EP0051261A1 - Process for the production of discharge-resist prints on textile materials - Google Patents

Abstract

In the process for producing etching reserve prints on textile materials which consist of hydrophobic fibers or contain such fibers, a dye of the formula I <IMAGE> in which X¹, X², X³, Y¹, Y², R¹ and R² are used as non-water-soluble, in the case of disperse dyes there are customary substituents, with the proviso that at most one of the radicals X¹, X², X³, Y¹, Y², R¹ or R² carries an alkoxycarbonyl group, and uses an etching reserve printing paste which contains a base as etching agent which contains 5% strength aqueous solution produces at least a pH of 8.

Description

The present invention relates to a method for the manufacture _lu ng of Ätzreservedrucken on textile materials consisting of hydbphoben fibers, preferably polyester fibers, or if such fibers in admixture with cellulose fibers contained, wherein to the textile material a weißätzbarer disperse dye and optionally a ätzmittelbeständiger disperse dye in the form of a dye liquor or applied printing paste and then dried or partially dried, is then printing and a discharge reserve printing paste, optionally containing in addition to the etchant or caustic resistant dyes in the desired pattern, and subsequent heat treatment at temperatures of 100-230 ⁰ C.

It has always been a problem in textile printing to produce white or colored, sharply defined patterns on a deep-colored background. The direct printing of the textile material completely fails, particularly when producing filigree-like patterns on a dark background. To produce such designs, it is 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 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.

There is a problem with the transfer of these known methods to synthetic fiber materials or textile materials, which preferably consist of hydrophobic synthetic fibers, in that the etching of polyester fibers stained, for example, with disperse dyes is very difficult. Disperse dyes that are once fixed in the polyester fiber, i.e. solved, are largely removed from the access of aqueous agents and thus also from attack by 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 dried or dried on, but no fixation of the dye, i.e. The dye can be dissolved in the hydrophobic fiber. 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, with the base dye immigrating into the polyester at the unprinted areas, i.e. is fixed and the dye is destroyed at the printed areas, i.e. no coloring takes place. In view of this mechanism, this method is also called 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 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, in particular if the polyester fiber also contains accompanying fibers, such as cellulose fibers. Furthermore, this etchant are generally not bi _l - lig, and in the case of Schwermetallätzmittel they represent an additional environmental burden or cause them additional expenses in sewage treatment. In addition, there are relatively few types of dyes that are resistant to such etchants, so that the selection of etch-resistant dyes that can be used to produce colored etchings is relatively small.

In order to overcome these difficulties, disperse dyes are required for the background coloring, which can be etched with pure white agents. Disperse dyes are known from German published patent application 26 12 740, 26 12 741, 26 12 742, 26 12 790, 26 12 791, 26 12 792 which contain at least two esterified carboxyl groups in their molecule. Such dyes saponify when treated with aqueous alkalis to form alkali-soluble dyes containing carboxylate groups. The use of such dyes as disperse dyes for dyeing polyester materials has the advantage that unfixed dye residues can be washed off the textile material by simple treatment with alkaline agents. It is also already known that dyeings with disperse dyes which contain pyridone derivatives as the coupling component can easily remove dye residues from the fiber by alkali treatment. However, as far as pyridone dyes are concerned, these dyes which are soluble in aqueous alkalis have the disadvantage that they essentially consist of finally can be used for yellow or reddish yellow shades, as far as dyes with esterified carboxyl groups are concerned, that after the saponification of the ester groups they have a certain affinity for hydrophilic fibers, such as wool, cotton or polyamide fibers, and stain or stain them. In addition, the diazo or coupling components that are required for the production of dyes containing carboxylic acid ester groups are not common substances in the large chemical industry, but have to be produced separately for these types of dyes, which is generally uneconomical. The need to use pure white etchable dispersion dyes in the process of etching reserve printing on hydrophobic textile materials under relatively mild etching conditions could therefore not be satisfied by the types of dyes specified above.

worin X¹ ₃ X² und X³ unabhängig voneinander Nitro, Cyan, Alkylsulfonyl mit 1 bis 4 C-Atomen, gegebenenfalls durch Chlor,It has now surprisingly been found that the difficulties in carrying out the etching reserve printing on textile materials which consist entirely or predominantly of hydrophobic synthetic fibers can be overcome by dispersing white dyes and optionally etching-resistant disperse dyes in the form of a Applied dye liquor or printing paste, then the fabric dries or dries and then printed in the desired pattern with an etching reserve printing paste, which optionally contains an etchant-resistant disperse dye in addition to the etchant, if one of the formula 1 as the white-etchable disperse dye

in which X ¹ ₃ X ² and X ³ independently of one another nitro, cyano, alkylsulfonyl having 1 to 4 carbon atoms, optionally by chlorine,

Bromine or methyl substituted phenylsulfonyl, dialkylphosphono with 1 to 4 carbon atoms in each alkyl radical, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy radical which is optionally substituted by hydroxyl, methoxy, ethoxy or methoxyethoxy, aminosulfonyl, alkyl- or dialkylaminosulfonyl with 1 to 4 carbon atoms in the individual alkyl groups which are optionally substituted by hydroxy, methoxy, ethoxy, methoxyethoxy or trifluoromethyl, with the proviso that no more than 2 of the radicals x ^1, x ² or x ³ is A _m i _no - sulfonyl optionally substituted alkyl or dialkylaminosulfonyl, trifluoromethyl, dialkylphosphono having 1 to ₄ carbon atoms in each alkyl radical or alkoxycarbonyl having 1 to 4 carbon atoms in the optionally substituted alkoxy radical; Y ¹ and y2 independently of one another are hydrogen, chlorine, bromine, optionally by hydroxy mono- or disubstituted alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, which is optionally by alkoxycarbonyl having 1 to 4 carbon atoms in the Alkoxy group or can be monosubstituted by hydroxy or can be disubstituted by hydroxy, optionally by hydroxyl mono- or polysubstituted alkoxy having 3 to 8 carbon atoms, the carbon chain of which is interrupted by 1 to 3 oxygen atoms,

