EP0590397B1 - Verfahren zur Herstellung von Färbungen gemäss der "Ink-Jet"-Drucktechnik auf modifizierten Fasermaterialien mit anionischen Textilfarbstoffen - Google Patents

Verfahren zur Herstellung von Färbungen gemäss der "Ink-Jet"-Drucktechnik auf modifizierten Fasermaterialien mit anionischen Textilfarbstoffen Download PDF

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Publication number
EP0590397B1
EP0590397B1 EP93114661A EP93114661A EP0590397B1 EP 0590397 B1 EP0590397 B1 EP 0590397B1 EP 93114661 A EP93114661 A EP 93114661A EP 93114661 A EP93114661 A EP 93114661A EP 0590397 B1 EP0590397 B1 EP 0590397B1
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Prior art keywords
carbon atoms
group
methyl
substituted
ethoxy
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German (de)
English (en)
French (fr)
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EP0590397A1 (de
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Andreas Dr. Von Der Eltz
Andreas Dr. Schrell
Werner Hubert Dr. Russ
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Hoechst AG
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Hoechst AG
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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
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/6426—Heterocyclic compounds
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B1/00—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
    • D06B1/02—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by spraying or projecting
    • 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
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive 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
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5292—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds containing Si-atoms
    • 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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive 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
    • D06P5/30—Ink jet printing

Definitions

  • Textile materials such as woven, knitted, game and nonwovens which contain cellulose fibers can be dyed using anionic dyes by known processes.
  • spraying techniques have been added to the classic dyeing methods of printing, exhausting and padding processes, which was first used on paper under the name "Ink-Jet Printing", later also on textile materials.
  • All processes have in common that alkali is required for fixing the dye to the fiber, especially when dyeing with reactive dyes.
  • the alkali is added to the dyeing process before, after or during the application of the dye to the fiber material; After fixing, the alkali must be removed together with dye hydrolyzates in complex washing processes.
  • the dye hydrolyzates produced in conventional processes cause heavy bleeding or at least a blurring of sharp contours if they cannot be washed out sufficiently.
  • the ink-jet or ink-jet printing process is the only way of producing color images quickly, quietly and in high resolution.
  • This process typically uses aqueous inks that are sprayed directly onto the substrate in small droplets.
  • a distinction is made between a continuous process in which the ink is pressed evenly through a nozzle and directed onto the paper or into an ink catcher by an electric field, depending on the pattern to be printed, and an interrupted ink jet or "drop-on-demand""-Procedure, in which the ink is ejected only where a colored dot is to be set, in the latter method exerting pressure on the ink system via a piezoelectric crystal or a heated cannula (bubble or thermo-jet method) and so on an ink drop is thrown out.
  • Such Procedures are in text. Chem. Color. 19 (8), 23-29, and 21 (6), 27-32.
  • R 10 is preferably hydrogen or alkyl of 1 to 3 carbon atoms, such as methyl and ethyl, and particularly preferably hydrogen, methyl or ethyl, especially hydrogen.
  • R 11 is preferably hydrogen, alkyl of 1 to 4 carbon atoms, in particular methyl and ethyl, phenyl or alkyl of 2 to 4 carbon atoms, which is substituted by methoxy or ethoxy, of which less preferably hydrogen.
  • the group of the formula (8a) preferably represents a secondary amino group, such as in particular the methylamino or ethylamino group.
  • radicals R A and R B represents an alkyl group with a group of the formula (5a) or (5b).
  • alkyl, alkenyl and alkylene radicals mentioned for the above formula radicals can be straight-chain or branched. Within the scope of their given meaning, the individual formula residues can have meanings which are the same or different from one another.
