EP1144755B1 - Method for printing fibrous textile materials according to the ink jet printing technique - Google Patents

Method for printing fibrous textile materials according to the ink jet printing technique Download PDF

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Publication number
EP1144755B1
EP1144755B1 EP99934562A EP99934562A EP1144755B1 EP 1144755 B1 EP1144755 B1 EP 1144755B1 EP 99934562 A EP99934562 A EP 99934562A EP 99934562 A EP99934562 A EP 99934562A EP 1144755 B1 EP1144755 B1 EP 1144755B1
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EP
European Patent Office
Prior art keywords
halogen
alkyl
weight
hydrogen
ink
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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.)
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EP99934562A
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German (de)
French (fr)
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EP1144755A2 (en
EP1144755A3 (en
Inventor
Mickael Mheidle
Bénédicte GALEA
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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Publication of EP1144755A3 publication Critical patent/EP1144755A3/en
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5285—Polyurethanes; Polyurea; Polyguanides
    • 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
    • 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
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/651—Compounds without nitrogen
    • D06P1/65106—Oxygen-containing compounds
    • D06P1/65118—Compounds containing hydroxyl groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/30—Ink jet printing

Definitions

  • the present invention relates to a method for printing on textiles Fiber materials according to the inkjet printing process.
  • Inkjet printing processes have been in the textile industry for several years applied. These processes make it possible to produce a product that is otherwise customary Eliminate the printing stencil, so that considerable cost and time savings are achieved can be. Especially in the production of sample templates can be within reacted to changing needs much less time.
  • Corresponding inkjet printing processes should in particular be optimal have application properties. To be mentioned in this Relationship properties such as viscosity, stability, surface tension and Conductivity of the inks used. There are also increased quality requirements of the prints obtained, e.g. regarding color strength and wet fastness properties. These requirements are not met by all of the known methods Properties fulfilled, so that there is still a need for new processes for the textile Inkjet printing exists.
  • the dyes of the formulas are of particular interest as pigment dyes and
  • pigment Yellow 7 C.I. Pigment Black 7, C.I. Pigment Red 101, C.I. Pigment Yellow 17, C.I. Pigment Yellow 34, C.I. Pigment Yellow 83 and C.I. pigment Yellow 128.
  • the pigment dyes mentioned are known or can be analogous to known Manufacturing processes such as diazotization, coupling, addition and condensation reactions, be preserved.
  • the pigment dye binders are dispersible in water or preferably in water soluble. Examples include Carboset® 531 and Sancure® AU-4010 from BFGoodrich called.
  • the polymers considered as binders have no sulfo or sulfato groups.
  • the inks preferably contain a total dye content of 1 to 35% by weight, in particular 1 to 30 wt .-% and preferably 1 to 20 wt .-%, based on the Total ink weight.
  • the lower limit here is a limit of 2.5% by weight, in particular 5% by weight and preferably 10% by weight, preferred.
  • the pigment dye binder is preferably in an amount of 2 to 30 in the ink % By weight, in particular in an amount of 5 to 20% by weight.
  • Preferred inks for the process according to the invention are those which have a viscosity from 1 to 40 mPa ⁇ s (millipascal second), in particular 1 to 20 mPa ⁇ s and preferably 1 up to 10 mPa ⁇ s.
  • Inks with a viscosity of. are of particular importance 2 to 5 mPa ⁇ s. Also important are inks with a viscosity of 10 up to 30 mPa ⁇ s.
  • the inks can include in order to adjust the viscosity, natural or thickener contain synthetic origin.
  • thickeners are commercial alginate thickeners, starch ethers or called locust bean gum ether. Cellulose ethers may also be mentioned.
  • cellulose ether come e.g. Methyl, ethyl, carboxymethyl, hydroxyethyl, Methythydroxyäthyl-, hydroxypropyl or hydroxypropylmethyl cellulose into consideration. Carboxymethyl cellulose and hydroxypropyl methyl cellulose are preferred.
  • the Cellulose ethers are preferably water-soluble.
  • synthetic thickeners further e.g. those based on poly (meth) acrylic acids or poly (meth) acrylamides called.
  • alkali alginates and preferably sodium alginate come as alginates into consideration.
  • the thickeners are usually present in the ink in an amount of 0.01 to 2% by weight, in particular 0.01 to 1% by weight and preferably 0.01 to 0.5% by weight, based on the total weight of the ink used. These thickeners allow Setting a specific viscosity of the ink.
  • the inks can also contain surfactants, redispersants or humectants contain.
  • the commercially available anionic or nonionic surfactants are suitable as surfactants.
  • a redispersant e.g. Mention betaine.
  • the pigment dyes are expediently used in dispersed form.
  • the customary dispersants preferably nonionic dispersants can be used.
  • Suitable components (ca) are polyadducts of 4 to 40 moles of ethylene oxide with 1 mole of a phenol which has at least one C 4 -C 12 alkyl group, a phenyl group; has a tolyl group, an a-tolylethyl group, a benzyl group, an a-methylbenzyl group or an a, a-dimethylbenzyl group, such as butylphenol, tributylphenol, octylphenol, ncnylphenol, dinonylphenol, o-phenylphenol, benzylphenol, dibenzylphenol, d-tolylylphenol, (nonyl) phenol, a-methylbenrylphenol, bis (a-methylbenzyl) phenol or tris (amethylbenzyl) phenol, which adducts can be used individually or in a mixture.
  • Adducts of 6 to 30 moles of ethylene oxide are of particular interest as component (ca) 1 mol of 4-nonylphenol, 1 mol of dinonylphenol or especially 1 mol of compounds, which are prepared by adding 1 to 3 moles of styrenes to 1 mole of phenols.
  • the styrene addition products are preferably produced in a known manner in Presence of catalysts such as sulfuric acid, p-totoluenesulfonic acid or especially zinc chloride.
  • catalysts such as sulfuric acid, p-totoluenesulfonic acid or especially zinc chloride.
  • styrenes are styrene, a-methylstyrene or vinyl toluene (4-methylstyrene).
  • the phenols are phenol, cresols or xylenols.
  • Ethylene oxide adducts of the formula (21) are very particularly preferred wherein m 3 is 1 to 3 and n 3 is 8 to 30.
  • Ethylene oxide adducts of the formula are also preferred wherein Y 2 is C 4 -C 12 alkyl, phenyl, tolyl, tolyl-C 1 -C 3 alkyl or phenyl-C 1 -C 3 alkyl, such as a-methyl or a, a-dimethylbenzyl, and m 2 are 1 to 3 and n 2 4 to 40.
  • Preferred components (cc) are ethylene oxide adducts with polypropylene oxide (so-called EO-PO block polymers) and propylene oxide adducts with polyethylene oxide (so-called reverse EO-PO block polymers).
  • Ethylene oxide-propylene oxide block polymers with molecular weights are particularly preferred the polypropylene oxide base from 1700 to 4000 and an ethylene oxide content in the whole molecule from 30-80%, especially 60-80%.
  • dispersants based on naphthalene sulfonates are also of interest.
  • the inks particularly preferably contain humectants, usually in an amount from 2 to 30% by weight, in particular 5 to 30% by weight and preferably 5 to 25% by weight, based on the total weight of the ink.
  • humectants polyhydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, With tetraethylene glycol, propylene glycol, dipropylene glycol, glycerin and polyethylene glycols a molecular weight of preferably 200 to 800.
  • Glycerin propylene glycol or diethylene glycol are of interest. Is particularly interesting Propylene glycol or a mixture of diethylene glycol and glycerin e.g. in one Weight ratio of 10: 1 to 1:10, preferably 5: 1 to 1: 5 and in particular 3: 1 to 1: 3.
  • the inks can also be acid donors such as butyrolactone or Sodium hydrogen phosphate, preservative, fungal and / or bacterial growth inhibiting substances, foam suppressants, wetting agents, sequestering agents, emulsifiers, contain water-insoluble solvents, oxidizing agents or deaerating agents.
  • Suitable preservatives are, above all, formaldehyde-releasing agents, such as, for example, paraformaldehyde and trioxane, especially aqueous, approximately 30 to 40 percent by weight formaldehyde solutions, and sequestering agents, for example sodium nitrilotriacetic acid, sodium ethylenediaminetetraacetic acid, especially sodium polymethaphosphate, in particular sodium hexamethaphosphate, as emulsifiers especially adducts of an alkylene oxide and a fatty alcohol, especially an adduct of oleyl alcohol and ethylene oxide, as a water-insoluble solvent, high-boiling, saturated hydrocarbons, especially paraffins with a boiling range of about 160 to 210 ° C (so-called mineral spirits), as an oxidizing agent, for example an aromatic nitro compound , especially an aromatic mono- or dinitrocarboxylic acid or sulfonic acid, which is optionally present as an alkylene oxide ad
  • constituents of the ink are chemicals such as alkali in amounts of e.g. 0.1 to 5 wt .-%, in particular 0.5 to 2 wt .-%, called.
  • alkali aqueous ammoniacal solutions and dimethylethanolamine should be mentioned.
  • the inks can be mixed in the usual way for pigment dyes
  • Ingredients can be prepared in the desired amount of water.
  • the pigment particles preferably have a defined grain spectrum in the finished ink and should in particular a certain grain size, e.g. 10 ⁇ m, in particular 5 ⁇ m, is not exceed.
  • the pigment particles preferably have an average grain size of 1 ⁇ m or less.
  • a defined com spectrum can be obtained, for example, if the pigments are ground wet and the com spectrum continuously Laser size analysis is monitored.
  • the method according to the invention for printing on textile fiber materials can also be used performed on inkjet printers known per se and suitable for textile printing become.
  • fiber materials containing hydroxyl groups come as textile fiber materials into consideration.
  • As further fiber materials be wool, silk, polyvinyl, polyacrylonitrile, polyamide, aramid, polypropylene and Called polyurethane.
  • the fiber materials mentioned are preferably flat textile fabrics, knitted fabrics or webs.
  • the fiber material is advantageously dried, preferably at temperatures up to 150 ° C, especially 80 to 120 ° C, and then the pressure fixed.
  • Fixing the pressure can e.g. by heat treatment, which is preferably carried out at a temperature of 120 to 190 ° C.
  • the fixation takes place preferably 1 to 8 minutes.
  • fixation can also be carried out with ionizing radiation or by irradiation with UV light respectively.
  • the printed or dyed fiber material is advantageously at elevated temperature, e.g. between 40 and 120 ° C, in particular between 60 and 100 ° C, irradiated and fixed.
  • elevated temperature e.g. between 40 and 120 ° C, in particular between 60 and 100 ° C
  • the irradiation can take place either immediately after the drying process, or you can also print the cold printed fiber material to the desired one before irradiation Warm temperature, e.g. in an infrared heater.
  • Ionizing radiation is to be understood to mean radiation which has an ionization chamber can be demonstrated. It consists of either electrically charged, Directly ionizing particles, which generate ions in gases along their path by impact or from uncharged, indirectly ionizing particles or photons that are in matter directly generate ionizing charged secondary particles like the secondary electrons of X-ray or ⁇ -rays or the recoil nuclei (especially protons) of fast neutrons; Also indirectly ionizing particles are slow neutrons that pass through Nuclear reactions partly direct, partly via photons from ( ⁇ , ⁇ ) processes with high energy can generate charged particles. Protons come as heavy charged particles, Atomic nuclei or ionized atoms. Of particular importance for the inventive Process are lightly charged particles, e.g. Electrons. As x-rays both the bremsstrahlung and the characteristic radiation come in Consideration. The ⁇ radiation is an important particle radiation of heavily charged particles called.
