Classifications

• • 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
• • 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 process for the production of reserve effects on textile materials based on mixed fibers of polyester and cellulose, in particular polyester-cotton fibers, by impregnating the materials with dye liquors which, in addition to conventional dyeing and padding aids, contain disperse and reactive dyes which contain the reservation agents react and which may contain further dispersing and reactive dyes which are resistant to the reservation agents, drying or drying the padded materials and then printing on a reserve paste which, if desired, in addition to the reservation agent contains dispersing and reactive dyes which are resistant to the reservation agent, heat treatment at temperatures from 100 to 190 ° C and subsequent alkaline fixation of the reactive dye in a manner known per se, characterized in that the etchable disperse dyes are those of the formula 1 wherein R 1 is hydrogen, cyano, optionally substituted alkyl or phenyl; X 1 is hydrogen, halogen, optionally substituted alkyl or alkoxy; Y 1 is hydrogen, halogen, optionally substituted alkyl or
• deralkylcarbonyl, sulfamoyl, lower alkylsulfonyl, lower alkylcarbonylamino or lower alkoxycarbonyl and Z represents hydrogen or lower alkyl; or disperse dyes free of water-solubilizing groups, which contain at least two carboxylic ester groups, as etchable reactive dyes those which contain reactive radicals of the formulas III to VI in which M is hydrogen or a metal cation and hal is halogen, and a reserve paste which contains a) an alkali metal sulfite or an alkali metal hydrogen sulfite in combination with alkali metal carbonate or alkali metal hydrogen carbonate and optionally an aldehyde and b) optionally a nonionic detergent as the reservation agent.
• the textile material is colored at the printed areas by the indestructible dye.
• Colored prints on a dark background can also be obtained if the dark background is made with a mixture of an etchable and a differently colored non-etchable dye by introducing both types of dye into the padding liquor.
• German patent specification 23 26 522 describes a process for producing reserve effects with reactive dyes on native or regenerated cellulose fiber materials.
• the textile material is printed with sulfites, thiosulfites or thioureas as a reservation agent, alkalis as a fixing agent and reactive dyes, which a) react with the reservation agent and have the ß-sulfatoethylsulfonyl or ß-sulfatoethylsulfonamide group as reactive group and b) do not have on fixing react with the reservation agents and have as a reactive group the chloraminotriazine, dichloropyrimidine, trichloropyrimidine, dichlorotriazine, monochlorotriazine, quaternized chlorotriazine or the dichloropyridazine group, in the form or overpressure process, then dries and fixes the dyes by steaming or Hot air treatment.
• the Simpl se 'he method of ⁇ tzreservedrucks includes a number of technical difficulties that make its use often. It is usually not easy to completely destroy the base dye with the etchant. If this does not succeed, a colored residue remains on the etched areas, the shade of which can vary between yellow-brown and dull violet or reddish gray tones and which soils the white background at the etched areas. This leads to white etching which appears to be unclean or, in the event that a colored etching is to be produced, to a falsification of the shade of the etching-resistant dye.
• etching pastes 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.
• strong etching agents such as sodium dithionite in combination with alkali, alkali formaldehyde sulfoxylates or even heavy metal salts such as tin-2-chloride.
• these etchants are usually not cheap, and in the case of Sc l lwermetalliserstoff they represent an additional environmental burden or they cause additional expenses in the purification of waste water.
• dispersions and reactive dyes that are resistant to such etchants, and so the selection of etch-resistant dyes that can be used to produce colored etchings is relatively small.
• Alkyl radicals with 1-6 C atoms, which R 1 in formula I can represent, are, for example, methyl; Ethyl; Propyl; Isopropyl; Butyl; 1- and 2-isobutyl; Pentyl- (1), - (2) and - (3); 2- or 3-methylbutyl- (1) or - (2); Hexyl- (1), - (2) or - (3); 1-, 2- or 3-ethylbutyl- (1) or - (2); 2-, 3- or 4-methylpentyl- (1).