  • Compounds (1), (2), (3a) and (3b) which can be used according to the invention are, for example, ⁇ -sulfato-ethylamine, 2-oxo-1,3-oxazolidine, 4-aminomethyl-2-oxo-1,3-oxazolidine, 5-aminomethyl-2-oxo-1,3-oxazolidine, 4- (trimethylammonium-methyl) -2-oxo-1,3-oxazolidine chloride, 5- (trimethylammonium-methyl) -2-oxo-1,3- oxazolidine chloride, 1- (trimethylammonium methyl) ethylene carbonate chloride, N- ( ⁇ -sulfatoethyl) piperazine, N- [ ⁇ - ( ⁇ '-sulfatoethoxy) ethyl] piperazine, N- ( ⁇ -sulfato- ⁇ - hydroxypropyl) piperidine, N- ( ⁇ -sulfato- ⁇ -hydroxypropyl)
  • Silane compounds of the general formula (4) which can be used according to the invention are, for example: [ ⁇ - ( ⁇ '-aminoethoxy) propyl] trimethoxy silane, [ ⁇ - ( ⁇ '-aminoethylamino) propyl] trimethoxy silane, [ ⁇ - ( ⁇ '-aminoethoxy) propyl] methyl diethoxy silane, [ ⁇ - ( ⁇ '-aminoethyl amino) propyl] methyl dimethoxy silane, 3- or 4-aminophenyltrimethoxy silane , [ ⁇ - (4-aminophenoxy) propyl] trimethoxysilane, N- [ ⁇ - (trimethoxysilyl) propyl] -N, N-di- ( ⁇ '-aminoethyl) amine, ( ⁇ -aminopropyl ) -trimethoxy-silane, ( ⁇ -aminopropyl) -ethoxy-dimethyl-
  • the compounds (1) and (2) which can be used according to the invention can be prepared in accordance with known procedures, as described in large numbers in the literature (see Houben-Weyl, Methods of Organic Chemistry, 4th edition, volume E4, pages 82-88 and 192 ff.), for example by reacting an alkanediol which has a latent nitrogen-containing functional group in the side chain with phosgene in aqueous solution at a pH between 7 and 9 to prepare the heterocycloaliphatic carbonates or, for example, by reacting Aminoalkanols with phosgene in aqueous solution to the heterocycloaliphatic carbamic acid compounds (2-oxo-1,3-oxazolidines).
  • the compounds (3a) and (3b) which can be used according to the invention can be prepared in such a way that their corresponding hydroxyl-containing compounds are esterified in a conventional manner by reaction with the acids or the corresponding acylating agents, where, if one of compounds containing amino groups with more than one hydroxyl group, preferably only one of these hydroxyl groups esterified.
  • Such procedures are known in the literature; the compounds which can be used according to the invention can be prepared analogously to such known procedures.
  • the esterification of amino alcohols to their sulfuric acid esters is described in Houben-Weyl, Methods of Organic Chemistry, Volume VI / 2, pages 452-457, and Volume E11, pages 997 ff.
  • Esterification and acylating agents which can serve as starting compounds for the preparation of the compounds containing ester and amino groups which can be used according to the invention are, for example, sulfuric acid, phosphoric acid, polyphosphoric acid, lower alkane carboxylic acids and their chlorides or anhydrides, such as, for example, acetic acid (glacial acetic acid) and acetic anhydride, benzenesulfonic acid and the on the benzene nucleus by substituents from the group sulfo, carboxy, lower alkyl, lower alkoxy and nitro substituted benzenesulfonic acids or their sulfochlorides.
  • the sulfato compounds can be prepared from the corresponding hydroxy compounds by adding the hydroxy compounds in the required amount, ie preferably an equimolar amount, of concentrated sulfuric acid and stirring them at a temperature between 5 and 30 ° C. for some time until the solution is complete. They are isolated from the sulfuric acid solution by pouring the solution onto ice and neutralization, by precipitating the sulfate ions using calcium carbonate as calcium sulfate and then filtering and evaporating the aqueous solution.
  • the example of the sulfato compounds gives crystalline or semi-crystalline substances which can be used directly in the process of modifying the fiber material.
  • silane compounds used in accordance with the invention are described in large numbers in the literature and some are commercially available. Not known as species Silane compounds can be synthesized analogously to the procedures for the preparation of the known silane compounds, such as, for example, analogously to the information in German Patent DE-C-1 186 061.
  • the starting compounds of the general formulas (15a) and (15b) are prepared in a conventional manner by starting from the corresponding hydroxy compound (amino alcohol) and using the metallic alkali metal, such as sodium and especially potassium, in a manner known per se in the implements solvents mentioned above.
  • the reaction takes place at a temperature between 50 and 150 ° C., preferably between 80 and 110 ° C. It is advantageous to choose a solvent with a boiling point which is sufficiently high that the alkali metal can be heated above its melting point in order to simplify and accelerate the reaction.
  • Solvents suitable for this are, in particular, aliphatic hydrocarbons with a boiling range from 70 to 150 ° C., such as heptane and dodecane, and mixtures thereof, furthermore aromatic hydrocarbons, such as, for example, alkyl-substituted benzenes and naphthalenes, such as in particular toluene and xylene, and furthermore aliphatic, in particular cycloaliphatic Ether compounds such as tetrahydrofuran.
