MXPA98004843A - Process for printing textile fiber materials according to the it jet printing process - Google Patents

Abstract

The present invention relates to a process for printing textile fiber materials according to the inkjet printing process, wherein the fiber materials are printed with an aqueous ink comprising: a) at least one reactive dye from the formula (1), or at least one reactive dye of the formula (2), wherein the substituents are as defined in claim 1, and b) water-soluble nonionic cellulose, or an alginate. The process is suitable especially for printing cellulosic fiber materials. The impressions obtained have good firmness properties, while having a high yield of cabbage

Description

PROCESS FOR PRINTING TEXTILE FIBER MATERIALS ACCORDING TO THE INK JET PRINTING PROCESS The present invention relates to a process for printing textile fiber materials using reactive dyes according to the inkjet printing process (Jet and inkjet processes), and the inks used for that process. Inkjet printing processes have been used in the textile industry for some years. These processes make it possible to eliminate the otherwise customary production of a printing screen, so that considerable savings can be made in terms of cost and time. Especially in the case of the production of pattern originals, it is possible to respond to a change in the requirements within a significantly shorter period of time. These ink jet printing processes must have especially optimum characteristics from the point of view of the application technology. In connection with this, features such as viscosity, stability, surface tension, and conductivity of the inks used can be mentioned. In addition, higher demands are made on the quality of the resulting prints, for example, with respect to color fastness, fiber-dye bond stability, and firmness to moisture. These demands are not met by the known processes in all the characteristics, in such a way that there is still a need for new processes for the printing of textile inkjet. The invention relates to a process for printing textile fiber materials according to the inkjet printing process, wherein: the fiber materials are printed with an aqueous ink comprising: a) at least one reactive dye of the formula: wherein: R -? _, R, R3, and R4 are each independently of the others, hydrogen or unsubstituted or substituted alkyl of 1 to 4 carbon atoms, B? is an organic bridging member, AL is the monoazoic, polyazoic, azoic chromium complexed radical of metal, anthraquinone, phthalocyanine, formazan, or dioxazine, which has at least one sulfo group, and A2 is as defined for TO? , or is hydrogen or unsubstituted or substituted alkyl of 1 to 4 carbon atoms, phenyl or naphthyl, or at least one reactive dye of the formula: wherein: R5 is hydrogen or unsubstituted or substituted alkyl of 1 to 4 carbon atoms, Xx is halogen, A3 is the radical of a monoazoic, polyazoic, azoic chromium complex complexed with metal, anthraquinone, phthalocyanine, formazan, or dioxazine, which has at least one sulfo group, and V is a radical that reacts with fiber, of the formula: R N - alkylene S02-Z (3a) N-alkylene-E-alkylene-S02-Z (3b), R-, N-arylene S0- O-C: R- N-arylene - (alkylene) t- -alkylene '-S02- R (3d) N N alkylene-S02-Z (3e) wherein: alkylene and alkylene are each independently of the other, alkylene of 1 to 6 carbon atoms, arylene is a phenylene or naphthylene radical which is unsubstituted or substituted by sulfo, carboxy, alkyl d 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, by halogen, Z is vinyl or a radical -CH2-CH2-U1, and Ux is an output group, R is hydrogen, hydroxy, sulfo, sulfate, carboxy, cyano, halogen, alkoxy from 1 to 4 carbon atoms-carbonyl, alkanoyloxy of 1 to 4 carbon atoms, carba oyl, or the group -S02-Z, R6 is hydrogen, alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by hydroxy, sulfo, sulfate, carboxy, or by cyano, or a radical of the formula: -alkylene-S02-Z, | R R7 is hydrogen or alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by carboxy, cyano, hydroxy, sulfo, or sulfate, E is the radical -O- or -NR8-, and R8 is hydrogen or alkyl of 1 to 4 carbon atoms, is a group of the formula -S02-NR6, -CONR6-, or -NRgCO-, and Rg is as defined above, and t is 0 or 1, and b) a nonionic cellulose ether soluble in water, or an alginate. »Radicals Rl? R2, R3, R4 and R5 as alkyl radicals may be further substituted, for example, by hydroxy, sulfo, sulfate, cyano, or carboxy. R1 t R2, R3, R4, and R5 are preferably each independently of the others, hydrogen or alkyl of 1 to 4 carbon atoms, especially hydrogen. Xx is preferably chlorine, or especially fluorine.

