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EP0924335B1 - Process for printing textile fibres materials according to the ink-jet printing process - Google Patents

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

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Publication number
EP0924335B1
EP0924335B1 EP98811210A EP98811210A EP0924335B1 EP 0924335 B1 EP0924335 B1 EP 0924335B1 EP 98811210 A EP98811210 A EP 98811210A EP 98811210 A EP98811210 A EP 98811210A EP 0924335 B1 EP0924335 B1 EP 0924335B1
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EP
European Patent Office
Prior art keywords
acid
hydrogen
ink
weight
alkyl
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.)
Expired - Lifetime
Application number
EP98811210A
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German (de)
French (fr)
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EP0924335A1 (en
Inventor
Marc Burglin
Mickael Mheidle
Peter Scheibli
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Huntsman Advanced Materials Switzerland GmbH
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Huntsman Advanced Materials Switzerland GmbH
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Priority to EP98811210A priority Critical patent/EP0924335B1/en
Publication of EP0924335A1 publication Critical patent/EP0924335A1/en
Application granted granted Critical
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/30—Ink jet printing
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
    • D06P1/18—Azo dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
    • D06P1/19—Nitro dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
    • D06P1/20—Anthraquinone dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5228—Polyalkenyl alcohols, e.g. PVA
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5242—Polymers of unsaturated N-containing compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
    • D06P1/5257—(Meth)acrylic acid