  • aliphatic hydrocarbons with a boiling range from 70 to 150 ° C. such as heptane and dodecane, and mixtures thereof
  • aromatic hydrocarbons such as, for example, alkyl-substituted benzenes and naphthalenes, such as in particular toluene and xylene
  • aliphatic, in particular cycloaliphatic Ether compounds such as tetrahydrofuran.
  • Fiber materials are understood to mean natural and synthetic fiber materials which contain hydroxyl and / or carbonamide groups, such as silk, wool and other animal hair, and also synthetic polyamide fiber materials and polyurethane fiber materials, for example polyamide-4, polyamide-6 and polyamide-11, and in particular fiber materials which Base bodies of ⁇ , ⁇ -glucose contain, such as cellulose fiber materials, for example cotton, hemp, jute and linen, and their regenerated derivatives, such as viscose silk and cellulose, or mixtures of such fiber materials, the fiber material in the present ink-jet dyeing process as a flat structure (Piece goods), such as woven or knitted fabrics, must be present.
  • anionic dyes are meant those which are anionic, i.e. contain acidic groups, such as sulfo and carboxy groups, or their salts, such as alkali metal salts, and are accordingly water-soluble.
  • anionic dyes which have a fiber-reactive group, i.e. a group that is usually able to react with the carbonamide or hydroxy groups of the fiber material and to be able to form a connection with them.
  • the modification of the fiber material with the amino group-containing compounds can be carried out, for example, in such a way that the fiber material with one of these compounds which can be used according to the invention or a mixture of such compounds in alkaline aqueous solution and the compound containing amino groups at a temperature between 60 and 230 ° C., preferably between 90 and 190 ° C, can act on the fiber material.
  • the concentration of this compound in the alkaline aqueous solution is generally between 1 and 20% by weight, preferably between 5 and 10% by weight.
  • the alkaline agent such as sodium hydroxide, sodium carbonate and potassium carbonate, is dissolved in a concentration between 0.1 and 20% by weight, preferably between 5 and 10% by weight.
  • this alkaline aqueous solution has a pH between 10 and 14.
  • the fiber material can be present both in the modification and in the modified form when used in the dyeing process according to the invention in a mixture with other fiber materials, for example in the form of cotton / polyester fiber materials and in the form of blended fabrics with other fiber materials.
  • the amino group-containing compounds which can be used to modify the fiber material can be brought into contact with the fiber material in an alkaline aqueous solution in a variety of ways, for example by treating the fiber material in an alkaline, aqueous solution of the amino group-containing compound (analogously to a dye-drawing process) at a temperature between 15 and 100 ° C, the modification of the fiber material already taking place, in particular at the higher temperatures.
  • Other possibilities are to pad the fiber material with the aqueous, alkaline solution, to splash or to spray the solution onto the fiber material.
  • the impregnation of the fiber material with this alkaline, aqueous solution occurs by introducing the fiber material into this solution or by padding (padding), the impregnated material is then squeezed out by excess liquor so that the absorption of this aqueous, alkaline solution between 50 and 120% by weight, preferably between 70 and 100% by weight, based on the fiber material.
  • the impregnation (by padding, splashing or treatment in the solution itself) takes place at a temperature between 10 and 60 ° C., preferably at a temperature between 15 and 30 ° C.
  • the solution is sprayed onto the fiber material, which usually takes place at a temperature between 10 and 40 ° C, a liquid absorption of preferably between 10 and 50% by weight.
  • the amino group-containing compound that can be used according to the invention can also advantageously be applied to the cellulose fiber material to be modified directly after the mercerization process, in which the mercerized material still contains the alkali, for example by using the aqueous solution to obtain the one obtained after the mercerization process Alkali-impregnated material, if necessary, squeezed to a required liquid content and the alkaline-impregnated material impregnated with the aqueous solution of the compound containing amino groups that can be used according to the invention, the impregnation being carried out by padding, spraying and similar process steps which are customary and known in the art.
  • the impregnated material is dried; as a rule, the drying of the compound modifying the fiber is carried out simultaneously with the drying, a temperature between 100 and 230 ° C., in particular between 120 and 190 ° C., preferably being chosen for the drying and fixing. As a rule, drying and simultaneous fixing take place by treatment with hot air for 1 to 5 minutes.
