EP0924335A1 - Process for printing textile fibres materials according to the ink-jet printing process - Google Patents

Process for printing textile fibres materials according to the ink-jet printing process Download PDF

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Publication number
EP0924335A1
EP0924335A1 EP98811210A EP98811210A EP0924335A1 EP 0924335 A1 EP0924335 A1 EP 0924335A1 EP 98811210 A EP98811210 A EP 98811210A EP 98811210 A EP98811210 A EP 98811210A EP 0924335 A1 EP0924335 A1 EP 0924335A1
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EP
European Patent Office
Prior art keywords
hydrogen
alkyl
acid
halogen
weight
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Application number
EP98811210A
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German (de)
French (fr)
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EP0924335B1 (en
Inventor
Marc Burglin
Mickael Mheidle
Peter Scheibli
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Huntsman Advanced Materials Switzerland GmbH
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Ciba Geigy AG
Ciba Spezialitaetenchemie Holding AG
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Priority to EP98811210A priority Critical patent/EP0924335B1/en
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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
    • 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
    • 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
    • D06P1/16—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 dispersed, e.g. acetate, dyestuffs
    • 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
    • D06P1/16—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 dispersed, e.g. acetate, dyestuffs
    • D06P1/18—Azo 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
    • D06P1/16—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 dispersed, e.g. acetate, dyestuffs
    • D06P1/19—Nitro 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
    • D06P1/16—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 dispersed, e.g. acetate, dyestuffs
    • D06P1/20—Anthraquinone 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
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • 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
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5228—Polyalkenyl alcohols, e.g. PVA
    • 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
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5242—Polymers of unsaturated N-containing 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
    • 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
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
    • D06P1/5257—(Meth)acrylic acid

Definitions

  • the present invention relates to a method for printing textile fiber materials with disperse dyes according to the inkjet printing process (jet and inkjet processes) as well as corresponding printing inks.
  • Inkjet printing processes have been used in the textile industry for several years. These methods make it possible to produce a printing stencil that is otherwise customary to do without, so that considerable cost and time savings are achieved can. Especially when producing sample templates can be significantly less within Time to be reacted to changing needs.
  • Corresponding inkjet printing processes should, in particular, optimal application technology Have properties.
  • properties should be mentioned such as viscosity, stability, surface tension and conductivity of the used Inks.
  • the present invention relates to a method for printing textile fiber materials according to the inkjet printing process, which is characterized in that that you print the fiber materials with an aqueous ink, which at least one Disperse dye, an anionic copolymer and / or a nonionic block polymer and / or contains a dispersant.
  • Suitable disperse dyes for the process according to the invention are those dyes which in the Color Index, 3rd edition (3rd revision 1987 including Additions and Amendments to No. 85) are described under "Disperse Dyes”. Examples include nitro, amino, aminoketone, ketoninim, methine, carboxylic acid and / or sulfonic acid group-free Polymethine, diphenylamine, quinoline, benzimidazole, xanthene, oxazine or coumarin dyes and in particular anthraquinone and azo dyes, such as mono- or disazo dyes.
  • the dyes of the formulas are particularly preferred in the process according to the invention used.
  • the disperse dyes of the formulas (1) to (23) are known or can be prepared in analogy to known compounds by known standard processes, for example by customary diazotization, coupling, addition and condensation reactions.
  • the inks generally contain a total content of disperse dyes of the above Formulas (1) to (23) from 1 to 35% by weight, in particular 1 to 20% by weight, especially 1 to 10% by weight based on the total weight of the ink.
  • the disperse dyes are advantageously in the inks according to the invention, in a finely dispersed form.
  • the disperse dyes are ground, see above that their particle size averages between 0.1 and 10 microns, preferably between 1 and 5 microns, more preferably between 0.5 and 2 microns. Grinding can be done in In the presence of dispersants.
  • the dried disperse dye ground with a dispersant or in paste form with a dispersant kneaded and optionally dried in vacuo or by atomization. With the so obtained Preparations can be made after adding water and, if necessary, other auxiliaries produce the inks according to the invention.
  • Suitable anionic copolymers for the process according to the invention are primarily copolymers based on acrylic acid, methacrylic acid or maleic acid. Among these, preference is given to those which are obtained by polymerizing acrylic and / or methacrylic acid and one or more copolymerizable monomers from the group of maleic acid, N-vinylformamide, N-vinyl acetamide, allylamine or diallylamine derivatives, N-vinylpyrrolidone, N-vinyl -N-methyl-formamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl-acetamide, vinyl acetate, vinyl propionate, acrylonitrile, styrene, methacrylonitrile, acrylamide, methacrylamide and N-mono / N, N-di -C 1 -C 10 alkyl (meth) acrylamide are available.
  • Anionic copolymers which are obtainable by copolymerization of acrylic or methacrylic acid and styrene are particularly preferred.
  • Acrylic and methacrylic acid-styrene copolymers with a are very particularly preferred Molecular weight from 3000 to 16000, in particular from 3000 to 10000.
  • Suitable nonionic block polymers for the process according to the invention are, in particular, alkylene oxide condensation products such as, for example, ethylene oxide adducts with polypropylene oxide (so-called EO-PO block polymers) and propylene oxide adducts with polyethylene oxide (so-called reverse EO-PO block polymers), and block polymers which are caused by the addition of styrene Polypropylene and / or polyethylene oxide are available.
  • Lignosulfonates are primarily those ligninsulfonates or their alkali metal salts used, the content of sulfo groups does not exceed 25 wt .-%. Are preferred Lignin sulfonates containing 5 to 15% by weight of sulfo groups.
  • formaldehyde condensation products (bi) come e.g. Condensation products of lignin sulfonates and / or phenol and formaldehyde, condensation products of formaldehyde with aromatic sulfonic acids, e.g.
  • Condensation products of ditolyl ether sulfonates and formaldehyde condensation products of naphthalenesulfonic acid with formaldehyde and / or naphthol or naphthylaminosulfonic acids with formaldehyde, condensation products of phenol sulfonic acids and / or sulfonated dihydroxydiphenyl sulfone and phenols or cresols with formaldehyde and / or urea and condensation products of diphenyl oxide disulfonic acid derivatives with formaldehyde.
  • the total content of anionic copolymer, nonionic block polymer and dispersant in the ink according to the invention is 3 to 9% by weight, based on the total weight the ink.
  • the ratio: anionic copolymer: nonionic block polymer: dispersant in the finished ink can vary widely, e.g. 1.5: 0.5: 1; 1: 0.5: 1.5; 1: 1: 1; 1: 0: 1; 1: 1: 0; 1: 0: 0; 0: 1: 1 or 0: 0: 1.
  • Inks which contain an anionic copolymer are preferred for the process according to the invention and nonionic block polymer or anionic copolymer and dispersant or contain nonionic block polymer and dispersant.
  • Inks which are anionic copolymer, nonionic block polymer are particularly preferred and dispersants.
  • the ink can expediently contain thickeners of natural or synthetic origin, such as, for example, commercially available alginate thickeners, starch ether or locust bean gum ether, in particular sodium alginate alone or in Mixture with modified cellulose, in particular with preferably 20 to 25 percent by weight carboxymethyl cellulose.
  • thickeners such as those based on poly (meth) acrylic acids or poly (meth) acrylamides are preferably used in the inks according to the invention.
  • Preferred inks for the process according to the invention are those which have a viscosity from 1 to 40 mPa.s (millipascal second), in particular 1 to 20 mPa.s, especially 1 to 10 have mPa.s.
  • inks which have a Surface tension between 60 and 30 Newton / cm, especially between 50 and 40 Newton / cm.
  • Inks that have a conductivity of 0 are important for the method according to the invention up to 3000 ⁇ S / cm, in particular from 100 to 700 ⁇ S / cm, based on a 10% aqueous suspension.
  • the inks may also contain buffer substances, e.g. Borax, borate or citrate.
  • buffer substances e.g. Borax, borate or citrate.
  • borax e.g. borax, sodium borate, sodium tetraborate and sodium citrate.
  • she are obtained in particular in amounts of 0.1 to 3% by weight, especially 0.1 to 1% by weight on the total weight of the ink used to adjust a pH of e.g. 4 to 10, preferably 5 to 8.
  • the inks can also contain surfactants, redispersants and humectants contain.
  • the commercially available anionic or nonionic surfactants are suitable as surfactants.
  • a redispersant e.g. Mention betaine monohydrate.
  • a humectant is preferably a mixture of Na lactate (advantageously in the form of a 50 to 60% aqueous solution) and glycerin and / or propylene glycol in amounts of preferably 7 to 20 percent by weight used in the ink used in the invention.
  • the inks can also contain acid donors such as butyrolactone or sodium hydrogen phosphate, Preservatives, substances that inhibit fungal and / or bacterial growth, foam suppressants, sequestering agents, emulsifiers, water-insoluble solvents, Contain oxidizing agents or venting agents.
  • acid donors such as butyrolactone or sodium hydrogen phosphate
  • Preservatives substances that inhibit fungal and / or bacterial growth
  • foam suppressants such as butyrolactone or sodium hydrogen phosphate
  • sequestering agents such as butyrolactone or sodium hydrogen phosphate
  • emulsifiers such as water-insoluble solvents
  • Contain oxidizing agents or venting agents such as butyrolactone or sodium hydrogen phosphate
  • Suitable preservatives are, in particular, formaldehyde-releasing agents, such as, for example, paraformaldehyde and trioxane, especially aqueous, approximately 30 to 40 percent by weight formaldehyde solutions, and sequestering agents, for example sodium nitrilotriacetic acid, sodium ethylenediaminetetraacetic acid, especially sodium polymetaphosphate, especially sodium hexametaphosphate, as emulsifiers especially adducts of an alkylene oxide and a fatty alcohol, especially an adduct of oleyl alcohol and ethylene oxide, as water-insoluble solvents, high-boiling, saturated hydrocarbons, especially paraffins with a boiling range of about 160 to 210 ° C (so-called mineral spirits), as an oxidizing agent, for example an aromatic nitro compound , especially an aromatic mono- or dinitrocarboxylic acid or sulfonic acid, which is optionally present as an alkylene oxide adduct,
  • the inks are e.g. made so that one or more disperse dyes of formulas (1) to (23) mixed with a dispersant / copolymer / block polymer mixture and then in a wet mill to a defined grinding degree of one average particle size between 0.2 to 1.0 microns are ground.
  • the concentrated regrind optionally using e.g. suitable thickeners, Dispersants, copolymers, surfactants, humectants, redispersants, Sequestrants and / or preservatives, as well as water, to the desired Concentration set.
  • Portions can advantageously be a filtration of the finished ink through a microsieve of about 1 ⁇ m.
  • the method according to the invention for printing textile fiber materials can with performed on known ink jet printers suitable for textile printing become.
  • the inkjet printing process In the case of the inkjet printing process, individual drops of the ink are checked out sprayed onto the substrate using a nozzle.
  • the continuous ink jet method is predominantly used for this as well as the drop on demand method.
  • the ink-jet method generates the drops continuously, which are not for printing required drops are drained into a collecting container and are usually recycled.
  • the drips are generated as desired and printed, i.e. drops are only generated when necessary for printing is.
  • the generation of the drops can e.g. advantageously by means of a piezo inkjet head or by means of thermal energy (so-called bubble jet). Is preferred for the invention Process of printing according to the continuous ink-jet method or the Drop on demand method.
  • the fiber material is preferably at temperatures up to 150 ° C. Dried 80 ° to 120 ° C.
  • the ink used in the invention can on various types of fiber materials such as Wool, silk, cellulose, polyvinyl, polyacrylonitrile, polyamide, aramid, polypropylene, polyester or polyurethane can be applied.
  • fiber materials such as Wool, silk, cellulose, polyvinyl, polyacrylonitrile, polyamide, aramid, polypropylene, polyester or polyurethane can be applied.
  • Polyester-containing fiber materials are preferred.
  • Suitable polyester-containing fiber materials are materials which consist entirely or partially of polyester. Examples are cellulose ester fibers, such as cellulose-21 ⁇ 2-acetate fibers and triacetate fibers, and particularly linear polyester fibers, which are optionally also acid-modified, which are, for example, by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane are obtained, as well as fibers from copolymers of terephthalic and isophthalic acid with ethylene glycol. Also suitable are polyester-containing mixed fiber materials, ie mixtures of polyester and other fibers.
  • the present invention furthermore relates to an aqueous printing ink for the inkjet printing process, which is characterized in that it contains at least 1 to 35% by weight a disperse dye of the above formulas (1) to (23), an anionic copolymer and / or contains a nonionic block polymer and / or a dispersant.
  • the anionic copolymers, the nonionic Block polymers and the dispersants have the meanings given above and favors.
  • the prints obtainable by the process according to the invention have good general fastness properties on; e.g. they have high fiber-dye binding stability in both acidic as well as in the alkaline range, good light fastness, good wet fastness properties, such as Water, wash, sea water, over-dyeing and perspiration fastness, good chlorine fastness, Rubbing fastness, ironing fastness and pleating fastness as well as sharp contours and a high Color strength.
  • the printing inks used are characterized by good stability and good viscosity properties out.
  • the ink produced according to Example 1 is printed on a polyester fabric using an inkjet printer using drop on demand piezo technology.
  • the print is dried and fixed in the superheated steam at 180 ° C for 8 minutes.
  • a brilliant yellow print with good general fastness properties is also obtained, in particular Wet and light fastness, if you use the dried print for 1 minute with a Hot air fixed at 200 ° C.
  • the ink produced according to Example 3 is printed on a polyester fabric using an inkjet printer using drop on demand piezo technology.
  • the print is dried and fixed in the superheated steam at 180 ° C for 8 minutes.
  • a blue print with good general fastness properties, in particular wet and light fastness properties, is obtained.
  • a blue print with good general fastness properties, in particular wet and light fastness properties, is also obtained if the dried print is fixed with hot air at 200 ° C. for 1 minute.
  • the ink produced according to Example 5 is printed on a polyester fabric using an inkjet printer using drop on demand piezo technology.
  • the print is dried and fixed in the superheated steam at 180 ° C for 8 minutes.
  • the ink produced according to Example 7 is printed on a polyester fabric using an inkjet printer using the drop on demand piezo technique.
  • the print is dried and fixed in the superheated steam at 180 ° C for 8 minutes.
  • a pink-red print is obtained with good general fastness properties, in particular wet and light fastness properties.
  • a pink-red print with good general fastness properties is also obtained, in particular Wet and light fastness, if you dry the print for 1 minute with hot air fixed at 200 ° C.
  • the ink produced according to Example 9 is printed on a polyester fabric using an inkjet printer using drop on demand piezo technology.
  • the print is dried and fixed in the superheated steam at 180 ° C for 8 minutes.
  • a purple print with good general fastness properties is also obtained, in particular Wet and light fastness, if you dry the print for 1 minute with hot air fixed at 200 ° C.
  • the ink produced according to Example 11 is printed on a polyester fabric using an inkjet printer using drop on demand piezo technology.
  • the print is dried and fixed in the superheated steam at 180 ° C for 8 minutes.
  • a blue print with good general fastness properties, in particular wet and light fastness properties, is obtained.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Coloring (AREA)