Definitions

  • the present invention relates to a process for printing textile fiber materials with disperse dyes by the inkjet printing process (jet and ink jet processes) and corresponding printing inks.
  • Inkjet printing processes have been used in the textile industry for several years now. These methods make it possible to dispense with the usual production of a printing stencil, so that significant cost and time savings can be achieved. In particular, in the production of templates can be responded to changing needs within a much shorter time.
  • the present invention is a process for printing textile fiber materials by the ink jet printing process, which is characterized in that the fiber materials are printed with an aqueous ink containing at least one disperse dye, an anionic copolymer based on acrylic acid, methacrylic acid or maleic acid and contains a betaine monohydrate.
  • Suitable disperse dyes for the process according to the invention are those dyes which are described in the Color Index, 3rd edition (3rd revision 1987 including Additions and Amendments to No. 85) under "Disperse Dyes". They are, for example, carboxylic acid and / or sulfonic acid group-free nitro, amino, aminoketone, ketoninim, methine, polymethine, diphenylamine, quinoline, benzimidazole, xanthene, oxazine or coumarin dyes and in particular anthraquinone and azo dyes, such as mono- or disazo dyes.
  • Disperse dyes of the formulas are preferred in the process according to the invention wherein R 16 halogen, nitro or cyano, R 17 is hydrogen, halogen, nitro or cyano, R 18 halogen or cyano, R 19 is hydrogen, halogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy, R 20 is hydrogen, halogen or acylamino, and R 21 and R 22 independently of one another are hydrogen, C 1 -C 4 -alkyl which is unsubstituted or substituted by hydroxyl, cyano, acetoxy or phenoxy, wherein R 23 is hydrogen, phenyl or phenylsulfoxy, where the benzene ring in phenyl and phenylsulfoxy is optionally substituted by C 1 -C 4 -alkyl, sulfo or C 1 -C 4 -alkylsulfo, R 25 is unsubstituted or C
  • the disperse dyes of the formulas (1) to (23) are known or can be prepared in analogy to known compounds by known standard methods, for example by conventional diazotization, coupling, addition and condensation reactions.
  • the inks generally contain a total content of disperse dyes of the above formulas (1) to (23) of 1 to 35 wt .-%, in particular 1 to 20 wt .-%, especially 1 to 10 wt .-%, based on the total weight of the ink.
  • the disperse dyes are advantageously present in the inventive inks, in a finely dispersed form.
  • the disperse dyes are ground, so that their particle size on average between 0.1 and 10 microns, preferably between 1 and 5 microns, more preferably between 0.5 and 2 microns.
  • the milling can be carried out in the presence of dispersants.
  • the dried disperse dye is ground with a dispersant or kneaded in paste form with a dispersant and optionally dried in a vacuum or by sputtering.
  • the inks according to the invention can be prepared after the addition of water and optionally further auxiliaries.
  • Suitable anionic copolymers for the process according to the invention are copolymers based on acrylic acid, methacrylic acid or maleic acid. Preferred among these are those obtained by polymerizing acrylic and / or methacrylic acid and one or more copolymerizable monomers selected from the group consisting of maleic acid, N-vinylformamide, N-vinylacetamide, allylamine or diallylamine derivatives, N-vinylpyrrolidone, N-vinyl N-methyl-formamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl-acetamide, vinyl acetate, vinyl propionate, acrylonitrile, styrene, methacrylonitrile, acrylamide, methacrylamide and N-mono / N, N-di C 1 -C 10 alkyl (meth) acrylamide are available.
  • anionic copolymers which are obtainable by copolymerization of acrylic or methacrylic acid and styrene.
  • the ink in the process according to claim 1 may also be a nonionic block polymer and / or dispersants.
  • Suitable nonionic block polymers for the process according to the invention are, in particular, alkylene oxide condensation products such as ethylene oxide adducts of polypropylene oxide (so-called EO-PO block polymers) and propylene oxide adducts of polyethylene oxide (so-called reversed EO-PO block polymers), and block polymers which adhere by addition of styrene Polypropylene and / or polyethylene oxide are available.
  • ethylene-propylene oxide block polymers having molecular weights of between 2,000 and 20,000, especially between 8,000 and 16,000, and an ethylene oxide content in the total molecule of from 30 to 80%, in particular from 60 to 80%.
  • Suitable dispersants are, in particular, anionic dispersants from the group of (ba) acid esters or their salts of alkylene oxide adducts of the formula wherein X is the acid radical of an inorganic, oxygen-containing acid, such as sulfuric acid or, preferably, phosphoric acid, or else the radical of an organic acid, and Y is C 1 -C 12 -alkyl, aryl or aralkyl, "alkylene” is the ethylene radical or propylene radical, and m is 1 to 4, and n is 4 to 50, (bb) polystyrenesulfonates, (bc) fatty acid taurides, (bd) alkylated diphenyloxide mono- or di-sulphonates, (be) sulfonates of polycarboxylic esters, (bf) with an organic dicarboxylic acid, or an inorganic polybasic acid adduct of from 1 to 60, preferably from 2 to 30, moles of
  • the lignosulfonates (bg) used are above all those lignosulfonates or their alkali metal salts whose content of sulfo groups does not exceed 25% by weight.
  • Preferred are lignosulfonates having a content of 5 to 15 wt .-% of sulfo groups.
  • condensation products of formaldehyde condensation products (bi) are condensation products of formaldehyde and aromatic sulfonic acids, such as condensation products of ditolyl ether sulfonates and formaldehyde, condensation products of naphthalenesulfonic acid with formaldehyde and / or naphtholaminosulfonic acids with formaldehyde, condensation products of phenolsulfonic acids and / or sulfonated dihydroxydiphenylsulfone and phenols or cresols with formaldehyde and / or urea and condensation products of diphenyloxide-disulfonic acid derivatives with formaldehyde into consideration.
  • aromatic sulfonic acids such as condensation products of ditolyl ether sulfonates and formaldehyde, condensation products of naphthalenesulfonic acid with formaldehyde and / or naphtholaminosulfonic acids with formaldehyde, condensation products of
  • (bi) is the compound of the formula wherein X is the direct bond or oxygen, A is the radical of an aromatic compound which is bonded to the methylene group by means of a ring carbon atom, M is hydrogen or a salt-forming cation, for example an alkali metal, alkaline earth metal or ammonium and n and p independently of one another denote a number from 1 to 4.
  • Very particularly preferred as (bi) is a compound based on a sulfonated condensation product of Chlormethyldiphenyl isomer mixture and naphthalene of the formula wherein (SO 3 Na) 1.4-1.6 means an average degree of sulfonation of 1.4 to 1.6.
  • the total content of anionic copolymer, nonionic block polymer and dispersant in the ink of the present invention is 3 to 9% by weight based on the total weight of the ink.
  • Ratio: anionic copolymer: nonionic block polymer: dispersant in the finished ink can vary widely, e.g. 1.5: 0.5: 1; 1: 0.5: 1.5; 1: 1: 1; 1: 0: 1; 1: 1: 0; 1: 0: 0; 0: 1: 1 or 0: 0: 1.
  • Preferred for the process of claim 1 of the present invention are inks containing anionic copolymer and nonionic block polymer or anionic copolymer and dispersant.
  • inks containing anionic copolymer, nonionic block polymer and dispersant are particularly preferred.
  • the ink may conveniently contain thickening agents of natural or synthetic origin, such as commercial alginate thickeners, starch ethers or locust bean flour ethers, especially sodium alginate, alone or in the Mixture with modified cellulose, in particular with preferably 20 to 25 weight percent carboxymethylcellulose.
  • thickening agents such as commercial alginate thickeners, starch ethers or locust bean flour ethers, especially sodium alginate, alone or in the Mixture with modified cellulose, in particular with preferably 20 to 25 weight percent carboxymethylcellulose.
  • Synthetic thickeners are preferably used in the novel inks, such as those based on poly (meth) acrylic acids or poly (meth) acrylamides.
  • Preferred inks for the process according to the invention are those inks which have a viscosity of 1 to 40 mPa.s (millipascal second), in particular 1 to 20 mPa.s, especially 1 to 10 mPa.s.
  • inks which have a surface tension between 60 and 30 Newton / cm, in particular between 50 and 40 Newton / cm.
  • inks which have a conductivity of from 0 to 3000 ⁇ S / cm, in particular from 100 to 700 ⁇ S / cm, based on a 10% strength aqueous suspension.
  • the inks may contain buffering substances, such as e.g. Borax, borate or citrate.
  • buffering substances such as e.g. Borax, borate or citrate.
  • borax, sodium borate, sodium tetraborate and sodium citrate are used in amounts of from 0.1 to 3% by weight, especially from 0.1 to 1% by weight, based on the total weight of the ink, to obtain a pH of e.g. 4 to 10, preferably 5 to 8 set.
  • the inks may contain surfactants, redispersants, and humectants.
  • Suitable surfactants are the commercially available anionic or nonionic surfactants. Betaine monohydrate is to be mentioned as redispersant.
  • the humectant used is preferably a mixture of Na lactate (advantageously in the form of a 50 to 60% aqueous solution) and glycerol and / or propylene glycol in amounts of preferably 7 to 20 percent by weight in the ink used according to the invention.
  • the inks may also contain acid donors such as butyrolactone or sodium hydrogen phosphate, preservatives, fungal and / or bacterial growth inhibiting agents, antifoaming agents, sequestering agents, emulsifying agents, water-insoluble solvents, oxidizing agents or deaerating agents.
  • Suitable preservatives are especially formaldehyde donating agents, such as paraformaldehyde and trioxane, especially aqueous, about 30 to 40 weight percent formaldehyde solutions, as sequestering agents such as sodium nitrilotriacetate, ethylenediaminetetraacetic acid sodium, especially sodium polymetaphosphate, especially sodium hexametaphosphate, as emulsifiers especially Adducts of an alkylene oxide and a fatty alcohol, in particular an adduct of oleyl alcohol and ethylene oxide, as water-insoluble Solvents high-boiling, saturated hydrocarbons, especially paraffins having a boiling range of about 160 to 210 ° C (so-called mineral spirits), as an oxidizing agent such as an aromatic nitro compound, especially an aromatic mono- or dinitrocarboxylic acid or sulfonic acid, which is optionally present as Alkylenoxidaddukt, in particular a nitrobenzenesulfonic acid
  • the inks are e.g. prepared such that one or more disperse dyes of the formulas (1) to (23) are mixed with a dispersant / copolymer / block polymer mixture and then in a wet mill to a defined freeness of an average particle size between 0.2 to 1.0 microns be ground. Thereafter, the concentrated millbase, optionally using e.g. suitable thickening agents, dispersants, copolymers, surfactants, humectants, redispersing agents, sequestering agents and / or preservatives, and water, adjusted to the desired concentration. In order to remove any coarser components which may be present, it is advantageously possible to filter the finished ink through a microsieve of approximately 1 ⁇ m.
  • the process according to the invention for printing textile fiber materials can be carried out with ink jet printers which are known per se and suitable for textile printing.
  • the continuous ink-jet method In the case of the ink-jet printing method, individual drops of the ink are injected in a controlled manner from a nozzle onto the substrate.
  • the continuous ink-jet method and the drop-on-demand method are predominantly used.
  • the drops are generated continuously, wherein the non-pressure required for the drops are discharged into a collecting container and recycled as a rule.
  • the drips are created as desired and printed, ie only drops are produced when required for printing.
  • the generation of the drops can be carried out, for example, advantageously by means of a piezo-inkjet head or by means of thermal energy (so-called bubble jet).
  • printing by the continuous ink-jet method or the drop-on-demand method is preferred.
  • the fiber material is dried after printing at temperatures up to 150 ° C, preferably 80 ° to 120 ° C.
  • the ink used according to the invention can be applied to various types of fiber materials, such as wool, silk, cellulose, polyvinyl, polyacrylonitrile, polyamide, aramid, polypropylene, polyester or polyurethane.
  • fiber materials such as wool, silk, cellulose, polyvinyl, polyacrylonitrile, polyamide, aramid, polypropylene, polyester or polyurethane.
  • polyester-containing fiber materials are those materials which consist wholly or partly of polyester.
  • Suitable polyester-containing fiber materials are those materials which consist wholly or partly of polyester. Examples are Celluloseesterfasern such as cellulose-2 1/2 acetate and triacetate fibers, polyester fibers, and especially linear, optionally also acid-modified which, for example (by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis hydroxymethyl) cyclohexane, as well as fibers of copolymers of terephthalic and isophthalic acid with ethylene glycol.
  • polyester-containing mixed fiber materials ie mixtures of polyester and other fibers.
  • the present invention further provides an aqueous printing ink for the ink-jet printing process, which is characterized in that it contains 1 to 35 wt .-% of at least one disperse dye of the above formulas (1) to (23), an anionic copolymer and / or nonionic block polymer and / or a dispersant.
  • the anionic copolymers, the nonionic block polymers and the dispersants for the printing ink according to the invention and for the disperse dyes of the formulas (1) to (23) used in this ink, the anionic copolymers, the nonionic block polymers and the dispersants, the meanings and preferences given above apply.
  • the prints obtainable by the process according to the invention have good fastness properties; they have e.g. a high fiber-dye binding stability in both the acidic and in the alkaline range, good light fastness, good wet fastness properties, such as water, washing, seawater, overdyeing and perspiration fastness, good chlorine fastness, rub fastness, ironing fastness and pleating fastness and sharp contours and a high color intensity.
  • the printing inks used are characterized by good stability and good viscosity properties.
  • the ink prepared according to Example 1 is printed on a polyester fabric with an inkjet printer with drop on demand piezo technology.
  • the pressure is dried and fixed in superheated steam at 180 ° C for 8 minutes. This gives a brilliant yellow print with good fastness properties, in particular wet and light fastness.
  • a brilliant yellow print having good fastness properties in particular wet fastnesses and light fastnesses, is obtained when the dried print is fixed for 1 minute with a hot air at 200 ° C.
  • the ink prepared according to Example 3 is printed on a polyester fabric with an inkjet printer with drop on demand piezo technology.
  • the pressure is dried and fixed in superheated steam at 180 ° C for 8 minutes. This gives a blue print with good fastness properties, especially wet and light fastness. It also gives a blue print with good fastness properties, especially wet and light fastness, if the dried pressure for 1 minute with a hot air of 200 ° C fixed.
  • the ink prepared according to Example 5 is printed on a polyester fabric with an inkjet printer with drop on demand piezo technology.
  • the pressure is dried and fixed in superheated steam at 180 ° C for 8 minutes. This gives a blue print with good fastness properties, especially wet and light fastness.
  • the ink prepared according to Example 7 is printed on a polyester fabric with an inkjet printer with drop on demand piezo technology.
  • the pressure is dried and fixed in superheated steam at 180 ° C for 8 minutes. This gives a pink-red print with good fastness properties, especially wet and light fastness.
  • the ink prepared according to Example 9 is printed on a polyester fabric with an inkjet printer with drop on demand piezo technology.
  • the pressure is dried and fixed in superheated steam at 180 ° C for 8 minutes. This gives a violet print with good fastness properties, especially wet and light fastness.
  • the ink prepared according to Example 11 is printed on a polyester fabric with an inkjet printer with drop on demand piezo technology.
  • the pressure is dried and fixed in superheated steam at 180 ° C for 8 minutes. This gives a blue print with good fastness properties, especially wet and light fastness.

