EP0665326A2 - Process for printing fibrous material by direct printing - Google Patents

Process for printing fibrous material by direct printing Download PDF

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Publication number
EP0665326A2
EP0665326A2 EP95810032A EP95810032A EP0665326A2 EP 0665326 A2 EP0665326 A2 EP 0665326A2 EP 95810032 A EP95810032 A EP 95810032A EP 95810032 A EP95810032 A EP 95810032A EP 0665326 A2 EP0665326 A2 EP 0665326A2
Authority
EP
European Patent Office
Prior art keywords
weight
acrylamide
printing paste
printing
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP95810032A
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German (de)
French (fr)
Other versions
EP0665326A3 (en
Inventor
Paul Schafflützel
Philippe Ouziel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Geigy AG
Ciba Spezialitaetenchemie Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG, Ciba Spezialitaetenchemie Holding AG filed Critical Ciba Geigy AG
Publication of EP0665326A2 publication Critical patent/EP0665326A2/en
Publication of EP0665326A3 publication Critical patent/EP0665326A3/en
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—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
    • D06P1/46—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 natural macromolecular substances or derivatives thereof
    • D06P1/48—Derivatives of carbohydrates
    • 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
    • D06P1/46—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 natural macromolecular substances or derivatives thereof
    • D06P1/48—Derivatives of carbohydrates
    • D06P1/50—Derivatives of cellulose
    • 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
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D06P3/663—Natural or regenerated cellulose using reactive dyes reactive group directly attached to heterocyclic group
    • 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
    • D06P5/001—Special chemical aspects of printing textile materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/62—Natural or regenerated cellulose using direct dyes

Definitions

  • the present invention relates to a method for printing fiber material, e.g. cellulose-containing textile material, wool, silk or synthetic fabric such as polyester or polyamide, in direct printing and the printing paste used for this printing.
  • fiber material e.g. cellulose-containing textile material, wool, silk or synthetic fabric such as polyester or polyamide
  • the present invention was therefore based on the object of providing printing pastes using the classic thickeners which do not have the disadvantages mentioned above and, in particular, give prints with excellent contour sharpness without loss of the handle of the printed fabric.
  • This object is surprisingly achieved by adding small amounts of an acrylamide homo- or copolymer to the printing paste.
  • the present invention thus relates to a method for printing fiber material in direct printing, in which a printing paste containing at least one dye, a cellulose derivative or an alginate as a thickener and other conventional additives is applied to the fiber material and the dye is subsequently fixed, characterized in that the printing paste ⁇ 5 wt .-%, based on the printing paste of a homo- or copolymer based on acrylamide contains.
  • the acrylamide homopolymers and copolymers used according to the invention have an average molecular weight of, for example, 0.5 to 15 million, preferably 1 to 10 million, particularly preferably 1 to 5 million and particularly preferably 1 to 2.5 million.
  • Acrylamide homopolymers or copolymers of acrylamide and one or more comonomers are suitable.
  • Examples of such comonomers are: Monomers with a carboxyl function: (Meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, vinyl acetic acid, vinyl oxyacetic acid, vinyl propionic acid, crotonic acid, aconitic acid, allylacetic acid, allyloxyacetic acid, ⁇ , ⁇ -dimethylacrylic acid, allylmalonic acid, allyloxymalonic acid 2, hydroxylmalonic acid 2-hydroxymalonic acid, methylene malonic acid, methylene malonic acid, methylene acid -Halogeno (meth) acrylic acid, ⁇ -ethyl acrylic acid, acrylamidoglycolic acid, glutaconic acid, ⁇ -carboxyethyl acrylate, allyloxy-3-hydroxybutanoic acid and allylsuccinic acid.
  • Monomers with a phosphoric acid group vinylphosphonic acid, (meth) allylphosphonic acid and acrylamidomethylpropanephosphonic acid.
  • Monomers with a sulfonic acid group (Meth) acrylamidomethanesulfonic acid, vinylsulfonic acid, (meth) allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3- (meth) acrylamidopropanesulfonic acid, 3-sulfopropyl (meth) acrylate, bis- (3-sulfopropylitaconate), 4-styrenesulfonic acid and 3-allyloxy -2-hydroxypropylsulfonic acid.
  • Nitrogenous and non-ionic co-monomers N-vinylpyrrolidone, N-vinylformamide, N-vinyl-N-methyl-formamide, N-vinylacetamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl-acetamide, N-vinylimidazole, N-vinyl N-methyl-imidazole, N-vinylimidazoline, N-vinyl-2-methylimidazoline, N-vinylcaprolactam, vinyl acetate, vinyl propionate, vinyl butyrate, C1-C22-alkyl vinyl ketone, C1-C22-alkyl vinyl ether, olefins (ethylene, propylene, isobutene), 1 , 2-dimethoxyethylene, styrene derivatives, hydroxyethyl / propyl / butyl / - (meth) acrylate, (Meth) acrylic
  • Preferred polymers used in the printing paste according to the invention are acrylamide homopolymers or copolymers of acrylamide and acrylic acid or N-methyl-N-vinyl acetamide.
  • a preferred embodiment of the present invention relates to the use of an acrylamide homopolymer with an average molecular weight of 0.5-15 million and preferably 1-10 million as an additive to the printing paste.
  • Another preferred embodiment of the present invention relates to the use of a copolymer of acrylamide and acrylic acid with an average molecular weight of e.g. 0.5 to 15 million, preferably 1 to 10 million and particularly preferably 1.5 to 3 million, as an additive to the printing paste.
  • the preferred copolymers consist of 30 to 99.9% by weight of acrylamide and 0.1 to 70% by weight of acrylic acid, each based on the weight of the monomers.
  • a particularly preferred embodiment of the present invention relates to the use of copolymers of 75 to 90% by weight of acrylamide and 10 to 25% by weight of acrylic acid, in each case based on the weight of the monomers.
  • Another preferred embodiment of the present invention relates to the use of a copolymer of e.g. 30 to 99.9% by weight of acrylamide and 0.1 to 70% by weight of N-vinyl-N-methylacetamide, in each case based on the weight of the monomers, as an additive to the printing paste.
  • Copolymers of 40 to 60% by weight of acrylamide and 60 to 40% by weight of N-vinyl-N-methylacetamide are preferred, and copolymers of 50% by weight of acrylamide and 50% by weight of N-vinyl-N are particularly preferred -methyl acetamide, in each case based on the weight of the monomers.
  • the acrylamide / N-vinyl-N-methylacetamide copolymers can additionally contain a small amount, e.g. ⁇ 10% by weight, based on the weight of the acrylamide or N-vinyl-N-methylacetamide monomers, of an alkoxylated fatty alcohol, e.g. of an adduct of ethylene oxide and / or propylene oxide with glycerin, which is advantageously added in the synthesis of the copolymers.
  • an alkoxylated fatty alcohol e.g. of an adduct of ethylene oxide and / or propylene oxide with glycerin
  • the homopolymers and copolymers used according to the invention are known or can be prepared by methods known per se.
  • the acrylamide homopolymer or copolymer of the printing paste is preferably used in an amount of ⁇ 1% by weight and particularly preferably ⁇ 0.5% by weight, based in each case on the Weight of the printing paste, too. Too high a polymer concentration can limit printability and negatively affect the handle.
  • the process is carried out in the presence of 0.002 to 1% by weight and in particular 0.01 to 0.5% by weight of acrylamide homo- or copolymer, in each case based on the printing paste.
  • the printing paste used according to the invention contains a conventional cellulose derivative, e.g. a cellulose ether such as methyl, ethyl, hydroxyethyl, methylhydroxyethyl, hydroxypropyl, hydroxypropylmethyl, carboxymethyl, carboxyethyl or cyanoethyl cellulose or a cellulose ester such as e.g. Acetyl cellulose, or preferably an alginate, e.g. Na alginate.
  • the amount of thickener in the printing paste can vary within wide limits depending on the desired viscosity; advantageously used e.g. 10 to 100 g / kg and preferably 15 to 70 g / kg printing paste.
  • the printing paste can also contain conventional additives, e.g. B. hydrotroping agents, defoaming or deaerating agents, reducing agents, preservatives, sequestering agents or bases.
  • B. hydrotroping agents, defoaming or deaerating agents, reducing agents, preservatives, sequestering agents or bases e.g. B. hydrotroping agents, defoaming or deaerating agents, reducing agents, preservatives, sequestering agents or bases.
  • the printing paste contains a hydrotroping agent, it is preferably urea, which e.g. is present in an amount of 0.1 to 20 wt .-% and preferably 0.1 to 10 wt .-%, based on the finished printing paste.
  • deaeration agents can be used as deaeration agents, provided that the rheological properties of the printing paste according to the invention are not negatively influenced. Because of their good defoaming properties, low-silicone oil-free silicone oil-free deaerating agents are preferred, which generally contain 0 to about 5, in particular 0.1 to 1 percent by weight of a conventional silicone oil.
  • Preferred deaerators contain, for example, high-boiling hydrocarbons, hydrogenated naphthalenes, mineral oils, fatty oils or insoluble metal soaps or mixtures thereof as the active substance and, if appropriate, have the silicone oil content indicated above.
  • they can also be present as aqueous solutions which generally contain, in addition to the active substances of the type mentioned, a nonionic surfactant, for example ethylene oxide adducts from an alkylphenol or sorbitan stearate.
  • the preferred ingredients or active substances of the deaerating agents are higher Alcohols with boiling points above about 100 ° C, turpentine oils, mineral oils or their mixtures mentioned.
  • Hydrocarbon mixtures which generally have a flash point above approximately 120 ° C., preferably from approximately 150 to 220 ° C. and a boiling range from approximately 250 to 500 ° C. under normal conditions are preferably used.
  • venting agents that contain a higher alcohol, such as e.g. Contain 2-ethyl-n-hexanol or 2-hexyldecanol or their mixture with high-boiling hydrocarbon mixtures and have the above-mentioned content of silicone oils;
  • the alcohols or alcohol / hydrocarbon mixtures mentioned are optionally in the form of an aqueous preparation and then advantageously contain, in addition to the active substances, a surfactant, e.g. Ethylene oxide adducts of an alkylphenol with 6 to 12 carbon atoms in the alkyl radical or an ethylene oxide adduct of sorbitan tristearate.
  • the printing paste contains the deaerating agent e.g. in an amount of ⁇ 5% by weight and preferably 0.1 to 1% by weight, based on the weight of the finished printing paste.
  • a reducing agent such.
  • a reducing agent is e.g. present in an amount of 0.1 to 4% by weight and preferably 0.8 to 2% by weight, based in each case on the finished printing paste.
  • Suitable sequestrants are e.g. To name phosphates such as sodium hexametaphosphate.
  • the printing paste contains bases, for example for fixing the reactive dyes in reactive printing, for example sodium carbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, sodium acetate, sodium propionate, sodium hydrogen carbonate, aqueous ammonia or alkali donors, such as sodium trichloroacetate or sodium formate.
  • bases for example sodium carbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, sodium acetate, sodium propionate, sodium hydrogen carbonate, aqueous ammonia or alkali donors, such as sodium trichloroacetate or sodium formate.
  • a mixture of water glass and a 25% aqueous sodium carbonate solution can also be used as the fixing alkali.
  • the pH of the printing paste containing fixing alkali is generally 7.5 to 13.2, preferably 8.5 up to 12.5.
  • the amount of fixing alkali is chosen so that the pH of the ready-to-use printing paste is in the alkaline range, preferably between pH 7.5 and 12; the amount of fixing alkali can accordingly vary within wide limits, for example between 0.5 and 10% by weight, based on the finished printing paste.
  • the dyes used in the process according to the invention are the dyes usually used for dyeing or printing textile materials, such as those e.g. in the Color Index, 3rd edition 1971 and the supplements to it under the headings "Reactive dyes", “Acid dyes”, “Mordant dyes”, “Vat dyes” or "Disperse Dyes”.
  • reactive dyes are dyes of different classes, e.g. to those from the monoazo or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane or dioxazine series, which contain at least one reactive group.
  • Reactive groups are fiber-reactive radicals which are able to react with the hydroxyl groups of cellulose, the amino, carboxy, hydroxyl and thiol groups in wool and silk, or with the amino and possibly carboxy groups of synthetic polyamides to form covalent chemical bonds .
  • the reactive groups are usually bound to the dye residue directly or via a bridge link.
  • Suitable reactive groups are, for example, those which contain at least one removable substituent on an aliphatic, aromatic or heterocyclic radical or in which the radicals mentioned are a radical suitable for reaction with the fiber material, such as e.g. contain a halotriazinyl, halopyrimidinyl or vinyl radical.
  • aliphatic reactive groups are those of the formulas -SO2Z, -SO2-NH-Z, -NH-CO-alk-SO2Z, -CO-NH-alk-SO2Z, or -NH-CO-Z1, wherein Z is a leaving group, e.g. is ⁇ -sufatoethyl, ⁇ -thiosulfatoethyl, ⁇ -phosphatoethyl, ⁇ -acyloxyethyl, ⁇ -haloethyl or vinyl, Z1 e.g. represents an ⁇ , ⁇ -dihaloethyl or ⁇ -haloethenyl radical, alk is C2-C4alkylene and halogen is preferably chlorine or bromine, preferably.
  • Z is a leaving group, e.g. is ⁇ -sufatoethyl, ⁇ -thiosulfatoethyl, ⁇ -phosphatoethyl, ⁇ -acyloxye
  • Preferred heterocyclic, fiber-reactive radicals are 1,3,5-triazine radicals of the formula in which T1 is fluorine, chlorine or carboxypyridinium and the substituents V1 on the triazine ring which may be mentioned in particular: fluorine or chlorine; -NH2, optionally substituted alkylamino or N, N-dialkylamino groups, for example N-mono- or N, N-di-C1-C4-alkylamino optionally substituted by hydroxy, sulfo or sulfato; Cycloalkylamino; Aralkylamino, for example benzylamino; Arylamino groups such as phenylamino optionally substituted by sulfo, methyl, methoxy or chlorine; mixed substituted amino groups such as N-alkyl-N-cyclohexylamino or N-alkyl-N-phenylamino groups; and morpholino.
  • T1 is fluorine,
  • reactive dyes which contain at least one monohalotriazine group, preferably a monochlorotriazine group.
  • Dyes with two or more identical or different reactive groups can also be used.
  • the amount of the dyes used is generally dependent on the desired color strength and is expediently from 0.01 to 400 g, advantageously from 0.5 to 300 and preferably from 1 to 200 g per kg of printing paste.
  • the printing paste used according to the invention is new and represents a further subject of the invention.
  • the printing paste according to the invention is produced in a simple manner by mixing the components, and finally the required amount of water is added, so that a viscosity suitable for direct printing is established, which e.g. is between 1500 and 10000 mPa ⁇ s and preferably between 1500 and 7000 mPa ⁇ s.
  • the printing paste according to the invention is characterized by good homogeneity, good storage stability and simple handling.
  • the printing paste is applied over the entire surface, preferably in a pattern, to the substrate, printing presses of conventional design, for example rotary film printing or flat film printing machines can be used appropriately.
  • the printed textile material is preferably dried and then subjected to a heat treatment process in order to complete the print or to fix the dye.
  • the heat treatment can be carried out by a warm dwell process, a thermal insulation process or preferably by a steaming process.
  • the printed textile materials are subjected to a treatment in a steamer with possibly superheated steam, expediently at a temperature of 98 to 210 ° C., advantageously 100 to 180 ° C. and preferably 100 to 120 ° C.
  • the completion of the prints by the so-called thermal insulation process can take place after or without intermediate drying, e.g. at a temperature of 100 to 210 ° C.
  • the thermal insulation is preferably carried out at a temperature of 120 to 210 ° C., preferably 140 to 180 ° C. and after intermediate drying at 80 to 140 ° C. of the printed goods.
  • the thermal insulation can take 20 seconds to 5 minutes, preferably 30 seconds to 4 minutes.
  • the textile material is washed out in the usual way in order to remove unfixed dye.
  • the substrate is treated with water, for example at from 40 ° C. to cooking temperature, to which a soap or a synthetic detergent can optionally be added.
  • the fiber materials to be printed are e.g. around textile materials made from natural, semi-synthetic or fully synthetic fibers; Mixtures of the fibers mentioned are also suitable.
  • the semi-synthetic fibers are e.g. regenerated cellulose fibers, e.g. Viscose fibers or acetate fibers (2 1 / 2- and triacetate) and, in the case of fully synthetic fibers, mainly polyacrylonitrile, polyamide or polyester fibers.
  • natural fibers e.g. Silk, wool or natural cellulose, especially cotton, are possible.
  • the method is particularly preferably suitable for printing on viscose, cotton or cotton / polyester mixed fibers; in the latter, the cotton and polyester portion can advantageously be printed simultaneously with a mixture of reactive dye and disperse dye.
  • these are mainly sheet-like textile materials, such as Fleeces, felts, carpets, knitted fabrics and in particular fabrics.
  • the process according to the invention is suitable for fiber materials which may have been pretreated with sodium hydroxide solution, for cellulose material and regenerated cellulose or mixtures thereof.
  • the present process gives strong, pattern-like prints on a white background with good levelness and good fastness properties, e.g. Fastness to light, washing and rubbing; the prints also have practically no dichroism. Particularly noteworthy is the sharpness of the contours of the prints obtained, which is greatly improved compared to a process without the addition of acrylamide homo- or copolymer.
  • Another advantage relates to the comparatively low penetration of the dye into the textile material when using the method according to the invention, i.e. you get a surface pressure; consequently, a predetermined color strength can be produced with a reduced application of printing paste.
  • the printing paste has a pH of 10.7.
  • the viscosity is 5,300 mPa.s, measured on the Brookfield RVT viscometer, spindle 6, 20 rpm at 25 ° C.
  • the printed fabric is dried at 90 ° C. and fixed for 8 minutes to fix the dye. treated with saturated steam at 100 to 102 ° C.
  • the fabric is then rinsed with cold and boiling water until the unfixed portions of the dye and auxiliary agents have been removed. After drying the fabric at 90 to 100 ° C, you get a strong, level, turquoise print with sharp contours.
  • the treated fabric also has a soft feel.
  • Example 2 The procedure described in Example 1 is followed and a printing paste is used which contains 480 g / kg Na alginate medium viscosity (6% mixture containing 5 g / kg sodium hexametaphosphate and 3 g / kg 37% formaldehyde) instead of 480 g / kg Na alginate medium viscosity (6% mixture containing 5 g / kg sodium hexametaphosphate and 5 g / kg 37% formaldehyde), 30 g / kg 1% aqueous solution of a copolymer of approx. 15% acrylic acid and 85% acrylamide (molecular weight approx. 2 million) instead of 75 g / kg 0.8% aqueous solution of a copolymer of approx. 15% acrylic acid and 85% acrylamide (molecular weight approx. 2 million) and 232 g / kg water instead of 187 g / kg water contains similarly good results.
  • Example 1 or 1A If one proceeds as described in Example 1 or 1A and prints a bleached viscose fabric instead of the bleached, mercerized cotton fabric, one also obtains a strong, level print with sharp contours and a soft handle, which has a turquoise shade.
  • the pH of the printing paste is 10.7 and its viscosity is 5,800 mPa.s, measured on the Brookfield RVT viscometer, spindle 6, 20 rpm at 25 ° C. It contains a strong, level, green print with sharp contours.
  • the treated fabric also has a soft feel.
  • Example 3 The procedure described in Example 3 is followed and a printing paste is used which is 480 g / kg Na alginate medium viscosity (6% batch containing 5 g / kg sodium hexametaphosphate and 3 g / kg 37% formaldehyde) instead of 480 g / kg Na alginate medium viscosity (6% batch containing 5 g / kg sodium hexametaphosphate and 5 g / kg 37% formaldehyde), 30 g / kg 1% aqueous solution of a copolymer of approx. 15% acrylic acid and 85% acrylamide (molecular weight approx. 2 million) instead of 75 g / kg 0.8% aqueous solution of a copolymer of approx. 15% acrylic acid and 85% acrylamide (molecular weight approx. 2 million) and 212 g / kg water instead of 167 g / kg water, similarly good results Get results.
  • the printing paste has a viscosity of approx. 5,000 mPa.s, measured on the Brookfield RVT viscometer, spindle 6, 20 rpm at 25 ° C.
  • the printed fabric is dried at 70 to 80 ° C and for 10 minutes to fix the dye. treated with saturated steam at 100 to 102 ° C.
  • the tissue is rinsed with cold water and then 5 min. treated at 50 ° C with 2 g / l H2O2 35% and 1 g / l acetic acid 80%.
  • the reoxidized tissue is then rinsed with warm water, soaped at the boil for about 5 minutes and rinsed again with warm and cold water. After drying the fabric at 60 to 100 ° C, you get a strong, level, olive-colored print with sharp contours.
  • the treated fabric also has a soft feel.
  • the printing paste has a pH of 6.1.
  • the viscosity is approx. 5,400 mPa.s, measured on the Brookfield RVT viscometer, spindle 6, 20 rpm at 25 ° C.
  • the printed fabric is dried at 70 to 80 ° C and for 8 minutes to fix the dye. treated with saturated steam at 175 ° C.
  • the fabric is rinsed with cold water, soaped at 40 ° C with 1 g / l of a nonionic fatty acid ethoxylate and then at 40 to 70 ° C with 1.5 g / l Na2S2O4, 2 g / l sodium hydroxide solution 36 ° Bé and 1 g / l of said fatty acid ethoxylate reductively cleaned.
  • the treated fabric also has a soft feel.
  • the printed fabric is dried at 70 to 80 ° C and to fix the dye for 35 min. treated with saturated steam at 100 to 102 ° C. To finish, the fabric is rinsed with cold water, soaped at 30 ° C and rinsed cold again. After the fabric has dried, it contains a strong, level, green print with sharp contours. The treated fabric also has a soft feel.

