MXPA98010804A - Procedure for printing textile fiber materials according to the procedure of stamping by it jet - Google Patents

Abstract

The invention relates to a process for the stamping of textile fiber materials, according to the inkjet printing process, which is characterized in that the fiber materials are sta with an aqueous ink, which contains at least one dye of dispersion, an anionic copolymer and / or a non-ionogenic block polymer and / or a dispersing agent, as well as inks including said component

Description

PROCEDURE FOR PRINTING TEXTILE FIBER MATERIALS ACCORDING TO THE INJECTION PROCEDURE FOR INJECTION The present invention relates to a process for printing textile fiber materials with dispersion dyes, according to the inkjet printing process (Jet and Ink-Jet process) / as well as to the corresponding printing inks. Inkjet printing processes have been used in the textile industry for some years. Said methods allow to renounce the manufacture of a pattern of stamping, in other usual cases, so that considerable savings can be achieved in terms of costs and time. In particular in the production of samples, within a considerably shorter time it can react to changing needs. The corresponding inkjet printing processes must in particular have optimum properties of the application technique. In this context, properties such as viscosity, stability, surface tension and conductivity of the inks used must be mentioned. In addition, higher requirements are raised for the quality of the prints obtained, such as, for example, I regarding color intensity, fiber-dye bond stability, as well as wet dye fastness properties. Known processes do not meet these requirements in all properties, so that there remains a need for new methods for textile inkjet printing. The object of the present invention is a process for the stamping of textile fiber materials, according to the inkjet printing process, which is characterized in that the fiber materials are stamped with an aqueous ink, which contains at least one anionic copolymer and / or a non-ionogenic block polymer and / or a dispersing agent. Dispersing dyes suitable for the process according to the invention are those dyes described in the Coloring Catalog, 3a. edition (3rd revision 1987, including supplements and amendments up to No. 85), under "Disperse Dyes". They are, for example, nitro, amino, aminoketone, ketoninim, methine, polymethine, diphenylamino, quinoline, benzimidazole, xanthene, oxazine or Cu-marine dyes, free of carboxylic acid groups or sulfonic acids, in particular anthraquinone and azo dyes, mono or disazo dyes. In the process according to the invention, dispersion dyes of the formulas are preferred: i? wherein Ri 6 means halogen, nitro or cyano, R 17 means hydrogen, halogen, nitro or cyano, Ris means halogen or cyano, R 19 means hydrogen, halogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms R2o means hydrogen, halogen or acylamino, and R21 and R22, independently of one another, mean alkyl having 1 to 4 carbon atoms, which is unsubstituted or substituted with hydroxy, acetoxy or phenoxy, wherein R23 signifies hydrogen, phenyl or phenylsulfoxy, wherein the benzene ring on phenyl or phenylsulfoxy is optionally substituted with alkyl having 1 to 4 carbon atoms or alkylsulfo with 1 to 4 carbon atoms, R25 means amino or hydroxy, R26 means hydrogen or alkoxy with 1 to 4 carbon atoms, R27 means hydrogen or the radical -0-C, H5-SO-NH- (CH2) 3-0-CH5 / R30 means hydrogen, hydroxy or nitro, and R7 signifies hydrogen, hydroxy or nitro, wherein R2s means alkyl having 1 to 4 carbon atoms, which is unsubstituted or substituted with hydroxy, R29 means alkyl with 1 to 4 carbon atoms, R3o means cyano, R3? means the radical of the formula - (CH2) 3-0- (CH2) 2- 0-C6H5, R32 means halogen, nitro or cyano, and R33 means hydrogen, halogen, nitro or cyano, R34 means alkyl with 1 to 4 carbon atoms, R35 means alkyl with 1 to 4 carbon atoms, which is unsubstituted or substituted with alkoxy with 1 to 4 carbon atoms, and w means the radical -COOCH2CH2OCÓH5 and x means hydrogen, ow means hydrogen and Wx means -N = NC¿H5, in which the rings A "and B" are unsubstituted or substituted one or more times with halogen, wherein R34 means alkyl having 1 to 4 carbon atoms, which is unsubstituted or substituted with hydroxy, alkoxy with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms-alkoxy with 1 to 4 carbon atoms In the process according to the invention, dyes of the formulas are particularly preferred: The dispersion dyes of