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

Description

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

Tintenstrahldruck-Verfahren werden bereits seit einigen Jahren in der Textilindustrie angewendet. Diese Verfahren ermöglichen es, auf die sonst übliche Herstellung einer Druckschablone zu verzichten, so dass erhebliche Kosten- und Zeiteinsparungen erzielt werden können. Insbesondere bei der Herstellung von Mustervorlagen kann innerhalb deutlich geringerer Zeit auf veränderte Bedürfnisse reagiert werden.Inkjet printing processes have been used in the textile industry for several years now. These methods make it possible to dispense with the usual production of a printing stencil, so that significant cost and time savings can be achieved. In particular, in the production of templates can be responded to changing needs within a much shorter time.

Entsprechende Tintenstrahldruck-Verfahren sollten insbesondere optimale anwendungstechnische Eigenschaften aufweisen. Zu erwähnen seien in diesem Zusammenhang Eigenschaften wie Viskosität, Stabilität, Oberflächenspannung und Leitfähigkeit der verwendeten Tinten. Ferner werden erhöhte Anforderungen an die Qualität der erhaltenen Drucke gestellt, wie z.B. bezüglich Farbstärke, Faser-Farbstoff-Bindungsstabilität sowie Nassechtheitseigenschaften. Von den bekannten Verfahren werden diese Anforderungen nicht in allen Eigenschaften erfüllt, so dass weiterhin ein Bedarf nach neuen Verfahren für den textilen Tintenstrahldruck besteht. Dokument EP-A-0 655 527 beschreibt Tinten für den Tintenstrahldruck enthaltend einen Dispersionsforbstoff und ein Bisphenol/Ethylenoxid-Addukt als Dispergiermittel.Corresponding inkjet printing processes should in particular have optimal performance properties. Worth mentioning in this context are properties such as viscosity, stability, surface tension and conductivity of the inks used. Furthermore, increased demands are placed on the quality of the prints obtained, e.g. in terms of color strength, fiber-dye binding stability and wet fastness properties. These known requirements do not meet all of these requirements, so that there is still a need for new processes for textile inkjet printing. Document EP-A-0 655 527 describes inks for inkjet printing comprising a disperse pulp and a bisphenol / ethylene oxide adduct as a dispersant.

Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Bedrucken von textilen Fasermaterialien nach dem Tintenstrahldruck-Verfahren, welches dadurch gekennzeichnet ist, dass man die Fasermaterialien mit einer wässrigen Tinte bedruckt, welche mindestens einen Dispersionsfarbstoff, ein anionisches Copolymer auf Basis von Acrylsäure, Methacrylsäure oder Maleinsäure und ein Betain-Monohydrat enthält.The present invention is a process for printing textile fiber materials by the ink jet printing process, which is characterized in that the fiber materials are printed with an aqueous ink containing at least one disperse dye, an anionic copolymer based on acrylic acid, methacrylic acid or maleic acid and contains a betaine monohydrate.

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

Bevorzugt werden in dem erfindungsgemässen Verfahren Dispersionsfarbstoffe der Formeln

Figure imgb0001
worin
R16 Halogen, Nitro oder Cyano,
R17 Wasserstoff, Halogen, Nitro oder Cyano,
R18 Halogen oder Cyano,
R19 Wasserstoff, Halogen, C1-C4-Alkyl oder C1-C4-Alkoxy,
R20 Wasserstoff, Halogen oder Acylamino, und
R21 und R22 voneinander unabhängig Wasserstoff, C1-C4-Alkyl, welches unsubstituiert oder durch Hydroxy, Cyano, Acetoxy oder Phenoxy substituiert ist,
Figure imgb0002
 worin
R23 Wasserstoff, Phenyl oder Phenylsulfoxy ist, wobei der Benzolring in Phenyl und Phenylsulfoxy gegebenenfalls durch C1-C4-Alkyl, Sulfo oder C1-C4-Alkylsulfo substituiert ist,
R25 unsubstituiertes oder durch C1-C4-Alkyl substituiertes Amino oder Hydroxy,
R26 Wasserstoff oder C1-C4-Alkoxy,
R27 Wasserstoff oder den Rest -O-C6H5-SO2-NH-(CH2)3-O-C2H5,
R36 Wasserstoff, Hydroxy oder Nitro und
R37 Wasserstoff, Hydroxy oder Nitro bedeuten,
Figure imgb0003
 worin
R28 C1-C4-Alkyl welches unsubstituiert oder durch Hydroxy substituiert ist,
R29 C1-C4-Alkyl,
R30 Cyano,
R31 den Rest der Formel -(CH2)3-O-(CH2)2-O-C6H5,
R32 Halogen, Nitro oder Cyano, und
R33 Wasserstoff, Halogen, Nitro oder Cyano, bedeuten,
Figure imgb0004
 worin
R34 C1-C4-Alkyl,
R35 C1-C4-Alkyl welches unsubstituiert oder durch C1-C4-Alkoxy substituiert ist und
W den Rest -COOCH2CH2OC6H5 und W1 Wasserstoff oder
W Wasserstoff und W1 -N=N-C6H5 bedeuten, sind,
Figure imgb0005
 wobei die Ringe A'' und B'' unsubstituiert oder ein- oder mehrfach mit Halogen substituiert sind,
Figure imgb0006
 worin
R34 C1-C4-Alkyl, welches unsubstituiert oder mit Hydroxy, C1-C4-Alkoxy oder C1-C4-Alkoxy-C1-C4-Alkoxy substituiert ist, und
Figure imgb0007
 verwendet.Disperse dyes of the formulas are preferred in the process according to the invention
Figure imgb0001
 wherein
R 16 halogen, nitro or cyano,
R 17 is hydrogen, halogen, nitro or cyano,
R 18 halogen or cyano,
R 19 is hydrogen, halogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy,
R 20 is hydrogen, halogen or acylamino, and
R 21 and R 22 independently of one another are hydrogen, C 1 -C 4 -alkyl which is unsubstituted or substituted by hydroxyl, cyano, acetoxy or phenoxy,
Figure imgb0002
 wherein
R 23 is hydrogen, phenyl or phenylsulfoxy, where the benzene ring in phenyl and phenylsulfoxy is optionally substituted by C 1 -C 4 -alkyl, sulfo or C 1 -C 4 -alkylsulfo,
R 25 is unsubstituted or C 1 -C 4 -alkyl-substituted amino or hydroxyl,
R 26 is hydrogen or C 1 -C 4 -alkoxy,
R 27 is hydrogen or the radical -OC 6 H 5 -SO 2 -NH- (CH 2 ) 3 -OC 2 H 5 ,
R 36 is hydrogen, hydroxy or nitro and
R 37 is hydrogen, hydroxy or nitro,
Figure imgb0003
 wherein
R 28 is C 1 -C 4 -alkyl which is unsubstituted or substituted by hydroxy,
R 29 is C 1 -C 4 -alkyl,
R 30 cyano,
R 31 is the radical of the formula - (CH 2 ) 3 -O- (CH 2 ) 2 -OC 6 H 5 ,
R 32 is halogen, nitro or cyano, and
R 33 is hydrogen, halogen, nitro or cyano,
Figure imgb0004
 wherein
R 34 is C 1 -C 4 -alkyl,
R 35 is C 1 -C 4 -alkyl which is unsubstituted or substituted by C 1 -C 4 -alkoxy and
W is the radical -COOCH 2 CH 2 OC 6 H 5 and W 1 is hydrogen or
W is hydrogen and W 1 is -N = NC 6 H 5 ,
Figure imgb0005
 the rings A '' and B '' being unsubstituted or mono- or polysubstituted by halogen,
Figure imgb0006
 wherein
R 34 is C 1 -C 4 -alkyl which is unsubstituted or substituted by hydroxy, C 1 -C 4 -alkoxy or C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy, and
Figure imgb0007
 used.

