WO2004031473A1 - Pre-treatment liquor for preparing textile substrates for inkjet printing - Google Patents

Pre-treatment liquor for preparing textile substrates for inkjet printing Download PDF

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Publication number
WO2004031473A1
WO2004031473A1 PCT/EP2003/010632 EP0310632W WO2004031473A1 WO 2004031473 A1 WO2004031473 A1 WO 2004031473A1 EP 0310632 W EP0310632 W EP 0310632W WO 2004031473 A1 WO2004031473 A1 WO 2004031473A1
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WO
WIPO (PCT)
Prior art keywords
compounds
aqueous pretreatment
pretreatment liquor
liquor according
textile substrate
Prior art date
Application number
PCT/EP2003/010632
Other languages
German (de)
French (fr)
Inventor
Ulrike Hees
Michael Kluge
Mike Freche
Dieter Freyberg
Karl Siemensmeyer
Heinz Heissler
Friedrich-Wilhelm Raulfs
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AT03756468T priority Critical patent/ATE435327T1/en
Priority to EP03756468A priority patent/EP1549798B1/en
Priority to DE50311669T priority patent/DE50311669D1/en
Priority to JP2004540693A priority patent/JP4096036B2/en
Priority to US10/529,078 priority patent/US20060010619A1/en
Priority to AU2003299147A priority patent/AU2003299147A1/en
Publication of WO2004031473A1 publication Critical patent/WO2004031473A1/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
    • D06P1/60—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 polyethers
    • D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5242—Polymers of unsaturated N-containing compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—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 polyethers
    • D06P1/613—Polyethers without nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/649—Compounds containing carbonamide, thiocarbonamide or guanyl 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 invention relates to aqueous pretreatment liquors for preparing textile substrates for inkjet printing.
  • EP-A 0 928 841 describes the use of natural thickeners and divalent metal salts in the printing of direct dyes and pigments on silk. Polyquaternary or polycationic compounds and disperse dyes are not mentioned.
  • WO 99/33669 discloses the pretreatment of a textile to be printed with cationic compounds to improve the ink level of disperse dye inks, only low molecular weight cationic compounds being mentioned. Polyquaternary or polycationic compounds are not mentioned.
  • US 6,001,137 describes the use of polycationic compounds based on epichlorohydrin copolymers to improve fixation. An improvement in the ink level is not described.
  • WO 00/03081 describes a pretreatment of textiles with textile binders and melamine crosslinkers for ink jet printing with pigments. The pretreatment results in good fastness properties of the prints. There is no mention of an improvement in the printed image due to better ink level and the use of cationic compounds.
  • JP 62231787 describes the use of divalent inorganic metal salts and / or cationic compounds and crosslinkers for the preparation of textiles for ink-jet printing with pigments.
  • the crosslinker leads to crosslinking with a binder which is contained in the ink.
  • polycationic compounds is not mentioned, nor is the use of polyethylene glycol derivatives or other thickeners.
  • WO 00/56972 describes the use of cationic polymers and copolymers and of polymer latices as binders for the pretreatment of textile substrates for ink-jet printing.
  • a disadvantage of the methods of the prior art is that the definition of the printed image on the textile substrate is often insufficient. This is caused by the bleeding of the inks on the substrate.
  • the object of the invention is to provide pretreatment liquors for the preparation of textile substrates for ink-jet printing, which result in an improved ink level on the printed textile substrates.
  • the object of the invention is in particular to improve the ink level in the case of cellulose-containing textile substrates printed with pigment inks and in the case of textile substrates made of polyester fibers printed with disperse dye inks. It is also an object of the invention to improve the fixation for printing with disperse dye inks and thus to enable the prints to have an increased brilliance and color strength.
  • the task is solved by an aqueous pretreatment liquor for the preparation of textile substrates for ink jet printing containing
  • the aqueous pretreatment liquors according to the invention contain one or more polycationic compounds as component (A).
  • Suitable polycationic compounds are, for example, cationic homopolymers or copolymers of diallyldialkylammonium monomers, such as
  • Preferred polycationic compounds (A) are homo- or copolymers of diallyldialkylammonium monomers, such as polydiallyldimethylammonium chloride (polyDADMAC), polydiallyldiethylammonium chloride (polyDADEAC), polydiallyldimethylammonium bromide (polyDADMAB), particularly preferred are polydiallyldiethylammonium chloride, especially preferred are dydlmethyldonylimonium bromide (DADMAB), especially preferred are polydiallyldiethylammonium chloride, especially preferred are polydiallyldimethylammonium chloride (polyDADMAB) is diallyldimethylammonium chloride homopolymer (polyDADMAC).
  • polyDADMAC polydiallyldimethylammonium chloride
  • polyDADEAC polydiallyldiethylammonium chloride
  • polyDADMAB polydiallyldimethylammonium bromide
  • polyDADMAB
  • Copolymers of the monomers mentioned can also contain, as comonomers, nonionic monomers, for example vinylpyrrolidone, (partially saponified) vinyl acetate or hydroxy (meth) acrylate.
  • nonionic monomers for example vinylpyrrolidone, (partially saponified) vinyl acetate or hydroxy (meth) acrylate.
  • the aqueous pretreatment liquors contain polymers or copolymers of diallyldialkylammonium monomers, preferably polymers or copolymers of diallyldimethylammonium chloride, particularly preferably Diallyldimethylammonium chloride homopolymer, as polycationic compounds (A), and one or more thickeners (B).
  • the aqueous pretreatment liquors according to the invention contain one or more thickeners as component (B).
  • Suitable thickeners (B) are natural thickeners such as alginates, polysaccharides, starch, carboxymethyl cellulose, gua flour and their derivatives, and synthetic thickeners such as, if appropriate, acrylic acid homo- and copolymers.
  • Preferred thickeners (B) are associative thickeners of the general formula (I), (U) and / or (UI)
  • (M) y is a unit derived from polyalkylene ether, where M is a single alkylene ether
  • Means unit and y can be from 1 to 100,000, preferably 10 to 10,000,
  • T identical or different, a unit derived from a diisocyanate, x a number of 1 to 500 on average, preferably 1 to 2, particularly preferably approximately 1.
  • U identical or different, one of aliphatic or aromatic alcohols, alkoxylated alcohols, Unit derived from thiols, amines or carboxylic acids and having at least 4 carbon atoms, preferably at least 6 carbon atoms.
  • the aqueous pretreatment liquors contain one or more polycationic compounds (A) and one or more associative thickeners of the general formula (I) and / or (II).
  • Associative thickeners of the general formula (I) can be obtained by reacting
  • R is a hydrophobic aliphatic or aromatic radical with at least 4 C atoms and R-OH can also be alkoxylated, and further derivatives of these compounds capable of forming a urethane, thiourethane or urea bond.
  • Polyether diols (i) for the purposes of the present invention are polyethylene glycol, polypropylene glycol and polytetrahydrofuran, but also copolymers of ethylene oxide and propylene oxide or butylene oxide or terpolymers of ethylene oxide, propylene oxide and butylene oxide, it being possible for the copolymers to be present as block copolymers or statistical copolymers or terpolymers.
  • Suitable diisocyanates (ii) are diisocyanates with NCO groups of the same or different reactivity.
  • diisocyanates having NCO-groups of the same reactivity are aromatic or aliphatic diisocyanates are preferred aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, Tetradecamethylendiisocyanat, trimethylhexane diisocyanate, tetramethylhexane diisocyanate, 1,4-, 1,3- or 1 , 2-diisocyanatocyclohexane, 4,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone di
  • Preferred diisocyanates with NCO groups of different reactivity are the easily and inexpensively available isocyanates such as, for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4 '-MDI), triisocyanatotoluene as representatives for aromatic Diisocyanates or aliphatic diisocyanates, such as 2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,4'-methylenebis (cyclohexyl) diisocyanate and 4-methylcyclohexane-1, 3-diisocyanate (H-TDI).
  • 2,4-tolylene diisocyanate (2,4-TDI)
  • 2,4'-diphenylmethane diisocyanate 2,4
  • isocyanates with groups of different reactivity are 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl diisocyanate, tolidine diisocyanate and 2,6-tolylene diisocyanate.
  • mixtures of at least two of the above-mentioned isocyanates can also be used.
  • polyisocyanates can also be used, for example in amounts of up to 10% by weight, based on the total amount of di- and polyisocyanate.
  • Suitable polyisocyanates are, for example, biurets and allophanates from HDI or TDI.
  • Particularly preferred diisocyanates are HDI, IPDI, MDI and TDI.
  • the ratio of polyether diols (i) to diisocyanates (ii) is generally from 0.3: 1 to 1: 1, preferably about 0.5: 1.
  • the reaction of the diisocyanates with the polyether diols is usually carried out with the addition of a catalyst.
  • the catalysts are preferably used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight. You can implement it in one
  • Suitable catalysts which in particular accelerate the reaction between the NCO groups of the diisocyanates and the hydroxyl groups of the polyether diols, are the tertiary amines known and customary in the prior art, such as e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane and the like, and in particular organic metal compounds such as titanium acid esters, iron compounds such as e.g. Iron (DT) acetylacetonate, tin compounds e.g.
  • Triethylamine dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane and the like
  • organic metal compounds such as
  • Tin diacetate, tin dioctoate, tin dilaurate or the dialkyl derivatives of tin dialkyl salts of aliphatic carboxylic acids such as dibutyl tin diacetate, dibutyl tin dilaurate or the like.
  • the associative thickeners are generally synthesized in bulk or in an aprotic solvent, for example in tetrahydrofuran, diethyl ether, diisopropyl ether, chloroform, dichloromethane, di-n-butyl ether, acetone, N-methylpyrrolidone (NMP), xylene, toluene, methyl ethyl ketone (MEK ), Methyl isobutyl ketone (MD3K) or 1,4-dioxane.
  • NMP N-methylpyrrolidone
  • MEK methyl ethyl ketone
  • MD3K Methyl isobutyl ketone
  • 1,4-dioxane Preferred reaction temperatures are in the range of -20 ° C up to the boiling point of the solvent used.
  • the reaction is generally carried out without pressure, but reactions in autoclaves at up to 20 bar are also suitable.
  • hydrophobicized products By reacting the NCO-terminated products with aliphatic or aromatic alcohols, thiols, primary or secondary amines or carboxylic acids (ii), hydrophobicized products can be obtained from the reaction products of components (i) and (ii) which contain free isocyanate groups.
