EP0293745A2 - Process for the production of discharge prints - Google Patents
Process for the production of discharge prints Download PDFInfo
- Publication number
- EP0293745A2 EP0293745A2 EP88108362A EP88108362A EP0293745A2 EP 0293745 A2 EP0293745 A2 EP 0293745A2 EP 88108362 A EP88108362 A EP 88108362A EP 88108362 A EP88108362 A EP 88108362A EP 0293745 A2 EP0293745 A2 EP 0293745A2
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- optionally substituted
- cyano
- textile material
- alkyl
- phenyl
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/15—Locally discharging the dyes
- D06P5/17—Azo dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/12—Reserving parts of the material before dyeing or printing ; Locally decreasing dye affinity by chemical means
Definitions
- the present invention relates to a new process for producing etching prints on synthetic textile material, wherein the textile material is treated with a thiophenazo dye and alkaline printing paste in any order and the textile material treated in this way is then steamed and washed.
- etching prints on synthetic textile material by means of alkaline compounds is known per se and is described for example in GB-A-1 543 724 or GB-A-2 071 707.
- the etchable disperse dyes used in this process often have shortcomings.
- the object of the present invention was to provide a new method for producing etching prints, by means of which the etching prints are obtained in an advantageous manner.
- etching prints on synthetic textile material by treating the textile material with dye and alkaline printing paste in any order and then steaming and washing the treated textile material advantageously succeeds if the textile material with thiopheneazo dyes of the formula I treated in the X cyano, nitro, C1-C4 alkanoyl, benzoyl or C1-C4 alkoxycarbonyl, Y halogen, hydroxy, mercapto, optionally substituted by phenyl C1-C6-alkoxy, C5-C7-cycloalkoxy, optionally substituted phenoxy, optionally substituted by phenyl C1-C6-alkylthio, C5-C7-cycloalkylthio, optionally substituted phenylthio, C1-C6 Alkylsulfonyl or optionally substituted phenylsulfonyl, Z is C1-C4-alkyl, chlorine, bromine, nitro,
- alkyl radicals which are interrupted by one or more oxygen atoms occur in the abovementioned formula I, those radicals which are interrupted by one to three, in particular one or two, oxygen atoms are preferred.
- X and Z are, for example, formyl, acetyl, propionyl, butyryl or isobutyryl.
- Z also stands for example for methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.
- X is furthermore, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl or isobutoxycarbonyl.
- B1 and B2 are still z. B.
- pentyloxycarbonyl isopentyloxycarbonyl, sec-pentyloxycarbonyl, hexyloxycarbonyl, 2-methoxyethoxycarbonyl, 2-ethoxyethoxycarbonyl, 2-butoxyethoxycarbonyl, allyloxycarbonyl, methallyloxycarbonyl, Ethyl allyloxycarbonyl, 4-methylphenyl, 2-ethoxyphenyl, 4-chlorophenyl or 2,4-dichlorophenyl.
- B1 and B2 like Y and Z, furthermore represent, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, or butylsulfonyl.
- Y furthermore represents fluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, hexyloxy, benzyloxy, 1- or 2-phenylethoxy, cyclopentyloxy , Cyclohexyloxy, cycloheptyloxy, 4-methylphenoxy, 4-isopropylphenoxy, 4-methoxyphenoxy, 4-bromophenoxy, methylthio, ethylthio, isopropylthio, benzylthio, 2-phenylethylthio, cyclohexylthio, 4-chlorophenylthio, pentylsulfonyl, isopentylsulfonylsulfylylsulfonylsulfonylsulfony
- B3 stands for example for methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.
- R2 stands for example for methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, benzyl, 1- or 2-phenylethyl, cyclopentyl, cyclohexyl , 2-methylcyclohexyl, cycloheptyl, C2H4OH, CH2-CHOH-CH3, CH2-CHOH-C2H5, CH (CH3) -CH2OH, CH2CH2-CH2OH, CH (C2H5) -CH2OH, C2H4OCOCH3, C2H4OCOC2H5, C2HCHOCH5OCH COCH , C2H4OCOOC4H9, C2H4OCONH-C3H7, C2H4OCONHC4H9, C2H4OCONHC6
- R1, like R2, is for example CH2-COOCH3, CH2-COOC2H5, CH2COOC3H7, CH2COOC4H9 (n), CH2COOCH2-CH (CH3) 2, C2H4COOCH3, C2H4COOC2H5, C2H4COOC3H7, C2H4COOCH (CH3) 2, C2H C2H4COOC6H11, C2H4COOCH2C6H5, C2H4COOC2H4C6H5, C2H4COOC2H4OC6H5, C2H4COOC2H4OCH3, C2H4COOC2H4OC2H5, C2H4COOC2H4OC4H9, CH (CH (CH)
- R3 is substituted C1-C6-alkanoylamino
- z. B chlorine, cyano, hydroxy, C1-C4-alkoxy, phenoxy or C1-C4-alkoxycarbonyl.
- Residues R3 are in addition to those already mentioned, for example NHCOCH3, NHCOC2H5, NHCOC3H7, NHCOCH2OCH3, NHCOCH2OC2H5, NHCOCH2OC6H5, NHCOCH2OH, NHCOCH2OCOCH3, NHCOCH2Cl, NHCOCH2CN or NHCOC2H4OCH3.
- Preferred is a procedure in which the textile material is treated with thiopheneazo dyes of the formula I in which X cyano or C1-C4 alkoxycarbonyl Y chlorine, bromine, C1-C4alkoxy, phenoxy, C1-C4alkylthio, phenylthio or phenylsulfonyl, Z formyl, cyano, nitro or a group of the formula -CH CB1B2, where B1 and B2 are identical or different and are each independently cyano or C1-C4-alkoxycarbonyl, R1 C1-C4 alkoxycarbonylethyl and R2 is C2-C4-hydroxyalkyl, C1-C4-alkanoyloxy-C2-C4-alkyl or C1-C4-alkoxycarbonylethyl and R3 and R4 each have the meaning given above.