Besonders bevorzugt werden in dem erfindungsgemässen Verfahren die Farbstoffe der Formeln

Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
 und
Figure imgb0023
 verwendet.
Die Dispersionsfarbstoffe der Formeln (1) bis (23) sind bekannt oder können in Analogie zu bekannten Verbindungen nach bekannten Standard-Verfahren hergestellt werden, wie z.B. durch übliche Diazotierungs-, Kupplungs-, Addition- und Kondensationsreaktionen.Particular preference is given in the process according to the invention to the dyes of the formulas
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
 and
Figure imgb0023
 used.
The disperse dyes of the formulas (1) to (23) are known or can be prepared in analogy to known compounds by known standard methods, for example by conventional diazotization, coupling, addition and condensation reactions.

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

Die Dispersionsfarbstoffe liegen in der erfindungsgemässen Tinten vorteilhafterweise, in einer feindispergierten Form vor. Hierzu werden die Dispersionsfarbstoffe vermahlen, so dass ihre Teilchengrösse im Mittel zwischen 0,1 und 10 Mikron, bevorzugt zwischen 1 und 5 Mikron, besonders bevorzugt zwischen 0,5 und 2 Mikron beträgt. Das Vermahlen kann in Gegenwart von Dispergiermitteln erfolgen. Beispielsweise wird der getrocknete Dispersionsfarbstoff mit einem Dispergiermittel gemahlen oder in Pastenform mit einem Dispergiermittel geknetet und gegebenenfalls im Vakuum oder durch Zerstäuben getrocknet. Mit den so erhaltenen Präparaten kann man nach Zugabe von Wasser und gegebenenfalls weiteren Hilfsmitteln die erfindungsgemässen Tinten herstellen.The disperse dyes are advantageously present in the inventive inks, in a finely dispersed form. For this purpose, the disperse dyes are ground, so that their particle size on average between 0.1 and 10 microns, preferably between 1 and 5 microns, more preferably between 0.5 and 2 microns. The milling can be carried out in the presence of dispersants. For example, the dried disperse dye is ground with a dispersant or kneaded in paste form with a dispersant and optionally dried in a vacuum or by sputtering. With the preparations thus obtained, the inks according to the invention can be prepared after the addition of water and optionally further auxiliaries.

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

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

Ganz besonders bevorzugt sind Acryl- und Methacrylsäure-Styrol-Copolymere mit einem Molekulargewicht von 3000 bis 16000, insbesondere von 3000 bis 10000. Ausser dem Dispersionsfarbstoff, das anionische Copolymer und das Betain-Monohydrat kann die Tinte im Verfahren nach Anspruch 1 auch ein nichtionogenes Blockpolymer und/oder Dispergiermittel enthalten.Very particular preference is given to acrylic and methacrylic acid-styrene copolymers having a molecular weight of from 3,000 to 16,000, in particular from 3,000 to 10,000. Apart from the disperse dye, the anionic copolymer and the betaine monohydrate, the ink in the process according to claim 1 may also be a nonionic block polymer and / or dispersants.

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

Als Dispergiermittel kommen in Betracht vor allem anionische Dispergatoren aus der Gruppe der
(ba) sauren Ester oder deren Salze von Alkylenoxidaddukten der Formel

Figure imgb0024
worin
X den Säurerest einer anorganischen, Sauerstoff enthaltenden Säure, wie z.B. Schwefelsäure oder vorzugsweise Phosphorsäure, oder auch den Rest einer organischen Säure, und
Y C1-C12-Alkyl, Aryl oder Aralkyl bedeuten, "Alkylen" für den Ethylenrest oder Propylenrest steht, und
m 1 bis 4, und n 4 bis 50 sind,
(bb) Polystyrolsulfonate,
(bc) Fettsäuretauride,
(bd) alkylierten Diphenyloxid -mono- oder di-sulfonate,
(be) Sulfonate von Polycarbonsäureestern,
(bf) mit einer organischen Dicarbonsäure, oder einer anorganischen mehrbasischen Säure
in einen sauren Ester überführten Anlagerungsprodukt von 1 bis 60, vorzugsweise 2 bis 30 Mol Ethylenoxid und/oder Propylenoxid an Fettamine, Fettamide, Fettsäuren oder Fettalkohole je mit 8 bis 22 Kohlenstoffatomen oder an drei- bis sechswertige Alkanole mit 3 bis 6 Kohlenstoffatomen,
(bg) Ligninsulfonate,
(bh) Naphthalinsulfonate, und
(bi) Formaldehyd-Kondensationsprodukte.Suitable dispersants are, in particular, anionic dispersants from the group of
(ba) acid esters or their salts of alkylene oxide adducts of the formula
Figure imgb0024
 wherein
X is the acid radical of an inorganic, oxygen-containing acid, such as sulfuric acid or, preferably, phosphoric acid, or else the radical of an organic acid, and
Y is C 1 -C 12 -alkyl, aryl or aralkyl, "alkylene" is the ethylene radical or propylene radical, and
m is 1 to 4, and n is 4 to 50,
(bb) polystyrenesulfonates,
(bc) fatty acid taurides,
(bd) alkylated diphenyloxide mono- or di-sulphonates,
(be) sulfonates of polycarboxylic esters,
(bf) with an organic dicarboxylic acid, or an inorganic polybasic acid
adduct of from 1 to 60, preferably from 2 to 30, moles of ethylene oxide and / or propylene oxide with fatty amines, fatty amides, fatty acids or fatty alcohols each containing from 8 to 22 carbon atoms or trihydric to hexahydric alkanols containing from 3 to 6 carbon atoms,
(bg) lignosulfonates,
(bh) naphthalenesulfonates, and
(bi) formaldehyde condensation products.