The following are considered as organic bridge members B1, for example: alkylene radicals of 2 to 12 carbon atoms, especially alkylene radicals of 2 to 6 carbon atoms, which may be interrupted by 1, 2, or 3 members of the group -NH-, -N (CH3) -, -O-, especially -O-, and are unsubstituted or substituted by hydroxy, sulfo, sulfato, cyano, or by carboxy, the preferred substituents of the alkylene radicals mentioned for B? they are hydroxy, sulfo, and sulfate, especially hydroxy; cycloalkylene radicals of 5 to 9 carbon atoms, such as especially the cyclohexylene radicals, which are unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkanoyl of 2 to 4 carbon atoms carbon-amino, sulfo, halogen, or carboxy, especially by alkyl of 1 to 4 carbon atoms; methylene-cyclohexylene-methylene radicals which are unsubstituted or substituted on the cyclohexylene ring by alkyl of 1 to 4 carbon atoms; C 1 -C 6 -alkylene- phenylene, or preferably phenylene, which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkanoyl of 2 to 4 carbon atoms-amino , sulfo, halogen, or carboxy. It is also suitable as a radical of the formula -N (R2) -B1-N (R3) -, a radical of the formula: -N N - / Preferably, B1 is an alkylene radical of 2 to 12 carbon atoms. carbon that can be interrupted by 1, 2, or 3 members of the group -NH-, -N (CH3) -, and -0-, and is unsubstituted or substituted by hydroxy, sulfo, sulfate, cyano, or by carboxy; or a phenylene radical which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkanoyl of 2 to 4 carbon atoms-amino, sulfo, halogen, or by carboxy. B? is especially an alkylene radical of 2 to 12 carbon atoms which may be interrupted by 1, 2, or 3, members of the group -NH-, -N (CH3) -, and -0-, especially -0-, and it is unsubstituted or substituted by hydroxy, sulfo, sulfate, cyano, or by carboxy. The alkylene radical is preferably unsubstituted or substituted by hydroxy, sulfo, or by sulfate, especially by hydroxy. Bx is more especially an alkylene radical of 2 to 12 carbon atoms, especially an alkylene radical of 2 to 6 carbon atoms, which may be interrupted by 1, 2, or 3 members -O-, and is unsubstituted or substituted by hydroxy. The members of bridge B? Of special interest are the alkylene radicals of 2 to 6 carbon atoms. Alkylene and alkylene are each independently of the other, for example, a radical of methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, or 1,6-hexylene, or an isomer branched from them. Alkylene and alkylene are preferably an alkylene radical of 2 to 3 carbon atoms, and especially an ethylene radical. Arylene is preferably a 1,3- or 1,4-phenylene radical that is unsubstituted or substituted, for example, by sulfo, methyl, methoxy, or carboxy. The exit group U? is, for example, -Cl, -Br, -F, -OSOsH, -OCO-CH3, -OP03H2, -OCO-C8H5, -OS02 -alkyl of 1 to 4 carbon atoms, or -0S0 -N (alkyl of 1 to 4 carbon atoms) 2. UL is preferably a group of the formula -Cl, -OS03H, -SS03H, -OCO-CH3, -OCO-C6H5, or -OP03H2, especially -Cl or -OS03H, and more especially -OS03H. Z is preferably vinyl or a radical of the formula -CH2-CH2-0S03H, especially vinyl. E is preferably -NH, or especially -O-. it is preferably a group of the formula -NHCO-, or especially -C0NH-. R is preferably hydrogen or the group -S02-Z, wherein Z is subject to the definitions and preferences indicated above. R is especially hydrogen.

Rg is preferably hydrogen, alkyl of 1 to 4 carbon atoms, or an -alkylene-S02-Z group, wherein alkylene and Z are each as defined above. R6 is especially hydrogen or alkyl of 1 to 4 carbon atoms, more especially hydrogen. R7 is preferably hydrogen or an alkyl radical of 1 to 4 carbon atoms, and especially hydrogen. t is preferably the number 0. Special interest is given to the radicals that react with fiber V, wherein: alkylene and alkylene are each independently of the other alkyl of 2 to 3 carbon atoms, R7 is hydrogen, Z is vinyl or a radical of the formula -CH2-CH2-OS03H, especially vinyl, E is the radical -0-, W is a group of the formula -CONH-, and t is the number 0.