- thiopheneazo dyes of the formula I in which X cyano or C1-C2 alkoxycarbonyl, Y chlorine, bromine, ethoxy, phenylthio or phenylsulfonyl, especially chlorine, Z formyl or cyano, especially formyl, R1 C1-C4 alkoxycarbonylethyl, R2 C2-C4-hydroxyalkyl, C1-C4-alkanoyloxy-C2-C4-alkyl or C1-C4-alkoxycarbonylethyl, in particular C1-C4-alkoxycarbonylethyl, R3 is hydrogen, methyl, methoxy, chlorine, acetylamino or benzoylamino R4 signify hydrogen, methoxy or ethoxy.
- the dyes used in the process according to the invention are known per se and are described, for example, in EP-A-201 896 or DE-A-3 535 133.
- the synthetic textile material used is based on polyacrylonitrile, polyamide or polyester, textile material based on polyester being preferred.
- the process according to the invention is generally carried out in such a way that the textile material is treated either first with the thiopheneazo dye of the formula I and then with an alkaline printing paste or first with the alkaline printing paste and then with the thiopheneazo dye of the formula I.
- the treatment of the textile material with the dye is always carried out over the entire surface, while the alkaline printing paste, expediently with the aid of a stencil, is only applied to those areas of the textile material which should ultimately be free from thiopheneazo dye.
- the dye is first applied to the textile material, this is expediently carried out by padding and subsequent drying (for example 60 to 90 seconds) at a temperature of, for example, 80 to 100 ° C.
- the alkaline printing paste is then printed on and then dried at a temperature of, for example, 80 to 100.degree.
- the dye is printed immediately afterwards, also expediently in the form of a printing paste, the so-called background printing paste.
- rapid drying e.g. 60 to 120 sec
- the alkaline printing paste generally contains, in addition to water, alkaline agents, thickeners, solubilizers, glycerol and optionally other auxiliaries, e.g. Wetting or dispersing agent.
- alkaline agent z. B alkali metal hydroxides, alkali metal carbonates or alkali metal bicarbonates.
- the lithium, sodium or potassium salts should be mentioned in particular.
- Tetraalkylammonium hydroxides, such as tetraethylammonium hydroxide, are also suitable as alkaline agents.
- Thickeners are usually those based on polysaccharides, e.g. B. galactomannans, alginates, xanthans or carboxymethylated polysaccharides, or also based on polyacrylic acid derivatives.
- Polyethylene glycol with a molecular weight of 200 to 600 is mainly used as a solubilizer.
- the dye is also printed in the form of a printing paste, this contains, in addition to the dye and water, also the thickeners already mentioned and an acid donor (usually citric acid) and optionally other auxiliaries, e.g. Wetting or dispersing agent.
- an acid donor usually citric acid
- auxiliaries e.g. Wetting or dispersing agent.
- the steaming process takes place.
- the textile material is treated with superheated steam at a temperature of approx. 160 to 190 ° C. This treatment usually lasts for 5 to 10 minutes.
- the thiophenazo dye is converted into a water-soluble compound at the points which have both dye and alkaline printing paste by the influence of the alkaline agent, which is removed from the textile material in the subsequent washing process, which usually contains a reductive cleaning.
- a padding liquor which contained 925 ml of water, 8 g of monosodium phosphate, 7 g of sodium chlorate and 10 g of a polymerization product based on acrylic acid as an anti-migration agent. It was padded on a two-roll foulard with a liquor intake of 70%.
- a printing paste which contained 275 g of a 10% strength by weight starch ether, 275 g of a 10% strength alginate thickener, 80 g potash, 75 g polyethylene glycol (molecular weight 300), 75 g glycerol and 220 ml water was used. overprinted. After drying at 90-100 ° C was fixed for 7 minutes at 175 ° C with superheated steam, then reductively cleaned, rinsed and dried.
- a polyester fabric was printed with a printing paste which contained 300 g of a 10% by weight starch ether thickener, 300 g of a 10% by weight core meal ether thickener, 80 g soda, 80 g polyethylene glycol (molecular weight 400) and 240 ml water with a patterned flat film printing stencil.
- a second stencil which is completely open, was overprinted with a printing paste containing 50 g of the dye of the formula in dispersed form, 2 g of citric acid, 550 g of a 10% by weight alginate thickener and 398 ml of water.
Abstract
Description
Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung von Ätzdrucken auf synthetischem Textilmaterial, wobei man das Textilmaterial mit einem Thiophenazofarbstoff und alkalisch wirkender Druckpaste in beliebiger Reihenfolge behandelt und das so behandelte Textilmaterial anschließend dämpft und wäscht.The present invention relates to a new process for producing etching prints on synthetic textile material, wherein the textile material is treated with a thiophenazo dye and alkaline printing paste in any order and the textile material treated in this way is then steamed and washed.
Die Herstellung von Ätzdrucken auf synthetischem Textilmaterial mittels alkalischen Verbindungen ist an sich bekannt und beispielsweise in der GB-A-1 543 724 oder GB-A-2 071 707 beschrieben. Die bei diesem Verfahren verwendeten ätzbaren Dispersionsfarbstoffe weisen allerdings häufig Mängel auf.The production of etching prints on synthetic textile material by means of alkaline compounds is known per se and is described for example in GB-A-1 543 724 or GB-A-2 071 707. However, the etchable disperse dyes used in this process often have shortcomings.
Aufgabe der vorliegenden Erfindung war es, ein neues Verfahren zur Herstellung von Ätzdrucken bereitzustellen, mittels dessen die Ätzdrucke in vorteilhafter Weise erhalten werden.The object of the present invention was to provide a new method for producing etching prints, by means of which the etching prints are obtained in an advantageous manner.