  • Alcohols and primary or secondary amino acids are particularly suitable
  • o-alkyl radicals such as n-octyl, n-nonyl, n-decyl, n-dodecyl, n-hexadecyl or n-eicosyl;
  • C 6 -C 14 aryl radicals such as phenyl, ⁇ -naphthyl, ⁇ -naphthyl, 1-anthracenyl, 2-anthracenyl or 9-anthracenyl or heteroaromatic radicals such as ⁇ -pyridyl, ⁇ -pyridyl, ⁇ -pyridyl, N-pyrryl, ⁇ -pyrryl, ⁇ -pyrryl, porphyrinyl, 2-furanyl, 3-furanyl, 2-thiophenyl, 3-thiophenyl, N-pyrazolyl, N-imidazolyl, N-triazolyl, N-oxazolyl, N-indolyl, N-carbazolyl, 2-benzofuranyl, 2-benzothiophenyl, N-indazolyl, benzotriazolyl, 2-quinolinyl, 3-isoquinolinyl or ⁇ -phenanthrolinyl;
  • aralkyl preferably C 7 to C 12 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Methyl- 1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl.
  • phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Methyl- 1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzy
  • the alcohols R-OH can also be alkoxylated with ethylene oxide, propylene oxide or butylene oxide, it being possible to use both homo- and (block) copolymers of the alkylene oxides mentioned, usually with about 20 to 500 alkylene oxide units.
  • the alcohols R-OH can also be alkoxylated with THF.
  • the compound (iii) is used at least stoichiometrically with respect to the free isocyanate groups, but frequently in a stoichiometric excess, for example from 50 to 100%, based on free NCO groups.
  • hydrophobic group R can also be attached to the via an ester or ether bridge Polyetherdiol (ii) are attached.
  • Associative thickeners of the general formula (D) can thus be obtained by reacting
  • R-OH or R-COOH Compounds of the general formula R-OH or R-COOH, where R is a hydrophobic aliphatic or aromatic radical with at least 4 carbon atoms and has the meanings given above, where R-OH can also (as stated above) be alkoxylated , as well as other derivatives of these compounds capable of forming an ether or ester bond.
  • compounds of the formula (DT) are obtained from the diisocyanates (ii) and the compounds (iii) without polyether diols (i) being present.
  • the compounds (iii) can be used in a stoichiometric excess.
  • the aqueous pretreatment liquors according to the invention contain polymers or copolymers of
  • Diallyldialkylammonium monomers in particular diallyldimethylammonium chloride homopolymer, as polycationic compounds (A) and one or more associative thickeners of the formula (I) and / or (D) as thickeners (B).
  • the aqueous treatment liquors according to the invention can contain conventional additives as component (C).
  • Common additives are, for example, defoamers, emulsifiers, solvents, biocides, deaerators and wetting agents.
  • the aqueous treatment liquors according to the invention usually contain
  • both the properties of cotton fabrics and the properties of polyester fabrics for printing with pigment inks or with disperse dye inks can be significantly improved.
  • Cotton or cotton blended fabrics are usually made with pigment inks, polyester fabrics usually printed with disperse dye inks.
  • the pretreatment has a positive effect on the fixation when printing with disperse dye inks, which enables more brilliant and darker (in particular black) colors.
  • the invention also relates to a treatment agent comprising components (A), (B) and optionally (C), from which the aqueous treatment liquors according to the invention can be obtained by dilution with water.
  • Another aspect of the present invention is a method for printing flat textile substrates according to the ink jet method, which is characterized in that the textile substrates to be printed are pretreated with the aqueous pretreatment liquors.
  • Another aspect of the present invention is also the printed textile substrates themselves.
  • Another aspect of the present invention is a method for pretreating textile substrates with the aqueous pretreatment liquors according to the invention.
  • the pretreatment process for ink-jet printing includes the application of the pretreatment liquor and the subsequent drying of the impregnated textile substrate.
  • the pretreatment liquor can be applied by means of a pull-out process or by a continuous process with a forced order.
  • Extraction processes are always suitable if the pretreatment agent has a clear affinity for the substrate. This is particularly the case when the pretreatment agent and substrate have different ionogenicity, for example the pretreatment agent is cationic in nature and the substrate fiber is anionic in nature.
  • the textile can be wound up. The treatment liquor is pressed under pressure through the wound textile, the treatment liquor can flow from the inside out or, in fully flooded apparatus, also from the outside in. In order to ensure an even application, changing the flow direction of the treatment liquor is advantageous.
  • the tissue is exposed in the pretreatment liquor and is moved with it.
  • the textile can also be pulled through a standing bath.
  • the textile is preferably pulled several times through the treatment bath, the direction of movement of the textile should be reversed. This promotes the uniformity of the job. Further details on these application methods can be found in the relevant literature, for example finishing of textiles, VEB subuchverlag für, 1st edition 1976, page 93 ff.
  • Suitable continuous methods for application are all methods in which the pretreatment agent according to the invention can be applied over the entire surface or in an image. All printing processes and all processes in which the textile is completely impregnated with the pretreatment agent are particularly suitable here. The fundamental difference to the pull-out procedure is that a compulsory order is implemented here. The pretreatment liquor does not need to have an affinity for the fibers for these processes.
  • screen printing is an important process that is used, among other things, in the production of printed fabrics.
  • the "printing inks” are pressed through a fine mesh using a doctor blade and transferred to the substrate to be printed.
  • the network can be made of synthetic fibers, such as in flat film printing systems, or metals, such as in rotary printing systems.
  • defined amounts of the pretreatment liquor can be applied by generally known spraying and pouring techniques.
  • the textile is dried.
  • the impregnated textile can be heated to such an extent that the water present can evaporate. Is preferably carried out at temperatures of 80 and 120 ° C.
  • the heat required can be introduced in the form of heated air as a heat exchanger.
  • the use of infrared or microwave radiators is also suitable.
  • the textile is preferably kept under tension during this process in order to avoid the formation of wrinkles.
  • the textile substrates to be printed which are pretreated according to the invention, are, for example, fibers, game, yarns, knitwear, woven goods, non-wovens and made-up goods made of polyester, modified polyester, polyester blend, cellulose-containing materials such as cotton, cotton blend, jute, flax, hemp and Ramie, viscose, wool, silk, polyamide, polyamide blend, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride, polyester microfibre and glass fiber fabrics are suitable.
  • the ink jet process the usually aqueous inks are sprayed directly onto the substrate in small droplets.
  • pressure is exerted on the ink system either via a piezoelectric crystal or a heated cannula (bubble jet method) and the ink drops are thus thrown out.
  • Such procedures are in text. Chem. Color, volume 19 (8), pages 23 to 29, 1987, and volume 21 (6), pages 27 to 32, 1989.
  • the inkjet inks used in the process according to the invention for printing on textile substrates usually contain, in addition to dispersing agents, water or a water / solvent mixture and, in water or in the water / solvent mixture, preferably finely divided organic or inorganic colorants, for example after as defined in DESf 55944 pigments.
  • Disperse dyes can also be used instead of pigments.
  • the inks can also contain direct, acid, reactive and vat dyes as dissolved dyes.
  • the soluble dyes mentioned can be present in pigment preparations as fining agents, soluble dyes similar to the pigment, in particular direct, acid or reactive dyes, being used in the shade.
  • Component A associative thickener, reaction product of HDI with ethoxylated fatty alcohol with a molecular weight of about 10,000 g / mol, the ethoxylated fatty alcohol being used in an excess of 50%, based on isocyanate groups;
  • Component B diallyldimethylammonium chloride homopolymer as a polycationic compound
  • the fabric is then dried at 80 ° C.
  • the cotton fabric (1) and the cotton / polyester blend (3) are with a pigment ink (Helizarin® ink) on a printer of the Mimaki brand
  • polyester fabric (2) is printed with a disperse dye ink (Bafixan® ink) on an Epson 3000 printer.
  • the color application is 100 to 400%.
  • the prints are then reductively cleaned by (i) rinsing them first in cold, then in warm water, (ii) then 10-12 min at 80 ° C in a mixture of 2g / L concentrated hydrosulfite solution, 2mL / L 50% by weight sodium hydroxide solution, 1 ml / L Kieralon DB, 2 ml / L Trilon TA, (iii) then rinsed cold for 2-3 minutes, (iv) neutralized in a solution of 1 ml / L glacial acetic acid, (v ) rinsed cold again.
  • the pretreatment of the fabric has improved the ink level, so you get a better resolution.
  • the handle of the textile is not affected by the pretreatment.

Abstract

An aqueous pretreatment liquor for preparing textile substrates for inkjet printing containing (A) one or several polycationic compounds, (B) one or several thickening agents, (C) optionally usual additives, (D) water. Preferred polycationic compounds (A) are polymers or copolymers of diallyldialkylammonium monomers. Preferred thickening agents are obtained from (i) polyetherdiols, (ii) diisocyanates and (iii) compounds of general formula R-OH, R-SH, R-NH2, RR'NH or R-COOH, wherein R, R' represents a hydrophobic, aliphatic or aromatic radical having at least 4 C atoms and R-OH can also be alkoxylated, in addition to other derivatives of said compounds capable of producing a urethane, thiourethane or urea bond (i), or can be obtained from polyetherdiols with (iv) compounds of general formula R-OH or R-COOH, wherein R is a hydrophobic, aliphatic or aromatic radical having at least 4 C atoms and R-OH can also be alkoxylated, in addition to other derivatives of said compounds capable of producing ether or an ester bond, and/or from compounds (ii) or (iii).

Description

Vorbehandlungsflotte zur Vorbereitung von textilen Substraten für den Ink- Jet- Druck Pretreatment liquor for the preparation of textile substrates for ink jet printing
Die Erfindung betrifft wässrige Vorbehandlungsflotten zur Vorbereitung von textilen Substraten für den Ink- Jet-Druck.The invention relates to aqueous pretreatment liquors for preparing textile substrates for inkjet printing.
Es ist bekannt, textile Materialien, die nach dem Ink- Jet-Druckverfahren bedruckt werden sollen, zur Verbesserung der anwendungstechnischen Eigenschaften der bedruckten Textilien mit einer Vorbehandlungsflotte zu behandeln. Durch diese Vorbehandlung soll der Stand der Tinten auf dem textilen Substrat verbessert, eine höhere Farbstärke sowie eine bessere Fixierung der Tinten auf dem Substrat erreicht werden. Angestrebt werden deutlich schärfere Konturen (verbesserte Definition) der Drucke auf dem Substrat, um höhere Auflösungen (höhere dpi) der Drucke zu realisieren.It is known to treat textile materials which are to be printed by the ink jet printing process with a pretreatment liquor in order to improve the application properties of the printed textiles. This pretreatment is intended to improve the state of the inks on the textile substrate, to achieve a higher color strength and to better fix the inks on the substrate. The aim is to achieve sharper contours (improved definition) of the prints on the substrate in order to achieve higher resolutions (higher dpi) of the prints.