Arylene in this case is preferably a radical of 1,3- or 1,4-phenylene which is unsubstituted or substituted, for example, by sulfo, methyl, methoxy, or by carboxy. R and R6 in this case are preferably hydrogen. The radicals that react with preferred fiber V are those of formulas (3b) to (3d), especially of formula (3b) or (3d), and preferably of formula (3b). When A2 is alkyl of 1 to 4 carbon atoms, phenyl, or unsubstituted or substituted naphthyl, it can be, for example, alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by sulfo, sulfate, hydroxy, carboxy, 0 for phenyl; or phenyl or naphthyl, each of which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, carboxy, sulfo, or by halogen. Preference is given to phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, carboxy, sulfo, or by halogen. A2 is preferably the radical of a monoazoic, polyazoic, azoic chromosome complexed with metal, of anthraquinone, of phthalocyanine, of formazan, or of dioxazine, having at least one sulfo group. A radical Al7 A2, or A3 as the radical of a monoazoic, polyazoic, azoic chromium complexed with metal, anthraquinone, phthalocyanine, formazan, or dioxazine, can have customary substituents in the organic dyes bonded to its base structure. The following may be mentioned as examples of substituents on the radicals I A2, and A3: alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, or butyl, it being possible for the alkyl radicals they are additionally substituted, for example, by hydroxy, sulfo, or by sulfate; alkoxy groups having from 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, or butoxy, it being possible for the alkyl radicals to be further substituted, for example, by hydroxy, sulfo ,. or by sulfate; phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen, carboxy, or by sulfo; acylamino groups having from 1 to 8 carbon atoms, especially the alkanoylamino groups, for example, acetylamino, or propionylamino; benzoylamino which is unsubstituted or substituted on the phenyl ring by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen, or by sulfo; phenylamino which is unsubstituted or substituted on the phenyl ring by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen, or by sulfo; N, N-di- / 3-hydroxyethylamino; N, N-di- / 3-sulfatoethylamino; sulfobenzylamino; N, -disulfobenzylamino; alkoxycarbonyl having from 1 to 4 carbon atoms in the alkoxy radical, such as methoxycarbonyl or ethoxycarbonyl; alkylsulfonyl having from 1 to 4 carbon atoms, such as methylsulfonyl or ethylsulfonyl; trifluoromethyl; nitro; Not me; cyano; halogen, such as fluorine, chlorine, or bromine; carbamoyl; N-alkylcarbamoyl having 1 to 4 carbon atoms in the alkyl radical, such as N-methylcarbamoyl or N-ethylcarbamoyl; sulfamollo; N-mono- or N, N-di-alkylsulfamoyl, each having 1 to 4 carbon atoms, such as N-methylsulfamollo, N-ethylsulphamoyl, N-propylsulfamollo, N-isopropylsulphamoyl, N-butylsulphamoyl, it being possible for alkyl radicals are further substituted, for example, by hydroxy or by sulfo; N- (3-hydroxyethyl) -sulfamoyl; N, N-di (3-hydroxyethyl) -sulfamoyl; N-phenylsulfamoyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen, carboxy, or by sulfo; ureido; hydroxy; carboxy; sulfomethyl, or sulfo, and radicals that react with fiber. Examples of radicals that react with fiber include those of the formula -NH-CO-Y, and especially S02-Z, where Z is subject to the definitions and preferences indicated above, and Y is a radical of the formula -CH (Hal) -CH2-Hal, or -C (Hal) = CH2, and Hal is halogen, especially chlorine , or preferably bromine. When A, A2, and A3 are the radical of a monoazoic, polyazoic, or azoic chromophore complexed with metal, the following radicals are especially suitable: Monochrome or monoazo dye chromophore radicals of the formula: DN = N - (MN = N) UK- (4a), DN = N- (MN = N) UK (4b), where D is the radical of a diazo component of the benzene or naphthalene series, M is the radical of a middle component of the benzene or naphthalene series, K is the radical of a coupling component of the benzene, naphthalene series , pyrazolone, 6-hydroxypyridone- (2), or arylamide of acetoacetic acid, and u is the number 0 or 1, it being possible, in the case of the azo dyes, that D, M, and K bear the customary substituents, for example , alkyl of 1 to 4 cn atoms or alkoxy of 1 to 4 cn atoms, each of which is unsubstituted, or may be further substituted by hydroxy, sulfo, or by sulfate; halogen; cxy; sulfo; nitro; cyano; trifluoromethyl; sulfamoyl; cmoyl; Not me; ureido; hydroxy; cxy; sulfomethyl; alkanoyl of 2 to 4 cn-amino atoms; benzoylamino which is unsubstituted or substituted on the phenyl ring by alkyl of 1 to 4 cn atoms, alkoxy of 1 to 4 cn atoms, halogen, or by sulfo; phenyl which is unsubstituted or substituted by alkyl of 1 to 4 cn atoms, alkoxy of 1 to 4 cn atoms, halogen, cxy, or by sulfo; and radicals that react with fiber. Also suitable are metal complexes derived from the above dye radicals of formulas (4a) and (4b), especially the dye radicals of an azo dye complexed with copper in 1: 1 of the benzene or naphthalene series. , wherein the copper atom is linked to a group capable of metalating, for example, a hydroxy group, on each side of the ortho position for the azo bridge. If a radical of chromophore of the formula (4a) or (4b) carries a reactive radical, that radical preferably corresponds to the formula -S02Z indicated above. The radicals of the formulas (4a) and (4b) are preferably those of the formula: wherein (£ 9) 0-3 denotes from 0 to 3 identical or different substituents from the group of alkyl of 1 to 4 cn atoms, alkoxy of 1 to 4 cn atoms, halogen, cxy, and sulfo, and Z it's as defined above, where Z is as defined above, (5c), wherein (R? O'o-4) denotes from 0 to 4 identical or different substituents from the group of halogen, nitro, cyano, trifluoromethyl, sulfamoyl, cmoyl, alkyl of 1 to 4 cn atoms, alkoxy from 1 to 4 cn atoms, amino, acetylamino, ur'eído, hydroxy, cxy, sulfomethyl, and sulfo, and Z is as defined above, wherein (Rn) 0_3 denotes 0 to 3 identical or different substituents from the group of alkyl of 1 to 4 cn atoms, alkoxy of 1 to 4 cn atoms, halogen, cxy, and sulfo, wherein R12 and R1 are each independently of the other, alkyl of 1 to 4 cn atoms or phenyl, and R13 is hydrogen, cyano, cmoyl, or sulfomethyl, where (R9) 0_3, (R? o ^ o-3 '(R?) o -3' and z are ca * a as defined above, and (Rg) o-3 denotes 0 to 3 substituents identical or different from the alkyl group of 1 to 4 cn atoms, alkoxy of 1 to 4 cn atoms, halogen, cxy, and sulfo The radicals of formulas (5a) to (5e) are of special interest The radical of a formazan chromophore is preferably a radical of the formula: (7b), (7a) wherein Z is as defined above, and the benzene cores do not contain other substituents, or are further substituted by alkyl of 1 to 4 cn atoms, alkoxy of 1 to 4 cn atoms, alkyl from 1 to 4 cn atoms - sulfonyl, halogen, or cxy. The radicals of formulas (7a) and (7b) preferably do not contain other substituents and no radical -S02-Z. The radical of a phthalocyanine chromophore is preferably a radical of the formula: (S02W ^ / Pe. \ S0, -NA- (8), where Pe is the radical of a metal phthalocyanine, especially the radical of a copper or nickel phthalocyanine, W is -OH and / or _NR1gR16 /, and R16 and R16 / are each independently of the other, hydrogen, or alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by hydroxy or by sulfo, R15 is hydrogen or alkyl of 1 to 4 carbon atoms, A is a phenylene radical that is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, halogen, carboxy, or by sulfo, or is an alkylene radical of 2 to 6 carbon atoms, and k is from 1 to 3.