Abstract

Ink-jet printing on textile fiber materials uses an aqueous ink containing disperse dye(s) and an anionic copolymer, nonionic block polymer and/or dispersant. Independent claims are also included for (a) the aqueous ink; and (b) textile fiber materials printed with the ink.

Description

Die vorliegende Erfindung betrifft ein Verfahren zum Bedrucken von textilen Fasermaterialien mit Dispersionsfarbstoffen nach dem Tintenstrahldruck-Verfahren (Jet- und Ink-Jet-Verfahren) sowie entsprechende Drucktinten.The present invention relates to a method for printing textile fiber materials with disperse dyes according to the inkjet printing process (jet and inkjet processes) as well as corresponding printing inks.

Tintenstrahldruck-Verfahren werden bereits seit einigen Jahren in der Textilindustrie angewendet. Diese Verfahren ermöglichen es, auf die sonst übliche Herstellung einer Druckschablone zu verzichten, so dass erhebliche Kosten- und Zeiteinsparungen erzielt werden können. Insbesondere bei der Herstellung von Mustervorlagen kann innerhalb deutlich geringerer Zeit auf veränderte Bedürfnisse reagiert werden.Inkjet printing processes have been used in the textile industry for several years. These methods make it possible to produce a printing stencil that is otherwise customary to do without, so that considerable cost and time savings are achieved can. Especially when producing sample templates can be significantly less within Time to be reacted to changing needs.

Entsprechende Tintenstrahldruck-Verfahren sollten insbesondere optimale anwendungstechnische Eigenschaften aufweisen. Zu erwähnen seien in diesem Zusammenhang Eigenschaffen wie Viskosität, Stabilität, Oberflächenspannung und Leitfähigkeit der verwendeten Tinten. Ferner werden erhöhte Anforderungen an die Qualität der erhaltenen Drucke gestellt, wie z.B. bezüglich Farbstärke, Faser-Farbstoff-Bindungsstabilität sowie Nassechtheitseigenschaffen. Von den bekannten Verfahren werden diese Anforderungen nicht in allen Eigenschaften erfüllt, so dass weiterhin ein Bedarf nach neuen Verfahren für den textilen Tintenstrahldruck besteht.Corresponding inkjet printing processes should, in particular, optimal application technology Have properties. In this context, properties should be mentioned such as viscosity, stability, surface tension and conductivity of the used Inks. There are also increased demands on the quality of the prints obtained, such as. in terms of color strength, fiber-dye bond stability and wet fastness properties. These requirements are not met in all properties by the known methods met, so that there is still a need for new processes for textile inkjet printing consists.

Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Bedrucken von textilen Fasermaterialien nach dem Tintenstrahldruck-Verfahren, welches dadurch gekennzeichnet ist, dass man die Fasermaterialien mit einer wässrigen Tinte bedruckt, welche mindestens einen Dispersionsfarbstoff, ein anionisches Copolymer und/oder ein nichtionogenes Blockpolymer und/oder ein Dispergiermittel enthält.The present invention relates to a method for printing textile fiber materials according to the inkjet printing process, which is characterized in that that you print the fiber materials with an aqueous ink, which at least one Disperse dye, an anionic copolymer and / or a nonionic block polymer and / or contains a dispersant.

Als Dispersionsfarbstoff eignen sich für das erfindungsgemässe Verfahren solche Farbstoffe, welche im Colour Index, 3. Auflage (3. Revision 1987 inclusive Additions and Amendments bis No. 85) unter "Disperse Dyes" beschrieben sind. Es sind beispielsweise carbonsäure- und/oder sulfosäuregruppenfreie Nitro-, Amino-, Aminoketon-, Ketoninim-, Methin-, Polymethin-, Diphenylamin-, Chinolin-, Benzimidazol-, Xanthen-, Oxazin- oder Cumarinfarbstoffe und insbesondere Anthrachinon- und Azofarbstoffe, wie Mono- oder Disazofarbstoffe. Suitable disperse dyes for the process according to the invention are those dyes which in the Color Index, 3rd edition (3rd revision 1987 including Additions and Amendments to No. 85) are described under "Disperse Dyes". Examples include nitro, amino, aminoketone, ketoninim, methine, carboxylic acid and / or sulfonic acid group-free Polymethine, diphenylamine, quinoline, benzimidazole, xanthene, oxazine or coumarin dyes and in particular anthraquinone and azo dyes, such as mono- or disazo dyes.

Bevorzugt werden in dem erfindungsgemässen Verfahren Dispersionsfarbstoffe der Formeln