Es wurde nun gefunden, daß die Herstellung von Ätzdrucken auf synthetischem Textilmaterial durch Behandlung des Textilmaterials mit Farbstoff und alkalisch wirkender Druckpaste in beliebiger Reihenfolge und anschließendem Dämpfen und Waschen des behandelten Textilmaterials vorteilhaft gelingt, wenn man das Textilmaterial mit Thiophenazofarbstoffen der Formel I
X Cyano, Nitro, C₁-C₄-Alkanoyl, Benzoyl oder C₁-C₄-Alkoxycarbonyl,
Y Halogen, Hydroxy, Mercapto, gegebenenfalls durch Phenyl substituiertes C₁-C₆-Alkoxy, C₅-C₇-Cycloalkoxy, gegebenenfalls substituiertes Phenoxy, gegebenenfalls durch Phenyl substituiertes C₁-C₆-Alkylthio, C₅-C₇-Cycloalkylthio, gegebenenfalls substituiertes Phenylthio, C₁-C₆-Alkylsulfonyl oder gegebenenfalls substituiertes Phenylsulfonyl,
Z C₁-C₄-Alkyl, Chlor, Brom, Nitro, Cyano, C₁-C₄-Alkanoyl, Benzoyl, C₁-C₄-Alkylsulfonyl, Phenylsulfonyl oder eine Gruppe der Formel -CH=CB¹B² oder -CH=N-B³, wobei B¹ und B² gleich oder verschieden sind und unabhängig voneinander jeweils für Cyano, C₁-C₆-Alkoxycarbonyl, dessen Alkylkette gegebenenfalls durch ein oder mehrere Sauerstoffatome unterbrochen ist, oder C₃-C₆-Alkenyloxycarbonyl oder ein Rest B¹ oder B² für Cyano und der andere für C₁-C₄-Alkylsulfonyl, gegebenenfalls substituiertes Phenyl, Benzoyl, Phenylsulfonyl oder Carbamoyl und B³ für Hydroxy, C₁-C₄-Alkoxy, Phenoxy oder Phenylamino stehen,
R¹ den Rest A-COOB⁴, wobei A für C₁-C₄-Alkylen und B⁴ für C₁-C₆-Alkyl, das gegebenenfalls durch ein oder mehrere Sauerstoffatome unterbrochen und/oder durch Phenyl substituiert ist, C₅-C₇-Cycloalkyl oder Phenyl stehen,
R² den Rest R¹, Wasserstoff, gegebenenfalls durch Phenyl substituiertes C₁-C₆-Alkyl, C₅-C₇-Cycloalkyl oder C₂-C₄-Alkyl, das durch Hydroxy, C₁-C₄-Alkanoyloxy, gegebenenfalls substituiertes Benzoyl, C₁-C₄-Alkoxycarbonyloxy, C₁-C₄-Mono-oder Dialkylaminocarbonyloxy oder gegebenenfalls substituiertes Phenylaminocarbonyloxy substituiert ist,
R³ Wasserstoff, Methyl, Methoxy, Chlor, gegebenenfalls substituiertes C₁-C₆-Alkanoylamino oder Benzoylamino und
R⁴ Wasserstoff, Methyl, Methoxy oder Ethoxy bedeuten.It has now been found that the production of etching prints on synthetic textile material by treating the textile material with dye and alkaline printing paste in any order and then steaming and washing the treated textile material advantageously succeeds if the textile material with thiopheneazo dyes of the formula I
X cyano, nitro, C₁-C₄ alkanoyl, benzoyl or C₁-C₄ alkoxycarbonyl,
Y halogen, hydroxy, mercapto, optionally substituted by phenyl C₁-C₆-alkoxy, C₅-C₇-cycloalkoxy, optionally substituted phenoxy, optionally substituted by phenyl C₁-C₆-alkylthio, C₅-C₇-cycloalkylthio, optionally substituted phenylthio, C₁-C₆ Alkylsulfonyl or optionally substituted phenylsulfonyl,
Z is C₁-C₄-alkyl, chlorine, bromine, nitro, cyano, C₁-C Alk-alkanoyl, benzoyl, C₁-C₄-alkylsulfonyl, phenylsulfonyl or a group of the formula -CH = CB¹B² or -CH = N-B³, where B¹ and B² are the same or different and are each independently cyano, C₁-C₆-alkoxycarbonyl, the alkyl chain of which may be interrupted by one or more oxygen atoms, or C₃-C₆-alkenyloxycarbonyl or a radical B¹ or B² is cyano and the other is C₁-C₄-alkylsulfonyl, optionally substituted phenyl, benzoyl, phenylsulfonyl or carbamoyl and B³ is hydroxy, C₁-C₄-alkoxy, phenoxy or phenylamino,
R¹ is the radical A-COOB⁴, where A is C₁-C₄-alkylene and B⁴ is C₁-C₆-alkyl which is optionally interrupted by one or more oxygen atoms and / or is substituted by phenyl, C₅-C₇-cycloalkyl or phenyl,
R² is R¹, hydrogen, optionally substituted by phenyl C₁-C₆-alkyl, C₅-C₇-cycloalkyl or C₂-C₄-alkyl, which by hydroxy, C₁-C₄-alkanoyloxy, optionally substituted benzoyl, C₁-C₄-alkoxycarbonyloxy, C₁ -C₄-mono- or dialkylaminocarbonyloxy or optionally substituted phenylaminocarbonyloxy is substituted,
R³ is hydrogen, methyl, methoxy, chlorine, optionally substituted C₁-C₆ alkanoylamino or benzoylamino and
R⁴ signify hydrogen, methyl, methoxy or ethoxy.
Alle in den obigen Resten auftretenden Alkyl- und Alkenylgruppen können sowohl geradekettig als auch verzweigt sein.All alkyl and alkenyl groups occurring in the above radicals can be both straight-chain and branched.
Für den Fall, daß in der obengenannten Formel I substituierte Phenylreste auftreten, kommen als Substituenten z. B. C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Halogen, insbesondere Chlor oder Brom, in Betracht.In the event that substituted phenyl radicals occur in the above formula I, z. B. C₁-C₄ alkyl, C₁-C₄ alkoxy or halogen, especially chlorine or bromine, into consideration.
Für den Fall, daß in der obengenannten Formel I Alkylreste auftreten, die durch ein oder mehrere Sauerstoffatome unterbrochen sind, sind solche Reste bevorzugt, die durch ein bis drei, insbesondere ein oder zwei Sauerstoffatome unterbrochen sind.In the event that alkyl radicals which are interrupted by one or more oxygen atoms occur in the abovementioned formula I, those radicals which are interrupted by one to three, in particular one or two, oxygen atoms are preferred.
X und Z stehen beispielsweise für Formyl, Acetyl, Propionyl, Butyryl oder Isobutyryl.X and Z are, for example, formyl, acetyl, propionyl, butyryl or isobutyryl.
Z steht weiterhin beispielsweise für Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl oder sec-Butyl.Z also stands for example for methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.
X steht weiterhin, ebenso wie B¹ und B², beispielsweise für Methoxycarbonyl, Ethoxycarbonyl, Propoxycarbonyl, Isopropoxycarbonyl, Butoxycarbonyl oder Isobutoxycarbonyl.