  • the ionizing radiation can be generated by one of the customary methods. For example, spontaneous core transformations as well as nuclear reactions (forced Core transformations) can be used for generation. Coming as sources of radiation corresponding to natural or artificial radioactive substances and especially nuclear reactors in Consideration. The radioactive fission products resulting from nuclear fission in such reactors represent another important source of radiation.
  • Another possible method of generating radiation is by means of an x-ray tube.
  • Electron beams are of particular importance for the method of the present invention. These are generated by accelerating and concentrating electrons, which are emitted from a cathode by glow, field or photoemission as well as by electron or ion bombardment. Radiation sources are conventional electron guns and accelerators. Examples of radiation sources are known from the literature, for example the International Journal of Electron Beam & Gamma Radiation Processing, in particular 1/89 pages 11-15; Optik, 77 (1987), pages 99-104.
  • ⁇ -emitters e.g. the strontium-90 into consideration.
  • the ⁇ -rays are also technically advantageously applicable ionizing rays called, which can be easily produced in particular with cesium-137 or cobalt-60 isotope sources are.
  • the fixation with ionizing radiation is usually carried out in such a way that a printed and dried textile fiber material by the beam of an electron accelerator is carried out at temperatures between 60 and 100 ° C. This happens with such a speed that a certain radiation dose is reached.
  • the radiation doses normally to be used are between 0.1 and 15 Mrad an accelerator voltage between 160 and 300 kV, the radiation dose being advantageous is between 0.1 and 4 Mrad. At a dose less than 0.1 Mrad is generally the degree of fixation too low, damage often occurs at a dose of more than 15 Mrad of the fiber material and the dye.
  • Embodiment especially according to the type of ionizing radiation to be used and their mode of production. For example, if the printed fiber material with ⁇ rays are irradiated, this is enclosed in a cell exposed to the radiation. If higher radiation doses are desired with low radiation intensity, this can be done material to be irradiated are exposed to the radiation in several passes.
  • photoinitiator When using ultraviolet radiation, it is usually necessary to have a photoinitiator.
  • the photoinitiator absorbs the radiation to generate free radicals that initiate the polymerization.
  • photoinitiators or photoinitiators used according to the invention are carbonyl compounds such as 2,3-hexanedione.
  • Diacetylacetophenone, benzoin and benzoin ethers such as dimethyl, ethyl and butyl derivatives, for example 2,2-diethoxyacetophenone and 2,2-dimethoxyacetophenone, benzophenone or a benzophenone salt and phenyl (1-hydroxycyclohexyl) ketone or a ketone of the formula
  • Benzophenone in combination with a catalyst such as triethylamine, N, N'-dibenrylamine and dimethylaminoethanol and benzophenone plus Michler's ketone; acylphosphine oxides; nitrogen-containing compounds such as diazomethane, azo-bis-isobutyronitrile, hydrazine, phenylhydrazine as well as trimethylbenzylammonium chloride; and sulfur-containing compounds such as Benzenesulfonate, diphenyl disulfide and tetramethylthiuram disulfide, as well as those containing phosphorus Connections such as Phosphine oxides.
  • a catalyst such as triethylamine, N, N'-dibenrylamine and dimethylaminoethanol and benzophenone plus Michler's ketone
  • acylphosphine oxides such as diazomethane, azo-bis-isobutyronitrile, hydra
  • the proportion of photoinitiators in the applied coloring components directly before the irradiation is 0.01-20%, preferably 0.1-5%, based on the total amount of colorless polymerizable compounds used.
  • Cationic photoinitiators such as triarylsulfonium salts, diaryliodonium salts, Diaryle complexes or general structures as described in “Chemistry & Technology of UV & EB Formulation for coatings, inks & paints "Volume 3, published by SITA Technology Ltd., Gardiner House, Broomhill Road, London, 1991.
  • Acylphosphine oxides such as. B. (2,4,6 trimethylbenzoyl) (diphenyl) phosphine oxide, or photoinitiators of the formula used or a photoinitiator of the formula together with a photoinitiator of the two aforementioned formulas or a photoinitiator of the formula or benzophenone together with a photoinitiator of the above three formulas.
  • photoinitiators are very particularly preferably used: as well as the mixture of the compounds of the formulas in a weight ratio of 50:50 to 10:90 and the mixture of the compound of the formula and 2,4,6-trimethylbenzoyldiphenylphosphine in a weight ratio of 20:80 to 60:40.
  • the UV light to be used is radiation whose emission is between 200 and 450 nm, in particular between 210 and 400 nm.
  • the radiation is preferred Artificially with high, medium or low pressure mercury vapor lamps, halogen lamps, Metal halide, xenon or tungsten lamps, carbon arc or fluorescent lamps, H and D lamps, superactin fluorescent tubes and lasers.
  • Capillary high-pressure mercury lamps or high-pressure mercury lamps are advantageous or low pressure mercury lamps are used.
  • high-pressure mercury lamps and medium-pressure mercury lamps which also e.g. can be doped with iron or gallium halide.
  • This Lamps can also be operated with microwaves or pulsed to operate Concentrate radiation in peaks. Pulsed operation is also possible with xenon lamps, if you need a higher proportion of boring UV light.
  • UV radiation sources are as described in "Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints”, Volume 1, published by SITA Technology, Gardiner House, Broomhill Road, London, 1991.
  • the exact exposure time of the prints will depend on the luminosity of the UV source, the distance from the light source, the type and amount of photoinitiator and the permeability the formulation and the textile substrate for UV light.
  • Usual irradiation times with the UV light are 1 second to 20 minutes, preferably 5 seconds to 2 minutes.
  • the fixation can be done by interrupting the light be ended so that it can also be carried out discontinuously.
  • the radiation can be in the atmosphere of an inert protective gas, e.g. under nitrogen be performed to prevent inhibition by oxygen.
  • the oxygen inhibition can also be effective by adding so-called "anti-blocking agents" that are amines and especially amino acrylates.
  • the printed fiber material can be washed out in the usual way and be dried
  • Ink-jet printing as well as the subsequent drying and fixing can can also be carried out in a single step. This means in particular that these steps are carried out continuously. That that successive apparatuses for the ink-jet printing, drying and fixation by which this is done printing fiber material is continuously moved through.
  • the equipment for the Ink-jet printing, drying and fixing can also be done in a single machine be united. The fiber material is continuously transported through this machine and is then finished after leaving this machine.
  • the drying can e.g. by means of thermal energy (such as specified above) or in particular by means of infrared radiation (IR).
  • the fixation can e.g. such as. given above.
  • ink-jet printing can also be done separately and drying and Fixations are continuous as indicated above, e.g. in a single machine, executed.
  • a flat fiber material on both sides.
  • one side of the fiber material is printed in one shade, e.g. all over, and the other side of the fiber material is made with a pattern in one or more of each other different shades printed.
  • this page can of course also can also be printed on the entire surface in one shade.
  • Such a method can e.g. so be carried out on each side of the flat fibrous material to be printed or more printheads are available. It then becomes both sides of the fiber material printed at the same time.
  • the print heads on the respective side of the fiber material can be stand directly opposite or installed laterally offset from each other. The fiber material is usually moved between these print heads.
  • Another interesting embodiment relates to the so-called imaging.
  • a template i.e. digitized an image to be reproduced with the print, e.g. using a video camera or a scanner.
  • the digitized image is on one Transfer computer, which then uses an inkjet printer to transfer the image onto the Fiber material prints.
  • the digitized image can already be found in the Computers are stored so that digitization is not necessary.
  • one can be printed Picture e.g. have been created on the computer with graphics software.
  • At the one to be printed Picture it can e.g. also letters, numbers, words, any pattern or deal with complex, different-colored images. Different colored images can e.g. by Using multiple inks with different shades can be created.
  • the prints obtainable by the process according to the invention have good general fastness properties on; e.g. they have good light fastness, good wet fastness properties, such as Water, wash, sea water, over-dyeing and perspiration fastness, good chlorine fastness, Rubbing fastness, ironing fastness and pleating fastness as well as sharp contours and a high Color strength.
  • the printing inks used are characterized by good stability and good viscosity properties out.
  • parts are parts by weight and percentages percentages by weight, unless otherwise noted. Parts by weight relate to parts by volume in the ratio of kilograms to liters.
  • a cotton fabric is containing A with an aqueous ink 5% by weight of the pigment dye of the formula 10% by weight of a commercial polyacrylate binder (Carboset® 531) present in water in dispersed form, 2% by weight of a commercially available polyurethane acrylate binder (Sancure® AU-4010) present in water in dispersed form, 15% by weight diethylene glycol, 5% by weight glycerol, 2% by weight of a commercially available defoaming agent, and 61% by weight of water, printed with a drop-on-demand piezo inkjet head.
  • the print is dried completely and then fixed at 190 ° C for 90 seconds. You get a print with good general fastness properties.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coloring (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)
  • Treatment Of Fiber Materials (AREA)

Abstract

A method for printing fibrous textile materials according to the ink-jet printing technique, which method includes printing the fibrous materials with an aqueous ink includinga) a pigment dyeb) a water-dispersible or water-soluble mixture of pigment dye binders wherein one component of the mixture is based on the polymerization product of acrylic acid and another component of the mixture is based on the polymerization product of acrylic acid and urethane, andc) glycerol, propylene glycol or diethylene glycol.

Description

Die vorliegende Erfindung betrifft ein Verfahren zum Bedrucken von textilen Fasermaterialien nach dem Tintenstrahldruck-Verfahren.The present invention relates to a method for printing on textiles Fiber materials according to the inkjet printing process.

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 in the textile industry for several years applied. These processes make it possible to produce a product that is otherwise customary Eliminate the printing stencil, so that considerable cost and time savings are achieved can be. Especially in the production of sample templates can be within reacted to changing needs much less time.