the formulas (1) to (23) are known or can be obtained in analogy to known compounds, according to known standard procedures, such as, for example, by usual diazotization, coupling, addition and condensation reactions. The inks usually contain a total dispersion dye content of the above formulas (1) to (23) of 1 to 35% by weight, in particular 1 to 20% by weight, especially 1 to 10% by weight, referred to the total weight of the ink. Among the inks of the invention, the dispersed dyes are advantageously in a finely dispersed form. For this, the dyes are ground to an average particle size of between 0.1 and 10 microns, preferably between 1 and 5 microns, particularly preferred between 0.5 and 2 microns. The grinding can be carried out in the presence of dispersants. For example, the dry disperse dye is milled with a dispersant or kneaded to a pasty form with a dispersant and, if desired, dried under reduced pressure or by spraying. The resulting preparations can be used to prepare the inks of the invention, adding water and, if desired, other auxiliaries. For the process according to the invention, copolymers based on acrylic acid, methacrylic acid or maleic acid are especially suitable as anionic copolymers. Among them, those obtainable by polymerization of acrylic and / or methacrylic acid and one or more copolymerizable monomers, selected from the group consisting of maleic acid, N-vinylformamide, N-vinylacetamide, allylamine derivatives or diallylaramine, are preferred. , N-vinylpyrrolidone, N-vinyl-N-methyl-formamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl-acetamide, vinyl acetate, vinyl propionate, acryl nitrile, styrene, nitrile of methacryl, acrylamide, raetacrilamide and N-mono / NN-di-alkyl-C? -C? o- (meth) acrylamide. Particularly preferred are anionic copolymers obtainable by copolymerization of acrylic or methacrylic acid and styrene. Particularly preferred are copolymers of acrylic acid and methacrylic-styrene, with a molecular weight of 3,000 to 1,000,000, in particular 3,000 to 10,000. For the process according to the invention, the alkylene oxide condensation products, such as, for example, adducts of ethylene oxide in polypropylene oxide (the so-called block polymers E0-PO), are suitable as block polymers. the adducts of propylene oxide in polyethylene oxide (the so-called reverse block polymers E0-PO), and block polymers, which can be obtained by the addition of styrene in polypropylene oxide and / or polyethylene. Ethylene-propylene oxide block polymers are preferred, with molecular weights between 2'000 and 20'000, mainly between 8'000 and 16'000, and an ethylene oxide content in the entire molecule of 30-80% , in particular from 60 to 80%. Suitable dispersing agents are, in particular, anionic dispersants of the group of (ba) acid esters or their alkylene oxide adducts, of the formula //. V-o-f-Alkylep - O -) - (24), (Y wherein "X" means the acid radical of an inorganic acid containing oxygen, such as, for example, sulfuric acid or, preferably, phosphoric acid, or also the radical of an organic acid, and Y means alkyl with 1 to 12 atoms carbon, aryl or aralkyl, "alkylene" means the ethylene or propylene radical, and m means 1 to 4, and n means 4 to 50, (bb) polystyrene sulfonates, (be) fatty acid taurides, (bd) mono or di -alkylated diphenyl oxide sulphonates, (be) sulfonates of polycarboxylic acid esters, (bf) addition product from 1 to 60, preferably 2 to 30 moles of ethylene oxide and / or propylene oxide in fatty amines, fatty amides, fatty acids or fatty alcohols, respectively with 8 to 22 carbon atoms or in tri to hexavalent alkanols, with 3 to 6 carbon atoms, transformed into an acid ester with an organic dicarboxylic acid or a polybasic inorganic acid, (bg) lignin sulphonates, (bh) naphthalene sulphonates, and (bi) formaldehyde condensation products. As lignin sulphonates (bg), those lignin sulphonates or their alkali metal salts whose sulfo group content does not exceed 25% by weight are mainly used. Lignin sulfonates with a content of 5 to 15% by weight of sulfo groups are preferred. Suitable condensation products of formaldehyde (bi) are, for example, the condensation products of lignin sulfonates and / or phenol and formaldehyde, the condensation products of formaldehyde with aromatic sulfonic acids, such as, for example, condensation products. of dithylethylsulfonates and formaldehyde, the condensation products of naphthalenesulfonic acid with formaldehyde and / or naphthol or naphthylaminosulfonic acids with formaldehyde, the