B¹ und B² stehen weiterhin z. B. für Pentyloxycarbonyl, Isopentyloxycarbonyl, sec-Pentyloxycarbonyl, Hexyloxycarbonyl,2-Methoxyethoxycarbonyl, 2-Ethoxyethoxycarbonyl, 2-Butoxyethoxycarbonyl, Allyloxycarbonyl, Methallyloxycarbonyl, Ethylallyloxycarbonyl, 4-Methylphenyl, 2-Ethoxyphenyl, 4-Chlorphenyl oder 2,4-Dichlorphenyl.X, like B¹ and B², is furthermore, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl or isobutoxycarbonyl.
B¹ and B² are still z. B. for pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, hexyloxycarbonyl, 2-methoxyethoxycarbonyl, 2-ethoxyethoxycarbonyl, 2-butoxyethoxycarbonyl, allyloxycarbonyl, methallyloxycarbonyl, Ethyl allyloxycarbonyl, 4-methylphenyl, 2-ethoxyphenyl, 4-chlorophenyl or 2,4-dichlorophenyl.
B¹ und B² stehen weiterhin, ebenso wie Y und Z, beispielsweise für Methylsulfonyl, Ethylsulfonyl, Propylsulfonyl, Isopropylsulfonyl, oder Butylsulfonyl.B¹ and B², like Y and Z, furthermore represent, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, or butylsulfonyl.
Y steht weiterhin für Fluor, Chlor, Brom, Methoxy, Ethoxy, Propoxy, Isopropoxy, Butoxy, Isobutoxy, sec-Butoxy, Pentyloxy, Isopentyloxy, sec-Pentyloxy, tert-Pentyloxy, Hexyloxy, Benzyloxy, 1- oder 2-Phenylethoxy, Cyclopentyloxy, Cyclohexyloxy, Cycloheptyloxy, 4-Methylphenoxy, 4-Isopropylphenoxy, 4-Methoxyphenoxy, 4-Bromphenoxy, Methylthio, Ethylthio, Isopropylthio, Benzylthio, 2-Phenylethylthio, Cyclohexylthio, 4-Chlorphenylthio, Pentylsulfonyl, Isopentylsulfonyl, Hexylsulfonyl oder 4-Methylphenylsulfonyl.Y furthermore represents fluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, hexyloxy, benzyloxy, 1- or 2-phenylethoxy, cyclopentyloxy , Cyclohexyloxy, cycloheptyloxy, 4-methylphenoxy, 4-isopropylphenoxy, 4-methoxyphenoxy, 4-bromophenoxy, methylthio, ethylthio, isopropylthio, benzylthio, 2-phenylethylthio, cyclohexylthio, 4-chlorophenylthio, pentylsulfonyl, isopentylsulfonylsulfylylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulphonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsyl or sulfonylsulfonylsulfonyl.
B³ steht beispielsweise für Methoxy, Ethoxy, Propoxy, Isopropoxy, Butoxy, Isobutoxy oder sec-Butoxy.B³ stands for example for methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.
R² steht beispielsweise für Methyl, Ethyl, Propyl, Isopropyl, Butyl, Isobutyl, sec-Butyl, tert-Butyl, Pentyl, Isopentyl, sec-Pentyl, tert-Pentyl, Hexyl, Benzyl, 1- oder 2-Phenylethyl, Cyclopentyl, Cyclohexyl, 2-Methylcyclohexyl, Cycloheptyl, C₂H₄OH, CH₂-CHOH-CH₃, CH₂-CHOH-C₂H₅, CH(CH₃)-CH₂OH, CH₂CH₂-CH₂OH, CH(C₂H₅)-CH₂OH, C₂H₄OCOCH₃, C₂H₄OCOC₂H₅, C₂H₄OCOC₆H₅, C₂H₄OCOOCH₃, C₂H₄OCOOC₂H₅, C₂H₄OCOOC₃H₇, C₂H₄OCOOC₄H₉, C₂H₄OCONH-C₃H₇, C₂H₄OCONHC₄H₉, C₂H₄OCONHC₆H₅, CH₂-CH(CH₃)OCOCH₃, CH₂CH(CH₃)OCOC₂H₅, CH₂CH(C₂H₅)OCOCH₃, CH₂CH(C₂H₅)OCOC₂H₅, CH(CH₃)CH₂OCOCH₃, CH(CH₃)CH₂OCOC₂H₅, CH(C₂H₅)CH₂OCOCH₃ oder CH(C₂H₅)CH₂OCOC₂H₅.
R¹ steht, ebenso wie R², beispielsweise für
CH₂-COOCH₃, CH₂-COOC₂H₅, CH₂COOC₃H₇, CH₂COOC₄H₉(n), CH₂COOCH₂-CH(CH₃)₂, C₂H₄COOCH₃, C₂H₄COOC₂H₅, C₂H₄COOC₃H₇, C₂H₄COOCH(CH₃)₂, C₂H₄COOC₄H₉(n), C₂H₄COOCH₂CH(CH₃)₂, C₂H₄COOC₆H₁₃, C₂H₄COOC₆H₅, C₂H₄COOC₆H₁₁, C₂H₄COOCH₂C₆H₅, C₂H₄COOC₂H₄C₆H₅, C₂H₄COOC₂H₄OC₆H₅, C₂H₄COOC₂H₄OCH₃, C₂H₄COOC₂H₄OC₂H₅, C₂H₄COOC₂H₄OC₄H₉, CH(CH₃)CH₂COOCH₃, CH(CH₃)CH₂COOC₂H₅, CH(CH₃)CH₂COOC₄H₉ oder CH(CH₃)CH₂COOC₂H₄OC₂H₅.R² stands for example for methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, benzyl, 1- or 2-phenylethyl, cyclopentyl, cyclohexyl , 2-methylcyclohexyl, cycloheptyl, C₂H₄OH, CH₂-CHOH-CH₃, CH₂-CHOH-C₂H₅, CH (CH₃) -CH₂OH, CH₂CH₂-CH₂OH, CH (C₂H₅) -CH₂OH, C₂H₄OCOCH₃, C₂H₄OCOC₂H₅, C₂HCHOCH₅OCH COCH , C₂H₄OCOOC₄H₉, C₂H₄OCONH-C₃H₇, C₂H₄OCONHC₄H₉, C₂H₄OCONHC₆H₅, CH₂-CH (CH₃) OCOCH₃, CH₂CH (CH₃) OCOC₂H₅, CH₂CH (C₂H₅) OCOCH₃, CH₂CH (C₂H₅ (C₂H₅) CH₂OCOCH₃ or CH (C₂H₅) CH₂OCOC₂H₅.
