, alkoxy or hydroxyalkoxy having 1 to 4 C atoms, phenyl, alkanoyloxy having 2 to 4 C atoms or alkylaminocarbonyloxy having 2 to 4 C atoms -Atoms, hydroxyalkyl having 2 to 4 carbon atoms, alkenyl having 3 to 6 carbon atoms or phenyl, or those which correspond to one of the possible tautomeric forms of the formula II,

where D is phenyl which optionally contains at least one substituent which consists of chlorine, bromine, nitro, cyano, trifluoromethyl, thiocyano, lower alkyl, lower alkoxy, lower alkylcarbonyl, lower alkylsulfonyl, lower alkylcarbonylamino, carbamoyl and N-lower alkyl and N, N-diniederal alkyl derivatives thereof, sulfamoyl and N-lower alkyl and N, N-di-lower alkyl derivatives thereof, sulfamato and N-lower alkyl and N, N-lower alkyl derivatives thereof; X _{2 represents} hydrogen, lower alkyl, carbamoyl, cyano, chlorine, bromine, nitroso, nitro, lower alkylcarbonyl, sulfamoyl, lower alkylsulfonyl or lower alkylcarbonylamino; Z represents hydrogen or lower alkyl; as etchable reactive dyes are those which contain reactive radicals of the formulas III to VI

where M is hydrogen or a metal cation and hal is halogen, and a reserve paste which acts as a reservation agent

• a) an alkali sulfite or an alkali hydrogen sulfite in combination with alkali carbonate or alkali hydrogen carbonate and optionally an aldehyde and
• b) optionally contains a nonionic detergent,

starts.

The following sections serve to describe in detail the disperse dyes of the formula which can be used particularly advantageously according to the invention

Alkyl radicals with 1 to 6 carbon atoms, which R ₁ in formula I can represent, are, for example, methyl; Ethyl; Propyl; Isopropyl; Butyl; 1- and 2-isobutyl; Pentyl- (1), - (2) and - (3); 2- or 3-methylbutyl- (1) or - (2); Hexyl- (1), - (2) or- (3); 1-, 2- or 3-ethylbutyl- (1) or - (2); 2-, 3- or 4-methylpentyl- (1).

Examples of substituents for which X ₁ in formula I can stand are: chlorine; Bromine; Ethyl; Methyl; Propyl; Isopropyl; Butyl- (1) or - (2); Isobutyl; β-chloro, bromine, cyano or hydroxyethyl; β-chloro, bromine, cyano or hydroxypropyl; y-chloro, bromine, cyan or hydroxypropyl; β- or y-chloro, bromine, cyano or hydroxybutyl (1); 3-chloro, bromine, cyan or hydroxybutyl (2); Methoxy, ethoxy, propoxy, isopropoxy; But-1-or-2-oxy; Isobutoxy; β-hydroxyethoxy; β- or γ-hydroxypropoxy; Hydroxyisopropoxy; β-, y- or δ-hydroxybutoxy; Hydroxyisobutoxy; ß-methoxyethoxy; ß-ethoxyethoxy; β-propoxyethoxy; β-butoxyethoxy; β- or y-propoxypropoxy; β-, y- or δ-methoxy or ethoxybutoxy.

Examples of substituents which Y ₁ can represent are: methyl; Ethyl; Propyl- (1) or - (2); n-butyl- (1) or - (2); Isobutyl- (1), - (2) or - (3); 2-chloroethyl; 2-chloropropyl; 3-chloropropyl; 2-bromoethyl; 2-cyanoethyl; 2-cyanopropyl; 3-cyanopropyl; 1- or 2-hydroxyethyl; 2- or 3-hydroxypropyl- (1); Methoxy; Ethoxy; Propoxy; Isopropoxy; Butoxy; Isobutoxy; β-hydroxyethoxy; 2- or 3-hydroxypropoxy; 2- or 4-hydroxy-but-2-oxy; Methoxyethoxy; Athoxymethoxy; 2- or 3-methoxyprop-1-oxy; 2- or 3-ethoxyprop-l-oxy; 2- or 4-methoxybut-1-oxy; 2- or 4-ethoxybut-1-oxy; 4-methoxy or ethoxybut-2-oxy; 1- or 2-meth or ethoxybut-2-oxy; Acetylamino; Propionylamino; Butyrylamino; Phenacetylamino; Chloro, bromine, cyano or hydroxyacetylamino; 2- or 3-chloro or bromopropionylamino; 2- or 3-hydroxypropionylamino; 2- or 3-cyanopropionylamino; 2-, 3- or 4-chloro or bromobutyrylamino; 2-, 3- or 4-cyanobutyrylamino; 2-, 3- or 4-hydroxybutyrylamino; Methoxyacetylamino; 2- or 3-methoxy- or -ethoxypropionylamino; 2-, 3- or 4-methoxybutyrylamino; Phenoxyacetylamino; Benzoylamino; Aminocarbonylamino; Methyl, ethyl, propyl or butylaminocarbonylamino; Isopropylamino-carbonylamino; Iso- or sec-butylaminocarbonylamino.