• substituents for which X 1 in formula I can stand are: chlorine; Bromine; Ethyl; Methyl; Propyl; Isopropyl; Butyl- (1) or - (2); Isobutyl; ⁇ -chloro, bromine, cyano or hydroxyethyl; ⁇ -chloro, bromine, cyano or hydroxypropyl; y-chloro, bromine, cyan or hydroxypropyl; ⁇ - or y-chloro -, - bromine, cyano or hydroxybutyl (1); 3-chloro, bromine, cyan or hydroxybutyl (2); Methoxy, ethoxy, propoxy, isopropoxy; But-1- or -2-oxy; Isobutoxy; ⁇ -hydroxyethoxy; ⁇ - or y-hydroxypropoxy; Hydroxyisopropoxy; ⁇ -, y- or ⁇ -hydroxybutoxy; Hydroxyisobutoxy; ⁇ -methoxyeth
• substituents for which Y 1 can stand are: .methyl; Ethyl; Propyl- (1) or - (2); n-butyl- (l) or - (2); Isobutyl- (1), - (2) or - (3); 2-chloroethyl; 2-chloropropyl; 3-chloropropyl; 2-bromoethyl; 2-cyanoethyl; 2-cyanopropyl; 3-cyanopropyl; 1- or 2-hydroxyethyl; 2- or 3-hydroxypropyl- (l); Methoxy; Ethoxy; Propoxy; Isopropoxy; Butoxy; Isobutoxy; ⁇ -hydroxyethoxy; 2- or 3-hydroxypropoxy; 2- or 4-hydroxy-but-2-oxy; Methoxyethoxy; Ethoxymethoxy; 2- or 3-metboxyprop-l-oxy; 2- or 3-ethoxyprop-l-oxy; 2- or 4-metboxybut-1-oxy; 2- or 4-ethoxybut-1-oxy; 4-ethoxy
• Optionally substituted lower alkyl groups with 1-6 C atoms are for example: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. Butyl, pentyl-1, -2 or -3, hexyl-1, -2 or -3, 2-chloro, bromine or cyanoethyl, 2- or 3-chloro, bromine or cyanopropyl- (1) ; 2-, 3- or 4-chloro, bromine or cyanobutyl- (1); 1-, 3- or 4-chloro, bromine or cyanobutyl (2); Methoxy, ethoxy, propoxy, isopropoxy or butoxyethyl; ß- (ß-Hydroxyäthoxy) ethyl; 2- or 3-methoxy or ethoxy propyl (1); Benzyl; Phenethyl; Phenylpropyl; Acetyloxy, propion
• Alkenyl groups which R 2 or R 3 represent are, for example: allyl; Methally; Crotyl; Buten-3-yl- (1); Buten-3-yl (2); Penten-2-, -3- or -4-yl- (1); Penten-3- or -4-yl- (2); Hexen-2-, -3-, -4- or -5-yl- (1).
• alkyl and alkoxyalkyl groups which R 4 can represent are: methyl; Ethyl; Isopropyl; Propyl; (n) butyl; sec butyl; Isobutyl; Pentyl; Hexyl; 2-ethylhexyl- (1); Methoxy, ethoxy or propoxyethyl; 2- or 3-methoxy, ethoxy or propoxypropyl (1); 2-, 3- or 4-methoxy-, ethoxy- or propoxybutyl- (l); 1-, 3- or 4-methoxy, ethoxy or propoxybutyl (2); Methoxy, ethoxy or propoxypentyl and ethoxyhexyl.
• Dyes of the formula I in which R 1 is hydrogen and R 2 is free from alkoxycarbonyl and hydroxyalkoxycarbonyl groups are particularly preferred for use in the process according to the invention.
• Another preferred group of dyes of the formula I comprises those dyes which contain hydroxyl groups in the radicals R 2 and / or R 3 , in particular those in which R 2 is ethyl or ⁇ -hydroxyethyl and R 3 is ⁇ -hydroxyethyl or those in which R 2 is hydrogen and R 3 is an alkoxycarbonylalkyl radical, in particular a 2-alkoxycarbonylpropyl-2 radical.
• Another class of disperse monoazo dyes which is particularly preferred for the use according to the invention are the dyes of the formula 1 in which X 1 is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxyalkyl having a total of 3 to 6 carbon atoms, hydroxyalkyl having 2 to 4 carbon atoms, chlorine; Y l represents chlorine, alkyl having 1 to 4 carbon atoms or -NH-CO-Y 2 and R 1 , R 2 , R 3 and y 2 have the meanings given above.
• Preferred -NH-COY 2 - "groups are alkanoylamino groups with unsubstituted alkanoyl radicals with 2 to 4 carbon atoms, especially acetylamino groups.
• dyes which have a combination of preferred features are particularly preferred for use in the process according to the invention wherein R 2 is ethyl or ß-hydroxyethyl, or dyes of the formulas
• the dyes of the formula II used in the process according to the invention and their preparation are known from German Offenlegungsschrift 26 12 741. They can exist in a number of possible tautomeric forms. For the sake of convenience, the dyes are only formulated in one of the possible forms. However, it should be noted that the invention also encompasses the use of dyes in any of the possible tautomeric forms.