Drucke mit Pigmenttinten lassen sich prinzipiell auf allen textilen Flächengebilden durchführen. Zahlreiche Patentveröffentlichungen beschreiben die Verwendung von kationischen Substanzen oder Verdickern zur Verbesserung des Tintenstandes beim InkJet-Druck mit Reaktivfarbstoffen auf Baumwolle oder anderen cellulosehaltigen Fasern.In principle, prints with pigment inks can be carried out on all textile fabrics. Numerous patent publications describe the use of cationic substances or thickeners to improve the ink level in inkjet printing with reactive dyes on cotton or other cellulose-containing fibers.
EP-A 0 928 841 beschreibt die Verwendung von natürlichen Verdickern und zweiwertigen Metallsalzen beim Drucken von Direktfarbstoffen und Pigmenten auf Seide. Polyquatemäre oder polykationische Verbindungen sowie Dispersionsfarbstoffe sind nicht erwähnt.EP-A 0 928 841 describes the use of natural thickeners and divalent metal salts in the printing of direct dyes and pigments on silk. Polyquaternary or polycationic compounds and disperse dyes are not mentioned.
WO 99/33669 offenbart die Vorbehandlung eines zu bedruckenden Textils mit kationischen Verbindungen zur Verbesserung des Tintenstandes von Dispersionsfarbstoff- Tinten, wobei nur niedermolekulare kationische Verbindungen genannt werden. Polyquatemäre oder polykationische Verbindungen werden nicht erwähnt.WO 99/33669 discloses the pretreatment of a textile to be printed with cationic compounds to improve the ink level of disperse dye inks, only low molecular weight cationic compounds being mentioned. Polyquaternary or polycationic compounds are not mentioned.
US 6,001,137 beschreibt die Verwendung von polykationischen Verbindungen auf Basis von Epichlorhydrin-Copolymeren zur Verbesserung der Fixierung. Eine Verbesserung des Tintenstandes ist nicht beschrieben. WO 00/03081 beschreibt eine Vorbehandlung von Textilien mit Textilbindemitteln und Melaminvemetzem für den Ink- Jet-Druck mit Pigmenten. Die Vorbehandlung resultiert in guten Echtheiten der Drucke. Eine Verbesserung des Druckbildes durch besseren Tintenstand und die Verwendung von kationischen Verbindungen ist nicht erwähnt.US 6,001,137 describes the use of polycationic compounds based on epichlorohydrin copolymers to improve fixation. An improvement in the ink level is not described. WO 00/03081 describes a pretreatment of textiles with textile binders and melamine crosslinkers for ink jet printing with pigments. The pretreatment results in good fastness properties of the prints. There is no mention of an improvement in the printed image due to better ink level and the use of cationic compounds.
JP 62231787 beschreibt die Verwendung von zweiwertigen anorganischen Metallsalzen und/oder kationischen Verbindungen und Vemetzem zur Vorbereitung von Textil für den Ink- Jet-Druck mit Pigmenten. Der Vernetzer führt zur Vernetzung mit einem Binder, der in der Tinte enthalten ist. Die Verwendung von polykationischen Verbindungen ist nicht erwähnt, auch nicht die Verwendung von Polyethylenglycolderivaten oder anderen Verdickem.JP 62231787 describes the use of divalent inorganic metal salts and / or cationic compounds and crosslinkers for the preparation of textiles for ink-jet printing with pigments. The crosslinker leads to crosslinking with a binder which is contained in the ink. The use of polycationic compounds is not mentioned, nor is the use of polyethylene glycol derivatives or other thickeners.
WO 00/56972 beschreibt die Verwendung von kationischen Polymeren und Copolymeren sowie von Polymerlatices als Bindemittel für die Vorbehandlung textiler Substrate für den Ink-Jet-Druck.WO 00/56972 describes the use of cationic polymers and copolymers and of polymer latices as binders for the pretreatment of textile substrates for ink-jet printing.
Nachteilig an den Verfahren des Standes der Technik ist eine häufig nicht ausreichende Definition des Druckbildes auf dem textilen Substrat. Dies wird durch das Verlaufen der Tinten auf dem Substrat verursacht.A disadvantage of the methods of the prior art is that the definition of the printed image on the textile substrate is often insufficient. This is caused by the bleeding of the inks on the substrate.
Aufgabe der Erfindung ist es, Vorbehandlungsflotten zur Vorbereitung von textilen Substraten für den Ink-Jet-Druck bereitzustellen, welche einen verbesserten Tintenstand auf den bedruckten textilen Substraten ergeben. Aufgabe der Erfindung ist es insbesondere, den Tintenstand bei mit Pigmenttinten bedruckten cellulosehaltigen textilen Substraten und bei mit Dispersionsfarbstofftinten bedruckten textilen Substraten aus Polyesterfasern zu verbessern. Aufgabe der Erfindung ist ferner, für den Druck mit Dispersionsfarbstofftinten die Fixierung zu verbessern und so eine erhöhte Brillanz und Farbstärke der Drucke zu ermöglichen.The object of the invention is to provide pretreatment liquors for the preparation of textile substrates for ink-jet printing, which result in an improved ink level on the printed textile substrates. The object of the invention is in particular to improve the ink level in the case of cellulose-containing textile substrates printed with pigment inks and in the case of textile substrates made of polyester fibers printed with disperse dye inks. It is also an object of the invention to improve the fixation for printing with disperse dye inks and thus to enable the prints to have an increased brilliance and color strength.
Gelöst wird die Aufgabe durch eine wässrige Vorbehandlungsflotte zur Vorbereitung von textilen Substraten für den Ink-Jet-Druck enthaltendThe task is solved by an aqueous pretreatment liquor for the preparation of textile substrates for ink jet printing containing
(A) eine oder mehrere polykationische Verbindungen,(A) one or more polycationic compounds,
(B) einen oder mehrere Verdicker, (C) gegebenenfalls übliche Additive(B) one or more thickeners, (C) optionally conventional additives
(D) Wasser. Als Komponente (A) enthalten die erfindungsgemäßen wässrigen Vorbehandlungsflotten eine oder mehrere polykationische Verbindungen.(D) water. The aqueous pretreatment liquors according to the invention contain one or more polycationic compounds as component (A).
Geeignete polykationische Verbindungen sind beispielsweise kationische Homopolymere oder Copolymere von Diallyldialkylammonium-Monomeren, wieSuitable polycationic compounds are, for example, cationic homopolymers or copolymers of diallyldialkylammonium monomers, such as
Diallyldimethylammoniumchlorid, kationische Acrylate und Acrylamide wie Acryloxyethyldimethylammoniumchlorid oder Acrylamidoethyldimethyl- ammoniumchlorid, quaternäre Vinylpyridine wie Methylvinylpyridinchlorid, Polyalkylaminpolymere und -copolymere, femer Polyallylaminhydrochlorid, Allylaminhydrochlorid-Diallylaminhydrochlorid-Copolymer, N-Vinylacrylamidinhydro- chlorid-Acrylamid-Copolymer, Dialkylamin-Epichlorohydrin-Polymer, Polyamid- Polyamin-Epichlorohydrin-Polymer, Dicyandiamid-Formaldehyd-Polykondensat, Poly- ethylenpolyamin-Dicyandiamid-Polykondensat, Polyethyleniminhydrochlorid, Poly- (meth)acryloyloxyalkyldialkylaminhydrochlorid, (Meth)acryloyloxyalkyldialkylamin- hydrochlorid-Acrylamid-Copolymer und Poly(meth)acryloyloxyalkyltrialkyl- ammoniumchlorid.Diallyldimethylammonium chloride, cationic acrylates and acrylamides such as acryloxyethyldimethylammonium chloride or acrylamidoethyldimethylammonium chloride, quaternary vinylpyridines such as methylvinylpyridine chloride, polyalkylamine polymers and copolymers, furthermore polyallylamine hydrochloride, allylamine hydrochloride diallylamine hydrochloride copolymer, nylonhydroamide vinylchloride copolymer, polyamine-epichlorohydrin polymer, dicyandiamide-formaldehyde polycondensate, poly ethylene polyamine dicyandiamide polycondensate Polyethyleniminhydrochlorid, poly (meth) acryloyloxyalkyldialkylaminhydrochlorid, (meth) acryloyloxyalkyldialkylaminhydrochlorid-acrylamide copolymer and poly (meth) acryloyloxyalkyltrialkyl- ammonium chloride.
Bevorzugte polykationische Verbindungen (A) sind Homo- oder Copolymere von Diallyldialkylammonium-Monomeren, wie Polydiallyldimethylammoniumchlorid (polyDADMAC), Polydiallyldiethylammoniumchlorid (polyDADEAC), Polydiallyldi- methylammoniumbromide (polyDADMAB), Polydiallyldiethylammoniumbromid (polyDADEAB), besonders bevorzugt sind Polymere oder Copolymere von Diallyldimethylammoniumchlorid, insbesondere bevorzugt ist Diallyldi- methylammoniumchlorid-Homopolymer (polyDADMAC).Preferred polycationic compounds (A) are homo- or copolymers of diallyldialkylammonium monomers, such as polydiallyldimethylammonium chloride (polyDADMAC), polydiallyldiethylammonium chloride (polyDADEAC), polydiallyldimethylammonium bromide (polyDADMAB), particularly preferred are polydiallyldiethylammonium chloride, especially preferred are dydlmethyldonylimonium bromide (DADMAB), especially preferred are polydiallyldiethylammonium chloride, especially preferred are polydiallyldimethylammonium chloride (polyDADMAB) is diallyldimethylammonium chloride homopolymer (polyDADMAC).
Copolymere der genannten Monomere können als Comonomere auch nichtionische Monomere, beispielsweise Vinylpyrrolidon, (teilverseiftes) Vinylacetat oder Hydroxy(meth)acrylat enthalten.Copolymers of the monomers mentioned can also contain, as comonomers, nonionic monomers, for example vinylpyrrolidone, (partially saponified) vinyl acetate or hydroxy (meth) acrylate.
Verfahren zur Herstellung der Diallyldialkylammoniumhomo- oder -copolymere sind beispielsweise in US 4,742,134, US 5,283,306 und EP-A 0264 710 beschrieben. In einer Ausführungsform der Erfindung enthalten die wässrigen Vorbehandlungsflotten Polymere oder Copolymere von Diallyldialkylammonium-Monomeren, bevorzugt Polymere oder Copolymere von Diallyldimethylammoniumchlorid, besonders bevorzugt Diallyldimethylammoniumchlorid-Homopolymer, als polykationische Verbindungen (A), und einen oder mehrere Verdicker (B).Methods for producing the diallyldialkylammonium homo- or copolymers are described, for example, in US 4,742,134, US 5,283,306 and EP-A 0264 710. In one embodiment of the invention, the aqueous pretreatment liquors contain polymers or copolymers of diallyldialkylammonium monomers, preferably polymers or copolymers of diallyldimethylammonium chloride, particularly preferably Diallyldimethylammonium chloride homopolymer, as polycationic compounds (A), and one or more thickeners (B).