  • the fiber-modifying compound can be fixed on the fiber material by simple drying at higher temperatures; it can be hung up in drying cabinets to dry and fix the modifying compound on the fiber material and exposed to the required higher temperatures, such as 80 to 105 ° C.
  • the modified fiber material is aftertreated by rinsing with cold and hot water and optionally by treatment in an aqueous bath containing a small amount of an acid, such as acetic acid, to remove the alkali from the fiber material and then drying.
  • an acid such as acetic acid
  • the dye solutions are applied to the modified fiber material (woven, knitted or non-woven) with the help of commercially available inkjet printers, which are converted if necessary for large-scale purposes.
  • Neutral, preferably aqueous, solutions of the anionic dyes are used, the anionic dyes preferably containing a fiber-reactive group.
  • the dye solutions can contain auxiliaries such as are usually present in the inks for inkjet printers, such as anti-aggregation agents such as N-methyl-pyrrolidone, dimethylformamide and dimethylacetamide, and wetting agents such as ionic or non-ionic surfactants.
  • auxiliaries that are usually required for dyeing with anionic, in particular fiber-reactive, dyes can be dispensed with.
  • anionic dyes are expediently used in the form free from electrolyte salts, such as sodium chloride and sodium sulfate.
  • electrolyte salts such as sodium chloride and sodium sulfate.
  • commercially available dye preparations with up to 50% by weight of electrolyte salt can generally also be applied without problems in the process according to the invention using the inkjet printing technique.
  • multi-color printing several ink cartridges can be connected in series, which can be controlled with the means common today to generate the print on the moving material web. Modern multi-chamber inkjet cartridges can also be used, with which several colors can be applied in one pass.
  • the dye solution (ink) is applied to the modified material to be colored in accordance with the inkjet printing process, specifically in tiny drops of ink.
  • the material dyed in this way is then subjected to a treatment with superheated steam, hot air or by means of another energy, such as by means of radiation with electromagnetic waves in the microwave or radio frequency range, the dyes being fixed on the modified fiber material.
  • a treatment with superheated steam, hot air or by means of another energy such as by means of radiation with electromagnetic waves in the microwave or radio frequency range
  • the dyeing process can be carried out without exposure to any waste water which, for example, contains dye, alkali and electrolyte salts which have not been fixed according to the dyeing processes hitherto customary, or without exposure to other waste products.
  • any waste water which, for example, contains dye, alkali and electrolyte salts which have not been fixed according to the dyeing processes hitherto customary, or without exposure to other waste products.
  • strongly colored print samples with the usual good fastness properties are obtained.
  • Different deeply colored shades of the same color tone can be achieved very easily by using the inkjet process, for example by controlling the application quantity of the dye solution, for example by overprinting the same line several times, or by rasterizing and printing a fine dot pattern, which is the case with today's inkjet -Printers, depending on the process, can even be over 400 dpi.
  • a large number of color intensities (color saturations) can be obtained without having to recreate the dyeing liquor.
  • All water-soluble, preferably anionic dyes which preferably have one or more sulfo and / or carboxy groups and which can optionally contain fiber-reactive groups, are suitable for the dyeing methods according to the invention.
  • fiber-reactive dyes they can belong to the class of azo development dyes, direct dyes, vat dyes and acid dyes, which include, for example, azo dyes, copper complex, cobalt complex and chromium complex azo dyes, copper and nickel phthalocyanine dyes, anthraquinone and copper formazan - And triphendioxazine dyes.
  • azo development dyes direct dyes
  • vat dyes and acid dyes which include, for example, azo dyes, copper complex, cobalt complex and chromium complex azo dyes, copper and nickel phthalocyanine dyes, anthraquinone and copper formazan - And triphendioxazine dyes.
  • azo dyes copper complex, cobalt complex and
  • Fiber-reactive dyes are those organic dyes that contain 1, 2, 3 or 4 fiber-reactive residues of the aliphatic, aromatic or heterocyclic series contain. Such dyes have been extensively described in the literature.
  • the dyes can belong to a wide variety of dye classes, for example the class of monoazo, disazo, polyazo and metal complex azo dyes, such as 1: 1 copper, 1: 2 chromium and 1: 2 cobalt complex monoazo and -Disazo dyes, further the series of anthraquinone dyes, copper and cobalt phthalocyanine dyes, copper formazan dyes, azomethine, nitroaryl, dioxazine, triphendioxazine, phenazine and stilbene dyes.