Entsprechende Tintenstrahldruck-Verfahren sollten insbesondere optimale anwendungstechnische Eigenschaften aufweisen. Zu erwähnen seien in diesem Zusammenhang Eigenschaften wie die Viskosität, Stabilität, Oberflächenspannung und Leitfähigkeit der verwendeten Tinten. Ferner werden erhöhte Anforderungen an die Qualität der erhaltenen Drucke gestellt, wie z.B. bezüglich Farbstärke 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.Corresponding inkjet printing processes should in particular be optimal have application properties. To be mentioned in this Relationship properties such as viscosity, stability, surface tension and Conductivity of the inks used. There are also increased quality requirements of the prints obtained, e.g. regarding color strength and wet fastness properties. These requirements are not met by all of the known methods Properties fulfilled, so that there is still a need for new processes for the textile Inkjet printing exists.

Die US-A-5 631 071, WO A-98/20084 und die DE-A-43 28 215 offenbaren Tintenstrahldruckverfahren mit pigmenthaltigen Tinten.US-A-5 631 071, WO A-98/20084 and DE-A-43 28 215 disclose Inkjet printing process with pigment-based inks.

Gegenstand der Erfindung ist ein Verfahren zum Bedrucken von textilen Fasermaterialien nach dem Tintenstrahldruck-Verfahren, wobei diese Fasermaterialien mit einer wässrigen Tinte bedruckt werden, welche

  • a) einen Pigmentfarbstoff der Formel
    Figure 00010001
    worin
    R52 Wasserstoff, Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, Nitro oder Cyano,
    R53 Wasserstoff, Halogen, Nitro oder Cyano,
    R54 Wasserstoff, Halogen oder Phenylaminocarbonyl,
    R55 Wasserstoff oder Hydroxy, und
    R56 Wasserstoff oder ein Rest der Formel
    Figure 00020001
    ist, wobei
    R57 Wasserstoff, C1-C4-Alkyl oder C1-C4-Alkoxy,
    R58 Wasserstoff, C1-C4-Alkoxy oder Halogen, und
    R59 Wasserstoff, C1-C4-Alkyl, C1-C4-Alkoxy oder Halogen ist,
    Figure 00020002
    worin
    R60 und R61 voneinander unabhängig C1-C4-Alkyl und R62 und R63 Halogen sind,
    Figure 00020003
    wobei die Ringe A, B, D und E unsubstituiert oder ein- oder mehrfach mit Halogen substituiert sind,
    Figure 00030001
    worin
    R64 C1-C4-Alkyl,
    R65 Wasserstoff, Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, Nitro oder Cyano,
    R66 Wasserstoff, Halogen, Nitro oder Cyano,
    R67 Wasserstoff, Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, Nitro oder Cyano sind,
    Figure 00030002
    wobei die Ringe A' und B' unsubstituiert oder ein- oder mehrfach mit Halogen substituiert sind,
    Figure 00030003
    worin
    (R68)0-2 und (R68')0-2 unabhängig voneinander für 0 bis 2 Substituenten ausgewählt aus der Gruppe Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, Nitro oder Cyano stehen, und
    K1 und K2 unabhängig voneinander einen Rest der Formel
    Figure 00030004
    bedeuten, wobei
    (R69)0-3 und (R69')0-3 unabhängig voneinander für 0 bis 3 Substituenten ausgewählt aus der Gruppe Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, Nitro oder Cyano, insbesondere Halogen,
    C1-C4-Alkyl und C1-C4-Alkoxy, stehen, oder
    C.I. Pigment Yellow 34 oder C.I. Pigment Yellow 128,
    oder anorganische Pigmentfarbstoffe auf der Basis von Russ oder Eisenoxiden,
  • b) eine in Wasser dispergierbare oder in Wasser lösliche Mischung von Pigmentfarbstoffbindem, wobei eine Mischungskomponente auf dem Polymerisationsprodukt von Acrylsäure und eine weitere Mischungskomponente auf dem Polymerisationsprodukt von Acrylsäure und Urethan basiert, und
  • c) Glycerin, Propylenglykol oder Diethylenglykol enthält.
    • The invention relates to a method for printing textile fiber materials according to the ink jet printing method, wherein these fiber materials are printed with an aqueous ink, which
  • a) a pigment dye of the formula
    Figure 00010001
    wherein
    R 52 is hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro or cyano,
    R 53 is hydrogen, halogen, nitro or cyano,
    R 54 is hydrogen, halogen or phenylaminocarbonyl,
    R 55 is hydrogen or hydroxy, and
    R 56 is hydrogen or a radical of the formula
    Figure 00020001
    is where
    R 57 is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy,
    R 58 is hydrogen, C 1 -C 4 alkoxy or halogen, and
    R 59 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogen,
    Figure 00020002
    wherein
    R 60 and R 61 are independently C 1 -C 4 alkyl and R 62 and R 63 are halogen,
    Figure 00020003
    where the rings A, B, D and E are unsubstituted or mono- or polysubstituted by halogen,
    Figure 00030001
    wherein
    R 64 C 1 -C 4 alkyl,
    R 65 is hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro or cyano,
    R 66 is hydrogen, halogen, nitro or cyano,
    R 67 are hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro or cyano,
    Figure 00030002
    where the rings A 'and B' are unsubstituted or substituted one or more times with halogen,
    Figure 00030003
    wherein
    (R 68 ) 0-2 and (R 68 ') 0-2 independently of one another represent 0 to 2 substituents selected from the group halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro or cyano, and
    K 1 and K 2 independently of one another are a radical of the formula
    Figure 00030004
    mean where
    (R 69 ) 0-3 and (R 69 ') 0-3 independently of one another for 0 to 3 substituents selected from the group halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro or cyano, in particular Halogen,
    C 1 -C 4 alkyl and C 1 -C 4 alkoxy, or
    CI Pigment Yellow 34 or CI Pigment Yellow 128,
    or inorganic pigment dyes based on soot or iron oxides,
  • b) a water-dispersible or water-soluble mixture of pigment dye binders, one mixture component being based on the polymerization product of acrylic acid and another mixture component based on the polymerization product of acrylic acid and urethane, and
  • c) contains glycerin, propylene glycol or diethylene glycol.

    • Von besonderem Interesse als Pigmentfarbstoffe sind die Farbstoffe der Formeln

    Figure 00040001
    Figure 00040002
    Figure 00040003
    Figure 00050001
    Figure 00050002
    Figure 00050003
    Figure 00050004
    und
    Figure 00060001
    The dyes of the formulas are of particular interest as pigment dyes
    Figure 00040001
    Figure 00040002
    Figure 00040003
    Figure 00050001
    Figure 00050002
    Figure 00050003
    Figure 00050004
    and
    Figure 00060001

    Weitere interessante Pigmentfarbstoffe sind C.I. Pigment Black 7, C.I. Pigment Red 101, C.I. Pigment Yellow 17, C.I. Pigment Yellow 34, C.I. Pigment Yellow 83 sowie C.I. Pigment Yellow 128.Other interesting pigment dyes are C.I. Pigment Black 7, C.I. Pigment Red 101, C.I. Pigment Yellow 17, C.I. Pigment Yellow 34, C.I. Pigment Yellow 83 and C.I. pigment Yellow 128.

    Besonders bevorzugt verwendet man in dem erfindungsgemässen Verfahren als Pigmentfarbstoffe solche der Formel (7e), (7g) sowie C.I. Pigment Yellow 83 und C.I. Pigment Black 7.It is particularly preferably used as in the process according to the invention Pigment dyes of the formula (7e), (7g) and C.I. Pigment Yellow 83 and C.I. Pigment Black 7.

    Die genannten Pigmentfarbstoffe sind bekannt oder können in Analogie zu bekannten Herstellungsverfahren, wie Diazotierungs-, Kupptungs-, Additions- und Kondensationsreaktionen, erhalten werden.The pigment dyes mentioned are known or can be analogous to known Manufacturing processes such as diazotization, coupling, addition and condensation reactions, be preserved.

    Die Pigmentfarbstoffbinder sind in Wasser dispergierbar oder vorzugsweise in Wasser löslich. Als Beispiele seien Carboset® 531 und Sancure® AU-4010 der Firma BFGoodrich genannt.The pigment dye binders are dispersible in water or preferably in water soluble. Examples include Carboset® 531 and Sancure® AU-4010 from BFGoodrich called.

    In einer ganz besonderen Ausführungsform des erfindungsgemässen Verfahrens enthalten die als Binder in Betracht kommenden Polymerisate keine Sulfo- oder Sulfatogruppen.Contained in a very special embodiment of the method according to the invention the polymers considered as binders have no sulfo or sulfato groups.

    Die Tinten enthalten bevorzugt einen Gesamtgehalt an Farbstoffen von 1 bis 35 Gew.-%, insbesondere 1 bis 30 Gew.-% und vorzugsweise 1 bis 20 Gew.-%, bezogen auf das Gesamtgewicht der Tinte. Als untere Grenze ist hierbei eine Grenze von 2,5 Gew.-%, insbesondere 5 Gew.-% und vorzugsweise 10 Gew.-%, bevorzugt. The inks preferably contain a total dye content of 1 to 35% by weight, in particular 1 to 30 wt .-% and preferably 1 to 20 wt .-%, based on the Total ink weight. The lower limit here is a limit of 2.5% by weight, in particular 5% by weight and preferably 10% by weight, preferred.

    Der Pigmentfarbstoffbinder liegt in der Tinte vorzugsweise in einer Menge von 2 bis 30 Gew.-%, insbesondere in einer Menge von 5 bis 20 Gew.-%, vor.The pigment dye binder is preferably in an amount of 2 to 30 in the ink % By weight, in particular in an amount of 5 to 20% by weight.

    Bevorzugt sind für das erfindungsgemässe Verfahren solche Tinten, welche eine Viskosität von 1 bis 40 mPa·s (Millipascalsekunde), insbesondere 1 bis 20 mPa·s und vorzugsweise 1 bis 10 mPa·s aufweisen. Von besonderer Bedeutung sind Tinten, welche eine Viskosität von 2 bis 5 mPa·s aufweisen. Ferner sind Tinten von Bedeutung welche eine Viskosität von 10 bis 30 mPa·s aufweisen.Preferred inks for the process according to the invention are those which have a viscosity from 1 to 40 mPa · s (millipascal second), in particular 1 to 20 mPa · s and preferably 1 up to 10 mPa · s. Inks with a viscosity of. Are of particular importance 2 to 5 mPa · s. Also important are inks with a viscosity of 10 up to 30 mPa · s.

    Die Tinten können, u.a. zwecks Einstellung der Viskosität, Verdickungsmittel natürlicher oder synthetischer Herkunft enthalten.The inks can include in order to adjust the viscosity, natural or thickener contain synthetic origin.

    Als Beispiele für Verdickungsmittel seien handelsübliche Alginatverdickungen, Stärkeether oder Johannisbrotkernmehlether genannt. Ferner seien Celluloseäther genannt.Examples of thickeners are commercial alginate thickeners, starch ethers or called locust bean gum ether. Cellulose ethers may also be mentioned.