Y in addition also —NHCOZ, in which Z represents methyl, ethyl, propyl or i-propyl, which can be substituted by hydroxy, chlorine, bromine, cyano, phenyl or phenoxy or alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy group, Alkyl with 2 to 8 carbon atoms, which is interrupted one to three times by oxygen and can be substituted by hydroxy, phenyl, amino, N-alkylamino with 1 to 4 carbon atoms, R ^{1 is} hydrogen, alkyl with 1 - 4 C atoms by chlorine, bromine, cyan, by alkoxycarbonyl having 1 to 2 C atoms in the alkoxy group optionally substituted by hydroxyl, methoxy, ethoxy, chlorine, bromine or cyan, by alkanoyloxy having 2 to 4 C atoms Phenoxyacetoxy, monosubstituted by alkylaminocarbonyloxy having 1 to 4 carbon atoms in the alkyl group, by phenyl, by phenoxy or hydroxyl or disubstituted by hydroxyl or at the same time substituted by chlorine and hydroxyl or hydroxyl and phenoxy, Alkenyl with 3 to 4 carbon atoms, benzyl, cycloalkyl with 5 or 6 carbon atoms, alkyl with 3 to 8 carbon atoms, the carbon chain of which is interrupted by 1 to 3 oxygen atoms and one or more by hydroxy, chlorine, bromine or cyano can be substituted several times,

R ² alkyl with 1 to 4 carbon atoms, which is monosubstituted by chlorine, bromine, cyan, by alkanoyloxy with 2 to 4 carbon atoms, alkylaminocarbonyloxy with 2 to 4 carbon atoms or hydroxy or disubstituted by hydroxy or simultaneously by chlorine and hydroxy may be substituted, alkenyl having 3 to 4 carbon atoms or alkyl having 3 to 8 carbon atoms, the carbon chain of which is interrupted by 1 to 3 oxygen atoms and may be substituted one or more times by hydroxyl, chlorine, bromine or cyano,

mean, with the proviso that at most one of the radicals X ¹ , X ² , X ³ , Y ¹ , y ² , _R ¹ or _R ² carries an alkoxycarbonyl group having 1 to 4 carbon atoms in the optionally substituted alkoxy radical, and uses one Etching reserve printing paste is used which contains a base as etchant which produces at least a pH of 8 in 5% strength aqueous solution. Alkyl or alkoxy radicals, even if they are part of other radicals, can be straight-chain or branched. In the case of multiple substitution of the alkyl radical with 3 to 8 carbon atoms which stands for R ¹ and / or R ² and whose carbon chain is interrupted by 1 to 3 oxygen atoms, there is in particular a double substitution, especially by 2 OH groups or by an OH Group and a chlorine atom.

Examples of alkyl radicals with 1 to 4 carbon atoms in the alkylsulfonyl and dialkylphosphono substituents which can represent X ¹ ₉ X ² or X ³ are methyl, ethyl, propyl, butyl and i-butyl.

Examples of substituents which can represent Y ¹ are: hydrogen, chlorine, bromine, methyl, ethyl, propyl, i-propyl, n-butyl, butyl-2, i-butyl, t-butyl, hydroxymethyl, a- or β-hydroxyethyl, a-hydroxy-n-propyl, -i-propyl, -n-butyl, -butyl-2 or -i-butyl, dihydroxypropyl; Methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, i-butoxy, sec.-butoxy, ß-hydro xyethoxy, β-hydroxypropoxy, y-hydroxypropoxy, γ-hydroxybutoxy, δ-hydroxybutoxy, β, y-dihydroxypropoxy; Methoxycarbonylmethoxy, ethoxycarbonylmethoxy, 2- (methoxycarbonyl) ethoxy, 2- (propoxycarbonyl) ethoxy; 2- (methoxycarbonyl) propoxy, 2- (methoxycarbonyl) -1-methyl-ethoxy; 2-methoxy-ethoxy, 2-ethoxy-ethoxy, 2-butoxy-ethoxy, 3-methoxy-propoxy, 3-ethoxy-propoxy, 4-methoxy-butoxy, 4-propoxy-butoxy, 2- (ß-hydroxyethoxy) - ethoxy, 2- (ß-methoxyethoxy) ethoxy, 2- (ß-ethoxyethoxy) ethoxy, 9-hydroxy-1,4,7-trioxa-nonyl (= hydroxyethoxyethoxyethoxy), 1,4,7,10-tetraoxa- dodecyl (= ethoxyethoxyethoxyethoxy), 3- (ß-hydroxyethoxy) propoxy, 3- (ß-methoxyethoxy) propoxy, 10-hydroxy-1,5,8-trioxa-decenyl (= 3- (hydroxyethoxyethoxy) propoxy), 1,5,8,11-tetraoxa-tridecyl (= 3- (ethoxyethoxyethoxy) propoxy), 4- (β-hydroxyethoxy) butoxy, 4- (β-ethoxyethoxy) butoxy, 11-hydroxy-1,6, 9-trioxa-undecyl (= 4- (hydroxyethoxy-ethoxy) -butoxy), 1,6,9,12-tetraoxa-tridecyl (= 4- ( _M et _hox y-ethoxyethoxy) -butoxy), 2- (ß, y-dihydroxypropoxy) ethoxy.