Figure 00020001
worin

  • R16 Halogen, Nitro oder Cyano,
  • R17 Wasserstoff, Halogen, Nitro oder Cyano,
  • R18 Halogen oder Cyano,
  • R19 Wasserstoff, Halogen, C1-C4-Alkyl oder C1-C4-Alkoxy,
  • R20 Wasserstoff, Halogen oder Acylamino, und
  • R21 und R22 voneinander unabhängig Wasserstoff, C1-C4-Alkyl, welches unsubstituiert oder durch Hydroxy, Cyano, Acetoxy oder Phenoxy substituiert ist,
    Figure 00020002
    worin
  • R23 Wasserstoff, Phenyl oder Phenylsulfoxy ist, wobei der Benzolring in Phenyl und Phenylsulfoxy gegebenenfalls durch C1-C4-Alkyl, Sulfo oder C1-C4-Alkylsulfo substituiert ist,
  • R25 unsubstituiertes oder durch C1-C4-Alkyl substituiertes Amino oder Hydroxy,
  • R26 Wasserstoff oder C1-C4-Alkoxy,
  • R27 Wasserstoff oder den Rest -O-C6H5-SO2-NH-(CH2)3-O-C2H5,
  • R36 Wasserstoff, Hydroxy oder Nitro und
  • R37 Wasserstoff, Hydroxy oder Nitro bedeuten,
    Figure 00020003
    worin
  • R28 C1-C4-Alkyl welches unsubstituiert oder durch Hydroxy substituiert ist,
  • R29 C1-C4-Alkyl,
  • R30 Cyano,
  • R31 den Rest der Formel -(CH2)3-O-(CH2)2-O-C6H5,
  • R32 Halogen, Nitro oder Cyano, und
  • R33 Wasserstoff, Halogen, Nitro oder Cyano, bedeuten,
    Figure 00030001
    worin
  • R34 C1-C4-Alkyl,
  • R35 C1-C4-Alkyl welches unsubstituiert oder durch C1-C4-Alkoxy substituiert ist und
  • W den Rest -COOCH2CH2OC6H5 und W1 Wasserstoff oder
  • W Wasserstoff und W1 -N=N-C6H5 bedeuten, sind,
    Figure 00030002
    wobei die Ringe A'' und B'' unsubstituiert oder ein- oder mehrfach mit Halogen substituiert sind,
    Figure 00030003
    worin
  • R34 C1-C4-Alkyl, welches unsubstituiert oder mit Hydroxy, C1-C4-Alkoxy oder C1-C4-Alkoxy-C1-C4-Alkoxy substituiert ist, und
    Figure 00040001
    verwendet.
    • Disperse dyes of the formulas are preferred in the process according to the invention
    Figure 00020001
    wherein
  • R 16 halogen, nitro or cyano,
  • R 17 is hydrogen, halogen, nitro or cyano,
  • R 18 halogen or cyano,
  • R 19 is hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy,
  • R 20 is hydrogen, halogen or acylamino, and
  • R 21 and R 22 independently of one another are hydrogen, C 1 -C 4 -alkyl which is unsubstituted or substituted by hydroxy, cyano, acetoxy or phenoxy,
    Figure 00020002
    wherein
  • R 23 is hydrogen, phenyl or phenylsulfoxy, the benzene ring in phenyl and phenylsulfoxy optionally being substituted by C 1 -C 4 -alkyl, sulfo or C 1 -C 4 -alkylsulfo,
  • R 25 is unsubstituted or substituted by C 1 -C 4 alkyl or hydroxy,
  • R 26 is hydrogen or C 1 -C 4 alkoxy,
  • R 27 is hydrogen or the radical -OC 6 H 5 -SO 2 -NH- (CH 2 ) 3 -OC 2 H 5 ,
  • R 36 is hydrogen, hydroxy or nitro and
  • R 37 denotes hydrogen, hydroxy or nitro,
    Figure 00020003
    wherein
  • R 28 C 1 -C 4 alkyl which is unsubstituted or substituted by hydroxy,
  • R 29 C 1 -C 4 alkyl,
  • R 30 cyano,
  • R 31 represents the rest of the formula - (CH 2 ) 3 -O- (CH 2 ) 2 -OC 6 H 5 ,
  • R 32 halogen, nitro or cyano, and
  • R 33 is hydrogen, halogen, nitro or cyano,
    Figure 00030001
    wherein
  • R 34 C 1 -C 4 alkyl,
  • R 35 is C 1 -C 4 alkyl which is unsubstituted or substituted by C 1 -C 4 alkoxy and
  • W is the radical -COOCH 2 CH 2 OC 6 H 5 and W 1 is hydrogen or
  • W is hydrogen and W 1 -N = NC 6 H 5 are
    Figure 00030002
    where the rings A ″ and B ″ are unsubstituted or mono- or polysubstituted by halogen,
    Figure 00030003
    wherein
  • R 34 is C 1 -C 4 alkyl which is unsubstituted or substituted by hydroxy, C 1 -C 4 alkoxy or C 1 -C 4 alkoxy-C 1 -C 4 alkoxy, and
    Figure 00040001
    used.

    • Besonders bevorzugt werden in dem erfindungsgemässen Verfahren die Farbstoffe der Formeln

    Figure 00040002
    Figure 00050001
    Figure 00060001
    verwendet.
    Die Dispersionsfarbstoffe der Formeln (1) bis (23) sind bekannt oder können in Analogie zu bekannten Verbindungen nach bekannten Standard-Verfahren hergestellt werden, wie z.B. durch übliche Diazotierungs-, Kupplungs-, Addition- und Kondensationsreaktionen.The dyes of the formulas are particularly preferred in the process according to the invention
    Figure 00040002
    Figure 00050001
    Figure 00060001
    used.
    The disperse dyes of the formulas (1) to (23) are known or can be prepared in analogy to known compounds by known standard processes, for example by customary diazotization, coupling, addition and condensation reactions.

    Die Tinten enthalten in der Regel einen Gesamtgehalt an Dispersionsfarbstoffen der obigen Formeln (1) bis (23) von 1 bis 35 Gew.-%, insbesondere 1 bis 20 Gew.-%, vor allem 1 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Tinte.The inks generally contain a total content of disperse dyes of the above Formulas (1) to (23) from 1 to 35% by weight, in particular 1 to 20% by weight, especially 1 to 10% by weight based on the total weight of the ink.

    Die Dispersionsfarbstoffe liegen in der erfindungsgemässen Tinten vorteilhafterweise, in einer feindispergierten Form vor. Hierzu werden die Dispersionsfarbstoffe vermahlen, so dass ihre Teilchengrösse im Mittel zwischen 0,1 und 10 Mikron, bevorzugt zwischen 1 und 5 Mikron, besonders bevorzugt zwischen 0,5 und 2 Mikron beträgt. Das Vermahlen kann in Gegenwart von Dispergiermitteln erfolgen. Beispielsweise wird der getrocknete Dispersionsfarbstoff mit einem Dispergiermittel gemahlen oder in Pastenform mit einem Dispergiermittel geknetet und gegebenenfalls im Vakuum oder durch Zerstäuben getrocknet. Mit den so erhaltenen Präparaten kann man nach Zugabe von Wasser und gegebenenfalls weiteren Hilfsmitteln die erfindungsgemässen Tinten herstellen.The disperse dyes are advantageously in the inks according to the invention, in a finely dispersed form. For this purpose, the disperse dyes are ground, see above that their particle size averages between 0.1 and 10 microns, preferably between 1 and 5 microns, more preferably between 0.5 and 2 microns. Grinding can be done in In the presence of dispersants. For example, the dried disperse dye ground with a dispersant or in paste form with a dispersant kneaded and optionally dried in vacuo or by atomization. With the so obtained Preparations can be made after adding water and, if necessary, other auxiliaries produce the inks according to the invention.

    Als anionisches Copolymer kommen für das erfindungsgemässe Verfahren vor allem Copolymere auf Basis von Acrylsäure, Methacrylsäure oder Maleinsäure in Betracht.
    Unter diesen sind solche bevorzugt, welche durch Polymerisation von Acryl- und/oder Methacrylsäure und einem oder mehreren copolymerisierbaren Monomeren ausgewählt aus der Gruppe Maleinsäure, N-Vinylformamid, N-Vinylacetamid, Allylamin- oder Diallylamin-Derivate, N-Vinylpyrrolidon, N-Vinyl-N-methyl-formamid, N-Vinyl-N-methyl-acetamid, N-Vinyl-N-ethyl-acetamid, Vinylacetat, Vinylpropionat, Acrylnitril, Styrol, Methacrylnitril, Acrylamid, Methacrylamid und N-Mono/N,N-Di-C1-C10-Alkyl-(meth)acrylamid erhältlich sind.    Suitable anionic copolymers for the process according to the invention are primarily copolymers based on acrylic acid, methacrylic acid or maleic acid.
    Among these, preference is given to those which are obtained by polymerizing acrylic and / or methacrylic acid and one or more copolymerizable monomers from the group of maleic acid, N-vinylformamide, N-vinyl acetamide, allylamine or diallylamine derivatives, N-vinylpyrrolidone, N-vinyl -N-methyl-formamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl-acetamide, vinyl acetate, vinyl propionate, acrylonitrile, styrene, methacrylonitrile, acrylamide, methacrylamide and N-mono / N, N-di -C 1 -C 10 alkyl (meth) acrylamide are available.

    Besonders bevorzugt sind anionischen Copolymere welche durch Copolymerisation von Acryl- oder Methacrylsäure und Styrol erhältlich sind.Anionic copolymers which are obtainable by copolymerization of acrylic or methacrylic acid and styrene are particularly preferred.

    Ganz besonders bevorzugt sind Acryl- und Methacrylsäure-Styrol-Copolymere mit einem Molekulargewicht von 3000 bis 16000, insbesondere von 3000 bis 10000.Acrylic and methacrylic acid-styrene copolymers with a are very particularly preferred Molecular weight from 3000 to 16000, in particular from 3000 to 10000.

    Als nichtionogene Blockpolymere eignen sich für das erfindungsgemässe Verfahren vor allem Alkylenoxid-Kondensationsprodukte wie z.B. Ethylenoxidaddukte an Polypropylenoxid (sogenannte EO-PO-Blockpolymere) und Propylenoxidaddukte an Polyethylenoxid (sogenannte umgekehrte EO-PO-Blockpolymere), und Blockpolymere, welche durch Anlagerung von Styrol an Polypropylen- und/oder Polyethylenoxid erhältlich sind.
    Bevorzugt sind Ethylen-Propylenoxid-Blockpolymere mit Molekulargewichten zwischen 2000 und 20000, vor allem zwischen 8000 und 16000, und einem Ethylenoxidgehalt im Gesamtmolekül von 30 bis 80%, insbesondere von 60 bis 80%.    Suitable nonionic block polymers for the process according to the invention are, in particular, alkylene oxide condensation products such as, for example, ethylene oxide adducts with polypropylene oxide (so-called EO-PO block polymers) and propylene oxide adducts with polyethylene oxide (so-called reverse EO-PO block polymers), and block polymers which are caused by the addition of styrene Polypropylene and / or polyethylene oxide are available.
    Preference is given to ethylene-propylene oxide block polymers with molecular weights between 2,000 and 20,000, especially between 8,000 and 16,000, and an ethylene oxide content in the total molecule of 30 to 80%, in particular 60 to 80%.

    Als Dispergiermittel kommen in Betracht vor allem anionische Dispergatoren aus der Gruppe der

  • (ba) sauren Ester oder deren Salze von Alkylenoxidaddukten der Formel
    Figure 00080001
    worin
  • X den Säurerest einer anorganischen, Sauerstoff enthaltenden Säure, wie z.B. Schwefelsäure oder vorzugsweise Phosphorsäure, oder auch den Rest einer organischen Säure, und
  • Y C1-C12-Alkyl, Aryl oder Aralkyl bedeuten, "Alkylen" für den Ethylenrest oder Propylenrest steht, und
  • m 1 bis 4, und n 4 bis 50 sind,
  • (bb) Polystyrolsulfonate,
  • (bc) Fettsäuretauride,
  • (bd) alkylierten Diphenyloxid -mono- oder di-sulfonate,
  • (be) Sulfonate von Polycarbonsäureestern,
  • (bf) mit einer organischen Dicarbonsäure, oder einer anorganischen mehrbasischen Säure in einen sauren Ester überführten Anlagerungsprodukt von 1 bis 60, vorzugsweise 2 bis 30 Mol Ethylenoxid und/oder Propylenoxid an Fettamine, Fettamide, Fettsäuren oder Fettalkohole je mit 8 bis 22 Kohlenstoffatomen oder an drei- bis sechswertige Alkanole mit 3 bis 6 Kohlenstoffatomen,
  • (bg) Ligninsulfonate,
  • (bh) Naphthalinsulfonate, und
  • (bi) Formaldehyd-Kondensationsprodukte.
    • Above all, anionic dispersants from the group of
  • (ba) acidic esters or their salts of alkylene oxide adducts of the formula
    Figure 00080001
    wherein
  • X is the acid residue of an inorganic, oxygen-containing acid, such as sulfuric acid or preferably phosphoric acid, or the rest of an organic acid, and
  • YC 1 -C 12 alkyl, aryl or aralkyl, "alkylene" represents the ethylene radical or propylene radical, and
  • m are 1 to 4 and n are 4 to 50,
  • (bb) polystyrene sulfonates,
  • (bc) fatty acid taurides,
  • (bd) alkylated diphenyl oxide mono- or disulfonates,
  • (be) sulfonates of polycarboxylic acid esters,
  • (bf) with an organic dicarboxylic acid, or an inorganic polybasic acid converted adduct of 1 to 60, preferably 2 to 30, moles of ethylene oxide and / or propylene oxide onto fatty amines, fatty amides, fatty acids or fatty alcohols each having 8 to 22 carbon atoms or an trihydric to hexavalent alkanols having 3 to 6 carbon atoms,
  • (bg) lignin sulfonates,
  • (bh) naphthalene sulfonates, and
  • (bi) formaldehyde condensation products.