    Als Celluloseäther kommen z.B. Methyl-, Aethyl-, Carboxymethyl-, Hydroxyäthyl-, Methythydroxyäthyl-, Hydroxypropyl- oder Hydroxypropylmethylcellulose in Betracht. Bevorzugt sind Carboxymethylcellulose und Hydroxypropylmethylcellulose. Die Celluloseäther sind vorzugsweise wasserlöslich. Als synthetische Verdickungsmittel seien ferner z.B. solche auf Basis von Poly(meth)acrylsäuren oder Poly(meth)acrylamiden genannt. Als Alginate kommen insbesondere Alkalialginate und vorzugsweise Natriumalginat in Betracht. Die Verdickungsmittel werden in der Tinte üblicherweise in einer Menge von 0,01 bis 2 Gew.-%, insbesondere 0,01 bis 1 Gew.-% und vorzugsweise 0,01 bis 0,5 Gew.-%, bezogen auf das Gesamtgewicht der Tinte, verwendet. Diese Verdickungsmittel erlauben die Einstellung einer bestimmten Viskosität der Tinte.As cellulose ether come e.g. Methyl, ethyl, carboxymethyl, hydroxyethyl, Methythydroxyäthyl-, hydroxypropyl or hydroxypropylmethyl cellulose into consideration. Carboxymethyl cellulose and hydroxypropyl methyl cellulose are preferred. The Cellulose ethers are preferably water-soluble. As synthetic thickeners further e.g. those based on poly (meth) acrylic acids or poly (meth) acrylamides called. In particular, alkali alginates and preferably sodium alginate come as alginates into consideration. The thickeners are usually present in the ink in an amount of 0.01 to 2% by weight, in particular 0.01 to 1% by weight and preferably 0.01 to 0.5% by weight, based on the total weight of the ink used. These thickeners allow Setting a specific viscosity of the ink.

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

    Als Tenside kommen die handelsüblichen anionischen oder nichtionogenen Tenside in Betracht. Als Redispergiermittel ist z.B. Betain zu erwähnen.The commercially available anionic or nonionic surfactants are suitable as surfactants. As a redispersant e.g. Mention betaine.

    Die Pigmentfarbstoffe werden zweckmässigerweise in dispergierter Form eingesetzt. The pigment dyes are expediently used in dispersed form.

    Zur Herstellung der Farbstoffdispersionen können die üblichen Dispergiermittel, vorzugsweise nichtionogene Dispergiermittel, verwendet werden.To prepare the dye dispersions, the customary dispersants, preferably nonionic dispersants can be used.

    Als nichtionogene Dispergiermittel eignen sich insbesondere Verbindungen, welche aus der Gruppe der

  • (ca) Alkylenoxidaddukte der Formel
    Figure 00080001
    worin Y1 C1-C12-Alkyl, Aryl oder Aralkyl bedeutet,
    "Alkylen" für den Ethylenrest oder Propylenrest steht und
    m1 1 bis 4 und n1 4 bis 50 sind,
  • (cb) Alkylenoxiaddukte an
  • (cba) gesättigte oder ungesättigte 1-6-wertige aliphatische Alkohole,
  • (cbb) Fettsäuren,
  • (cbc) Fettamine,
  • (cbd) Fettamide,
  • (cbe) Diamine,
  • (cbf) Sorbitanester,
  • (cc) Alkylenoxid-Kondensationsprodukte (Blockpolymerisate)
  • (cd) Polymerisate von Vinylpyrrolidon, Vinylacetat oder Vinylalkohol und
  • (ce) Co- oder Ter-polymere von Vinylpyrrolidon mit Vinylacetat und/oder Vinylalkohol, ausgewählt sind.
    • Particularly suitable nonionic dispersants are compounds which belong to the group of
  • (ca) alkylene oxide adducts of the formula
    Figure 00080001
    wherein Y 1 is C 1 -C 12 alkyl, aryl or aralkyl,
    "Alkylene" stands for the ethylene radical or propylene radical and
    m 1 are 1 to 4 and n 1 4 to 50,
  • (cb) alkylene oxy adducts
  • (cba) saturated or unsaturated 1-6-valent aliphatic alcohols,
  • (cbb) fatty acids,
  • (cbc) fatty amines,
  • (cbd) fatty amides,
  • (cbe) diamines,
  • (cbf) sorbitan esters,
  • (cc) alkylene oxide condensation products (block polymers)
  • (cd) polymers of vinyl pyrrolidone, vinyl acetate or vinyl alcohol and
  • (ce) copolymers or terpolymers of vinylpyrrolidone with vinyl acetate and / or vinyl alcohol.

    • Geeignete Komponenten (ca) sind Polyaddukte von 4 bis 40 Mol Ethylenoxid an 1 Mol eines Phenols, das mindestens eine C4-C12-Alkylgruppe, eine Phenylgruppe; eine Tolylgruppe, eine a-Tolylethylgruppe, eine Benzylgruppe, eine a-Methylbenzylgruppe oder eine a,a-Dimethylbenzylgruppe aufweist, wie z.B. Butylphenol, Tributylphenol, Octylphenol, Ncnylphenol, Dinonylphenol, o-Phenylphenol, Benzylphenol, Dibenzylphenol, a-Tolylethylphenol, Dibenzyl-(nonyl)-phenol, a-Methylbenrylphenol, Bis-(a-Methylbenzyl)-phenol oder Tris-(amethylbenzyl)-phenol, wobei diese Addukte einzeln oder in Mischung verwendet werden können.Suitable components (ca) are polyadducts of 4 to 40 moles of ethylene oxide with 1 mole of a phenol which has at least one C 4 -C 12 alkyl group, a phenyl group; has a tolyl group, an a-tolylethyl group, a benzyl group, an a-methylbenzyl group or an a, a-dimethylbenzyl group, such as butylphenol, tributylphenol, octylphenol, ncnylphenol, dinonylphenol, o-phenylphenol, benzylphenol, dibenzylphenol, d-tolylylphenol, (nonyl) phenol, a-methylbenrylphenol, bis (a-methylbenzyl) phenol or tris (amethylbenzyl) phenol, which adducts can be used individually or in a mixture.

    Von besonderem Interesse als Komponente (ca) sind Addukte von 6 bis 30 Mol Ethylenoxid an 1 Mol 4-Nonylphenol, an 1 Mol Dinonylphenol oder besonders an 1 Mol von Verbindungen, die durch Anlagerung von 1 bis 3 Mol von Styrolen an 1 Mol Phenole hergestellt werden.Adducts of 6 to 30 moles of ethylene oxide are of particular interest as component (ca) 1 mol of 4-nonylphenol, 1 mol of dinonylphenol or especially 1 mol of compounds, which are prepared by adding 1 to 3 moles of styrenes to 1 mole of phenols.

    Die Herstellung der Styrolanlagerungsprodukte erfolgt in bekannter Weise vorzugsweise in Gegenwart von Katalysatoren, wie Schwefelsäure, p-Totuolsulfonsäure oder vor allem Zinkchlorid. Als Styrole kommen zweckmässigerweise Styrol, a-Methylstyrol oder Vinyltoluol (4-Methylstyrol) in Betracht. Beispiele für die Phenole sind Phenol, Kresole oder Xylenole.The styrene addition products are preferably produced in a known manner in Presence of catalysts such as sulfuric acid, p-totoluenesulfonic acid or especially zinc chloride. Appropriately styrenes are styrene, a-methylstyrene or vinyl toluene (4-methylstyrene). Examples of the phenols are phenol, cresols or xylenols.

    Ganz besonders bevorzugt sind Ethylenoxidaddukte der Formel (21)

    Figure 00090001
    worin m3 1 bis 3 und n3 8 bis 30 bedeuten.Ethylene oxide adducts of the formula (21) are very particularly preferred
    Figure 00090001
    wherein m 3 is 1 to 3 and n 3 is 8 to 30.

    Ebenfalls bevorzugt sind Ethylenoxidaddukte der Formel

    Figure 00090002
    worin Y2 C4-C12-Alkyl, Phenyl, Tolyl, Tolyl-C1-C3-alkyl oder Phenyl-C1-C3-alkyl, wie z.B. a-Methyl- oder a,a-Dimethylbenzyl bedeutet, und m2 1 bis 3 und n2 4 bis 40 sind.Ethylene oxide adducts of the formula are also preferred
    Figure 00090002
    wherein Y 2 is C 4 -C 12 alkyl, phenyl, tolyl, tolyl-C 1 -C 3 alkyl or phenyl-C 1 -C 3 alkyl, such as a-methyl or a, a-dimethylbenzyl, and m 2 are 1 to 3 and n 2 4 to 40.

    Die nichtionogene Komponente (cb) ist vorteilhafterweise

    • ein Alkylenoxidanlagerungsprodukt von 1 bis 100 Mol Alkylenoxid, z.B. Ethylenoxid und/oder Propylenoxid, an 1 Mol eines aliphatischen Monoalkohols mit mindestens 4 Kohlenstoffatomen, eines 3- bis 6-wertigen aliphatischen Alkohols oder eines gegebenenfalls durch Alkyl, Phenyl, a-Tolylethyl, Benzyl, a-Methylbenzyl oder a,a-Dimethylbenzyl substituierten Phenols (cba);
    • ein Alkylenoxidanlagerungsprodukt von 1 bis 100, vorzugsweise 2 bis 80 Mol Ethylenoxid wobei einzelne Ethylenoxideinheiten durch substituierte Epoxide, wie Styroloxid und/oder Propylenoxid, ersetzt sein können, an höhere ungesättigte oder gesättigte Monoalkohole (cba), Fettsäuren (cbb), Fettamine (cbc) oder Fettamide (cbd) mit 8 bis 22 Kohlenstoffatomen;
    • ein Alkylenoxidanlagerungsprodukt, vorzugsweise ein Ethylenoxid-Propylenoxid-Addukt an Ethylendiamin (cbe);
    • ein ethoxyliertes Sorbitanester mit langkettigen Estergruppen, wie z.B. Polyoxiethylen-Sorbitanmonolaurat mit 4 bis 20 Ethylenoxideinheiten oder Polyoxiethylen-Sorbitantrioleat mit 4 bis 20 Ethylenoxideinheiten (cbf).
    The nonionic component (cb) is advantageous
    • an alkylene oxide adduct of 1 to 100 moles of alkylene oxide, for example ethylene oxide and / or propylene oxide, on 1 mole of an aliphatic monoalcohol having at least 4 carbon atoms, a 3- to 6-valent aliphatic alcohol or one optionally substituted by alkyl, phenyl, a-tolylethyl, benzyl, a-methylbenzyl or a, a-dimethylbenzyl substituted phenol (cba);
    • an alkylene oxide addition product of 1 to 100, preferably 2 to 80, moles of ethylene oxide, where individual ethylene oxide units can be replaced by substituted epoxides, such as styrene oxide and / or propylene oxide, to higher unsaturated or saturated monoalcohols (cba), fatty acids (cbb), fatty amines (cbc) or fatty amides (cbd) with 8 to 22 carbon atoms;
    • an alkylene oxide adduct, preferably an ethylene oxide-propylene oxide adduct with ethylenediamine (cbe);
    • an ethoxylated sorbitan ester with long-chain ester groups, such as, for example, polyoxyethylene sorbitan monolaurate with 4 to 20 ethylene oxide units or polyoxyethylene sorbitan trioleate with 4 to 20 ethylene oxide units (cbf).