The radical of a dioxazine chromophore is preferably a radical of the formula: wherein A 'is a phenylene radical which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, halogen, carboxy, or by sulfo, or is an alkylene radical of 2 to 6 carbon atoms, r, s, v, and v 'are each independently of the others, the number 0 or 1, and Z is as defined above.

The radical of an anthraquinone chromophore is preferably a radical of the formula: wherein G is a phenylene radical which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen, carboxy, or by sulfo, or is a radical of cyclohexylene, phenylenemethylene, or alkylene of 2 to 6 carbon atoms. The radicals A-_, A2, and A3 are preferably radicals of the formulas (5a) to (5e), (6a) to (6d), (7a), (7b), (8), (9), or (10), the radicals of formulas (6a) to (6d), (7a) and (7b) preferably not containing any radical that reacts with fiber. Of particular interest are the radicals of formulas (5a) to (5e), (7a), (7b), and (10), especially the radicals of formulas (5a), (5b), (5c), and (5e). The radicals Ax, A2, and A3 preferably contain each, from 1 to 4 sulfo groups, and preferably from 1 to 3 sulfo groups. The reactive dyes of formulas (1) and (2) each contain at least two groups that react with fiber. For example, the reactive dye of formula (1) contains two triazine radicals which react with fiber, and the reactive dye of formula (2) contains a triazine radical which reacts with fiber, and a radical V which reacts with fiber. The reactive dyes of formulas (1) and (2) preferably each contain only two groups that react with fiber. Special interest is given to the reactive dyes of the formulas: The reactive dyes of formulas (1) and (2) are known, or can be obtained in a manner analogous to the known compounds, for example, by customary reactions of diazotization, coupling, and condensation. The reactive dyes of the formulas (1) and (2) used in the inks, preferably must have a low salt content, that is, they must have a total salt content of less than 0.5 weight percent, based on the weight of the dyes. Reactive dyes having relatively high salt contents as a result of their preparation, and / or as a result of the subsequent addition of diluents, can be desalted, for example, by membrane separation methods, such as ultrafiltration, reverse osmosis, or dialysis The inks preferably comprise as dye exclusively reactive dyes containing sulfo groups, soluble in water, such as those of the formulas (1) and (2) above. The inks preferably have a total content of reactive dyes of the formulas (1) and (2) above, of the to 35 weight percent, especially 10 to 35 weight percent, and more especially 10 to 20 weight percent, based on the total weight of the ink. Suitable water-soluble nonionic cellulose ethers are, for example, methyl, ethyl, hydroxyethyl, methylhydroxyethyl, hydroxypropyl, and hydroxypropylmethyl cellulose. Methyl cellulose and especially hydroxyethyl cellulose are preferred. Cellulose ethers are usually used in ink in an amount of 0.01 to 2 percent by weight, especially 0.02 to 1 percent by weight, and more especially 0.01 to 0.5 percent by weight, based on the total weight of the ink. Suitable alginates are especially alkaline alginates, and preferably sodium alginate. These are used in the ink usually in an amount of 0.01 to 2. percent by weight, especially 0.01 to 1 percent by weight, and more especially 0.01 to 0.5 percent by weight, based on the total weight of the ink . Both the water-soluble nonionic cellulose ethers and the alginates are used as so-called viscosifiers, and make it possible to obtain an ink of a specific viscosity. Preference is given to inks having a viscosity of 1 to 40 mPa-s, especially 5 to 40 mPa-s, and more especially 10 to 40 mPa-s. Especially preferred are inks having a viscosity of 10 to 30 mPa-s. The inks may also comprise pH regulating substances, for example, borax, borates, or citrates. Examples that may be mentioned include sodium borate, sodium tetraborate, and sodium citrate. These are used especially in amounts of 0.1 to 3 weight percent, preferably 0.1 to 1 weight percent, based on the total weight of the ink, in order to establish a pH value, for example, of 5. to 9, especially from 6 to 8. In the case of inks containing alginate, it is preferable to use a citrate regulator. As other additives, the inks may comprise, for example, N-methyl 2-pyrrolidone, or especially 1,2-propylene glycol. These are used in the ink usually in an amount of 5 to 30 weight percent, especially 5 to 20 weight percent, and more especially 10 to 20 weight percent, based on the total weight of the ink. The inks can also comprise customary additives, such as antifoaming agents, or especially substances that inhibit the growth of fungi and / or bacteria. These additives are normally used in amounts of 0.01 to 1 percent by weight, based on the total weight of the ink. The process for printing textile fiber materials according to the invention, can be carried out using ink jet printers, which are known per se, and are suitable for textile printing. In inkjet printing, individual drops of the ink are sprayed onto a substrate in a controlled manner from a nozzle. For this purpose, the continuous ink jet method and the drop on demand method are predominantly used. In the continuous inkjet method, the droplets are produced continuously, and any droplets not required for printing, are transported to a collection container and recycled. However, in the drop-on-demand method, drops are produced and printed according to. required; that is, the drops are produced only when they are required for printing. The production of the droplets can be effected, for example, by means of a piezo-ink jet head, or by means of thermal energy (bubble jet). For the process according to the invention, printing according to the drop-on-demand method is preferred, especially using a piezo-ink jet head. The textile fiber materials that come into consideration, especially fiber materials containing hydroxy group. Preference is given to cellulosic fiber materials that consist wholly or partly of cellulose. Examples are natural fiber materials, such as cotton, linen, and hemp, and regenerated fiber materials, for example viscous and lyocell. A special preference is given to viscose, and especially to cotton. These fiber materials are preferably in the form of textile spun fabrics in sheet form, woven fabrics, or meshes. According to a preferred embodiment of the present invention, prior to printing, the fiber material is subjected to a pretreatment where the fiber material to be printed is first treated with an aqueous alkaline liquor, and optionally Dry the treated fiber material. The aqueous alkaline liquor comprises at least one of the customary bases used to fix reactive dyes in. the conventional reactive printing processes. The base is used, for example, in an amount of 10 to 100 grams / liter of liquor, preferably 10 to 50 grams / liter of liquor. Suitable bases are, for example, sodium carbonate, sodium hydroxide, sodium diphosphate, sodium triphosphate, sodium acetate, sodium propionate, sodium acid carbonate, aqueous ammonia or alkali sources, such as sodium chloroacetate or sodium format. It is preferable to use sodium acid carbonate, sodium carbonate, or a glass mixture of water and sodium carbonate. The pH value of the alkaline liquor is generally from 7.5 to 13.5, preferably from 8.5 to 12.5. In addition to the bases, the aqueous alkaline liquor may also comprise other additives, for example hydrotropic agents. The hydrotropic agent used is preferably urea, which is used, for example, in an amount of 25 to 200 grams / liter of liquor, preferably 50 to 150 grams / liter of liquor. Preferably, the fiber material is dried after the previous pretreatment. After printing, the fiber material is conveniently dried, preferably at temperatures up to 150 ° C, especially 80 ° C to 120 ° C, and then subjected to a heat treatment process, in order to finish the printing, that is, to fix the dye. The heat treatment can be carried out, for example, by means of a hot batch process, a thermosol process, or preferably by means of a vaporization process. In the case of the vaporization process, the printed fiber material is subjected, for example, to a treatment in a steam vaporizer which optionally superheats, in a convenient manner at a temperature of 95 ° C to 180 ° C, more especially in saturated steam. Subsequently, the printed fiber material is generally washed with water in the customary manner in order to remove the unfixed dye. The present invention also relates to aqueous printing inks for the ink jet printing process, which comprise: a) from 5 to 35 weight percent of at least one reactive dye of the formula (1) above, or at least one reactive dye of formula (2) above, and b) 0.01 to 2 weight percent of a water-soluble nonionic cellulose ether, or of an alginate. The printing inks and reactive dyes of formulas (1) and (2) are subject to the definitions and preferences mentioned hereinbefore. The impressions that can be obtained in accordance with the process of the invention, have good overall properties; for example, they have a high degree of fiber-dye bond stability in both the acid and alkaline ranges, good light fastness, good moisture fastness, such as wash fastness, water fastness, to sea water, cross-dyeing and sweat, and good chlorine firmness, firmness to rubbing, firmness to hot ironing, and firmness to the crease, as well as sharp delineation and high color fastness. The printing inks used are distinguished by good stability and good viscosity characteristics. For example, the viscosity remains virtually unchanged, even when high shear forces occur during printing. The following examples serve to illustrate the invention. The temperatures are given in degrees Celsius, the parts are parts by weight, and the percentages refer to the percentage by weight, unless otherwise indicated. The parts by weight refer to the parts by volume in a proportion of kilograms to liters.