condensation products of phenolsulfonic acids and / or sulfonated dihydroxydiphenylsulfone and phenols or cresols with formaldehyde and / or urea, as well as condensation products of disulfonic acid derivatives of diphenyl oxide with formaldehyde. As (bi) are preferred:. - the condensation products of ditolylether sulfonates and formaldehyde, as described, for example, in US Pat. No. 4,386,037, the condensation products of phenol and formaldehyde with lignin sulphonates, as described, for example , in the US Patent US-A-3, 931, 072, - the condensation products of acid-β-naphthol- (2) -sulfonic acid, cresol, sodium bisulfite and formaldehyde [see FIAT report 1013 (1946)], and - the condensation products of diphenyl and formaldehyde derivatives, as described, for example, in US Pat. No. 4,202,838. As (bi) the compound of the formula is particularly preferred: wherein X means the direct bond or oxygen, A means the radical of an aromatic compound, which is linked to the methylene group by an annular carbon atom, M means hydrogen or a salt-forming cation, for example, an alkali metal , an alkaline earth metal or ammonium, ynyp, independently of each other, mean a number from 1 to 4. As (bi) a compound of the formula is very particularly preferred: in which (S03Na) 1.4-1.1- means an average sulfonation degree of 1.4 to 1.6. The above dispersing agents are known or can be obtained in analogy to known compounds, according to methods of general knowledge. The total content of anionic copolymer, non-ionogenic block polymer and dispersing agent in the ink according to the invention is from 3 to 9% by weight, based on the total weight of the ink. The proportion of anionic copolymer: non-ionogenic block polymer: dispersing agent in the finished ink, can vary within a wide range, for example, 1.5: 0.5: 1, 1: 0.5: 1.5, 1: 1: 1, 1: 0: 1, 1: 1: 0, 1: 0: 0, 0: l: l or 0: 0: 1. Inks containing anionic copolymer and non-ionogenic block polymer or anionic copolymer and dispersing agent or non-ionogenic block polymer and dispersing agent are preferred. Particularly preferred are inks containing anionic copolymer, non-ionogenic block polymer and dispersing agent. In addition to the dispersion dyes of the formulas (1) to (23), the anionic copolymers, the non-ionogenic block polymers and the dispersing agents, the ink can conveniently contain thickeners of natural origin Or synthetic, such as, for example, commercially customary alginate thickeners, starch ether or carob seed meal ether, in particular sodium alginate by itself or in a mixture with modified cellulose, especially with, preferably, 20 to 25%. % by weight of carboxymethylcellulose. Synthetic thickeners are preferably used in the ink according to the invention, such as, for example, those based on poly (meth) acrylic acids or poly (meth) acrylamides. For the process according to the invention, those inks having a viscosity of 1 to 40 mPa.s (millipascalsecond), in particular, are preferred. 1 to 20 raPa.s, mainly 1 to 10 mPa.s. Similarly, for the process according to the invention, tubs with a surface tension of between 60 and 30 Newtons per centimeter (N / cm), in particular between 50 and 40 N / cm, are preferred. Important inks for the process are those with a conductivity of 0 to 3000 μS / cm, in particular 100 to 700 μS / cm, based on a 10% aqueous suspension. In addition, the inks may contain buffer substances, such as, for example, borax, borate or citrate. As examples, borax, sodium borate, sodium tetraborate, as well as sodium citrate are mentioned, being used in particular in amounts of 0.1 to 3% by weight, mainly 0.1 to 1% by weight, based on the total weight of the product. ink, to adjust a pH of, for example, 4 to 10, preferably 5 to 8. The inks may contain as other surfactant additives, redispersing agents and moisture preserving agents As surfactants come into consideration the anionic and non-ionogenic surfactants commercially. As a redispersing agent, mention should be made, for example, of betaine monohydrate, preferably a mixture of sodium lactate (advantageously in the form of a 50-60% aqueous solution) and glycerin and / or propylene glycol in a preferred manner. amounts, preferably, 7 to 20% by weight in the ink used according to the invention, if desired, the inks can also contain acid donors, such as butyrolactone or hydrophosphate hatred, preservatives, substances to inhibit the growth of fungi and / or bacteria, antifoaming agents, sequestrants, emulsifiers, insoluble solvents in water, oxidants or deaerators.

