EP0013378A1 - Process for the production of reserve effects on polyester-cellulose blended textile materials - Google Patents

Abstract

Process for producing reserve effects on textile materials based on mixed fibers made of polyester and cellulose, by impregnating the materials with dye liquors which, in addition to conventional dyeing and padding aids, contain disperse and reactive dyes which react with the reservation agents and, if appropriate, further dispersions which are resistant to the reservation agents - And reactive dyes contain, drying or drying the padded materials and then printing on a reserve paste, which, if desired, contains dispersing and reactive dyes resistant to the reservation agent if desired, heat treatment at temperatures of 100 to 190 ° C and optionally subsequent alkaline fixing of the reactive dye. The etchable disperse dyes are those of the formula I <IMAGE> or those which correspond to <IMAGE> in one of the possible tautomeric forms of the formula II or disperse dyes which are free from water-solubilizing groups and which contain at least two carboxylic ester groups from the nitro, methine and azomethine -, Antrachinon- and especially azo and especially monoazo series, where in the formulas D stands for phenyl, which is optionally substituted by non-water-solubilizing substituents common in disperse dyes and R1, R2, R3, X1, X2, and Y2 likewise such Substituents or hydrogen are used.

Description

worin R₁ Wasserstoff, Cyan, gegebenenfalls substituiertes Alkyl oder Phenyl; X₁ Wasserstoff, Halogen, gegebenenfalls substituiertes Alkyl oder Alkoxy; Y₁ Wasserstoff, Halogen, gegebenenfalls substituiertes Alkyl oder Alkoxy, -NH-CO-Y₂, -NH-SO₂- Y₂ worin Y₂für Alkyl, Phenyl oder Amino steht; R₂ Wasserstoff, ein gegebenenfalls substituiertes Alkyl oder Alkenyl; R₃ ein gegebenenfalls substituiertes Alkyl, Alkenyl oder Phenyl bedeuten oder solche der Formel II

worin D für Phenyl steht, das gegebenenfalls mindestens einen Substituenten enthält; X₂für Wasserstoff, Niederalkyl, Carbamoyl, Cyano, Chlor, Brom, Nitroso, Nitro, Nie-. deralkylcarbonyl,Sulfamoyl, Niederalkylsulfonyl, Niederalkylcarbonylamino oder Niederalkoxycarbonyl und Z für Wasserstoff oder Niederalkyl steht; oder von wasserlöslichmachenden Gruppen freie Dispersionsfarbstoffe, die mindestens zwei Carbonsäureestergruppen enthalten, als ätzbare Reaktivfarbstoffe solche, die reaktive Reste der Formeln III 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 which may contain further dispersing and reactive dyes which are resistant to the reservation agents, drying or drying the padded materials and then printing on a reserve paste which, if desired, in addition to the reservation agent contains dispersing and reactive dyes which are resistant to the reservation agent, heat treatment at temperatures from 100 to 190 ° C and subsequent alkaline fixation of the reactive dye in a manner known per se, characterized in that the etchable disperse dyes are those of the formula 1

wherein R _{1 is} hydrogen, cyano, optionally substituted alkyl or phenyl; X _{1 is} hydrogen, halogen, optionally substituted alkyl or alkoxy; Y _{1 is} hydrogen, halogen, optionally substituted alkyl or alkoxy, -NH-CO-Y ₂ , -NH-SO ₂ - Y ₂ where Y _{2 is} alkyl, phenyl or amino; R _{2 is} hydrogen, an optionally substituted alkyl or alkenyl; R _{3 is} an optionally substituted alkyl, alkenyl or phenyl or those of the formula II

wherein D is phenyl which optionally contains at least one substituent; X ₂ for hydrogen, lower alkyl, carbamoyl, cyano, chlorine, bromine, nitroso, nitro, Nie-. deralkylcarbonyl, sulfamoyl, lower alkylsulfonyl, lower alkylcarbonylamino or lower alkoxycarbonyl and Z represents hydrogen or lower alkyl; or disperse dyes free of water-solubilizing groups, which contain at least two carboxylic ester groups, as etchable reactive dyes those which contain reactive radicals of the formulas III to VI

in which M is hydrogen or a metal cation and hal is halogen, and a reserve paste which contains a) an alkali metal sulfite or an alkali metal hydrogen sulfite in combination with alkali metal carbonate or alkali metal hydrogen carbonate and optionally an aldehyde and b) optionally a nonionic detergent as the reservation agent.

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 fund coloring 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 23 26 522 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, thiosulfites 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 simultaneously 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, this is why is known discharge printing modified in such a way, since the textile material _ß first with a disperse dye and reactive dye-containing dye bath is padded and dried, or partially dried, but no fixing of the dye, that solution may of Disperionsfarbstoffs in the hydrophobic fiber occur. The desired pattern is then printed on the dried or dried-on, padded fabric with the etching printing paste, and the padded and printed fabric is then subjected to a heat treatment, the base dye immersing in the non-printed areas in the polyester and the reactive dye being fixed on the cellulose and the dye is destroyed at the printed areas, ie no coloring takes place. In view of this mechanism, this method is also called etching reserve pressure.

The Simpl se _'he method of Ätzreservedrucks includes a number of technical difficulties that make its use often. 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 vary between yellow-brown and dull violet or reddish gray tones and which soils the white background at the etched areas. This leads to white etching which appears to be unclean or, in the event that a colored etching is to be produced, to a falsification of the shade of the etching-resistant dye. To overcome this difficulty, etching pastes are used which contain relatively strong reducing or oxidizing agents such as sodium dithionite in combination with alkali, alkali formaldehyde sulfoxylates or even heavy metal salts such as tin-2-chloride. 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 when the polyester fiber is also accompanied by fibers, such as cellulose contains fibers. Further, these etchants are usually not cheap, and in the case of Sc _l lwermetallätzmittel they represent an additional environmental burden or they cause additional expenses in the purification of 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 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. Such combinations of etchants, however, have a negative influence on the fixing behavior of the dyes, i.e. in the case of the production of colored reserves, the color yields of the dyes that are resistant to caustic agents are reduced.