Example 1; a) A mercerized cotton satin is dyed on a cushion with a liquor comprising 30 grams / liter of sodium carbonate (70% liquor withdrawal), and dried. b) the cotton satin previously treated according to step a) is printed with an aqueous ink containing: - - 15 weight percent of the reactive dye of the formula: 0.3 percent by weight of hydroxyethyl cellulose, 0.5 percent by weight of borax, and 84.2 percent by weight of water, using a continuous-flow inkjet head. The print is completely dried and fixed for 4 minutes at 102 ° C in saturated steam, rinsed cold, washed to the boil, rinsed again, and dried. A yellow print is obtained which has very good washing resistance.

In point 2: a) A mercerized cotton satin is dyed in a cushion with a liquor comprising 30 grams / liter of sodium carbonate and 50 grams / liter of urea (70% liquor withdrawal), and dried. b) the cotton satin previously treated according to step a), is printed with an aqueous ink containing: 15 weight percent of the reactive dye of the formula: 0.3 percent by weight of hydroxyethyl cellulose, 15 percent by weight of 1,2-propylene glycol, 0.5 percent by weight of borax, and 69.2 percent by weight of water, using a piezo head. Drop stream on demand. The print is completely dried and fixed for 4 minutes at 102 ° C in saturated steam, rinsed cold, washed to the boil, rinsed again, and dried. A blue print is obtained which has very good washing resistance.