Als Komponente (B) enthalten die erfindungsgemäßen wässrigen Vorbehandlungsflotten einen oder mehrere Verdicker.The aqueous pretreatment liquors according to the invention contain one or more thickeners as component (B).
Geeignete Verdicker (B) sind natürliche Verdicker wie Alginate, Polysaccharide, Stärke, Carboxymethylcellulose, Guakemmehl sowie deren Derivate, und synthetische Verdicker wie gegebenenfalls Acrylsäurehomo- und -copolymere.Suitable thickeners (B) are natural thickeners such as alginates, polysaccharides, starch, carboxymethyl cellulose, gua flour and their derivatives, and synthetic thickeners such as, if appropriate, acrylic acid homo- and copolymers.
Bevorzugte Verdicker (B) sind Assoziativverdicker der allgemeinen Formel (I), (U) und/oder (UI)Preferred thickeners (B) are associative thickeners of the general formula (I), (U) and / or (UI)
U-[-T-(M)y-]x-U (I)U - [- T- (M) y -] x -U (I)
U-(M)y-U ( T)U- (M) y -U (T)
U-T-U (DT)U-T-U (DT)
Darin bedeutenMean in it
(M)y eine von Polyalkylenether abgeleitete Einheit, wobei M eine einzelne Alkylenether-(M) y is a unit derived from polyalkylene ether, where M is a single alkylene ether
Einheit bedeutet und y von 1 bis 100 000, bevorzugt 10 bis 10 000 sein kann,Means unit and y can be from 1 to 100,000, preferably 10 to 10,000,
T, gleich oder verschieden, eine von einem Diisocyanat abgeleitete Einheit, x eine Zahl von im Mittel 1 bis 500, vorzugsweise 1 bis 2, besonders bevorzugt ca. 1. U, gleich oder verschieden, eine von aliphatischen oder aromatischen Alkoholen, alkoxylierten Alkoholen, Thiolen, Aminen oder Carbonsäuren abgeleitete Einheit mit mindestens 4 C-Atomen, bevorzugt mindestens 6 C-Atomen.T, identical or different, a unit derived from a diisocyanate, x a number of 1 to 500 on average, preferably 1 to 2, particularly preferably approximately 1. U, identical or different, one of aliphatic or aromatic alcohols, alkoxylated alcohols, Unit derived from thiols, amines or carboxylic acids and having at least 4 carbon atoms, preferably at least 6 carbon atoms.
In einer Ausführungsform der Erfindung enthalten die wässrigen Vorbehandlungsflotten eine oder mehrere polykationische Verbindungen (A) und einen oder mehrere Assoziativverdicker der allgemeinen Formel (I) und/oder (II).In one embodiment of the invention, the aqueous pretreatment liquors contain one or more polycationic compounds (A) and one or more associative thickeners of the general formula (I) and / or (II).
Assoziativverdicker der allgemeinen Formel (I) sind erhältlich durch Umsetzung vonAssociative thickeners of the general formula (I) can be obtained by reacting
(i) Polyetherdiolen, (ii) Diisocyaten und (iii) Verbindungen der allgemeinen Formel R-OH, R-SH, R-NH2, RR NH oder R-(i) polyether diols, (ii) diisocyanates and (iii) compounds of the general formula R-OH, R-SH, R-NH 2 , RR NH or R-
COOH, wobei R, R ein hydrophober aliphatischer oder aromtaischer Rest mit mindestens 4 C-Atomen ist und R-OH auch alkoxyliert sein kann, sowie weiteren zur Ausbildung einer Urethan-, Thiourethan- oder Harnstoffbindung befähigten Derivaten dieser Verbindungen.COOH, where R, R is a hydrophobic aliphatic or aromatic radical with at least 4 C atoms and R-OH can also be alkoxylated, and further derivatives of these compounds capable of forming a urethane, thiourethane or urea bond.
Polyetherdiole (i) im Sinne der vorliegenden Erfindungen sind Polyethylenglykol, Polypropylenglykol und Polytetrahydrofuran, aber auch Copolymere aus Ethylenoxid und Propylenoxid oder Butylenoxid oder Terpolymere aus Ethylenoxid, Propylenoxid und Butylenoxid, wobei die Copolymere als Blockcopolymere oder statistische Copolymere beziehungsweise Terpolymere vorliegen können.Polyether diols (i) for the purposes of the present invention are polyethylene glycol, polypropylene glycol and polytetrahydrofuran, but also copolymers of ethylene oxide and propylene oxide or butylene oxide or terpolymers of ethylene oxide, propylene oxide and butylene oxide, it being possible for the copolymers to be present as block copolymers or statistical copolymers or terpolymers.
Geeignete Diisocyante (ii) sind Diisocyanate mit NCO-Gruppen gleicher oder verschiedener Reaktivität. Beispiele für Diisocyanate mit NCO-Gruppen gleicher Reaktivität sind aromatische oder aliphatische Diisocyanate, bevorzugt sind aliphatische Diisocyanate wie Tetramethylendiisocyanat, Hexamethylendiisocyanat (HDI), Octamethylendiisocyanat, Decamethylendiisocyanat, Dodecamethylendiisocyanat, Tetradecamethylendiisocyanat, Trimethylhexandiisocyanat, Tetramethylhexandiisocyanat, 1,4-, 1,3- oder 1,2-Diisocyanatocyclohexan, 4,4'-Di(isocyanatocyclohexyl)methan, 1- Isocyanato-3,3,5-trimethyl-5-(isocyanatomethyl)cyclohexan (Isophorondiisocyanat) und 2,4- und 2,6-Diisocyanato-l-methylcyclohexan, wobei Hexamethylendiisocyanat und Isophorondiisocyanat besonders bevorzugt sind. Ein weiteres besonders bevorzugtes Diisocyanat ist m-Tetramethylxyloldiisocyanat (TMXDI).Suitable diisocyanates (ii) are diisocyanates with NCO groups of the same or different reactivity. Examples of diisocyanates having NCO-groups of the same reactivity are aromatic or aliphatic diisocyanates are preferred aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, Tetradecamethylendiisocyanat, trimethylhexane diisocyanate, tetramethylhexane diisocyanate, 1,4-, 1,3- or 1 , 2-diisocyanatocyclohexane, 4,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate) and 2,4- and 2,6-diisocyanato-l -methylcyclohexane, with hexamethylene diisocyanate and isophorone diisocyanate being particularly preferred. Another particularly preferred diisocyanate is m-tetramethylxylene diisocyanate (TMXDI).
Bevorzugte Diisocyanate mit NCO-Gruppen unterschiedlicher Reaktivität sind die leicht und billig verfügbaren Isocyanate wie beispielsweise 2,4— Toluylendiisocyanat (2,4— TDI), 2,4'-Diphenylmethandiisocyanat (2,4' -MDI), Triisocyanatotoluol als Vertreter für aromatische Diisocyanate oder aliphatische Diisocyanate, wie 2-Butyl-2- ethylpentamethylendiisocyanat, 2-Isocyanatopropylcyclohexylisocyanat, 2,4,4- oder 2,2,4- Trimethylhexamethylendiisocyanat, 2,4'-Methylenbis(cyclohexyl)diisocyanat und 4— Methylcyclohexan-1 ,3-diisocyanat (H-TDI).Preferred diisocyanates with NCO groups of different reactivity are the easily and inexpensively available isocyanates such as, for example, 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4 '-MDI), triisocyanatotoluene as representatives for aromatic Diisocyanates or aliphatic diisocyanates, such as 2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,4'-methylenebis (cyclohexyl) diisocyanate and 4-methylcyclohexane-1, 3-diisocyanate (H-TDI).
Weitere Beispiele von Isocyanaten mit Gruppen unterschiedlicher Reaktivität sind 1,3- Phenylendiisocyanat, 1,4-Phenylendiisocyanat, 1,5-Naphthylendiisocyanat, Diphenyl- diisocyanat, Tolidindiisocyanat und 2,6-Toluylendiisocyanat. Natürlich kann man auch Mischungen von mindestens zwei der vorstehend genannten Isocyanate verwenden.Further examples of isocyanates with groups of different reactivity are 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl diisocyanate, tolidine diisocyanate and 2,6-tolylene diisocyanate. Of course, mixtures of at least two of the above-mentioned isocyanates can also be used.
In gewissem Umfang können neben Dusocyanaten auch Polyisocyanate eingesetzt werden, beispielsweise in Mengen bis zu 10 Gew.-%, bezogen auf die Gesamtmenge an Di- und Polyisocyanat. Geeignete Polyisocyanate sind beispielsweise Biurete und Allophanate von HDI oder TDI.To a certain extent, in addition to diisocyanates, polyisocyanates can also be used, for example in amounts of up to 10% by weight, based on the total amount of di- and polyisocyanate. Suitable polyisocyanates are, for example, biurets and allophanates from HDI or TDI.
Ganz besonders bevorzugte Diisocyanate sind HDI, IPDI, MDI und TDI.Particularly preferred diisocyanates are HDI, IPDI, MDI and TDI.
Das Verhältnis Polyetherdiole (i) zu Dusocyanaten (ii) beträgt im allgemeinen von 0,3 : 1 bis 1 : 1, vorzugsweise ca. 0,5 : 1 .The ratio of polyether diols (i) to diisocyanates (ii) is generally from 0.3: 1 to 1: 1, preferably about 0.5: 1.
Die Umsetzung der Diisocyanate mit den Polyetherdiolen erfolgt üblicherweise unter Zugabe eines Katalysators.The reaction of the diisocyanates with the polyether diols is usually carried out with the addition of a catalyst.
Die Katalysatoren werden vorzugsweise in einer Menge von 0,01 bis 10 Gew.-%, vorzugsweise 0,05 bis 5 Gew.-%, eingesetzt. Man kann die Umsetzung in einemThe catalysts are preferably used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight. You can implement it in one
Lösemittel durchführen, wobei als Lösemittel prinzipiell alle Lösemittel geeignet sind, die weder mit dem Polyurethan noch mit dem Polyetherderivat reagieren.Carry out solvents, whereby in principle all solvents which do not react with the polyurethane or with the polyether derivative are suitable as solvents.