R¹, like R², is for example
CH₂-COOCH₃, CH₂-COOC₂H₅, CH₂COOC₃H₇, CH₂COOC₄H₉ (n), CH₂COOCH₂-CH (CH₃) ₂, C₂H₄COOCH₃, C₂H₄COOC₂H₅, C₂H₄COOC₃H₇, C₂H₄COOCH (CH₃) ₂, C₂H C₂H₄COOC₆H₁₁, C₂H₄COOCH₂C₆H₅, C₂H₄COOC₂H₄C₆H₅, C₂H₄COOC₂H₄OC₆H₅, C₂H₄COOC₂H₄OCH₃, C₂H₄COOC₂H₄OC₂H₅, C₂H₄COOC₂H₄OC₄H₉, CH (CH (CH)
Für den Fall, daß R³ für substituiertes C₁-C₆-Alkanoylamino steht, kommen als Substituenten z. B. Chlor, Cyano, Hydroxy, C₁-C₄-Alkoxy, Phenoxy oder C₁-C₄-Alkoxycarbonyl in Betracht.In the event that R³ is substituted C₁-C₆-alkanoylamino, z. B. chlorine, cyano, hydroxy, C₁-C₄-alkoxy, phenoxy or C₁-C₄-alkoxycarbonyl.
Reste R³ sind im einzelnen neben den bereits genannten, beispielsweise NHCOCH₃, NHCOC₂H₅, NHCOC₃H₇, NHCOCH₂OCH₃, NHCOCH₂OC₂H₅, NHCOCH₂OC₆H₅, NHCOCH₂OH, NHCOCH₂OCOCH₃, NHCOCH₂Cl, NHCOCH₂CN oder NHCOC₂H₄OCH₃.Residues R³ are in addition to those already mentioned, for example NHCOCH₃, NHCOC₂H₅, NHCOC₃H₇, NHCOCH₂OCH₃, NHCOCH₂OC₂H₅, NHCOCH₂OC₆H₅, NHCOCH₂OH, NHCOCH₂OCOCH₃, NHCOCH₂Cl, NHCOCH₂CN or NHCOC₂H₄OCH₃.
Bevorzugt ist eine Verfahrensweise, in der man das Textilmaterial mit Thiophenazofarbstoffen der Formel I behandelt, in der
X Cyano oder C₁-C₄-Alkoxycarbonyl
Y Chlor, Brom, C₁-C₄-Alkoxy, Phenoxy, C₁-C₄-Alkylthio, Phenylthio oder Phenylsulfonyl,
Z Formyl, Cyano, Nitro oder eine Gruppe der Formel -CH=CB¹B², wobei B¹ und B² gleich oder verschieden sind und jeweils unabhängig voneinander für Cyano oder C₁-C₄-Alkoxycarbonyl stehen,
R¹ C₁-C₄-Alkoxycarbonylethyl und
R² C₂-C₄-Hydroxyalkyl, C₁-C₄-Alkanoyloxy-C₂-C₄-alkyl oder C₁-C₄-Alkoxycarbonylethyl bedeuten und
R³ und R⁴ jeweils die obengenannte Bedeutung besitzen.Preferred is a procedure in which the textile material is treated with thiopheneazo dyes of the formula I in which
X cyano or C₁-C₄ alkoxycarbonyl
Y chlorine, bromine, C₁-C₄alkoxy, phenoxy, C₁-C₄alkylthio, phenylthio or phenylsulfonyl,
Z formyl, cyano, nitro or a group of the formula -CH = CB¹B², where B¹ and B² are identical or different and are each independently cyano or C₁-C₄-alkoxycarbonyl,
R¹ C₁-C₄ alkoxycarbonylethyl and
R² is C₂-C₄-hydroxyalkyl, C₁-C₄-alkanoyloxy-C₂-C₄-alkyl or C₁-C₄-alkoxycarbonylethyl and
R³ and R⁴ each have the meaning given above.
Insbesondere bevorzugt ist eine Verfahrensweise, in der man das Textilmaterial mit Thiophenazofarbstoffen der Formel I behandelt, in der
X Cyano oder C₁-C₂-Alkoxycarbonyl,
Y Chlor, Brom, Ethoxy, Phenylthio oder Phenylsulfonyl, insbesondere Chlor,
Z Formyl oder Cyano, insbesondere Formyl,
R¹ C₁-C₄-Alkoxycarbonylethyl,
R² C₂-C₄-Hydroxyalkyl, C₁-C₄-Alkanoyloxy-C₂-C₄-alkyl oder C₁-C₄-Alkoxycarbonylethyl, insbesondere C₁-C₄-Alkoxycarbonylethyl,
R³ Wasserstoff, Methyl, Methoxy, Chlor, Acetylamino oder Benzoylamino
R⁴ Wasserstoff, Methoxy oder Ethoxy bedeuten.Particularly preferred is a procedure in which the textile material is treated with thiopheneazo dyes of the formula I in which
X cyano or C₁-C₂ alkoxycarbonyl,
Y chlorine, bromine, ethoxy, phenylthio or phenylsulfonyl, especially chlorine,
Z formyl or cyano, especially formyl,
R¹ C₁-C₄ alkoxycarbonylethyl,
R² C₂-C₄-hydroxyalkyl, C₁-C₄-alkanoyloxy-C₂-C₄-alkyl or C₁-C₄-alkoxycarbonylethyl, in particular C₁-C₄-alkoxycarbonylethyl,
R³ is hydrogen, methyl, methoxy, chlorine, acetylamino or benzoylamino
R⁴ signify hydrogen, methoxy or ethoxy.
Die im erfindungsgemäßen Verfahren verwendeten Farbstoffe sind an sich bekannt und beispielsweise in der EP-A-201 896 oder der DE-A-3 535 133 beschrieben.The dyes used in the process according to the invention are known per se and are described, for example, in EP-A-201 896 or DE-A-3 535 133.