Substituents for which Y ² can represent are, for example, hydrogen, chlorine, bromine; Methyl, ethyl, propyl, i-propyl, n-butyl, butyl-2, i-butyl, t-butyl; Hydroxymethyl, a- or β-hydroxyethyl, a-hydroxy-n-propyl, -i-propyl, -butyl, -butyl-2. or -i-butyl; Dihydroxypropyl; Methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, i-butoxy, sec.-butoxy, ß-hydroxy-ethoxy, -propoxy, y-hydroxy-propoxy, -butoxy, δ-hydroxybutoxy, ß, y-dihydroxypropoxy ; Methoxycarbonylmethoxy, propoxycarbonylmethoxy, 2- (methoxycarbonyl) ethoxy, 2- (butoxycarbonyl) ethoxy; 2- (ethoxycarbonyl) propoxy, 2- (methoxycarbonyl) -1-methylethoxy; Methoxyethoxy, 2-ethoxy-ethoxy, 2-propoxy-ethoxy, 3-methoxy-propoxy, 3-propoxy-propoxy, 4-methoxy-butoxy, 4-butoxy-butoxy, 2- (ß-hydroxyethoxy) ethoxy, 2- (ß-methoxyethoxy) ethoxy, 2- (ß-ethoxyethoxy) ethoxy, 9-hydroxy-l, 4,7-trioxa-nonyl (= hydroxyethoxyethoxyethoxy), 1,4,7,10-tetraoxadodecyl ( = Ethoxyethoxyethoxyethoxy), 10-hydroxy-1,5,8-trioxadecenyl (= 3- (hydroxyethoxypropoxy), 3- (ß-ethoxyethoxy) propoxy, 10-hydroxy-1,5,8-trioxadecenyl (= 3- (hydroxyethoxyethoxy) propoxy), 1,5,8,11-tetraoxetridecyl (= 3- (ethoxyethoxyethoxy) propoxy), 4- (ß-hydroxyethoxy) butoxy, 4- (ß-ethoxy - ethoxy) butoxy, 11-hydroxy-1,6,9-trioxa-undecyl (= 4- (Hyd _r oxy-ethoxyethoxy) butoxy), 1,6,9,12-tetraoxa-tridecyl (= 4- (meth - oxyethoxyethoxy) butoxy), 2- (β-dihydroxypropoxy) ethoxy; Acetylamino, n-propionylamino, n-butyrylamino, i-butyrylamino; Chlorine, bromine, cyano, hydroxy, methoxycarbonyl, ethoxycarbonyl, phenyl, phenoxyacetylamino; 2- or 3-chloro, 2- or 3-bromo, 2- or 3-cyano or 2- or 3-hydroxypropionylamino, 3- (methoxycarbonyl) propionylamino; 2-chloro, 2-bromo, 2-cyano or 2-hydroxy-n- or -i-butyrylamino; Methoxy- or ethoxyacetylamino, 2- or 3-methoxy- or 2- or 3-ethoxy-propionylamino, 2-methoxy- or 2-butoxy-, n- or i-butyrylamino; Hydroxy, methoxy or propoxyethoxyacetylamino, 2- or 3-hydroxy, methoxy or butoxyethoxypropionylamino; Hydroxy, ethoxy or propoxyethoxyethoxyacetylamino, 3-hydroxy-n- or i-propoxyethoxyethoxypropionylamino; 2,3-dihydroxypropoxy acetylamino; 3- (2,3-dihydroxypropoxy) propionylamino; Benzoylamino; Aminocarbonylamino; Methyl, ethyl, propyl, i-propyl, butyl, sec-butyl or i-butylaminocarbonylamino.

Alkyl radicals for which R ¹ and / or R ^{2 can} stand are, for example, methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, sec-butyl; 2-chloro, 2-bromo or 2-cyanoethyl; 2- or 3-chloro, bromine or cyanopropyl; 2-, 3- or 4-chloro, bromine or cyanobutyl; 2,3-dihydroxypropyl, 2-hydroxy-3-chloropropyl; 2-acetoxy-, 2-propionyloxy- or 2-butyryloxyethyl, 2- or 3-acetoxy-, - propionyloxy- or-butyryloxypropyl, 3- or 4-acetoxy-, - propionyloxy- or-butyryloxy-butyl; Methyl, ethyl, propyl or butyl aminocarbonyloxethyl, methyl, ethyl, propyl or butyl aminocarbonyloxyprop-3-yl, methyl, ethyl, propyl or butyl aminocarbonyloxybut-4-yl; 2-hydroxyethyl, 2- or 3-hydroxypropyl, hydroxypropyl-2, 2-, 3- or 4-hydroxybutyl, 1-, 3- or 4-hydroxybutyl-2; Allyl; Methallyl, crotyl; Methoxy, ethoxy, propoxy or butoxyethyl, prop-3-yl, but-4-yl, but-3-yl or but-2-yl; Hydroxy-, methoxy-, propoxy- or butoxy-ethoxyethyl, -pro-3-yl, -but-4-yl, -but-3-yl or -but2-yl, hydroxy-, methoxy-, Ethoxyethoxyethoxy-ethyl, prop-3-yl, -but-4-yl, _{-but-3-y l} or - _bu t-2-yl; 2,3-dihydroxypropoxy-ethyl, _-prop-3- y _l, -buty _l - ₄ -y _l, -but-3-yl, -but-2-yl; 2-hydroxy-3-chloro-p _ro poxy-ethyl; 2-hydroxy-3-methoxypropyl, _{2-hydroxy-3-ethox} y-propyl, 2-hydroxy-3-butoxy-propyl, _{2-hydroxy-3-methoxy-ethox} y _- propyl, _2-hydroxy-3- ethoxyethoxypropyl, 2-hydroxy-3- (3-methoxypropoxy) propyl, 2-hydroxy-3- (4-ethoxybutoxy) propyl.

R ¹ can furthermore be, for example: benzyl, phenethyl, phenoxyethyl, prop-3-yl, but-4-yl, but-3-yl or but-2-yl; Cyclohexyl, cyclopentyl; Methoxy, ethoxy, propoxy, hydroxyethoxy, chloroethoxy or methoxyethoxycarbonylethyl, carbonyl-1-methylethyl or carbonyl-2-methylethyl; 2-acetoxy, 2-propionyloxy or 2-butyryloxyethyl, 2- or 3-acetoxy, propionyloxy or butyryloxy propyl, 3- or 4-acetoxy, propionyloxy or butyryloxy butyl.

Bases which are contained in the etching reserve printing paste as etching agents and which produce at least a pH of 8 in 5% aqueous solution are known in large numbers. Examples of such bases are the hydroxides of the alkali and alkaline earth metals, salts of alkaline earth and alkali metals with weak organic or inorganic acids, such as, for example, alkali acetate, alkali metal carbonates or bicarbonates, trialkali phosphates, ammonia or else aliphatic amines, such as, for example, triethyl or tripropyl or tributylamine, ethanolamine, dinethyl- or diethylethanolamine, diethanolamine, methyl-, ethyl- or propyl-diethanolamine or triethanolamine. Alkaline earth metal hydroxides such as calcium hydroxide, alkali metal hydroxides such as sodium or potassium hydroxide, or alkali metal salts of weak inorganic acids such as sodium carbonate or trisodium phosphate are usually used as bases. Sodium or potassium hydroxide or is preferably used as the base in the etching reserve printing pastes especially sodium or potassium carbonate or sodium or potassium bicarbonate used. Mixtures of different bases can also be used. The concentration of the base in the etching reserve printing pastes is expediently 25 to 250 g / kg, preferably 50 to 130 g / kg. In addition to the bases mentioned, the etching reserve printing pastes contain the usual additives contained in textile printing pastes, in particular thickeners such as alginates, starch products, synthetic polymeric thickeners, mineral oils, hydrotropic substances such as urea, as well as additives which promote wetting, penetration and dye absorption. The presence of nonionic detergents which are expediently contained in the etching reserve printing pastes, such as, for example, glycerol and / or polyglycols, such as polyethylene glycol with an average molecular weight of 300 to 400, is particularly favorable for the etching process.