    Bevorzugte Komponenten (cc) sind Ethylenoxidaddukte an Polypropylenoxid (sogenannte EO-PO-Blockpolymere) und Propylenoxidaddukte an Polyethylenoxid (sogenannte umgekehrte EO-PO-Blockpolymere).Preferred components (cc) are ethylene oxide adducts with polypropylene oxide (so-called EO-PO block polymers) and propylene oxide adducts with polyethylene oxide (so-called reverse EO-PO block polymers).

    Besonders bevorzugt sind Ethylenoxid-Propylenoxid-Blockpolymere mit Molekulargewichten der Polypropylenoxidbasis von 1700 bis 4000 und einem Ethylenoxidgehalt im Gesamtmolekül von 30-80%, insbesondere 60-80%.Ethylene oxide-propylene oxide block polymers with molecular weights are particularly preferred the polypropylene oxide base from 1700 to 4000 and an ethylene oxide content in the whole molecule from 30-80%, especially 60-80%.

    Von Interesse sind ferner Dispergiermittel auf der Basis von Naphthalinsulfonaten.Also of interest are dispersants based on naphthalene sulfonates.

    Besonders bevorzugt enthalten die Tinten Feuchthaltemittel, üblicherweise in einer Menge von 2 bis 30 Gew.-%, insbesondere 5 bis 30 Gew.-% und vorzugsweise 5 bis 25 Gew.-%, bezogen auf das Gesamtgewicht der Tinte. Als Feuchthaltemittel kommen insbesondere mehrwertige Alkohole, wie Ethylenglykol, Diethylenglykol, Triethylenglykol, Tetraethylenglykol, Propylenglykol, Dipropylenglykol, Glycerin und Polyethylenglykole mit einem Molekulargewicht von vorzugsweise 200 bis 800, in Betracht. Von besonderem Interesse sind Glycerin, Propylenglykol oder Diethylenglykol. Ganz besonders interessant ist Propylenglykol oder eine Mischung aus Diethylenglykol und Glycerin, z.B. in einem Gewichtsverhältnis von 10:1 bis 1:10, vorzugsweise 5:1 bis 1:5 und insbesondere 3:1 bis 1:3.The inks particularly preferably contain humectants, usually in an amount from 2 to 30% by weight, in particular 5 to 30% by weight and preferably 5 to 25% by weight, based on the total weight of the ink. In particular, come as humectants polyhydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, With tetraethylene glycol, propylene glycol, dipropylene glycol, glycerin and polyethylene glycols a molecular weight of preferably 200 to 800. Of particular Glycerin, propylene glycol or diethylene glycol are of interest. Is particularly interesting Propylene glycol or a mixture of diethylene glycol and glycerin e.g. in one Weight ratio of 10: 1 to 1:10, preferably 5: 1 to 1: 5 and in particular 3: 1 to 1: 3.

    Gewünschtenfalls können die Tinten noch Säurespender wie Butyrolacton oder Natriumhydrogenphosphat, Konservierungsmittel, Pilz- und/oder Bakteriewachstum hemmende Stoffe, schaumdämpfende Mittel, Netzmittel, Sequestriermittel, Emulgatoren, wasserunlösliche Lösungsmittel, Oxidationsmittel oder Entlüftungsmittel enthalten.If desired, the inks can also be acid donors such as butyrolactone or Sodium hydrogen phosphate, preservative, fungal and / or bacterial growth inhibiting substances, foam suppressants, wetting agents, sequestering agents, emulsifiers, contain 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-Polymethaphosphat, insbesondere Natrium-Hexamethaphosphat, 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-nhexanol. Diese werden üblicherweise in Mengen von 0,01 bis 5 Gew.-%, insbesondere 0,01 bis 5 Gew.-%, bezogen auf das Gesamtgewicht der Tinte, verwendet.Suitable preservatives are, above all, formaldehyde-releasing agents, such as, for example, paraformaldehyde and trioxane, especially aqueous, approximately 30 to 40 percent by weight formaldehyde solutions, and sequestering agents, for example sodium nitrilotriacetic acid, sodium ethylenediaminetetraacetic acid, especially sodium polymethaphosphate, in particular sodium hexamethaphosphate, as emulsifiers especially adducts of an alkylene oxide and a fatty alcohol, especially an adduct of oleyl alcohol and ethylene oxide, as a water-insoluble solvent, high-boiling, saturated hydrocarbons, especially paraffins with a boiling range of about 160 to 210 ° C (so-called mineral spirits), as an oxidizing agent, for example an aromatic nitro compound , especially an aromatic mono- or dinitrocarboxylic acid or sulfonic acid, which is optionally present as an alkylene oxide adduct, in particular a nitrobenzenesulfonic acid and as a deaerating agent, for example high-boiling solvents, especially turpentine oils, high ere alcohol, preferably C 8 to C 10 alcohols, terpene alcohols or deaerating agents based on mineral and / or silicone oils, in particular commercial formulations of about 15 to 25 percent by weight of a mineral and silicone oil mixture and about 75 to 85 percent by weight of a C 8 alcohol such as 2-ethyl-nhexanol. These are usually used in amounts of 0.01 to 5% by weight, in particular 0.01 to 5% by weight, based on the total weight of the ink.

    Als weitere Bestandteile der Tinte seien Chemikalien, wie Alkali, in Mengen von z.B. 0,1 bis 5 Gew.-%, insbesondere 0,5 bis 2 Gew.-%, genannt. Als Beispiele für solche Chemikalien sind wässrige ammoniakalische Lösungen sowie Dimethylethanolamin zu nennen.Other constituents of the ink are chemicals such as alkali in amounts of e.g. 0.1 to 5 wt .-%, in particular 0.5 to 2 wt .-%, called. As examples of such chemicals aqueous ammoniacal solutions and dimethylethanolamine should be mentioned.

    Die Tinten können in der für Pigmentfarbstoffe üblichen Weise durch Mischen der einzelnen Bestandteile in der gewünschten Menge Wasser hergestellt werden. Die Pigmentpartikel weisen in der fertigen Tinte vorzugsweise ein definiertes Kornspektrum auf und sollten insbesondere eine bestimmte Komgrösse, die z.B. 10 µm, insbesondere 5 µm, beträgt, nicht überschreiten. Vorzugsweise weisen die Pigmentpartikel eine mittlere Komgrösse von 1 µm oder weniger auf. Ein definiertes Komspektrum kann beispielsweise erhalten werden, wenn die Pigmente nass gemahlen werden und das Komspektrum laufend durch Laserkomgrössenanalyse überwacht wird.The inks can be mixed in the usual way for pigment dyes Ingredients can be prepared in the desired amount of water. The pigment particles preferably have a defined grain spectrum in the finished ink and should in particular a certain grain size, e.g. 10 µm, in particular 5 µm, is not exceed. The pigment particles preferably have an average grain size of 1 μm or less. A defined com spectrum can be obtained, for example, if the pigments are ground wet and the com spectrum continuously Laser size analysis is monitored.

    Das erfindungsgemässe Verfahren zum Bedrucken von textilen Fasermaterialien kann mit an und für sich bekannten für den textilen Druck geeigneten Tintenstrahldruckem ausgeführt werden.The method according to the invention for printing on textile fiber materials can also be used performed on inkjet printers known per se and suitable for textile printing become.

    Im Falle des Tintenstrahldruck-Verfahrens werden einzelne Tropfen der Tinte kontrolliert aus einer Düse auf ein Substrat gespritzt. Ueberwiegend 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 nicht für den Druck benötigte Tropfen in einen Auffangbehälter abgeleitet und rezykliert werden. Im Falle der Drop on demand-Methode hingegen werden Tropfen 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. mittels eines Piezo-Inkjet-Kopfes erfolgen. Bevorzugt ist für das erfindungsgemässe Verfahren der Druck nach der kontinuierlichen Ink-Jet-Methode.In the case of the inkjet printing process, individual drops of the ink are checked out sprayed onto a substrate using a nozzle. The continuous ink jet method is predominantly used for this as well as the drop on demand method. In the case of continuous The ink-jet method creates the drops continuously, not for printing required drops are drained into a collecting container and recycled. In case of Drop on demand method, however, drops are created and printed as desired; i.e. drops are only generated when this is necessary for printing. The Generation of the drops can e.g. by means of a piezo inkjet head. Is preferred for the process according to the invention, printing by the continuous ink-jet method.

    Als textile Fasermaterialien kommen insbesondere hydroxylgruppenhaltige Fasermaterialien in Betracht. Bevorzugt sind cellulosehaltige Fasermaterialien, die ganz oder teilweise aus Cellulose bestehen. Beispiele sind natürliche Fasermaterialien wie Baumwolle, Leinen oder Hanf und regenerierte Fasermaterialien wie z.B. Viskose sowie Lyocell. Besonders bevorzugt sind hierbei Viskose oder vorzugsweise Baumwolle. Als weitere Fasermaterialien seien Wolle, Seide, Polyvinyl, Polyacrylnitril, Polyamid, Aramid, Polypropylen und Polyurethan genannt. Die genannten Fasermaterialien liegen vorzugsweise als flächige textile Gewebe, Gewirke oder Bahnen vor.In particular, fiber materials containing hydroxyl groups come as textile fiber materials into consideration. Preferred are cellulosic fiber materials that are made up entirely or in part Cellulose exist. Examples are natural fiber materials such as cotton, linen or Hemp and regenerated fiber materials such as Viscose and lyocell. Especially viscose or preferably cotton are preferred. As further fiber materials be wool, silk, polyvinyl, polyacrylonitrile, polyamide, aramid, polypropylene and Called polyurethane. The fiber materials mentioned are preferably flat textile fabrics, knitted fabrics or webs.

    Nach dem Bedrucken wird das Fasermaterial vorteilhafterweise getrocknet, vorzugsweise bei Temperaturen bis 150°C, insbesondere 80 bis 120°C, und anschliessend wird der Druck fixiert. After printing, the fiber material is advantageously dried, preferably at temperatures up to 150 ° C, especially 80 to 120 ° C, and then the pressure fixed.