• lower alkyl and lower alkoxy refer to alkyl or alkoxy radicals having 1 to 4 carbon atoms.
• substituents which may be present on the phenyl radical D are lower alkyl radicals, such as, for example, methyl, lower alkoxy radicals, such as, for example, methoxy and ethoxy, lower alkylcarbonyl radicals, such as, for example, acetyl, lower alkylsulfonyl radicals, such as, for example, ethylsulfonyl, lower alkylcarbonylamino radicals, such as, for example, acetylamino and N, N-lower alkyl -Di-lower-alkylcarbamoyl radicals, such as, for example, N-ethylcarbamoyl, N-butylcarbamoyl and N, N-dimethylcarbamoyl, N-lower alkyl and N, N-di-lower alkylsulfamoyl radilcale, such as, for example, N-ethyls,
• lower alkyl radicals X 2 and Z are ethyl and methyl.
• lower alkyl canonyl radicals X 2 are acetyl and propionyl.
• lower alkoxycarbonyl radicals X 2 are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl and butoxycarbonyl.
• An example of a lower alkyl sulfonyl radical X 2 is ethyl sulfonyl.
• An example of a lower alkylcarbonylamino radical X 2 is acetylamino.
• a preferred class of disperse monoazo dyes for use in accordance with the invention are the dyes of formula VIII in which X 2 and Z have the meanings given above, r is 0 or 1
• Y 3 is lower alkyl, lower alkoxy-lower alkyl, lower alkoxy-lower alkoxy-lower alkyl, hydroxy-lower alkyl or hydroxy-lower alkoxy-lower alkyl and the benzene ring D 1 is furthermore chlorine, Bromine, nitro, lower alkoxycarbonyl, lower alkyl or lower alkoxy can be substituted.
• Y 3 is lower alkyl
• stent r is 0
• X 2 is -CN.
• the disperse dyes to be used according to the invention which contain at least two carboxylic ester groups of the formula _CO0R 5 , and their preparation are known from DOS 2612740, 2612742, 2612790, 2612791 and 2612792.
• a cycloalkyl radical such as cyclohexyl, a monocyclic aryl radical such as phenyl, tolyl and xylyl, or substituted derivative thereof such as anisyl, chlorophenyl and bromophenyl, a monocyclic Ar y lalkylradikal as eg benzyl or ⁇ -phenylethyl, or preferably an alkyl radical, such as hexyl, octyl, dodecyl, but very particularly a lower alkyl radical with 1 to 4 carbon atoms, such as ethyl, propyl, butyl and especially methyl.
• a cycloalkyl radical such as cyclohexyl
• a monocyclic aryl radical such as phenyl, tolyl and xylyl
• substituted derivative thereof such as anisyl, chlorophenyl and bromophenyl
• R S can be a substituted alkyl radical, in particular a substituted lower alkyl radical, such as a hydroxy lower alkyl radical, for example ⁇ -hydroxyethyl, or a lower alkoxy lower alkyl radical, for example y-methoxypropyl.
• the carboxylic ester groups mentioned can be attached directly to carbon atoms of one or more benzene or heterocyclic rings in the substance molecule or bonded to a bridge group, such as -0-alkylene or -N-alkylene.
• a preferred class of such azo dyes includes dyes of Formula IX wherein A represents the rest of a diazo component of the aromatic or heterocyclic series, E represents the rest of a coupling component, R 5 has the meaning given above and n and m each independently represent 0, 1 or 2, the sum of n and m is at least 2.
• a second preferred class of azo dyes includes the dyes of Formula IXa in which A 1 represents the radical of a diazo component of the aromatic or heterocyclic series, the benzene ring B can optionally contain substituents, R 5 has the meaning given and X 3 and X 4 each independently represent lower alkylene or lower alkylene-0-lower alkylene radicals, wherein lower alkylene refers to alkylene radicals having 1 to 6 carbon atoms.
• Another preferred class of azo dyes includes the dyes of Formula IXb in which B, X 3 and R 5 have the meanings given above, Z 1 represents a hydrogen atom or an optionally substituted alkyl, cycloalkyl or aryl radical, A 2 represents the radical of a diazo component of the aromatic or heterocyclic series and p represents 1 or 2 stands.
• Another preferred class of azo dyes includes those of Formula IXc wherein A 2 , B, R s and X 3 have the meanings given, R 6 is lower alkyl and q is 2 or preferably 1.