    • Als Ligninsulfonate (bg) werden vor allem solche Ligninsulfonate oder deren Alkalimetallsalze eingesetzt, deren Gehalt an Sulfogruppen 25 Gew.-% nicht übersteigt. Bevorzugt sind Ligninsulfonate mit einem Gehalt von 5 bis 15 Gew.-% an Sulfogruppen. Als Formaldehydkondensationsprodukte (bi) kommen z.B. Kondensationsprodukte von Ligninsulfonaten und/oder Phenol und Formaldehyd, Kondensationsprodukte von Formaldehyd mir aromatischen Sulfonsäuren, wie z.B. Kondensationsprodukte von Ditolylethersulfonaten und Formaldehyd, Kondensationsprodukte von Naphthalinsulfonsäure mit Formaldehyd und/oder Naphthol- oder Naphthylaminosulfonsäuren mit Formaldehyd, Kondensationsprodukte von Phenolsulfonsäuren und/oder sulfoniertem Dihydroxydiphenylsulfon und Phenolen bzw. Kresolen mit Formaldehyd und/oder Harnstoff sowie Kondensationsprodukte von Diphenyloxid-disulfonsäure-Derivaten mit Formaldehyd in Betracht. Lignosulfonates (bg) are primarily those ligninsulfonates or their alkali metal salts used, the content of sulfo groups does not exceed 25 wt .-%. Are preferred Lignin sulfonates containing 5 to 15% by weight of sulfo groups. As formaldehyde condensation products (bi) come e.g. Condensation products of lignin sulfonates and / or phenol and formaldehyde, condensation products of formaldehyde with aromatic sulfonic acids, e.g. Condensation products of ditolyl ether sulfonates and formaldehyde, condensation products of naphthalenesulfonic acid with formaldehyde and / or naphthol or naphthylaminosulfonic acids with formaldehyde, condensation products of phenol sulfonic acids and / or sulfonated dihydroxydiphenyl sulfone and phenols or cresols with formaldehyde and / or urea and condensation products of diphenyl oxide disulfonic acid derivatives with formaldehyde.

    Bevorzugt als (bi) sind

    • Kondensationsprodukte von Ditolylethersulfonaten und Formaldehyd wie sie z.B. in US-A-4,386,037 beschrieben sind,
    • Kondensationsprodukte von Phenol und Formaldehyd mit Ligninsulfonaten, wie sie z.B. in US-A-3,931,072 beschrieben sind,
    • Kondensationsprodukte von Naphthol-(2)-sulfonsäure-6, Kresol, Natriumbisulfit und Formaldehyd [vgl. FIAT-Report 1013 (1946)], und
    • Kondensationsprodukte aus Diphenylderivaten und Formaldehyd, wie sie z.B. in US-A-4,202,838 beschrieben sind.
    Are preferred as (bi)
    • Condensation products of ditolyl ether sulfonates and formaldehyde as described, for example, in US Pat. No. 4,386,037,
    • Condensation products of phenol and formaldehyde with lignin sulfonates, as described, for example, in US Pat. No. 3,931,072,
    • Condensation products of naphthol (2) sulfonic acid 6, cresol, sodium bisulfite and formaldehyde [cf. FIAT Report 1013 (1946)], and
    • Condensation products from diphenyl derivatives and formaldehyde, as described, for example, in US Pat. No. 4,202,838.

    Besonders bevorzugt als (bi) ist die Verbindung der Formel

    Figure 00090001
    worin

  • X die direkte Bindung oder Sauerstoff,
  • A den Rest einer aromatischen Verbindung, welcher mittels eines Ringkohlenstoffatomes an die Methylengruppe gebunden ist,
  • M Wasserstoff oder ein salzbildendes Kation, z.B. ein Alkalimetall, Erdalkalimetall oder Ammonium und
  • n und p unabhängig voneinander eine Zahl von 1 bis 4 bedeuten.
    • Ganz besonders bevorzugt als (bi) ist eine Verbindung auf Basis eines sulfonierten Kondensationsproduktes aus Chlormethyldiphenyl-Isomerengemisch und Naphthalin der Formel
    Figure 00090002
    worin (SO3Na)1,4-1,6 einen durchschnittlichen Sulfonierungsgrad von 1,4 bis 1,6 bedeutet. The compound of the formula is particularly preferred as (bi)
    Figure 00090001
    wherein
  • X the direct bond or oxygen,
  • A is the residue of an aromatic compound which is bonded to the methylene group by means of a ring carbon atom,
  • M is hydrogen or a salt-forming cation, for example an alkali metal, alkaline earth metal or ammonium and
  • n and p independently of one another represent a number from 1 to 4.
    • A compound based on a sulfonated condensation product of a chloromethyldiphenyl isomer mixture and naphthalene of the formula is very particularly preferred as (bi)
    Figure 00090002
    wherein (SO 3 Na) 1.4-1.6 means an average degree of sulfonation of 1.4 to 1.6.

    Die obigen Dispergiermittel sind bekannt oder können in Analogie zu bekannten Verbindungen nach allgemein bekannten Verfahren hergestellt werden.The above dispersants are known or can be used in analogy to known compounds can be produced by generally known processes.

    Der Gesamtgehalt an anionischem Copolymer, nichtionogenem Blockpolymer und Dispergiermittel in der erfindungsgemässen Tinte beträgt 3 bis 9 Gew.-% bezogen auf das Gesamtgewicht der Tinte.The total content of anionic copolymer, nonionic block polymer and dispersant in the ink according to the invention is 3 to 9% by weight, based on the total weight the ink.

    Das Verhältnis: anionisches Copolymer:nichtionogenes Blockpolymer:Dispergiermittel in der fertiggestellten Tinte kann dabei in breitem Rahmen variieren, z.B. 1,5:0,5:1; 1:0,5:1,5; 1:1:1; 1:0:1; 1:1:0; 1:0:0; 0:1:1 oder 0:0:1 .The ratio: anionic copolymer: nonionic block polymer: dispersant in the finished ink can vary widely, e.g. 1.5: 0.5: 1; 1: 0.5: 1.5; 1: 1: 1; 1: 0: 1; 1: 1: 0; 1: 0: 0; 0: 1: 1 or 0: 0: 1.

    Beworzugt für das erfindungsgemässe Verfahren sind Tinten, welche anionisches Copolymer und nichtionogenes Blockpolymer oder anionisches Copolymer und Dispergiermittel oder nichtionogenes Blockpolymer und Dispergiermittel enthalten.Inks which contain an anionic copolymer are preferred for the process according to the invention and nonionic block polymer or anionic copolymer and dispersant or contain nonionic block polymer and dispersant.

    Besonders bevorzugt sind Tinten, welche anionisches Copolymer, nichtionogenes Blockpolymer und Dispergiermittel enthalten.Inks which are anionic copolymer, nonionic block polymer are particularly preferred and dispersants.

    Ausser den Dispersionsfarbstoffen der Formeln (1) bis (23), den anionischen Copolymeren, den nichtionogenen Blockpolymeren und den Dispergiermitteln kann die Tinte zweckmässigerweise Verdickungsmittel natürlicher oder synthetischer Herkunft enthalten, wie z.B. handelsübliche Alginatverdickungen, Stärkeether oder Johannisbrotkemmehlether, insbesondere Natriumalginat für sich allein oder im Gemisch mit modifizierter Cellulose, insbesondere mit vorzugsweise 20 bis 25 Gewichtsprozent Carboxymethylcellulose.
    Vorzugsweise werden in den erfindungsgemässen Tinten synthetische Verdickungsmittel eingesetzt, wie z.B. solche auf Basis von Poly(meth)acrylsäuren oder Poly(meth)acrylamiden.    In addition to the disperse dyes of the formulas (1) to (23), the anionic copolymers, the nonionic block polymers and the dispersants, the ink can expediently contain thickeners of natural or synthetic origin, such as, for example, commercially available alginate thickeners, starch ether or locust bean gum ether, in particular sodium alginate alone or in Mixture with modified cellulose, in particular with preferably 20 to 25 percent by weight carboxymethyl cellulose.
    Synthetic thickeners such as those based on poly (meth) acrylic acids or poly (meth) acrylamides are preferably used in the inks according to the invention.

    Bevorzugt sind für das erfindungsgemässe Verfahren solche Tinten, welche eine Viskosität von 1 bis 40 mPa.s (Millipascalsekunde), insbesondere 1 bis 20 mPa.s, vor allem 1 bis 10 mPa.s aufweisen. Preferred inks for the process according to the invention are those which have a viscosity from 1 to 40 mPa.s (millipascal second), in particular 1 to 20 mPa.s, especially 1 to 10 have mPa.s.

    Ebenfalls bevorzugt für das erfindungsgemässe Verfahren sind solche Tinten, welche eine Oberflächenspannung zwischen 60 und 30 Newton/cm, insbesondere zwischen 50 und 40 Newton/cm aufweisen.Also preferred for the method according to the invention are those inks which have a Surface tension between 60 and 30 Newton / cm, especially between 50 and 40 Newton / cm.

    Wichtig für das erfindungsgemässe Verfahren sind Tinten, welche eine Leitfähigkeit von 0 bis 3000 µS/cm, insbesondere von 100 bis 700 µS/cm aufweisen, bezogen auf eine 10%-ige wässrige Suspension.Inks that have a conductivity of 0 are important for the method according to the invention up to 3000 µS / cm, in particular from 100 to 700 µS / cm, based on a 10% aqueous suspension.

    Ferner können die Tinten Puffersubstanzen enthalten, wie z.B. Borax, Borat oder Citrat. Als Beispiele seien Borax, Natriumborat, Natriumtetraborat sowie Natriumcitrat genannt. Sie werden insbesondere in Mengen von 0,1 bis 3 Gew.-%, vor allem 0,1 bis 1 Gew.-%, bezogen auf das Gesamtgewicht der Tinte, verwendet, um einen pH-Wert von z.B. 4 bis 10, vorzugsweise 5 bis 8, einzustellen.The inks may also contain buffer substances, e.g. Borax, borate or citrate. As Examples include borax, sodium borate, sodium tetraborate and sodium citrate. she are obtained in particular in amounts of 0.1 to 3% by weight, especially 0.1 to 1% by weight on the total weight of the ink used to adjust a pH of e.g. 4 to 10, preferably 5 to 8.

    Als weitere Zusätze können die Tinten Tenside, Redispergiermittel und Feuchthaltemittel enthalten.The inks can also contain surfactants, redispersants and humectants contain.

