TW200946600A - Fibre-reactive dyestuffs containing a trifluoromethyl group - Google Patents

Abstract

The present invention claims dyestuffs of the formula (I) wherein X, RG and M are defined as given in claim 1, a method for their preparation and their use.

Description

200946600 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to the technical field of fiber-reinforced azo dyes. [Prior Art] Dyes containing a trifluoromethyl group and a coloring agent are known and described in the literature. 〇 For example, GB732 12 1 discloses a monoazo acid dye comprising a trifluoromethylbenzenesulfonic acid. Azo pigments derived from trifluoromethylaminobenzenesulfonic acid are known from CAN6 1 : 33096, CAN 66: 96276 and CAN 67: 1 0098 1 . For fiber-reactive dyes, trifluoromethyl groups are, for example, GB 2 259 710 A, EP 0 094 020 Al, EP 0 354 409 Al, EP 0 3 85 426 Al, EP 0 433 764 Al, EP 470 93 0 Al, EP 0 603 1 1 6 Al and the genus of EP 0 872 523 A2 are taught. However, all of these reference files lack the exact teaching content of such dyes. Surprisingly, it has been found that a fiber-reactive dye obtained from a trifluoromethyl-containing aminobenzenesulfonic acid as a diazo-based component exhibits a particularly advantageous firmness profile when applied in an active manner to cotton products, in particular Lightness, chlorine fastness and sweat fastness. Again, these dyes give a uniform hue with good contact fastness after washing off. SUMMARY OF THE INVENTION Accordingly, the present invention provides a dye having the following formula (I) 200946600

Wherein the lanthanide is an aromatic or heteroaromatic divalent group;

RG is a reactive group capable of forming a covalent bond to cellulose under dyeing conditions or a group comprising a covalent bond capable of forming a cellulose bond under dyed conditions. a reactive group; or a group having the following formula (VIII)

〇B is 1,2-phenylene, 1,3-phenylene or 1,4-phenylene, which are unsubstituted or substituted by -S03M, -COOM or R1, or (C2_C6)-alkylene Or (Ci-C4)-subhomo-phenylene, which are unsubstituted or substituted by R1; each R1 is independently hydrogen, (Ci-Ce)-alkyl, thio-(c^ -Ce)-alkyl 'phenyl or by (C!-C4)-homo, (C!-C4)-homoyloxy, thiol, -S〇3M, halogen, -COOM, ethylamino, or Urea-substituted phenyl; Q3 is chloro, fluoro, cyanoamino, hydroxy, (Ci-CJ-alkoxy, phenoxy, thiophenoxy, fluorenyl, (Ct-Ce)-alkyl fluorenyl , pyridyl, carboxypyridyl or carbamopyridinyl; -6- 200946600 and an equivalent of hydrazine hydrogen, an alkali metal or an alkaline earth metal. A preferred aromatic or heteroaromatic divalent representing X The group corresponds to one of the following formulas (Ila) to (Ilj)

among them

Ar-phenyl or phenyl substituted by 1, 2 or 3 substituents selected from the group consisting of: (CrCd-alkyl, (C^Cd-alkoxy, and -S) Ο 3 Μ ; Ε 1 has one of the meanings of Ar, a naphthyl group or a naphthyl group substituted by 1, 2 or 3 substituents selected from the group consisting of: (C!- 200946600 C4) _alkyl, (Ci-C4)-alkoxy, ·8〇3Μ, amino, ethylamino, or thiol; or a 5- or 6-membered heterocyclic residue including one or two heteroatoms' The hetero atom is selected from the group consisting of nitrogen to oxygen and sulfur, or a 5- or 6-membered heterocyclic residue comprising one or two heteroatoms selected from the group consisting of the group consisting of Nitrogen, oxygen and sulfur, the residue being substituted by 1, 2 or 3 substituents selected from the group consisting of: (Ci-c4)-alkyl and (Cl_c4)-alkane E2 is a phenylene group or a naphthylene group which is unsubstituted or substituted by 1, 2 ❹ or 3 substituents selected from the group consisting of: (CrC*) )-alkyl, (Ci-CU)-alkoxy, -so3m, amino, ethylamino Or a thiol group; or a divalent 5- or 6-membered heterocyclic residue comprising one or two heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur; Or a divalent 5- or 6-membered heterocyclic residue comprising one or two heteroatoms selected from the group consisting of: nitrogen, gas, and sulfur' '2 or 3 substituents, the substituents being selected from the group consisting of: (CrC4)-alkyl and (Ci_c4) _ _ _ oxy; or a group having the following formula (VIII)