• substituents which may be present on the benzene ring B are lower alkyl radicals, in particular methyl, lower alkoxy radicals, such as, for example, methoxy and ethoxy, chlorine, bromine and acylamino radicals, in particular acylamino radicals of the formulas wherein T 1 , T 4 and T 5 each independently represent hydrogen or lower alkyl, T 2 stands for hydrogen, lower alkyl or monocyclic aryl and T 3 stands for lower alkyl or monocyclic aryl.
• the abovementioned acylamino group preferably has the formula: -NHCO-lower alkyl .
• the radicals of the diazo components A, A 1 and A 2 can be radicals of any diazo components of the heterocyclic series, in particular optionally substituted thiazol-2-yl-, benzthiazol-2-yl-, thien-2-yl-, benz-2, l-isothiazol-3-yl-, benz-1,2-isothiazol-3-yl-, 1,2,4-thiadiazol-5-yl-, 1,3,4-thiadiazol-2-yl-, isothiazol- 5-yl, pyrazol-3-yl, imidazole (2- or -5-) yl, 1,2,4-triazol-3-yl and tetrazol-5-yl radicals.
• A, A 1 and A 2 are radicals of a diazo component of the aromatic series and very particularly optionally substituted naphthyl and especially optionally substituted phenyl radicals. kale.
• the substituent or substituents which are present on such radicals can be any substituents, other than carboxylic acid and sulfonic acid groups, which are not present on the diazo radicals of disperse azo dyes, such as chlorine, bromine, nitro, cyano, trifluoromethyl, lower alkyl, lower alkoxy , Lower alkylsulfonyl, lower alkylcarbonyl, acylamino, especially lower alkylcarbonylamino, sulfonamido and N-substituted and N, N-disubstituted derivatives thereof, carbonamido and N-substituted and N, N-disubstituted derivatives thereof and carboxylic ester groups, especially lower alkoxycarbonyl.
• A, A 1 and A2 are preferably optionally substituted phenyl radicals and in particular radicals of the formulas wherein L 1 and L 2 each independently represent lower alkyl, U and W each independently represent hydrogen, lower alkyl, chlorine, bromine, lower alkoxy, nitro, cyano or lower alkoxycarbonyl and V represents hydrogen, nitro, chlorine, bromine, lower alkyl, lower alkoxy , Cyano, lower alkoxycarbonyl, sulfonamido or carbonamido and N- and N, N-substituted derivatives thereof, lower alkylcarbonyl and lower alkylsulfonyl.
• V is preferably nitro.
• A, A 1 and A 2 preferably represent a phenyl radical which may contain up to 3 substituents, preferably the substituents exemplified above as substituents on the diazo radical mentioned. were.
• a special group of azo disperse dyes containing carboxylic acid ester groups corresponds to the formula IXd .
• L 3 represents optionally substituted lower alkyl
• L 4 represents optionally substituted lower alkyl or optionally substituted amino
• Y 1 represents hydrogen or nitro
• Y 4 represents hydrogen or lower alkoxy
• R 7 represents lower alkyl or cyano-lower alkyl
• a 3 and A 4 each independently represent lower alkylene; and X 5 represents cyano, lower alkoxy, lower alkoxy-lower alkoxy, lower alkoxy-lower alkoxy-lower alkoxy, chlorine, bromine, lower alkoxycarbonyl, lower alkylcarbonyl, optionally substituted phenoxycarbonyl, optionally substituted phenylcarbonyl, optionally substituted phenoxy, hydroxymethyl or lower alkylcarbonyloxymethyl.
• lower alkyl refers to alkyl, alkoxy or alkylene radicals having 1 to 4 carbon atoms.
• Examples of lower alkylene radicals A 3 and A 4 are methylene, trimethylene, tetramethylene, propylene and especially ethylene.
• Examples of cyano-lower alkyl radicals R7 are cyanomethyl, ⁇ -cyanopropyl, ⁇ -cyanobutyl and especially ⁇ -cyanoethyl.
• Examples of lower alkyl radicals L 3 , L 4 and R 7 are methyl, ethyl, n-propyl and n-butyl.
• Examples of lower alkoxy radicals Y 4 are ethoxy and especially methoxy.