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Abstract

In direct printing on fibrous material by applying a paste contg. dye(s), a cellulose deriv. or alginate as thickener and other usual additives and then fixing the dye, the paste contains at most 5 wt.% (co)polyacrylamide (I). Also claimed are an aq. printing paste and its use in direct printing.

Description

Die vorliegende Erfindung betrifft ein Verfahren zum Bedrucken von Fasermaterial, wie z.B. cellulosehaltiges Textilmaterial, Wolle, Seide oder synthetisches Gewebe wie Polyester oder Polyamid, im Direktdruck sowie die für diesen Druck verwendete Druckpaste.The present invention relates to a method for printing fiber material, e.g. cellulose-containing textile material, wool, silk or synthetic fabric such as polyester or polyamide, in direct printing and the printing paste used for this printing.

Es ist schon seit langer Zeit bekannt, Fasermaterialien mit Druckpasten zu bedrucken, die Cellulosederivate oder insbesondere Alginate als Verdicker enthalten. Dabei muss die Druckpaste im Hinblick auf eine genügende Oberflächendeckung bzw. Egalität des Drucks in das vorgelegte Gewebe eindringen. Ein zu starkes Eindringen bzw. Aufbringen der Druckpaste kann jedoch zum "Fliessen" der Drucke führen. Es ist ausserdem öfters festzustellen, dass aufgrund des tiefen, möglicherweise ungleichmässigen Eindringens der Druckpaste Unegalitäten oder Dichroismus resultieren. Die vorbekannten Drucke weisen ausserdem oftmals eine ungenügende Konturenschärfe auf.It has been known for a long time to print fiber materials with printing pastes which contain cellulose derivatives or, in particular, alginates as thickeners. The print paste must penetrate into the fabric in order to ensure sufficient surface coverage or levelness of the print. However, excessive penetration or application of the printing paste can cause the prints to "flow". In addition, it can often be found that the deep, possibly uneven penetration of the printing paste results in irregularities or dichroism. The previously known prints also often have insufficient contour sharpness.

Der vorliegenden Erfindung lag daher die Aufgabe zu Grunde, Druckpasten unter Verwendung der klassischen Verdicker bereitzustellen, die die obengenannten Nachteile nicht aufweisen und insbesondere Drucke mit einer hervorragenden Konturenschärfe ohne Einbussen an den Griff des bedruckten Gewebes ergeben. Diese Aufgabe wird überraschenderweise dadurch gelöst, dass man der Druckpaste geringe Mengen eines Acrylamid-Homo- oder Copolymers zusetzt.The present invention was therefore based on the object of providing printing pastes using the classic thickeners which do not have the disadvantages mentioned above and, in particular, give prints with excellent contour sharpness without loss of the handle of the printed fabric. This object is surprisingly achieved by adding small amounts of an acrylamide homo- or copolymer to the printing paste.