Optionally substituted lower alkyl groups with 1 to 6 carbon atoms, for which R ₂ or R ₃ stand, are for example: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl-1, -2 or -3, Hexyl-1, -2 or -3, 2-chloro, bromine or cyanoethyl, 2- or 3-chloro, bromine or cyanopropyl- (1); 2-, 3- or 4-chloro, bromine or cyanobutyl- (1); 1-, 3- or 4-chloro, bromine or cyanobutyl- (2); Methoxy, ethoxy, propoxy, isopropoxy or butoxyethyl; ß- (ß-Hydroxyethoxy) ethyl; 2- or 3-methoxy or ethoxy propyl (1); Benzyl; Phenethyl; Phenylpropyl; Acetyloxy, propionyloxy or butyryloxyethyl; 2- or 3-acetyloxy, propionyloxy or butyryloxypropyl (1); 2-, 3- or 4-acetyloxybutyl- (1); Phenoxyacetoxyethyl, propyl or butyl; Methyl, ethyl, propyl, butyl or phenylaminocarbonyloxyethyl (2) or - (3); Methyl, ethyl, propyl or butylaminocarbonyloxypropyl (1) or butyl (1); 2-hydroxyethyl; 2- or 3-hydroxypropyl- (1); 3-hydroxypropyl- (2); 2-, 3- or 4-hydroxybutyl- (1); 1-, 3- or 4-hydroxybutyl- (2).

Alkenyl groups which R ₂ or R _{3 represent} are, for example: allyl; Methallyl; Crotyl; Buten-3-yl- (1); Buten-3-yl- (2); Penten-2-, -3- or -4-yl- (1); Penten-3- or -4-yl- (2); Hexen-2-, -3-, -4-or -5-yl- (1).

Dyes of the formula I in which R _{1 is} hydrogen and R _{2 is} free from alkoxycarbonyl and hydroxyalkoxycarbonyl groups are particularly preferred for use in the process according to the invention. Another preferred group of dyes of the formula I comprises those dyes which contain hydroxyl groups in the radicals R ₂ and / or R ₃ , in particular those in which R _{2 is} ethyl or β-hydroxyethyl and R _3ß -hydroxyethyl.

worin X₁ für Wasserstoff, Alkyl mit 1 bis 4 C-Atomen, Alkoxyalkoxy mit insgesamt 3 bis 6 C-Atomen, Hydroxyalkyl mit 2 bis 4 C-Atomen, Chlor; Y₁ für Chlor, Alkyl mit 1 bis 4 C-Atomen oder - NH - CO - Y₂ stehen und R_i, R₂, R₃ und Y₂ die oben angegebenen Bedeutungen haben.Another class of disperse monoazo dyes which is particularly preferred for the use according to the invention are the dyes of the formula

wherein X _{1 is} hydrogen, alkyl with 1 to 4 carbon atoms, alkoxyalkoxy with a total of 3 to 6 carbon atoms, hydroxyalkyl with 2 to 4 carbon atoms, chlorine; Y _{1 represents} chlorine, alkyl having 1 to 4 carbon atoms or - NH - CO - Y ₂ and R _i , R ₂ , R ₃ and Y _{2 have} the meanings given above.

Preferred -NH-CO-Y ₂ groups are alkanoylamino groups with unsubstituted alkanoyl radicals with 2 to 4 carbon atoms, in particular acetylamino groups.

worin R₂ Äthyl oder β-Hydroxyäthyl ist, oder Farbstoffe der Formeln

Those dyes which have a combination of preferred features, for example dyes of the formula VII, are particularly preferred for use in the process according to the invention

wherein R _{2 is} ethyl or β-hydroxyethyl, or dyes of the formulas

The dyes of the formula II used in the process according to the invention and their preparation are known from German Offenlegungsschrift 2,612,741. They can exist in a number of possible tautomeric forms. For the sake of convenience, the dyes are only formulated in one of the possible forms. However, it should be noted that the invention also encompasses the use of dyes in any of the possible tautomeric forms.

In the following description, the terms "lower alkyl" and "lower alkoxy" refer to alkyl or alkoxy radicals having 1 to 4 carbon atoms.