Als Ligninsulfonate (bg) werden vor allem solche Ligninsulfonate oder deren Alkalimetallsalze eingesetzt, deren Gehalt an Sulfogruppen 25 Gew.-% nicht übersteigt. Bevorzugt sind Ligninsulfonate mit einem Gehalt von 5 bis 15 Gew.-% an Sulfogruppen.
Als Formaldehydkondensationsprodukte (bi) kommen z.B. Kondensationsprodukte von Ligninsulfonaten und/oder Phenol und Formaldehyd, Kondensationsprodukte von Formaldehyd mir aromatischen Sulfonsäuren, wie z.B. Kondensationsprodukte von Ditolylethersulfonaten und Formaldehyd, Kondensationsprodukte von Naphthalinsulfonsäure mit Formaldehyd und/oder Naphthol- oder Naphthylaminosulfonsäuren mit Formaldehyd, Kondensationsprodukte von Phenolsulfonsäuren und/oder sulfoniertem Dihydroxydiphenylsulfon und Phenolen bzw. Kresolen mit Formaldehyd und/oder Harnstoff sowie Kondensationsprodukte von Diphenyloxid-disulfonsäure-Derivaten mit Formaldehyd in Betracht.The lignosulfonates (bg) used are above all those lignosulfonates or their alkali metal salts whose content of sulfo groups does not exceed 25% by weight. Preferred are lignosulfonates having a content of 5 to 15 wt .-% of sulfo groups.
Examples of condensation products of formaldehyde condensation products (bi) are condensation products of formaldehyde and aromatic sulfonic acids, such as condensation products of ditolyl ether sulfonates and formaldehyde, condensation products of naphthalenesulfonic acid with formaldehyde and / or naphtholaminosulfonic acids with formaldehyde, condensation products of phenolsulfonic acids and / or sulfonated dihydroxydiphenylsulfone and phenols or cresols with formaldehyde and / or urea and condensation products of diphenyloxide-disulfonic acid derivatives with formaldehyde into consideration.

Bevorzugt als (bi) sind

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

Besonders bevorzugt als (bi) ist die Verbindung der Formel

Figure imgb0025
worin
X die direkte Bindung oder Sauerstoff,
A den Rest einer aromatischen Verbindung, welcher mittels eines Ringkohlenstoffatomes an die Methylengruppe gebunden ist,
M Wasserstoff oder ein salzbildendes Kation, z.B. ein Alkalimetall, Erdalkalimetall oder Ammonium und
n und p unabhängig voneinander eine Zahl von 1 bis 4 bedeuten.
Ganz besonders bevorzugt als (bi) ist eine Verbindung auf Basis eines sulfonierten Kondensationsproduktes aus Chlormethyldiphenyl-Isomerengemisch und Naphthalin der Formel
Figure imgb0026
 worin (SO3Na)1,4-1,6 einen durchschnittlichen Sulfonierungsgrad von 1,4 bis 1,6 bedeutet.Particularly preferred as (bi) is the compound of the formula
Figure imgb0025
 wherein
X is the direct bond or oxygen,
A is the radical of an aromatic compound which is bonded to the methylene group by means of a ring carbon atom,
M is hydrogen or a salt-forming cation, for example an alkali metal, alkaline earth metal or ammonium and
n and p independently of one another denote a number from 1 to 4.
Very particularly preferred as (bi) is a compound based on a sulfonated condensation product of Chlormethyldiphenyl isomer mixture and naphthalene of the formula
Figure imgb0026
 wherein (SO 3 Na) 1.4-1.6 means an average degree of sulfonation of 1.4 to 1.6.

Die obigen Dispergiermittel sind bekannt oder können in Analogie zu bekannten Verbindungen nach allgemein bekannten Verfahren hergestellt werden.The above dispersants are known or can be prepared in analogy to known compounds by well-known methods.

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

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

Beworzugt für das erfindungsgemässe Verfahren nach Anspruch 1 sind Tinten, welche anionisches Copolymer und nichtionogenes Blockpolymer oder anionisches Copolymer und Dispergiermittel enthalten.Preferred for the process of claim 1 of the present invention are inks containing anionic copolymer and nonionic block polymer or anionic copolymer and dispersant.

Besonders bevorzugt sind Tinten, welche anionisches Copolymer, nichtionogenes Blockpolymer und Dispergiermittel enthalten.Particularly preferred are inks containing anionic copolymer, nonionic block polymer and dispersant.

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

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

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

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

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

Als weitere Zusätze können die Tinten Tenside, Redispergiermittel und Feuchthaltemittel enthalten.As further additives, the inks may contain surfactants, redispersants, and humectants.

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

Gewünschtenfalls können die Tinten noch Säurespender wie Butyrolacton oder Natriumhydrogenphosphat, Konservierungsmittel, Pilz- und/oder Bakteriewachstum hemmende Stoffe, schaumdämpfende Mittel, Sequestriermittel, Emulgatoren, wasserunlösliche Lösungsmittel, Oxidationsmittel oder Entlüftungsmittel enthalten.If desired, the inks may also contain acid donors such as butyrolactone or sodium hydrogen phosphate, preservatives, fungal and / or bacterial growth inhibiting agents, antifoaming agents, sequestering agents, emulsifying agents, water-insoluble solvents, oxidizing agents or deaerating agents.

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

Bevorzugt werden die Tinten z.B. so hergestellt, dass ein oder mehrere Dispersionsfarbstoffe der Formeln (1) bis (23) mit einem Dispergator/Copolymer/Blockpolymer-Gemisch angerührt und anschliessend in einer Nassmühle bis auf einen definierten Mahlgrad von einer durchschnittlichen Partikelgrösse zwischen 0,2 bis 1,0 µm gemahlen werden. Danach wird das konzentrierte Mahlgut, gegebenenfalls unter Verwendung von z.B. geeigneten Verdickungsmitteln, Dispergatoren, Copolymeren, Tensiden, Feuchthaltemitteln, Redispergiermittel, Sequestriermitteln und/oder Konservierungsmitteln, sowie Wasser, auf die gewünschte Konzentration eingestellt. Zur Entfernung der gegebenenfalls vorhandenen gröberen Anteile kann vorteilhafterweise eine Filtration der fertiggestellten Tinte durch ein Mikrosieb von ca. 1 µm erfolgen.Preferably, the inks are e.g. prepared such that one or more disperse dyes of the formulas (1) to (23) are mixed with a dispersant / copolymer / block polymer mixture and then in a wet mill to a defined freeness of an average particle size between 0.2 to 1.0 microns be ground. Thereafter, the concentrated millbase, optionally using e.g. suitable thickening agents, dispersants, copolymers, surfactants, humectants, redispersing agents, sequestering agents and / or preservatives, and water, adjusted to the desired concentration. In order to remove any coarser components which may be present, it is advantageously possible to filter the finished ink through a microsieve of approximately 1 μm.

Das erfindungsgemässe Verfahren zum Bedrucken von textilen Fasermaterialien kann mit an und für sich bekannten für den textilen Druck geeigneten Tintenstrahldruckern ausgeführt werden.The process according to the invention for printing textile fiber materials can be carried out with ink jet printers which are known per se and suitable for textile printing.