• 1. als ätzbare Dispersionsfarbstoffe solche der Formel I
  
  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 - 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; Y₁Wasserstoff, 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 bic 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; R₃ Wasserstoff, ein gegebenenfalls durch Chlor, Brom, Cyan, Hydroxy, Alkoxy oder Hydroxyalkoxy mit 1 bis 4 C-Atomen, Phenyl, Alkanoyloxy mit 2 - 4 C-Atomen, Alkoxycarbonyl mit 1 bis 4 C-Atomen, Hydroxycarbonyl mit 2 - 4 C-Atomen, Alkylaminocarbonyloxy mit 2 - 4 C-Atomen oder Phenylaminocarbonyloxy substituiertes Alkyl mit 1 - 6 C-Atomen, Hydroxyallcyl 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, Alkoxycarbonyl mit 1 bis 4 C-Atomen, Hydroxycarbonyl mit 2 - 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 und, sofern R₂ Wasserstoff ist, auch die Gruppe -C(CH₃)₂-COOR₄, worin R₄ Alkyl mit 4 bis 8 C-Atomen oder Methoxy- Äthoxy-oder Propoxyalkyl mit insgesamt 4 bis 8 C-Atomen 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-Diniederalkylderivaten davon, Sulfamoyl und N-Niederalkyl-und N,N- Diniederalkylderivaten davon, Sulfamato und N-Niederalkyl- und N,N-Diniederalkylderivaten davon, Niederalkoxycarbonyl, Niederalkoxy-niederalkoxycarbonyl, Niederalkoxy-niederalkoxy-niederalkoxycarbonyl, Hydroxyniederalkoxycarbonyl, Hydroxy-niederalkoxy-niederalkoxy- carbonyl und Niederalkoxycarbonyl-niederalkyl ausgewählt ist; X₂für Wasserstoff, Niederalkyl, Carbamoyl, Cyapo, Chlor, Brom, Nitroso, Nitro, Niederalkylcarbonyl, Sulfamoyl, Niederalkylsulfonyl, Niederalkylcarbonylamino oder Niederalkoxycarbonyl steht; Z für Wasserstoff oder Niederalkyl steht; oder von wasserlöslichmachenden Gruppen freie Dispersionsfarbstoffe, die mindestens zwei Carbonsäureestergruppen enthalten, aus der Nitro-, Methin-, Azomethin-, Antrachinon- und vor allem Azo-und ganz besonders Monoazoreihe, wobei die Carbonsäureestergruppen vorzugsweise die Formel -COOR₅besitzen, worin R₅für ein gegebenenfalls substituiertes Kohlenwasserstoff- oder heterocyclisches Radikal steht,
• 2. als ätzbare Reaktivfarbstoffe solche, die reaktive Reste der Formeln III 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 Alkalihyarogencarbonat und gegebenenfalls einem Aldehyd und
  • b) gegebenenfalls ein nichtionogences Detergens enthält, einsetzt.

The above-mentioned disadvantages of the known processes for producing 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 any other dispersing and reactive dyes that are resistant to the reservation agents and optionally alkali metal formate containing drying or drying the padded materials and subsequently printing a reserve paste containing, if desired, in addition to the reservation agent for the reservation-resistant disperse and reactive dyes, heat treatment at Temper _a - temperatures of 100 to 190 ° C and, optionally, it then alkaline fixation
of the reactive dye in a manner known per se can be surprisingly overcome by:

• 1. as etchable disperse dyes those of the formula I
  
  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 1-4 carbon atoms, alkoxy having 1 to 4 carbon atoms, hydroxyalkoxy having 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 with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxyalkoxy with 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, hydroxy, alkoxy with 1 to 2 carbon atoms or phenoxy can be substituted, phenyl, amino, N-alkylamino with 1 to 4 carbon atoms; R _{3 is} hydrogen, optionally by chlorine, bromine, cyano, hydroxyl, alkoxy or hydroxyalkoxy having 1 to 4 carbon atoms, phenyl, alkanoyloxy having 2 to 4 carbon atoms, alkoxycarbonyl having 1 to 4 carbon atoms, hydroxycarbonyl having 2 - 4 carbon atoms, alkylaminocarbonyloxy with 2 to 4 carbon atoms or phenylaminocarbonyloxy substituted alkyl with 1 to 6 carbon atoms, hydroxyallcyl with 2 to 4 carbon atoms or alkenyl with 3 to 6 carbon atoms; R _{3 is} optionally chlorine, bromine, cyano, hydroxy, alkoxy or hydroxyalkoxy with 1 to 4 carbon atoms, phenyl, alkanoyloxy with 2 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms, hydroxycarbonyl with 2 to 4 carbon atoms -Atoms or alkylaminocarbonyloxy with 2 to 4 carbon atoms, substituted alkyl with 1 to 6 carbon atoms, hydroxyalkyl with 2 to 4 carbon atoms, alkenyl with 3 to 6 carbon atoms or phenyl and, if R _{2 is} hydrogen, also the group -C (CH ₃ ) ₂ -COOR ₄ , in which R _{4 is} alkyl with 4 to 8 C atoms or methoxyethoxy or propoxyalkyl with a total of 4 to 8 C atoms or those which are in one of the possible tautomeric forms correspond to formula II,
  
  wherein 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-diniederalkyl 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, lower alkoxycarbonyl, lower alkoxy-lower alkoxycarbonyl, lower alkoxy-lower alkoxy-lower alkoxycarbonyl, hydroxy-lower alkoxycarbonyl, hydroxy-lower alkoxy-lower alkoxycarbonyl and lower alkoxycarbonyl-lower alkyl is selected; X _{2 represents} hydrogen, lower alkyl, carbamoyl, cyapo, chlorine, bromine, nitroso, nitro, lower alkylcarbonyl, sulfamoyl, lower alkylsulfonyl, lower alkylcarbonylamino or lower alkoxycarbonyl; Z represents hydrogen or lower alkyl; or water-solubilizing groups-free disperse dyes which contain at least two carboxylic acid ester groups from the nitro, methine, azomethine, antrachinone and especially azo and very particularly monoazo series, the carboxylic acid ester groups preferably having the formula -COOR ₅ , where R ₅ represents an optionally substituted hydrocarbon or heterocyclic radical,
• 2. as etchable reactive dyes, those containing the 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 is used as a reser means of payment
  • a) an alkali sulfite or an alkali hydrogen sulfite in combination with alkali carbonate or alkali metal carbonate and optionally an aldehyde and
  • b) optionally contains a nonionic detergent.

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

Alkyl radicals with 1-6 C 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 y-hydroxypropoxy; Hydroxyisopropoxy; β-, y- or δ-hydroxybutoxy; Hydroxyisobutoxy; β-methoxyethoxy; β-ethoxyethoxy; β-propoxy-ethoxy; β-butoxyethoxy; β- or γ-propoxypropoxy; β-, γ- or δ-methoxy or ethoxybutoxy.

Examples of substituents for which Y _{1 can} stand are: .methyl; Ethyl; Propyl- (1) or - (2); n-butyl- (l) 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- (l); Methoxy; Ethoxy; Propoxy; Isopropoxy; Butoxy; Isobutoxy; β-hydroxyethoxy; 2- or 3-hydroxypropoxy; 2- or 4-hydroxy-but-2-oxy; Methoxyethoxy; Ethoxymethoxy; 2- or 3-metboxyprop-l-oxy; 2- or 3-ethoxyprop-l-oxy; 2- or 4-metboxybut-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 1-6 C atoms, which R ₂ or R ₃ represent, 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-Hydroxyäthoxy) 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); Methoxy, ethoxy, propoxy, isopropoxy, Eut (1) oxy, but (2) oxy or isobutoxycarbonyl; β-hydroxy, ethoxy, hydroxypropoxy or hydroxybutoxycarbonyl.

Alkenyl groups which R ₂ or R _{3 represent} are, for example: allyl; Methally; 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).

Examples of alkyl and alkoxyalkyl groups which R ₄ can represent are: methyl; Ethyl; Isopropyl; Propyl; (n) butyl; sec butyl; Isobutyl; Pentyl; Hexyl; 2-ethylhexyl- (1); Methoxy, ethoxy or propoxyethyl; 2- or 3-methoxy, ethoxy or propoxypropyl (1); 2-, 3- or 4-methoxy-, ethoxy- or propoxybutyl- (l); 1-, 3- or 4-methoxy, ethoxy or propoxybutyl (2); Methoxy, ethoxy or propoxypentyl and ethoxyhexyl.