• X¹:Methoxy- oder Ethoxycarbonyl, Cyan oder Nitro. Falls X³ Alkoxycarbonyl mit 1 bis 4 C-Atomen im Alkoxyrest, der gegebenenfalls durch Hydroxy, Methoxy, Ethoxy oder Methoxyethoxy substituiert sein kann, bedeutet, kann X¹ vorzugsweise auch Methyl- oder Ethylsulfonyl oder Trifluormethyl sein.
• X²:Nitro oder Cyan. Falls X 3 Alkoxycarbonyl mit 1 bis 4 C-Atomen im Alkoxyrest, der gegebenenfalls durch Hydroxy, Methoxy, Ethoxy oder Methoxyethoxy, substituiert sein kann, bedeutet, kann x² vorzugsweise auch Methyl- oder Ethylsulfonyl sein.
• X³:Alkylsulfonyl mit 1 bis 4 C-Atomen, gegebenenfalls durch Chlor, Brom oder Methyl substituiertes Phenylsulfonyl, Cyan, Nitro, Alkoxycarbonyl mit 1 bis 4 C-Atomen im Alkoxyrest, der gegebenenfalls durch Hydroxy, Methoxy, Ethoxy oder Methoxyethoxy substituiert ist oder Aminosulfonyl oder Alkylaminosulfonyl mit 1 bis 4 C-Atomen, dessen Alkylgruppe gegebenenfalls durch Hydroxy, Methoxy, Ethoxy oder Methoxyethoxy substituiert sein kann.

The dyes of the formula I preferably have the following radicals:

• X ¹ : methoxy or ethoxycarbonyl, cyan or nitro. If X ^{3 is} alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, which may optionally be substituted by hydroxy, methoxy, ethoxy or methoxyethoxy, X ^{1 can} preferably also be methyl or ethylsulfonyl or trifluoromethyl.
• X ² : nitro or cyan. If X 3 is alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, which may optionally be substituted by hydroxyl, methoxy, ethoxy or methoxyethoxy, x ^{2 can} preferably also be methyl or ethylsulfonyl.
• X ³ : alkylsulfonyl having 1 to 4 carbon atoms, optionally substituted by chlorine, bromine or methyl, phenylsulfonyl, cyano, nitro, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, which is optionally substituted by hydroxy, methoxy, ethoxy or methoxyethoxy or Aminosulfonyl or alkylaminosulfonyl with 1 to 4 carbon atoms, the alkyl group of which may be hydroxyl, methoxy, ethoxy or Methoxyethoxy can be substituted.

It is particularly preferred to use those dyes of the formula I which carry the preferred radicals indicated above for 2 or 3 of the substituents of X ¹ , _X ² , X ³ , but at most one radical of X ¹ , X ² or X ³ _Alk - oxycarbonyl may be.

Preferred combinations X ¹ / X ² are nitro / methyl or ethylsulfonyl, nitro / trifluoromethyl, cyano / methyl or ethylsulfonyl, methylsulfonyl / methylsulfonyl, ethylsulfonyl / ethylsulfonyl.

Very particularly preferred combinations X ¹ / X ² are nitro / cyan, nitro / nitro, nitro / methoxy or ethoxycarbonyl, cyan / cyan.

Preferred combinations X ¹ / X ² / X ³ are methylsulfonyl / methylsulfonyl / alkoxycarbonyl, ethylsulfonyl / ethylsulfonyl / alkoxycarbonyl and nitro / methyl or ethylsulfonyl / alkoxycarbonyl, the alkoxy radical of the alkoxycarbonyl group carrying optionally substituted 1 to 4 carbon atoms.

Very particularly preferred combinations of X ¹ / X ² / X ³ are _N it _{ro /} Cyan / Nitro, Nitro / nitro / Nitro, Nitro / Nitro / cyano, nitro / methoxy or ethoxycarbonyl / Nitro, Nitro / Cyan / optionally substituted alkoxycarbonyl, Nitro / nitro / optionally substituted alkoxycarbonyl, cyan / cyan / optionally substituted alkoxycarbonyl, nitro / nitro / aminosulfonyl or optionally substituted alkylaminosulfonyl, nitro / cyan / amino- or optionally substituted alkylaminosulfonyl or cyan / cyan / amino- or optionally substituted alkylaminosulfonyl.

A further preferred group of dyes of the formula I comprises those dyes which are in the radicals R1 and / or _R ² and / or in the alkyl or alkoxy radicals which are Y1 or _Y ² and / or in the alkyl radicals which are Z stand, carry one or more hydroxyl groups. Are particularly preferred the 2-hydroxyethyl and the 2,3-dihydroxypropyl radical. Dyes in which the radicals R ¹ and / or R ² and / or the alkyl or alkoxy radicals which represent Y ¹ , Y ² or Z are also particularly preferred for (CH ₂ ) _m (OCH ₂ CH ₂ ) _n OH stand, where m can take the values 2 to 4 and n can take the values 1 to 3, the values for m and n being chosen so that the group contains a maximum of 8 carbon atoms.

Further preferred radicals for R ¹ and R ² are alkyl radicals with 3 to 8 carbon atoms, for Z alkyl radicals with 2 to 8 carbon atoms and for Y ¹ and Y ² alkoxy radicals with 3 to 8 carbon atoms, the carbon chain of the alkyl - and alkoxy radicals interrupted by 1 to 3 oxygen atoms and optionally substituted by hydroxy. Preferred dyes are also dyes of the general formula I which carry alkoxycarbonylalkyl groups in the radicals R ¹ , Y ¹ , Y and Z. Alkoxycarbonyl-methyl, alkoxycarbonyl-ethyl or alkoxycarbonyl-methylethyl radicals are particularly preferred for R ¹ and alkoxycarbonyl- or alkoxycarbonyl-alkyl having 1 to 4 carbon atoms in the alkyl group for Z. Alkoxy radicals in the alkoxycarbonylalkyl groups which stand for R ¹ or Z are preferably methoxy, ethoxy, i-propoxy, n-propoxy, methoxyethoxy or ethoxyethoxy.

The process according to the invention is preferably suitable for textile materials which consist of hydrophobic fibers, in particular polyester fibers. However, it is also suitable for textile materials that predominantly use hydrophobic fibers alongside other fibers, e.g. Cell or cotton.