  • monoazo, disazo, polyazo and metal complex azo dyes such as 1: 1 copper, 1: 2 chromium and 1: 2 cobalt complex monoazo and -Disazo dyes, further the series of anthraquinone dyes, copper and cobalt phthalocyanine dyes, copper formazan dyes, azomethine, nitroaryl, dioxazine, triphendioxazine, phena
  • Fiber-reactive dyes are understood to mean those which have a “fiber-reactive” group, ie a group which contains the hydroxyl groups of cellulose, the amino, carboxy, hydroxyl and thiol groups of wool and silk or the amino and possibly carboxy groups of synthetic polyamides can react to form a covalent chemical bond.
  • the fiber-reactive residue can be bound to the dye residue directly or via a bridge member; it is preferably directly or via an optionally monoalkylated amino group, such as, for example, a group of the formula -NH-, -N (CH 3 ) -, -N (C 2 H 5 ) - or -N (C 3 H 7 ) -, or via an aliphatic radical, such as a methylene, ethylene or propylene radical or an alkylene radical of 2 to 8 carbon atoms, which is interrupted by one or two oxi and / or amino groups, or via a bridge member containing an amino group, such as for example a phenylamino group attached to the dye residue.
  • an optionally monoalkylated amino group such as, for example, a group of the formula -NH-, -N (CH 3 ) -, -N (C 2 H 5 ) - or -N (C 3 H 7 ) -, or via an aliphatic radical,
  • Particularly interesting fiber-reactive radicals are fluorine and chloro-1,3,5-triazine radicals of the formula (16) in which Hal is chlorine or fluorine and Q is an amino, alkylamino, N, N-dialkylamino, cycloalkylamino, N, N-dicycloalkylamino, aralkylamino, arylamino, N-alkyl-N-cyclohexylamino, N- Alkyl-N-arylamino group or an amino group which contains a heterocyclic radical which may have a further fused-on carbocyclic ring, or amino groups in which the amino nitrogen atom is a member of an N-heterocyclic ring which optionally contains further heteroatoms, and hydrazino and semicarbazido groups , where the alkyl radicals mentioned can be straight-chain or branched and low molecular weight and higher molecular weight, preferably those having 1 to 6 carbon atoms.
  • Suitable cycloalkyl, aralkyl and aryl radicals are, in particular, cyclohexyl, benzyl, phenethyl, phenyl and naphthyl radicals; Heterocyclic residues are especially furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole and benzoxazole residues.
  • Amino groups in which the amino nitrogen atom is a member of an N-heterocyclic ring, are preferably residues of six-membered N-heterocyclic compounds which may contain nitrogen, oxygen or sulfur as further heteroatoms.
  • alkyl, cycloalkyl, aralkyl and aryl radicals mentioned above, the heterocyclic radicals and the N-heterocyclic rings can additionally be substituted, for example by halogen, such as fluorine, chlorine and bromine, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C. 1 -C 4 alkyl, C 1 -C 4 alkoxy, acylamino groups such as acetylamino or benzoylamino, ureido, hydroxy, carboxy, sulfomethyl or sulfo.
  • halogen such as fluorine, chlorine and bromine
  • sulfamoyl carbamoyl
  • C. 1 -C 4 alkyl C 1 -C 4 alkoxy
  • acylamino groups such as acetylamino or benzoylamino, urei
  • amino groups are: -NH 2 , methylamino, ethylamino, propylamino, isopropylamino, butylamino, hexylamino, ⁇ -methoxyethylamino, ⁇ -methoxypropylamino, ⁇ -ethoxyethylamino, N, N-dimethylamino, N, N-diethylamino, ⁇ - Chloroethylamino, ⁇ -cyanoethylamino, ⁇ -cyanopropylamino, ⁇ -carboxyethylamino, sulfomethylamino, ⁇ -sulfoethylamino, ⁇ -hydroxyethylamino, N, N-di- ⁇ -hydroxyethylamino, ⁇ -hydroxypropylamino, benzylamino, phenethylamino, cyclohexylamino, pheni
  • Q can be an amino radical of the general formula -NR 20 R 21 , in which R 20 is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl or ethyl, and R 21 is phenyl, which is directly by a fiber-reactive radical of the vinylsulfone series or is substituted by a methylamino, ethylamino, methylene, ethylene or propylene group and which can also be substituted by 1 or 2 substituents from the group methoxy, ethoxy, methyl, ethyl, chlorine, carboxy and sulfo, or R 21 alkyl of 2 to 4 carbon atoms, such as ethyl or n-propyl, which is substituted by a fiber-reactive group of the vinylsulfone series, or alkylenephenyl with an alkylene radical of 1 to 4 carbon atoms, the phenyl of which is substituted by a fiber-reactive radical of the vinylsulfone series
  • Fiber-reactive groups of the vinylsulfone series are those of the general formula -SO 2 -Y, in which Y is vinyl or ethyl which is substituted in the ⁇ -position by an alkali-eliminable substituent, such as, for example, chlorine, sulfato, phosphato, thiosulfato, acetyloxy, Sulfobenzoyloxy and dimethylamino.