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 _{3 is} β-hydroxyethyl or those in which R _{2 is} hydrogen and R _{3 is} an alkoxycarbonylalkyl radical, in particular a 2-alkoxycarbonylpropyl-2 radical.

worin X₁für Wasserstoff, Alkyl mit 1 - 4 C-Atomen, Alkoxyalkyl mit insgesamt 3 bis 6 C-Atomen, Hydroxyalkyl mit 2 - 4.C-Atomen, Chlor; Y_lfür Chlor, Alkyl mit 1 - 4 C-Atomen oder -NH-CO-Y₂stehen und R₁, 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 1

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

Preferred -NH-COY ₂ - "groups are alkanoylamino groups with unsubstituted alkanoyl radicals with 2 to 4 carbon atoms, especially acetylamino groups.

worin R₂ Äthyl oder ß-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 ß-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 26 12 741. 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, for example, methyl, lower alkoxy radicals, such as, for example, methoxy and ethoxy, lower alkylcarbonyl radicals, such as, for example, acetyl, lower alkylsulfonyl radicals, such as, for example, ethylsulfonyl, lower alkylcarbonylamino radicals, such as, for example, acetylamino and N, N-lower alkyl -Di-lower-alkylcarbamoyl radicals, such as, for example, N-ethylcarbamoyl, N-butylcarbamoyl and N, N-dimethylcarbamoyl, N-lower alkyl and N, N-di-lower alkylsulfamoyl radilcale, such as, for example, N-ethylsulfamoyl and N, N - Dimethylsulfamoyl, N-lower alkyl and N, N-di-lower alk ^y lsulfamato radicals (-O.S0 ₂ NH ₂ ), such as N-methylsulfamato and N, N-diethylsulfamato, lower alkoxycarbonyl radicals such as methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl and butyloxycarbonyl, lower alkoxy-lower alkoxycarbonyl radicals, such as, for example, β- (methoxy- or ethoxy-) ethoxycarbonyl, lower alkoxy-lower alkoxy-lower alkoxycarbonyl radicals, such as, for example, β- (β'-methoxyethoxy) ethoxycarbonyl, hydroxy-lower alkoxycarbonyl radicals, such as for example, β-hydroxyethoxycarbonyl, hydroxy-lower alkoxy-lower alkoxycarbonyl radicals, such as, for example, y- (β'-hydroxyethoxy) propoxycarbonyl, and lower alkoxycarbonyl-lower alkyl radicals, such as, for example, ethoxycarbonylmethyl.

Examples of lower alkyl radicals X ₂ and Z are ethyl and methyl. Examples of lower alkyl canonyl radicals X ₂ are acetyl and propionyl. Examples of lower alkoxycarbonyl radicals X ₂ are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and butoxycarbonyl. An example of a lower alkyl sulfonyl radical X ₂ is ethyl sulfonyl. An example of a lower alkylcarbonylamino radical X ₂ is acetylamino.

worin X₂und Z die oben angegebenen Bedeutungen besitzen, r für 0 oder 1 steht, Y₃für Niederalkyl, Niederalkoxy-niederalkyl, Niederalkoxy-niederalkoxy-niederalkyl, Hydroxyniederalkyl oder Hydroxy-niederalkoxy-niederalkyl steht und der Benzolring D ¹ weiter durch Chlor, Brom, Nitro, Niederalkoxycarbonyl, Niederalkyl oder Niederalkoxy substituiert sein kann. Vorzugsweise steht Y₃ für Niederalkyl, stent r für 0 und steht X₂für -CN.A preferred class of disperse monoazo dyes for use in accordance with the invention are the dyes of formula VIII

in which X ₂ and Z have the meanings given above, r is 0 or 1, Y _{3 is} lower alkyl, lower alkoxy-lower alkyl, lower alkoxy-lower alkoxy-lower alkyl, hydroxy-lower alkyl or hydroxy-lower alkoxy-lower alkyl and the benzene ring D ¹ is furthermore chlorine, Bromine, nitro, lower alkoxycarbonyl, lower alkyl or lower alkoxy can be substituted. Preferably Y _{3 is} lower alkyl, stent r is 0 and X _{2 is} -CN.

stoffmolekül oder aber an eine Brückengruppe, wie z.B. -0-Alkylen oder -N-Alkylen-, gebunden sein. Eine bevorzugte Klasse von solchen Azofarbstoffen umfaßt Farbstoffe der Formel IX

worin A für den Rest einer Diazokomponente der aromatischen oder heterocyclischen Reihe steht, E für den Rest einer Kupplungskomponente steht, R₅die oben angegebene Bedeutung besitzt und n und m jeweils unabhängig voneinander für 0, 1 oder 2 stehen, wobei die Summe aus n und m mindestens 2 ist.The disperse dyes to be used according to the invention, which contain at least two carboxylic ester groups of the formula _CO0R ₅ , and their preparation are known from DOS 2612740, 2612742, 2612790, 2612791 and 2612792. In this dye group R contained in the Carbonsäureestergruppen ₅ is especially a cycloalkyl radical such as cyclohexyl, a monocyclic aryl radical such as phenyl, tolyl and xylyl, or substituted derivative thereof such as anisyl, chlorophenyl and bromophenyl, a monocyclic Ar ^y lalkylradikal as eg benzyl or β-phenylethyl, or preferably an alkyl radical, such as hexyl, octyl, dodecyl, but very particularly a lower alkyl radical with 1 to 4 carbon atoms, such as ethyl, propyl, butyl and especially methyl. Alternatively, R _S can be a substituted alkyl radical, in particular a substituted lower alkyl radical, such as a hydroxy lower alkyl radical, for example β-hydroxyethyl, or a lower alkoxy lower alkyl radical, for example y-methoxypropyl. The carboxylic ester groups mentioned can be attached directly to carbon atoms of one or more benzene or heterocyclic rings in the

substance molecule or bonded to a bridge group, such as -0-alkylene or -N-alkylene. A preferred class of such azo dyes includes dyes of Formula IX

wherein A represents the rest of a diazo component of the aromatic or heterocyclic series, E represents the rest of a coupling component, R _{5 has} the meaning given above and n and m each independently represent 0, 1 or 2, the sum of n and m is at least 2.

worin A₁ für das Radikal einer Diazokomponente der aromatischen oder heterocyclischen Reihe steht, der Benzolring B gegebenenfalls Substituenten enthalten kann, R₅die angegebene Bedeutung besitzt und X₃ und X₄ jeweils unabhängig voneinander Niederalkylen- oder Niederalkylen-0-niederalkylen-Radikale bedeuten, worin Niederalkylen sich auf Alkylenradikale mit 1 bis 6 Kohlenstoffatomen bezieht.A second preferred class of azo dyes includes the dyes of Formula IXa

in which A _{1 represents} the radical of a diazo component of the aromatic or heterocyclic series, the benzene ring B can optionally contain substituents, R _{5 has} the meaning given and X ₃ and X ₄ each independently represent lower alkylene or lower alkylene-0-lower alkylene radicals, wherein lower alkylene refers to alkylene radicals having 1 to 6 carbon atoms.

worin B, X₃ und R₅die oben angegebenen Bedeutungen besitzen, Z₁für ein Wasserstoffatom oder ein gegebenenfalls substituiertes Alkyl-, Cycloaklyl- oder Arylradikal steht, A₂ für das Radikal einer Diazokomponente der aromatischen oder heterocyclischen Reihe steht und p für 1 oder 2 steht.Another preferred class of azo dyes includes the dyes of Formula IXb

in which B, X ₃ and R _{5 have} the meanings given above, Z _{1 represents} a hydrogen atom or an optionally substituted alkyl, cycloalkyl or aryl radical, A _{2 represents} the radical of a diazo component of the aromatic or heterocyclic series and p represents 1 or 2 stands.