Examples of substituents which may be present on the phenyl radical D are lower alkyl radicals, such as. As methyl, lower alkoxy radicals, such as. B. methoxy and ethoxy, lower alkylcarbonyl radicals, such as. B. acetyl, lower alkyl sulfonyl radicals, such as. B. ethyl sulfonyl, lower alkylcarbonylamino radicals, such as. B. acetylamino, N-lower alkyl and N, N-di-lower alkylcarbamoyl radicals, such as. B. N-ethyl carbamoyl, N-butyl carbamoyl and N, N-dimethyl carbamoyl, N-lower alkyl and N, N-di-lower alkyl sulfamoyl radicals, such as. B. N-ethyl sulfamoyl and N, N-dimethyl sulfamoyl, N-lower alkyl and N, N-di-lower alkyl sulfamato radicals (-O · S0 ₂ NH ₂ ), such as. B. N-methylsulfamato and N, N-diethylsulfamato, examples of lower alkyl radicals X ₂ and Z are ethyl and methyl. Examples of lower alkylcarbonyl radicals X ₂ are acetyl and propionyl. An example of a lower alkyl sulfonyl radical X ₂ is ethyl sulfonyl. An example of a lower alkylcarbonylamino radical X ₂ is acetylamino.

The reactive dyes used in the process according to the invention contain one of the fiber-reactive radicals of the formulas III to VI given above. It is common to the radicals of the formulas 111 to V that they form a vinylsulfonyl group in the presence of alkali with the elimination of a sulfate or halide anion. This group formed in the presence of alkali fixes in the same way as the vinylsulfonyl radical of the formula V which is bonded directly to the dye radical by adding one of the OH groups of the cellulose to the vinyl double bond. Reactive dyes that have one of the reactive radicals mentioned above can all technically important dye groups belong to. Examples of reactive dyes which are suitable for carrying out the process according to the invention are the monoazo dyes CI-Yellow 13-17 and 72-74, Orange 7, 15, 16, 23, 24, 55, Red 21-23, 35, 36 , 50, 63, 103-107, 112-114, Blue 28, Brown 16; the disazo dyes CI-Blue 76, Blue 98, Black 5, 31; the mono- or disazo metal complex dyes CI-Violet 4, 5, Blue 20, Brown 18; the anthraquinone dyes CI-Violet 22, Blue 19 and 27; the phthalocyanine dyes CI-Blue 21, 38, 77.91 and Green 14 called.

Particularly preferred etchable reactive dyes are those which contain at least one fiber-reactive radical of the formulas IV or V as reactive anchor.

The amounts of the dyes which are contained in the padding liquors to be used according to the invention are, as usual, matched to the depth of color of the desired color and intensity of the reserve effect. In addition, the amount of dyes suitable for one of the fiber types involved also corresponds to the mass fraction of this fiber type in the total fiber mass. For example, a padding liquor that is prepared for a base color of a certain shade contains, in the event that the substrate predominantly contains cellulose fibers, a high proportion of etchable and possibly non-etchable reactive dyes and a low proportion of etchable and possibly non-etchable disperse dyes, and in the event that Substrate mainly contains polyester fibers, a high proportion of disperse dyes and a low proportion of reactive dyes.

The method according to the invention is primarily intended for the finishing of textiles made of cellulose polyester fibers. However, the quantity ratio of the two types of fibers is not subject to any restrictions, taking into account the criteria given above for the composition of the padding liquor, and in the limit case, the process can also be used to produce reserve effects on pure cellulose textiles or pure polyester textiles, in which case the padding liquors are exclusively etchable and optionally contain non-etchable reactive dyes or exclusively etchable and possibly non-etchable disperse dyes.

The reserve paste to be used in carrying out the process according to the invention contains either an alkali sulfite or an alkali hydrogen sulfite in combination with alkali carbonate or alkali hydrogen carbonate as a reservation agent. The alkali hydrogen sulfite can also be replaced in whole or in part by an equivalent amount of an alkali hydrogen sulfite-aldehyde adduct. It is also possible to produce this adduct in the reserve paste itself by adding alkali hydrogen sulfite, alkali hydrogen carbonate and an aldehyde to the reserve paste. As alkali sulfite, alkali hydrogen sulfite and alkali hydrogen carbonate, the sodium or potassium salts, preferably the sodium salts, are particularly suitable for industrial use. As aldehydes, which can be contained as alkali hydrogen sulfite adducts in the reserve pastes, come in principle all technically easily accessible, such as. B. formaldehyde, acetaldehyde, glyoxal, benzaldehyde, into consideration. Since the aldehyde-alkali hydrogen sulfite adducts are in equilibrium with the individual components of the adduct, preference is given to those aldehydes which, in the free state, do not have too high a vapor pressure and therefore cannot give rise to unpleasant odors. Glyoxal, for example, is particularly suitable for the use according to the invention.

The use of separately prepared addition compounds of these two components offers particular advantages in the preparation of printing pastes which contain sodium bisulfite in combination with an aldehyde. For example, the use of such an adduct avoids the troublesome foaming that can occur in the most unfavorable cases when printing pastes containing alkali metal bicarbonate are produced. The concentration of the reservation agent in the printing pastes is expediently 25 to 250 g / kg, preferably 50 to 130 g / kg, calculated on sodium bisulfite.