  • the dyeings of the modified cellulose fiber materials obtainable in the manner according to the invention do not require any further aftertreatment after the dye has been fixed on the substrate, in particular no complicated aftertreatment process including washing. If necessary at all, it is sufficient to rinse the colored substrate once or several times with warm or hot and, if appropriate, cold water, which may optionally contain a nonionic wetting agent or a fiber-reactive aftertreatment agent, such as, for example, condensation products from one mole of cyanuric chloride and two moles of 4- ( ⁇ -Sulfatoethylsulfonyl) aniline, from equivalent amounts of cyanuric chloride, 4- ( ⁇ -sulfatoethylsulfoanyl) aniline and 4,8-disulfo-2-amino-naphthalene or from equivalent amounts of cyanuric chloride, 4-sulfo-aniline and 4.8- Disulfo-2-aminonaphthalene.
  • a fiber-reactive aftertreatment agent is advisable if the fiber material modified according to the invention has been dyed only in slight depths of shade or if a dye has been used which does not have satisfactory fiber reactivity. In these cases, there are still sufficient dye-reactive spots on the modified fiber, which, for example, can react with other dyes in rinsing baths contaminated with these dyes.
  • the still active areas of the invention modified fiber is deactivated, and the originally desired clear color is obtained even in a rinsing water used in a technical process and contaminated with dyes.
  • a final boiling treatment of the colored substrate with a washing solution to improve the fastness properties is not necessary.
  • an amino group-containing compound which can be used according to the invention and which serves to modify the fiber material
  • a mixture of 750 parts by volume of a 100% strength sulfuric acid and 75 parts by volume of a 20% sulfuric acid-containing sulfuric acid (20% strength oleum) is added 10 ° C slowly with stirring 500 parts by volume of N- ( ⁇ -hydroxyethyl) piperidine, the reaction temperature being kept between 20 and 25 ° C with constant cooling.
  • the reaction mixture is stirred into 1000 parts of ice water, the pH is adjusted to 4 with calcium carbonate, the batch is briefly heated to 50 ° C. and the calcium sulfate formed is then filtered off. Calcium ions still present are precipitated from the filtrate with sodium oxalate.
  • the aqueous solution of the N- ( ⁇ -sulfatoethyl) piperidine is evaporated to dryness under reduced pressure. A yellow, oily product is obtained which crystallizes and melts at 124 ° C. with decomposition.
  • N- ( ⁇ -sulfato- ⁇ -hydroxypropyl) piperidine To prepare N- ( ⁇ -sulfato- ⁇ -hydroxypropyl) piperidine, slowly add 100 parts of N- ( ⁇ , ⁇ -dihydroxypropyl) piperidine to 67 parts of 100% sulfuric acid with stirring at 20 ° C. . The mixture is stirred for a further hour and the piperidine compound according to the invention is isolated in the manner described in Example A. It is initially obtained as an oily product which crystallizes after some time. It melts at 170 to 175 ° C with decomposition.
  • N- ( ⁇ -sulfato- ⁇ -hydroxy-propyl) pyrrolidine 50 parts of N- ( ⁇ , ⁇ -dihydroxy-propyl) pyrrolidine in 98 parts of 100% sulfuric acid are slowly added with stirring at 20 ° C. . The batch is stirred for a further hour and the compound formed is then isolated as an oily product in the manner given in Example A.
  • a silane compound which can be used according to the invention 67.9 parts of N-methylaminoethanol are slowly added to 35.2 parts of potassium in 1000 parts by volume of tetrahydrofuran, the exothermic reaction being kept at a temperature between 30 and 40 ° C. by external cooling. The mixture is then heated under reflux until the potassium has reacted completely (about 5 hours). The mixture is then cooled to about 20 ° C. and 190.3 parts of ⁇ -chloropropyl- (methyl) - (diethoxy) -silane are added, the reaction temperature being kept below 40 ° C. by external cooling if necessary.