• substituted lower alkyl radilals L 3 and L 4 are hydroxy-lower alkyl, such as, for example, ⁇ -hydroxyethyl, chloro-lower alkyl, such as, for example, ⁇ -chloroethyl, cyano-lower alkyl, such as, for example, ⁇ -cyanoethyl, lower alkoxy-lower alkyl, such as, for example, ⁇ -ethoxyethyl and y-methoxypropyl, phenyl- lower alkyl such as benzyl and ⁇ -phenylethyl, and phenoxy lower alkyl such as phenoxymethyl.
• hydroxy-lower alkyl such as, for example, ⁇ -hydroxyethyl
• chloro-lower alkyl such as, for example, ⁇ -chloroethyl
• cyano-lower alkyl such as, for example, ⁇ -cyanoethyl
• substituted amino groups L are lower alkylamino, e.g. Methylamino and ethylamino.
• L 3 is lower alkyl. It is also preferred that L 4 is lower alkyl, especially methyl.
• groups X 5 are lower alkoxy radicals, such as methoxy, ethoxy, n-propoxy and n-butoxy, lower alkoxy lower alkoxy radicals, such as ⁇ -ethoxy-ethoxy and y methoxypropoxy, lower alkoxy-lower alkoxy lower alkoxy radicals, such as ⁇ - ( ⁇ '-Nethoxyäthoxy) äthoxy, Niederalkoxycarbonyl radicals, such as methoxycarbonyl, ⁇ thoxycarbonyl and n-butoxycarbonyl, Niederalkylcabonyl radicals, such as acetyl and propionyl, optionally substituted phenoxycarbonyl radicals, such as phenoxycarbonyl itself, p-methylphenoxycarbonoxy and m-chlorophenoxycarbonyl and m-chloro substituted phenylcarbonyl radicals, such as benzoyl and m-nitrobenzoyl, optionally substituted phenoxy radicals, such
• X 5 represents cyano, lower alkoxy, lower alkoxy-lower alkoxy, lower alkoxycarbonyl, lower alkylcarbonyl, hydroxymethyl or lower alkylcarbonyloxymethyl.
• a preferred class of dyes according to the invention includes those of formula IXe wherein R 7 has the meaning given; L 3 represents lower alkyl; Y 4 represents hydrogen or methoxy; and X 5 represents cyano, lower alkoxy, lower alkoxy-lower alkoxy, lower alkoxycarbonyl, lower alkylcarbonyl, hydroxymethyl or lower alkylcarbonyloxymethyl.
• Another special group of azo disperse dyes containing carboxylic acid ester groups corresponds to the formula IXf in which X 6 represents lower alkyl, s represents 1, 2 or 3, Z 2 represents hydrogen, lower alkyl or lower alkoxy, Y 5 represents hydrogen, lower alkyl, lower alkoxy, chlorine, bromine, -NHCOX 7 or -NHSO 2 X 8 , X 7 represents lower alkyl, lower alkoxy, amino or N-lower alkylamino, X 8 represents lower alkyl, A 5 and A 6 each independently represent lower alkylene and R 8 and R 9 each independently represent lower alkyl or hydroxyalkyl having 2 to 4 carbon atoms .
• Examples of lower alkyl radicals X 67 Z 2 , Y 5 , X 7 , X 8 , R 8 and R 9 are methyl, ethyl, n-propyl, isopropyl and n-butyl.
• Examples of lower alkoxy radicals X 77 Z 2 and Y 5 are ethoxy and preferably methoxy.
• Examples of lower alkylene radicals A 5 and A 6 are methylene, trimethylene, propylene, tetramethylene, hexamethylene and especially ethylene.
• Examples of hydroxyalkyl radicals R 8 and R 9 are ⁇ -hydroxyethyl, ⁇ - or y-hydroxypropyl and ⁇ -, y- or ⁇ -hydroxybutyl.
• Examples of N-lower alkylamino radicals X 7 are methylamino and ethylamino.
• a preferred class of dyes according to the invention includes those of formula IXg wherein X 6 , Y 5 , Z 2 , R 8 and Rg have the meanings given above.
• Y 5 preferably represents hydrogen or lower alkylcarbonylamino.
• azo disperse dyes containing carboxylic acid ester groups corresponds to the formula IXh wherein X 9 is nitro or C yano; Y 6 represents hydrogen, chlorine, bromine, cyano, nitro, lower alkoxy or lower alkoxycarbonyl; T 6 represents methoxy or ethoxy; Z 3 represents hydrogen, chlorine, bromine, lower alkyl or lower alkoxy; A 7 and A 8 each independently represent lower alkylene and R 10 and R 11 each independently represent lower alkyl or hydroxyalkyl having 2 to 4 carbon atoms.