    Als Tenside kommen die handelsüblichen anionischen oder nichtionogenen Tenside in Betracht. Als Redispergiermittel ist z.B. Betain-Monohydrat zu erwähnen. Als Feuchthaltemittel wird bevorzugt eine Mischung von Na-Lactat (vorteilhafterweise in Form einer 50 bis 60%-igen wässrigen Lösung) und Glyzerin und/oder Propylenglykol in Mengen von vorzugsweise 7 bis 20 Gewichtsprozent in der erfindungsgemäss eingesetzten Tinte verwendet.The commercially available anionic or nonionic surfactants are suitable as surfactants. As a redispersant e.g. Mention betaine monohydrate. As a humectant is preferably a mixture of Na lactate (advantageously in the form of a 50 to 60% aqueous solution) and glycerin and / or propylene glycol in amounts of preferably 7 to 20 percent by weight used in the ink used in the invention.

    Gewünschtenfalls können die Tinten noch Säurespender wie Butyrolacton oder Natriumhydrogenphosphat, Konservierungsmittel, Pilz- und/oder Bakteriewachstum hemmende Stoffe, schaumdämpfende Mittel, Sequestriermittel, Emulgatoren, wasserunlösliche Lösungsmittel, Oxidationsmittel oder Entlüftungsmittel enthalten.If desired, the inks can also contain acid donors such as butyrolactone or sodium hydrogen phosphate, Preservatives, substances that inhibit fungal and / or bacterial growth, foam suppressants, sequestering agents, emulsifiers, water-insoluble solvents, Contain oxidizing agents or venting agents.

    In Betracht kommen als Konservierungsmittel vor allem formaldehydabgebende Mittel, wie z.B. Paraformaldehyd und Trioxan, vor allem wässrige, etwa 30 bis 40-gewichtsprozentige Formaldehydlösungen, als Sequestriermittel z.B. nitrilotriessigsaures Natrium, ethylendiamintetraessigsaures Natrium, vor allem Natrium-Polymetaphosphat, insbesondere Natrium-Hexametaphosphat, als Emulgatoren vor allem Addukte aus einem Alkylenoxid und einem Fettalkohol, insbesondere einem Addukt aus Oleylalkohol und Ethylenoxid, als wasserunlösliche Lösungsmittel hochsiedende, gesättigte Kohlenwasserstoffe, vor allem Paraffine mit einem Siedebereich von etwa 160 bis 210°C (sogenannte Lackbenzine), als Oxidationsmittel z.B. eine aromatische Nitroverbindung, vor allem eine aromatische Mono- oder Dinitrocarbonsäure oder -sulfonsäure, die gegebenenfalls als Alkylenoxidaddukt vorliegt, insbesondere eine Nitrobenzolsulfonsäure und als Entlüftungsmittel z.B. hochsiedende Lösungsmittel, vor allem Terpentinöle, höhere Alkohle, vorzugsweise C8- bis C10-Alkohole, Terpenalkohole oder Entlüftungsmittel auf Basis von Mineral- und/oder Silikonölen, insbesondere Handelsformulierungen aus etwa 15 bis 25 Gewichtsprozent eines Mineral- und Silikonölgemisches und etwa 75 bis 85 Gewichtsprozent eines C8-Alkohols wie z.B. 2-Ethyl-n-hexanol.
    Die Tinten können in üblicher Weise durch Mischen der einzelnen Bestandteile in der gewünschten Menge Wasser hergestellt werden.    Suitable preservatives are, in particular, formaldehyde-releasing agents, such as, for example, paraformaldehyde and trioxane, especially aqueous, approximately 30 to 40 percent by weight formaldehyde solutions, and sequestering agents, for example sodium nitrilotriacetic acid, sodium ethylenediaminetetraacetic acid, especially sodium polymetaphosphate, especially sodium hexametaphosphate, as emulsifiers especially adducts of an alkylene oxide and a fatty alcohol, especially an adduct of oleyl alcohol and ethylene oxide, as water-insoluble solvents, high-boiling, saturated hydrocarbons, especially paraffins with a boiling range of about 160 to 210 ° C (so-called mineral spirits), as an oxidizing agent, for example an aromatic nitro compound , especially an aromatic mono- or dinitrocarboxylic acid or sulfonic acid, which is optionally present as an alkylene oxide adduct, in particular a nitrobenzenesulfonic acid and as a deaerating agent, for example high-boiling solvents, especially turpentine oils, higher e Alcohol, preferably C 8 to C 10 alcohols, terpene alcohols or deaerating agents based on mineral and / or silicone oils, in particular commercial formulations of about 15 to 25 percent by weight of a mineral and silicone oil mixture and about 75 to 85 percent by weight of a C 8 alcohol such as 2-ethyl-n-hexanol.
    The inks can be prepared in a conventional manner by mixing the individual components in the desired amount of water.

    Bevorzugt werden die Tinten z.B. so hergestellt, dass ein oder mehrere Dispersionsfarbstoffe der Formeln (1) bis (23) mit einem Dispergator/Copolymer/Blockpolymer-Gemisch angerührt und anschliessend in einer Nassmühle bis auf einen definierten Mahlgrad von einer durchschnittlichen Partikelgrösse zwischen 0,2 bis 1,0 µm gemahlen werden. Danach wird das konzentrierte Mahlgut, gegebenenfalls unter Verwendung von z.B. geeigneten Verdickungsmitteln, Dispergatoren, Copolymeren, Tensiden, Feuchthaltemitteln, Redispergiermittel, Sequestriermitteln und/oder Konservietungsmitteln, sowie Wasser, auf die gewünschte Konzentration eingestellt. Zur Entfernung der gegebenenfalls vorhandenen gröberen Anteile kann vorteilhafterweise eine Filtration der fertiggestellten Tinte durch ein Mikrosieb von ca. 1 µm erfolgen.Preferably the inks are e.g. made so that one or more disperse dyes of formulas (1) to (23) mixed with a dispersant / copolymer / block polymer mixture and then in a wet mill to a defined grinding degree of one average particle size between 0.2 to 1.0 microns are ground. After that the concentrated regrind, optionally using e.g. suitable thickeners, Dispersants, copolymers, surfactants, humectants, redispersants, Sequestrants and / or preservatives, as well as water, to the desired Concentration set. To remove any coarser ones that may be present Portions can advantageously be a filtration of the finished ink through a microsieve of about 1 µm.

    Das erfindungsgemässe Verfahren zum Bedrucken von textilen Fasermaterialien kann mit an und für sich bekannten für den textilen Druck geeigneten Tintenstrahldruckern ausgeführt werden.The method according to the invention for printing textile fiber materials can with performed on known ink jet printers suitable for textile printing become.

    Im Falle des Tintenstrahldruck-Verfahrens werden einzelne Tropfen der Tinte kontrolliert aus einer Düse auf das Substrat gespritzt. Überwiegend werden hierzu die kontinuierliche Ink-Jet-Methode sowie die Drop on demand-Methode verwendet. Im Falle der kontinuierlichen Ink-Jet-Methode werden die Tropfen kontinuierlich erzeugt, wobei die nicht für den Druck benötigte Tropfen in einen Auffangbehälter abgeleitet und in der Regel rezykliert werden. Im Falle der Drop on demand-Methode hingegen werden die Tropften nach Wunsch erzeugt und gedruckt, d.h. es werden nur dann Tropfen erzeugt, wenn dies für den Druck erforderlich ist. Die Erzeugung der Tropfen kann z.B. vorteilhafterweise mittels eines Piezo-Inkjet-Kopfes oder mittels thermischer Energie (sog. Bubble Jet) erfolgen. Bevorzugt ist für das erfindungsgemässe Verfahren der Druck nach der kontinuierlichen Ink-Jet-Methode oder der Drop on demand-Methode.In the case of the inkjet printing process, individual drops of the ink are checked out sprayed onto the substrate using a nozzle. The continuous ink jet method is predominantly used for this as well as the drop on demand method. In the case of continuous The ink-jet method generates the drops continuously, which are not for printing required drops are drained into a collecting container and are usually recycled. in the In the case of the drop on demand method, on the other hand, the drips are generated as desired and printed, i.e. drops are only generated when necessary for printing is. The generation of the drops can e.g. advantageously by means of a piezo inkjet head or by means of thermal energy (so-called bubble jet). Is preferred for the invention Process of printing according to the continuous ink-jet method or the Drop on demand method.

    Das Fasermaterial wird nach dem Bedrucken bei Temperaturen bis 150°C, vorzugsweise 80° bis 120°C getrocknet.After printing, the fiber material is preferably at temperatures up to 150 ° C. Dried 80 ° to 120 ° C.

    Die anschliessende Fixierung des Fasermaterials geschieht im allgemeinen durch Trockenhitze (Thermofixierung) oder überhitzten Wasserdampf unter atmosphärischem Druck (HT-Fixierung). Die Fixierung wird dabei unter folgenden Bedingungen durchgeführt:

    • Thermofixierung: 1 bis 2 Minuten bei 190 bis 230°C.
    • HT-Fixierung: 4 bis 9 Minuten bei 170 bis 190°C
    The subsequent fixing of the fiber material is generally done by dry heat (heat setting) or superheated steam under atmospheric pressure (HT fixing). The fixation is carried out under the following conditions:
    • Heat setting: 1 to 2 minutes at 190 to 230 ° C.
    • HT fixation: 4 to 9 minutes at 170 to 190 ° C

    Die erfindungsgemäss verwendete Tinte kann auf verschiedenartigen Fasermaterialien, wie Wolle, Seide, Cellulose, Polyvinyl, Polyacrylnitril, Polyamid, Aramid, Polypropylen, Polyester oder Polyurethan appliziert werden.The ink used in the invention can on various types of fiber materials such as Wool, silk, cellulose, polyvinyl, polyacrylonitrile, polyamide, aramid, polypropylene, polyester or polyurethane can be applied.

    Bevorzugt sind polyesterhaltige Fasermaterialien.
    Als polyesterhaltige Fasermaterialien kommen solche Materialien in Betracht, die ganz oder teilweise aus Polyester bestehen. Beispiele sind Celluloseesterfasern, wie z.B. Cellulose-2½-acetatfasern und -triacetatfasern, und besonders lineare Polyesterfasem, die gegebenenfalls auch sauer modifiziert sind, welche z.B. durch Kondensation von Terephthalsäure mit Ethylenglykol oder von Isophthalsäure oder Terephthalsäure mit 1,4-Bis(hydroxymethyl)cyclohexan erhalten werden, sowie Fasern aus Mischpolymeren von Terephthal- und Isophthalsäure mit Ethylenglykol. Geeignet sind weiter polyesterhaltige Mischfasermaterialien, d.h. Mischungen aus Polyester und anderen Fasern.    Polyester-containing fiber materials are preferred.
    Suitable polyester-containing fiber materials are materials which consist entirely or partially of polyester. Examples are cellulose ester fibers, such as cellulose-2½-acetate fibers and triacetate fibers, and particularly linear polyester fibers, which are optionally also acid-modified, which are, for example, by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) cyclohexane are obtained, as well as fibers from copolymers of terephthalic and isophthalic acid with ethylene glycol. Also suitable are polyester-containing mixed fiber materials, ie mixtures of polyester and other fibers.