Im Falle des Tintenstrahldruck-Verfahrens werden einzelne Tropfen der Tinte kontrolliert aus einer Düse auf das Substrat gespritzt. Überwiegend werden hierzu die kontinuierliche Ink-Jet-Methode sowie die Drop on demand-Methode verwendet. Im Falle der kontinuierlichen Ink-Jet-Methode werden die Tropfen kontinuierlich erzeugt, wobei die nicht für den Druck benötigte Tropfen in einen Auffangbehälter abgeleitet und in der Regel rezykliert werden. Im Falle der Drop on demand-Methode hingegen werden die Tropften nach Wunsch erzeugt und gedruckt, d.h. es werden nur dann Tropfen erzeugt, wenn dies für den Druck erforderlich ist. Die Erzeugung der Tropfen kann z.B. vorteilhafterweise mittels eines Piezo-Inkjet-Kopfes oder mittels thermischer Energie (sog. Bubble Jet) erfolgen. Bevorzugt ist für das erfindungsgemässe Verfahren der Druck nach der kontinuierlichen Ink-Jet-Methode oder der Drop on demand-Methode.In the case of the ink-jet printing method, individual drops of the ink are injected in a controlled manner from a nozzle onto the substrate. For this purpose, the continuous ink-jet method and the drop-on-demand method are predominantly used. In the case of the continuous ink-jet method, the drops are generated continuously, wherein the non-pressure required for the drops are discharged into a collecting container and recycled as a rule. In the case of the drop on demand method, however, the drips are created as desired and printed, ie only drops are produced when required for printing. The generation of the drops can be carried out, for example, advantageously by means of a piezo-inkjet head or by means of thermal energy (so-called bubble jet). For the process according to the invention, printing by the continuous ink-jet method or the drop-on-demand method is preferred.

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

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

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

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

Bevorzugt sind polyesterhaltige Fasermaterialien.
Als polyesterhaltige Fasermaterialien kommen solche Materialien in Betracht, die ganz oder teilweise aus Polyester bestehen. Beispiele sind Celluloseesterfasern, wie z.B. Cellulose-21/2-acetatfasern und -triacetatfasern, und besonders lineare Polyesterfasem, die gegebenenfalls auch sauer modifiziert sind, welche z.B. durch Kondensation von Terephthalsäure mit Ethylenglykol oder von Isophthalsäure oder Terephthalsäure mit 1,4-Bis(hydroxymethyl) cyclohexan erhalten werden, sowie Fasern aus Mischpolymeren von Terephthal- und Isophthalsäure mit Ethylenglykol. Geeignet sind weiter polyesterhaltige Mischfasermaterialien, d.h. Mischungen aus Polyester und anderen Fasern.Preference is given to polyester-containing fiber materials.
Suitable polyester-containing fiber materials are those materials which consist wholly or partly of polyester. Examples are Celluloseesterfasern such as cellulose-2 1/2 acetate and triacetate fibers, polyester fibers, and especially linear, optionally also acid-modified which, for example (by condensation of terephthalic acid with ethylene glycol or of isophthalic acid or terephthalic acid with 1,4-bis hydroxymethyl) cyclohexane, as well as fibers of copolymers of terephthalic and isophthalic acid with ethylene glycol. Also suitable are polyester-containing mixed fiber materials, ie mixtures of polyester and other fibers.

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

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

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

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

Beispiel: (nicht erfindungsgemäß) Example: (not according to the invention)

2,0 Gewichtsteile des Dispersionsfarbstoffes der Formel

Figure imgb0027
werden mit

  • 0,3 Gewichtsteilen eines Dispergators auf Basis eines sulfonierten Kondensationsproduktes aus Chlormethyldiphenyl-Isomerengemisch und Naphthalin und
  • 3,0 Gewichtsteilen eines anionischen Copolymers aus Acrylsäure und Styrol, angerührt und anschliessend in einer Nassmühle zu einer durchschnittlichen Partikelgrösse von 0,2 bis 1,0 µm vermahlen. Danach wird durch unter gutem Rühren erfolgte Zugabe von
  • 1,0 Gewichtsteil eines handelsüblichen Tensids,
  • 3,7 Gewichtsteilen eines handelsüblichen Redispergiermittels,
  • 0,2 Gewichtsteilen eines handelsüblichen Konservierungsmittels,
  • 20,0 Gewichtsteilen eines handelsüblichen Feuchthaltemittels und
  • 69,8 Gewichtsteilen Wasser
die Tinte auf ein Farbstoffgehalt von 2 Gewichtsprozent eingestellt.2.0 parts by weight of the disperse dye of the formula
Figure imgb0027
 be with
  • 0.3 parts by weight of a dispersant based on a sulfonated condensation product of Chlormethyldiphenyl isomer mixture and naphthalene and
  • 3.0 parts by weight of an anionic copolymer of acrylic acid and styrene, stirred and then ground in a wet mill to an average particle size of 0.2 to 1.0 microns. It is then added by stirring with good stirring
  • 1.0 part by weight of a commercially available surfactant,
  • 3.7 parts by weight of a commercial redispersant,
  • 0.2 parts by weight of a commercial preservative,
  • 20.0 parts by weight of a commercial humectant and
  • 69.8 parts by weight of water
the ink is adjusted to a dye content of 2% by weight.

Beispiel : (nicht erfindungsgemäß) Example: (not according to the invention)

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

Man erhält ebenfalls einen brillanten gelben Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten, wenn man den getrockneten Druck 1 Minute mit einem Heissluft von 200° C fixiert.Likewise, a brilliant yellow print having good fastness properties, in particular wet fastnesses and light fastnesses, is obtained when the dried print is fixed for 1 minute with a hot air at 200 ° C.

Beispiel 1: (erfindungsgemäß) Example 1: (according to the invention)

3,0 Gewichtsteile des Dispersionsfarbstoffes der Formel

Figure imgb0028
werden mit

  • 2,0 Gewichtsteilen eines Dispergators auf Basis eines sulfonierten Kondensationsproduktes aus Chlormethyldiphenyl-Isomerengemisch und Naphthalin und
  • 6,5 Gewichtsteilen eines anionischen Copolymers aus Acrylsäure und Styrol (®Narlex DX2020 der Firma National Starch & Chemical),
    angerührt und anschliessend in einer Nassmühle zu einer durchschnittlichen Partikelgrösse von 0,2 bis 1,0 µm vermahlen. Danach wird durch unter gutem Rühren erfolgte Zugabe von 12,0 Gewichtsteilen Glyzerin 85%-ig,
  • 5,0 Gewichtsteilen Diethylenglykol,
  • 3,0 Gewichtsteilen Betain Monohydrat,
  • 0,1 Gewichtsteilen N-Hydroxymethylchloracetamid und
  • 68,4 Gewichtsteilen Wasser
die Tinte auf ein Farbstoffgehalt von 3 Gewichtsprozent eingestellt.3.0 parts by weight of the disperse dye of the formula
Figure imgb0028
 be with
  • 2.0 parts by weight of a dispersant based on a sulfonated condensation product of Chlormethyldiphenyl isomer mixture and naphthalene and
  • 6.5 parts by weight of an anionic copolymer of acrylic acid and styrene ( ® Narlex DX2020 from National Starch & Chemical),
    stirred and then ground in a wet mill to an average particle size of 0.2 to 1.0 micron. Thereafter, with vigorous stirring, addition of 12.0 parts by weight of glycerol is 85% pure,
  • 5.0 parts by weight of diethylene glycol,
  • 3.0 parts by weight of betaine monohydrate,
  • 0.1 parts by weight of N-hydroxymethylchloroacetamide and
  • 68.4 parts by weight of water
the ink is adjusted to a dye content of 3% by weight.