Example 3: a) a causticized spunbonded viscose fabric is dyed in a cushion with a liquor comprising 30 grams / liter of sodium carbonate, and 100 grams / liter of urea (collecting the liquor 70%), and dried. b) The causticized spunbonded viscose fabric pretreated according to step a) is printed with an aqueous ink containing: 15 weight percent of the reactive dye of the formula: 0.3 percent by weight of hydroxyethyl cellulose, 15 percent by weight of 2-pyrrolidone N-methyl, 0.5 percent by weight of borax, and 69.2 percent by weight of water, using a piezo-jet head Drop ink on demand. The print is completely dried and fixed for 4 minutes at 102 ° C in saturated steam, rinsed cold, washed to the boil, rinsed again, and dried. A yellow print is obtained which has very good washing resistance.

Example 4; a) a causticized spunbonded viscose fabric is dyed in a cushion with a liquor comprising 30 grams / liter of sodium carbonate, and 150 grams / liter of urea (collecting the liquor 70%), and dried. b) The causticized spunbonded viscose fabric pretreated according to step a) is printed with an aqueous ink containing: 15 weight percent of the reactive dye of the formula: 0.3 percent by weight of hydroxyethyl cellulose, 0.5 percent by weight of borax, and 84.2 percent by weight of water, using a continuous-flow ink jet head. The print is completely dried and fixed for 4 minutes at 102 ° C in saturated steam, rinsed cold, washed to the boil, rinsed again, and dried. An orange print is obtained that has very good washing resistance.

Example 5; a) The mercerized cotton satin is dyed in a cushion with a liquor comprising 30 grams / liter of sodium carbonate (70% liquor withdrawal), and dried. b) The cotton satin previously treated according to step a) is printed with an aqueous ink containing: 15 weight percent of the reactive dye of the formula: 0.3 percent by weight of hydroxyethyl cellulose, and 84.7 percent by weight of water, using a continuous-flow ink jet head. The print is completely dried and fixed for 4 minutes at 102 ° C in saturated steam, rinsed cold, washed to the boil, rinsed again, and dried. You get a red print that has very good wash resistance.

Example 6; a) The mercerized cotton satin is dyed in a cushion with a liquor comprising 30 grams / liter of sodium carbonate, and 50 grams / liter of urea (70% liquor withdrawal), and dried. b) The cotton satin previously treated according to step a) is printed with an aqueous ink containing: 15 weight percent of the reactive dye of the formula: 0.3 percent by weight of hydroxyethyl cellulose, 0.5 percent by weight of sodium citrate, and 84.2 percent by weight of water, using a continuous-flow ink jet head. The print is completely dried and fixed for 4 minutes at 102 ° C in saturated steam, rinsed cold, washed to the boil, rinsed again, and dried. You get a red print that has very good wash resistance.

Example 7; a) The mercerized cotton satin is dyed in a cushion with a liquor comprising 30 grams / liter of sodium carbonate (70% liquor withdrawal), and dried. b) The cotton satin previously treated according to step a) is printed with an aqueous ink containing: 15 weight percent of the reactive dye of the formula (lia), 0.3 weight percent of the sodium, 0.5 percent by weight of sodium citrate, and 84.2 percent by weight of water, using a continuous-flow ink jet head. The print is completely dried and fixed for 4 minutes at 102 ° C in saturated steam, rinsed cold, washed to the boil, rinsed again, and dried. A yellow print is obtained which has very good washing resistance.

Example 8: a) The mercerized cotton satin is dyed in a cushion with a liquor comprising 30 grams / liter of sodium carbonate, and 50 grams / liter of urea (collecting the liquor 70%), and dried. b) The cotton satin previously treated according to step a) is printed with an aqueous ink containing: 15 weight percent of the reactive dye of the formula (11b), 0.3 weight percent of the sodium, 15 weight percent of 1,2-propylene glycol, 0.5 weight percent of sodium citrate, and 69.2 weight percent of water, using a piezo head-drop ink jet demand. The print dries completely and is fixed during 4 minutes at 102 ° C in saturated steam, cold rinse, wash until boiling, rinse again, and dry.

A blue print is obtained which has very good washing resistance.

Example 9: a) a causticized spunbonded viscose fabric is dyed on a cushion with a liquor comprising 30 grams / liter of sodium carbonate, and 100 grams / liter of urea (70% liquor withdrawal), and dried. b) The causticized spunbonded viscose fabric previously treated according to step a) is printed with an aqueous ink containing: 15 weight percent of the reactive dye of the formula (11c), 0.3 weight percent of the sodium alginate, - 15 weight percent of 2-pyrrolidone N-methyl, 0.5 weight percent of sodium citrate, And 69.2 percent by weight of water, using a piezo-jet ink head on demand. The print is completely dried and fixed for 4 minutes at 102 ° C in saturated steam, rinsed cold, washed to the boil, rinsed again, and dried. A yellow print is obtained which has very good washing resistance.