The reserve pastes contain, in addition to the reservation agents mentioned, the usual additives contained in textile printing pastes, in particular thickeners, such as. B. alginates, starch products, synthetic polymeric thickeners, mineral oils, hydrotropic substances such as urea, and wetting, penetration and dye-promoting additives. The presence of nonionic detergents, which can expediently be contained in the etching printing pastes, is particularly favorable for the etching process. As such, z. B. glycerol and / or polyglycols, such as polyethylene glycol with an average molecular weight of 300 to 400.

It has now been found that it is particularly favorable for fixing the non-etched dyes not to use the additives contained in known printing pastes, but instead to use esters of higher molecular weight polyglycols with carboxylic acids. The use of polyglycol esters is particularly advantageous when colored etchings are to be produced, i. that is, if disperse and reactive dyes resistant to the reservation agent are used in the coloring of the fond at the point printed with the reserve paste or are contained in the reserve paste. Polyglycol carboxylic acid esters which can be used with particular advantage in the reserve pastes to be used according to the invention are described, for example, in German Patent Specification 1,138,735.

The process according to the invention is carried out in a manner known per se by padding the textile material composed of polyester and cellulose fibers with dye liquors, the one or more of the above-mentioned alkali-etchable disperse dyes and one or more reactive dyes fe which have one of the above-mentioned reactive radicals of the formulas 111 to VI, preferably the ß-sulfatoethylsulfonyl or ß-sulfatoethylsulfonamide groups, in addition to the known customary dyeing aids, such as, for example, dispersants, wetting agents, foam suppressants and padding aids and, if colored etching prints are to be produced , additionally contain dispersing and reactive dyes that are resistant to the etchant, and squeezing the padded fabric webs to a liquor absorption of 50-120%. The fabric webs are then dried by warm air with any preceding infrared radiation, the temperature being approximately 80 to a maximum of approximately 150 ° C. with a corresponding reduction in time. The fabric webs prepared in this way are then printed with the etching reserve printing paste, which contains the reservation agents described above and the additives known in printing pastes for textile printing, in particular thickeners. Then the padded and printed textile fabrics are subjected to a heat treatment between 100 and 190 ° C. The heat is preferably supplied by superheated steam. The heat treatment causes a) an inhibition of the reservable disperse and reactive dyes at the points printed with the reserve paste and a fixation of the possibly available, non-reservable dispersion and reactive dyes, b) a fixation of the disperse dyes at the points not printed with the reserve paste and, if so the padding liquor contained an alkali metal formate, including the reactive dyes. Inhibition of the dye is to be provided with the change in the dye molecule caused by the reservation agent, which leads to the dye in question no longer staining the substrate. In the two-phase process, ie if the padding liquor did not contain any alkali metal formate, the reactive dyes are then fixed in the base coloring, ie at the points not printed with reserve paste.

Finally, the dyeings or prints are rinsed hot and cold and dried. A special embodiment of the method according to the invention consists in that the padding liquor contains, in addition to reservable disperse and reactive dyes, those which are resistant to the reservation agent and are therefore not destroyed by the etching reserve printing pastes to be used according to the invention. If you proceed as indicated above, you get multi-colored designs. A further embodiment of the method according to the invention is that the reservable dyes are not applied to the entire fabric by padding with a pad liquor, but are also printed on the fabric in the form of printing pastes and then overprinted with the etching reserve printing paste. The textile prints are then fixed and completed as described above. With this method, too, it is possible to add dyes to the color printing pastes printed first, which are resistant to the reservation agent. In this case too, multi-colored designs are obtained. A further possibility for carrying out the method according to the invention is that etching reserve printing pastes, which in turn contain dyes which are resistant to the reservation agent, are printed on the fund, which is padded or printed with reservable dyes. With subsequent fixation and completion of the textile materials, as described above, multi-colored designs are also obtained here.

The disperse dyes of the formula I are present in the padding liquors or in the printing pastes in finely dispersed form, as is customary and known for disperse dyes, while the reactive dyes are dissolved. The padding liquors or printing pastes which are to be used according to the invention are also prepared in a manner known per se by mixing the liquor or printing paste constituents with the necessary amount of water and liquid finely dispersed or solid redispersible settings of the disperse dyes and solutions or settings of the reactive dyes.

Disperse dyes which are resistant to the reservation agent and which can be combined with the reservable dye of the formula to produce multicolored designs are the known commercial dyes from the group of azo or azomethine, quinophthalone, nitro or anthraquinone dyes. Some examples of resistant disperse dyes are:

• Cyanurchlorid, Cyanurbromid, Cyanurfluorid, Dihalogenmono-amino-triazine, wie 2,6-Dichlor-4-amino-triazin, 2,6-Dichlor-4-methylamino-triazin, 2,6-Dichlor-4-oxäthylaminotriazin, 2,6-Dichlor-4-phenyl- aminotriazin, 2,6-Dichlor-4-(o-, m- oder p-sulfophenyl)-aminotriazin, Dihalogenalkoxy- und -aryloxy- sym.-triazine, Tetrahalogenpyrimidine, 2,4,6-Trihalogenpyrimidine, Derivate heterocyclischer Carbon-oder Sulfonsäuren, wie 3,6-Dichlorpyridazin-4-carbonsäurechlorid, 2,4-Dichlorpyrimidin-5-carbonsäurechlorid, 2,4,6-Trichlorpyrimidin-5-carbonsäurechlorid, 4,5-Dichlor-6-pyridazonylpropionylchlorid, 1,4-Dichlorphthalazin-6-carbonsäurechlorid, 5,6-Dichlor-4-methyl-2-methylsulfonyl-pyrimidin, 2- oder 3-Monochlorchinoxalin-6-carbonsäurechlorid oder -6-sulfonsäurechlorid, 2,3-Dichlorchinoxalin-6-carbonsäurechlorid oder -6-sulfonsäurechlorid, 1,4-Dichlorphthalazin-6-carbons.äurechlorid oder -6-sulfonsäurechlorid, 2,4-Dichlorchinazolin-6- oder -7-carbonsäurechlorid oder -sulfonsäurechlorid, 2-Chlorbenzthiazol-5- oder -6-carbonsäurechlorid oder -5- oder -6-sulfonsäurechlorid, 2-Methylsulfonyl- oder 2-Äthylsulfonyl- oder 2-Phenylsulfonylbenzthiazol-5- oder -6-sulfonsäurechlorid, Acrylsäurechlorid und 3-Chlorpropionsäurechlorid.

Reactive dyes which are resistant to the reservation agent and which can be combined with the reservable reactive dye of the formula I to produce multicolored designs are the known commercial dyes from the group of azo or azomethine, quinophthalone, nitro or anthraquinone dyes, which form a fiber-reactive radical from the class of triazines, quinoxalines, phthalazines, pyridazines, pyrimidines or _IX , ß-unsaturated aliphatic carboxylic acids. The most important compounds from which the fiber-reactive residues of the non-reserved, ie reactive dyes resistant to the etchant, are derived are representative of the entire class:

• Cyanuric chloride, cyanuric bromide, cyanuric fluoride, dihalomomono-triazines such as 2,6-dichloro-4-amino-triazine, 2,6-dichloro-4-methylamino-triazine, 2,6-dichloro-4-oxyethylaminotriazine, 2.6 -Dichlor-4-phenyl-aminotriazine, 2,6-dichloro-4- (o-, m- or p-sulfophenyl) -aminotriazine, dihaloalkoxy- and -aryloxy- sym.-triazines, tetrahalopyrimidines, 2,4,6- Trihalopyrimidines, derivatives of heterocyclic carboxylic or sulfonic acids, such as 3,6-dichloropyridazine-4-carboxylic acid chloride, 2,4-dichloropyrimidine-5-carboxylic acid chloride, 2,4,6-trichloropyrimidine-5-carboxylic acid chloride, 4,5-dichloro-6- pyridazonylpropionyl chloride, 1,4-dichlorophthalazine-6-carboxylic acid chloride, 5,6-dichloro-4-methyl-2-methylsulfonyl-pyrimidine, 2- or 3-monochloroquinoxaline-6-carboxylic acid chloride or -6-sulfonic acid chloride, 2,3-dichloroquinoxaline 6-car bonic acid chloride or -6-sulfonic acid chloride, 1,4-dichlorophthalazine-6-carboxylic acid chloride or -6-sulfonic acid chloride, 2,4-dichloroquinazoline-6- or -7-carboxylic acid chloride or -sulfonic acid chloride, 2-chlorobenzothiazole-5- or -6 -carboxylic acid chloride or -5- or -6-sulfonic acid chloride, 2-methylsulfonyl or 2-ethylsulfonyl or 2-phenylsulfonylbenzthiazole-5- or -6-sulfonic acid chloride, acrylic acid chloride and 3-chloropropionic acid chloride.

Insofar as solutions of substances are used in the following exemplary embodiments, unless another solvent is expressly stated, they are aqueous solutions. Percentages are percentages by weight.