Geeignete Katalysatoren, welche insbesondere die Reaktion zwischen den NCO-Gruppen der Diisocyanate und den Hydroxylgruppen der Polyetherdiole beschleunigen, sind die nach dem Stand der Technik bekannten und üblichen tertiären Amine, wie z.B. Triethylamin, Dimethylcyclohexylamin, N-Methylmorpholin, N,N'-Dimethylpiperazin, 2-(Dimethylaminoethoxy)ethanol, Diazabicyclo(2,2,2)octan und ähnliche sowie insbesondere organische Metallverbindungen wie Titansäureester, Eisenverbindungen wie z.B. Eisen(DT)acetylacetonat, Zinnverbindungen, z.B. Zinndiacetat, Zinndioctoat, Zinndilaurat oder die Dialkylderivate von Zinndialkylsalzen aliphatischer Carbonsäuren wie Dibutylzinndiacetat, Dibutylzinndilaurat oder ähnliche.Suitable catalysts, which in particular accelerate the reaction between the NCO groups of the diisocyanates and the hydroxyl groups of the polyether diols, are the tertiary amines known and customary in the prior art, such as e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane and the like, and in particular organic metal compounds such as titanium acid esters, iron compounds such as e.g. Iron (DT) acetylacetonate, tin compounds e.g. Tin diacetate, tin dioctoate, tin dilaurate or the dialkyl derivatives of tin dialkyl salts of aliphatic carboxylic acids such as dibutyl tin diacetate, dibutyl tin dilaurate or the like.
Die Synthese der Assoziativverdicker wird im Allgemeinen in Substanz oder in einem aprotischen Lösemittel durchgeführt, beispielsweise in Tetrahydrofuran, Diethylether, Diisopropylether, Chloroform, Dichlormethan, Di-n-butylether, Aceton, N- Methylpyrrolidon (NMP), Xylol, Toluol, Methylethylketon (MEK), Methylisobutylketon (MD3K) oder 1,4-Dioxan. Bevorzugte Reaktionstemperaturen liegen im Bereich von -20°C bis zum Siedepunkt des eingesetzten Lösemittels. Die Reaktion wird im Allgemeinen drucklos durchgeführt, jedoch sind auch Reaktionen in Autoklaven bei bis zu 20 bar geeignet.The associative thickeners are generally synthesized in bulk or in an aprotic solvent, for example in tetrahydrofuran, diethyl ether, diisopropyl ether, chloroform, dichloromethane, di-n-butyl ether, acetone, N-methylpyrrolidone (NMP), xylene, toluene, methyl ethyl ketone (MEK ), Methyl isobutyl ketone (MD3K) or 1,4-dioxane. Preferred reaction temperatures are in the range of -20 ° C up to the boiling point of the solvent used. The reaction is generally carried out without pressure, but reactions in autoclaves at up to 20 bar are also suitable.
Durch Umsetzung der NCO-terminierten Produkte mit aliphatischen oder aromatischen Alkoholen, Thiolen, primären oder sekundären Aminen oder Carbonsäuren (ii) lassen sich aus den Umsetzungsprodukten der Komponenten (i) und (ii), die freie Isocyanatgruppen enthalten, hydrophobierte Produkte erhalten.By reacting the NCO-terminated products with aliphatic or aromatic alcohols, thiols, primary or secondary amines or carboxylic acids (ii), hydrophobicized products can be obtained from the reaction products of components (i) and (ii) which contain free isocyanate groups.
Geeignet sind insbesondere Alkohole und primäre oder sekundäre A ine mitAlcohols and primary or secondary amino acids are particularly suitable
- C8-C4o-Alkylresten wie n-Octyl, n-Nonyl, n-Decyl, n-Dodecyl, n-Hexadecyl oder n- Eicosyl;- C 8 -C 4 o-alkyl radicals such as n-octyl, n-nonyl, n-decyl, n-dodecyl, n-hexadecyl or n-eicosyl;
- C6-C14-Arylresten wie Phenyl, α-Naphthyl, ß-Naphthyl, 1-Anthracenyl, 2-Anthracenyl oder 9-Anthracenyl oder heteroaromatische Reste wie α-Pyridyl, ß-Pyridyl, γ-Pyridyl, N- Pyrryl, ß-Pyrryl, γ-Pyrryl, Porphyrinyl, 2-Furanyl, 3-Furanyl, 2-Thiophenyl, 3-Thiophenyl, N-Pyrazolyl, N-Imidazolyl, N-Triazolyl, N-Oxazolyl, N-Indolyl, N-Carbazolyl, 2- Benzofuranyl, 2-Benzothiophenyl, N-Indazolyl, Benztriazolyl, 2-Chinolinyl, 3- Isochinolinyl oder α-Phenanthrolinyl;C 6 -C 14 aryl radicals such as phenyl, α-naphthyl, β-naphthyl, 1-anthracenyl, 2-anthracenyl or 9-anthracenyl or heteroaromatic radicals such as α-pyridyl, β-pyridyl, γ-pyridyl, N-pyrryl, β-pyrryl, γ-pyrryl, porphyrinyl, 2-furanyl, 3-furanyl, 2-thiophenyl, 3-thiophenyl, N-pyrazolyl, N-imidazolyl, N-triazolyl, N-oxazolyl, N-indolyl, N-carbazolyl, 2-benzofuranyl, 2-benzothiophenyl, N-indazolyl, benzotriazolyl, 2-quinolinyl, 3-isoquinolinyl or α-phenanthrolinyl;
- C7-C13-Aralkyl, bevorzugt C7- bis C12-Phenylalkyl wie Benzyl, 1-Phenethyl, 2-Phenethyl, 1-Phenyl-propyl, 2-Phenyl-propyl, 3-Phenyl-propyl, Neophyl (1 -Methyl- 1-phenylethyl), 1- Phenyl-butyl, 2-Phenyl-butyl, 3-Phenyl-butyl und 4-Phenyl-butyl, besonders bevorzugt Benzyl.- C 7 -C 13 aralkyl, preferably C 7 to C 12 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Methyl- 1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl.
Die Alkohole R-OH können auch mit Ethylenoxid, Propylenoxid oder Butylenoxid alkoxyliert sein, wobei sowohl Homo- als auch (Block)copolymere der genannten Alkylenoxide eingesetzt werden können, üblicherweise mit ca. 20 bis 500 Alkylenoxid- Einheiten. Femer können die Alkohole R-OH mit THF alkoxyliert sein.The alcohols R-OH can also be alkoxylated with ethylene oxide, propylene oxide or butylene oxide, it being possible to use both homo- and (block) copolymers of the alkylene oxides mentioned, usually with about 20 to 500 alkylene oxide units. The alcohols R-OH can also be alkoxylated with THF.
Im allgemeinen wird die Verbindung (iii) bezüglich der freien Isocyanatgruppen zumindest stöchiometrisch, häufig jedoch in stöchiometrischem Überschuß, beispielsweise von 50 bis 100%, bezogen auf freie NCO-Gruppen, eingesetzt.In general, the compound (iii) is used at least stoichiometrically with respect to the free isocyanate groups, but frequently in a stoichiometric excess, for example from 50 to 100%, based on free NCO groups.
Die hydrophobe Gruppe R kann auch über eine Ester- oder Etherbrücke an das Polyetherdiol (ii) angeknüpft werden. Assoziativverdicker der allgemeinen Formel (D) sind somit erhältlich durch Umsetzung vonThe hydrophobic group R can also be attached to the via an ester or ether bridge Polyetherdiol (ii) are attached. Associative thickeners of the general formula (D) can thus be obtained by reacting
(i) Polyetherdiolen mit(i) polyether diols with
(iv) Verbindungen der allgemeinen Formel R-OH oder R-COOH, wobei R ein hydrophober aliphatischer oder aromatischer Rest mit mindestens 4 C-Atomen ist und die oben genannten Bedeutungen hat, wobei R-OH auch (wie oben ausgeführt) alkoxyliert sein kann, sowie weiteren zur Ausbildung einer Ether- oder Esterbindung befähigten Derivaten dieser Verbindungen.(iv) Compounds of the general formula R-OH or R-COOH, where R is a hydrophobic aliphatic or aromatic radical with at least 4 carbon atoms and has the meanings given above, where R-OH can also (as stated above) be alkoxylated , as well as other derivatives of these compounds capable of forming an ether or ester bond.
Verbindungen der Formel (DT) werden schließlich aus den Dusocyanaten (ii) und den Verbindungen (iii) erhalten, ohne dass Polyetherdiole (i) zugegen sind. Dabei können die Verbindungen (iii) in stöchiometrischem Überschuss eingesetzt werden.Finally, compounds of the formula (DT) are obtained from the diisocyanates (ii) and the compounds (iii) without polyether diols (i) being present. The compounds (iii) can be used in a stoichiometric excess.
In einer besonders bevorzugten Ausführungsform enthalten die erfindungsgemäßen wässrigen Vorbehandlungsflotten Polymere oder Copolymere vonIn a particularly preferred embodiment, the aqueous pretreatment liquors according to the invention contain polymers or copolymers of
Diallyldialkylammonium-Monomeren, insbesonder Diallyldimethylammoniumchlorid- Homopolymer, als polykationische Verbindungen (A) und einen oder mehrere Assoziativverdicker der Formel (I) und/oder (D) als Verdicker (B).Diallyldialkylammonium monomers, in particular diallyldimethylammonium chloride homopolymer, as polycationic compounds (A) and one or more associative thickeners of the formula (I) and / or (D) as thickeners (B).
Neben den Komponenten (A) und (B) können die erfindungsgemäßen wässrigen Behandlungsflotten als Komponente (C) übliche Additive enthalten. Übliche Additive sind beispielsweise Entschäumer, Emulgatoren, Lösemittel, Biozide, Entlüfter und Netzmittel.In addition to components (A) and (B), the aqueous treatment liquors according to the invention can contain conventional additives as component (C). Common additives are, for example, defoamers, emulsifiers, solvents, biocides, deaerators and wetting agents.
Die erfindungsgemäßen wässrigen Behandlungsflotten enthalten üblicherweiseThe aqueous treatment liquors according to the invention usually contain
(a) 0,1 bis 50 Gew.-%, bevorzugt 0,5 bis 30 Gew.-% der polykationischen Verbindungen (A),(a) 0.1 to 50% by weight, preferably 0.5 to 30% by weight, of the polycationic compounds (A),
(b) 0, 1 bis 50 Gew.-%, bevorzugt 0,5 bis 30 Gew.-% der Verdicker (B),(b) 0.1 to 50% by weight, preferably 0.5 to 30% by weight, of the thickeners (B),
(c) 0 bis 30 Gew.-%, bevorzugt 0,5 bis 20 Gew.-% übliche Additive (C), und (d) Wasser zur Ergänzung auf 100 Gew.-%.(c) 0 to 30% by weight, preferably 0.5 to 20% by weight of conventional additives (C), and (d) water to make up to 100% by weight.