Die vorliegende Erfindung betrifft somit ein Verfahren zum Bedrucken von Fasermaterial im Direktdruck, worin man auf das Fasermaterial eine Druckpaste enthaltend mindestens einen Farbstoff, ein Cellulosederivat oder ein Alginat als Verdicker und weitere übliche Zusätze aufbringt und den Farbstoff anschliessend fixiert, dadurch gekennzeichnet, dass die Druckpaste ≦ 5 Gew.-%, bezogen auf die Druckpaste eines Homo- oder Copolymers auf der Basis von Acrylamid enthält.The present invention thus relates to a method for printing fiber material in direct printing, in which a printing paste containing at least one dye, a cellulose derivative or an alginate as a thickener and other conventional additives is applied to the fiber material and the dye is subsequently fixed, characterized in that the printing paste ≦ 5 wt .-%, based on the printing paste of a homo- or copolymer based on acrylamide contains.

Die erfindungsgemäss verwendeten Acrylamid-Homo- und -Copolymere weisen einen durchschnittliches Molekulargewicht von z.B. 0,5 bis 15 Millionen, vorzugsweise 1 bis 10 Millionen, besonders bevorzugt 1 bis 5 Millionen und insbesondere bevorzugt 1 bis 2,5 Millionen auf. Geeignet sind Acrylamid-Homopolymere oder Copolymere aus Acrylamid und einem oder mehreren Comonomeren.The acrylamide homopolymers and copolymers used according to the invention have an average molecular weight of, for example, 0.5 to 15 million, preferably 1 to 10 million, particularly preferably 1 to 5 million and particularly preferably 1 to 2.5 million. Acrylamide homopolymers or copolymers of acrylamide and one or more comonomers are suitable.

Beispiele für solche Comonomeren sind:
Monomere mit Carboxylfunktion:
(Meth)acrylsäure, Maleinsäure, Fumarsäure, Itaconsäure, Mesaconsäure, Citraconsäure, Vinylessigsäure, Vinyloxyessigsäure, Vinylpropionsäure, Crotonsäure, Aconitsäure, Allylessigsäure, Allyloxyessigsäure, α,β-Dimethylacrylsäure, Allylmalonsäure, Allyloxymalonsäure, Methylenmalonsäure, 2-Hydroxy(meth)acrylsäure, 2-Halogeno(meth)acrylsäure, α-Ethylacrylsäure, Acrylamidoglycolsäure, Glutaconsäure, β-Carboxyethylacrylat, Allyloxy-3-hydroxybutansäure und Allylbernsteinsäure.Examples of such comonomers are:
Monomers with a carboxyl function:
(Meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, vinyl acetic acid, vinyl oxyacetic acid, vinyl propionic acid, crotonic acid, aconitic acid, allylacetic acid, allyloxyacetic acid, α, β-dimethylacrylic acid, allylmalonic acid, allyloxymalonic acid 2, hydroxylmalonic acid 2-hydroxymalonic acid, methylene malonic acid, methylene malonic acid, methylene acid -Halogeno (meth) acrylic acid, α-ethyl acrylic acid, acrylamidoglycolic acid, glutaconic acid, β-carboxyethyl acrylate, allyloxy-3-hydroxybutanoic acid and allylsuccinic acid.

Monomere mit Phosphorsäuregruppe: Vinylphosphonsäure, (Meth)allylphosphonsäure und Acrylamidomethylpropanphosphonsäure.Monomers with a phosphoric acid group: vinylphosphonic acid, (meth) allylphosphonic acid and acrylamidomethylpropanephosphonic acid.

Monomere mit Sulfonsäuregruppe:
(Meth)acrylamidomethansulfonsäure, Vinylsulfonsäure, (Meth)allylsulfonsäure, 2-Acrylamido-2-methylpropansulfonsäure, 3-(Meth)acrylamidopropansulfonsäure, 3-Sulfopropyl(meth)acrylat, Bis-(3-sulfopropylitaconat), 4-Styrolsulfonsäure und 3-Allyloxy-2-hydroxypropylsulfonsäure.Monomers with a sulfonic acid group:
(Meth) acrylamidomethanesulfonic acid, vinylsulfonic acid, (meth) allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3- (meth) acrylamidopropanesulfonic acid, 3-sulfopropyl (meth) acrylate, bis- (3-sulfopropylitaconate), 4-styrenesulfonic acid and 3-allyloxy -2-hydroxypropylsulfonic acid.

Stickstoffhaltige und nicht-ionische Co-monomere:
N-Vinylpyrrolidon, N-Vinylformamid, N-Vinyl-N-methyl-formamid, N-Vinylacetamid, N-Vinyl-N-methyl-acetamid, N-Vinyl-N-ethyl-acetamid, N-Vinylimidazol, N-Vinyl-N-methyl-imidazol, N-Vinylimidazolin, N-Vinyl-2-methylimidazolin, N-Vinylcaprolactam, Vinylacetat, Vinylpropionat, Vinylbutyrat, C₁-C₂₂-Alkylvinylketon, C₁-C₂₂-Alkylvinylether, Olefine (Ethylen, Propylen, Isobuten), 1,2-Dimethoxyethylen, Styrolderivate, Hydroxy-ethyl/propyl/butyl/-(meth)acrylat,
(Meth)acrylsäurealkylester-C₁-C₄, (Meth)acrolein, (Meth)acrylnitril, Methacrylamid, Ester/(subst.) Amide/Nitrile der Monomeren mit Carboxylfunktion, N-Mono/N-Disubstituiertes (Meth)acrylamid, (C₁-C₄)-Alkoxy-(meth)acrylate, EOx-POy-ButOz mit x,y,z = 0-250, Alkyl-(meth)acrylate-(C₅-C₂₂), N-Mono/Disubstituierte Acrylamide-(C₅-C₂₂), Alkylvinylether-(C₅-C₂₂), Alkylvinylketone-(C₅-C₂₂) und Dimethyl/Diethyl-aminoethyl/propyl/butyl(meth)acrylate in Form der Salze oder in quaternierter Form, wobei geeignete Quaternierungsmittel z.B. Dimethyl/ethyl-sulfat, Methyl/ethyl-chlorid oder Benzylchlorid sind.Nitrogenous and non-ionic co-monomers:
N-vinylpyrrolidone, N-vinylformamide, N-vinyl-N-methyl-formamide, N-vinylacetamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl-acetamide, N-vinylimidazole, N-vinyl N-methyl-imidazole, N-vinylimidazoline, N-vinyl-2-methylimidazoline, N-vinylcaprolactam, vinyl acetate, vinyl propionate, vinyl butyrate, C₁-C₂₂-alkyl vinyl ketone, C₁-C₂₂-alkyl vinyl ether, olefins (ethylene, propylene, isobutene), 1 , 2-dimethoxyethylene, styrene derivatives, hydroxyethyl / propyl / butyl / - (meth) acrylate,
(Meth) acrylic acid alkyl ester-C₁-C₄, (meth) acrolein, (meth) acrylonitrile, methacrylamide, ester / (subst.) Amides / nitriles of the monomers with carboxyl function, N-mono / N-disubstituted (meth) acrylamide, (C₁- C₄) -alkoxy- (meth) acrylates, EO x -PO y -ButO z with x, y, z = 0-250, alkyl- (meth) acrylates- (C₅-C₂₂), N-mono / disubstituted acrylamides- ( C₅-C₂₂), alkyl vinyl ether (C₅-C₂₂), alkyl vinyl ketone (C₅-C₂₂) and dimethyl / diethylaminoethyl / propyl / butyl (meth) acrylates in the form of the salts or in quaternized form, suitable quaternizing agents, for example dimethyl / ethyl -sulfate, methyl / ethyl chloride or benzyl chloride.

Bevorzugte in der erfindungsgemässen Druckpaste verwendete Polymere sind Acrylamid-Homopolymere oder Copolymere aus Acrylamid und Acrylsäure oder N-Methyl-N-vinylacetamid.Preferred polymers used in the printing paste according to the invention are acrylamide homopolymers or copolymers of acrylamide and acrylic acid or N-methyl-N-vinyl acetamide.

Eine bevorzugte Ausführungsform der vorliegenden Erfindung betrifft die Verwendung eines Acrylamid-Homopolymers mit einem durchschnittlichen Molekulargewicht von 0,5-15 Millionen und vorzugsweise 1-10 Millionen als Zusatz zur Druckpaste.A preferred embodiment of the present invention relates to the use of an acrylamide homopolymer with an average molecular weight of 0.5-15 million and preferably 1-10 million as an additive to the printing paste.

Eine weitere bevorzugte Ausführungsform der vorliegenden Erfindung betrifft die Verwendung eines Copolymers aus Acrylamid und Acrylsäure mit einem durchschnittlichen Molekulargewicht von z.B. 0,5 bis 15 Millionen, vorzugsweise 1 bis 10 Millionen und besonders bevorzugt 1,5 bis 3 Millionen, als Zusatz zur Druckpaste. Die bevorzugten Copolymere bestehen aus 30 bis 99,9 Gew.-% Acrylamid und 0,1 bis 70 Gew.-% Acrylsäure, jeweils bezogen auf das Gewicht der Monomeren. Besonders bevorzugt ist die Verwendung von Acrylamid/Acrylsäure-Copolymeren mit einem Acrylamidgehalt von > 60 Gew.-%, bezogen auf das Gewicht der Monomeren. Eine insbesondere bevorzugte Ausführungsform der vorliegenden Erfindung betrifft die Verwendung von Copolymeren aus 75 bis 90 Gew.-% Acrylamid und 10 bis 25 Gew.-% Acrylsäure, jeweils bezogen auf das Gewicht der Monomeren.Another preferred embodiment of the present invention relates to the use of a copolymer of acrylamide and acrylic acid with an average molecular weight of e.g. 0.5 to 15 million, preferably 1 to 10 million and particularly preferably 1.5 to 3 million, as an additive to the printing paste. The preferred copolymers consist of 30 to 99.9% by weight of acrylamide and 0.1 to 70% by weight of acrylic acid, each based on the weight of the monomers. The use of acrylamide / acrylic acid copolymers with an acrylamide content of> 60% by weight, based on the weight of the monomers, is particularly preferred. A particularly preferred embodiment of the present invention relates to the use of copolymers of 75 to 90% by weight of acrylamide and 10 to 25% by weight of acrylic acid, in each case based on the weight of the monomers.

Eine weitere bevorzugte Ausführungsform der vorliegenden Erfindung betrifft die Verwendung eines Copolymers aus z.B. 30 bis 99,9 Gew.-% Acrylamid und 0,1 bis 70 Gew.-% N-Vinyl-N-methylacetamid, jeweils bezogen auf das Gewicht der Monomeren, als Zusatz zur Druckpaste. Bevorzugt sind hierbei Copolymere aus 40 bis 60 Gew.-% Acrylamid und 60 bis 40 Gew.-% N-Vinyl-N-methylacetamid und insbesondere bevorzugt Copolymere aus 50 Gew.-% Acrylamid und 50 Gew.-% N-Vinyl-N-methylacetamid, jeweils bezogen auf das Gewicht der Monomeren. Die Acrylamid/N-Vinyl-N-methylacetamid-Copolymere können zusätzlich noch eine geringe Menge, z.B. ≦ 10 Gew.-%, bezogen auf das Gewicht der Acrylamid- oder N-Vinyl-N-methylacetamid-Monomere, eines alkoxylierten Fettalkohols, z.B. eines Anlagerungsprodukts von Ethylenoxid und/oder Propylenoxid an Glyzerin, enthalten, welches vorteilhaft bei der Synthese der Copolymere zugesetzt wird.Another preferred embodiment of the present invention relates to the use of a copolymer of e.g. 30 to 99.9% by weight of acrylamide and 0.1 to 70% by weight of N-vinyl-N-methylacetamide, in each case based on the weight of the monomers, as an additive to the printing paste. Copolymers of 40 to 60% by weight of acrylamide and 60 to 40% by weight of N-vinyl-N-methylacetamide are preferred, and copolymers of 50% by weight of acrylamide and 50% by weight of N-vinyl-N are particularly preferred -methyl acetamide, in each case based on the weight of the monomers. The acrylamide / N-vinyl-N-methylacetamide copolymers can additionally contain a small amount, e.g. ≦ 10% by weight, based on the weight of the acrylamide or N-vinyl-N-methylacetamide monomers, of an alkoxylated fatty alcohol, e.g. of an adduct of ethylene oxide and / or propylene oxide with glycerin, which is advantageously added in the synthesis of the copolymers.