• Examples of lower alkyl radicals Z 3 , R 10 and R 11 are mathyl, ethyl, n-propyl and n-butyl.
• Examples of lower alkoxy radicals Y 6 and Z 3 are methoxy and ethoxy.
• Examples of Niederalkoxycarbonylradikale Y 6 are methoxycarbonyl, p ⁇ thoxycarbo yl, n-propoxycarbonyl, n-butoxycarbonyl, iso-propoxycarbonyl, sec-butoxycarbonyl and isobutoxycarbonyl.
• hydroxyalkyl radicals R 10 and R 11 are ⁇ -hydroxyethyl, y-hydroxypropyl and ⁇ -hydroxy-n-butyl.
• lower alkylene radicals A 7 and A 8 are methylene, trimethylene, propylene, tetramethylene, hexamethylene, ⁇ , ⁇ -dimethylethylene and especially ethylene.
• a preferred class of dyes according to the invention is represented by those of the formula IXi where Y 6 Bromine, nitro or cyano stands and and R 11 have the meanings given above.
• azo disperse dyes containing carboxylic acid ester groups Formula IXk wherein X 10 is cyano, optionally substituted methoxycarbonyl, optionally substituted ethoxycarbonyl, optionally substituted carbonamido, lower alkylcarbonyl, lower alkylsulfonyl, optionally substituted arylcarbonyl or arylsulfonyl, chlorine or bromine; Y 7 represents hydrogen, lower alkyl, optionally substituted aryl or lower alkoxycarbonyl; Z4 represents hydrogen, nicderalkyl, chlorine, bromine, nitro, cyano, optionally substituted lower alkoxycarbonyl or optionally substituted carbonamido; with the restriction that X 10 and Z 4 are not both optionally substituted carbonamido and that Y 7 and Z 4 are not both hydrogen; W l for hydrogen,.
• V 2 represents hydrogen, chlorine, bromine, lower alkyl, lower alkoxy or acylamino; with the restriction that V 2 and W 1 are not both hydrogen;
• a 9 and A 10 each independently represent lower alkylene; and
• R 12 and R 13 each independently represent lower alkyl or hydroxy lower alkyl.
• the optionally substituted carbonamido groups X 10 and Z 4 have the formula: wherein T 7 is hydrogen, lower alkyl or phenyl and T 8 is hydrogen or lower alkyl.
• Examples of lower alkyl radicals Z 4 , Y 7 , T 7 , T 8 V 2 , V 1 , R 12 and R 13 are methyl, ethyl, n-propyl and n-butyl.
• Examples of lower alkoxy radicals V 2 and W 1 are ethoxy and preferably methoxy
• examples of lower alkylene radicals Ag and A 10 are methylene, trimethylene, propylene, tetramethylene and especially ethylene.
• the acylamino groups Y 2 preferably have the formula -NHCOT 9 or -NHSO 2 T 10 wherein T 9 is hydrogen or lower alkyl and T 10 is lower alkyl.
• D preferably have 10 Acylamino groups have the formula -NHCOT 9 where T 9 is lower thanyl.
• Specific examples of acylamino groups V 2 are methylsulfonamido, benzenesulfonylamino, benzoylamino, ureido, formylamino and preferably acetylamino, propionylamino and butyrylamino.
• Examples of Mederalkexycarbonylradikal (carboniederalkoxy radicals) Y 7 and Z 4 are methoxycarbonyl and ethoxycarbonyl.
• Examples of substituted lower alkoxycarbonyl radicals Z 4 are For example, ⁇ -hydroxyethoxycarbonyl, cyano-lower alkoxycarbonyl, such as, for example, ⁇ -cyanoethoxycarbonyl, lower alkoxy-lower alkoxycarbonyl, such as, for example, ⁇ -methexyathoxycarbonyl and Kederalk and Ar y lsulfon y lrad i kale X 10 are optionally substituted benzoyl and phenylsulfonyl radicals, in particular nitrobenzoyl, methylbenzoyl, methoxybenzoyl, nitrobenzoyl and p-tolylsulfonyl.
• Examples of optionally substituted aryl radicals Y 7 are
• a preferred class of dyes according to the invention comprises those of the formula IX 1 wherein X 10 is cyano, methoxycarbonyl or ethoxycarbonyl and W 1 , V 2 , A 9 , A 10 ' R 12 and R 13 have the meanings given above.