Suitable preservatives are, in particular, formaldehyde-providing agents, for example paraformaldehyde and trioxane, in particular aqueous formaldehyde solutions, approximately 30 to 40% by weight; as sequestrants, for example, sodium nitrilotriacetate, sodium ethylenediaminetetraacetate, mainly sodium polymetaphosphate, in particular sodium hexametaphosphate; as emulsifiers, especially adducts of an alkylene oxide and a fatty alcohol, in particular an adduct of oleyl alcohol and ethylene oxide; as water-insoluble solvents, high-boiling saturated hydrocarbons, mainly paraffins with a boiling range of about 160 to 210 ° C (called lacquer benzines); as oxidants, for example, an aromatic nitro compound, especially a mono- or dinitrocarbonic or sulphonic acid, which is optionally an alkylene oxide adduct, in particular a nitrobenzenesulfonic acid; and as a deaerator, for example, high-boiling solvents, mainly turpentine, high molecular weight alcohols, preferably alcohols with 8 to 10 carbon atoms, terpene alcohols or deaerators based on mineral and / or silicone oils, in particular commercial formulations of about 15 to 25% by weight of a mixture of mineral oil and silicone and about 75 to 85% by weight of an alcohol with 8 carbon atoms, such as, for example, 2-ethyl-n-hexanol. The inks can be prepared in the usual manner, by mixing the components in the desired amount of water. Preferably, the inks are prepared in such a way that one or more dispersion dyes of the formulas (1) to (23) are stirred with a dispersant / copolymer / block polymer mixture and then ground in a mill in wet, up to a defined milling degree of an average particle size between 0.2 and 1.0 micrometers. Subsequently, the concentrated ground product, optionally using, for example, thickeners, dispersants, copolymers, surfactants, moisture-conserving agents, redispersants, suitable sequestrants and / or preservatives, as well as water, is adjusted to the desired concentration. To remove the coarsest portions possibly present, a filtration of the finished ink can be carried out through a micro-sieve of approx. 5 micrometers. The process according to the invention for printing textile fiber materials, it can be carried out with inkjet printers known per se, suitable for textile printing. In the case of the ink jet printing process, droplets of ink are injected from the nozzle onto the substrate in a controlled manner. For this, the Ink-Jet continuous method, as well as the on-demand drip method, are mainly used. In the case of the Ink-Jet continuous method, the droplets are generated continuously, deviating the particles that are not required for stamping to a collector tank from where, as a rule, they are recycled. In the case of the drop-on-demand method, on the other hand, droplets are generated and stamped as desired, ie, drops are only generated if they are required for stamping. The generation of the drops can be carried out, for example, by means of an injection piezohead or by thermal energy (called Bubble Jet). For the process according to the invention, printing according to the continuous Ink-Jet method or the drip-on-demand method is preferred. After stamping, the fiber material is dried at temperatures of 150 ° C, preferably 80 to 120 ° C. The next fixing of the fiber material is generally carried out by dry heat (thermofixation) or superheated steam at atmospheric pressure (HT fixation). The fixation is carried out under the following conditions: - thermofixation: 1 to 2 minutes at 190 to 230 ° C; - HT fixation: 4 to 9 minutes at 170 to 190 ° C. The ink used according to the invention can be applied to various types of fiber materials, such as cotton, silk, cellulose, polyvinyl, polyacrylonitrile, polyamide, aramid, polypropylene, polyester or polyurne.