  • Example A To prepare a silane compound which can be used according to the invention, the procedure of Example A is followed, but the equivalent amount of ⁇ -chloropropyl-triethoxysilane is used instead of the ⁇ -chloropropyl-methyl-diethoxy-silane compound.
  • the [ ⁇ - ( ⁇ '-N-methylaminoethoxy) propyl] triethoxysilane of the formula according to the invention is obtained by fractional distillation at a boiling range between 104 and 118 ° C at 5 • 10 -2 mbar.
  • a silane compound is prepared according to the procedure of Example A, but instead of the ⁇ -chloropropyl-methyl-diethoxy-silane compound, the equivalent amount of ( ⁇ -chloropropyl) - (dimethyl) - (ethoxy) -silane is used.
  • the compound according to the invention [ ⁇ - ( ⁇ '-N-methylaminoethoxy) propyl] - (dimethyl) - (ethoxy) silane of the formula is obtained by fractional distillation at a boiling range between 90 and 105 ° C at 5 • 10 -2 mbar.
  • a mercerized and bleached cotton fabric is impregnated with an aqueous solution of 50 parts of sodium hydroxide and 100 parts of the monosulfate of 2,3-dihydroxy-1-aminopropane in 1000 parts of water at a temperature between 25 and 30 ° C with a liquor absorption of 85% and then to Fixation of the aminopropane compound on the fiber material treated with hot air at 150 ° C. for about 3 minutes, the impregnated fabric drying at the same time.
  • the modified material is then freed from excess alkali by treatment with cold water at 60 ° C.
  • the thus modified, dried material is passed under a stainless steel sheet with the aid of a rubber roller and printed in one operation with the aqueous solutions of fiber-reactive dyes in the basic colors of the subtractive color mixture by means of an ink jet print head which works according to the "drop on demand" process.
  • the web is then passed through a continuously working microwave dryer for fixation.
  • the dyed material can then be finished by washing; however, a short, hot wash bath and subsequent drying is usually sufficient.
  • the fabric obtained shows a very sharp color print of the chosen pattern; the dye itself has good wash fastness.
  • the fabric obtained shows a very sharp color print of the chosen pattern; the dye itself has good wash fastness.
  • a cellulose fiber material modified according to the invention such as, for example, a cellulose fiber material modified in accordance with the above exemplary embodiments, is printed on using the procedure of an inkjet printer, for example analogously using one of the methods described in the above exemplary embodiments, using aqueous solutions of one or more known dyes specified in the table examples below (the dyes are written in the form of the free acid; however, they are used in the form of their alkali metal salts). Clear, strong-colored print samples are obtained with the color shade given in the respective table example and the fastness properties, in particular good fastness to washing, which are good for the respective dye.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coloring (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP93114661A 1992-09-26 1993-09-13 Verfahren zur Herstellung von Färbungen gemäss der "Ink-Jet"-Drucktechnik auf modifizierten Fasermaterialien mit anionischen Textilfarbstoffen Expired - Lifetime EP0590397B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4232331 1992-09-26
DE4232331 1992-09-26

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EP0590397A1 EP0590397A1 (de) 1994-04-06
EP0590397B1 true EP0590397B1 (de) 1997-03-12

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US (1) US5348557A (enrdf_load_stackoverflow)
EP (1) EP0590397B1 (enrdf_load_stackoverflow)
JP (1) JPH06192976A (enrdf_load_stackoverflow)
KR (1) KR940007285A (enrdf_load_stackoverflow)
CN (1) CN1087694A (enrdf_load_stackoverflow)