worin A₂, B, R_sund X₃ die angegebenen Bedeutungen besitzen, R₆ für Niederalkyl steht und q für 2 oder vorzugsweise 1 steht.Another preferred class of azo dyes includes those of Formula IXc

wherein A ₂ , B, R _s and X _{3 have} the meanings given, R _{6 is} lower alkyl and q is 2 or preferably 1.

worin T₁, T₄ und T₅ jeweils unabhängig voneinander für Wasserstoff oder Niederalkyl stehen, T₂ für Wasserstoff, Niederalkyl oder monocyclisches Aryl steht und T₃ für Niederalkyl oder monocyclisches Aryl steht.Vorzugsweise besitzt die ervähnte Acylaminogruppe die Formel: -NHCO-Niederalkyl.Examples of substituents which may be present on the benzene ring B are lower alkyl radicals, in particular methyl, lower alkoxy radicals, such as, for example, methoxy and ethoxy, chlorine, bromine and acylamino radicals, in particular acylamino radicals of the formulas

wherein T ₁ , T ₄ and T ₅ each independently represent hydrogen or lower alkyl, T _{2 stands} for hydrogen, lower alkyl or monocyclic aryl and T _{3 stands} for lower alkyl or monocyclic aryl. The abovementioned acylamino group preferably has the formula: -NHCO-lower alkyl .

Throughout the description, the terms ^u lower alkyl "and" lower alkoxy "refer to alkyl or alkoxy radicals having 1 to 4 carbon atoms.

The radicals of the diazo components A, A ₁ and A ₂ can be radicals of any diazo components of the heterocyclic series, in particular optionally substituted thiazol-2-yl-, benzthiazol-2-yl-, thien-2-yl-, benz-2, l-isothiazol-3-yl-, benz-1,2-isothiazol-3-yl-, 1,2,4-thiadiazol-5-yl-, 1,3,4-thiadiazol-2-yl-, isothiazol- 5-yl, pyrazol-3-yl, imidazole (2- or -5-) yl, 1,2,4-triazol-3-yl and tetrazol-5-yl radicals.

worin L₁ und L₂ jeweils unabhängig voneinander für Niederalkyl stehen, U und W jeweils unabhängig voneinander für Wasserstoff, Niederalkyl, Chlor, Brom, Niederalkoxy, Nitro, Cyano oder Niederalkoxycarbonyl stehen und V für Wasserstoff, Nitro, Chlor, Brom, Niederalkyl, Niederalkoxy, Cyano, Niederalkoxycarbonyl, Sulfonamido oder Carbonamido und N- und N,N-substituierte Derivate davon, Niederalkylcarbonyl und Niederalkylsulfonyl steht. V ist vorzugsweise Nitro.In particular, A, A ₁ and A _{2 are} radicals of a diazo component of the aromatic series and very particularly optionally substituted naphthyl and especially optionally substituted phenyl radicals. kale. The substituent or substituents which are present on such radicals can be any substituents, other than carboxylic acid and sulfonic acid groups, which are not present on the diazo radicals of disperse azo dyes, such as chlorine, bromine, nitro, cyano, trifluoromethyl, lower alkyl, lower alkoxy , Lower alkylsulfonyl, lower alkylcarbonyl, acylamino, especially lower alkylcarbonylamino, sulfonamido and N-substituted and N, N-disubstituted derivatives thereof, carbonamido and N-substituted and N, N-disubstituted derivatives thereof and carboxylic ester groups, especially lower alkoxycarbonyl. A, A ₁ and A2 are preferably optionally substituted phenyl radicals and in particular radicals of the formulas

wherein L ₁ and L ₂ each independently represent lower alkyl, U and W each independently represent hydrogen, lower alkyl, chlorine, bromine, lower alkoxy, nitro, cyano or lower alkoxycarbonyl and V represents hydrogen, nitro, chlorine, bromine, lower alkyl, lower alkoxy , Cyano, lower alkoxycarbonyl, sulfonamido or carbonamido and N- and N, N-substituted derivatives thereof, lower alkylcarbonyl and lower alkylsulfonyl. V is preferably nitro.

In the above classes, A, A ₁ and A ₂ preferably represent a phenyl radical which may contain up to 3 substituents, preferably the substituents exemplified above as substituents on the diazo radical mentioned. were.

. worin L₃ für gegebenenfalls substituiertes Niederalkyl steht; L₄ für gegebenenfalls substituiertes Niederalkyl oder gegebenenfalls substituiertes Amino steht; Y₁ für Wasserstoff oder Nitro steht; Y₄für Wasserstoff oder Niederalkoxy steht; R₇ für Niederalkyl oder Cyano-niederalkyl steht;A special group of azo disperse dyes containing carboxylic acid ester groups corresponds to the formula IXd

. wherein L _{3 represents} optionally substituted lower alkyl; L _{4 represents} optionally substituted lower alkyl or optionally substituted amino; Y _{1 represents} hydrogen or nitro; Y _{4 represents} hydrogen or lower alkoxy; R _{7 represents} lower alkyl or cyano-lower alkyl;

A ₃ and A ₄ each independently represent lower alkylene; and X _{5 represents} cyano, lower alkoxy, lower alkoxy-lower alkoxy, lower alkoxy-lower alkoxy-lower alkoxy, chlorine, bromine, lower alkoxycarbonyl, lower alkylcarbonyl, optionally substituted phenoxycarbonyl, optionally substituted phenylcarbonyl, optionally substituted phenoxy, hydroxymethyl or lower alkylcarbonyloxymethyl.

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

Examples of lower alkylene radicals A ₃ and A ₄ are methylene, trimethylene, tetramethylene, propylene and especially ethylene. Examples of cyano-lower alkyl radicals R7 are cyanomethyl, γ-cyanopropyl, δ-cyanobutyl and especially β-cyanoethyl. Examples of lower alkyl radicals L ₃ , L ₄ and R ₇ are methyl, ethyl, n-propyl and n-butyl. Examples of lower alkoxy radicals Y ₄ are ethoxy and especially methoxy.

Examples of substituted lower alkyl radilals L ₃ and L ₄ are hydroxy-lower alkyl, such as, for example, β-hydroxyethyl, chloro-lower alkyl, such as, for example, β-chloroethyl, cyano-lower alkyl, such as, for example, β-cyanoethyl, lower alkoxy-lower alkyl, such as, for example, β-ethoxyethyl and y-methoxypropyl, phenyl- lower alkyl such as benzyl and β-phenylethyl, and phenoxy lower alkyl such as phenoxymethyl.

Examples of substituted amino groups L are lower alkylamino, e.g. Methylamino and ethylamino.

However, it is preferred that L _{3 is} lower alkyl. It is also preferred that L _{4 is} lower alkyl, especially methyl.

Specific examples of groups X ₅ are lower alkoxy radicals, such as methoxy, ethoxy, n-propoxy and n-butoxy, lower alkoxy lower alkoxy radicals, such as β-ethoxy-ethoxy and y methoxypropoxy, lower alkoxy-lower alkoxy lower alkoxy radicals, such as β- (β'-Nethoxyäthoxy) äthoxy, Niederalkoxycarbonyl radicals, such as methoxycarbonyl, Äthoxycarbonyl and n-butoxycarbonyl, Niederalkylcabonyl radicals, such as acetyl and propionyl, optionally substituted phenoxycarbonyl radicals, such as phenoxycarbonyl itself, p-methylphenoxycarbonoxy and m-chlorophenoxycarbonyl and m-chloro substituted phenylcarbonyl radicals, such as benzoyl and m-nitrobenzoyl, optionally substituted phenoxy radicals, such as phenoxy itself, tolyloxy and chlorophenoxy, and lower alkylcarbonyloxymethyl radicals, such as acetoxymethyl.