    Die Fixierung des Drucks kann z.B. durch eine Hitzebehandlung erfolgen, welche vorzugsweise bei einer Temperatur von 120 bis 190°C ausgeführt wird. Die Fixierung erfolgt hierbei bevorzugt 1 bis 8 Minuten.Fixing the pressure can e.g. by heat treatment, which is preferably carried out at a temperature of 120 to 190 ° C. The fixation takes place preferably 1 to 8 minutes.

    Die Fixierung kann jedoch auch mit ionisierender Strahlung oder durch Bestrahlung mit UV-Licht erfolgen.However, the fixation can also be carried out with ionizing radiation or by irradiation with UV light respectively.

    Vorteilhafterweise wird das bedruckte oder gefärbte Fasermaterial bei erhöhter Temperatur, z.B. zwischen 40 und 120° C, insbesondere zwischen 60 und 100° C, bestrahlt und fixiert. Die Bestrahlung kann dabei entweder unmittelbar nach dem Trocknungsvorgang stattfinden, oder man kann auch das kalte bedruckte Fasermaterial vor der Bestrahlung auf die gewünschte Temperatur erwärmen, z.B. in einem Infrarotheizgerät.The printed or dyed fiber material is advantageously at elevated temperature, e.g. between 40 and 120 ° C, in particular between 60 and 100 ° C, irradiated and fixed. The irradiation can take place either immediately after the drying process, or you can also print the cold printed fiber material to the desired one before irradiation Warm temperature, e.g. in an infrared heater.

    Unter ionisierender Strahlung soll eine Strahlung verstanden werden, die mit einer lonisationskammer nachgewiesen werden kann. Sie besteht entweder aus elektrisch geladenen, direkt ionisierenden Teilchen, die in Gasen längs ihrer Bahn durch Stoss Ionen erzeugen oder aus ungeladenen, indirekt ionisierenden Teilchen oder Photonen, die in Materie direkt ionisierende geladene Sekundärteilchen erzeugen, wie die Sekundärelektronen von Röntgen- oder γ-Strahlen oder die Rückstosskerne (insbesondere Protonen) von schnellen Neutronen; ebenfalls indirekt ionisierende Teilchen sind langsame Neutronen, die durch Kernreaktionen teils unmittelbar, teils über Photonen aus (β,γ)-Prozessen energiereiche geladene Teilchen erzeugen können. Als schwere geladene Teilchen kommen Protonen, Atomkerne oder ionisierte Atome in Betracht. Von besonderer Wichtigkeit für den erfindungsgemässen Prozess sind leichte geladene Teilchen, z.B. Elektronen. Als Röntgenstrahlung kommt sowohl die Bremsstrahlung als auch die charakteristische Strahlung in Betracht. Als wichtige Teilchenstrahlung schwerer geladener Teilchen sei die α-Strahlung genannt.Ionizing radiation is to be understood to mean radiation which has an ionization chamber can be demonstrated. It consists of either electrically charged, Directly ionizing particles, which generate ions in gases along their path by impact or from uncharged, indirectly ionizing particles or photons that are in matter directly generate ionizing charged secondary particles like the secondary electrons of X-ray or γ-rays or the recoil nuclei (especially protons) of fast neutrons; Also indirectly ionizing particles are slow neutrons that pass through Nuclear reactions partly direct, partly via photons from (β, γ) processes with high energy can generate charged particles. Protons come as heavy charged particles, Atomic nuclei or ionized atoms. Of particular importance for the inventive Process are lightly charged particles, e.g. Electrons. As x-rays both the bremsstrahlung and the characteristic radiation come in Consideration. The α radiation is an important particle radiation of heavily charged particles called.

    Die Erzeugung der ionisierenden Strahlung kann nach einer der üblichen Methoden erfolgen. So können z.B. spontane Kemumwandlungen als auch Kernreaktionen (erzwungene Kemumwandlungen) zur Erzeugung herangezogen werden. Als Strahlenquellen kommen entsprechend natürliche oder künstliche radioaktive Stoffe und vor allem Atomreaktoren in Betracht. Die in solchen Reaktoren durch Kernspaltung anfallenden radioaktiven Spaltprodukte stellen eine weitere wichtige Strahlenquelle dar. The ionizing radiation can be generated by one of the customary methods. For example, spontaneous core transformations as well as nuclear reactions (forced Core transformations) can be used for generation. Coming as sources of radiation corresponding to natural or artificial radioactive substances and especially nuclear reactors in Consideration. The radioactive fission products resulting from nuclear fission in such reactors represent another important source of radiation.

    Eine weitere in Betracht kommende Methode der Erzeugung von Strahlung ist die mittels einer Röntgenröhre.Another possible method of generating radiation is by means of an x-ray tube.

    Von besonderer Bedeutung sind Strahlen, die aus in elektrischen Feldem beschleunigten Teilchen bestehen. Als Strahlenquellen kommen hier Thermo-, Elektronenstoss-, Niederspannungsbogen-, Kaltkathoden- und Hochfrequenzionenquellen in Betracht.
    Von besonderer Bedeutung für das Verfahren der vorliegenden Erfindung sind Elektronenstrahlen. Diese werden durch Beschleunigung und Bündelung von Elektronen erzeugt, die durch Glüh-, Feld- oder Photoemission sowie durch Elektronen- oder Ionenbombardement aus einer Kathode emittiert werden. Strahlenquellen sind Elektronenkanonen und Beschleuniger üblicher Bauart. Beispiele für Strahlenquellen sind aus der Literatur bekannt, z.B. Intemational Journal of Electron Beam & Gamma Radiation Processing, insbesondere 1/89 Seiten 11-15; Optik, 77 (1987), Seiten 99-104.    Rays consisting of particles accelerated in electrical fields are of particular importance. Thermal, electron impact, low-voltage arc, cold cathode and high-frequency ion sources come into consideration here as radiation sources.
    Electron beams are of particular importance for the method of the present invention. These are generated by accelerating and concentrating electrons, which are emitted from a cathode by glow, field or photoemission as well as by electron or ion bombardment. Radiation sources are conventional electron guns and accelerators. Examples of radiation sources are known from the literature, for example the International Journal of Electron Beam & Gamma Radiation Processing, in particular 1/89 pages 11-15; Optik, 77 (1987), pages 99-104.

    Als Strahlenquellen für Elektronenstrahlen kommen ferner β-Strahler, wie z.B. das Strontium-90 in Betracht.Other sources of radiation for electron beams are β-emitters, e.g. the strontium-90 into consideration.

    Als technisch vorteilhaft anwendbare ionisierende Strahlen seien ausserdem die γ-Strahlen genannt, die insbesondere mit Cäsium-137- oder Kobalt-60-Isotopenquellen leicht herstellbar sind.The γ-rays are also technically advantageously applicable ionizing rays called, which can be easily produced in particular with cesium-137 or cobalt-60 isotope sources are.

    Die Fixierung mit ionisierender Strahlung erfolgt in der Regel so, dass ein erfindungsgemäss bedrucktes und getrocknetes Textilfasermaterial durch den Strahl eines Elektronenbeschleunigers bei Temperaturen zwischen 60 und 100° C hindurchgeführt wird. Dies geschieht mit einer solchen Geschwindigkeit, dass eine bestimmte Bestrahlungsdosis erreicht wird. Die normalerweise anzuwendenden Bestrahlungsdosen liegen zwischen 0,1 und 15 Mrad bei einer Beschleunigerspannung zwischen 160 und 300 kV, wobei die Bestrahlungsdosis vorteilhaft zwischen 0,1 und 4 Mrad liegt. Bei einer Dosis von weniger als 0,1 Mrad ist im allgemeinen der Fixiergrad zu gering, bei einer Dosis von mehr als 15 Mrad tritt häufig Schädigung des Fasermaterials und des Farbstoffes ein. Bei der Ausführung der Fixierung mittels ionisierender Strahlung muss selbstverständlich auf die jeweiligen technischen Voraussetzungen Rücksicht genommen werden. So richtet sich die spezielle Ausführungsform vor allem nach der Art der zu verwendenden ionisierenden Strahlen und ihrer Erzeugungsweise. Soll zum Beispiel das bedruckte Fasermaterial mit γ-Strahlen bestrahlt werden, so wird diese in eine Zelle eingeschlossen der Strahlung ausgesetzt. Werden bei geringer Strahlenintensität höhere Bestrahlungsdosen gewünscht, so kann das zu bestrahlende Material in mehreren Durchgängen der Strahlung ausgesetzt werden.The fixation with ionizing radiation is usually carried out in such a way that a printed and dried textile fiber material by the beam of an electron accelerator is carried out at temperatures between 60 and 100 ° C. This happens with such a speed that a certain radiation dose is reached. The radiation doses normally to be used are between 0.1 and 15 Mrad an accelerator voltage between 160 and 300 kV, the radiation dose being advantageous is between 0.1 and 4 Mrad. At a dose less than 0.1 Mrad is generally the degree of fixation too low, damage often occurs at a dose of more than 15 Mrad of the fiber material and the dye. When carrying out the fixation with Ionizing radiation must of course be based on the respective technical Prerequisites are taken into account. So the special is aimed Embodiment especially according to the type of ionizing radiation to be used and their mode of production. For example, if the printed fiber material with γ rays are irradiated, this is enclosed in a cell exposed to the radiation. If higher radiation doses are desired with low radiation intensity, this can be done material to be irradiated are exposed to the radiation in several passes.

    Bei Verwendung ultravioletter Strahlung ist in der Regel das Vorliegen eines Photoinitiators erforderlich. Der Photoinitiator absorbiert die Strahlung, um freie Radikale, die die Polymerisation einleiten, zu erzeugen. Beispiele für erfindungsgemäss verwendete Photoinitiatoren beziehungsweise Photoinitiatoren sind Carbonylverbindungen wie 2,3-Hexandion. Diacetylacetophenon, Benzoin und Benzoinether wie Dimethyl-, Ethyl- und Butylderivate, z.B. 2,2-Diethoxyacetophenon und 2,2-Dimethoxyacetophenon, Benzophenon bzw. ein Benzophenon-Salz und Phenyl-(1-hydroxycyclohexyl)-keton oder ein Keton der Formel

    Figure 00150001
    When using ultraviolet radiation, it is usually necessary to have a photoinitiator. The photoinitiator absorbs the radiation to generate free radicals that initiate the polymerization. Examples of photoinitiators or photoinitiators used according to the invention are carbonyl compounds such as 2,3-hexanedione. Diacetylacetophenone, benzoin and benzoin ethers such as dimethyl, ethyl and butyl derivatives, for example 2,2-diethoxyacetophenone and 2,2-dimethoxyacetophenone, benzophenone or a benzophenone salt and phenyl (1-hydroxycyclohexyl) ketone or a ketone of the formula
    Figure 00150001

    Benzophenon in Kombination mit einem Katalysator wie Triäthylamin, N,N'-Dibenrylamin und Dimethylaminoethanol und Benzophenon plus Michlers Keton; Acylphosphinoxide; stickstoffhaltige Verbindungen wie Diazomethan, Azo-bis-isobutyronitril, Hydrazin, Phenylhydrazin sowie Trimethylbenzylammoniumchlorid; und schwefelhaltige Verbindungen wie Benzolsulfonat, Diphenyl-disulfid sowie Tetramethylthiuramdisulfid, sowie phophorhaltige Verbindungen, wie z.B. Phosphinoxide. Derartige Photoinitiatoren werden für sich allein oder in Kombination miteinander verwendet.Benzophenone in combination with a catalyst such as triethylamine, N, N'-dibenrylamine and dimethylaminoethanol and benzophenone plus Michler's ketone; acylphosphine oxides; nitrogen-containing compounds such as diazomethane, azo-bis-isobutyronitrile, hydrazine, phenylhydrazine as well as trimethylbenzylammonium chloride; and sulfur-containing compounds such as Benzenesulfonate, diphenyl disulfide and tetramethylthiuram disulfide, as well as those containing phosphorus Connections such as Phosphine oxides. Such photoinitiators are used alone or used in combination.