Example 10: a) a causticized spunbonded viscose fabric is dyed in a cushion with a liquor comprising 30 grams / liter of sodium carbonate, and 150 grams / liter of urea (collecting the liquor 70%), and dried. b) The causticized spunbonded viscose fabric previously treated according to step a) is printed with an aqueous ink containing: 15 weight percent of the reactive dye of the formula (lid), 0.3 weight percent of the sodium alginate, 0.5 weight percent sodium citrate, and 84.2 weight percent water, using a continuous-flow ink jet head. The print is completely dried and fixed for 4 minutes at 102 ° C in saturated steam, rinsed cold, washed to the boil, rinsed again, and dried. An orange print is obtained that has very good washing resistance.

Example 11; a) The mercerized cotton satin is dyed in a cushion with a liquor comprising 30 grams / liter of sodium carbonate (70% liquor withdrawal), and dried. b) The cotton satin previously treated according to step a), is printed with an aqueous ink containing: 15 weight percent of the reactive dye of the formula (lie), 0.3 weight percent of the sodium, And 84.7 percent by weight of water, using a continuous-flow inkjet head. The print is completely dried and fixed for 4 minutes at 102 ° C in saturated steam, rinsed cold, washed to the boil, rinsed again, and dried. You get a red print that has very good wash resistance.

Example 12; a) The mercerized cotton satin is dyed in a cushion with a liquor comprising 30 grams / liter of sodium carbonate, and 50 grams / liter of urea (70% liquor withdrawal), and dried. b) The cotton satin previously treated according to step a) is printed with an aqueous ink containing: 15 weight percent of the reactive dye of the formula (Ilf), 0.3 weight percent of the alginate sodium, and 0.5 percent by weight of sodium citrate, And 84.2 percent by weight of water, using a continuous-flow ink jet head. The print is completely dried and fixed for 4 minutes at 102 ° C in saturated steam, cold rinse, wash until boiling, rinse again, and dry. You get a red print that has very good wash resistance.

Claims (15)

1. A process for printing textile fiber materials according to the inkjet printing process, wherein the fiber materials are printed with an aqueous ink comprising: a) at least one reactive dye of the formula: wherein: R1, R2, R3, and R4 are each independently of the others, hydrogen or alkyl of 1 to 4 carbon atoms unsubstituted or substituted, B1 is an organic bridge member, A is the monoazoic, polyazoic chromophore radical , azoic complexed with metal, of anthraquinone, of phthalocyanine, of formazan, or of dioxazine, having at least one sulfo group, and A2 is as defined for Ax, or is hydrogen or alkyl of 1 to 4 unsubstituted carbon atoms or substituted, phenyl or naphthyl, or at least one reactive dye of the formula: wherein: R5 is hydrogen or unsubstituted or substituted alkyl of 1 to 4 carbon atoms, Xj_ is halogen, A3 is the radical of a monoazoic, polyazoic, azoic chromium complex complexed with metal, anthraquinone, phthalocyanine, formazan, or dioxazine, which has at least one sulfo group, and V is a radical that reacts with fiber, of the formula: R N alkylene SO, (3a) N-alkylene-E-alkylene -SO, -Z (3b), I R-7 N arylene S02-Z (3c) R- / \ í N alkylene-S02-Z (3e) \ / wherein: alkylene and alkylene are each independently of the other, alkylene of 1 to 6 carbon atoms, arylene is a phenylene or naphthylene radical which is unsubstituted or substituted by sulfo, carboxy, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, or by halogen, Z is vinyl or a radical -CH ^ CH ^ UL, and O1 is an outlet group, R is hydrogen, hydroxy, sulfo, sulfate, carboxy, cyano, halogen, alkoxy of 1 to 4 carbon atoms-carbonyl, alkanoyloxy of 1 to 4 carbon atoms, carbamoyl, or the group -so2-z, R6 is hydrogen, alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by hydroxy, sulfo, sulfate, carboxy, or by cyano, or a radical of the formula: -alkylene-SO-j-Z, I R R7 is hydrogen or alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by carboxy, cyano, hydroxy, sulfo, or sulfate, E is the radical -O- or -NR8-, and R8 is hydrogen or alkyl of 1 to 4 carbon atoms, is a group of the formula -S02-NR6, -CONRg-, or -NRgCO-, and Rg is as defined above, and t is 0 or 1, and b) a non-ionic cellulose ether soluble in water, or an alginate.

2. A process according to claim 1, wherein R 1 R2, R

3, R, and R 5 are each independently of the others, hydrogen or alkyl of 1 to 4 carbon atoms. A process according to claim 1 or claim 2, wherein B is an alkylene radical of 2 to 12 carbon atoms which may be interrupted by 1, 2, or 3 members of the -NH- group, - N (CH3) -, and -O-, and is unsubstituted or substituted by hydroxy, sulfo, sulfate, cyano, or by carboxy.

4. A process according to any of claims 1 to 3, wherein X-L is fluorine or chlorine, especially fluorine.

5. A process according to any of claims 1 to 4, wherein V is a radical of the formula (3b) or (3d).

6. A process according to any of claims 1 to 5, wherein: alkylene and alkylene are each independently of the other alkyl of 2 to 3 carbon atoms, R7 is hydrogen, Z is vinyl or a radical of the formula -CH2-CH2-OS03H, E is the radical -O-, is a group of the formula -CONH-, and t is the number 0.