example 1

A mercerized blended fabric made of polyester-cotton 50:50 is padded with a fleet of 20 parts by weight of the liquid commercial form of 5- (4-nitro-2-methylphen-1-yl) -azo-4-methyl-3-cyan-2, 6-dihydroxypyridine, 20 parts by weight of the liquid commercial form of CI Disperse Violet 48, 40 parts by weight of the commercial form of a mixture of 40% by weight C.I. Reactive Yellow 17 and 60% by weight C.I. Reactive Violet 5, 200 parts by weight of water at 80 ° C., 687 parts by weight of water cold, 10 parts by weight of sodium m-nitrobenzenesulfonate, 20 parts by weight of an anti-migration agent based on polyacrylic acid and 3 parts by weight of monosodium phosphate. It is carefully dried in a hot flue at 80 to 100 ° C and overprinted using the film printing process with a printing paste which is produced as follows: 30 parts by weight of the commercial form from C.I. Reactive Red 24, 30 parts by weight of the liquid commercial form of C.I. Disperse Red 132, 100 parts by weight of urea and 10 parts by weight of sodium m-nitrobenzenesulfonate are dissolved in 150 parts by weight of water at 80.degree. This solution is stirred into 500 parts by weight of a stock thickener, the 230 parts by weight of an aqueous 4% alginate thickener, 80 parts by weight of an aqueous 10% strength starch ether thickener, 85 parts by weight of water, 25 parts by weight of an aqueous 10% solution of the condensation product of polyglycol 2000 with stearic acid and 80 Contains parts by weight of heavy gasoline. Then 100 parts by weight of the etching reserve are added, which was previously prepared by mixing 65 parts by weight of a 40% aqueous glyoxal solution, 310 parts by weight of sodium bisulfite solution 38 ° Bé, 125 parts by weight of water and 500 parts by weight of sodium hydrogen carbonate. After drying, steam for 7 minutes at 175 ° C in a high-temperature steamer, padding the fabric with a fixing solution consisting of 700 volumes of water, 150 volumes of sodium carbonate, 150 volumes of sodium chloride, 100 volumes of sodium hydroxide solution 38 ° Bé, 50 volumes of potassium carbonate (the solution is washed with water set to 1000 parts by volume) and dampens in a two-phase flash damper for 10 seconds at 110-115 ° C.

It is then rinsed cold and aftertreated with 2 g / l of an aid based on fatty acid polyglycol ester at 40, 60 and 80 ° C., rinsed and dried.

You get red colored effects on a brown background.

Example 2

A leached mixed fabric made of polyester cellulose 70:30 is padded with the dye liquor described in Example 1, carefully dried in a hot flue at 80-100 ° C. and overprinted in film printing with a printing paste consisting of 40 parts by weight of the liquid commercial form of C.I. Disperse Red 200, 30 parts by weight of the commercial form by C.I. Reactive Red 33, 80 parts by weight of urea, 274 parts by weight of water at 80 ° C, 10 parts by weight of sodium m-nitrobenzenesulfonate, 500 parts by weight of stock thickening according to Example 1, 30 parts by weight of sodium carbonate, 30 parts by weight of sodium bisulfite solution 38 ° Be, 6 parts by weight of 40% glyoxal solution. After drying, the steam is steamed for 7 minutes to increase the reserve effect, and then the disperse dyes and the reactive dyes which are resistant to alkali sulfites are fixed in a high-temperature steamer at 185 ° C. for 6 minutes. Then, to fix the base coloring, padding is carried out with the fixing solution specified in Example 1, steaming at 110-115 ° C. for 10 seconds and completion as indicated in Example 1.

You get scarlet colored effects on a brown background.

Example 3

40 Gewichtsteilen der flüssigen Handelsform von C.I. Reactive Blue 122, 808 Gewichtsteilen Wasser kalt, 10 Gewichtsteilen m-nitrobenzolsulfonsaurem Natrium, 20 Gewichtsteilen eines Antimigriermittels auf Polyacrylsäurebasis, 2 Gewichtsteilen Mononatriumphosphat, 20 Gewichtsteilen Natriumformiat.A mercerized blend of 65:35 polyester-cotton is padded with a batch consisting of 100 parts by weight of a 20% liquid setting of the dye of the formula

40 parts by weight of the liquid commercial form of CI Reactive Blue 122, 808 parts by weight of water cold, 10 parts by weight of sodium m-nitrobenzenesulfonate, 20 parts by weight of a polyacrylic acid-based antimigrant, 2 parts by weight of monosodium phosphate, 20 parts by weight of sodium formate.

• 25 Gewichtsteilen der Handelsform von 1-[5-(3,6-Dichlorpyridazin-4-yl-carbonylamino)-2-methyl-3-sulfophenyl]-3-carboxy-4-(2-sulfophenyl-azo)-5-pyrazolon-(5), 40 Gewichtsteilen der flüssigen Handelsform von C.I. Disperse Yellow 63, 150 Gewichtsteilen Harnstoff, 199 Gewichtsteilen Wasser kalt, 10 Gewichtsteilen m-nitrobenzolsulfonsaurem Natrium, 500 Gewichtsteilen Stammverdickung gemäß Beispiel 1, 40 Gewichtsteilen Natriumhydrogencarbonat, 30 Gewichtsteilen Natriumhydrogensulfitlösung 38° Be, 6 Gewichtsteilen 40%iger Glyoxallösung.

It is carefully dried in a hot flue at 80-100 ° C and overprinted in film printing with a printing paste

• 25 parts by weight of the commercial form of 1- [5- (3,6-dichloropyridazin-4-yl-carbonylamino) -2-methyl-3-sulfophenyl] -3-carboxy-4- (2-sulfophenyl-azo) -5-pyrazolone - (5), 40 parts by weight of the liquid commercial form of CI Disperse Yellow 63, 150 parts by weight of urea, 199 parts by weight of cold water, 10 parts by weight of sodium m-nitrobenzenesulfonate, 500 parts by weight of stock thickening according to Example 1, 40 parts by weight of sodium hydrogen carbonate, 30 parts by weight of sodium bisulfite solution 38 ° Be, 6 parts by weight of 40% glyoxal solution.