The white-etchable disperse dyes of the formula I can be applied to the textile material in the form of liquors or printing pastes. The textile material is impregnated with the dye liquor in a manner known per se, for example padded or splashed. The dye liquors can be one or more disperse dyes of the formula 1 in addition to the known dyeing aids, such as dispersing agents agents, wetting agents, foam suppressants and block aids. The impregnated fabric web is squeezed to a liquor absorption of 50 to 120%. The fabric webs are then dried by warm air with any preceding infrared radiation, the temperature being approximately 80 ° C., maximum approximately 90 ° C. with a corresponding reduction in time. The fabric webs prepared in this way are then printed with an etching reserve printing paste which contains one of the bases specified in more detail above as an etching agent and the known additives, in particular thickening agents, which are customary in printing pastes for textile printing. The impregnated and printed fabric webs are then subjected to a heat treatment between 100 and 230 ° C. In the lower temperature range of approximately 100 to 110 ^° C., the heat is preferably supplied by superheated steam. For heat treatments that are carried out between 160 and 230 ° C, hot air is preferably used as the heat transfer medium. After the heat treatment, which results in the disperse dyes of the formula I being fixed at the points not overprinted with the etching reserve printing paste and the destruction of the disperse dyes in the formula 1 at the points printed with the etching reserve printing paste, the textiles are post-treated in the manner customary for polyester , rinsed hot and cold and dried.

A particular embodiment of the process according to the invention consists in that the dye liquor contains, in addition to dispersion dyes of the formula I, one or more dispersion dyes which are alkali-resistant and are therefore not destroyed by the alkaline etching reserve printing pastes to be used according to the invention. If one proceeds as above, then multicolored designs are obtained.

As already mentioned, the disperse dyes of the formula I can also be printed onto the fabric in the form of printing pastes and then overprinted with the etching reserve printing paste. The textile prints are then fixed and finished as described above. With this method, too, it is possible to add one or more disperse dyes which are alkali-resistant to the color printing paste printed first, which can also contain several disperse dyes of the formula I. In this case too, multi-colored designs are obtained. A further possibility for carrying out the process according to the invention is that etching reserve printing pastes which in turn contain alkali-resistant disperse dyes are printed on the fund impregnated or printed with disperse dyes of the formula I. With subsequent fixation and completion of the textile materials as described above, multicolored designs are also obtained here.

oder

oder

oder

worin X Wasserstoff oder ein Metallkation, insbesondere das Natriumkation, und Hal Halogen, insbesondere Chlor oder Brom, bedeuten und gegebenenfalls einen oder mehrere ätzbeständige Reaktivfarbstoffe enthält und wenn die Ätzreservedruckpaste neben Alkalicarbonat oder Alkalihydrogencarbonat ein Alkalisulfit oder Alkalihydrogensulfit und gegebenenfalls einen Aldehyd enthält und wenn im übrigen wie bereits angegeben gearbeitet wird.According to the method according to the invention, etching reserve prints can be applied not only to textile materials which consist of hydrophobic fibers, in particular polyester fibers, or predominantly contain such fibers, but also to textile materials which contain hydrophobic fibers, in particular polyester fibers, and cellulose fibers in comparable proportions. Such polyester / cellulose blended fabrics can have, for example, a weight ratio of polyester / cellulose of 75:25, 65:35 or 50:50. The application of etching reserve prints to such blended fabrics by the process according to the invention is possible if the dye liquor or printing paste, which contains at least one white-etchable disperse dye of the formula I and optionally one or more etch-resistant disperse dyes, also contains at least one etchable reactive dye with a reactive residue of formula

or

or

or

in which X is hydrogen or a metal cation, in particular the sodium cation, and Hal is halogen, in particular chlorine or bromine, and optionally contains one or more etch-resistant reactive dyes and if the etching reserve printing paste contains an alkali metal sulfate or alkali metal hydrogen carbonate and optionally an aldehyde, and if not otherwise, in addition to alkali metal carbonate or alkali metal hydrogen carbonate work as already stated.

The etchable reactive dyes to be used contain one of the above-mentioned fiber-reactive radicals of the formulas II to V. The radicals of the formulas II to IV have in common that they are in the presence of alkali with the elimination of a sulfate or Halide anion form a vinylsulfonyl group. This group formed in the presence of alkali fixes on cotton or cellulose in the same way as the vinylsulfonyl radical of the formula V bonded directly to the dye radical by adding an OH group of the cellulose to the vinyl double bond. Etchable reactive dyes which have one of the reactive radicals mentioned above can belong to all technically important dye groups. Examples of suitable reactive dyes are the monoazo dyes CI-Yellow 13 to 17 and 72 to 74, -Orange 7, 15, 16, 23, 24, 55, -Red 21 to 23, 35 36, 50, 63, 103 to 107, 112 to 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 as etchable reactive dyes are those which contain at least one fiber-reactive radical of the formulas III or IV as reactive anchor.

The amounts of the disperse and reactive dyes which are contained in the padding liquors or printing pastes in the treatment of mixed fabrics are, as usual, matched to the depth of color of the desired color and intensity of the reactive 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 dyeing of a certain color shade, in the case that the mixed fabric 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 dispersion dyes and in the case that the substrate predominantly Contains polyester fibers, a high proportion or only disperse dyes and a low proportion or no reactive dyes.

If, in carrying out the method according to the invention, the padding liquor or printing paste in addition to one or more etchable disperse dyes of the formula I also contains one or more etchable reactive dyes with reactive radicals of the formulas II to V, an etching reserve printing paste is used which, in addition to alkali carbonate or alkali hydrogen carbonate, also contains an alkali sulfite or alkali hydrogen sulfite as a reservation agent for the reactive dyes. 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. Aldehydes which may 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, 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 total of the reservation agents in the printing pastes is expediently 25 to 250 g / kg, preferably 50 to 130 g / kg.

Apart from the different composition of the padding liquor or printing paste and the etching reserve printing paste, the process steps in the production of etching reserve prints on polyester / cellulose blended fabrics are the same as in the treatment of fabrics which consist of polyester or predominantly contain polyester. However, in the production of etching reserve prints on polyester / cellulose blended fabrics after padding or printing on the fabric, drying or drying and then overprinting with the etching reserve printing paste, it is advisable to subject the padded and printed textile fabrics to heat treatment between 100 and 190 ° C and the heat is preferably supplied by superheated steam. The heat treatment a) inhibits the etchable dispersion and reactive dyes at the points printed with the etching reserve printing paste and fixes any non-reservable dispersion and reactive dyes that are present, b) fixes the dispersion dyes at the points not printed with etching reserve printing paste, and, if so the padding liquor or printing paste contained an alkali metal formate, and at the same time a fixation of the reactive dyes. Inhibition of the dye is to be understood here as meaning 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, i.e. if the padding liquor or printing paste did not contain any alkali metal formate, the reactive dyes are then fixed in the base coloring, i.e. in the areas not printed with etching reserve printing paste, in a manner known per se. Finally, the dyeings or prints on the blended fabrics are rinsed hot and cold and dried.