    Der Anteil an Photoinitiatoren in den aufgetragenen Färbekomponenten direkt vor der Bestrahlung beträgt 0,01-20%, vorzugsweise 0,1-5% , bezogen auf die gesamte Menge der eingesetzten farblosen polymerisierbaren Verbindungen.The proportion of photoinitiators in the applied coloring components directly before the irradiation is 0.01-20%, preferably 0.1-5%, based on the total amount of colorless polymerizable compounds used.

    Sowohl wasserlösliche wie auch wasserunlösliche Photoinitiatoren sind geeignet. Ausserdem sind copolymerisierbare Photoinitiatoren, wie sie z.B. in "Polymers Paint Colour Joumal, 180, S42f (1990)" erwähnt werden, von besonderem Vorteil. Both water-soluble and water-insoluble photoinitiators are suitable. In addition, copolymerizable photoinitiators such as those mentioned, for example, in "Polymers Paint Color Joumal, 180 , S42f (1990)" are particularly advantageous.

    Geeignet sind auch kationische Photoinitiatoren wie Triarylsulfoniumsalze, Diaryliodoniumsalze, Diaryleisenkomplexe oder allgemein Strukturen, wie beschrieben in "Chemistry & Technology of UV & EB Formulation for coatings, inks & paints" Band 3, herausgegeben von SITA Technology Ltd., Gardiner House, Broomhill Road, London, 1991.Cationic photoinitiators such as triarylsulfonium salts, diaryliodonium salts, Diaryle complexes or general structures as described in "Chemistry & Technology of UV & EB Formulation for coatings, inks & paints "Volume 3, published by SITA Technology Ltd., Gardiner House, Broomhill Road, London, 1991.

    Bevorzugt werden Acylphosphinoxide wie z. B. (2,4,6 Trimethylbenzoyl)(diphenyl)phosphinoxid,
    oder Photoinitiatoren der Formel

    Figure 00160001
    eingesetzt
    oder ein Photoinitiator der Formel
    Figure 00160002
    zusammen mit einem Photoinitiator der beiden zuvor genannten Formeln oder einem Photoinitiator der Formel
    Figure 00160003
    oder Benzophenon zusammen mit einem Photoinitiator der obigen drei Formeln eingesetzt.Acylphosphine oxides such as. B. (2,4,6 trimethylbenzoyl) (diphenyl) phosphine oxide,
    or photoinitiators of the formula
    Figure 00160001
    used
    or a photoinitiator of the formula
    Figure 00160002
    together with a photoinitiator of the two aforementioned formulas or a photoinitiator of the formula
    Figure 00160003
    or benzophenone together with a photoinitiator of the above three formulas.

    Ganz besonders bevorzugt werden die folgenden Photoinitiatoren eingesetzt:

    Figure 00160004
    Figure 00170001
    sowie die Mischung der Verbindungen der Formeln
    Figure 00170002
    im Gewichtsverhältnis von 50:50 bis 10:90
    sowie die Mischung der Verbindung der Formel
    Figure 00170003
    und 2,4,6-Trimethylbenzoyldiphenylphosphin im Gewichtsverhältnis 20:80 bis 60:40.The following photoinitiators are very particularly preferably used:
    Figure 00160004
    Figure 00170001
    as well as the mixture of the compounds of the formulas
    Figure 00170002
    in a weight ratio of 50:50 to 10:90
    and the mixture of the compound of the formula
    Figure 00170003
    and 2,4,6-trimethylbenzoyldiphenylphosphine in a weight ratio of 20:80 to 60:40.

    Bei dem zu verwendenden UV-Licht handelt es sich um Strahlung, deren Emission zwischen 200 und 450 nm, insbesondere zwischen 210 und 400 nm, liegt. Die Strahlung wird vorzugsweise künstlich mit Hoch -, Mittel - oder Nieder - Druck Quecksilber-Dampflampen, Halogenlampen, Metallhalogenid -, Xenon - oder Wolframlampen, Kohlelichtbogen - oder Fluoreszenzlampen, H - und D - Lampen, superaktinischen Leuchtstoffröhren und Laser erzeugt.The UV light to be used is radiation whose emission is between 200 and 450 nm, in particular between 210 and 400 nm. The radiation is preferred Artificially with high, medium or low pressure mercury vapor lamps, halogen lamps, Metal halide, xenon or tungsten lamps, carbon arc or fluorescent lamps, H and D lamps, superactin fluorescent tubes and lasers.

    Vorteilhafterweise werden Kapillar-Quecksilber-Hochdrucklampen oder Quecksilber-Hochdrucklampen oder Quecksilber-Niederdrucklampen verwendet.Capillary high-pressure mercury lamps or high-pressure mercury lamps are advantageous or low pressure mercury lamps are used.

    Von ganz besonderem Vorteil sind Quecksilber-Hochdrucklampen und Quecksilber-Mitteldrucklampen, die auch z.B. mit Eisen- oder Galliumhalogenid dotiert sein können. Diese Lampen können auch mit Mikrowellen angeregt oder gepulst betrieben werden, um die Strahlung in Peaks zu konzentrieren. Auch bei Xenonlampen ist gepulster Betrieb möglich, wenn man einen höheren Anteil an längerweiligem UV-Licht benötigt. Of particular advantage are high-pressure mercury lamps and medium-pressure mercury lamps, which also e.g. can be doped with iron or gallium halide. This Lamps can also be operated with microwaves or pulsed to operate Concentrate radiation in peaks. Pulsed operation is also possible with xenon lamps, if you need a higher proportion of boring UV light.

    Generell sind die üblichen UV-Strahlungsquellen wie beschrieben in "Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints", Band 1, herausgegeben von SITA Technology, Gardiner House, Broomhill Road, London, 1991, geeignet.In general, the usual UV radiation sources are as described in "Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints ", Volume 1, published by SITA Technology, Gardiner House, Broomhill Road, London, 1991.

    Die genaue Bestrahlungszeit der Drucke wird sich nach der Leuchtstärke der UV-Quelle, dem Abstand von der Lichtquelle, Art und Menge an Photoinitiator sowie der Durchlässigkeit der Formulierung und des textilen Substrats für UV-Licht richten.The exact exposure time of the prints will depend on the luminosity of the UV source, the distance from the light source, the type and amount of photoinitiator and the permeability the formulation and the textile substrate for UV light.

    Übliche Bestrahlungszeiten mit dem UV-Licht betragen 1 Sekunde bis 20 Minuten, vorzugsweise 5 Sekunden bis 2 Minuten. Die Fixierung kann durch Unterbrechung der Lichteinstrahlung beendet werden, so dass sie auch diskontinuierlich durchgeführt werden kann.Usual irradiation times with the UV light are 1 second to 20 minutes, preferably 5 seconds to 2 minutes. The fixation can be done by interrupting the light be ended so that it can also be carried out discontinuously.

    Die Bestrahlung kann in der Atmosphäre eines inerten Schutzgases, z.B. unter Stickstoff durchgeführt werden, um eine Inhibierung durch Sauerstoff zu verhindern. Die Sauerstoffinhibierung kann auch wirksam durch Zusatz von sogenannten "Anti Blocking Agents", das sind Amine und speziell vor allem auch Aminoacrylate, unterdrückt werden.The radiation can be in the atmosphere of an inert protective gas, e.g. under nitrogen be performed to prevent inhibition by oxygen. The oxygen inhibition can also be effective by adding so-called "anti-blocking agents" that are amines and especially amino acrylates.

    Im Anschluss an die Fixierung kann das bedruckte Fasermaterial in üblicher Weise ausgewaschen und getrocknet werdenAfter the fixation, the printed fiber material can be washed out in the usual way and be dried

    Sowohl der Ink-Jet Druck, als auch die nachfolgende Trocknung und die Fixierung können auch in einem einzigen Schritt ausgeführt werden. Gemeint ist hiermit insbesondere, dass diese Schritte kontinuierlich ausgeführt werden. D.h. dass hintereinander Apparaturen für den Ink-Jet Druck, die Trocknung und die Fixierung angebracht sind, durch welche das zu bedruckende Fasermaterial kontinuierlich hindurch bewegt wird. Die Apparaturen für den Ink-Jet Druck, die Trocknung und die Fixierung können auch in einer einzigen Maschine vereint sein. Das Fasermaterial wird kontinuierlich durch diese Maschine transportiert und ist dann nach Verlassen dieser Maschine fertiggestellt. Die Trocknung kann hierbei z.B. mittels thermischer Energie (wie z.B. oben angegeben) oder insbesondere mittels Infrarotstrahlung (IR) erfolgen. Die Fixierung kann hier z.B. wie z.B. oben angegeben erfolgen. Selbstverständlich kann auch der Ink-Jet Druck separat erfolgen und Trocknung und Fixierung werden wie oben angegeben kontinuierlich, z.B. in einer einzigen Maschine, ausgeführt. Ink-jet printing, as well as the subsequent drying and fixing can can also be carried out in a single step. This means in particular that these steps are carried out continuously. That that successive apparatuses for the ink-jet printing, drying and fixation by which this is done printing fiber material is continuously moved through. The equipment for the Ink-jet printing, drying and fixing can also be done in a single machine be united. The fiber material is continuously transported through this machine and is then finished after leaving this machine. The drying can e.g. by means of thermal energy (such as specified above) or in particular by means of infrared radiation (IR). The fixation can e.g. such as. given above. Of course, ink-jet printing can also be done separately and drying and Fixations are continuous as indicated above, e.g. in a single machine, executed.