After drying, the mixture is fixed at 175 ° C. with superheated steam for 7 minutes and aftertreated as described in Example 1.

Yellow colored effects are obtained on a navy blue floor.

Example 4

A leached knitted fabric made of polyester COLVERA 70: 30 is padded with the following liquor: 50 parts by weight of the liquid commercial form from C.I. Disperse Red 278, 40 parts by weight of the commercial form of C.I. Reactive Red 63, 200 parts by weight of water at 80 ° C., 660 parts by weight of water cold, 10 parts by weight of sodium m-nitrobenzenesulfonate, 20 parts by weight of an antimigrant based on polyacrylic acid, 20 parts by weight of sodium formate.

It is carefully dried in a hot flue at 80-100 ° C. and overprinted in film printing with a printing paste of 30 parts by weight of the commercial form of 1- [5- (3,6-dichloropyridazin-4-yl-carbonylamino) -3-sulfo-2, 4,6-trimethyl-phenylamino] -3-sulfo-4-amino-anthraquinone, 50 parts by weight of the liquid commercial form of CI Disperse Blue 73, 200 parts by weight of urea, 102 parts by weight of water at 80 ° C, 10 parts by weight of sodium m-nitrobenzenesulfonate, 500 parts by weight of stock thickening according to Example 1, 50 parts by weight of sodium hydrogen carbonate, 50 parts by weight of sodium bisulfite solution 38 ° Be and 8 parts by weight of a 40% glyoxal solution.

After drying, the mixture is fixed at 175 ° C. with superheated steam for 7 minutes and aftertreated as described in Example 1.

You get blue colored effects on a red floor.

Example 5

40 Gewichtsteilen der Handelsform von C.I. Reactive Blue 122, 767 Gewichtsteilen Wasser, 3 Gewichtsteilen Natriumchlorat, 20 Gewichtsteilen eines Antimigriermittels auf Basis Polyacrylsäure, 20 Gewichtsteilen Natriumformiat. Man trocknet vorsichtig in einer Hotflue bei 80-100°C und überdruckt im Rouleauxdruck mit einer Druckpaste bestehend aus 60 Gewichtsteilen des Farbstoffes der Formel

60 Gewichtsteilen der flüssigen Handelsform von C:I. Disperse Blue 87, 255 Gewichtsteilen Wasser, 600 Gewichtsteilen einer 4%igen Lösung eines Natriumalginats, 25 Gewichtsteilen Natriumsulfit.A block fabric of polyester and mercerized cotton in the ratio 65:35 is padded with a dye liquor composed of 150 parts by weight of a 20% liquid setting of the dye of the formula

40 parts by weight of the commercial form of CI Reactive Blue 122, 767 parts by weight of water, 3 parts by weight of sodium chlorate, 20 parts by weight of an antimigrant based on polyacrylic acid, 20 parts by weight of sodium formate. It is carefully dried in a hot flue at 80-100 ° C. and overprinted in rouleaux printing with a printing paste consisting of 60 parts by weight of the dye of the formula

60 parts by weight of the liquid commercial form of C: I. Disperse Blue 87, 255 parts by weight of water, 600 parts by weight of a 4% solution of sodium alginate, 25 parts by weight of sodium sulfite.

After drying, the mixture is fixed at 175 ° C. with superheated steam for 7 minutes and aftertreated as described in Example 1.

You get turquoise colored effects on a navy blue background.

Example 6

A mercerized blended fabric of 65:35 polyester-cotton is padded with an approach consisting of: 50 parts by weight of the liquid commercial form of 5- (4-nitro-2-methylphen-1-yl) -azo-4-methyl-3-cyan 2,6-dihydroxypyridine, 40 parts by weight of the commercial form of CI Reactive Yellow 42, 867 parts by weight of water, 3 parts by weight of sodium chlorate, 20 parts by weight of an anti-migration agent based on polyacrylic acid, 20 parts by weight of sodium formate. It is carefully dried in a hot flue at 80-100 ° C and overprinted in roulette with a printing paste made from 60 parts by weight of the commercial form from C.I. Reactive Red 24, 40 parts by weight of the liquid commercial form of C.I. Disperse Red 132, 275 parts by weight of water, 600 parts by weight of a 4% solution of sodium alginate, 25 parts by weight of sodium sulfite.

After drying, the mixture is fixed at 175 ° C. with superheated steam for 7 minutes and aftertreated as described in Example 1.

You get brilliant red colored effects on a yellow background.