A particular embodiment of the process according to the invention on blended fabrics consists in that the padding liquor or printing paste contains, in addition to etchable disperse and reactive dyes, additionally etch-resistant disperse and reactive dyes, which are therefore those used according to the invention Etching reserve printing pastes cannot be destroyed. If one proceeds as above, then multicolored designs are obtained. A further possibility for carrying out the process according to the invention in mixed fabrics is that etching reserve printing pastes are printed on the fund, which are sealed or printed with reservable dyes, which in turn contain dispersing and reactive dyes which are resistant to the reservation agent. With subsequent fixation and completion of the textile materials as described above, multicolored designs are also obtained here.

The application of the white-etchable disperse dyes of the formula I to the fabric by impregnation with a padding liquor is preferred.

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 which may be present are dissolved. The padding liquors or printing pastes which are to be used in the process 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 formulations of the disperse dyes and solutions or formulations of reactive dyes.

Alkali-resistant. Disperse dyes, which can be combined with the 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 alkali-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-oxäthyl- aminotriazin, 2,6-Dichlor-4-phenylaminotriazin, 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-Dichlor- phthalazin-6-carbonsäurechlorid, 5,6-Dichlor-4-methyl-2-methylsulfonyl-pyrimidin, 2- oder 3-Monochlorchinoxalin-G-carbonsäurechlorid oder -6-sulfonsäurechlorid, 2,3-Di- chlorchinoxalin-6-carbonsäurechlorid oder -6-sulfonsäurechlorid, l,4-Dich-lorphthalazin-6-carbonsäurechlorid oder -6-sulfonsäurechlorid, 2,4-Dichlorchinazolin-6- oder -7-carbonsäurechlorid oder -sulfonsäurechlorid, 2-Chlorbenz- thiazol-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 resistant to the reservation agent, which can be combined with the etchable reactive dyes to produce multicolored designs on polyester / cellulose blended fabrics, are the known commercial dyes from the group of azo or azomethine, quinophthalone, nitro or anthraquinone dyes, which are fiber-reactive The rest contain one from the class of triazines, quinoxalines, phthalazines, pyridazines, pyrimidines or the α, β-unsaturated aliphatic carboxylic acids. The most important compounds from which the fiber-reactive residues of the 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-dichloro-4-phenylaminotriazine, 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-G-carboxylic acid chloride or -6-sulfonic acid chloride, 2,3- Dechloroquinoxaline-6-carboxylic 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-chlorine orbenz-thiazole-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.

Most of the disperse dyes of the formula I to be used according to the invention are e.g. from German Offenlegungsschriften 12 90 915, 17 19 066, 18 09 920, 19 62 402, French Patents 145 833, 865 904, 816 950 and 1 465 508 and from Journal of the Chemical Society, Perkin I, 1979, p. 2634, known.

in dem X¹ Chlor, Brom, Nitro, Cyan, Alkylsulfonyl mit 1 bis 4 C-Atomen oder Phenylsulfonyl und X ² Chlor oder Brom bedeuten, diazotiert und auf ein Amin der Formel VII

kuppelt und in dem so erhaltenen Farbstoff der Formel VIII

in dem X¹ Chlor, Brom, Nitro, Cyan, Alkylsulfonyl mit 1 bis ₄ C-Atomen oder Phenylsulfonyl und X² Chlor oder Brom bedeuten, den für Chlor oder Brom stehenden Rest gegen Cyan, Nitro, Alkylsulfonyl mit 1 bis 4 C-Atomen, Arylsulfonyl oder Dialkylphosphono mit 1 bis 4 C-Atomen im Alkylrest eintauscht. Der Austausch gegen Cyan ist beschrieben in den deutschen Offenlegungsschriften 12 90 915, 19 62 402. Der Austausch gegen _Nitro ist beschrieben in den deutschen Offenlegungsschriften 19 62 402, 18 09 920, 18 07 642. Der Austausch gegen Alkyl/ Arylsulfonyl ist beschrieben in den deutschen Offenlegungsschriften 19 62 402, 29 05 274. Der Austausch gegen Dialkylphosphono ist beschrieben in Journal of the Chemical Society, Perkin 1,1979, Seite 2634.The disperse dyes of the formula I can be prepared in a manner known per se by diazotization and coupling, as described, for example, in Swiss patent 615 938 or in German patent application 16 44 144. Some of the disperse dyes of the general formula I can also be prepared in a manner known per se so that an amine of the formula VI

in which X ^{1 is} chlorine, bromine, nitro, cyano, alkylsulfonyl having 1 to 4 carbon atoms or phenylsulfonyl and X ^{2 is} chlorine or bromine, diazotized and on an amine of the formula VII

couples and in the dye of formula VIII thus obtained

in which X ^{1 is} chlorine, bromine, nitro, cyan, alkylsulfonyl having 1 to ₄ carbon atoms or phenylsulfonyl and X ^{2 is} chlorine or bromine, the radical representing chlorine or bromine is cyan, nitro, alkylsulfonyl having 1 to 4 carbon atoms , Arylsulfonyl or Dialkylphosphono with 1 to 4 carbon atoms in the alkyl radical. The exchange for cyan is described in German Offenlegungsschriften 12 90 915 19 62 402 is the substitution with _N itro described in German Offenlegungsschriften 19 62 402 18 09 920 18 07 642. The exchange alkyl / arylsulfonyl described in German Offenlegungsschriften 19 62 402, 29 05 274. The exchange for dialkylphosphono is described in Journal of the Chemical Society, Perkin 1,1979, page 2634.