However, it is preferred that X _{5 represents} cyano, lower alkoxy, lower alkoxy-lower alkoxy, lower alkoxycarbonyl, lower alkylcarbonyl, hydroxymethyl or lower alkylcarbonyloxymethyl.

worin R₇ die angegebene Bedeutung besitzt; L₃ für Niederalkyl steht; Y₄ für Wasserstoff oder Methoxy steht; und X₅ für Cyano, Niederalkoxy, Niederalkoxy-niederalkoxy, Niederalkoxycarbonyl, Niederalkylcarbonyl, Hydroxymethyl oder Niederalkylcarbonyloxymethyl steht.A preferred class of dyes according to the invention includes those of formula IXe

wherein R _{7 has} the meaning given; L _{3 represents} lower alkyl; Y _{4 represents} hydrogen or methoxy; and X _{5 represents} cyano, lower alkoxy, lower alkoxy-lower alkoxy, lower alkoxycarbonyl, lower alkylcarbonyl, hydroxymethyl or lower alkylcarbonyloxymethyl.

worin X₆für Niederalkyl steht, s für 1, 2 oder 3 steht, Z₂ für Wasserstoff, Niederalkyl oder Niederalkoxy steht, Y₅ für Wasserstoff, Niederalkyl, Niederalkoxy, Chlor, Brom, -NHCOX₇ oder -NHSO₂X₈ steht, X₇ für Niederalkyl, Niederalkoxy, Amino oder N-Niederalkylamino steht, X₈ für Niederalkyl steht, A₅ und A₆ jeweils unabhängig voneinander für Niederalkylen stehen und R₈ und R₉ jeweils unabhängig voneinander für Niederalkyl oder Hydroxyalkyl mit 2 bis 4 Kohlenstoffatomen stehen.Another special group of azo disperse dyes containing carboxylic acid ester groups corresponds to the formula IXf

in which X _{6 represents} lower alkyl, s represents 1, 2 or 3, Z _{2 represents} hydrogen, lower alkyl or lower alkoxy, Y _{5 represents} hydrogen, lower alkyl, lower alkoxy, chlorine, bromine, -NHCOX ₇ or -NHSO ₂ X ₈ , X _{7 represents} lower alkyl, lower alkoxy, amino or N-lower alkylamino, X _{8 represents} lower alkyl, A ₅ and A ₆ each independently represent lower alkylene and R ₈ and R ₉ each independently represent lower alkyl or hydroxyalkyl having 2 to 4 carbon atoms .

Examples of lower alkyl radicals X ₆₇ Z ₂ , Y ₅ , X ₇ , X ₈ , R ₈ and R ₉ are methyl, ethyl, n-propyl, isopropyl and n-butyl. Examples of lower alkoxy radicals X ₇₇ Z ₂ and Y ₅ are ethoxy and preferably methoxy. Examples of lower alkylene radicals A ₅ and A ₆ are methylene, trimethylene, propylene, tetramethylene, hexamethylene and especially ethylene. Examples of hydroxyalkyl radicals R ₈ and R ₉ are β-hydroxyethyl, β- or y-hydroxypropyl and β-, y- or δ-hydroxybutyl. Examples of N-lower alkylamino radicals X ₇ are methylamino and ethylamino.

worin X₆, Y₅, Z₂, R₈ und Rg die oben angegebenen Bedeutungen besitzen. Y₅steht vorzugsweise für Wasserstoff oder Niederalkylcarbonylamino.A preferred class of dyes according to the invention includes those of formula IXg

wherein X ₆ , Y ₅ , Z ₂ , R ₈ and Rg have the meanings given above. Y ₅ preferably represents hydrogen or lower alkylcarbonylamino.

worin X₉ für Nitro oder _Cyano steht; Y₆für Wasserstoff, Chlor, Brom, Cyano, Nitro, Niederalkoxy oder Niederalkoxycarbonyl steht; T₆für Methoxy oder Äthoxy steht; Z₃für Wasserstoff, Chlor, Brom, Niederalkyl oder Niederalkoxy steht; A₇ und A₈ jeweils unabhängig voneinander für Niederalkylen stehen und R₁₀und R₁₁ jeweils unabhängig voneinander für Niederalkyl oder Hydroxyalkyl mit 2 bis 4 Kohlenstoffatomen stehen.Another special group of azo disperse dyes containing carboxylic acid ester groups corresponds to the formula IXh

wherein X ₉ is nitro or _C yano; Y _{6 represents} hydrogen, chlorine, bromine, cyano, nitro, lower alkoxy or lower alkoxycarbonyl; T _{6 represents} methoxy or ethoxy; Z _{3 represents} hydrogen, chlorine, bromine, lower alkyl or lower alkoxy; A ₇ and A ₈ each independently represent lower alkylene and R ₁₀ and R ₁₁ each independently represent lower alkyl or hydroxyalkyl having 2 to 4 carbon atoms.

Examples of lower alkyl radicals Z ₃ , R ₁₀ and R ₁₁ are mathyl, ethyl, n-propyl and n-butyl. Examples of lower alkoxy radicals Y ₆ and Z ₃ are methoxy and ethoxy. Examples of Niederalkoxycarbonylradikale Y ₆ are methoxycarbonyl, ^p Äthoxycarbo yl, n-propoxycarbonyl, n-butoxycarbonyl, iso-propoxycarbonyl, sec-butoxycarbonyl and isobutoxycarbonyl.

Examples of hydroxyalkyl radicals R ₁₀ and R ₁₁ are β-hydroxyethyl, y-hydroxypropyl and δ-hydroxy-n-butyl. Examples of lower alkylene radicals A ₇ and A ₈ are methylene, trimethylene, propylene, tetramethylene, hexamethylene, α, β-dimethylethylene and especially ethylene.

gebildet, worin Y₆

Brom, Nitro oder Cyano steht und

und R₁₁ die oben angegebenen Bedeutungen besitzen.A preferred class of dyes according to the invention is represented by those of the formula IXi

where Y ₆

Bromine, nitro or cyano stands and

and R _{11 have} the meanings given above.

Formel IXk

worin X₁₀für Cyano, gegebenenfalls substituiertes Methoxycarbonyl, gegebenenfalls substituiertes Äthoxycarbonyl, gegebenenfalls substituiertes Carbonamido, Niederalkylcarbonyl, Niederalkylsulfonyl, gegebenenfalls substituiertes Arylcarbonyl oder Arylsulfonyl, Chlor oder Brom steht; Y₇ für Wasserstoff, Niederalkyl, gegebenenfalls substituiertes Aryl oder Niederalkoxycarbonyl steht; Z4 für Wasserstoff, Nicderalkyl, Chlor, Brom, Nitro, Cyano, gegebenenfalls substituiertes Niederalkoxycarbonyl oder gegebenenfalls substituiertes Carbonamido steht; mit der Einschränkung, daß X₁₀und Z₄ nicht beide für gegebenenfalls substituiertes Carbonamido stehen und daß Y₇ und Z₄ nicht beide für Wasserstoff stehen; W_lfür Wasserstoff, . Niederalkyl oder Niederalkoxy steht; V₂für Wasserstoff, Chlor, Brom, Niederalkyl, Niederalkoxy oder Acylamino steht; mit der Einschränkung, daß V₂und W₁nicht beide für Wasserstoff stehen; A₉ und A₁₀ jeweils unabhängig voneinander für Niederalkylen stehen; und R₁₂und R₁₃jeweils unabhängig voneinander für Niederalkyl oder Hydroxyniederalkyl stehen.Another special group of azo disperse dyes containing carboxylic acid ester groups