Die erfindungsgemäss verwendeten Homo- und Copolymere sind bekannt oder können nach an sich bekannten Methoden hergestellt werden.The homopolymers and copolymers used according to the invention are known or can be prepared by methods known per se.

Man setzt das Acrylamid-Homo- oder -Copolymer der Druckpaste vorzugsweise in einer Menge von ≦ 1 Gew.-% und besonders bevorzugt ≦ 0,5 Gew.-%, jeweils bezogen auf das Gewicht der Druckpaste, zu. Eine zu hohe Polymerkonzentration kann die Druckbarkeit einschränken und den Warengriff negativ beeinflussen. In einer besonders bevorzugten Ausführungsform der Erfindung wird das Verfahren in Gegenwart von 0,002 bis 1 Gew.-% und insbesondere 0,01 bis 0,5 Gew.-% Acrylamid-Homo- oder -Copolymer, jeweils bezogen auf die Druckpaste, durchgeführt.The acrylamide homopolymer or copolymer of the printing paste is preferably used in an amount of ≦ 1% by weight and particularly preferably ≦ 0.5% by weight, based in each case on the Weight of the printing paste, too. Too high a polymer concentration can limit printability and negatively affect the handle. In a particularly preferred embodiment of the invention, the process is carried out in the presence of 0.002 to 1% by weight and in particular 0.01 to 0.5% by weight of acrylamide homo- or copolymer, in each case based on the printing paste.

Die erfindungsgemäss verwendete Druckpaste enthält als Verdicker ein übliches Cellulosederivat, z.B. einen Celluloseether wie Methyl-, Ethyl-, Hydroxyethyl-, Methylhydroxyethyl-, Hydroxypropyl-, Hydroxypropylmethyl-, Carboxymethyl-, Carboxyethyl- oder Cyanethylcellulose oder einen Celluloseester wie z.B. Acetylcellulose, oder bevorzugt ein Alginat, z.B. Na-Alginat. Die Menge an Verdicker in der Druckpaste kann abhängig von der gewünschten Viskosität innerhalb weiter Grenzen variieren; vorteilhaft verwendet man z.B. 10 bis 100 g/kg und vorzugsweise 15 bis 70 g/kg Druckpaste.The printing paste used according to the invention contains a conventional cellulose derivative, e.g. a cellulose ether such as methyl, ethyl, hydroxyethyl, methylhydroxyethyl, hydroxypropyl, hydroxypropylmethyl, carboxymethyl, carboxyethyl or cyanoethyl cellulose or a cellulose ester such as e.g. Acetyl cellulose, or preferably an alginate, e.g. Na alginate. The amount of thickener in the printing paste can vary within wide limits depending on the desired viscosity; advantageously used e.g. 10 to 100 g / kg and preferably 15 to 70 g / kg printing paste.

Die Druckpaste kann ausserdem übliche Zusätze, z. B. Hydrotropiermittel, Entschäumungs- bzw. Entlüftungsmittel, Reduktionsschutzmittel, Konservierungsmittel, Sequestriermittel oder Basen, enthalten.The printing paste can also contain conventional additives, e.g. B. hydrotroping agents, defoaming or deaerating agents, reducing agents, preservatives, sequestering agents or bases.

Enthält die Druckpaste ein Hydrotropiermittel, handelt es sich bevorzugt um Harnstoff, der z.B. in einer Menge von 0,1 bis 20 Gew.-% und vorzugsweise 0,1 bis 10 Gew.-%, bezogen auf die fertige Druckpaste, anwesend ist.If the printing paste contains a hydrotroping agent, it is preferably urea, which e.g. is present in an amount of 0.1 to 20 wt .-% and preferably 0.1 to 10 wt .-%, based on the finished printing paste.

Als Entlüftungsmittel sind alle handelsüblichen Entlüftungsmittel einsetzbar, sofern die rheologischen Eigenschaften der erfindungsgemässen Druckpaste nicht negativ beeinflusst werden. Bevorzugt sind auf Grund ihrer guten Entschäumungseigenschaften silikonölarme bis silikonölfreie Entlüftungsmittel, die im allgemeinen 0 bis etwa 5, insbesondere 0,1 bis 1 Gewichtsprozent eines herkömmlichen Silikonöls enthalten.All commercially available deaeration agents can be used as deaeration agents, provided that the rheological properties of the printing paste according to the invention are not negatively influenced. Because of their good defoaming properties, low-silicone oil-free silicone oil-free deaerating agents are preferred, which generally contain 0 to about 5, in particular 0.1 to 1 percent by weight of a conventional silicone oil.

Bevorzugte Entlüftungsmittel enthalten z.B. als Aktivsubstanz hochsiedende Kohlenwasserstoffe, hydrierte Naphthalene, Mineralöle, fette Öle oder unlösliche Metallseifen oder deren Gemische und weisen gegebenenfalls den vorstehend angegebenen Gehalt an Silikonölen auf. Sie können aber auch als wässrige Lösungen vorliegen, die im allgemeinen, zusätzlich zu den Aktivsubstanzen der angegebenen Art ein nichtionisches Tensid, z.B. Ethylenoxidaddukte von einem Alkylphenol oder Sorbitanstearat, enthalten. Als bevorzugte Inhaltsstoffe bzw. Aktivsubstanzen der Entlüftungsmittel seien höhere Alkohole mit Siedepunkten über etwa 100°C, Terpentinöle, Mineralöle oder deren Gemische erwähnt. Bevorzugt werden Kohlenwasserstoffgemische eingesetzt, die im allgemeinen einen Flammpunkt über etwa 120°C, vorzugsweise von etwa 150 bis 220°C und einen Siedebereich von etwa 250 bis 500°C unter Normalbedingungen aufweisen.Preferred deaerators contain, for example, high-boiling hydrocarbons, hydrogenated naphthalenes, mineral oils, fatty oils or insoluble metal soaps or mixtures thereof as the active substance and, if appropriate, have the silicone oil content indicated above. However, they can also be present as aqueous solutions which generally contain, in addition to the active substances of the type mentioned, a nonionic surfactant, for example ethylene oxide adducts from an alkylphenol or sorbitan stearate. The preferred ingredients or active substances of the deaerating agents are higher Alcohols with boiling points above about 100 ° C, turpentine oils, mineral oils or their mixtures mentioned. Hydrocarbon mixtures which generally have a flash point above approximately 120 ° C., preferably from approximately 150 to 220 ° C. and a boiling range from approximately 250 to 500 ° C. under normal conditions are preferably used.

Im Vordergrund des Interesses stehen Entlüftungsmittel, die als Aktivsubstanz einen höheren Alkohol, wie z.B. 2-Ethyl-n-hexanol oder 2-Hexyldecanol oder deren Gemisch mit hochsiedenden Kohlenwasserstoffgemischen enthalten und den vorstehend angegebenen Gehalt an Silikonölen aufweisen; die genannten Alkohole bzw. Alkohol/Kohlenwasserstoff-Gemische liegen gegebenenfalls als wässrige Zubereitung vor und enthalten dann vorteilhaft zusätzlich zu den Aktivsubstanzen ein Tensid, z.B. Ethylenoxidaddukte von einem Alkylphenol mit 6 bis 12 Kohlenstoffatomen im Alkylrest oder ein Ethylenoxidaddukt von Sorbitan-Tristearat.In the foreground of interest are venting agents that contain a higher alcohol, such as e.g. Contain 2-ethyl-n-hexanol or 2-hexyldecanol or their mixture with high-boiling hydrocarbon mixtures and have the above-mentioned content of silicone oils; the alcohols or alcohol / hydrocarbon mixtures mentioned are optionally in the form of an aqueous preparation and then advantageously contain, in addition to the active substances, a surfactant, e.g. Ethylene oxide adducts of an alkylphenol with 6 to 12 carbon atoms in the alkyl radical or an ethylene oxide adduct of sorbitan tristearate.

Die Druckpaste enthält das Entlüftungsmittel z.B. in einer Menge von ≦ 5 Gew.-% und vorzugsweise 0,1 bis 1 Gew.-%, bezogen auf das Gewicht der fertigen Druckpaste.The printing paste contains the deaerating agent e.g. in an amount of ≦ 5% by weight and preferably 0.1 to 1% by weight, based on the weight of the finished printing paste.

Als Reduktionsschutzmittel kommen z. B. aromatische Nitroverbindungen, vor allem Salze von aromatischen Mono- oder Dinitrocarbonsäuren oder -sulfonsäuren, die gegebenenfalls als Alkylenoxide vorliegen, insbesondere Alkalisalze einer Nitrobenzolsulfonsäure, wie z.B. 2-Nitrobenzolsulfonsäure Na-Salz, in Betracht. Es ist bevorzugt, der erfindungsgemäss verwendeten Druckpaste ein Reduktionsschutzmittel zuzugeben; dieses ist z.B. in einer Menge von 0,1 bis 4 Gew.-% und vorzugsweise 0,8 bis 2 Gew.-%, jeweils bezogen auf die fertige Druckpaste, anwesend.As a reducing agent such. B. aromatic nitro compounds, especially salts of aromatic mono- or dinitrocarboxylic acids or sulfonic acids, which are optionally present as alkylene oxides, especially alkali salts of a nitrobenzenesulfonic acid, such as e.g. 2-nitrobenzenesulfonic acid Na salt. It is preferred to add a reducing agent to the printing paste used according to the invention; this is e.g. present in an amount of 0.1 to 4% by weight and preferably 0.8 to 2% by weight, based in each case on the finished printing paste.

Als Konservierungsmittel kommen alle üblichen Konservierungsmittel, z.B. Chloracetamid oder Formaldehyd in Frage. Als geeignete Sequestriermittel sind z.B. Phosphate wie Natriumhexametaphosphat zu nennen.All common preservatives, e.g. Chloroacetamide or formaldehyde in question. Suitable sequestrants are e.g. To name phosphates such as sodium hexametaphosphate.

Enthält die Druckpaste Basen, z.B. zur Fixierung der Reaktivfarbstoffe im Reaktivdruck, kommen beispielsweise Natriumcarbonat, Natriumhydroxid, Dinatriumphosphat, Trinatriumphosphat, Natriumacetat, Natriumpropionat, Natriumhydrogencarbonat, wässriges Ammoniak oder Alkalispender, wie zum Beispiel Natriumtrichloracetat oder Natriumformiat in Frage. Als Fixieralkali kann auch eine Mischung aus Wasserglas und einer 25%-igen wässrigen Natriumcarbonatlösung verwendet werden. Der pH-Wert der Fixieralkali enthaltenden Druckpaste beträgt in der Regel 7,5 bis 13,2, vorzugsweise 8,5 bis 12,5. Bei der Herstellung der Druckpaste wird die Menge des Fixieralkali so gewählt, dass der pH-Wert der gebrauchsfertigen Druckpaste im alkalischen Bereich liegt, vorzugsweise zwischen pH 7,5 und 12; die Menge des Fixieralkalis kann dementsprechend innerhalb weiter Grenzen schwanken, z.B. zwischen 0,5 und 10 Gew.-%, bezogen auf die fertige Druckpaste.If the printing paste contains bases, for example for fixing the reactive dyes in reactive printing, for example sodium carbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, sodium acetate, sodium propionate, sodium hydrogen carbonate, aqueous ammonia or alkali donors, such as sodium trichloroacetate or sodium formate. A mixture of water glass and a 25% aqueous sodium carbonate solution can also be used as the fixing alkali. The pH of the printing paste containing fixing alkali is generally 7.5 to 13.2, preferably 8.5 up to 12.5. When producing the printing paste, the amount of fixing alkali is chosen so that the pH of the ready-to-use printing paste is in the alkaline range, preferably between pH 7.5 and 12; the amount of fixing alkali can accordingly vary within wide limits, for example between 0.5 and 10% by weight, based on the finished printing paste.

Bei den im erfindungsgemässen Verfahren eingesetzten Farbstoffen handelt es sich um die üblicherweise zum Färben oder Bedrucken von Textilmaterialien verwendeten Farbstoffe, wie sie z.B. im Colour Index, 3. Auflage 1971 sowie den Nachträgen dazu unter den Rubriken "Reactive dyes", "Acid dyes", "Mordant dyes", "Vat dyes" oder "Disperse Dyes" beschrieben sind.The dyes used in the process according to the invention are the dyes usually used for dyeing or printing textile materials, such as those e.g. in the Color Index, 3rd edition 1971 and the supplements to it under the headings "Reactive dyes", "Acid dyes", "Mordant dyes", "Vat dyes" or "Disperse Dyes".