Unless otherwise stated, parts in the examples below are parts by weight and percentages by weight.

example 1

werden in feiner Verteilung zu einer Klotzflotte gegeben, die 905 Teile Wasser, 5 Teile Citronensäure und 60 Teile eines Polymerisationsprodukts auf Acrylsäurebasis als Antimigrationsmittel auf 1000 Teile enthält. Mit dieser Klotzflotte wird ein Gewebe aus Polyester auf der Basis von Polyethylenglykolterephthalat bei 20 bis 30°C mit einem Abquetscheffekt von ca. 80 % geklotzt. Das geklotzte Gewebe wird bei 60 bis 80°C vorsichtig getrocknet. Nach dem Trocknen wird mit einer Druckpaste, die 500 Teile einer wäßrigen 10 %igen Johanniskernmehlätherverdickung, 260 Teile Wasser, 80 Teile calciniertes Natriumcarbonat, 80 Teile Polyethylenglykol 400 und 80 Teile Glycerin auf 1000 Teile enthält, überdruckt. Nach dem Fixieren mit überhitztem Dampf während 7 Minuten bei 175°C, reduktivem Nachbehandeln, Seifen, anschließendem Spülen und Trocknen erhält man einen blauen Druck mit sehr guten Echtheiten, vor allem guter Licht-, Trockenhitzefixier-, Reib- und Waschechtheit. An den Stellen, auf die die sodahaltige Druckpaste aufgedruckt wird, erhält man einen sehr guten Weißfond mit scharfen Konturen.10 parts of the dye of the formula

are added in finely divided form to a padding liquor which contains 905 parts of water, 5 parts of citric acid and 60 parts of an acrylic acid-based polymerization product as an anti-migration agent per 1000 parts. This padding liquor is used to pad a polyester fabric based on polyethylene glycol terephthalate at 20 to 30 ° C with a squeezing effect of approx. 80%. The padded fabric is carefully dried at 60 to 80 ° C. After drying is overprinted with a printing paste containing 500 parts of an aqueous 10% St. John's wort ether thickener, 260 parts of water, 80 parts of calcined sodium carbonate, 80 parts of polyethylene glycol 400 and 80 parts of glycerol per 1000 parts. After fixing with superheated steam for 7 minutes at 175 ° C, reductive post-treatment, soaps closing rinsing and drying gives a blue print with very good fastness properties, especially good light, dry heat fixation, rub and wash fastness. At the points on which the soda-containing printing paste is printed, you get a very good white ground with sharp contours.

Example 2

verwendet und im übrigen so verfahren, wie im Beispiel 1 angegeben. Man erhält einen blauen Druck mit sehr guten coloristischen Eigenschaften, insbesondere guter Licht-, Trockenhitzefixier-, Reib- und Waschechtheit und an den geätzten Stellen einen sehr guten Weißfond mit scharfen Konturen.Instead of the dye in Example 1, 20 parts of the dye

used and otherwise proceed as indicated in Example 1. A blue print is obtained with very good coloristic properties, in particular good fastness to light, dry heat fixation, rubbing and washing, and a very good white background with sharp contours at the etched areas.

Example 3

verwendet und im übrigen so verfahren, wie im Beispiel 1 angegeben. Man erhält einen roten Druck mit sehr guten coloristischen Eigenschaften, insbesondere guter Licht-, Trockenhitzefixier-, Reib- und Waschechtheit und einen sehr guten Weißfond mit scharfen Konturen.Instead of the dye in Example 1, 20 parts of the dye of the formula

used and otherwise proceed as indicated in Example 1. You get a red print with very good coloristic properties, especially good light, dry heat fixation, rub and wash fastness and a very good white background with sharp contours.

Example 4

Instead of the dye in Example 1, 30 parts of the Dye of the formula

used and otherwise proceed as indicated in Example 1. You get a reddish blue print with very good coloristic properties, especially with good light, dry heat fixation, rub and wash fastness and very good white background with sharp contours.

Example 5

verwendet und im übrigen so verfahren, wie im Beispiel 1 angegeben. Man erhält einen orangefarbenen Druck mit sehr guten coloristischen Eigenschaften, insbesondere guter Licht-, Trockenhitzefixier-, Reib- und Waschechtheit und sehr gutem Weißfond mit scharfen Konturen.Instead of the dye in Example 1, 20 parts of the dye of the formula

used and otherwise proceed as indicated in Example 1. An orange-colored print is obtained with very good coloristic properties, in particular good light, dry heat fixation, rub and wash fastness and very good white background with sharp contours.

Example 6

40 Teilen der flüssigen Handelsform von CI Reactive Blue 122, 808 Teilen kaltem Wasser, 10 Teilen m-nitrobenzolsulfonsaurem Natrium, 20 Teilen eines Antimigriermittels auf Polyacrylsäurebasis, 2 Teilen Mononatriumphosphat, 20 Teilen Natriumformiat.A mercerized mixed fabric of polyester / cotton 65:35 is padded with a batch consisting of 100 parts of a 20% liquid setting of the dye of the formula

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

It is carefully dried in a hot flue at 80-100 ° C. and overprinted in film printing using a printing paste made from 25 parts of the commercial form of 1 - [- (3,6-dichloropyridazin-4-yl-carbonylamino) -2-methyl-3 -sulfopheny17-3-carboxyl-4- (2-sulfophenyl-azo) -5-pyrazolone- (5), 40 parts of the liquid commercial form of CI Disperse Yellow 63, 150 parts of urea, 199 parts of cold water, 10 parts of m-nitrobenzenesulfonic acid Sodium, 500 parts stock thickening, 40 parts sodium bicarbonate, 30 parts sodium bisulfite solution 38 ° Bé, 6 parts 40% glyoxal solution. The stock thickener consists of 230 parts of an aqueous 4% alginate thickener, 80 parts of an aqueous 10% starch ether thickener, 85 parts of water, 25 parts of an aqueous 10% solution of the condensation product of polyglycol 2000 with stearic acid and 80 parts of heavy gasoline.

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

You get yellow colored effects on a blue floor.

If, in Examples 1 to 6, instead of the disperse dyes specified there, equivalent amounts of the disperse dyes specified in the table below are used, etching reserve prints with very good coloristic properties are also obtained.