Formula IXk

wherein X _{10 is} cyano, optionally substituted methoxycarbonyl, optionally substituted ethoxycarbonyl, optionally substituted carbonamido, lower alkylcarbonyl, lower alkylsulfonyl, optionally substituted arylcarbonyl or arylsulfonyl, chlorine or bromine; Y _{7 represents} hydrogen, lower alkyl, optionally substituted aryl or lower alkoxycarbonyl; Z4 represents hydrogen, nicderalkyl, chlorine, bromine, nitro, cyano, optionally substituted lower alkoxycarbonyl or optionally substituted carbonamido; with the restriction that X ₁₀ and Z _{4 are} not both optionally substituted carbonamido and that Y ₇ and Z _{4 are} not both hydrogen; W _l for hydrogen,. Lower alkyl or lower alkoxy; V _{2 represents} hydrogen, chlorine, bromine, lower alkyl, lower alkoxy or acylamino; with the restriction that V ₂ and W _{1 are} not both hydrogen; A ₉ and A ₁₀ each independently represent lower alkylene; and R ₁₂ and R ₁₃ each independently represent lower alkyl or hydroxy lower alkyl.

worin T₇ für Wasserstoff, Niederalkyl oder Phenyl steht und T₈ für Wasserstoff oder Niederalkyl steht.The optionally substituted carbonamido groups X ₁₀ and Z ₄ have the formula:

wherein T _{7 is} hydrogen, lower alkyl or phenyl and T _{8 is} hydrogen or lower alkyl.

Acylaminogruppen die Formel -NHCOT₉ wobei T₉ Niederalsyl ist. Spezielle Beispiele fur Acylaminogruppen V₂ sind Methylsulfonamido, Benzolsulfonylamino, Benzoylamino, Ureido, Formylamino und vorzugsweise Acetylamino, Propionylamino und Butyrylamino.Examples of lower alkyl radicals Z ₄ , Y ₇ , T ₇ , T ₈ V ₂ , V ₁ , R ₁₂ and R ₁₃ are methyl, ethyl, n-propyl and n-butyl. Examples of lower alkoxy radicals V ₂ and W ₁ are ethoxy and preferably methoxy, examples of lower alkylene radicals Ag and A ₁₀ are methylene, trimethylene, propylene, tetramethylene and especially ethylene. The acylamino groups Y ₂ preferably have the formula -NHCOT ₉ or -NHSO ₂ T ₁₀ wherein T _{9 is} hydrogen or lower alkyl and T _{10 is} lower alkyl. D preferably have ₁₀

Acylamino groups have the formula -NHCOT ₉ where T ₉ is lower thanyl. Specific examples of acylamino groups V ₂ are methylsulfonamido, benzenesulfonylamino, benzoylamino, ureido, formylamino and preferably acetylamino, propionylamino and butyrylamino.

z.B. β-Hydroxyäthoxycarbonyl, Cyanoniederalkoxycarbonyl, wie z.B. ß-Cyanoäthoxycarbonyl, Niederalkoxy-niederalkoxy- carbonyl, wie z.B. ß-Methexyathoxycarbonyl und Kederalk-

und _Ary_lsulfony_lradi_kale X₁₀sind gegebenenfalls substituierte Benzoyl- und Phenylsulfonylradikale, insbesondere Nitrobenzoyl, Methylbenzoyl, Methoxybenzoyl, Nitrobenzoyl und p-Tolylsulfonyl. Beispiele für gegebenenfalls substituierte Arylradikalc Y₇ sind Phenyl, Nitrophenyl und Nitrotolyl.Examples of Mederalkexycarbonylradikal (carboniederalkoxy radicals) Y ₇ and Z ₄ are methoxycarbonyl and ethoxycarbonyl. Examples of substituted lower alkoxycarbonyl radicals Z ₄ are

For example, β-hydroxyethoxycarbonyl, cyano-lower alkoxycarbonyl, such as, for example, β-cyanoethoxycarbonyl, lower alkoxy-lower alkoxycarbonyl, such as, for example, β-methexyathoxycarbonyl and Kederalk

and _Ar y _lsulfon y _lrad i _kale X ₁₀ are optionally substituted benzoyl and phenylsulfonyl radicals, in particular nitrobenzoyl, methylbenzoyl, methoxybenzoyl, nitrobenzoyl and p-tolylsulfonyl. Examples of optionally substituted aryl radicals Y ₇ are phenyl, nitrophenyl and nitrotolyl.

worin X₁₀für Cyano, Methoxycarbonyl oder Äthoxycarbonyl steht und W₁, V₂, A₉, A_10' R₁₂ und R₁₃ die oben angegebenen Bedeutungen besitzen.A preferred class of dyes according to the invention comprises those of the formula IX 1

wherein X _{10 is} cyano, methoxycarbonyl or ethoxycarbonyl and W ₁ , V ₂ , A ₉ , A _{10 '} R ₁₂ and R _{13 have} the meanings given above.

Examples of disperse dyes of the anthraquinone series containing carboxylic acid ester groups to be used according to the invention are: 1,4-di (β-ethoxycarbonylethylamino) anthraquinone, 1-amino-4- [4 '- (α, β-di- {β'-hydroxyethoxy-carbonyl} ethyl ) anilino] anthraquinone, 1,4-di- (ß-methoxy-carbonylethylamino) anthraquinane, 1., 4-di- (o-methoxy-carbonylanilino) anthraquinone.

The reactive dyes used in the process according to the invention contain one of the fiber-reactive radicals of the formulas I I I to VI given above. It is common to the radicals of the formulas III.to V that they form a vinylsulfonyl group in the presence of alkali with the elimination of a sulfate or halo 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 residue by adding one of the OH groups of the cellulose to the vinyl double bond. Reactive dyes which have one of the reactive radicals mentioned above can belong to all technically important dye groups. 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 andrachinone dyes CI-Violet 22, Blue 19 and 27; the phthalocyanine dyes CI-Blue 21, 38, 77, 91 and Green 14 called.

Particularly preferred as 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 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 which is prepared for a base coloring of a particular color shade contains, in the event that the substrate predominantly contains cellaloze fibers, a high proportion of etchable and possibly non-etchable reactive dyes and a low proportion of etchable and optionally non-etchable disperse dyes and, in the event that the substrate predominantly contains polyester fibers, a high proportion of the disperse dyes and a low proportion of the 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 when 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 generate 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 optionally non-etchable disperse dyes.

The reserve paste to be used in carrying out the method 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 the alkali sulfite, alkali hydrogen sulfite and alkali hydrogen carbonate, the sodium or potassium salts, preferably the sodium salts, are particularly suitable for industrial use. Aldehydes which can be present in the reserve pastes as alkali metal bisulfite adducts are in principle all those which are technically readily accessible, such as, for example, formaldehyde, acetaldehyde, glyoxal, benzaldehyde. Since the aldehyde-alkali hydrogen sulfite adducts are in equilibrium with the individual components of the adduct

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 if colored etchings are to be produced, i.e. if, at the point printed with the reserve paste and resistant to the reservation agent, disperse and reactive dyes are used in the coloring of the background 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 Auslegeschrift 1138735.