• Examples of disperse dyes of the anthraquinone series containing carboxylic acid ester groups to be used according to the invention are: 1,4-di ( ⁇ -ethoxycarbonylethylamino) anthraquinone, 1-amino-4- [4 '- ( ⁇ , ⁇ -di- ⁇ '-hydroxyethoxy-carbonyl ⁇ ethyl ) anilino] anthraquinone, 1,4-di- (ß-methoxy-carbonylethylamino) anthraquinane, 1., 4-di- (o-methoxy-carbonylanilino) anthraquinone.
• the reactive dyes used in the process according to the invention contain one of the fiber-reactive radicals of the formulas I I I to VI given above. It is common to the radicals of the formulas III.to V that they form a vinylsulfonyl group in the presence of alkali with the elimination of a sulfate or halo anion. This group formed in the presence of alkali fixes in the same way as the vinylsulfonyl radical of the formula V which is bonded directly to the dye residue by adding one of the OH groups of the cellulose to the vinyl double bond.
• Reactive dyes which have one of the reactive radicals mentioned above can belong to all technically important dye groups.
• Examples of reactive dyes which are suitable for carrying out the process according to the invention are the monoazo dyes CI Yellow 13-17 and 72-74, Orange 7, 15, 16, 23, 24, 55, Red 21-23, 35, 36 , 50, 63, 103-107, 112-114, Blue 28, Brown 16; the disazo dyes CI-Blue 76, Blue 98, Black 5, 31; the mono- or disazo-metal complex dyes CI-Violet 4, 5, Blue 20, Brown 18; the andrachinone dyes CI-Violet 22, Blue 19 and 27; the phthalocyanine dyes CI-Blue 21, 38, 77, 91 and Green 14 called.
• etchable reactive dyes are those which contain at least one fiber-reactive radical of the formulas IV or V as reactive anchor.
• the amounts of the dyes contained in the padding liquors to be used according to the invention are, as usual, matched to the depth of color of the desired color and intensity of the reserve effect.
• 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.
• a padding liquor which is prepared for a base coloring of a particular color shade contains, in the event that the substrate predominantly contains cellaloze fibers, a high proportion of etchable and possibly non-etchable reactive dyes and a low proportion of etchable and optionally non-etchable disperse dyes and, in the event that the substrate predominantly contains polyester fibers, a high proportion of the disperse dyes and a low proportion of the reactive dyes.
• the method according to the invention is primarily intended for the finishing of textiles made of cellulose polyester fibers.
• the quantity ratio of the two types of fibers is not subject to any restrictions when taking into account the criteria given above for the composition of the padding liquor, and in the limit case, the process can also be used to generate reserve effects on pure cellulose textiles or pure polyester textiles, in which case the padding liquors are exclusively etchable and optionally contain non-etchable reactive dyes or exclusively etchable and optionally non-etchable disperse dyes.
• the reserve paste to be used in carrying out the method according to the invention contains either an alkali sulfite or an alkali hydrogen sulfite in combination with alkali carbonate or alkali hydrogen carbonate as a reservation agent.
• the alkali hydrogen sulfite can also be replaced in whole or in part by an equivalent amount of an alkali hydrogen sulfite-aldehyde adduct. It is also possible to produce this adduct in the reserve paste itself by adding alkali hydrogen sulfite, alkali hydrogen carbonate and an aldehyde to the reserve paste.
• alkali sulfite alkali hydrogen sulfite and alkali hydrogen carbonate
• the sodium or potassium salts preferably the sodium salts
• Aldehydes which can be present in the reserve pastes as alkali metal bisulfite adducts are in principle all those which are technically readily accessible, such as, for example, formaldehyde, acetaldehyde, glyoxal, benzaldehyde. Since the aldehyde-alkali hydrogen sulfite adducts are in equilibrium with the individual components of the adduct
• the process according to the invention is carried out in a manner known per se by padding the textile material composed of polyester and cellulose fibers with dye liquors which contain one or more of the above-mentioned alkali-etchable disperse dyes and one or more reactive dyes which contain one of the above-mentioned reactive radicals of the formulas III to VI, preferably the ⁇ -sulfatoethylsulfonyl or ⁇ -sulfatoethylsulfonamide groups, contain, in addition to the known customary dyeing aids, such as, for example, dispersants, wetting agents, foam suppressants and padding aids and, if colored etching prints are to be produced, additionally disperse and reactive dyes which are resistant to the etchant , and squeezing the padded fabric webs to a liquor absorption of 50-120%.
• dye liquors which contain one or more of the above-mentioned alkali-etchable disperse dyes and one or more reactive dyes which contain
• the fabric webs are then dried by warm air with any preceding infrared radiation, the temperature being approximately 80 to a maximum of approximately 150 ° C. with a corresponding reduction in time.