Fiber materials containing polyester are preferred. As such, those materials that consist totally or partially of polyester are considered. Examples are cellulose ester fibers, such as, for example, fibers of 2'-acetate or cellulose triacetate, and in particular linear fibers of polyester, which optionally are modified with acid, which are obtained, for example, by condensation of acid. terephthalic with ethylene glycol or isophthalic acid or terephthalic acid with 1,4-bis (hydroxymethyl) -cycothexane, as well as mixed polymer fibers of terephthalic and isophthalic acid with ethylene glycol. Mixed fiber materials containing polyester, ie blends of polyester and other fibers, are also suitable. The object of the present invention is also an aqueous printing ink for the inkjet printing process, which is characterized in that it contains 1 to 35% by weight of at least one dispersion dye of the above formulas (1) to (23), an anionic copolymer and / or a non-ionogenic block polymer and / or a dispersant. For the printing ink according to the invention, as well as for the dispersion dyes of the formulas (1) to (23), the anionic copolymers, the non-ionogenic block polymers and the dispersants used in said ink, the meanings and preferences indicated above. The patterns that can be obtained according to the process according to the invention have good general fastnesses; they have, for example, a high fiber-dye bond stability in both the acid and alkaline range, good photosolidity, good wet fastness, water fastness, wax, sea water, excess color and sweat. , good chlorine resistance, friction, ironing and folding, as well as clear contours and a high intensity of color. The printing inks used are characterized by good stability and good viscosity properties. The following examples serve to illustrate the invention. Unless otherwise indicated, the temperatures are in degrees centigrade, the parts are parts by weight and the percentages refer to percentages by weight. The parts by weight with respect to the parts by volume are in the ratio of kilogram to liter.