Als synthetisches Textilmaterial dient solches auf Basis von Polyacrylnitril, Polyamid oder Polyester, wobei Textilmaterial auf Basis von Polyester bevorzugt ist.The synthetic textile material used is based on polyacrylonitrile, polyamide or polyester, textile material based on polyester being preferred.
Das erfindungsgemäße Verfahren wird im allgemeinen so durchgeführt, daß das Textilmaterial entweder zunächst mit dem Thiophenazofarbstoff der Formel I und dann mit alkalisch wirkender Druckpaste oder zunächst mit der alkalisch wirkenden Druckpaste und dann mit dem Thiophenazofarbstoff der Formel I behandelt wird.The process according to the invention is generally carried out in such a way that the textile material is treated either first with the thiopheneazo dye of the formula I and then with an alkaline printing paste or first with the alkaline printing paste and then with the thiopheneazo dye of the formula I.
Die Behandlung des Textilmaterials mit dem Farbstoff erfolgt dabei immer über die gesamte Oberfläche, während die alkalisch wirkende Druckpaste, zweckmäßig mit Hilfe einer Schablone, nur auf diejenigen Stellen des Textilmaterials aufgebracht wird, die am Ende frei von Thiophenazofarbstoff sein sollen.The treatment of the textile material with the dye is always carried out over the entire surface, while the alkaline printing paste, expediently with the aid of a stencil, is only applied to those areas of the textile material which should ultimately be free from thiopheneazo dye.
Für den Fall, daß zunächst der Farbstoff auf das Textilgut aufgebracht wird, geschieht dies zweckmäßig durch Aufklotzen und anschließendem Trocknen (z.B. 60 bis 90 sec) bei einer Temperatur von beispielsweise 80 bis 100°C. Danach erfolgt das Aufdrucken der alkalisch wirkenden Druckpaste mit anschließendem Trocknen bei einer Temperatur von beispielsweise 80 bis 100°C.In the event that the dye is first applied to the textile material, this is expediently carried out by padding and subsequent drying (for example 60 to 90 seconds) at a temperature of, for example, 80 to 100 ° C. The alkaline printing paste is then printed on and then dried at a temperature of, for example, 80 to 100.degree.
Für den Fall, daß zunächst die alkalisch wirkende Druckpaste auf das Textilgut aufgedruckt wird, wird direkt anschließend der Farbstoff, zweckmäßig ebenfalls in Form einer Druckpaste, der sogenannten Fonddruckpaste, aufgedruckt. Danach erfolgt ein schnelles Trocknen (z.B. 60 bis 120 sec) bei einer Temperatur von beispielsweise 90 bis 120°C.In the event that the alkaline printing paste is first printed onto the textile material, the dye is printed immediately afterwards, also expediently in the form of a printing paste, the so-called background printing paste. This is followed by rapid drying (e.g. 60 to 120 sec) at a temperature of, for example, 90 to 120 ° C.
Die alkalisch wirkende Druckpaste enthält im allgemeinen neben Wasser alkalische Mittel, Verdickungsmittel, Lösungsvermittler, Glycerin sowie gegebenenfalls weitere Hilfsmittel, z.B. Netz- oder Dispergiermittel.The alkaline printing paste generally contains, in addition to water, alkaline agents, thickeners, solubilizers, glycerol and optionally other auxiliaries, e.g. Wetting or dispersing agent.
Als alkalische Mittel dienen z. B. Alkalihydroxide, Alkalicarbonate oder Alkalihydrogencarbonate. Insbesondere sind dabei die Lithium-, Natrium-oder Kaliumsalze zu nennen. Auch Tetraalkylammoniumhydroxide, wie Tetraethylammoniumhydroxid, sind als alkalische Mittel geeignet.As an alkaline agent z. B. alkali metal hydroxides, alkali metal carbonates or alkali metal bicarbonates. The lithium, sodium or potassium salts should be mentioned in particular. Tetraalkylammonium hydroxides, such as tetraethylammonium hydroxide, are also suitable as alkaline agents.
Verdickungsmittel sind meist solche auf Polysaccharidbasis, z. B. Galactomannane, Alginate, Xanthane oder carboxymethylierte Polysaccharide, oder auch auf Basis von Polyacrylsäurederivaten.Thickeners are usually those based on polysaccharides, e.g. B. galactomannans, alginates, xanthans or carboxymethylated polysaccharides, or also based on polyacrylic acid derivatives.
Als Lösungsvermittler dient überwiegend Polyethylenglykol mit einem Molekulargewicht von 200 bis 600.Polyethylene glycol with a molecular weight of 200 to 600 is mainly used as a solubilizer.
Für den Fall daß der Farbstoff ebenfalls in Form einer Druckpaste aufgedruckt wird, enthält diese neben dem Farbstoff und Wasser ebenfalls die bereits genannten Verdickungsmittel sowie einen Säurespender (üblicherweise Zitronensäure) und gegebenenfalls weitere Hilfsmittel, z.B. Netz- oder Dispergiermittel.In the event that the dye is also printed in the form of a printing paste, this contains, in addition to the dye and water, also the thickeners already mentioned and an acid donor (usually citric acid) and optionally other auxiliaries, e.g. Wetting or dispersing agent.
Nachdem das zu bedruckende Textilgut sowohl mit Farbstoff als auch mit alkalisch wirkender Druckpaste behandelt ist, erfolgt der Dämpfprozess. Dabei wird das Textilgut bei einer Temperatur von ca. 160 bis 190°C mit Heißdampf behandelt. Diese Behandlung erstreckt sich üblicherweise über einen Zeitraum von 5 bis 10 Minuten.After the textile to be printed has been treated with both dye and alkaline printing paste, the steaming process takes place. The textile material is treated with superheated steam at a temperature of approx. 160 to 190 ° C. This treatment usually lasts for 5 to 10 minutes.
Während des Dämpfprozesses wird an denjenigen Stellen, die sowohl Farbstoff als auch alkalisch wirkende Druckpaste aufweisen, der vorliegende Thiophenazofarbstoff durch den Einfluß des alkalischen Mittels in eine wasserlösliche Verbindung übergeführt, die beim anschließenden Waschprozeß, der üblicherweise eine reduktive Reinigung enthält, vom Textilmaterial entfernt wird.During the steaming process, the thiophenazo dye is converted into a water-soluble compound at the points which have both dye and alkaline printing paste by the influence of the alkaline agent, which is removed from the textile material in the subsequent washing process, which usually contains a reductive cleaning.