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 which contain one or more of the above-mentioned alkali-etchable disperse dyes and one or more reactive dyes which contain one of the above-mentioned reactive radicals of the formulas III to VI, preferably the β-sulfatoethylsulfonyl or β-sulfatoethylsulfonamide groups, contain, 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 disperse and reactive dyes which 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 included 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 supplied by means of superheated steam. The heat treatment effects a) an inhibition of the reservable dispersion and reactive dyes at the points printed with the reserve paste and a fixation of the possibly non-reservable dispersion and reactive dyes, b) a fixation of the dispersion dyes at the points not printed with reserve paste
and, if the padding liquor contained an alkali metal formate, the reactive dyes at the same time. Hiarbet is

Finally, the dyeings or prints are rinsed hot and cold and dried. A particular embodiment of the inventive method is that the _K lotzflotte except reservable disperse and reactive dyes additionally includes those that are resistant to the resisting agent, and thus will not be destroyed by the discharge reserve printing pastes used according to the invention. If one proceeds as above, then multicolored designs are obtained. A further embodiment of the method according to the invention consists in that the dyes which can be reserved 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 that are resistant to the reservation agent to the color printing pastes printed on first. 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, multicolored 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 produced in a manner known per se by mixing the liquor or printing paste components with the necessary amount of water and liquid finely dispersed or solid redispersible formulations of the disperse dyes and solutions or formulations of the Reactive dyes.

Dispersion dyes which are resistant to the reservation agent and which can be combined with the reserved 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. Some examples of resistant disperse dyes are:

• Cvanurchlorid, Cyanurbromid, Cyanurfluorid, Dihalogenmono-amino-triazinc, wie 2,6-Dichlor-4-amino-triazin, 2,6-Dichlor-4-methylamino-triazin, 2,6-Dichlor-4-oxäthyl- aminotriazin, 2,6-Dichlor-4-phenylaminotriazin, 2,6-Dichlor-4-(₀-, 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-carbonsäure- chlorid, 2,4,6-Trichlorpyrimidin-5-carbonsäurechlorid, 4,5-Dichlor-6-pyridazonylpronylchlorid, 1,4-Dichlor- phthalazin-6-carbonsäurechlorid, 5,6-Dichlor-4-methyl-2-methylsulfonyl-pyrimidin, 2- oder 3-Honochlorchinoxalip-6-carbonsäurechlorid oder -6-sulfonsäurechlorid, 2,3-Di- chlorchinoxalin-6-carbonsäurechlorid oder -6-sulfonsäure- chlorid, 1,4-Dichlorphthalazin-6-carbonsäurechlorid oder -6-sulfonsäurechlorid, 2,4-Dichlorchinazolina-6- oder -7- carbonsäurechlorid oder -sulfonsäurechlorid, 2-Chlorbenz- thiazol-5- oder -6-carbonsäurechlorid oder -5- oder -6- sulfonsaurechlorid, 2-Methylsulfonyl- oder 2-Athylsul- fonyl- oder 2-Phenylsulsnylbenzthiazol-5- oder -6-sul- Fosäurechlorid, Acrylsäulechlorid und 3-Chlorpropion- saurechlorid

The reactive dyes which are resistant to the reservation agent and which can be combined with the reserve reactive dye of the formula I to produce multicolored designs are the known llandel dyes from the group of azo or azomethine, quinophthalone, nitro or anthraquinone dyes, which act as a fiber-reactive radical from the class of triazines, quinoxalines, phthalazines, pyridazines, pyrimidines or of the, β-unsaturated aliphatic carboxylic acids. The most important compounds, of which the fiber-reactive residues of the non-reserved ones, ie against the etchant, are mentioned below as representative of the entire class
derive stable reactive dyes:

• Cvanuric chloride, cyanuric bromide, cyanuric fluoride, dihalomomono-triazine, such as 2,6-dichloro-4-aminotriazine, 2,6-dichloro-4-methylamino-triazine, 2,6-dichloro-4-oxyethylaminotriazine, 2 , 6-dichloro-4-phenylaminotriazine, 2,6-dichloro-4- ( ₀ -, 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-dichloropyridazin-4- carboxylic acid chloride, 2,4-dichloropyrimidine-5-carboxylic acid chloride, 2,4,6-trichloropyrimidine-5-carboxylic acid chloride, 4,5-dichloro-6-pyridazonylpronyl chloride, 1,4-dichlorophthalazine-6-carboxylic acid chloride, 5, 6-dichloro-4-methyl-2-methylsulfonyl-pyrimidine, 2- or 3-honochloroquinoxalip-6-carboxylic acid chloride or -6-sulfonic acid chloride, 2,3-di-chloroquinoxaline-6-carboxylic acid chloride or -6-sulfonic acid chloride, 1 , 4-dichlorophthalazine-6-carboxylic acid chloride or -6-sulfonic acid chloride, 2,4-dichloroquinazolina-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-phenylsulfylbenzthiazole-5- or -6-sulfonic acid chloride, acrylic acid chloride and 3-chloropropionic acid chloride

Example 1:

• 30 Gewichtsteile der Handelsform von C.I. Reactive Red 24, 30 Gewichtsteile der flüssigen Handelsform von
• C.I. Disperse Red 132, 100 Gewichtsteile Harnstoff und
• 10 Gewichtsteile m-nitrobenzolsulfonsaures Natrium werden in 150 Gewichtsteilen Wasser von 80°C gelöst.

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 CI Reactive Yellow 17 and 60 parts by weight CI Reactive Violet 5, 200 parts by weight water 80 ° C, 687 parts by weight 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 of CI Reactive Red 24, 30 parts by weight of the liquid commercial form of
• CI 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 thickening stock, the 230 parts by weight of an aqueous 4% alginate thickening and 80 parts by weight of an aqueous. Contains 10% starch ether thickening, 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 parts by weight of white spirit. 100 parts by weight of the etching reserve are then 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 ° Be, 125 parts by weight of water and 500 parts by weight of sodium hydrogen carbonate.

After drying, steam in a high-temperature damper at 175 ° C for 7 minutes, block the fabric with a fixer solution consisting of 700 volumes of water, 150 volumes of sodium arbonate, 150 volumes of sodium chloride, 100 volumes of sodium hydroxide solution at 38 ° B €, 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 / 1 of an auxiliary based on fatty acid polyglycol ester at 40, 60 and 8 ° 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 of 80 ^o , 10 parts by weight of sodium m-nitrobenzenesulfon, 500 parts by weight of thickening stock according to Example 1, 30 parts by weight of sodium arbonate, 30 parts by weight of sodium bisulfite solution 38 ° Be, 6 parts by weight of 40% glyoxal solution.

After drying, steam for 7 minutes in saturated steam to intensify the reserve effect and then fix the disperse dyes and the reactive dyes that are resistant to alkali sulfites in a high-temperature steamer at 185 ° C for 6 minutes. Then the base coloring is fixed with the fixing solution specified in Example 1,

Steamed at 110-115 ° C for 10 seconds and completed as indicated in Example 1.

You get scarlet colored effects on a brown background.

Example 3

wichtsteilen einer 20%igen Flussigeinstellung des farbstoffs der Formel

You block a merclized mesh fabric made of 65:35 Palrester cotton with one

important parts of a 20% liquid setting of the color substance of the formula

40 parts by weight of the liquid commercial form of C.I. Reactive Blue 122, 808 parts by weight of cold water, 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.