AT (1) ATE150110T1 (enrdf_load_stackoverflow)
BR (1) BR9303904A (enrdf_load_stackoverflow)
CA (1) CA2106893A1 (enrdf_load_stackoverflow)
DE (1) DE59305724D1 (enrdf_load_stackoverflow)
IL (1) IL107082A0 (enrdf_load_stackoverflow)
MX (1) MX9305879A (enrdf_load_stackoverflow)
TR (1) TR27347A (enrdf_load_stackoverflow)
TW (1) TW228543B (enrdf_load_stackoverflow)

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DE4306432A1 (de) * 1993-03-02 1994-09-08 Hoechst Ag Verfahren zum Bedrucken und Färben von Textilien (Inverser Reservedruck)
DE4306433A1 (de) * 1993-03-02 1994-09-08 Hoechst Ag Ink-Jet-Einphasen-Reaktivdruck
DE4402210A1 (de) * 1994-01-26 1995-07-27 Hoechst Ag Verfahren zur Herstellung aminierter Baumwollfasern
DE4422758A1 (de) * 1994-06-29 1996-01-04 Hoechst Ag Aminierte Cellulose-Regeneratfasern
ATE273412T1 (de) * 1994-04-15 2004-08-15 Canon Kk Tintenstrahldruckgewebe, tintenstrahldruckverfahren und damit hergestellte drucke
ATE168143T1 (de) * 1994-05-17 1998-07-15 Dystar Textilfarben Gmbh & Co Aminierung von cellulosischen synthesefasern
DE4417211A1 (de) * 1994-05-17 1995-11-23 Hoechst Ag Aminierung von Regeneratcellulose
JP3584094B2 (ja) * 1994-10-25 2004-11-04 キヤノン株式会社 インクジェット捺染用布帛、捺染方法及び捺染物
US5944852A (en) * 1996-10-23 1999-08-31 Solutia Inc. Dyeing process
US5830240A (en) * 1996-10-23 1998-11-03 Solutia Inc. Fibers and textile materials having enhanced dyeability and finish compositions used thereon
US6200667B1 (en) 1997-03-24 2001-03-13 Canon Kabushiki Kaisha Cloth for textile printing, and textile printing process using the cloth and print obtained thereby
US6350872B1 (en) 1998-10-28 2002-02-26 The Virkler Company Salt free dyeing of cellulosic fibers with anionic dyes
DE10004954A1 (de) * 2000-02-04 2001-08-16 Dystar Textilfarben Gmbh & Co Wässrige Drucktinten für den Einsatz nach dem Tintenstrahldruck-Verfahren, ihre Herstellung und ihre Verwendung auf textilen Fasermaterialien
US6962735B2 (en) * 2001-08-31 2005-11-08 Milliken & Company Textile printing substrate
JP5245147B2 (ja) * 2007-07-19 2013-07-24 独立行政法人産業技術総合研究所 含窒素有機珪素化合物
US8071694B2 (en) * 2008-02-20 2011-12-06 Sabic Innovative Plastics Ip B.V. Thermoplastic polycarbonate/polyester blend compositions with improved mechanical properties
JP5639347B2 (ja) * 2009-06-18 2014-12-10 旭化成せんい株式会社 ポリアミド繊維とセルロース繊維とポリウレタン繊維との混用糸状又は布帛染色品
CN103827232B (zh) 2011-09-30 2015-09-30 富士胶片株式会社 印染用水性着色组合物、印染方法及布帛
EP2776415B1 (en) * 2011-11-10 2016-02-03 Rhodia Operations Cyclic (poly)glycerol sulphates and preparation and use thereof
WO2013067915A1 (en) * 2011-11-10 2013-05-16 Rhodia Operations Novel method to manufacture surface active compounds such as sulfate betaine
PT106070A (pt) 2011-12-23 2013-06-24 Yd Ynvisible S A Solução de electrólito, método de impressão da mesma e electrólito sólido resultante
JP6409869B2 (ja) * 2014-05-08 2018-10-24 コニカミノルタ株式会社 インクジェット記録方法およびインクジェット記録装置
CN108193525B (zh) * 2018-02-01 2020-05-05 东莞长联新材料科技股份有限公司 用于纺织品涂料喷墨印花的处理液及其制备方法、涂料喷墨印花方法

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FR1294236A (fr) * 1961-04-12 1962-05-26 Dow Corning Procédé de teinture de fibres textiles non siliceuses
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TW223134B (enrdf_load_stackoverflow) * 1991-05-11 1994-05-01 Hoechst Ag
TW211595B (enrdf_load_stackoverflow) * 1991-12-07 1993-08-21 Hoechst Ag

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Publication number Publication date
DE59305724D1 (de) 1997-04-17
TW228543B (enrdf_load_stackoverflow) 1994-08-21
EP0590397A1 (de) 1994-04-06
MX9305879A (es) 1994-05-31
KR940007285A (ko) 1994-04-26
ATE150110T1 (de) 1997-03-15
US5348557A (en) 1994-09-20
JPH06192976A (ja) 1994-07-12
BR9303904A (pt) 1994-04-26
CA2106893A1 (en) 1994-03-27
CN1087694A (zh) 1994-06-08
TR27347A (tr) 1995-01-13
IL107082A0 (en) 1993-12-28

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