    Mit den oben genannten Druckverfahren ist es möglich, die Fasermaterialien sowohl in einer einzigen Nuance als auch in voneinander verschiedenen Nuancen zu bedrucken. Erfolgt das Bedrucken in einer Nuance, so kann das Bedrucken des Fasermaterials ganzflächig oder auch mit einem Muster erfolgen. Hierzu reicht naturgemäss die Verwendung einer einzigen Tinte; die gewünschte Nuance kann jedoch auch durch den Druck mit mehreren Tinten mit voneinander verschiedenen Nuancen erstellt werden. Soll ein Druck auf dem Fasermaterial erstellt werden, welcher mehrere voneinander verschiedene Nuancen aufweist, so erfolgt das Bedrucken des Fasermaterials mit mehreren Tinten, welche jeweils die gewünschte Nuance aufweisen oder so gedruckt werden, dass die jeweilige Nuance erstellt wird (z.B. dadurch, dass Tinten mit verschiedenen Nuancen übereinander auf das Fasermaterial gedruckt werden und so die zu erzielende Nuance ergeben).With the above printing process it is possible to print the fiber materials in one single shade as well as in different shades. Does that happen Printing in one shade, the printing of the fiber material over the entire surface or also be done with a pattern. The use of a single one is naturally sufficient for this Ink; however, the desired shade can also be achieved by printing with multiple inks different nuances are created. Should be a print on the fiber material created, which has several different shades, is done printing the fiber material with several inks, each of which is the desired one Have a shade or be printed in such a way that the respective shade is created (e.g. in that inks with different shades are stacked on top of the fiber material are printed and thus result in the nuance to be achieved).

    Ferner ist es möglich, ein flächiges Fasermaterial beidseitig zu bedrucken. Hierbei kann z.B. eine Seite des Fasermaterials in einer Nuance bedruckt werden, z.B. ganzflächig, und die andere Seite des Fasermaterials wird mit einem Muster in einer oder mehreren voneinander verschiedenen Nuancen bedruckt. Selbstverständlich kann prinzipiell diese Seite auch ebenfalls ganzflächig in einer Nuance bedruckt werden. Ein solches Verfahren kann z.B. so ausgeführt werden, dass an jeder Seite des zu bedruckenden flächigen Fasermaterials einer oder mehrere Druckköpfe vorhanden sind. Es werden dann beide Seiten des Fasermaterials gleichzeitig bedruckt. Die Druckköpfe der jeweiligen Seite des Fasermaterials können sich direkt gegenüberstehen oder auch seitlich versetzt voneinander installiert sein. Ueblicherweise wird das Fasermaterial zwischen diesen Druckköpfen hindurch bewegt. Mit dieser Ausführungsform lassen sich interessante Effekte erzielen, welche sich insbesondere beim Umschlagen des flächigen Fasermaterials erkennen lassen.It is also possible to print a flat fiber material on both sides. Here, e.g. one side of the fiber material is printed in one shade, e.g. all over, and the other side of the fiber material is made with a pattern in one or more of each other different shades printed. In principle, this page can of course also can also be printed on the entire surface in one shade. Such a method can e.g. so be carried out on each side of the flat fibrous material to be printed or more printheads are available. It then becomes both sides of the fiber material printed at the same time. The print heads on the respective side of the fiber material can be stand directly opposite or installed laterally offset from each other. The fiber material is usually moved between these print heads. With In this embodiment, interesting effects can be achieved, which are particularly noticeable when turning over the flat fiber material.

    Eine weitere interessante Ausführungsform betrifft das sogenannte imaging. Hierbei wird eine Vorlage, d.h. ein Bild welches mit dem Druck nachgestellt werden soll, digitalisiert, z.B. mittels einer Videokamera oder einem Scanner. Das digitalisierte Bild wird auf einen Computer übertragen, welcher dann mittels eines Ink-Jet Druckers das Bild auf das Fasermaterial druckt. Selbstverständlich kann das digitalisierte Bild auch bereits in dem Computer gespeichert sein, so dass die Digitalisierung entfällt. So kann ein zu druckendes Bild z.B. am Computer mit Graphik-Software erstellt worden sein. Bei dem zu druckenden Bild kann es sich z.B. auch um Buchstaben, Zahlen, Wörter, jegliche Muster oder auch komplexe verschiedenfarbige Bilder handeln. Verschiedenfarbige Bilder können z.B. durch Verwendung von mehreren Tinten mit voneinander verschiedenen Nuancen erstellt werden.Another interesting embodiment relates to the so-called imaging. Here will a template, i.e. digitized an image to be reproduced with the print, e.g. using a video camera or a scanner. The digitized image is on one Transfer computer, which then uses an inkjet printer to transfer the image onto the Fiber material prints. Of course, the digitized image can already be found in the Computers are stored so that digitization is not necessary. So one can be printed Picture e.g. have been created on the computer with graphics software. At the one to be printed Picture it can e.g. also letters, numbers, words, any pattern or deal with complex, different-colored images. Different colored images can e.g. by Using multiple inks with different shades can be created.

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

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

    Beispiel 1:Example 1:

    Ein Baumwollgewebe wird mit einer wässrigen Tinte A, enhaltend
    5 Gew.% des Pigmentfarbstoffs der Formel

    Figure 00200001
    10 Gew.-% eines handelsüblichen, in Wasser in dispergierter Form vorliegenden Polyacrylat-Binders (Carboset® 531),
    2 Gew.-% eines handelsüblichen, in Wasser in dispergierter Form vorliegenden Polyurethanacrylat-Binders (Sancure® AU-4010),
    15 Gew.-% Diethylenglykol,
    5 Gew.-% Glycerin,
    2 Gew.-% eines handelsüblichen Entschäumungsmittels, und
    61 Gew.-% Wasser,
    mit einem Drop-on-Demand Piezo Inkjet-Kopf aufgedruckt. Der Druck wird vollständig getrocknet und anschliessend 90 Sekunden bei 190°C fixiert. Man erhält einen Druck mit guten Allgemeinechtheiten.A cotton fabric is containing A with an aqueous ink
    5% by weight of the pigment dye of the formula
    Figure 00200001
    10% by weight of a commercial polyacrylate binder (Carboset® 531) present in water in dispersed form,
    2% by weight of a commercially available polyurethane acrylate binder (Sancure® AU-4010) present in water in dispersed form,
    15% by weight diethylene glycol,
    5% by weight glycerol,
    2% by weight of a commercially available defoaming agent, and
    61% by weight of water,
    printed with a drop-on-demand piezo inkjet head. The print is dried completely and then fixed at 190 ° C for 90 seconds. You get a print with good general fastness properties.

    Claims (10)

    1. A process for printing fibrous textile materials according to the ink-jet printing technique, the fibrous materials being printed with an aqueous ink comprising
      a) a pigment dye of formula
      Figure 00260001
      wherein
      R52 is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, nitro or cyano,
      R53 is hydrogen, halogen, nitro or cyano,
      R54 is hydrogen, halogen or phenylaminocarbonyl,
      R55 is hydrogen or hydroxy, and
      R56 is hydrogen or a radical of formula
      Figure 00260002
      wherein
      R57 is hydrogen, C1-C4alkyl or C1-C4alkoxy,
      R58 is hydrogen, C1-C4alkoxy or halogen, and
      R59 is hydrogen, C1-C4alkyl, C1-C4alkoxy or halogen,
      Figure 00260003
      wherein
      R60 and R61 are each independently of the other C1-C4alkyl and R62 and R63 are halogen,
      Figure 00270001
      wherein the rings A, B, D and E are unsubstituted or mono- or poly-substituted by halogen,
      Figure 00270002
      wherein
      R64 is C1-C4alkyl,
      R65 is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, nitro or cyano,
      R66 is hydrogen, halogen, nitro or cyano,
      R67 is hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, nitro or cyano,
      Figure 00270003
      wherein the rings A' and B' are unsubstituted or mono- or poly-substituted by halogen,
      Figure 00280001
      wherein
      (R68)0-2 and (R68')0-2 each independently of the other denote from 0 to 2 substituents selected from the group halogen, C1-C4alkyl, C1-C4alkoxy, nitro and cyano, and
      K1 and K2 are each independently of the other a radical of formula
      Figure 00280002
      wherein
      (R69)0-3 and (R69')0-3 each independently of the other denote from 0 to 3 substituents selected from the group halogen, C1-C4alkyl, C1-C4alkoxy, nitro and cyano, especially halogen, C1-C4alkyl and C1-C4alkoxy, or
      C.I. Pigment Yellow 34 or C.I. Pigment Yellow 128,
      or inorganic pigment dyes based on carbon black or iron oxides,
      b) a water-dispersible or water-soluble mixture of pigment dye binders, one component of the mixture being based on the polymerisation product of acrylic acid and another component of the mixture being based on the polymerisation product of acrylic acid and urethane, and
      c) glycerol, propylene glycol or diethylene glycol.
    2. A process according to claim 1, wherein there is used an ink having a total content of dyes of from 1 to 35 % by weight, especially from 2.5 to 30 % by weight and more especially from 5 to 20 % by weight, based on the total weight of the ink.
    3. A process according to either claim 1 or claim 2, wherein there is used an ink that, based on the total weight of the ink, contains from 2 to 30 % by weight, especially from 5 to 30 % by weight and more especially from 5 to 25 % by weight, glycerol, propylene glycol or diethylene glycol.
    4. A process according to any one of claims 1 to 3, wherein there is used an ink that, based on the total weight of the ink, contains from 2 to 30 % by weight, especially from 5 to 20 % by weight, pigment dye binder.
    5. A process according to any one of claims 1 to 4, wherein the fibrous material is printed by means of a piezo ink-jet head.
    6. A process according to any one of claims 1 to 5, wherein the fibrous material used is fibrous cellulosic material.
    7. A process according to any one of claims 1 to 6, wherein, after the printing, the fibrous material is fixed at a temperature of from 120 to 190°C.
    8. A process according to any one of claims 1 to 7, wherein, after the printing, the fibrous material is fixed using ionising radiation or by irradiation with UV light.
    9. A process according to any one of claims 1 to 8, wherein, after the printing, the print is subjected to drying and fixing, the drying and fixing being carried out continuously.
    10. A process according to claim 9, wherein the printing, the drying and the fixing of the print are carried out continuously.
    EP99934562A 1998-07-08 1999-07-02 Method for printing fibrous textile materials according to the ink jet printing technique Expired - Lifetime EP1144755B1 (en)

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    CH146098 1998-07-08
    CH146098 1998-07-08
    PCT/EP1999/004602 WO2000003079A2 (en) 1998-07-08 1999-07-02 Method for printing fibrous textile materials according to the ink jet printing technique

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    ATE266763T1 (en) 2004-05-15
    AU5030599A (en) 2000-02-01
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    EP1144755A2 (en) 2001-10-17
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