Überraschend ist insbesondere, dass mit den erfindungsgemäßen Vorbehandlungsflotten mit ein- und derselben Flotte sowohl die Eigenschaften von Baumwollge weben als auch die Eigenschaften von Polyestergeweben für das Bedrucken mit Pigmenttinten bzw. mit Dispersionsfarbstofftinten deutlich verbessert werden können. Baumwolle oder Baumwollmischgewebe werden üblicherweise mit Pigmenttinten, Polyestergewebe üblicherweise mit Dispersionsfarbstofftinten bedruckt. Außerdem wirkt sich die Vorbehandlung beim Drucken mit Dispersionsfarbstofftinten günstig auf die Fixierung aus, was brillantere wie auch dunklere (insbesondere Schwarz) Farben ermöglicht.It is particularly surprising that with the pretreatment liquors according to the invention with one and the same liquor, both the properties of cotton fabrics and the properties of polyester fabrics for printing with pigment inks or with disperse dye inks can be significantly improved. Cotton or cotton blended fabrics are usually made with pigment inks, polyester fabrics usually printed with disperse dye inks. In addition, the pretreatment has a positive effect on the fixation when printing with disperse dye inks, which enables more brilliant and darker (in particular black) colors.
Überraschend ist ferner, dass der Griff der erfindungsgemäß vorbehandelten Substrate nicht verschlechtert wird.It is also surprising that the grip of the substrates pretreated according to the invention is not deteriorated.
Gegenstand der Erfindung ist auch ein Behandlungsmittel enthaltend die Komponenten (A), (B) und gegebenenfalls (C), aus welchem durch Verdünnung mit Wasser die erfindungsgemäßen wässrigen Behandlungsflotten erhältlich sind.The invention also relates to a treatment agent comprising components (A), (B) and optionally (C), from which the aqueous treatment liquors according to the invention can be obtained by dilution with water.
Ein weiterer Aspekt der vorliegenden Erfindung ist ein Verfahren zum Bedrucken von flächigen textilen Substraten nach dem Ink- Jet- Verfahren, das dadurch gekennzeichnet ist, dass die zu bedruckenden textilen Substrate mit den wässrigen Vorbehandlungsflotten vorbehandelt werden.Another aspect of the present invention is a method for printing flat textile substrates according to the ink jet method, which is characterized in that the textile substrates to be printed are pretreated with the aqueous pretreatment liquors.
Ein weiterer Aspekt der vorliegenden Erfindung sind auch die bedruckten textilen Substrate selbst.Another aspect of the present invention is also the printed textile substrates themselves.
Ein weiterer Aspekt der vorliegenden Erfindung ist ein Verfahren zur Vorbehandlung textiler Substrate mit den erfindungsgemäßen wässrigen Vorbehandlungsflotten.Another aspect of the present invention is a method for pretreating textile substrates with the aqueous pretreatment liquors according to the invention.
Der Prozess der Vorbehandlung für den Ink-Jet-Druck umfasst die Auftragung der Vorbehandlungsflotte und die anschließende Trocknung des imprägnierten textilen Substrats.The pretreatment process for ink-jet printing includes the application of the pretreatment liquor and the subsequent drying of the impregnated textile substrate.
Die Auftragung der Vorbehandlungsflotte kann durch ein Ausziehverfahren oder durch ein kontinuierliches Verfahren mit Zwangsauftrag erfolgen.The pretreatment liquor can be applied by means of a pull-out process or by a continuous process with a forced order.
Ausziehverfahren sind immer dann geeignet, wenn das Vorbehandlungsmittel eine deutliche Affinität zum Substrat aufweist. Dies ist insbesondere dann der Fall, wenn Vorbehandlungsmittel und Substrat unterschiedliche Ionogenität aufweisen, beispielsweise das Vorbehandlungsmittel kationischer Natur und die Substrat-Faser anionischer Natur ist. Es gibt verschiedene Formen des Ausziehverfahrens, welche aus der Färberei prinzipiell bekannt sind. Beispielsweise kann das Textil aufgewickelt sein. Die Behandlungsflotte wird dabei unter Druck durch das aufwickelte Textil gepresst, wobei die Behandlungsflotte von innen nach außen oder, in voll gefluteten Apparaten, auch von außen nach innen fließen kann. Um eine gleichmäßige Auftragung zu gewährleisten ist ein Wechsel der Fließrichtung der Behandlungsflotte von Vorteil. In einer anderen Ausführungsform liegt das Gewebe frei in der Vorbehandlungsflotte und wird mit dieser bewegt. In einer weiteren Ausführungsform kann das Textil auch durch ein stehendes Bad gezogen werden. Das Textil wird dabei bevorzugt mehrfach durch das Behandlungsbad gezogen, wobei sich die Bewegungsrichtung des Textils umkehren sollte. Hierdurch wird die Gleichmäßigkeit des Auftrags gefördert. Nähere Einzelheiten zu diesen Auftragsverfahren können der einschlägigen Literatur , beispielsweise Veredlung von Textilien, VEB Fachbuchverlag Leipzig, 1. Auflage 1976, Seite 93 ff entnommen werden.Extraction processes are always suitable if the pretreatment agent has a clear affinity for the substrate. This is particularly the case when the pretreatment agent and substrate have different ionogenicity, for example the pretreatment agent is cationic in nature and the substrate fiber is anionic in nature. There are various forms of the exhaust process, which are known in principle from the dyeing. For example, the textile can be wound up. The treatment liquor is pressed under pressure through the wound textile, the treatment liquor can flow from the inside out or, in fully flooded apparatus, also from the outside in. In order to ensure an even application, changing the flow direction of the treatment liquor is advantageous. In another embodiment, the tissue is exposed in the pretreatment liquor and is moved with it. In a further embodiment, the textile can also be pulled through a standing bath. The textile is preferably pulled several times through the treatment bath, the direction of movement of the textile should be reversed. This promotes the uniformity of the job. Further details on these application methods can be found in the relevant literature, for example finishing of textiles, VEB Fachbuchverlag Leipzig, 1st edition 1976, page 93 ff.
Geeignete kontinuierliche Verfahren zum Auftragen sind alle Verfahren, bei denen vollflächig oder bildmäßig das erfϊndungsgemäße Vorbehandlungsmittel aufgetragen werden kann. Insbesondere geeignet sind hierbei alle Druckverfahren sowie alle Verfahren, bei denen das Textil vollflächig mit dem Vorbehandlungsmittel getränkt wird. Der grundsätzliche Unterschied zu den Ausziehverfahren besteht darin, dass hier ein Zwangsauftrag realisiert wird. Die Vorbehandlungsflotte braucht für diese Verfahren keine Affinität zur Faser aufweisen.Suitable continuous methods for application are all methods in which the pretreatment agent according to the invention can be applied over the entire surface or in an image. All printing processes and all processes in which the textile is completely impregnated with the pretreatment agent are particularly suitable here. The fundamental difference to the pull-out procedure is that a compulsory order is implemented here. The pretreatment liquor does not need to have an affinity for the fibers for these processes.
Als Druckverfahren sind beispielsweise alle Siebdruckverfahren geeignet. Der Siebdruck ist ein wichtiges Verfahren, welches unter anderem bei der Herstellung bedruckter Stoffe eingesetzt wird. Im Siebdruck werden die "Druckfarben" mittels einer Rakel durch ein feines Netz gedrückt und auf das zu bedruckende Substrat übertragen. Das Netz kann hierbei aus synthetischen Fasern, wie in Flachfilmdruckanlagen, oder Metallen, wie in Rotationsdruckanlagen, hergestellt sein.For example, all screen printing processes are suitable as printing processes. Screen printing is an important process that is used, among other things, in the production of printed fabrics. In screen printing, the "printing inks" are pressed through a fine mesh using a doctor blade and transferred to the substrate to be printed. The network can be made of synthetic fibers, such as in flat film printing systems, or metals, such as in rotary printing systems.
Aber auch Hochdruck, Tiefdruck oder Roleauxdruck als gängige textile Druckverfahren sind für die Auftragung der Vorbehandlungsflotte geeignet. Nähere Einzelheiten zu den einzelnen Druckverfahren findet man in der oben angegebenen Literaturstelle auf den Seiten 110 ff.However, letterpress, gravure or Roleaux printing are also suitable as common textile printing processes for applying the pretreatment liquor. Further details on the individual printing processes can be found in the above-mentioned literature on pages 110 ff.
Neben Druckverfahren sind aber auch alle Techniken geeignet, bei denen das Textil vollfächig mit der Vorbehandlungsflotte getränkt wird. Beispielsweise geschieht dies in der Form, dass das Textil durch ein mit dem Vorbehandlungsmittel gefüllten Trog geführt wird und anschließend durch zwei Rollen auf eine definierte Flüssigkeitsaufnahme abgequetscht wird. Der Auftrag kann aber auch in der Form geschehen, dass das Textil durch einen mit der Vorbehandlungsflotte gefüllten Zwickel, gebildet aus zwei sich drehenden Rollen, geführt wird. Die Rollen pressen dabei gleichzeitig das Textilgut auf die gewünschte Flüssigkeitsaufnahme ab. Darüber hinaus gibt es noch vielfältige andere Anordnungsmöglichkeiten dieser sogenannten Foulard-Technologie, die ebenfalls alle für die Auftragung der Vorbehandlungsflotte geeignet sind.In addition to printing processes, all techniques are also suitable in which the textile is completely impregnated with the pretreatment liquor. For example, this is done in such a way that the textile is guided through a trough filled with the pretreatment agent and is then squeezed by two rollers onto a defined liquid absorption. The order can also be done in the form that the textile through a gusset filled with the pretreatment liquor, formed from two rotating rollers. At the same time, the rollers press the textile material onto the desired liquid absorption. In addition, there are many other possible arrangements for this so-called foulard technology, all of which are also suitable for applying the pretreatment liquor.
Darüber hinaus können definierte Mengen der Vorbehandlungsflotte durch allgemein bekannten Sprüh- und Gießtechniken aufgetragen werden.In addition, defined amounts of the pretreatment liquor can be applied by generally known spraying and pouring techniques.