Beispiel 2: (erfindungsgemäß) Example 2: (according to the invention)

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

Beispiel: (nicht erfindungsgemäß) Example: (not according to the invention)

2,0 Gewichtsteile des Dispersionsfarbstoffes der Formel

Figure imgb0029
werden mit

  • 1,0 Gewichtsteilen eines Dispergators auf Basis eines sulfonierten Kondensationsproduktes aus Chlormethyldiphenyl-Isomerengemisch und Naphthalin und
  • 0,3 Gewichtsteilen eines nichtinogenen Alkylenoxid-Blockpolymeren (®Pluronic F108 der Firma Albright & Wilson)
    angerührt und anschliessend in einer Nassmühle zu einer durchschnittlichen Partikelgrösse von 0,2 bis 1,0 µm vermahlen. Danach wird durch unter gutem Rühren erfolgte Zugabe von 12,0 Gewichtsteilen Glyzerin 85%-ig,
  • 5,0 Gewichtsteilen Diethylenglykol,
  • 3,0 Gewichtsteilen Betain Monohydrat,
  • 0,1 Gewichtsteilen N-Hydroxymethylchloracetamid und
  • 76,6 Gewichtsteilen Wasser
die Tinte auf ein Farbstoffgehalt von 2 Gewichtsprozent eingestellt.2.0 parts by weight of the disperse dye of the formula
Figure imgb0029
 be with
  • 1.0 parts by weight of a dispersant based on a sulfonated condensation product of chloromethyldiphenyl isomer mixture and naphthalene and
  • 0.3 parts by weight of a non-ionic alkylene oxide block polymer ( ® Pluronic F108 from Albright & Wilson)
    stirred and then ground in a wet mill to an average particle size of 0.2 to 1.0 micron. Thereafter, with vigorous stirring, addition of 12.0 parts by weight of glycerol is 85% pure,
  • 5.0 parts by weight of diethylene glycol,
  • 3.0 parts by weight of betaine monohydrate,
  • 0.1 parts by weight of N-hydroxymethylchloroacetamide and
  • 76.6 parts by weight of water
the ink is adjusted to a dye content of 2% by weight.

Beispiel : (nicht erfindungsgemäß) Example : (not according to the invention)

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

Man erhält ebenfalls einen blauen Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten, wenn man den getrockneten Druck 1 Minute mit einem Heissluft von 200° C fixiert.It also gives a blue print with good fastness properties, especially wet and light fastness, if the dried pressure for 1 minute with a hot air of 200 ° C fixed.

Beispiel: (nicht erfindungsgemäß) Example: (not according to the invention)

1,2 Gewichtsteile des Dispersionsfarbstoffes der Formel

Figure imgb0030
und

  • 2,2 Gewichtsteile des Dispersionsfarbstoffes der Formel
    Figure imgb0031
werden mit
  • 1,0 Gewichtsteilen eines Dispergators auf Basis eines sulfonierten Kondensationsproduktes aus Chlormethyldiphenyl-Isomerengemisch und Naphthalin
    angerührt und anschliessend in einer Nassmühle zu einer durchschnittlichen Partikelgrösse von 0,2 bis 1,0 µm vermahlen. Danach wird durch unter gutem Rühren erfolgte Zugabe von 12,0 Gewichtsteilen Glyzerin 85%-ig,
  • 5,0 Gewichtsteilen Diethylenglykol,
  • 3,0 Gewichtsteilen Betain Monohydrat,
  • 0,1 Gewichtsteilen N-Hydroxymethylchloracetamid und
  • 75,5 Gewichtsteilen Wasser
die Tinte auf ein Farbstoffgehalt von 3,4 Gewichtsprozent eingestellt.1.2 parts by weight of the disperse dye of the formula
Figure imgb0030
 and
  • 2.2 parts by weight of the disperse dye of the formula
    Figure imgb0031
be with
  • 1.0 parts by weight of a dispersant based on a sulfonated condensation product of chloromethyldiphenyl isomer mixture and naphthalene
    stirred and then ground in a wet mill to an average particle size of 0.2 to 1.0 micron. Thereafter, with vigorous stirring, addition of 12.0 parts by weight of glycerol is 85% pure,
  • 5.0 parts by weight of diethylene glycol,
  • 3.0 parts by weight of betaine monohydrate,
  • 0.1 parts by weight of N-hydroxymethylchloroacetamide and
  • 75.5 parts by weight of water
the ink is adjusted to a dye content of 3.4% by weight.

Beispiel: (nicht erfindungsgemäß) Example: (not according to the invention)

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

Man erhält ebenfalls einen rosa-roten Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten, wenn man den getrockneten Druck 1 Minute mit einem Heissluft von 200° C fixiert.It also gives a pink-red print with good fastness properties, especially wet and light fastness, if the dried pressure for 1 minute with a hot air of 200 ° C fixed.

Beispiel 3: (erfindungsgemäß) Example 3: (according to the invention)

4,0 Gewichtsteile des Dispersionsfarbstoffes der Formel

Figure imgb0032
werden mit

  • 2,0 Gewichtsteilen eines Dispergators auf Basis eines sulfonierten Kondensationsproduktes aus Chlormethyldiphenyl-Isomerengemisch und Naphthalin,
  • 1,0 Gewichtsteilen eines nichtinogenen Alkylenoxid-Blockpolymeren (®Pluronic F108 der Firma Albright & Wilson), und
  • 8,0 Gewichtsteilen eines anionischen Copolymers aus Acrylsäure und Styrol (®Narlex DX2020 der Firma National Starch & Chemical),
    angerührt und anschliessend in einer Nassmühle zu einer durchschnittlichen Partikelgrösse von 0,2 bis 1,0 µm vermahlen. Danach wird durch unter gutem Rühren erfolgte Zugabe von 5,0 Gewichtsteilen Glyzerin 85%-ig,
  • 15,0 Gewichtsteilen Diethylenglykol,
  • 2,0 Gewichtsteilen Betain Monohydrat,
  • 0,1 Gewichtsteilen N-Hydroxymethylchloracetamid und
  • 62,9 Gewichtsteilen Wasser
die Tinte auf ein Farbstoffgehalt von 2 Gewichtsprozent eingestellt.4.0 parts by weight of the disperse dye of the formula
Figure imgb0032
 be with
  • 2.0 parts by weight of a dispersant based on a sulfonated condensation product of chloromethyldiphenyl isomer mixture and naphthalene,
  • 1.0 parts by weight of a non-ionic alkylene oxide block polymer ( ® Pluronic F108 from Albright & Wilson), and
  • 8.0 parts by weight of an anionic copolymer of acrylic acid and styrene ( ® Narlex DX2020 from National Starch & Chemical),
    stirred and then ground in a wet mill to an average particle size of 0.2 to 1.0 micron. Thereafter, with vigorous stirring, addition of 5.0 parts by weight of glycerol is 85% pure,
  • 15.0 parts by weight of diethylene glycol,
  • 2.0 parts by weight of betaine monohydrate,
  • 0.1 parts by weight of N-hydroxymethylchloroacetamide and
  • 62.9 parts by weight of water
the ink is adjusted to a dye content of 2% by weight.

Beispiel 4: (erfindungsgemäß) Example 4: (according to the invention)

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

Man erhält ebenfalls einen violetten Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten, wenn man den getrockneten Druck 1 Minute mit einem Heissluft von 200° C fixiert.One also obtains a violet print with good fastness properties, especially wet and light fastness, when the dried pressure for 1 minute with a hot air of 200 ° C fixed.