Example 1: 2.0 parts by weight of the dispersion dye of the formula are mixed by stirring: with 0.3 parts by weight of a dispersant based on a sulfonated condensation product of an isomeric mixture of chlormethyldiphenyl and naphthalene, and 3.0 parts by weight of an anionic copolymer of acrylic acid and styrene, and then ground in a wet mill for obtain an average particle size of 0.2 to 1.0 micrometers. Subsequently, by the addition under stirring of 1.0 part by weight of a commercially available surfactant, 3.7 parts by weight of a commercially available redispersant, 0.2 parts by weight of a commercially available preservative, 20.0 parts by weight of a commercially available moisture preservative and 69.8 parts by weight of water, the ink is adjusted to a dye content of 2% by weight.

Example 2: The ink obtained according to Example 1 is printed on a polyester fabric with an inkjet printer, by means of a drip-on-demand technique. The print is dried and fixed for 8 minutes in superheated steam at 180 ° C. A bright yellow pattern is obtained with good general solidities, particularly wet and light fastness. A bright yellow print is also obtained with good general fastnesses, particularly wet and light fastness, if the print is dried 1 minute with hot air at 200 ° C.

Example 3: 3.0 parts by weight of the dispersion dye of the formula are mixed by stirring: with 2.0 parts by weight of a dispersant based on a sulfonated condensation product of an isomeric mixture of chlormethyldiphenyl and naphthalene, and 6.5 parts by weight of an anionic copolymer of acrylic acid and styrene ('"Narlex DX2020 from National Starch & Chemical), and then ground in a wet mill to obtain an average particle size of 0.2 to 1.0 microns. Subsequently, by stirring addition of 12.0 parts by weight of 85% glycerol, 5.0 parts by weight of diethylene glycol, 3.0 parts by weight of bentaine monohydrate, 0.1 parts by weight of N-hydroxymethylchloroacetamide and 68.4 parts by weight of water, the ink is adjusted to a dye content of 3% by weight.

Example 4: The ink obtained according to Example 3 is printed on a polyester fabric with an inkjet printer, by means of a drip-on-demand technique. The print is dried and fixed for 8 minutes in superheated steam at 180 ° C. A blue print with good general solidities is obtained, in particular wet and light fastness. A blue print with good general fastness is also obtained, in particular wet and light fastness, if the print is dried 1 minute with hot air at 200 ° C.

Example 5: 2.0 parts by weight of the dispersion dye of the formula are mixed by stirring: with 1.0 part by weight of a dispersant based on a sulfonated condensation product of an isomeric mixture of chlormethyldiphenyl and naphthalene, and 0.3 parts by weight of a nonionic block polymer of alkylene oxide (Plubronic F108 of Albright & Wilson), and then ground in a wet mill to obtain an average particle size of 0.2 to 1.0 micrometer. Subsequently, by stirring addition of 12.0 parts by weight of 85% glycerol, 5.0 parts by weight of diethylene glycol, 3.0 parts by weight of bentaine monohydrate, 0.1 parts by weight of N-hydroxymethylchloroacetamide and 76.6 parts by weight of water, the ink is adjusted to a dye content of 2% by weight.

Example 6: The ink obtained according to Example 5 is printed on a polyester fabric with an inkjet printer, by means of a drip-on-demand technique. The print is dried and fixed for 8 minutes in superheated steam at 180 ° C. A blue print with good general solidities is obtained, in particular wet and light fastness. A blue print with good general fastness is also obtained, in particular wet and light fastness, if the print is dried 1 minute with hot air at 200 ° C.

Example 7: 1.2 parts by weight of the dispersion dye of the formula are mixed by stirring: and 2.2 parts by weight of the disperse dye of the formula with 1.0 part by weight of a dispersant based on a sulfonated condensation product of an isomeric mixture of chlormethyldiphenyl and naphthalene, and then the mixture is milled in a wet mill to obtain an average particle size of 0.2 to 1.0 micrometer. Subsequently, by stirring addition of 12.0 parts by weight of 85% glycerol, 5.0 parts by weight of diethylene glycol, 3.0 parts by weight of bentaine monohydrate, 0.1 parts by weight of N-hydroxymethylchloroacetamide and 75.5 parts by weight of water, the ink is adjusted to a dye content of 3.4% by weight.

Example 8: The ink obtained according to Example 7 is printed on a polyester fabric with an inkjet printer, by means of a drip-on-demand technique. The print is dried and fixed for 8 minutes in superheated steam at 180 ° C. A pink print is obtained with good general solidities, particularly wet and light fastness. A pink print is also obtained with good general fastnesses, particularly wet and light fastness, if the print is dried 1 minute with hot air at 200 ° C.

Example 9: 4.0 parts by weight of the dispersion dye of the formula are mixed by stirring: with 2.0 parts by weight of a dispersant based on a sulfonated condensation product of an isomeric mixture of chlormethyldiphenyl and naphthalene, and 1.0 part by weight of a nonionic block polymer of alkylene oxide (®Pluronic F108 by Albright &ilson) , and 8.0 parts by weight of an anionic copolymer of acrylic acid and styrene (Narlex DX2020 from National Starch &; Chemical), and then the mixture is milled in a wet mill to obtain an average particle size of 0.2 to 1.0 microns. Subsequently, by the stirring addition of 5.0 parts by weight of 85% glycerol, 15.0 parts by weight of diethylene glycol, 2.0 parts by weight of bentaine monohydrate, 0.1 parts by weight of N-hydroxymethylchloroacetamide and 62.9 parts by weight of water, the ink is adjusted to a dye content of 2% by weight.