Bevorzugt für das Bedrucken von cellulosischen Fasermaterialien ist die Verwendung von Reaktivfarbstoffen ("Reactive Dyes"); bei diesen Farbstoffen handelt es sich um Farbstoffe verschiedener Klassen, z.B. um solche aus der Monoazo- oder Polyazo-, Metallkomplexazo-, Anthrachinon-, Phthalocyanin-, Formazan-, oder Dioxazin-Reihe, die mindestens eine Reaktivgruppe enthalten.Preferred for printing cellulosic fiber materials is the use of reactive dyes ("reactive dyes"); these dyes are dyes of different classes, e.g. to those from the monoazo or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane or dioxazine series, which contain at least one reactive group.

Unter Reaktivgruppen sind faserreaktive Reste zu verstehen, die mit den Hydroxygruppen der Cellulose, den Amino-, Carboxy-, Hydroxy- und Thiolgruppen bei Wolle und Seide, oder mit den Amino- und eventuell Carboxygruppen von synthetischen Polyamiden unter Bildung kovalenter chemischer Bindungen zu reagieren vermögen. Die Reaktivgruppen sind in der Regel direkt oder über ein Brückenglied an den Farbstoffrest gebunden. Geeignete Reaktivgruppen sind beispielsweise solche, die mindestens einen abspaltbaren Substituenten an einem aliphatischen, aromatischen oder heterocyclischen Rest enthalten oder worin die genannten Reste einen zur Reaktion mit dem Fasermaterial geeigneten Rest, wie z.B. einen Halotriazinyl-, Halopyrimidinyl- oder Vinylrest, enthalten.Reactive groups are fiber-reactive radicals which are able to react with the hydroxyl groups of cellulose, the amino, carboxy, hydroxyl and thiol groups in wool and silk, or with the amino and possibly carboxy groups of synthetic polyamides to form covalent chemical bonds . The reactive groups are usually bound to the dye residue directly or via a bridge link. Suitable reactive groups are, for example, those which contain at least one removable substituent on an aliphatic, aromatic or heterocyclic radical or in which the radicals mentioned are a radical suitable for reaction with the fiber material, such as e.g. contain a halotriazinyl, halopyrimidinyl or vinyl radical.

Als aliphatische Reaktivgruppen sind solche der Formeln -SO₂Z, -SO₂-NH-Z, -NH-CO-alk-SO₂Z, -CO-NH-alk-SO₂Z, oder -NH-CO-Z₁, worin Z eine Abgangsgruppe, z.B. β-Sufatoethyl, β-Thiosulfatoethyl, β-Phosphatoethyl, β-Acyloxyethyl, β-Halogenoethyl oder Vinyl ist, Z₁ z.B. für einen α,β-Dihalogenethyl- oder α-Halogenethenylrest steht, alk C₂-C₄-Alkylen ist und Halogen bevorzugt Chlor oder Brom bedeutet, bevorzugt.As aliphatic reactive groups are those of the formulas -SO₂Z, -SO₂-NH-Z, -NH-CO-alk-SO₂Z, -CO-NH-alk-SO₂Z, or -NH-CO-Z₁, wherein Z is a leaving group, e.g. is β-sufatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl or vinyl, Z₁ e.g. represents an α, β-dihaloethyl or α-haloethenyl radical, alk is C₂-C₄alkylene and halogen is preferably chlorine or bromine, preferably.

Bevorzugt als heterocyclische, faserreaktive Reste sind 1,3,5-Triazinreste der Formel

Figure imgb0001

worin T₁ Fluor, Chlor oder Carboxypyridinium ist und als Substituenten V₁ am Triazinring insbesondere zu nennen sind: Fluor oder Chlor; -NH₂, gegebenenfalls substituierte Alkylamino- oder N,N-Dialkylaminogruppen, z.B. gegebenenfalls durch Hydroxy, Sulfo oder Sulfato substituiertes N-Mono- oder N,N-Di-C₁-C₄-Alkylamino; Cycloalkylamino; Aralkylamino-, z.B. Benzylamino; Arylaminogruppen wie gegebenenfalls durch Sulfo, Methyl, Methoxy oder Chlor substituiertes Phenylamino; gemischt substituierte Aminogruppen, wie N-Alkyl-N-cyclohexylamino- oder N-Alkyl-N-phenylaminogruppen; sowie Morpholino.Preferred heterocyclic, fiber-reactive radicals are 1,3,5-triazine radicals of the formula
Figure imgb0001
in which T₁ is fluorine, chlorine or carboxypyridinium and the substituents V₁ on the triazine ring which may be mentioned in particular: fluorine or chlorine; -NH₂, optionally substituted alkylamino or N, N-dialkylamino groups, for example N-mono- or N, N-di-C₁-C₄-alkylamino optionally substituted by hydroxy, sulfo or sulfato; Cycloalkylamino; Aralkylamino, for example benzylamino; Arylamino groups such as phenylamino optionally substituted by sulfo, methyl, methoxy or chlorine; mixed substituted amino groups such as N-alkyl-N-cyclohexylamino or N-alkyl-N-phenylamino groups; and morpholino.

Für das erfindungsgemässe Verfahren werden Reaktivfarbstoffe bevorzugt, die mindestens eine Monohalogentriazingruppe, vorzugsweise eine Monochlortriazingruppe, enthalten.For the process according to the invention, reactive dyes are preferred which contain at least one monohalotriazine group, preferably a monochlorotriazine group.

Es können auch Farbstoffe mit zwei oder mehreren gleich- oder verschiedenartigen Reaktivgruppen verwendet werden.Dyes with two or more identical or different reactive groups can also be used.

Die Menge der eingesetzten Farbstoffe richtet sich in der Regel nach der gewünschten Farbstärke und beträgt zweckmässig 0,01 bis 400 g, vorteilhaft 0,5 bis 300 und vorzugsweise 1 bis 200 g pro kg Druckpaste.The amount of the dyes used is generally dependent on the desired color strength and is expediently from 0.01 to 400 g, advantageously from 0.5 to 300 and preferably from 1 to 200 g per kg of printing paste.

Die erfindungsgemäss verwendete Druckpaste ist neu und stellt einen weiteren Gegenstand der Erfindung dar.The printing paste used according to the invention is new and represents a further subject of the invention.

In ihrer bevorzugten Ausführungsform enthält die Druckpaste

0,001 bis 40 Gew.-%
Farbstoff
1 bis 7 Gew.-%
Cellulosederivat oder Alginat als Verdicker,
0,002 bis 5 Gew.-%
Acrylamid-Homo- oder Copolymer,
0 bis 4 Gew.-%
Reduktionsschutzmittel,
0 bis 5 Gew.-%
Entschäumungs- bzw. Entlüftungsmittel,
0 bis 20 Gew.-%
Harnstoff,
0 bis 10 Gew.-%
Fixieralkali

und Wasser ad 100 Gew.-%.In its preferred embodiment, the printing paste contains
0.001 to 40% by weight
dye
1 to 7% by weight
Cellulose derivative or alginate as a thickener,
0.002 to 5% by weight
Acrylamide homo- or copolymer,
0 to 4% by weight
Reducing agents,
0 to 5% by weight
Defoaming or deaerating agents,
0 to 20% by weight
Urea,
0 to 10% by weight
Fixing alkali

and water ad 100 wt .-%.

Eine für den Reaktivdruck von cellulosehaltigen Fasermaterialien besonders bevorzugte Druckpaste enthält

0,05 bis 30 Gew.-%
Farbstoff,
1 bis 7 Gew.-%
Alginat,
0,002 bis 1 Gew.-%
Acrylamid-Homo- oder -Copolymer,
0,8 bis 2 Gew.-%
Reduktionsschutzmittel,
0,1 bis 1 Gew.-%
Entlüftungsmittel,
0,1 bis 20 Gew.-%
Harnstoff,
0,5 bis 10 Gew.-%
Fixieralkali

und Wasser ad 100 Gew.-%.Contains a printing paste which is particularly preferred for the reactive printing of cellulose-containing fiber materials
0.05 to 30% by weight
Dye,
1 to 7% by weight
Alginate,
0.002 to 1% by weight
Acrylamide homo- or copolymer,
0.8 to 2% by weight
Reducing agents,
0.1 to 1% by weight
Deaerating agent,
0.1 to 20% by weight
Urea,
0.5 to 10% by weight
Fixing alkali

and water ad 100 wt .-%.

Eine für den Reaktivdruck von cellulosehaltigen Fasermaterialien insbesondere bevorzugte Druckpaste enthält

0,1 bis 20 Gew.-%
Farbstoff,
1,5 bis 2,5 Gew.-%
Na-Alginat,
0,01 bis 1 Gew.-%
Acrylamid/Acrylsäure-Copolymer,
0,8 bis 2 Gew.-%
Alkalisalz einer Nitrobenzolsulfonsäure als Reduktionsschutzmittel,
0,1 bis 1 Gew.-%
Entlüftungsmittel auf der Basis eines höheren Alkohols, z.B. 2-Ethyl-n-hexanol oder 2-Hexyldecanol,
0,1 bis 10 Gew.-%
Harnstoff,
0,5 bis 10 Gew.-%
Fixieralkali

und Wasser ad 100 Gew.-%.Contains a printing paste which is particularly preferred for the reactive printing of cellulose-containing fiber materials
0.1 to 20% by weight
Dye,
1.5 to 2.5% by weight
Na alginate,
0.01 to 1% by weight
Acrylamide / acrylic acid copolymer,
0.8 to 2% by weight
Alkali salt of a nitrobenzenesulfonic acid as reducing agent,
0.1 to 1% by weight
Deaerating agents based on a higher alcohol, for example 2-ethyl-n-hexanol or 2-hexyldecanol,
0.1 to 10% by weight
Urea,
0.5 to 10% by weight
Fixing alkali

and water ad 100 wt .-%.

Die Herstellung der erfindungsgemässen Druckpaste erfolgt in einfacher Weise durch Mischen der Komponenten, wobei zum Schluss noch die benötigte Menge an Wasser zugesetzt wird, sodass sich eine für den Direktdruck geeignete Viskosität einstellt, die z.B. zwischen 1500 und 10000 mPa·s und vorzugsweise zwischen 1500 und 7000 mPa·s liegt.The printing paste according to the invention is produced in a simple manner by mixing the components, and finally the required amount of water is added, so that a viscosity suitable for direct printing is established, which e.g. is between 1500 and 10000 mPa · s and preferably between 1500 and 7000 mPa · s.

Die erfindungsgemässe Druckpaste zeichnet sich durch eine gute Homogenität, gute Lagerstabilität sowie einfache Handhabung aus.The printing paste according to the invention is characterized by good homogeneity, good storage stability and simple handling.

Beim Bedrucken wird die Druckpaste ganzflächig, bevorzugt musterförmig auf das Substrat aufgebracht, wobei Druckmaschinen üblicher Bauart, z.B. Rotationsfilmdruck- oder Flachfilmdruckmaschienen zweckmässig eingesetzt werden.When printing, the printing paste is applied over the entire surface, preferably in a pattern, to the substrate, printing presses of conventional design, for example rotary film printing or flat film printing machines can be used appropriately.

Nach dem Auftrag der Druckpaste wird das bedruckte Textilgut vorzugsweise getrocknet und dann einem Hitzebehandlungsprozess unterworfen, um den Druck zu vervollständigen bzw. den Farbstoff zu fixieren.After the printing paste has been applied, the printed textile material is preferably dried and then subjected to a heat treatment process in order to complete the print or to fix the dye.

Die Hitzebehandlung kann durch ein Warmverweilverfahren, einen Thermosolierprozess oder vorzugsweise durch ein Dämpfverfahren durchgeführt werden.The heat treatment can be carried out by a warm dwell process, a thermal insulation process or preferably by a steaming process.

Beim Dämpfverfahren werden die bedruckten Textilmaterialien einer Behandlung in einem Dämpfer mit gegebenenfalls überhitztem Dampf, zweckmässigerweise bei einer Temperatur von 98 bis 210°C, vorteilhafterweise 100 bis 180°C und vorzugsweise 100 bis 120°C unterzogen.In the steaming process, the printed textile materials are subjected to a treatment in a steamer with possibly superheated steam, expediently at a temperature of 98 to 210 ° C., advantageously 100 to 180 ° C. and preferably 100 to 120 ° C.