Die folgenden Beispiele sollen die Erfindung näher erläutern.The following examples are intended to explain the invention in more detail.
50 g des Farbstoffs der Formel
Es resultierte ein blauer Druck mit guten Echtheiten und mit einem an den geätzten Stellen sehr guten Weißfond mit scharfen Konturen.The result was a blue print with good fastness properties and with a very good white background with sharp contours at the etched areas.
Man bedruckte ein Polyestergewebe mit einer Druckpaste, die 300 g einer 10 gew.%igen Stärkeetherverdickung, 300 g einer 10 gew.%igen Kernmehletherverdickung, 80 g Soda, 80 g Polyethylenglykol (Molgewicht 400) und 240 ml Wasser enthielt mit einer gemusterten Flachfilmdruckschablone. Im gleichen Arbeitsgang wurde mit einer zweiten Schablone, die vollflächig offen ist, mit einer Druckpaste überdruckt, die 50 g des Farbstoffs der Formel
Nach einer Zwischentrocknung bei 80°C wurde 6 Minuten bei 180°C mit überhitztem Dampf fixiert, danach reduktiv gereinigt, gespült und getrocknet.After an intermediate drying at 80 ° C was fixed for 6 minutes at 180 ° C with superheated steam, then reductively cleaned, rinsed and dried.
Man erhielt einen marineblauen Druck mit guten Echtheiten, der an den mit der sodahaltigen Druckpaste vorgedruckten Stellen weiße Muster mit scharfem Stand aufweist.A navy-blue print with good fastness properties was obtained, which has white patterns with a sharp stand at the areas pre-printed with the printing paste containing soda.
Analog den Beispielen 1 und 2 erhält man ebenfalls durch Alkali weißätzbare Drucke mit sehr guten coloristischen Eigenschaften, wenn die in der folgenden Tabelle aufgeführten Farbstoffe der Formel
Claims (3)
X Cyano, Nitro, C₁-C₄-Alkanoyl, Benzoyl oder C₁-C₄-Alkoxycarbonyl,
Y Halogen, Hydroxy, Mercapto, gegebenenfalls durch Phenyl substituiertes C₁-C₆-Alkoxy, C₅-C₇-Cycloalkoxy, gegebenenfalls substituiertes Phenoxy, gegebenenfalls durch Phenyl substituiertes C₁-C₆-Alkylthio, C₅-C₇-Cycloalkylthio, gegebenenfalls substituiertes Phenylthio, C₁-C₆-Alkylsulfonyl oder gegebenenfalls substituiertes Phenylsulfonyl,
Z C₁-C₄-Alkyl, Chlor, Brom, Nitro, Cyano, C₁-C₄-Alkanoyl, Benzoyl, C₁-C₄-Alkylsulfonyl, Phenylsulfonyl oder eine Gruppe der Formel -CH=CB¹B² oder -CH=N-B³, wobei B¹ und B² gleich oder verschieden sind und unabhängig voneinander jeweils für Cyano, C₁-C₆-Alkoxycarbonyl, dessen Alkylkette gegebenenfalls durch ein oder mehrere Sauerstoffatome unterbrochen ist, oder C₃-C₆-Alkenyloxycarbonyl oder ein Rest B¹ oder B² für Cyano und der andere für C₁-C₄-Alkylsulfonyl, gegebenenfalls substituiertes Phenyl, Benzoyl, Phenylsulfonyl oder Carbamoyl und B³ für Hydroxy, C₁-C₄-Alkoxy, Phenoxy oder Phenylamino stehen,
R¹ den Rest A-COOB⁴, wobei A für C₁-C₄-Alkylen und B⁴ für C₁-C₆-Alkyl, das gegebenenfalls durch ein oder mehrere Sauerstoffatome unterbrochen und/oder durch Phenyl substituiert ist, C₅-C₇-Cycloalkyl oder Phenyl stehen,
R² den Rest R¹, Wasserstoff, gegebenenfalls durch Phenyl substituiertes C₁-C₆-Alkyl, C₅-C₇-Cycloalkyl oder C₂-C₄-Alkyl, das durch Hydroxy, C₁-C₄-Alkanoyloxy gegebenenfalls substituiertes Benzoyloxy, C₁-C₄-Alkoxycarbonyloxy, C₁-C₄-Mono-oder Dialkylaminocarbonyloxy oder gegebenenfalls substituiertes Phenylaminocarbonyloxy substituiert ist,
R³ Wasserstoff, Methyl, Methoxy, Chlor, gegebenenfalls substituiertes C₁-C₆-Alkanoylamino oder Benzoylamino und
R⁴ Wasserstoff, Methyl, Methoxy oder Ethoxy bedeuten.1. A method for producing etching prints on synthetic textile material by treating the textile material with dye and alkaline printing paste in any order and then steaming and washing the treated textile material, characterized in that the textile material with thiopheneazo dyes of the formula I
X cyano, nitro, C₁-C₄ alkanoyl, benzoyl or C₁-C₄ alkoxycarbonyl,
Y halogen, hydroxy, mercapto, optionally substituted by phenyl C₁-C₆-alkoxy, C₅-C₇-cycloalkoxy, optionally substituted phenoxy, optionally substituted by phenyl C₁-C₆-alkylthio, C₅-C₇-cycloalkylthio, optionally substituted phenylthio, C₁-C₆ Alkylsulfonyl or optionally substituted phenylsulfonyl,
Z is C₁-C₄-alkyl, chlorine, bromine, nitro, cyano, C₁-C Alk-alkanoyl, benzoyl, C₁-C₄-alkylsulfonyl, phenylsulfonyl or a group of the formula -CH = CB¹B² or -CH = N-B³, where B¹ and B² are the same or different and are each independently cyano, C₁-C₆-alkoxycarbonyl, the alkyl chain of which may be interrupted by one or more oxygen atoms, or C₃-C₆-alkenyloxycarbonyl or a radical B¹ or B² for cyano and the other for C₁-C₄ Alkylsulfonyl, optionally substituted phenyl, benzoyl, phenylsulfonyl or carbamoyl and B³ is hydroxy, C₁-C₄alkoxy, phenoxy or phenylamino,
R¹ is the radical A-COOB⁴, where A is C₁-C₄-alkylene and B⁴ is C₁-C₆-alkyl which is optionally interrupted by one or more oxygen atoms and / or is substituted by phenyl, C₅-C₇-cycloalkyl or phenyl,
R² is R¹, hydrogen, optionally substituted by phenyl C₁-C₆-alkyl, C₅-C₇-cycloalkyl or C₂-C₄-alkyl, benzoyloxy, C₁-C₄-alkoxycarbonyloxy, C₁-C₄-alkoxycarbonyloxy optionally substituted by hydroxy, C₁-C Hydrox-alkanoyloxy C₄-mono- or dialkylaminocarbonyloxy or optionally substituted phenylaminocarbonyloxy is substituted,
R³ is hydrogen, methyl, methoxy, chlorine, optionally substituted C₁-C₆ alkanoylamino or benzoylamino and
R⁴ signify hydrogen, methyl, methoxy or ethoxy.