• the fabric webs prepared in this way are then included the etching reserve printing paste, which contains the reservation agents described above and the additives known in printing pastes for textile printing, in particular thickeners.
• the padded and printed textile fabrics are subjected to a heat treatment between 100 and 190 ° C. The heat is supplied by means of superheated steam.
• the heat treatment effects a) an inhibition of the reservable dispersion and reactive dyes at the points printed with the reserve paste and a fixation of the possibly non-reservable dispersion and reactive dyes, b) a fixation of the dispersion dyes at the points not printed with reserve paste and, if the padding liquor contained an alkali metal formate, the reactive dyes at the same time.
• Hiarbet is
• the dyeings or prints are rinsed hot and cold and dried.
• the K lotzflotte except reservable disperse and reactive dyes additionally includes those that are resistant to the resisting agent, and thus will not be destroyed by the discharge reserve printing pastes used according to the invention. If one proceeds as above, then multicolored designs are obtained.
• a further embodiment of the method according to the invention consists in that the dyes which can be reserved are not applied to the entire fabric by padding with a pad liquor but are also printed on the fabric in the form of printing pastes and then overprinted with the etching reserve printing paste. The textile prints are then fixed and completed as described above. With this method, too, it is possible to add dyes that are resistant to the reservation agent to the color printing pastes printed on first.
• etching reserve printing pastes which in turn contain dyes which are resistant to the reservation agent, are printed on the fund which is padded or printed with reservable dyes. With subsequent fixation and completion of the textile materials as described above, multicolored designs are also obtained here.
• the disperse dyes of the formula I are present in the padding liquors or in the printing pastes in finely dispersed form, as is customary and known for disperse dyes, while the reactive dyes are dissolved.
• the padding liquors or printing pastes which are to be used according to the invention are also produced in a manner known per se by mixing the liquor or printing paste components with the necessary amount of water and liquid finely dispersed or solid redispersible formulations of the disperse dyes and solutions or formulations of the Reactive dyes.
• Dispersion dyes which are resistant to the reservation agent and which can be combined with the reserved dye of the formula I to produce multicolored designs are the known commercial dyes from the group of azo or azomethine, quinophthalone, nitro or anthraquinone dyes.
• Some examples of resistant disperse dyes are:
• This solution is stirred into 500 parts by weight of a thickening stock, the 230 parts by weight of an aqueous 4% alginate thickening and 80 parts by weight of an aqueous.
• a thickening stock containing 10% starch ether thickening, 85 parts by weight of water, 25 parts by weight of an aqueous 10% solution of the condensation product of polyglycol 2000 with stearic acid and 80 parts by weight of white spirit.
• 100 parts by weight of the etching reserve are then added, which was previously prepared by mixing 65 parts by weight of a 40% aqueous glyoxal solution, 310 parts by weight of sodium bisulfite solution 38 ° Be, 125 parts by weight of water and 500 parts by weight of sodium hydrogen carbonate.
• a leached mixed fabric made of polyester cellulose 70:30 is padded with the dye liquor described in Example 1, carefully dried in a hot flue at 80-100 ° C. and overprinted in film printing with a printing paste consisting of 40 parts by weight of the liquid commercial form of C.I. Disperse Red 200, 30 parts by weight of the commercial form by C.I. Reactive Red 33, 80 parts by weight of urea,
• a block fabric of polyester and mercerized cotton in the ratio 65:35 is padded with a dye liquor composed of 150 parts by weight of a 20% liquid setting of the dye of the formula 40 parts by weight of the commercial form of CI Reactive Blue 122, 767 parts by weight of water, 3 parts by weight of sodium chlorate, 20 parts by weight of an antimigrant based on polyacrylic acid, 20 parts by weight of sodium formate. It is carefully dried in a hot flue at 80-100 ° C. and overprinted in rouleaux printing with a printing paste consisting of 60 parts by weight of the dye of the formula

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• 1978
  • 1978-12-27 DE DE19782856283 patent/DE2856283A1/de not_active Withdrawn
• 1979
  • 1979-12-14 DE DE7979105182T patent/DE2964074D1/de not_active Expired
  • 1979-12-14 EP EP79105182A patent/EP0013378B1/fr not_active Expired
  • 1979-12-19 US US06/105,204 patent/US4265629A/en not_active Expired - Lifetime
  • 1979-12-26 JP JP54168436A patent/JPS5830439B2/ja not_active Expired

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