7. A process according to any of claims 1 to 6, wherein A1, A2, and A3 are each independently of the others, a radical of the formula: wherein (Rg) or -3 denotes 0 to 3 identical or different substituents from the alkyl group of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen, carboxy, and sulfo, and Z is as defined in claim 1, wherein Z is as defined in claim 1, wherein (R? o ^ o- denotes from 0 to 4 identical or different substituents from the group of halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 atoms of carbon, amino, acetylamino, ureido, hydroxy, carboxy, sulfomethyl, and sulfo, and Z is as defined in claim 1, wherein (Rn) or- denotes 0 to 3 identical or different substituents from the group of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen, carboxy, and sulfo, wherein R12 and R14 are each independently of the other, alkyl of 1 to 4 carbon atoms or phenyl, and R13 is hydrogen, cyano, carbamoyl, or sulfomethyl, where (R9) 0_3, (R? o ^ o-3 '(R? ^ o-3' 'z are given as defined above, and (R9) 0-3 denotes 0 to 3 identical or different substituents from the group of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen, carboxy, and sulfo, wherein Z is as defined above, and the benzene cores do not contain other substituents, or are further substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atoms -sulfonyl, halogen, or carboxy, wherein Pe is the radical of a metal phthalocyanine, especially the radical of a copper or nickel phthalocyanine, W is -OH and / or -NR16R16,, and R16 and R16, are each independently of the other, hydrogen, or alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by hydroxy or by sulfo, R15 is hydrogen or alkyl of 1 to 4 carbon atoms, A is a phenylene radical which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, halogen, carboxy, or by sulfo, or is an alkylene radical of 2 to 6 carbon atoms, and k is from 1 to 3, H- wherein A 'is a phenylene radical which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, halogen, carboxy, or by sulfo, or is an alkylene radical of 2 to 6 carbon atoms, r, 's, v, and v' are each independently of the others, the number 0 or 1, and Z is as defined above, or wherein G is a phenylene radical which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, halogen, carboxy, or by sulfo, or is a radical of cyclohexylene, phenylenemethylene, or alkylene of 2 to 6 carbon atoms.

8. A process according to claim 1, wherein at least one of the reactive dyes of the formulas are used as reactive dyes of the formula (1) or (2):

9. A process according to any of claims 1 to 8, wherein the water-soluble nonionic cellulose ether used is methyl cellulose, or especially hydroxyethyl cellulose.

10. A process according to any of claims 1 to 8, wherein an ink comprising an alginate, especially sodium alginate, is used.

11. A process according to any of claims 1 to 10, wherein an ink having a viscosity of 1 to 40 mPa-s, especially 10 to 30 mPa- s, is used.

12. A process according to any of claims 1 to 11, wherein an ink comprising a pH regulating substance is used.

13. A process according to any of claims 1 to 12, wherein cellulosic fiber materials, especially cotton or viscose, are printed.

14. An aqueous printing ink for the ink jet printing process, which comprises: a) from 5 to 35 weight percent of at least one reactive dye of the formula: wherein: R-_, R2, R3, and R4 are each independently of the others, hydrogen or unsubstituted or substituted alkyl of 1 to 4 carbon atoms, B-_ is an organic bridging member, A? is the monoazoic, polyazoic, azoic chromium complex complexed with metal, anthraquinone, phthalocyanine, formazan, or dioxazine, which has at least one sulfo group, and A2 is as defined for A ?, or is hydrogen or alkyl from 1 to 4 carbon atoms unsubstituted or substituted, phenyl or naphthyl, or at least one reactive dye of the formula: wherein: R5 is hydrogen or unsubstituted or substituted C1-4 alkyl, X1 is halogen, A3 is the radical of a monoazo, polyazoic, azoic chromium complex complexed with metal, anthraquinone, phthalocyanine, formazan, or dioxazine, which has at least one sulfo group, and V is a radical that reacts with fiber, of the formula: R N - alkylene SO- (3a) N-alkylene-E-alkylene '-S02-Z (3b R- N arylene S02-Z! 3c), R- N-arylene - (alkylene) t-W-alkylene '-S02-Z wherein: alkylene and alkylene are each independently of the other, alkylene of 1 to 6 carbon atoms, arylene is a phenylene or naphthylene radical which is unsubstituted or substituted by sulfo, carboxy, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, or by halogen, Z is vinyl or a radical -CH ^ CH ^ UL, and UL is an exit group, R is hydrogen, hydroxy, sulfo, sulfate, carboxy, cyano, halogen, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkanoyloxy, carbamoyl, or the group -S0 2 -Z, R 6 is hydrogen, C 1 -C 4 alkyl which is unsubstituted or substituted by hydroxy, sulfo, sulfate, carboxy, or by cyano, or a radical of the formula: -alkylene-S02-Z, R R7 is hydrogen or alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by carboxy, cyano, hydroxy, sulfo, or sulfate, E is the radical -O- or -NR8-, and R8 is hydrogen or alkyl of 1 to 4 carbon atoms, W is a group of the formula -S02-NRg, -CONR6-, or -NRgCO-, and Rg is as defined above, and t is 0 or 1, and b) from 0.01 to 2 percent in weight of a nonionic cellulose ether soluble in water, or an alginate.

15. An aqueous printing ink according to claim 14, which comprises 0.01 to 2 weight percent of an alginate.