It is carefully dried in a hot flue at 80-100 ° C. and overprinted in film printing using a printing paste comprising 25 parts by weight of the commercial form of 1- / 5- (3,6-dichloropyridazin-4-yl-carbonylamino) -2-methyl-3- sulfophenyl7-3-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 m-nitrobenzene- sulphonate sodium, 500 parts by weight of stock thickener according to example 1, 40 parts by weight of sodium hydrogen carbonate, 30 parts by weight of sodium hydrogen sulfite 38 ° Be, 6 parts by weight of 40% Glyox _a llösung.

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

Yellow colored effects are obtained on a navy blue floor.

Example 4

• 50 Gewichtsteile der flüssigen Handelsform von C.I. Disperse Red 278, 40 Gewichtsteile der Handelsform von C.I. Reactive Red 63, 200 Gowichtsteile wasserv 80°C, 660 Ge- wichtsteile Wasser Kalt, 10 Gewichtsteile m-nitrobenzol- sulfonsaures Natrium, 20 Gewiehtsteile eines Antimigriermittels auf Basis Polyacrylsäure, 20 Gewichtsteile Natriumformiat.

A leached knitted fabric made of polyester COLVERA 70:30 is padded with the following dye liquor:

• 50 parts by weight of the liquid commercial form of CI Disperse Red 278, 40 parts by weight of the commercial form of CI Reactive Red 63, 200 parts by weight of water at 80 ° C., 660 parts by weight of water cold, 10 parts by weight of m-nitrobenzenesulfonic acid sodium, 20 parts by weight of an antimigrant based Polyacrylic acid, 20 parts by weight sodium formate.

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 Natriumechlorat, 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 Farbstoffs der Formel

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 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

• 50 Gewichtsteilen der flüssigen Handelsform von 5-(4-Nitro-2-methylphen-1-yl)-azo-4-methyl1-3-cyan-2,6-dihydroxy- pyridin, 40 Gewichtsteilen der Handelsform von C.I. Reactive Yellow, 867 Gewichtsteilen Wasser, 3 Gewichtsteilen Natriumchlorat, 20 Gewichtsteilen eines Antimigriermittels auf Basis Polyacrylsäure, 20 Gewichtsteilen Natriumformiat. Man trocknet vorsichtig in einer Hot- flue bei 80 - 100%C und überdruekt im Rouleauxdruek mit einer Druckpaste aus 60 Gewichtsteilen der Handels- form von C.I. Reactive Red 24, 40 Gewiehtseilen der flüssigen Handelsform von C.I. Disperse Red 132, 275 Gewichtsteilen Wasser 600 Gewichtsteilen
  einer 4%igen Lösung eines Natriumalginats, 25 Gewichtstteilen Natriumsulfit.
  Nach dem Trocknen wird 7 Minuten bei 175°C mit überhitztem Wasserdampf fixiert und wie im Beispiel 1 angegeben nachbehandelt.

Block a mercerized blend of 65:35 polyester-cotton with an approach consisting of:

• 50 parts by weight of the liquid commercial form of 5- (4-nitro-2-methylphen-1-yl) -azo-4-methyl1-3-cyan-2,6-dihydroxy-pyridine, 40 parts by weight of the commercial form of CI Reactive Yellow, 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. You dry carefully in a hot Flue at 80 - 100% C and press in the Rouleauxdruek with a printing paste of 60 parts by weight of the commercial form of CI Reactive Red 24, 40 parts by weight of the liquid commercial form of CI Disperse Red 132, 275 parts by weight of water and 600 parts by weight
  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 (8)

1. Process 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 react with the reservation agents and which, if appropriate contain further disperse and reactive dyes which are resistant to the reservation agents and, if appropriate, alkali metal formate, drying or drying the padded materials and then printing on a reserve paste which, if desired, contains, besides the reservation agent, disperse and reactive dyes which are resistant to the reservation agent, heat treatment at temperatures from 100 to 190.degree and optionally subsequent alkaline fixing of the reactive dye in a manner known per se, characterized in that the etchable disperse dyes are those of the formula I

wherein R _{1 is} hydrogen, alkyl having 1-6 C atoms, cyan, 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 chlorine, bromine, cyano, hydroxyl and has 1-4 C atoms, alkoxy with 1-4 C atoms, hydroxyalkoxy with 2-4 C atoms and Alkoxy-alkoxy with a total of 3-6 C atoms; Y _{1 is} hydrogen, chlorine, bromine, optionally substituted by a substituent from the group chlorine, bromine, cyano, hydroxy-alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, hydroxyalkoxy with 2 to 4 carbon atoms, alkoxyalkoxy with a total of 3 - 6 carbon atoms, -NH-CO-Y ₂ , -NH-SO ₂ -Y _{2 '} wherein Y ₂ for alkyl with 1 - 4 C atoms, the Al- kylrest may optionally be substituted with a substituent from the group phenyl, chlorine, bromine, cyano, hydroxy, alkoxy with 1 to 2 carbon atoms or phenoxy, phenyl, amino, N-alkylamino wit 1 to 4 carbon atoms; R _{2 is} hydrogen, optionally by chlorine, bromine, cyano, hydroxy, alkoxy or hydrexyalkoxy with 1 to 4 carbon atoms, phenyl, alkayloxy with 2 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms, hydroxycarbonyl with 2 - 4 carbon atoms, alkylaminocarbinyloxy with 2 to 4 carbon atoms or phenylamicarbonyloxy substituted alkyl with 1 to 6 carbon atoms, hydroxyalkyl with 2 to 4 carbon atoms or alkenyl with 3 to 6 carbon atoms; R _{3 is} optionally chlorine, Bren cyano, hydroxy, alkoxy or hydroxyalkoxy with 1 to 4 carbon atoms, phenyl, alkanoyloxy with 2 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms,

in which D represents phenyl which optionally contains at least one substituent which consists of chlorine, bromine, nitro, cyano, trifluoromethyl, thlocyano ni-alkyl,

Lower alkoxy-lower alkoxy-nicalkoxycarbonyl, hydroxy-lower alkoxycarbonyl, hydroxy-lower alkoxy-lower alkoxycarbonyl and lower alkoxycarbonyl-lower alkyl is selected; X represents hydrogen, lower alkyl, carbamoyl, cyano, chlorine, bromine, nitroso, nitro, lower alkylcarbonyl, sulfamoyl, lower alkylsulfonyl, lower alkylcarbonylamino or lower alkoxycarbonyl; Z represents hydrogen or lower alkyl; or water-solubilizing groups-free disperse dyes which contain at least two carboxylic acid ester groups from the nitro, methine, azomethine, antrachinone and especially azo and very particularly monoazo series, the carboxylic acid ester groups preferably having the formula -COOR ₅ , where R ₅ represents an optionally substituted hydrocarbon or heterocyclic radical, 2. as etchable reactive dyes, those containing the reactive radicals of the formulas III to VI

where M is hydrogen or a metal cation and hal is halogen, and 3. a reserve paste that serves 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 non-ionic detergent. 2. The method according to claim 1, characterized in that those of the formula I are used as the etchable disperse dyes. 3. Process according to claims 1 and 2, characterized in that those which contain reactive radicals of the formulas IV and V are used as the etchable reactive dyes. 4. The method according to claims 1 to 3, characterized. records that the reserve paste contains as a reservation agent a prefabricated aldehyde-alkali hydrogen sulfite, adduct. 5. The method according to claims 1 to 4, characterized in that the reserve paste contains a polyglycol carboxylic acid ester as a nonionic detergent. 6. The fabricated with the effects of claims 1 to 5, provided with reserve effects textile materials.