Im Anschluss an die Auftragung des Vorbehandlungsmittels wird das Textil getrocknet. Hierzu kann das imprägnierte Textil soweit erhitzt werden, dass das vorhandene Wasser abdampfen kann. Bevorzugt wird bei Temperaturen von 80 und 120 °C gearbeitet. Die benötigte Wärme kann in Form von erhitzter Luft als Wärmeüberträger eingebracht werden. Geeignet ist aber auch die Verwendung von Infrarotstrahlem oder Mikrowellenstrahlem. Vorzugsweise wird das Textil bei diesem Vorgang unter Spannung gehalten, um die Bildung von Falten zu vermeiden.Following the application of the pretreatment agent, the textile is dried. For this purpose, the impregnated textile can be heated to such an extent that the water present can evaporate. Is preferably carried out at temperatures of 80 and 120 ° C. The heat required can be introduced in the form of heated air as a heat exchanger. However, the use of infrared or microwave radiators is also suitable. The textile is preferably kept under tension during this process in order to avoid the formation of wrinkles.
Als zu bedruckende textile Substrate, die erfindungsgemäß vorbehandelt werden, sind beispielsweise Fasern, Game, Zwirne, Maschenware, Webware, Non-wovens und konfektionierte Ware aus Polyester, modifiziertem Polyester, Polyestermischgewebe, cellulosehaltige Materialien wie Baumwolle, Baumwollmischgewebe, Jute, Flachs, Hanf und Ramie, Viskose, Wolle, Seide, Polyamid, Polyamidmischgewebe, Polyacrylnitril, Triacetat, Acetat, Polycarbonat, Polypropylen, Polyvinylchlorid, Polyestermikrofasern und Glasfasergewebe geeignet.The textile substrates to be printed, which are pretreated according to the invention, are, for example, fibers, game, yarns, knitwear, woven goods, non-wovens and made-up goods made of polyester, modified polyester, polyester blend, cellulose-containing materials such as cotton, cotton blend, jute, flax, hemp and Ramie, viscose, wool, silk, polyamide, polyamide blend, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride, polyester microfibre and glass fiber fabrics are suitable.
Beim Ink-Jet- Verfahren werden die üblicherweise wässrigen Tinten in kleinen Tröpfchen direkt auf das Substrat gesprüht. Man unterscheidet dabei ein kontinuierliches Verfahren, bei dem die Tinte gleichmäßig durch eine Düse gepresst und durch ein elektrisches Feld, abhängig vom zu druckenden Muster, auf das Substrat gelenkt wird, und ein unterbrochenes Tintenstrahl- oder "Drop-on-Demand"- Verfahren, bei dem der Tintenausstoß nur dort erfolgt, wo ein farbiger Punkt gesetzt werden soll. Bei dem letztgenannten Verfahren wird entweder über einen piezoelektrischen Kristall oder eine beheizte Kanüle (Bubble- Jet- Verfahren) Druck auf das Tintensystem ausgeübt und so die Tintentropfen herausgeschleudert. Solche Verfahrensweisen sind in Text. Chem. Color, Band 19 (8), Seiten 23 bis 29, 1987, und Band 21 (6), Seiten 27 bis 32, 1989, beschrieben. Die in dem erfindungsgemäßen Verfahren zum Bedrucken textiler Substrate eingesetzten InkJet-Tinten enthalten üblicherweise neben Dispergiermitteln Wasser oder ein Wasser/Lösungsmittel-Gemisch sowie in Wasser oder in dem Wasser/Lösungsmittel- Gemisch vorzugsweise schwer lösliche, feinteilige organische oder anorganische Farbmittel, das sind beispielsweise nach der Definition in DESf 55944 Pigmente. Statt Pigmenten lassen sich auch Dispersionsfarbstoffe einsetzen. Die Tinten können aber auch als gelöste Farbstoffe Direkt-, Säure-, Reaktiv- und Küpenfarbstoffe enthalten. Die genannten löslichen Farbstoffe können als Schönungsmittel in Pigmentzubereitungen enthalten sein, wobei im Farbton dem Pigment ähnliche lösliche Farbstoffe, insbesondere Direkt-, Säure- oder Reaktivfarbstoffe, eingesetzt werden.In the ink jet process, the usually aqueous inks are sprayed directly onto the substrate in small droplets. A distinction is made between a continuous process in which the ink is pressed evenly through a nozzle and directed onto the substrate by an electric field, depending on the pattern to be printed, and an interrupted inkjet or "drop-on-demand" process, where the ink is only ejected where a colored dot is to be set. In the latter method, pressure is exerted on the ink system either via a piezoelectric crystal or a heated cannula (bubble jet method) and the ink drops are thus thrown out. Such procedures are in text. Chem. Color, volume 19 (8), pages 23 to 29, 1987, and volume 21 (6), pages 27 to 32, 1989. The inkjet inks used in the process according to the invention for printing on textile substrates usually contain, in addition to dispersing agents, water or a water / solvent mixture and, in water or in the water / solvent mixture, preferably finely divided organic or inorganic colorants, for example after as defined in DESf 55944 pigments. Disperse dyes can also be used instead of pigments. However, the inks can also contain direct, acid, reactive and vat dyes as dissolved dyes. The soluble dyes mentioned can be present in pigment preparations as fining agents, soluble dyes similar to the pigment, in particular direct, acid or reactive dyes, being used in the shade.
Die Erfindung wird durch das nachstehende Beispiel näher erläutert.The invention is illustrated by the example below.
Beispielexample
A Herstellung einer VorbehandlungsflotteA Preparation of a pretreatment liquor
Komponente A: Assoziativerdicker, Umsetzungsprodukt von HDI mit ethoxyliertem Fettalkohol mit einem Molgewicht von ca. 10 000 g/mol, wobei der ethoxylierte Fettalkohol in einem Uberschuss von 50 %, bezogen auf Isocyanatgruppen, eingesetzt wurde;Component A: associative thickener, reaction product of HDI with ethoxylated fatty alcohol with a molecular weight of about 10,000 g / mol, the ethoxylated fatty alcohol being used in an excess of 50%, based on isocyanate groups;
Komponente B: Diallyldimethylammoniumchlorid-Homopolymer als polykationische Verbindung;Component B: diallyldimethylammonium chloride homopolymer as a polycationic compound;
Zur Herstellung von 1 kg Flotte werden 889,8 g vollentsalztes Wasser mit 10 g Komponente A gerührt, bis sich alles gelöst hat. Anschließend werden unter Rühren 100 g der Komponente B und 0,2 g handelsüblicher Entschäumer (Entschäumer TC der BASF AG) zugegeben und homogenisiert.To produce 1 kg of liquor, 889.8 g of fully demineralized water are stirred with 10 g of component A until everything has dissolved. 100 g of component B and 0.2 g of commercially available defoamers (defoamer TC from BASF AG) are then added and homogenized with stirring.
B Vorbehandlung eines TextilgewebesB Pretreatment of a textile fabric
Folgende Stoffe wurden durch Aufklotzen der Vorbehandlungsflotte vorbehandelt: (1) Baumwolle 283 (2) Polyester-FahnenstoffThe following fabrics were pretreated by padding the pretreatment liquor: (1) cotton 283 (2) polyester flag fabric
(3) Baumwoll/Polyester-Mischgewebe 50/50 Die Flotte wird in den Foulard eingefüllt. Der Stoff wird durch die Flotte im Foulard geführt und sofort zwischen 2 Walzen abgequetscht.(3) 50/50 cotton / polyester blend The fleet is filled into the foulard. The fabric is passed through the fleet in the foulard and immediately squeezed between two rollers.
Anschließend wird der Stoff bei 80°C getrocknet.The fabric is then dried at 80 ° C.
C Bedrucken des vorbehandelten Stoffes mit einem MusterC Print a pattern on the pretreated fabric
a) Das Baumwollgewebe (1) und das Baumwoll/Polyester-Mischgewebe (3) werden mit einer Pigmenttinte (Helizarin® -Tinte) auf einem Drucker der Marke Mimakia) The cotton fabric (1) and the cotton / polyester blend (3) are with a pigment ink (Helizarin® ink) on a printer of the Mimaki brand
TX 1600 S bedruckt.Printed TX 1600 S.
b) Das Polyestergewebe (2) wird mit einer Dispersionsfarbstofftinte (Bafixan® -Tinte) auf einem Drucker der Marke Epson 3000 bedruckt.b) The polyester fabric (2) is printed with a disperse dye ink (Bafixan® ink) on an Epson 3000 printer.
Der Farbauftrag beträgt 100 bis 400%.The color application is 100 to 400%.
Im Falle des bedruckte Polyestergewebes (2) wird anschließend ca. 90 s mit Heißluft fixiert.In the case of the printed polyester fabric (2), it is then fixed with hot air for approx. 90 s.
D Reduktive Reinigung der DruckeD Reductive cleaning of the prints
Anschließend werden die Drucke reduktiv gereinigt, indem sie (i) zunächst in kaltem, dann in warmem Wasser gespült werden, (ii) anschließend 10-12 min bei 80°C in einer Mischung aus 2g/L konzentrierter Hydrosulfit-Lösung, 2mL/L 50 gew.-%ige Natronlauge, lmL/L Kieralon DB, 2mL/L Trilon TA behandeln werden, (iii) anschließend 2-3 min kalt gespült werden, (iv) in einer Lösung aus lmL/L Eisessig neutralisiert werden, (v) nochmals kalt gespült werden.The prints are then reductively cleaned by (i) rinsing them first in cold, then in warm water, (ii) then 10-12 min at 80 ° C in a mixture of 2g / L concentrated hydrosulfite solution, 2mL / L 50% by weight sodium hydroxide solution, 1 ml / L Kieralon DB, 2 ml / L Trilon TA, (iii) then rinsed cold for 2-3 minutes, (iv) neutralized in a solution of 1 ml / L glacial acetic acid, (v ) rinsed cold again.
E Quantitative Untersuchungen mittels Farbmetrik Die quantitativen Untersuchungen wurde mittels Farbmetrik durchgeführt. Zur Messung wurde ein X-Rite CA22 Spectrophotometer eingesetzt, als Auswerteprogramm wurde X- Rite Color Master verwendet.E Quantitative investigations using colorimetry The quantitative studies were carried out using colorimetry. An X-Rite CA22 spectrophotometer was used for the measurement, and X-Rite Color Master was used as the evaluation program.
Bei den Versuchen wurde die nicht vorbehandelte Ware jeweils als Standard für die Farbmetrikmessungen verwendet. Ein höherer Wert bei der Farbstärke und im Chroma (gemäß M. Richter, Einführung in die Farbmetrik, DeGruyter, Berlin 1981) für das erfindungsgemäß vorbehandelte Textil zeigt also die Verbesserung des Druckergebnisses an.In the tests, the non-pretreated goods were used as the standard for the colorimetric measurements. A higher value for the color strength and chroma (according to M. Richter, Introduction to Colorimetry, DeGruyter, Berlin 1981) for the textile pretreated according to the invention thus indicates the improvement in the printing result.