Die Fertigstellung der Drucke durch den sogenannten Thermosolierprozess kann nach einer oder ohne Zwischentrocknung, z.B. bei einer Temperatur von 100 bis 210°C erfolgen. Vorzugsweise erfolgt die Thermosolierung bei einer Temperatur von 120 bis 210°C, vorzugsweise 140 bis 180°C und nach einer Zwischentrocknung bei 80 bis 140°C der bedruckten Ware. Je nach der Temperatur kann die Thermosolierung 20 Sekunden bis 5 Minuten, vorzugsweise 30 Sekunden bis 4 Minuten dauern.The completion of the prints by the so-called thermal insulation process can take place after or without intermediate drying, e.g. at a temperature of 100 to 210 ° C. The thermal insulation is preferably carried out at a temperature of 120 to 210 ° C., preferably 140 to 180 ° C. and after intermediate drying at 80 to 140 ° C. of the printed goods. Depending on the temperature, the thermal insulation can take 20 seconds to 5 minutes, preferably 30 seconds to 4 minutes.

Im Anschluss an den Druckprozess wird das Textilgut in üblicher Weise ausgewaschen, um nichtfixierten Farbstoff zu entfernen. Man behandelt dazu das Substrat beispielsweise bei 40°C bis Kochtemperatur mit Wasser, welchem gegebenenfalls eine Seife oder ein synthetisches Waschmittel zugesetzt werden kann.After the printing process, the textile material is washed out in the usual way in order to remove unfixed dye. For this purpose, the substrate is treated with water, for example at from 40 ° C. to cooking temperature, to which a soap or a synthetic detergent can optionally be added.

Bei den zu bedruckenden Fasermaterialien handelt es sich z.B. um Textilmaterialien aus natürlichen, halbsynthetischen oder vollsynthetischen Fasern; in Frage kommen auch Gemische der erwähnten Fasern. Bei den halbsynthetischen Fasern handelt es sich z.B. um regenerierte Cellulosefasern, z.B. Viskosefasern oder Acetatfasern (2 1/2- und Triacetat) und bei den vollsynthetischen Fasern hauptsächlich um Polyacrylnitril-, Polyamid- oder Polyesterfasern. Bei den natürlichen Fasern kommen z.B. Seide, Wolle oder natürliche Cellulose, insbesondere Baumwolle, in Frage.The fiber materials to be printed are e.g. around textile materials made from natural, semi-synthetic or fully synthetic fibers; Mixtures of the fibers mentioned are also suitable. The semi-synthetic fibers are e.g. regenerated cellulose fibers, e.g. Viscose fibers or acetate fibers (2 1 / 2- and triacetate) and, in the case of fully synthetic fibers, mainly polyacrylonitrile, polyamide or polyester fibers. In the case of natural fibers, e.g. Silk, wool or natural cellulose, especially cotton, are possible.

Das Verfahren ist besonders geeignet für das Bedrucken von a) Fasermaterialien aus regenerierter oder insbesondere natürlicher Cellulose, wie z.B. aus Viskose, Celluloseacetat, Hanf, Leinen, Jute oder Baumwolle mit Reaktivfarbstoffen;

  • b) Polyestermaterialien mit Dispersfarbstoffen sowie
  • c) cellulosehaltigen Mischfasern, z.B. solchen aus Polyamid/Baumwolle oder aus Polyester/Baumwolle mit Reaktiv- und Dispersfarbstoffen.
The method is particularly suitable for printing a) fiber materials made from regenerated or, in particular, natural cellulose, such as from viscose, Cellulose acetate, hemp, linen, jute or cotton with reactive dyes;
  • b) polyester materials with disperse dyes and
  • c) cellulose-containing mixed fibers, for example those made from polyamide / cotton or from polyester / cotton with reactive and disperse dyes.

Das Verfahren ist insbesondere bevorzugt geeignet für das Bedrucken von Viskose, Baumwolle oder Baumwolle/Polyester-Mischfasern; bei letzteren kann der Baumwoll- und Polyester-Anteil vorteilhaft gleichzeitig mit einem Gemisch aus Reaktivfarbstoff und Dispersionsfarbstoff bedruckt werden.The method is particularly preferably suitable for printing on viscose, cotton or cotton / polyester mixed fibers; in the latter, the cotton and polyester portion can advantageously be printed simultaneously with a mixture of reactive dye and disperse dye.

Es handelt sich dabei in der Regel vor allem um flächenförmige Textilmaterialien, wie z.B. Vliese, Filze, Teppiche, Gewirke und insbesondere Gewebe. Das erfindungsgemässe Verfahren ist geeignet für Fasermaterialien, die gegebenenfalls mit Natronlauge vorbehandelt sind, für Cellulose-Material und Regenerat-Cellulose bzw. deren Mischungen.As a rule, these are mainly sheet-like textile materials, such as Fleeces, felts, carpets, knitted fabrics and in particular fabrics. The process according to the invention is suitable for fiber materials which may have been pretreated with sodium hydroxide solution, for cellulose material and regenerated cellulose or mixtures thereof.

Man erhält nach dem vorliegenden Verfahren farbstarke, musterförmige Drucke auf weissem Grund mit guter Egalität und guten Echtheiten, z.B. Licht-, Wasch- und Reibechtheit; die Drucke weisen ausserdem praktisch keinen Dichroismus auf. Besonders hervorzuheben ist die gegenüber einem Verfahren ohne Acrylamid-Homo- oder Copolymer-Zusatz stark verbesserte Konturenschärfe der erhaltenen Drucke. Ein weiterer Vorteil betrifft die vergleichsweise geringe Penetration des Farbstoffs in das Textilmaterial bei Anwendung des erfindungsgemässen Verfahrens, d.h. man erhält einen Oberflächendruck; folglich lässt sich eine vorgegebene Farbstärke mit reduziertem Druckpastenauftrag herstellen.The present process gives strong, pattern-like prints on a white background with good levelness and good fastness properties, e.g. Fastness to light, washing and rubbing; the prints also have practically no dichroism. Particularly noteworthy is the sharpness of the contours of the prints obtained, which is greatly improved compared to a process without the addition of acrylamide homo- or copolymer. Another advantage relates to the comparatively low penetration of the dye into the textile material when using the method according to the invention, i.e. you get a surface pressure; consequently, a predetermined color strength can be produced with a reduced application of printing paste.

Sofern nicht anders angegeben, beziehen sich die in den nachfolgenden Beispielen angegebenen Prozente auf das Gewicht.Unless stated otherwise, the percentages given in the examples below are based on weight.

Beispiel 1: Example 1 :

Ein Gewebe aus gebleichter, mercerisierter Baumwolle wird auf einer Flachfilmdruckmaschine mit einer Druckpaste folgender Zusammensetzung musterförmig bedruckt:

70 g/kg
einer handelsüblichen, flüssigen Formulierung des Farbstoffes der Formel
Figure imgb0002
10 g/kg
2-Nitrobenzolsulfonsäure Na-Salz,
75 g/kg
20%-ige, wässrige Na₂CO₃ calc. Lösung,
480 g/kg
Na-Alginat mittelviskos (6 %iger Ansatz enthaltend 5 g/kg Natriumhexametaphosphat und 5 g/kg 37% Formaldehyd),
100 g/kg
Harnstoff,
75 g/kg
0,8 %ige wässrige Lösung eines Copolymers aus ca. 15 % Acrylsäure und 85 % Acrylamid, Molekulargewicht ca. 2 Millionen
3 g/kg
Entlüftungsmittel auf Basis von 2-Ethyl-n-hexanol und
187 g/kg
Wasser
A fabric made of bleached, mercerized cotton is printed on a flat film printing machine with a printing paste of the following composition:
70 g / kg
a commercially available, liquid formulation of the dye of the formula
Figure imgb0002
10 g / kg
2-nitrobenzenesulfonic acid sodium salt,
75 g / kg
20% aqueous Na₂CO₃ calc. Solution,
480 g / kg
Na alginate medium viscosity (6% mixture containing 5 g / kg sodium hexametaphosphate and 5 g / kg 37% formaldehyde),
100 g / kg
Urea,
75 g / kg
0.8% aqueous solution of a copolymer of approx. 15% acrylic acid and 85% acrylamide, molecular weight approx. 2 million
3 g / kg
Deaerating agent based on 2-ethyl-n-hexanol and
187 g / kg
water

Die Druckpaste weist einen pH-Wert von 10,7 auf. Die Viskosität beträgt 5 300 mPa.s, gemessen am Viskosimeter Brookfield RVT, Spindel 6, 20 UpM bei 25° C. Das bedruckte Gewebe wird bei 90° C getrocknet und zur Fixierung des Farbstoffes während 8 min. mit Sattdampf bei 100 bis 102°C behandelt. Das Gewebe wird anschliessend mit kaltem und kochendem Wasser gespült, bis die nicht fixierten Anteile des eingesetzten Farbstoffes und der Hilfsmittel entfernt sind. Nach der Trocknung des Gewebes bei 90 bis 100° C enthält man einen farbstarken, egalen, türkisfarbenen Druck mit scharfen Konturen. Zudem weist das behandelte Gewebe einen weichen Griff auf.The printing paste has a pH of 10.7. The viscosity is 5,300 mPa.s, measured on the Brookfield RVT viscometer, spindle 6, 20 rpm at 25 ° C. The printed fabric is dried at 90 ° C. and fixed for 8 minutes to fix the dye. treated with saturated steam at 100 to 102 ° C. The fabric is then rinsed with cold and boiling water until the unfixed portions of the dye and auxiliary agents have been removed. After drying the fabric at 90 to 100 ° C, you get a strong, level, turquoise print with sharp contours. The treated fabric also has a soft feel.

Beispiel 1A: Example 1A :

Verfährt man wie im Beispiel 1 angegeben und verwendet eine Druckpaste, die 480 g/kg Na-Alginat mittelviskos (6 %iger Ansatz enthaltend 5 g/kg Natriumhexametaphosphat und 3 g/kg 37% Formaldehyd) anstelle von 480 g/kg Na-Alginat mittelviskos (6 %iger Ansatz enthaltend 5 g/kg Natriumhexametaphosphat und 5 g/kg 37% Formaldehyd), 30 g/kg 1 %ige wässrige Lösung eines Copolymers aus ca. 15 % Acrylsäure und 85 % Acrylamid ( Molekulargewicht ca. 2 Millionen) anstelle von 75 g/kg 0,8 %ige wässrige Lösung eines Copolymers aus ca. 15 % Acrylsäure und 85 % Acrylamid (Molekulargewicht ca. 2 Millionen) und 232 g/kg Wasser anstelle von 187 g/kg Wasser enthält, werden ähnlich gute Ergebnisse erhalten.The procedure described in Example 1 is followed and a printing paste is used which contains 480 g / kg Na alginate medium viscosity (6% mixture containing 5 g / kg sodium hexametaphosphate and 3 g / kg 37% formaldehyde) instead of 480 g / kg Na alginate medium viscosity (6% mixture containing 5 g / kg sodium hexametaphosphate and 5 g / kg 37% formaldehyde), 30 g / kg 1% aqueous solution of a copolymer of approx. 15% acrylic acid and 85% acrylamide (molecular weight approx. 2 million) instead of 75 g / kg 0.8% aqueous solution of a copolymer of approx. 15% acrylic acid and 85% acrylamide (molecular weight approx. 2 million) and 232 g / kg water instead of 187 g / kg water contains similarly good results.

Beispiel 2: Example 2 :

Verfährt man wie im Beispiel 1 oder 1A angegeben und bedruckt anstelle des gebleichten, mercerisierten Baumwollgewebes ein gebleichtes Viskosegewebe, erhält man ebenfalls einen farbstarken, egalen Druck mit scharfen Konturen und weichem Griff, der eine türkis Nuance aufweist.If one proceeds as described in Example 1 or 1A and prints a bleached viscose fabric instead of the bleached, mercerized cotton fabric, one also obtains a strong, level print with sharp contours and a soft handle, which has a turquoise shade.