    Gegenstand der vorliegenden Erfindung ist ferner eine wässrige Drucktinte für das Tintenstrahldruck-Verfahren, welche dadurch gekennzeichnet ist, dass sie 1 bis 35 Gew.-% mindestens eines Dispersionsfarbstoffes der obigen Formeln (1) bis (23), ein anionisches Copolymer und/oder ein nichtionogenes Blockpolymer und/oder ein Dispergiermittel enthält. The present invention furthermore relates to an aqueous printing ink for the inkjet printing process, which is characterized in that it contains at least 1 to 35% by weight a disperse dye of the above formulas (1) to (23), an anionic copolymer and / or contains a nonionic block polymer and / or a dispersant.

    Für die erfindungsgemässe Drucktinte sowie für die in dieser Tinte verwendeten Dispersionsfarbstoffe der Formeln (1) bis (23), die anionischen Copolymere, die nichtionogene Blockpolymere und die Dispergiermittel gelten hierbei die weiter oben angegebenen Bedeutungen und Bevorzugungen.For the printing ink according to the invention and for the disperse dyes used in this ink of the formulas (1) to (23), the anionic copolymers, the nonionic Block polymers and the dispersants have the meanings given above and favors.

    Die nach dem erfindungsgemässen Verfahren erhältlichen Drucke weisen gute Allgemeinechtheiten auf; sie besitzen z.B. eine hohe Faser-Farbstoff-Bindungsstabilität sowohl im sauren als auch im alkalischen Bereich, eine gute Lichtechtheit, gute Nassechtheiten, wie Wasser-, Wasch-, Seewasser-, Überfärbe- und Schweissechtheit, eine gute Chlorechtheit, Reibechtheit, Bügelechtheit und Plissierechtheit sowie scharfe Konturen und eine hohe Farbstärke. Die verwendeten Drucktinten zeichnen sich durch gute Stabilität und gute Viskositätseigenschaften aus.The prints obtainable by the process according to the invention have good general fastness properties on; e.g. they have high fiber-dye binding stability in both acidic as well as in the alkaline range, good light fastness, good wet fastness properties, such as Water, wash, sea water, over-dyeing and perspiration fastness, good chlorine fastness, Rubbing fastness, ironing fastness and pleating fastness as well as sharp contours and a high Color strength. The printing inks used are characterized by good stability and good viscosity properties out.

    Die nachfolgenden Beispiele dienen zur Erläuterung der Erfindung. Darin sind die Temperaturen in Celsiusgraden angegeben, Teile sind Gewichtsteile und die Prozentangaben beziehen sich auf Gewichtsprozente, sofern nicht anders vermerkt. Gewichtsteile stehen zu Volumenteilen im Verhältnis von Kilogramm zu Liter.The following examples serve to explain the invention. That's where the temperatures are expressed in degrees Celsius, parts are parts by weight and percentages are given percentages by weight unless otherwise noted. Parts by weight relate to parts by volume in the ratio of kilograms to liters.

    Beispiel 1:Example 1:

  • 2,0 Gewichtsteile des Dispersionsfarbstoffes der Formel
    Figure 00140001
    werden mit    2.0 parts by weight of the disperse dye of the formula
    Figure 00140001
    be with
  • 0,3 Gewichtsteilen eines Dispergators auf Basis eines sulfonierten Kondensationsproduktes aus Chlormethyldiphenyl-Isomerengemisch und Naphthalin und0.3 parts by weight of a dispersant based on a sulfonated condensation product from chloromethyldiphenyl isomer mixture and naphthalene and
  • 3,0 Gewichtsteilen eines anionischen Copolymers aus Acrylsäure und Styrol, angerührt und anschliessend in einer Nassmühle zu einer durchschnittlichen Partikelgrösse von 0,2 bis 1,0 µm vermahlen. Danach wird durch unter gutem Rühren erfolgte Zugabe von3.0 parts by weight of an anionic copolymer of acrylic acid and styrene, mixed and then in a wet mill to an average particle size ground from 0.2 to 1.0 µm. Then by adding with good stirring
  • 1,0 Gewichtsteil eines handelsüblichen Tensids,1.0 part by weight of a commercial surfactant,
  • 3,7 Gewichtsteilen eines handelsüblichen Redispergiermittels,3.7 parts by weight of a commercially available redispersant,
  • 0,2 Gewichtsteilen eines handelsüblichen Konsetuierungsmittels,0.2 parts by weight of a commercially available Konsetuierungsmittel,
  • 20,0 Gewichtsteilen eines handelsüblichen Feuchthaltemittels und20.0 parts by weight of a commercially available humectant and
  • 69,8 Gewichtsteilen Wasser
    die Tinte auf ein Farbstoffgehalt von 2 Gewichtsprozent eingestellt.    69.8 parts by weight of water
    the ink is adjusted to a dye content of 2 percent by weight.

    • Beispiel 2:Example 2:

    Die gemäss Beispiel 1 hergestellte Tinte wird mit einem Inkjet-Printer mit Drop on demand Piezo Technik auf ein Polyester-Gewebe aufgedruckt.
    Der Druck wird getrocknet und 8 Minuten im überhitzten Dampf bei 180° C fixiert.
    Man erhält einen brillanten gelben Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten.    The ink produced according to Example 1 is printed on a polyester fabric using an inkjet printer using drop on demand piezo technology.
    The print is dried and fixed in the superheated steam at 180 ° C for 8 minutes.
    A brilliant yellow print with good general fastness properties, in particular wet and light fastness properties, is obtained.

    Man erhält ebenfalls einen brillanten gelben Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten, wenn man den getrockneten Druck 1 Minute mit einem Heissluft von 200° C fixiert.A brilliant yellow print with good general fastness properties is also obtained, in particular Wet and light fastness, if you use the dried print for 1 minute with a Hot air fixed at 200 ° C.

    Beispiel 3:Example 3:

  • 3,0 Gewichtsteile des Dispersionsfarbstoffes der Formel
    Figure 00150001
    werden mit    3.0 parts by weight of the disperse dye of the formula
    Figure 00150001
    be with
  • 2,0 Gewichtsteilen eines Dispergators auf Basis eines sulfonierten Kondensationsproduktes aus Chlormethyldiphenyl-Isomerengemisch und Naphthalin und2.0 parts by weight of a dispersant based on a sulfonated condensation product from chloromethyldiphenyl isomer mixture and naphthalene and
  • 6,5 Gewichtsteilen eines anionischen Copolymers aus Acrylsäure und Styrol (®Narlex DX2020 der Firma National Starch & Chemical),
    angerührt und anschliessend in einer Nassmühle zu einer durchschnittlichen Partikelgrösse von 0,2 bis 1,0 µm vermahlen. Danach wird durch unter gutem Rühren erfolgte Zugabe von    6.5 parts by weight of an anionic copolymer of acrylic acid and styrene (®Narlex DX2020 from National Starch & Chemical),
    stirred and then ground in a wet mill to an average particle size of 0.2 to 1.0 µm. Then by adding with good stirring
  • 12,0 Gewichtsteilen Glyzerin 85%-ig,12.0 parts by weight of glycerin 85%,
  • 5,0 Gewichtsteilen Diethylenglykol,5.0 parts by weight of diethylene glycol,
  • 3,0 Gewichtsteilen Betain Monohydrat, 3.0 parts by weight of betaine monohydrate,
  • 0,1 Gewichtsteilen N-Hydroxymethylchloracetamid und0.1 parts by weight of N-hydroxymethylchloroacetamide and
  • 68,4 Gewichtsteilen Wasser
    die Tinte auf ein Farbstoffgehalt von 3 Gewichtsprozent eingestellt.    68.4 parts by weight of water
    the ink is adjusted to a dye content of 3 percent by weight.

    • Beispiel 4:Example 4:

    Die gemäss Beispiel 3 hergestellte Tinte wird mit einem Inkjet-Printer mit Drop on demand Piezo Technik auf ein Polyester-Gewebe aufgedruckt.
    Der Druck wird getrocknet und 8 Minuten im überhitzten Dampf bei 180° C fixiert. Man erhält einen blauen Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten.
    Man erhält ebenfalls einen blauen Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten, wenn man den getrockneten Druck 1 Minute mit einem Heissluft von 200° C fixiert.    The ink produced according to Example 3 is printed on a polyester fabric using an inkjet printer using drop on demand piezo technology.
    The print is dried and fixed in the superheated steam at 180 ° C for 8 minutes. A blue print with good general fastness properties, in particular wet and light fastness properties, is obtained.
    A blue print with good general fastness properties, in particular wet and light fastness properties, is also obtained if the dried print is fixed with hot air at 200 ° C. for 1 minute.

    Beispiel 5:Example 5:

  • 2,0 Gewichtsteile des Dispersionsfarbstoffes der Formel
    Figure 00160001
    werden mit    2.0 parts by weight of the disperse dye of the formula
    Figure 00160001
    be with
  • 1,0 Gewichtsteilen eines Dispergators auf Basis eines sulfonierten Kondensationsproduktes aus Chlormethyldiphenyl-Isomerengemisch und Naphthalin und1.0 part by weight of a dispersant based on a sulfonated condensation product from chloromethyldiphenyl isomer mixture and naphthalene and
  • 0,3 Gewichtsteilen eines nichtinogenen Alkylenoxid-Blockpolymeren (®Pluronic F108 der Firma Albright & Wilson)
    angerührt und anschliessend in einer Nassmühle zu einer durchschnittlichen Partikelgrösse von 0,2 bis 1,0 µm vermahlen. Danach wird durch unter gutem Rühren erfolgte Zugabe von    0.3 part by weight of a noninogenic alkylene oxide block polymer (®Pluronic F108 from Albright & Wilson)
    stirred and then ground in a wet mill to an average particle size of 0.2 to 1.0 µm. Then by adding with good stirring
  • 12,0 Gewichtsteilen Glyzerin 85%-ig,12.0 parts by weight of glycerin 85%,
  • 5,0 Gewichtsteilen Diethylenglykol,5.0 parts by weight of diethylene glycol,
  • 3,0 Gewichtsteilen Betain Monohydrat,3.0 parts by weight of betaine monohydrate,
  • 0,1 Gewichtsteilen N-Hydroxymethylchloracetamid und0.1 parts by weight of N-hydroxymethylchloroacetamide and
  • 76,6 Gewichtsteilen Wasser
    die Tinte auf ein Farbstoffgehalt von 2 Gewichtsprozent eingestellt.    76.6 parts by weight of water
    the ink is adjusted to a dye content of 2 percent by weight.

    • Beispiel 6:Example 6:

    Die gemäss Beispiel 5 hergestellte Tinte wird mit einem Inkjet-Printer mit Drop on demand Piezo Technik auf ein Polyester-Gewebe aufgedruckt.
    Der Druck wird getrocknet und 8 Minuten im überhitzten Dampf bei 180° C fixiert.
    Man erhält einen blauen Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten.    The ink produced according to Example 5 is printed on a polyester fabric using an inkjet printer using drop on demand piezo technology.
    The print is dried and fixed in the superheated steam at 180 ° C for 8 minutes.
    A blue print with good general fastness properties, in particular wet and light fastness properties, is obtained.