TABLE

Claims (10)

1. Process for the production of etching reserve prints on textile materials which consist of hydrophobic fibers, preferably polyester fibers, or contain such fibers in a mixture with cellulose fibers, a white etchable disperse dye and optionally an etch-resistant disperse dye in the form of a liquor or printing paste being applied to the textile material and then dried or is dried and then printing on an etching reserve printing paste, which optionally contains one or more etching-resistant dyes in addition to the etching agent, in the desired pattern and subsequent heat treatment at temperatures of 100 to 230 ° C, characterized in that one of the formula I as the white-etchable disperse dye

wherein X ¹ , X ² and x ³ independently of one another nitro, cyano, alkylsulfonyl having 1 to 4 carbon atoms, optionally by chlorine, Bromine or methyl-substituted phenylsulfonyl, dialkylphosphono having 1 to 4 carbon atoms in each alkyl radical, alkoxycarbonyl with 1 to 4 C atoms in the alkoxy group, the gege- _b enenfalls is substituted by hydroxy, methoxy, ethoxy or methoxyethoxy, aminosulfonyl, alkyl or dialkylaminosulfonyl having 1 to 4 carbon atoms in the individual alkyl groups, which are optionally substituted by hydroxy, methoxy, ethoxy, methoxyethoxy or trifluoromethyl, with the proviso that at most 2 of the radicals X ¹ ₂ X ² or X ³ for _Am i _no - sulfonyl, optionally substituted alkyl or dialkylamino sulfonyl, trifluoromethyl, dialkylphosphono having 1 to 4 carbon atoms in each alkyl radical or alkoxycarbonyl having 1 to 4 carbon atoms in the optionally substituted alkoxy radical; Y ¹ and Y ² independently of one another are hydrogen, chlorine, bromine, optionally mono- or disubstituted alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, which is optionally substituted by alkoxycarbonyl having 1 to 4 carbon atoms the alkoxy group or may be monosubstituted by hydroxyl or may be disubstituted by hydroxyl, optionally by hydroxyl mono- or polysubstituted alkoxy having 3 to 8 carbon atoms, the carbon chain of which is interrupted by 1 to 3 oxygen atoms, ^y2 additionally also —NHCOZ, in which Z for methyl, ethyl, propyl or i-propyl, which can be substituted by hydroxy, chlorine, bromine, cyano, phenyl or phenoxy or alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy group, alkyl with 2 to 8 carbon atoms , which is interrupted one to three times by oxygen and can be substituted by hydroxy, is phenyl, amino, N-alkylamino having 1 to 4 carbon atoms, R ^{1 is} hydrogen, alkyl having 1 to 4 carbon atoms, which is substituted by chlorine, Bromine, cyan, by alkoxyc arbonyl with 1 to 2 carbon atoms in the alkoxy group optionally substituted by hydroxy, methoxy, ethoxy, chlorine, bromine or cyano, by alkanoyloxy with 2 to 4 carbon atoms, by phenoxyacetoxy, by alkylaminocarbonyloxy with 1 to 4 carbon atoms in the Alkyl group, monosubstituted by phenyl, by phenoxy or hydroxyl or disubstituted by hydroxyl or at the same time substituted by chlorine and hydroxyl or hydroxyl and phenoxy, Alkenyl with 3 to 4 carbon atoms, benzyl, cycloalkyl with 5 or ₆ carbon atoms, alkyl with 3 to 8 carbon atoms, the carbon chain of which is interrupted by 1 to 3 oxygen atoms and one or more by hydroxy, chlorine, bromine or cyano can be substituted several times, _R ² alkyl having 1 to 4 carbon atoms, which is monosubstituted by chlorine, bromine, cyano, by alkanoyloxy having 2 to 4 carbon atoms, alkylaminocarbonyloxy having 2 to 4 carbon atoms or hydroxy or disubstituted by hydroxy or can be substituted at the same time by chlorine and hydroxy, alkenyl having 3 to 4 carbon atoms or alkyl having 3 to 8 carbon atoms, the carbon chain of which is interrupted by 1 to 3 oxygen atoms and substituted one or more times by hydroxyl, chlorine, bromine or cyano can be, with the proviso that at most one of the radicals X ¹ , X ² , X ³ , Y ¹ ₂ Y ² , R ¹ or R ² carries an alkoxycarbonyl group having 1 to 4 carbon atoms in the optionally substituted alkoxy radical, uses and uses an etching reserve printing paste, di e contains a base as etchant which produces at least a pH of 8 in 5% aqueous solution. 2. The method according to claim 1, characterized in that the base used is alkali metal carbonate or bicarbonate, in particular sodium carbonate. 3. Process according to claims 1 or 2, characterized in that in the case of polyester / cellulose blended fabrics, the padding liquor or printing paste additionally contains at least one etchable reactive dye with a reactive radical of the formula

or

or

or

wherein X is hydrogen or a metal cation, in particular _N sodium cation, and Hal is halogen, especially chlorine or bromine, and optionally one or more ätzbest _ä nd _i g _e reactive dyes, and in that a discharge resist printing paste is used, a next one alkali metal carbonate or alkali metal hydrogencarbonate Contains alkali sulfite or alkali hydrogen sulfite and optionally an aldehyde. _4th A method according to claim 3, characterized in that the heat treatment is carried out at temperatures from 100 to 110 ° C. 5. Process according to claims 1 to 4, characterized in that the textile material is impregnated with a padding liquor. 6. The method according to claims 1 to 5, characterized in that a dye of formula I is used in which X ^{1 is} methoxy or ethoxycarbonyl, cyano, nitro or, if X ³ for alkoxycarbonyl having 1 to 4 carbon atoms in optionally alkoxy radical substituted by hydroxy, methoxy or methoxyethoxy, also means methyl- or ethylsulfonyl or trifluoromethyl. 7. The method according to claims 1 to 6, characterized in that a dye of formula I is used in which X2 is _nitro , cyano or, if _X ³ for alkoxycarbonyl having 1 to 4 carbon atoms in optionally by hydroxy, methoxy or methoxyethoxy substituted alkoxy radical, also means methyl- or ethylsulfonyl. 8. The method according to claims 1 to 7, characterized in that a dye of formula I is used in which X ³ nitro, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, which is optionally substituted by hydroxy, methoxy, ethoxy or methoxyethoxy can be aminosulfonyl or alkylaminosulfonyl with 1 to 4 carbon atoms in the alkyl group, which may be replaced by hydroxyl, methoxy, ethoxy or methoxy may be ethoxy substituted, alkylsulfonyl having 1 to 4 carbon atoms, phenylsulfonyl or cyano optionally substituted by chlorine, bromine or methyl. 9. The method according to claims 1 to 8, characterized in that a dye of formula I is used in which X ¹ and X ² independently of one another are nitro or cyano and X ³ alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, which, if appropriate is substituted by hydroxy, methoxy, ethoxy or methoxyethoxy. 10. The method according to claims 1 to 9, characterized in that a dye of formula I is used in which X ¹ and X ^{2 are} independently nitro or cyano and X ³ nitro, aminosulfonyl or alkylaminosulfonyl having 1 to 4 carbon atoms in the alkyl group which is optionally substituted by hydroxy, methoxy, ethoxy or methoxyethoxy.