Beispiel 3:Example 3:

Man verfährt wie im Beispiel 1 angegeben, bedruckt aber das gebleichte, mercerisierte Baumwollgewebe mit einer Druckpaste folgender Zusammensetzung:

30 g/kg
einer handelsüblichen, flüssigen Formulierung des Farbstoffes der Formel:
Figure imgb0003
60 g/kg
einer handelsüblichen, flüssigen Formulierung des Farbstoffes der Formel
Figure imgb0004
10 g/kg
2-Nitrobenzolsulfonsäure Na-Salz,
75 g/kg
20%-ige, wässrige Na₂CO₃ calc. Lösung,
480 g/kg
Na-Alginat mittelviskos (6 %iger Ansatz enthaltend 5 g/kg Natriumhexametaphosphat und 5 g/kg 37% Formaldehyd)
100 g/kg
Harnstoff,
75 g/kg
0,8 %ige wässrige Lösung eines Copolymers aus ca. 15 % Acrylsäure und 85 % Acrylamid, Molekulargewicht ca. 2 Millionen,
3 g/kg
Entlüftungsmittel auf Basis von 2-Ethyl-n-hexanol und
167 g/kg
Wasser.
The procedure is as described in Example 1, but the bleached, mercerized cotton fabric is printed with a printing paste of the following composition:
30 g / kg
a commercially available, liquid formulation of the dye of the formula:
Figure imgb0003
60 g / kg
a commercially available, liquid formulation of the dye of the formula
Figure imgb0004
10 g / kg
2-nitrobenzenesulfonic acid sodium salt,
75 g / kg
20% aqueous Na₂CO₃ calc. Solution,
480 g / kg
Na alginate medium viscosity (6% mixture containing 5 g / kg sodium hexametaphosphate and 5 g / kg 37% formaldehyde)
100 g / kg
Urea,
75 g / kg
0.8% aqueous solution of a copolymer of approx. 15% acrylic acid and 85% acrylamide, molecular weight approx. 2 million,
3 g / kg
Deaerating agent based on 2-ethyl-n-hexanol and
167 g / kg
Water.

Der pH-Wert der Druckpaste beträgt 10,7 und ihre Viskosität 5 800 mPa.s, gemessen am Viskosimeter Brookfield RVT, Spindel 6, 20 UpM bei 25° C. Man enthält einen farbstarken, egalen, grünen Druck mit scharfen Konturen. Zudem weist das behandelte Gewebe einen weichen Griff auf.The pH of the printing paste is 10.7 and its viscosity is 5,800 mPa.s, measured on the Brookfield RVT viscometer, spindle 6, 20 rpm at 25 ° C. It contains a strong, level, green print with sharp contours. The treated fabric also has a soft feel.

Beispiel 3A: Example 3A :

Verfährt man wie im Beispiel 3 angegeben und verwendet eine Druckpaste, die 480 g/kg Na-Alginat mittelviskos (6 %iger Ansatz enthaltend 5 g/kg Natriumhexametaphosphat und 3 g/kg 37% Formaldehyd) anstelle von 480 g/kg Na-Alginat mittelviskos (6 %iger Ansatz enthaltend 5 g/kg Natriumhexametaphosphat und 5 g/kg 37% Formaldehyd), 30 g/kg 1 %ige wässrige Lösung eines Copolymers aus ca. 15 % Acrylsäure und 85 % Acrylamid ( Molekulargewicht ca. 2 Millionen) anstelle von 75 g/kg 0,8 %ige wässrige Lösung eines Copolymers aus ca. 15 % Acrylsäure und 85 % Acrylamid (Molekulargewicht ca. 2 Millionen) und 212 g/kg Wasser anstelle von 167 g/kg Wasser enthält, werden ähnlich gute Ergebnisse erhalten.The procedure described in Example 3 is followed and a printing paste is used which is 480 g / kg Na alginate medium viscosity (6% batch containing 5 g / kg sodium hexametaphosphate and 3 g / kg 37% formaldehyde) instead of 480 g / kg Na alginate medium viscosity (6% batch containing 5 g / kg sodium hexametaphosphate and 5 g / kg 37% formaldehyde), 30 g / kg 1% aqueous solution of a copolymer of approx. 15% acrylic acid and 85% acrylamide (molecular weight approx. 2 million) instead of 75 g / kg 0.8% aqueous solution of a copolymer of approx. 15% acrylic acid and 85% acrylamide (molecular weight approx. 2 million) and 212 g / kg water instead of 167 g / kg water, similarly good results Get results.

Beispiel 4: Example 4 :

Verfährt man wie im Beispiel 3 oder 3A angegeben und bedruckt anstelle des gebleichten, mercerisierten Baumwollgewebes ein gebleichtes Viskosegewebe, erhält man ebenfalls einen farbstarken, egalen, grünen Druck mit scharfen Konturen und weichem Griff.If one proceeds as described in example 3 or 3A and prints a bleached viscose fabric instead of the bleached, mercerized cotton fabric, one also obtains a strong, level, green print with sharp contours and a soft feel.

Beispiele 5-7: Examples 5-7 :

Verfährt man wie im Beispiel 1 beschrieben und verwendet anstelle des dort eingesetzten Acrylamid/Acrylsäure-Copolymer die äquivalente Menge eines der im folgenden genannten Polymere, werden ähnlich gute Ergebnisse erziehlt.

5
Acrylamid-Homopolymer mit einem mittleren Molekulargewicht von ca. 10 Millionen;
6
Gemisch enthaltend 98 Teile eines Copolymers aus ca. 50 Gew.-% Acrylamid und 50 Gew.-% Methyl-N-vinylacetamid, bezogen auf die Monomere, und 2 Teile eines Anlagerungsprodukts von 71 Propylenoxid-Einheiten an Glyzerin;
7
Copolymer aus ca. 70 Gew.-% Acrylamid und 30 Gew.-% Acrylsäure, mittleres Molekulargewicht > 1 Million.
If one proceeds as described in Example 1 and uses the equivalent amount of one of the polymers mentioned below instead of the acrylamide / acrylic acid copolymer used there, similarly good results are obtained.
5
Acrylamide homopolymer with an average molecular weight of approximately 10 million;
6
Mixture containing 98 parts of a copolymer of about 50% by weight of acrylamide and 50% by weight of methyl-N-vinylacetamide, based on the monomers, and 2 parts of an adduct of 71 propylene oxide units with glycerol;
7
Copolymer of approx. 70% by weight acrylamide and 30% by weight acrylic acid, average molecular weight> 1 million.

Beispiele 8-11: Examples 8-11 :

Verfährt man wie in den Beispielen 1, 1A oder 2 beschrieben und verwendet anstelle von 70 g/kg des dort eingesetzten Phthalocyanin-Farbstoffs die äquivalente Menge eines der unten angegebenen Farbstoffe, werden ähnlich gute Resultate erhalten.

Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
 If one proceeds as described in Examples 1, 1A or 2 and instead of 70 g / kg of the phthalocyanine dye used there, the equivalent amount of one of the dyes indicated below, similarly good results are obtained.
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008

Beispiel 12: Example 12 :

Ein Gewebe aus gebleichter, mercerisierter Baumwolle wird auf einer Flachfilmdruckmaschine mit einer Druckpaste folgender Zusammensetzung musterförmig bedruckt:

80 g/kg
einer handelsüblichen, flüssigen Formulierung des Farbstoffes der Formel
Figure imgb0009
100 g/kg
Hydroxymethansulfinsäure, Na-Salz,
96 g/kg
Pottasche (K₂CO₃),
448 g/kg
Stärkeether, 10%ige wässrige Lösung,
64 g/kg
Glycerin,
20 g/kg
1 %ige wässrige Lösung eines Copolymers aus ca. 15 % Acrylsäure und 85 % Acrylamid, Molekulargewicht ca. 2 Millionen,
4 g/kg
Entlüftungsmittel auf Basis von 2-Ethyl-n-hexanol und
188 g/kg
Wasser.
A fabric made of bleached, mercerized cotton is printed on a flat film printing machine with a printing paste of the following composition:
80 g / kg
a commercially available, liquid formulation of the dye of the formula
Figure imgb0009
100 g / kg
Hydroxymethanesulfinic acid, sodium salt,
96 g / kg
Potash (K₂CO₃),
448 g / kg
Starch ether, 10% aqueous solution,
64 g / kg
Glycerin,
20 g / kg
1% aqueous solution of a copolymer of approx. 15% acrylic acid and 85% acrylamide, molecular weight approx. 2 million,
4 g / kg
Deaerating agent based on 2-ethyl-n-hexanol and
188 g / kg
Water.

Die Druckpaste weist eine Viskosität von ca. 5 000 mPa.s, gemessen am Viskosimeter Brookfield RVT, Spindel 6, 20 UpM bei 25° C, auf.The printing paste has a viscosity of approx. 5,000 mPa.s, measured on the Brookfield RVT viscometer, spindle 6, 20 rpm at 25 ° C.

Das bedruckte Gewebe wird bei 70 bis 80° C getrocknet und zur Fixierung des Farbstoffes während 10 min. mit Sattdampf bei 100 bis 102°C behandelt. Das Gewebe wird mit kaltem Wasser gespült und anschliessend 5 min. bei 50°C mit 2 g/l H₂O₂ 35%ig und 1 g/l Essigsäure 80% behandelt. Danach wird das reoxidierte Gewebe mit warmem Wasser gespült, ca. 5 min kochend geseift und nochmals mit warmem und kaltem Wasser gespült. Nach der Trocknung des Gewebes bei 60 bis 100° C enthält man einen farbstarken, egalen, olivefarbenen Druck mit scharfen Konturen. Zudem weist das behandelte Gewebe einen weichen Griff auf.The printed fabric is dried at 70 to 80 ° C and for 10 minutes to fix the dye. treated with saturated steam at 100 to 102 ° C. The tissue is rinsed with cold water and then 5 min. treated at 50 ° C with 2 g / l H₂O₂ 35% and 1 g / l acetic acid 80%. The reoxidized tissue is then rinsed with warm water, soaped at the boil for about 5 minutes and rinsed again with warm and cold water. After drying the fabric at 60 to 100 ° C, you get a strong, level, olive-colored print with sharp contours. The treated fabric also has a soft feel.

Beispiel 13: Example 13 :

Polyester-Gewebe wird auf einer Flachfilmdruckmaschine mit einer Druckpaste folgender Zusammensetzung musterförmig bedruckt:

50 g/kg
einer handelsüblichen, flüssigen Formulierung des Farbstoffes der Formel
Figure imgb0010
480 g/kg
Na-Alginat mittelviskos (6 %iger Ansatz enthaltend 5 g/kg Natriumhexametaphosphat und 3 g/kg 37% Formaldehyd),
120 g/kg
Stärkeether, 10%ige wässrige Lösung,
10 g/kg
NaClO₃, 33%ige wässrige Lösung,
5 g/kg
NaH₂PO₄,
30 g/kg
1 %ige wässrige Lösung eines Copolymers aus ca. 15 % Acrylsäure und 85 % Acrylamid, Molekulargewicht ca. 2 Millionen,
3 g/kg
Entlüftungsmittel auf Basis von 2-Ethyl-n-hexanol und
302 g/kg
Wasser.
Polyester fabric is printed on a flat film printing machine with a printing paste of the following composition:
50 g / kg
a commercially available, liquid formulation of the dye of the formula
Figure imgb0010
480 g / kg
Na alginate medium viscosity (6% mixture containing 5 g / kg sodium hexametaphosphate and 3 g / kg 37% formaldehyde),
120 g / kg
Starch ether, 10% aqueous solution,
10 g / kg
NaClO₃, 33% aqueous solution,
5 g / kg
NaH₂PO₄,
30 g / kg
1% aqueous solution of a copolymer of approx. 15% acrylic acid and 85% acrylamide, molecular weight approx. 2 million,
3 g / kg
Deaerating agent based on 2-ethyl-n-hexanol and
302 g / kg
Water.

Die Druckpaste weist einen pH-Wert von 6,1 auf. Die Viskosität beträgt ca. 5 400 mPa.s, gemessen am Viskosimeter Brookfield RVT, Spindel 6, 20 UpM bei 25° C.The printing paste has a pH of 6.1. The viscosity is approx. 5,400 mPa.s, measured on the Brookfield RVT viscometer, spindle 6, 20 rpm at 25 ° C.

Das bedruckte Gewebe wird bei 70 bis 80° C getrocknet und zur Fixierung des Farbstoffes während 8 min. mit Sattdampf bei 175°C behandelt. Zur Fertigstellung wird das Gewebe mit kaltem Wasser gespült, bei 40°C mit 1 g/l eines nichtionischen Fettsäure-Ethoxylats geseift und danach bei 40 bis 70°C mit 1,5 g/l Na₂S₂O₄, 2 g/l Natriumhydroxidlösung 36°Bé und 1 g/l des genannten Fettsäure-Ethoxylats reduktiv gereinigt. Nach einem weiteren Spülvorgang mit warmem und kaltem Wasser und der Trocknung des Gewebes enthält man einen farbstarken, egalen, marineblauen Druck mit scharfen Konturen. Zudem weist das behandelte Gewebe einen weichen Griff auf.The printed fabric is dried at 70 to 80 ° C and for 8 minutes to fix the dye. treated with saturated steam at 175 ° C. To finish, the fabric is rinsed with cold water, soaped at 40 ° C with 1 g / l of a nonionic fatty acid ethoxylate and then at 40 to 70 ° C with 1.5 g / l Na₂S₂O₄, 2 g / l sodium hydroxide solution 36 ° Bé and 1 g / l of said fatty acid ethoxylate reductively cleaned. After a further rinsing process with warm and cold water and the drying of the fabric, you get a strong, level, navy blue print with sharp contours. The treated fabric also has a soft feel.