    Man erhält ebenfalls einen blauen Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten, wenn man den getrockneten Druck 1 Minute mit einem Heissluft von 200° C fixiert.You also get a blue print with good general fastness properties, especially wet and Lightfastness, if you dry the print with hot air for 1 minute Fixed at 200 ° C.

    Beispiel 7:Example 7:

  • 1,2 Gewichtsteile des Dispersionsfarbstoffes der Formel
    Figure 00170001
    und    1.2 parts by weight of the disperse dye of the formula
    Figure 00170001
    and
  • 2,2 Gewichtsteile des Dispersionsfarbstoffes der Formel
    Figure 00170002
    werden mit    2.2 parts by weight of the disperse dye of the formula
    Figure 00170002
    be with
  • 1,0 Gewichtsteilen eines Dispergators auf Basis eines sulfonierten Kondensationsproduktes aus Chlormethyldiphenyl-Isomerengemisch und Naphthalin
    angerührt und anschliessend in einer Nassmühle zu einer durchschnittlichen Partikelgrösse von 0,2 bis 1,0 µm vermahlen. Danach wird durch unter gutem Rühren erfolgte Zugabe von    1.0 part by weight of a dispersant based on a sulfonated condensation product of chloromethyldiphenyl isomer mixture and naphthalene
    stirred and then ground in a wet mill to an average particle size of 0.2 to 1.0 µm. Then by adding with good stirring
  • 12,0 Gewichtsteilen Glyzerin 85%-ig,12.0 parts by weight of glycerin 85%,
  • 5,0 Gewichtsteilen Diethylenglykol, 5.0 parts by weight of diethylene glycol,
  • 3,0 Gewichtsteilen Betain Monohydrat,3.0 parts by weight of betaine monohydrate,
  • 0,1 Gewichtsteilen N-Hydroxymethylchloracetamid und0.1 parts by weight of N-hydroxymethylchloroacetamide and
  • 75,5 Gewichtsteilen Wasser
    die Tinte auf ein Farbstoffgehalt von 3,4 Gewichtsprozent eingestellt.    75.5 parts by weight of water
    the ink is adjusted to a dye content of 3.4 percent by weight.

    • Beispiel 8:Example 8:

    Die gemäss Beispiel 7 hergestellte Tinte wird mit einem Inkjet-Printer mit Drop on demand Piezo Technik auf ein Polyester-Gewebe aufgedruckt.
    Der Druck wird getrocknet und 8 Minuten im überhitzten Dampf bei 180° C fixiert.
    Man erhält einen rosa-roten Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten.    The ink produced according to Example 7 is printed on a polyester fabric using an inkjet printer using the drop on demand piezo technique.
    The print is dried and fixed in the superheated steam at 180 ° C for 8 minutes.
    A pink-red print is obtained with good general fastness properties, in particular wet and light fastness properties.

    Man erhält ebenfalls einen rosa-roten Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten, wenn man den getrockneten Druck 1 Minute mit einem Heissluft von 200° C fixiert.A pink-red print with good general fastness properties is also obtained, in particular Wet and light fastness, if you dry the print for 1 minute with hot air fixed at 200 ° C.

    Beispiel 9:Example 9:

  • 4,0 Gewichtsteile des Dispersionsfarbstoffes der Formel
    Figure 00180001
    werden mit    4.0 parts by weight of the disperse dye of the formula
    Figure 00180001
    be with
  • 2,0 Gewichtsteilen eines Dispergators auf Basis eines sulfonierten Kondensationsproduktes aus Chlormethyldiphenyl-Isomerengemisch und Naphthalin,2.0 parts by weight of a dispersant based on a sulfonated condensation product from chloromethyldiphenyl isomer mixture and naphthalene,
  • 1,0 Gewichtsteilen eines nichtinogenen Alkylenoxid-Blockpolymeren (®Pluronic F108 der Firma Albright & Wilson), und1.0 part by weight of a noninogenic alkylene oxide block polymer (®Pluronic F108 der Albright & Wilson), and
  • 8,0 Gewichtsteilen eines anionischen Copolymers aus Acrylsäure und Styrol (®Narlex DX2020 der Firma National Starch & Chemical),
    angerührt und anschliessend in einer Nassmühle zu einer durchschnittlichen Partikelgrösse von 0,2 bis 1,0 µm vermahlen. Danach wird durch unter gutem Rühren erfolgte Zugabe von    8.0 parts by weight of an anionic copolymer of acrylic acid and styrene (®Narlex DX2020 from National Starch & Chemical),
    stirred and then ground in a wet mill to an average particle size of 0.2 to 1.0 µm. Then by adding with good stirring
  • 5,0 Gewichtsteilen Glyzerin 85%-ig, 5.0 parts by weight glycerin 85%,
  • 15,0 Gewichtsteilen Diethylenglykol,15.0 parts by weight of diethylene glycol,
  • 2,0 Gewichtsteilen Betain Monohydrat,2.0 parts by weight of betaine monohydrate,
  • 0,1 Gewichtsteilen N-Hydroxymethylchloracetamid und0.1 parts by weight of N-hydroxymethylchloroacetamide and
  • 62,9 Gewichtsteilen Wasser
    die Tinte auf ein Farbstoffgehalt von 2 Gewichtsprozent eingestellt.    62.9 parts by weight of water
    the ink is adjusted to a dye content of 2 percent by weight.

    • Beispiel 10:Example 10:

    Die gemäss Beispiel 9 hergestellte Tinte wird mit einem Inkjet-Printer mit Drop on demand Piezo Technik auf ein Polyester-Gewebe aufgedruckt.
    Der Druck wird getrocknet und 8 Minuten im überhitzten Dampf bei 180° C fixiert. Man erhält einen violetten Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten.    The ink produced according to Example 9 is printed on a polyester fabric using an inkjet printer using drop on demand piezo technology.
    The print is dried and fixed in the superheated steam at 180 ° C for 8 minutes. A purple print with good general fastness properties, in particular wet and light fastness properties, is obtained.

    Man erhält ebenfalls einen violetten Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten, wenn man den getrockneten Druck 1 Minute mit einem Heissluft von 200° C fixiert.A purple print with good general fastness properties is also obtained, in particular Wet and light fastness, if you dry the print for 1 minute with hot air fixed at 200 ° C.

    Beispiel 11:Example 11:

  • 4,0 Gewichtsteile des Dispersionsfarbstoffes der Formel
    Figure 00190001
    werden mit    4.0 parts by weight of the disperse dye of the formula
    Figure 00190001
    be with
  • 1,0 Gewichtsteilen eines Dispergators auf Basis eines sulfonierten Kondensationsproduktes aus Chlormethyldiphenyl-Isomerengemisch und Naphthalin und1.0 part by weight of a dispersant based on a sulfonated condensation product from chloromethyldiphenyl isomer mixture and naphthalene and
  • 3,0 Gewichtsteilen eines anionischen Copolymers auf Basis eines partiell sulfatierten Octylphenolethoxylates mit 25 Ethylenoxideinheiten pro 1 Mol Octylphenol (®Emulphor OPS 25 der Firma BASF)
    angerührt und anschliessend in einer Nassmühle zu einer durchschnittlichen Partikelgrösse von 0,2 bis 1,0 µm vermahlen. Danach wird durch unter gutem Rühren erfolgte Zugabe von    3.0 parts by weight of an anionic copolymer based on a partially sulfated octylphenol ethoxylate with 25 ethylene oxide units per 1 mol of octylphenol (®Emulphor OPS 25 from BASF)
    stirred and then ground in a wet mill to an average particle size of 0.2 to 1.0 µm. Then by adding with good stirring
  • 10,0 Gewichtsteilen Glyzerin 85%-ig,10.0 parts by weight of glycerin 85%,
  • 10,0 Gewichtsteilen Diethylenglykol, 10.0 parts by weight of diethylene glycol,
  • 1,7 Gewichtsteilen Betain Monohydrat,1.7 parts by weight of betaine monohydrate,
  • 0,1 Gewichtsteilen N-Hydroxymethylchloracetamid und0.1 parts by weight of N-hydroxymethylchloroacetamide and
  • 70,2 Gewichtsteilen Wasser
    die Tinte auf ein Farbstoffgehalt von 2 Gewichtsprozent eingestellt.    70.2 parts by weight of water
    the ink is adjusted to a dye content of 2 percent by weight.

    • Beispiel 12:Example 12:

    Die gemäss Beispiel 11 hergestellte Tinte wird mit einem Inkjet-Printer mit Drop on demand Piezo Technik auf ein Polyester-Gewebe aufgedruckt.
    Der Druck wird getrocknet und 8 Minuten im überhitzten Dampf bei 180° C fixiert.
    Man erhält einen blauen Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten.    The ink produced according to Example 11 is printed on a polyester fabric using an inkjet printer using drop on demand piezo technology.
    The print is dried and fixed in the superheated steam at 180 ° C for 8 minutes.
    A blue print with good general fastness properties, in particular wet and light fastness properties, is obtained.

    Man erhält ebenfalls einen blauen Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten, wenn man den getrockneten Druck 1 Minute mit einem Heissluft von 200° C fixiert.You also get a blue print with good general fastness properties, especially wet and Lightfastness, if you dry the print with hot air for 1 minute Fixed at 200 ° C.

    Man erhält ebenfalls Drucke mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten, wenn man die gemäss den Beispielen 1, 3, 5, 7, 9 und 11 hergestellten Tinten mit einem Inkjet-Printer mit Drop on demand Bubble Jet Technik auf ein Polyester-Gewebe aufdruckt und wie oben angegeben fertigstellt.One also obtains prints with good general fastness properties, in particular wet and light fastness, when the inks prepared according to Examples 1, 3, 5, 7, 9 and 11 with an inkjet printer with drop on demand bubble jet technology on a polyester fabric printed and finished as indicated above.

    Werden die gemäss den Beispielen 1, 3, 5, 7, 9 und 11 hergestellten Tinten nach einer kontinuierlichen Ink-Jet-Methode auf ein Polyester-Gewebe aufgedruckt und wie oben angegeben fertiggestellt, resultieren ebenfalls Drucke mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten.Are the inks prepared according to Examples 1, 3, 5, 7, 9 and 11 after a continuous Ink-jet method printed on a polyester fabric and as stated above completed, prints with good general fastness properties, in particular also result Wet and light fastness.