Example 10: The ink obtained according to Example 9 is printed on a polyester fabric with an inkjet printer, by means of a drip-on-demand technique. The print is dried and fixed for 8 minutes in superheated steam at 180 ° C. A violet print with good general solidities is obtained, in particular wet and light fastness. A violet print with good general fastness is also obtained, in particular wet and light fastness, if the print is dried 1 minute with hot air at 200 ° C.

Example 11: 4.0 parts by weight of the dispersion dye of the formula are mixed by stirring: with 1.0 part by weight of a dispersant based on a sulfonated condensation product of an isomeric mixture of chlormethyldiphenyl and naphthalene, and 3.0 parts by weight of an anionic copolymer based on a partially sulfated octylphenol ethoxylate with 25 units of ethylene oxide per mole of octylphenol (®Emulphor OPS 25 from BASF), and then the mixture is milled in a wet mill to obtain an average particle size of 0.2 to 1.0 micrometer. Subsequently, by the addition under stirring of 10.0 parts by weight of 85% glycerol, 10.0 parts by weight of diethylene glycol, 1.7 parts by weight of bentaine monohydrate, 0.1 parts by weight of N-hydroxymethylchloroacetamide and 70.2 parts by weight of water, the ink is adjusted to a dye content of 2% by weight.

Example 12: The ink obtained according to Example 11 is printed on a polyester fabric with an Inkjet printer, by means of a drip-on-demand technique. The print is dried and fixed for 8 minutes in superheated steam at 180 ° C. A blue print with good general solidities is obtained, in particular wet and light fastness. A blue print with good general fastness is also obtained, in particular wet and light fastness, if the print is dried 1 minute with hot air at 200 ° C. Prints are also obtained with good general solidities, particularly wet and light fastness, if the inks prepared according to examples 1, 3, 5, 7, 9 and 11 are stamped on polyester fabrics using an Inkjet printer, which works according to the bubble jet technique on demand and are treated as indicated above. If the inks prepared according to examples 1, 3, , 7, 9 and 11 are stamped on polyester fabrics using a continuous ink jet method and are treated as indicated above, the result is again a pattern with good general fastnesses, particularly wet and light fastness.

Claims (9)

NOVELTY OF THE INVENTION Having described the foregoing invention, it is considered a novelty, and therefore, the content of the following is claimed as property: CLAIMS

1. A process for the stamping of textile fiber materials, according to the inkjet printing process, characterized in that the fiber materials are stamped with an aqueous ink, which contains at least one dispersion dye, an anionic copolymer and / or a non-ionogenic block polymer and / or a dispersing agent.

2. A process according to claim 1, characterized in that a dispersion dye of the formula is used: in which 'Laughter means halogen, nitro or cyano; R 17 is hydrogen, halogen, nitro or cyano; Ri5 means halogen or cyano; Ri means hydrogen, halogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms; R2- > means hydrogen, halogen or acylamino; and R? and R-, independently of each other, mean alkyl having 1 to 4 carbon atoms, which is unsubstituted or substituted with hydroxy, acetoxy or phenoxy; wherein R23 means hydrogen, phenyl or phenylsulfoxy, wherein the benzene ring on phenyl or phenylsulfoxy is optionally substituted with alkyl having 1 to 4 carbon atoms or alkylsulfo with 1 to 4 carbon atoms; R2 = means amino or hydroxy; R2β means hydrogen or alkoxy with 1 to 4 carbon atoms; R27 means hydrogen or the radical -0-C6H5-S02-NH- (CH2) 3-0-C2H5; R36 is hydrogen, hydroxy or nitro, and R37 is hydrogen, hydroxy or nitro; wherein R23 means alkyl having 1 to 4 carbon atoms, which is unsubstituted or substituted with hydroxy; R:? means alkyl with 1 to 4 carbon atoms; R30 means cyano; R31 means the radical of the formula - (CH2) 3-0- (CH2) -0-C,; H5; R3: means halogen, nitro or cyano; and R33 means hydrogen, halogen, nitro or cyano; wherein R34 means alkyl with 1 to 4 carbon atoms; R35 means alkyl having 1 to 4 carbon atoms, which is unsubstituted or substituted by alkoxy with 1 to 4 carbon atoms; and means the radical -COOCH2CH2OC6H5 and Wx means hydrogen, or W means hydrogen and Wi means -N = N-C6H5; wherein the rings * A "and 'B" are unsubstituted or substituted one or more times with halogen; wherein R34 means alkyl having 1 to 4 carbon atoms, which is unsubstituted or substituted with hydroxy, alkoxy with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms-alkoxy with 1 to 4 carbon atoms; Y