Beispiel 14: Example 14 :

Ein Gewebe aus chlorierter Wolle wird auf einer Flachfilmdruckmaschine mit einer Druckpaste folgender Zusammensetzung musterförmig bedruckt:

25 g/kg
des Farbstoffes der Formel
Figure imgb0011
550 g/kg
Kernmehl- oder Guarmehlderivat, 8%ig,
50 g/kg
Harnstoff,
50 g/kg
Glyezin® A (Lösungsmittel),
20 g/kg
Glycerin
60 g/kg
Ammontartrat 15° Bé,
5 g/kg
1 %ige wässrige Lösung eines Copolymers aus ca. 15 % Acrylsäure und 85 % Acrylamid, Molekulargewicht ca. 2 Millionen,
5 g/kg
Irgapadol® PN neu (Antifrosting-Mittel)
3 g/kg
Entlüftungsmittel auf Basis von 2-Ethyl-n-hexanol und
232 g/kg
Wasser.
A fabric made of chlorinated wool is printed on a flat film printing machine with a printing paste of the following composition:
25 g / kg
of the dye of the formula
Figure imgb0011
550 g / kg
Kernel flour or guar flour derivative, 8%,
50 g / kg
Urea,
50 g / kg
Glyezin® A (solvent),
20 g / kg
Glycerin
60 g / kg
Ammontartrat 15 ° Bé,
5 g / kg
1% aqueous solution of a copolymer of approx. 15% acrylic acid and 85% acrylamide, molecular weight approx. 2 million,
5 g / kg
Irgapadol® PN new (antifrosting agent)
3 g / kg
Deaerating agent based on 2-ethyl-n-hexanol and
232 g / kg
Water.

Das bedruckte Gewebe wird bei 70 bis 80° C getrocknet und zur Fixierung des Farbstoffes während 35 min. mit Sattdampf bei 100 bis 102°C behandelt. Zur Fertigstellung wird das Gewebe mit kaltem Wasser gespült, bei 30°C geseift und nochmals kalt gespült. Nach der Trocknung des Gewebes enthält man einen farbstarken, egalen, grünen Druck mit scharfen Konturen. Zudem weist das behandelte Gewebe einen weichen Griff auf.The printed fabric is dried at 70 to 80 ° C and to fix the dye for 35 min. treated with saturated steam at 100 to 102 ° C. To finish, the fabric is rinsed with cold water, soaped at 30 ° C and rinsed cold again. After the fabric has dried, it contains a strong, level, green print with sharp contours. The treated fabric also has a soft feel.

Claims (17)

Verfahren zum Bedrucken von Fasermaterial im Direktdruck, worin man auf das Fasermaterial eine Druckpaste enthaltend mindestens einen Farbstoff, ein Cellulosederivat oder ein Alginat als Verdicker und weitere übliche Zusätze aufbringt und den Farbstoff anschliessend fixiert, dadurch gekennzeichnet, dass die Druckpaste ≦ 5 Gew.-%, bezogen auf die Druckpaste eines Homo- oder Copolymers auf der Basis von Acrylamid enthält.Process for printing fiber material in direct printing, in which a printing paste containing at least one dye, a cellulose derivative or an alginate as a thickener and other conventional additives are applied to the fiber material and the dye is subsequently fixed, characterized in that the printing paste ≦ 5% by weight , based on the printing paste of a homo- or copolymer based on acrylamide. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass das Homo- oder Copolymer auf der Basis von Acrylamid ein Acrylamid-Homopolymer oder ein Copolymer aus Acrylamid und Acrylsäure oder N-Methyl-N-vinylacetamid ist.A method according to claim 1, characterized in that the homo- or copolymer based on acrylamide is an acrylamide homopolymer or a copolymer of acrylamide and acrylic acid or N-methyl-N-vinyl acetamide. Verfahren gemäss Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Homo- oder Copolymer auf der Basis von Acrylamid ein Acrylamid-Homopolymer mit einem durchschnittlichen Molekulargewicht von 0,5 bis 15 Millionen und vorzugsweise 1 bis 10 Millionen ist.A method according to claim 1 or 2, characterized in that the homo- or copolymer based on acrylamide is an acrylamide homopolymer with an average molecular weight of 0.5 to 15 million and preferably 1 to 10 million. Verfahren gemäss Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Homo- oder Copolymer auf der Basis von Acrylamid ein Copolymer aus Acrylamid und Acrylsäure mit einem durchschnittlichen Molekulargewicht von 1 bis 10 Millionen und vorzugsweise 1,5 bis 3 Millionen ist.A method according to claim 1 or 2, characterized in that the homo- or copolymer based on acrylamide is a copolymer of acrylamide and acrylic acid with an average molecular weight of 1 to 10 million and preferably 1.5 to 3 million. Verfahren gemäss Anspruch 4, dadurch gekennzeichnet, dass das Copolymer aus 75 bis 90 Gew.-% Acrylamid und 10 bis 25 Gew.-% Acrylsäure, jeweils bezogen auf die Monomere, besteht.A method according to claim 4, characterized in that the copolymer consists of 75 to 90 wt .-% acrylamide and 10 to 25 wt .-% acrylic acid, each based on the monomers. Verfahren gemäss Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Homo- oder Copolymer auf der Basis von Acrylamid ein Copolymer aus 30 bis 99,9 Gew.-% Acrylamid und 0,1 bis 70 Gew.-% N-Vinyl-N-methylacetamid, jeweils bezogen auf die Monomere, ist.A method according to claim 1 or 2, characterized in that the homo- or copolymer based on acrylamide is a copolymer of 30 to 99.9% by weight of acrylamide and 0.1 to 70% by weight of N-vinyl-N- methylacetamide, based in each case on the monomers. Verfahren gemäss einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Homo- oder Copolymer auf der Basis von Acrylamid in einer Menge von ≦ 1 Gew.-% und bevorzugt ≦ 0,5 Gew.-%, bezogen auf die Druckpaste, in der Druckpaste anwesend ist.Method according to one of claims 1 to 6, characterized in that the homo- or copolymer based on acrylamide in an amount of ≦ 1 wt .-% and preferably ≦ 0.5 wt .-%, based on the printing paste, in the printing paste is present. Verfahren gemäss einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Druckpaste ein Alginat als Verdicker enthält.Method according to one of claims 1 to 7, characterized in that the Printing paste contains an alginate as a thickener. Verfahren gemäss einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Druckpaste als übliche Zusätze eine oder mehrere Komponenten aus der Gruppe der Hydrotropiermittel, Entlüftungsmittel, Reduktionsschutzmittel, Konservierungsmittel, Sequestriermittel und Basen enthält.Method according to one of claims 1 to 8, characterized in that the printing paste contains, as usual additives, one or more components from the group of hydrotroping agents, deaerating agents, reducing protection agents, preservatives, sequestering agents and bases. Verfahren gemäss einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Druckpaste einen höheren Alkohol mit einem Siedebereich über 100° C, Terpentinöle, Mineralöle oder deren Gemische als Entlüftungsmittel enthält.Method according to one of claims 1 to 9, characterized in that the printing paste contains a higher alcohol with a boiling range above 100 ° C, turpentine oils, mineral oils or mixtures thereof as a deaerating agent. Verfahren gemäss einem der Ansprüchen 1 bis 10, dadurch gekennzeichnet, dass die Druckpaste Harnstoff als Hydrotropiermittel enthält.Method according to one of claims 1 to 10, characterized in that the printing paste contains urea as a hydrotrope. Verfahren gemäss einem der Ansprüchen 1 bis 11, dadurch gekennzeichnet, dass die Druckpaste eine aromatische Nitroverbindung als Reduktionsschutzmittel enthält.Method according to one of claims 1 to 11, characterized in that the printing paste contains an aromatic nitro compound as a reducing protection agent. Verfahren gemäss den Ansprüchen 1 bis 11, dadurch gekennzeichnet, dass die Druckpaste 0,001 bis 40 Gew.-%   Farbstoff, 1 bis 7 Gew.-%   Cellulosederivat oder Alginat als Verdicker, 0,002 bis 5 Gew.-%   Acrylamid-Homo- oder Copolymer, 0 bis 4 Gew.-%   Reduktionsschutzmittel, 0 bis 5 Gew.-%   Entschäumungs- bzw. Entlüftungsmittel, 0 bis 20 Gew.-%   Harnstoff, 0 bis 10 Gew.-%   Fixieralkali und Wasser ad 100 Gew.-% enthält.Method according to claims 1 to 11, characterized in that the printing paste 0.001 to 40% by weight of dye, 1 to 7% by weight of cellulose derivative or alginate as a thickener, 0.002 to 5% by weight of acrylamide homo- or copolymer, 0 to 4% by weight of reducing agent, 0 to 5% by weight of defoaming or deaerating agents, 0 to 20% by weight of urea, 0 to 10% by weight fixing alkali and contains water ad 100 wt .-%. Verfahren gemäss den Ansprüchen 1 bis 12, dadurch gekennzeichnet, dass man als Fasermaterial cellulosehaltiges Fasermaterial verwendet.Process according to claims 1 to 12, characterized in that cellulose-containing fiber material is used as the fiber material. Verfahren gemäss Anspruch 14, dadurch gekennzeichnet, dass man als Farbstoff mindestens einen eine Monochlotriazingruppe enthaltenden Reaktivfarbstoff einsetzt.A method according to claim 14, characterized in that at least one reactive dye containing a monochlotriazine group is used as the dye. Wässrige Druckpaste enthaltend 0,001 bis 40 Gew.-%   Farbstoff, 1 bis 7 Gew.-%   Cellulosederivat oder Alginat als Verdicker, 0,002 bis 5 Gew.-%   Acrylamid-Homo- oder Copolymer, 0 bis 4 Gew.-%   Reduktionsschutzmittel, 0 bis 5 Gew.-%   Entschäumungs- bzw. Entlüftungsmittel, 0 bis 20 Gew.-%   Harnstoff, 0 bis 10 Gew.-%   Fixieralkali und Wasser ad 100 Gew.-%.Containing aqueous printing paste 0.001 to 40% by weight of dye, 1 to 7% by weight of cellulose derivative or alginate as a thickener, 0.002 to 5% by weight of acrylamide homo- or copolymer, 0 to 4% by weight of reducing agent, 0 to 5% by weight of defoaming or deaerating agents, 0 to 20% by weight of urea, 0 to 10% by weight fixing alkali and water ad 100 wt .-%. Verwendung der Druckpaste gemäss Anspruch 16 zum Bedrucken von textilem Fasermaterial im Direktdruck.Use of the printing paste according to claim 16 for printing textile fiber material in direct printing.
EP95810032A 1994-01-26 1995-01-17 Process for printing fibrous material by direct printing. Ceased EP0665326A3 (en)

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EP1584371A1 (en) * 2004-04-07 2005-10-12 Urea Casale S.A. Fluid bed granulation process and apparatus
US7727289B2 (en) 2005-06-07 2010-06-01 S.C. Johnson & Son, Inc. Composition for application to a surface
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US8846154B2 (en) 2005-06-07 2014-09-30 S.C. Johnson & Son, Inc. Carpet décor and setting solution compositions
US8557758B2 (en) 2005-06-07 2013-10-15 S.C. Johnson & Son, Inc. Devices for applying a colorant to a surface
US7776108B2 (en) 2005-06-07 2010-08-17 S.C. Johnson & Son, Inc. Composition for application to a surface
US8061269B2 (en) 2008-05-14 2011-11-22 S.C. Johnson & Son, Inc. Multilayer stencils for applying a design to a surface
JP2008081855A (en) * 2006-09-26 2008-04-10 Tokai Senko Kk Printing paste composition and method for producing printed product
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EP0457728A1 (en) * 1990-05-18 1991-11-21 Ciba-Geigy Ag Process for dyeing cellulosic fibres without tailing

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