Claims (6)

1. Process for production of resist effects on textile materials on the basis of mixed fibres of polyester and cellulose, in particular polyester-cotton fibres, by impregnating the materials with dye liquors containing, besides the usual dyeing and padding auxiliaries, disperse and reactive dyestuffs which react with the resisting agents and which, optionally, contain further disperse and reactive dyestuffs that are resistant to the resisting agent and which, optionally, contain alkali metal formiates, by drying or partially drying the padded materials and subsequently printing on the material a resist paste which, if desired, contains besides the resisting agent disperse and reactive dyestuffs resistant to the resisting agent, heat-treating at temperatures of from 100 to 190° C and, optionally, subsequent alkaline fixing of the reactive dyestuff in a manner known by itself, characterised in that the dischargeable disperse dyestuffs used are those of the formula I

wherein

R₁ is hydrogen, alkyl with 1-6 carbon atoms, cyano, trifluoromethyl or a phenyl radical which may carry a substituent being selected from the group consisting of chlorine, bromine, nitro and alkyl with 1 -4 carbon atoms;

X₁ is hydrogen, chlorine, bromine, alkyl with 1 -4 carbon atoms which may carry a substituent selected from the group consisting of chlorine, bromine, cyano and hydroxyl, alkoxy with 1-4 carbon atoms, hydroxyalkoxy with 2-4 carbon atoms, alkoxy-alkoxy with a total of 3-6 carbon atoms;

Y₁ is hydrogen, chlorine, bromine, alkyl with 1 -4 carbon atoms which may carry a substituent selected from the group consisting of chlorine, bromine, cyano and hydroxyl, alkoxy with 1 -4 carbon atoms, hydroxyalkoxy with 2-4 carbon atoms, alkoxyalkoxy with a total of 3-6 carbon atoms, -NH-CO-Y, -NH-S0₂-Y₂, wherein Y₂ denotes alkyl with 1-4carbon atoms, it being possible for the alkyl radical to carry a substituent selected from the group consisting of phenyl, chlorine, bromine, cyano, hydroxyl, alkoxy with 1 -2 carbon atoms and phenoxy, phenyl, amino, N-alkylamino with 1 -4 carbon atoms;

R₂ is hydrogen, alkyl with 1-6 carbon atoms which may carry a substituent selected from the group consisting of bromine, cyano, hydroxy, alkoxy or hydroxyalkoxy with 1 to 4 carbon atoms, phenyl, alkanoyloxy with 2-4 carbon atoms, alkylaminocarbonyloxy with 2-4 carbon atoms or phenylaminocarbonyloxy, hydroxyalkyl with 2-4 carbon atoms or alkenyl with 3-6 carbon atoms;

R₃ is unsubstituted or substituted alkyl with 1 to 6 carbon atoms which may carry a substituent being selected from the group consisting of chlorine, bromine, cyano, hydroxyl, alkoxy or hydroxyalkoxy with 1-4 carbon atoms, phenyl, alkanoyloxy with 2 to 4 carbon atoms and alkylaminocarbonyloxy with 2-4 carbon atoms, hydroxyalkyl with 2-4 carbon atoms, alkenyl with 3-6 carbon atoms or phenyl, or those which in one of the possible tautomeric forms correspond to the formula 11

wherein

D is phenyl which may carry at least one substituent selected from the group consisting of chlorine, bromine, nitro, cyano, trifluoromethyl, thiocyano, lower alkyl, lower alkoxy, lower alkylcarbonyl, lower alkylsulphonyl, lower alkylcarbonylamino, carbamoyl, N-lower alkyl- and N,N-di-lower alkyl derivatives thereof, sulpahmoyl, N-lower alkyl- and N,N-di-lower alkyl derivatives thereof, sulphamato, N-lower alkyl and N,N-di-lower alkyl derivatives thereof;

X₂ is hydrogen, lower alkyl, carbamoyl, cyano, chlorine, bromine, nitroso, nitro, lower alkylcarbonyl. sulphamoyl, lower alkylsulphonyl or lower alkylcarbonylamino;

Z is hydrogen or lower alkyl;

the dischargeable reactive dyestuffs being those
containing reactive moieties of the formulae III to VI

wherein

M is hydrogen or a metal cation and

hal is halogen,

and the resist paste used contains, as a resisting agent,

a) an alkali metal sulphite or an alkali metal bisulphite in combination with an alkali metal carbonate or alkali metal bicarbonate and optionally with an aldehyde, and, optionally,

b) a nonionogenic detergent.

2. The process according to claim 1 characterised in that the dischargeable disperse dyestuffs used are those of the formula I.

3. The process according to claims 1 and 2, characterised in that, that dischargeable reactive dyestuffs used are those which contain reactive moieties of formulae IV and V.

4. The process according to claims 1 to 3, characterised in that the resist past contains, as the resisting agent, a previously prepared aldehyde-alkali metal bisulphite adduct.

5. The process according to claims 1 to 4, characterised in that the resist paste contains, as a non-ionic detergent, a polyglycol carboxylic acid ester.

6. Textile materials having resist effects produced by the process of claims 1 to 5.