    Claims (9)

    Verfahren zum Bedrucken von textilen Fasermaterialien nach dem Tintenstrahldruck-Verfahren, dadurch gekennzeichnet, dass man die Fasermaterialien mit einer wässrigen Tinte bedruckt, welche mindestens einen Dispersionsfarbstoff, ein anionisches Copolymer und/oder ein nichtionogenes Blockpolymer und/oder ein Dispergiermittel enthält.Process for printing textile fiber materials according to the inkjet printing process, characterized in that the fiber materials with an aqueous ink printed, which at least one disperse dye, an anionic copolymer and / or contains a nonionic block polymer and / or a dispersant. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man ein Dispersionsfarbstoff der Formel
    Figure 00210001
    worin R16 Halogen, Nitro oder Cyano, R17 Wasserstoff, Halogen, Nitro oder Cyano, R18 Halogen oder Cyano, R19 Wasserstoff, Halogen, C1-C4-Alkyl oder C1-C4-Alkoxy, R20 Wasserstoff, Halogen oder Acylamino, und R21 und R22 voneinander unabhängig Wasserstoff, C1-C4-Alkyl, welches unsubstituiert oder durch Hydroxy, Cyano, Acetoxy oder Phenoxy substituiert ist,
    Figure 00210002
    worin     R23 Wasserstoff, Phenyl oder Phenylsulfoxy ist, wobei der Benzolring in Phenyl und Phenylsulfoxy gegebenenfalls durch C1-C4-Alkyl, Sulfo oder C1-C4-Alkylsulfo substituiert ist, R25 unsubstituiertes oder durch C1-C4-Alkyl substituiertes Amino oder Hydroxy, R26 Wasserstoff oder C1-C4-Alkoxy, R27 Wasserstoff oder den Rest -O-C6H5-SO2-NH-(CH2)3-O-C2H5, R36 Wasserstoff, Hydroxy oder Nitro und R37 Wasserstoff, Hydroxy oder Nitro bedeuten,
    Figure 00220001
    worin     R28 C1-C4-Alkyl welches unsubstituiert oder durch Hydroxy substituiert ist, R29 C1-C4-Alkyl, R30 Cyano, R31 den Rest der Formel -(CH2)3-O-(CH2)2-O-C6H5, R32 Halogen, Nitro oder Cyano, und R33 Wasserstoff, Halogen, Nitro oder Cyano, bedeuten,
    Figure 00220002
    worin     R34 C1-C4-Alkyl, R35 C1-C4-Alkyl welches unsubstituiert oder durch C1-C4-Alkoxy substituiert ist und W den Rest -COOCH2CH2OC6H5 und W1 Wasserstoff oder W Wasserstoff und W1 -N=N-C6H5 bedeuten, sind,
    Figure 00220003
    wobei die Ringe A'' und B'' unsubstituiert oder ein- oder mehrfach mit Halogen substituiert sind,
    Figure 00220004
    worin     R34 C1-C4-Alkyl, welches unsubstituiert oder mit Hydroxy, C1-C4-Alkoxy oder C1-C4-Alkoxy-C1-C4-Alkoxy substituiert ist,
    Figure 00230001
    verwendet.         A method according to claim 1, characterized in that a disperse dye of the formula
    Figure 00210001
    wherein R 16 halogen, nitro or cyano, R 17 hydrogen, halogen, nitro or cyano, R 18 halogen or cyano, R 19 hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy, R 20 hydrogen, Halogen or acylamino, and R 21 and R 22 independently of one another hydrogen, C 1 -C 4 -alkyl, which is unsubstituted or substituted by hydroxyl, cyano, acetoxy or phenoxy,
    Figure 00210002
    wherein     R 23 is hydrogen, phenyl or phenylsulfoxy, the benzene ring in phenyl and phenylsulfoxy optionally being substituted by C 1 -C 4 -alkyl, sulfo or C 1 -C 4 -alkylsulfo, R 25 is unsubstituted or by C 1 -C 4 -alkyl substituted amino or hydroxy, R 26 is hydrogen or C 1 -C 4 alkoxy, R 27 is hydrogen or the radical -OC 6 H 5 -SO 2 -NH- (CH 2 ) 3 -OC 2 H 5 , R 36 is hydrogen, hydroxy or nitro and R 37 is hydrogen, hydroxy or nitro,
    Figure 00220001
    wherein     R 28 C 1 -C 4 alkyl which is unsubstituted or substituted by hydroxy, R 29 C 1 -C 4 alkyl, R 30 is cyano, R 31 is the rest of the formula - (CH 2 ) 3 -O- (CH 2 ) 2 -OC 6 H 5 , R 32 is halogen, nitro or cyano, and R 33 is hydrogen, halogen, nitro or cyano ,
    Figure 00220002
    wherein     R 34 C 1 -C 4 alkyl, R 35 C 1 -C 4 alkyl which is unsubstituted or substituted by C 1 -C 4 alkoxy and W is the radical -COOCH 2 CH 2 OC 6 H 5 and W 1 is hydrogen or W is hydrogen and W 1 -N = NC 6 H 5 are
    Figure 00220003
    where the rings A ″ and B ″ are unsubstituted or mono- or polysubstituted by halogen,
    Figure 00220004
    wherein     R 34 is C 1 -C 4 alkyl which is unsubstituted or substituted by hydroxy, C 1 -C 4 alkoxy or C 1 -C 4 alkoxy-C 1 -C 4 alkoxy,
    Figure 00230001
    used.     Verfahren gemäss einem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass man als anionisches Copolymer einen Copolymer auf Basis von Acrylsäure, Methacrylsäure oder Maleinsäure verwendet.Method according to one of claims 1 and 2, characterized in that as anionic copolymer a copolymer based on acrylic acid, methacrylic acid or maleic acid used. Verfahren gemäss Anspruch 3, dadurch gekennzeichnet, dass man als anionisches Copolymer ein Copolymer aus Acryl- und/oder Methacrylsäure und einem oder mehreren copolymerisierbaren Monomeren aus der Gruppe Maleinsäure, N-Vinylformamid, N-Vinylacetamid, Allylamin- oder Diallylamin-Derivate, N-Vinylpyrrolidon, N-Vinyl-N-methyl-formamid, N-Vinyl-N-methyl-acetamid, N-Vinyl-N-ethyl-acetamid, Vinylacetat, Vinylpropionat, Acrylnitril, Styrol, Methacrylnitril, Acrylamid, Methacrylamid und N-Mono/N,N-Di-C1-C10 -Alkyl-(meth)acrylamid, verwendet.A method according to claim 3, characterized in that a copolymer of acrylic and / or methacrylic acid and one or more copolymerizable monomers from the group of maleic acid, N-vinylformamide, N-vinyl acetamide, allylamine or diallylamine derivatives, N- Vinyl pyrrolidone, N-vinyl-N-methyl-formamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl-acetamide, vinyl acetate, vinyl propionate, acrylonitrile, styrene, methacrylonitrile, acrylamide, methacrylamide and N-mono / N, N-Di-C 1 -C 10 alkyl (meth) acrylamide used. Verfahren gemäss einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass man als nichtionogenes Blockpolymer Alkylenoxid-Kondensationsprodukte oder Blockpolymere, welche durch Anlagerung von Styrol an Polypropylen- und/oder Polyethylenoxid erhältlich sind, verwendet.Method according to one of claims 1 to 4, characterized in that as non-ionic block polymer alkylene oxide condensation products or block polymers, which can be obtained by adding styrene to polypropylene and / or polyethylene oxide are used. Verfahren gemäss einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass man als Dispergiermittel einen anionischen Dispergator aus der Gruppe der (ba) sauren Ester oder deren Salze von Alkylenoxidaddukten der Formel
    Figure 00240001
    worin X den Säurerest einer anorganischen, Sauerstoff enthaltenden Säure oder den Rest einer organischen Säure, und Y C1-C12-Alkyl, Aryl oder Aralkyl bedeuten, "Alkylen" für den Ethylenrest oder Propylenrest steht, und m 1 bis 4, und n 4 bis 50 sind,     (bb) Polystyrolsulfonate, (bc) Fettsäuretauride, (bd) alkylierten Diphenyloxid -mono- oder di-sulfonate, (be) Sulfonate von Polycarbonsäureestern, (bf) mit einer organischen Dicarbonsäure, oder einer anorganischen mehrbasischen Säure in einen sauren Ester überführten Anlagerungsprodukt von 1 bis 60 Mol Ethylenoxid und/oder Propylenoxid an Fettamine, Fettamide, Fettsäuren oder Fettalkohole je mit 8 bis 22 Kohlenstoffatomen oder an drei- bis sechswertige Alkanole mit 3 bis 6 Kohlenstoffatomen, (bg) Ligninsulfonate, (bh) Naphthalinsulfonate, und (bi) Formaldehyd-Kondensationsprodukte
    verwendet.         Method according to one of claims 1 to 5, characterized in that an anionic dispersant from the group of (ba) acidic esters or their salts of alkylene oxide adducts of the formula
    Figure 00240001
    wherein X represents the acid residue of an inorganic, oxygen-containing acid or the residue of an organic acid, and YC 1 -C 12 alkyl, aryl or aralkyl, "alkylene" stands for the ethylene residue or propylene residue, and m 1 to 4, and n 4 are up to 50,     (bb) polystyrene sulfonates, (bc) fatty acid taurides, (bd) alkylated diphenyl oxide mono- or disulfonates, (be) sulfonates of polycarboxylic acid esters, (bf) with an organic dicarboxylic acid, or an inorganic polybasic acid converted adduct of 1 to 60 moles of ethylene oxide and / or propylene oxide onto fatty amines, fatty amides, fatty acids or fatty alcohols each having 8 to 22 carbon atoms or to trihydric to hexavalent alkanols with 3 to 6 carbon atoms, (bg) lignin sulfonates, (bh) naphthalene sulfonates, and (bi) formaldehyde condensation products
    used.     Verfahren gemäss Anspruch 6, dadurch gekennzeichnet, dass man als Dispergiermittel einen anionischen Dispergator der Formel
    Figure 00250001
    worin X die direkte Bindung oder Sauerstoff, A den Rest einer aromatischen Verbindung, welcher mittels eines Ringkohlenstoffatomes an die Methylengruppe gebunden ist, M Wasserstoff oder ein salzbildendes Kation, z.B. ein Alkalimetall, Erdalkalimetall oder Ammonium und n und p unabhängig voneinander eine Zahl von 1 bis 4 bedeuten, verwendet.     A method according to claim 6, characterized in that an anionic dispersant of the formula is used as the dispersant
    Figure 00250001
    wherein X is the direct bond or oxygen, A is the residue of an aromatic compound which is bonded to the methylene group by means of a ring carbon atom, M is hydrogen or a salt-forming cation, for example an alkali metal, alkaline earth metal or ammonium and n and p independently of one another are a number from 1 to 4 mean used.     Wässrige Drucktinte für das Tintenstrahldruck-Verfahren, dadurch gekennzeichnet, dass sie 1 bis 35 Gew.-% mindestens eines Dispersionsfarbstoffes der Formeln (1) bis (23), ein anionisches Copolymer und/oder ein nichtionogenes Blockpolymer und/oder ein Dispergiermittel enthält.Aqueous printing ink for the inkjet printing process, characterized in that they contain 1 to 35% by weight of at least one disperse dye of the formulas (1) to (23) anionic copolymer and / or a nonionic block polymer and / or a dispersant contains. Die mit der wässrigen Drucktinte gemäss Anspruch 8 nach dem Tintenstrahldruck-Verfahren bedruckten textilen Fasermaterialien.The with the aqueous printing ink according to claim 8 by the ink jet printing process printed textile fiber materials.
    EP98811210A 1997-12-17 1998-12-08 Process for printing textile fibres materials according to the ink-jet printing process Expired - Lifetime EP0924335B1 (en)

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