X Cyano oder C₁-C₄-Alkoxycarbonyl
Y Chlor, Brom, C₁-C₄-Alkoxy, Phenoxy, C₁-C₄-Alkylthio, Phenylthio oder Phenylsulfonyl,
Z Formyl, Cyano, Nitro oder eine Gruppe der Formel -CH=CB¹B², wobei B¹ und B² gleich oder verschieden sind und jeweils unabhängig voneinander für Cyano oder C₁-C₄-Alkoxycarbonyl stehen,
R¹ C₁-C₄-Alkoxycarbonylethyl und
R² C₂-C₄-Hydroxyalkyl, C₁-C₄-Alkanoyloxy-C₂-C₄-alkyl oder C₁-C₄-Alkoxycarbonylethyl bedeuten und
R³ und R⁴ jeweils die in Anspruch 1 genannte Bedeutung besitzen.2. The method according to claim 1, characterized in that treating the textile material with thiopheneazo dyes of the formula I in which
X cyano or C₁-C₄ alkoxycarbonyl
Y chlorine, bromine, C₁-C₄alkoxy, phenoxy, C₁-C₄alkylthio, phenylthio or phenylsulfonyl,
Z formyl, cyano, nitro or a group of the formula -CH = CB¹B², where B¹ and B² are identical or different and are each independently cyano or C₁-C₄-alkoxycarbonyl,
R¹ C₁-C₄ alkoxycarbonylethyl and
R² is C₂-C₄-hydroxyalkyl, C₁-C₄-alkanoyloxy-C₂-C₄-alkyl or C₁-C₄-alkoxycarbonylethyl and
R³ and R⁴ each have the meaning given in claim 1.
X Cyano oder C₁-C₂-Alkoxycarbonyl
Y Chlor, Brom, Ethoxy, Phenylthio oder Phenylsulfonyl,
Z Formyl oder Cyano
R¹ C₁-C₄-Alkoxycarbonylethyl,
R² C₂-C₄-Hydroxyalkyl, C₁-C₄-Alkanoyloxy-C₂-C₄-alkyl oder C₁-C₄-Alkoxycarbonylethyl,
R³ Wasserstoff, Methyl, Methoxy, Chlor, Acetylamino oder Benzoylamino und
R⁴ Wasserstoff, Methoxy oder Ethoxy bedeuten.3. The method according to claim 1, characterized in that the textile material is treated with thiopheneazo dyes of the formula I in which
X cyano or C₁-C₂ alkoxycarbonyl
Y chlorine, bromine, ethoxy, phenylthio or phenylsulfonyl,
Z formyl or cyano
R¹ C₁-C₄ alkoxycarbonylethyl,
R² C₂-C₄-hydroxyalkyl, C₁-C₄-alkanoyloxy-C₂-C₄-alkyl or C₁-C₄-alkoxycarbonylethyl,
R³ is hydrogen, methyl, methoxy, chlorine, acetylamino or benzoylamino and
R⁴ signify hydrogen, methoxy or ethoxy.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873718565 DE3718565A1 (en) | 1987-06-03 | 1987-06-03 | METHOD FOR PRODUCING PRINT PRINTS |
| DE3718565 | 1987-06-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0293745A2 true EP0293745A2 (en) | 1988-12-07 |
| EP0293745A3 EP0293745A3 (en) | 1991-08-14 |
Family
ID=6328943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19880108362 Withdrawn EP0293745A3 (en) | 1987-06-03 | 1988-05-26 | Process for the production of discharge prints |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0293745A3 (en) |
| JP (1) | JPS63309684A (en) |
| DE (1) | DE3718565A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0036252A2 (en) * | 1980-03-13 | 1981-09-23 | Imperial Chemical Industries Plc | Textile printing process |
| EP0121875A2 (en) * | 1983-04-07 | 1984-10-17 | BASF Aktiengesellschaft | Process for producing alkaline dischargeable dyeings and prints |
| EP0201896A1 (en) * | 1985-05-14 | 1986-11-20 | BASF Aktiengesellschaft | Dyestuffs with thiophene rests |
-
1987
- 1987-06-03 DE DE19873718565 patent/DE3718565A1/en not_active Withdrawn
-
1988
- 1988-05-26 EP EP19880108362 patent/EP0293745A3/en not_active Withdrawn
- 1988-06-03 JP JP63135737A patent/JPS63309684A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0036252A2 (en) * | 1980-03-13 | 1981-09-23 | Imperial Chemical Industries Plc | Textile printing process |
| EP0121875A2 (en) * | 1983-04-07 | 1984-10-17 | BASF Aktiengesellschaft | Process for producing alkaline dischargeable dyeings and prints |
| EP0201896A1 (en) * | 1985-05-14 | 1986-11-20 | BASF Aktiengesellschaft | Dyestuffs with thiophene rests |
Non-Patent Citations (1)
| Title |
|---|
| RESEARCH DISCLOSURE. vol. 198, no. 26, Oktober 1980, HAVANT GB Seiten 425 - 427; Disclosed anonysmously: "Discharge/resist printing of synthetic textile materials using thiophene-azo disperse dyestuffs in the presence of alcali." * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63309684A (en) | 1988-12-16 |
| EP0293745A3 (en) | 1991-08-14 |
| DE3718565A1 (en) | 1988-12-15 |
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