3. A process according to one of claims 1 and 2, characterized in that an copolymer based on acrylic acid, methacrylic acid or maleic acid is used as the anionic copolymer.

4. A process according to claim 3, characterized in that as copolymer anionic copolymer is used from acrylic and / or methacrylic acid and one or more copolymerizable monomers, selected from the group consisting of maleic acid, N-vinylformamide, N- vinylacetamide, allylamine or diallylamine derivatives, N-vinylpyrrolidone, N-vinyl-N-methyl-formamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl-acetamide, vinyl acetate, vinyl propionate, acryl nitrile, styrene, methacryl nitrile, acrylamide, methacrylamide and N-mono / NN-di-alkyl-C? -C? o- (meth) acrylamide. A process according to one of claims 1 to 4, characterized in that alkylene oxide condensation products or block polymers which can be obtained by the addition of styrene to polypropylene oxide and / are used as the non-ionogenic block polymer. or polyethylene. 6. A process according to claim 1, characterized in that an anionic dispersant of the group of (ba) acid esters or their salts of alkylene oxide adducts of the formula is used as the dispersing agent. O-f-Alkylen - O-- (24), (X wherein X means the acid radical of an inorganic acid containing oxygen, such as, for example, sulfuric acid or, preferably, phosphoric acid, or also the radical of an organic acid, and Y means alkyl with 1 to 12 carbon atoms. carbon, aryl or aralkyl; "Alkylene" means the ethylene or propylene radical; and m means 1 to 4; and n means 4 to 50; (bb) polystyrene sulfonates, (be) fatty acid taurides, (bd) mono or di-sulfonates of alkylated diphenyl oxide, (be) sulfonates of esters of polycarboxylic acids, (bf) addition product of 1 to 60, preferably 2 to 30 moles of ethylene oxide and / or propylene oxide in fatty amines, fatty amides, fatty acids or fatty alcohols, respectively with 8 to 22 carbon atoms or in tri to hexavalent alkanols, with 3 to 6 carbon atoms carbon, transformed into an acid ester with an organic dicarboxylic acid or a polybasic inorganic acid, (bg) lignin sulphonates, (bh) naphthalene sulfonates, and (bi) formaldehyde condensation products. 7. A process according to claim 6, characterized in that the dispersant used is an anionic dispersant of the formula: in which X means the direct bond or oxygen, A means the radical of an aromatic compound, which is linked to the group methylene by an annular carbon atom, M means hydrogen or a salt-forming cation, for example, an alkali metal, an alkaline earth metal or ammonium, and n and p, independently of each other, mean a number from 1 to 4. 8. An ink for aqueous printing for the inkjet printing process, characterized in that it contains 1 to 35% by weight of at least one dispersion dye of the formulas (1) to (23), an anionic copolymer and / or a non-block polymer ionogen and / or a dispersant. 9. A textile fiber material embossed by the ink jet printing process, with an aqueous printing ink in accordance with claim 8.