Beispiel: (nicht erfindungsgemäß) Example : (not according to the invention)

4,0 Gewichtsteile des Dispersionsfarbstoffes der Formel

Figure imgb0033
werden mit

  • 1,0 Gewichtsteilen eines Dispergators auf Basis eines sulfonierten Kondensationsproduktes aus Chlormethyldiphenyl-Isomerengemisch und Naphthalin und
  • 3,0 Gewichtsteilen eines anionischen Copolymers auf Basis eines partiell sulfatierten Octylphenolethoxylates mit 25 Ethylenoxideinheiten pro 1 Mol Octylphenol (®Emulphor OPS 25 der Firma BASF)
    angerührt und anschliessend in einer Nassmühle zu einer durchschnittlichen Partikelgrösse von 0,2 bis 1,0 µm vermahlen. Danach wird durch unter gutem Rühren erfolgte Zugabe von 10,0 Gewichtsteilen Glyzerin 85%-ig,
  • 10,0 Gewichtsteilen Diethylenglykol,
  • 1,7 Gewichtsteilen Betain Monohydrat,
  • 0,1 Gewichtsteilen N-Hydroxymethylchloracetamid und
  • 70,2 Gewichtsteilen Wasser
die Tinte auf ein Farbstoffgehalt von 2 Gewichtsprozent eingestellt.4.0 parts by weight of the disperse dye of the formula
Figure imgb0033
 be with
  • 1.0 parts by weight of a dispersant based on a sulfonated condensation product of chloromethyldiphenyl isomer mixture and naphthalene and
  • 3.0 parts by weight of an anionic copolymer based on a partially sulfated octylphenol ethoxylate with 25 ethylene oxide units per 1 mol of octylphenol ( ® Emulphor OPS 25 from BASF)
    stirred and then ground in a wet mill to an average particle size of 0.2 to 1.0 micron. Thereafter, with vigorous stirring, the addition of 10.0 parts by weight of glycerol is 85% pure,
  • 10.0 parts by weight of diethylene glycol,
  • 1.7 parts by weight of betaine monohydrate,
  • 0.1 parts by weight of N-hydroxymethylchloroacetamide and
  • 70.2 parts by weight of water
the ink is adjusted to a dye content of 2% by weight.

Beispiel: (nicht erfindungsgemäß) Example: (not according to the invention)

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

Man erhält ebenfalls einen blauen Druck mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten, wenn man den getrockneten Druck 1 Minute mit einem Heissluft von 200° C fixiert.It also gives a blue print with good fastness properties, especially wet and light fastness, if the dried pressure for 1 minute with a hot air of 200 ° C fixed.

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

Werden die gemäss den Beispielen 1, 3, 5, 7, 9 und 11 hergestellten Tinten nach einer kontinuierlichen Ink-Jet-Methode auf ein Polyester-Gewebe aufgedruckt und wie oben angegeben fertiggestellt, resultieren ebenfalls Drucke mit guten Allgemeinechtheiten, insbesondere Nass- und Lichtechtheiten.If the inks prepared according to Examples 1, 3, 5, 7, 9 and 11 are printed onto a polyester fabric by a continuous ink-jet method and finished as indicated above, prints having good fastness properties, in particular wet fastnesses and light fastnesses also result ,

Claims (8)

  1. A process for printing textile fibre materials by the ink-jet printing process, wherein the fibre materials are printed with an aqueous ink comprising at least one disperse dye, an anionic copolymer based on acrylic acid, methacrylic acid or maleic acid, and a betaine monohydrate.
  2. A process according to claim 1, wherein a disperse dye of the formula
    Figure imgb0038
     in which
    R16 is halogen, nitro or cyano, R17 is hydrogen, halogen, nitro or cyano, R18 is halogen or cyano, R19 is hydrogen, halogen, C1-C4alkyl or C1-C4alkoxy, R20 is hydrogen, halogen or acylamino, and R21 and R22 independently of one another are hydrogen or are C1-C4alkyl which is unsubstituted or substituted by hydroxyl, cyano, acetoxy or phenoxy,
    Figure imgb0039
     in which
    R23 is hydrogen, phenyl or phenylsulfoxy, the benzene ring in phenyl and phenylsulfoxy being unsubstituted or substituted by C1-C4alkyl, sulfo or C1-C4alkylsulfo, R25 is unsubstituted or C1-C4alkyl-substituted amino or hydroxyl, R26 is hydrogen or C1-C4alkoxy,
    R27 is hydrogen or the radical -O-C6H5-SO2-NH-(CH2)3-O-C2H5, R36 is hydrogen, hydroxyl or nitro and R37 is hydrogen, hydroxyl or nitro.
  3. A process according to claim 1, wherein the anionic copolymer used is a copolymer of acrylic and/or methacrylic acid with one or more copolymerizable monomers from the group consisting of maleic acid, N-vinylformamide, N-vinylacetamide, allylamine and diallylamine derivatives, N-vinylpyrrolidone, N-vinyl-N-methylformamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, vinyl acetate, vinyl propionate, acrylonitrile, styrene, methacrylonitrile, acrylamide, methacrylamide and N-mono/N,N-di-C1-C10alkyl(meth)acrylamide.
  4. A process according to any one of claims 1 to 3, wherein the nonionic block polymer used is also additionally an alkylene oxide condensate or a block polymer obtainable by addition of styrene onto polypropylene oxide and/or polyethylene oxide.
  5. A process according to any one of claims 1 to 4, wherein the dispersant used is also additionally an anionic dispersant from the group consisting of
    (ba) acidic esters or their salts of alkylene oxide adducts of the formula
    Figure imgb0040
     in which
    X is the acid radical of an inorganic, oxygen-containing acid or else the radical of an organic acid, Y is C1-C12alkyl, aryl or aralkyl,
    "Alkylen" is the ethylene radical or propylene radical, and m is from 1 to 4 and n is from 4 to 50,
    (bb) polystyrenesulfonates,
    (bc) fatty acid taurides,
    (bd) alkylated diphenyl oxide mono- or disulfonates,
    (be) sulfonates of polycarboxylic esters,
    (bf) an adduct of from 1 to 60 mol of ethylene oxide and/or propylene oxide with fatty amines, fatty amides, fatty acids or fatty alcohols each having 8 to 22 carbon atoms or with trihydric to hexahydric alkanols having 3 to 6 carbon atoms, the said adduct being converted into an acidic ester with an organic dicarboxylic acid or with an inorganic polybasic acid,
    (bg) ligninsulfonates,
    (bh) naphthalenesulfonates, and
    (bi) formaldehyde condensates.
  6. A process according to claim 5, wherein the dispersant used is an anionic dispersant of the formula
    Figure imgb0041
     in which
    X is a direct bond or oxygen, A is the radical of an aromatic compound and is attached to the methylene group by a ring carbon atom, M is hydrogen or a salt-forming cation, such as an alkali metal, alkaline earth metal or ammonium, and
    n and p independently of one another are a number from 1 to 4.
  7. An aqueous printing ink for the ink-jet printing process, which comprises from 1 to 35% by weight of at least one disperse dye of the formulae (1) to (23), an anionic copolymer based on acrylic acid, methacrylic acid or maleic acid, and a betaine monohydrate and a nonionic block polymer and/or a dispersant.
  8. A textile fibre material printed by the ink-jet printing process with an aqueous printing ink according to claim 7.
EP98811210A 1997-12-17 1998-12-08 Process for printing textile fibres materials according to the ink-jet printing process Expired - Lifetime EP0924335B1 (en)

Priority Applications (1)

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EP97810995 1997-12-17
EP97810995 1997-12-17
EP98811210A EP0924335B1 (en) 1997-12-17 1998-12-08 Process for printing textile fibres materials according to the ink-jet printing process

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