I. Helizarin® auf Baumwolle 283, Stoffgewicht =119,7g/m2, Baumwoll-Popeline,I. Helizarin® on cotton 283, fabric weight = 119.7g / m 2 , cotton poplin,
Stapellänge 25 - 30 mm, Entschlichtungsgrad nach Tegewa 9, Durchschnittspolymerisationsgrad >1800; Standard: unbehandeltes Gewebe. Die Ergebnisse sind in Tabelle 1 zusammengefasstStack length 25-30 mm, degree of desizing according to Tegewa 9, average degree of polymerization> 1800; Standard: untreated fabric. The results are summarized in Table 1
Tabelle 1Table 1
Figure imgf000016_0001
Figure imgf000016_0001
D. Helizarin® auf Baumwoll/Polyester-Mischgewebe (50% Baumwolle), Stoffgewicht = 114,7g/m2. Die Ergebnisse sind in Tabelle 2 zusammengefasst.D. Helizarin® on cotton / polyester blend (50% cotton), fabric weight = 114.7g / m 2 . The results are summarized in Table 2.
Tabelle 2Table 2
ID. Bafixan® auf Polyester-Fahnenstoff, Stoffgewicht = 104,7g/m2. Die Ergebnisse sind in Tabelle 3 zusammengefasst. ID. Bafixan® on polyester flag fabric, fabric weight = 104.7g / m 2 . The results are summarized in Table 3.
Tabelle 3Table 3
Figure imgf000017_0001
Figure imgf000017_0001
Qualitativer Vergleich:Qualitative comparison:
Durch die Vorbehandlung des Stoffes hat sich der Tintenstand verbessert, damit erhält man eine bessere Auflösung. Der Griff des Textils wird durch die Vorbehandlung nicht beeinträchtigt. The pretreatment of the fabric has improved the ink level, so you get a better resolution. The handle of the textile is not affected by the pretreatment.

Claims

Patentansprüche claims
1. Wässrige Vorbehandlungsflotte zur Vorbereitung von textilen Substraten für den Ink- Jet-Druck enthaltend1. Containing an aqueous pretreatment liquor for the preparation of textile substrates for inkjet printing
(A) eine oder mehrere polykationische Verbindung,(A) one or more polycationic compounds,
(B) eine oder mehrere Verdicker,(B) one or more thickeners,
(C) gegebenenfalls übliche Additive, (D) Wasser.(C) if appropriate conventional additives, (D) water.
2. Wässrige Vorbehandlungsflotte nach Anspmch 1, enthaltend als polykationische Verbindungen (A) Polymere oder Copolymere von Diallyldialkylammonium- Monomeren.2. Aqueous pretreatment liquor according to Claim 1, containing as polycationic compounds (A) polymers or copolymers of diallyldialkylammonium monomers.
3. Wässrige Vorbehandlungsflotte nach Anspmch 2, enthaltend als polykationische Verbindungen (A) Diallyldimethylammoniumchlorid-Homopolymer.3. Aqueous pretreatment liquor according to Anspmch 2, containing diallyldimethylammonium chloride homopolymer as polycationic compounds (A).
4. Wässrige Vorbehandlungsflotte nach einem der Ansprüche 1 bis 3, enthaltend als Verdicker (B) Assoziativverdicker der allgemeinen Formel (I), (D) und/oder (DT)4. Aqueous pretreatment liquor according to one of claims 1 to 3, containing as thickener (B) associative thickener of the general formula (I), (D) and / or (DT)
U-[-T-(M)y-]x-U (I)U - [- T- (M) y -] x -U (I)
U-(M)y-U (D)U- (M) y -U (D)
U-T-U (DI)U-T-U (DI)
worin bedeuten:in which mean:
(M)y eine von Polyalkylenether abgeleitete Einheit, wobei M eine einzelne Alkylenether-Einheit bedeutet und y von 1 bis 100 000 sein kann,(M) y is a unit derived from polyalkylene ether, where M is a single alkylene ether unit and y can be from 1 to 100,000,
T, gleich oder verschieden, eine von einem Diisocyanat abgeleitete Einheit, x eine Zahl von im Mittel 1 bis 500,T, identical or different, a unit derived from a diisocyanate, x a number from 1 to 500 on average,
U, gleich oder verschieden, eine von aliphatischen oder aromatischen Alkoholen, alkoxylierten Alkoholen, Thiolen, Aminen oder Carbonsäuren abgeleitete Einheit mit mindestens 4 C-Atomen. U, identical or different, is a unit derived from aliphatic or aromatic alcohols, alkoxylated alcohols, thiols, amines or carboxylic acids with at least 4 carbon atoms.
5. Wässrige Vorbehandlungsflotte nach Anspmch 4, dadurch gekennzeichnet, dass die Verbindungen der allgemeinen Formel (I) erhältlich sind aus5. Aqueous pretreatment liquor according to Anspmch 4, characterized in that the compounds of general formula (I) are obtainable from
(i) Polyetherdiolen, (ii) Dusocyanaten und(i) polyether diols, (ii) diisocyanates and
(iii) Verbindungen der allgemeinen Formel R-OH, R-SH, R-NH2, RR NH oder R-(iii) compounds of the general formula R-OH, R-SH, R-NH 2 , RR NH or R-
COOH, wobei R, R ein hydrophober aliphatischer oder aromtaischer Rest mit mindestens 4 C-Atomen ist und R-OH auch alkoxyliert sein kann, sowie weiteren zur Ausbildung einer Urethan-, Thiourethan- oder Harnstoffbindung befähigten Derivaten dieser Verbindungen,COOH, where R, R is a hydrophobic aliphatic or aromatic residue with at least 4 C atoms and R-OH can also be alkoxylated, and further derivatives of these compounds capable of forming a urethane, thiourethane or urea bond,
die Verbindungen der Formel (D) erhältlich sind austhe compounds of formula (D) are obtainable from
(i) Polyetherdiolen mit (iv) Verbindungen der allgemeinen Formel R-OH oder R-COOH, wobei R ein hydrophober aliphatischer oder aromatischer Rest mit mindestens 4 C- Atomen ist und R-OH auch alkoxyliert sein kann, sowie weiteren zur Ausbildung einer Ether- oder Esterbindung befähigten Derivaten dieser Verbindungen, und(i) polyether diols with (iv) compounds of the general formula R-OH or R-COOH, where R is a hydrophobic aliphatic or aromatic radical having at least 4 carbon atoms and R-OH can also be alkoxylated, and further to form an ether - or ester linkage capable derivatives of these compounds, and
die Verbindungen der Formel (DI) aus den Verbindungen (ii) und (iii) erhältlich sind.the compounds of formula (DI) are obtainable from compounds (ii) and (iii).
6. Wässrige Vorbehandlungsflotte nach Anspmch 4 oder 5, dadurch gekennzeichnet, dass die Polyetherdiole (ii) ausgewählt sind aus der Gruppe bestehend aus Polyethylenglykol, Polypropylenglykol und Polytetrahydrofuran und Copolymeren aus Ethylenoxid und Propylenoxid oder Butylenoxid und Terpolymeren aus Ethylenoxid und Propylenoxid und Butylenoxid.6. Aqueous pretreatment liquor according to claim 4 or 5, characterized in that the polyether diols (ii) are selected from the group consisting of polyethylene glycol, polypropylene glycol and polytetrahydrofuran and copolymers of ethylene oxide and propylene oxide or butylene oxide and terpolymers of ethylene oxide and propylene oxide and butylene oxide.
7. Wässrige Vorbehandlungsflotte nach einem der Ansprüche 1 bis 6, enthaltend (a) 0,1 bis 50 Gew.-% polykationische Verbindungen (A),7. Aqueous pretreatment liquor according to one of claims 1 to 6, containing (a) 0.1 to 50 wt .-% polycationic compounds (A),
(b) 0, 1 bis 50 Gew.-% Verdicker (B),(b) 0.1 to 50% by weight of thickener (B),
(c) 0 bis 30 Gew.-% übliche Additive (C), und(c) 0 to 30% by weight of conventional additives (C), and
(d) Wasser zur Ergänzung auf 100 Gew.-%.(d) Water to make up to 100% by weight.
8. Vorbehandlungsmittel, enthaltend die Komponenten (A), (B) und gegebenenfalls (C), wie in den Ansprüchen 1 bis 6 definiert. 8. pretreatment agent containing components (A), (B) and optionally (C) as defined in claims 1 to 6.
9. Verfahren zur Vorbereitung eines textilen Substrats für den Ink-Jet-Dmck, umfassend die Auftragung der wässrigen Vorbehandlungsflotte nach einem der Ansprüche 1 bis 7 auf das textile Substrat und die anschließende Trocknung des imprägnierten textilen Substrats.9. A method for preparing a textile substrate for ink-jet printing, comprising the application of the aqueous pretreatment liquor according to one of claims 1 to 7 to the textile substrate and the subsequent drying of the impregnated textile substrate.
10. Verfahren zum Bedmcken eines textilen Substrats nach dem Ink-Jet- Verfahren, umfassend die Auftragung der wässrigen Vorbehandlungsflotte nach einem der Ansprüche 1 bis 7, die Trocknung des imprägnierten textilen Substrats und das Bedmcken des imprägnierten textilen Substrats nach dem Ink- Jet- Verfahren.10. A method for covering a textile substrate by the ink jet method, comprising the application of the aqueous pretreatment liquor according to one of claims 1 to 7, the drying of the impregnated textile substrate and the covering of the impregnated textile substrate by the ink jet method ,
11. Das nach dem Verfahren gemäß Anspmch 10 erhältliche bedruckte textile Substrat. 11. The printed textile substrate obtainable by the method according to claim 10.
PCT/EP2003/010632 2002-09-26 2003-09-24 Pre-treatment liquor for preparing textile substrates for inkjet printing WO2004031473A1 (en)

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AT03756468T ATE435327T1 (en) 2002-09-26 2003-09-24 PRETREATMENT FLEET FOR PREPARING TEXTILE SUBSTRATES FOR INK-JET PRINTING
EP03756468A EP1549798B1 (en) 2002-09-26 2003-09-24 Pre-treatment liquor for preparing textile substrates for inkjet printing
DE50311669T DE50311669D1 (en) 2002-09-26 2003-09-24 PRE-TREATMENT BOX FOR PREPARING TEXTILE SUBSTRATES FOR INK-JET PRINTING
JP2004540693A JP4096036B2 (en) 2002-09-26 2003-09-24 Pretreatment liquid for the production of textile supports for ink jet printing
US10/529,078 US20060010619A1 (en) 2002-09-26 2003-09-24 Pre-treatment liquor for preparing textile substrates for inkjet printing
AU2003299147A AU2003299147A1 (en) 2002-09-26 2003-09-24 Pre-treatment liquor for preparing textile substrates for inkjet printing

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