-so3m, or via R.5 system (C1-C4)-hospital, (C1-C4)-homoyloxy, R1 is as defined above; -8- 200946600 R2 is a (CVC4)-alkyl or - COOM ; R3 is hydrogen, -CN or -CONH2 ; L has one of the meanings of B; - Μ is as defined above; and * is a bond to the group RG. Examples of 5- or 6-membered heterocyclic residues representing one or two heteroatoms of oxime 1 are pyridone, pyrazolone and diaminopyridine. Similarly, examples of the divalent 5- or 6-membered heterocyclic residue including one or two heteroatoms of the formulae 2 are divalent pyridone, pyrazolone, and diaminopyridine residues. • A particularly preferred aromatic or heteroaromatic divalent group representing X corresponds to the following formula (Ilk) to (Ilr)

The definitions of Μ and * are given above. -9- 200946600 represents a reactive group capable of forming a covalent bond to cellulose under dyeing conditions -S〇2-CH = CH2, -S02-CH2CH2Z1, or a group having the following formula (III) Mission - (III)

-NCR^-A wherein Z1 is a group capable of eliminating the domain; R1 is as defined above; A is a group having the formula (Ilia), (Illb) or (IIIc)

(lllc) V is fluorine or chlorine; U1 and U2 are independently fluorine, chlorine or hydrogen; and Q1 and Q2 are independently chlorine, fluorine, cyanoamino, hydroxyl, (C丨-C6)-alkoxy, phenoxy , thiophenoxy, fluorenyl, (C^-Cd-alkylindenyl, pyridyl, carboxypyridyl, carbacholyl or a group having the formula (IV) or (V) below N, WS 〇 2Z2 (IV) X — N, R 8 (V) 200946600 wherein R 6 has one of the meanings of R 1 ; R 7 and R 8 independently have one of the meanings of R 1 or are combined to form a 5′ β ΐ system oxygen, sulfur, Sulfonium, or -nR9_ and R9 (Ci-Ce)-alkyl; W-phenylene, which is unsubstituted or substituted by 1 or 2 substituents, © these substituents are selected from the group consisting of The group includes: (Ci-C*)-alkyl, (CVC4)-homolyl, carboxyl, sulfo, chloro and bromo; or (Cl_C4)-alkylene phenylene, (c2-c6)-Asia Alkyl groups, which may be interrupted by oxygen, sulfur, sulfonyl, amino, carbonyl or formamidine; or phenylene-CONH-phenylene, which is unsubstituted or substituted by 1 or 2 substituents Substituted, the substituents are selected from (CpQ)-alkyl, (C丨-C4 Alkoxy, hydroxy, sulfo, carboxy, amino, ureido, and halogen; or naphthylene, which is unsubstituted or substituted by one or two sulfo groups; and • Z2 series - CH = CH2 or -CH2CH2Z1. A particularly preferred group of reactive groups representing RG capable of forming a covalent bond to cellulose under dyeing conditions has groups of the following formulas (111d) to (Illi) -11 - 200946600 -S〇2-CH=CH2 (Hid) -SO2-CH2CH2OSO3M (llle)

(IMh) where R6 and M are as defined above. In the formula disclosed in the present specification, the alkyl group may be straight or branched, and particularly methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl And tert-butyl. (The CrCd.alkyl group may additionally be n-pentyl or n-hexyl. Methyl and ethyl are preferred. The same reasoning applies to alkoxy groups, and therefore the alkoxy group is preferably a methoxy group and an ethoxy group, and is suitable for an alkylene group. a group of groups, especially ethylene, propylene and butylene. Halogen is preferably bromine, chlorine and fluorine. The city is especially lithium, sodium or cesium; the equivalent of a soil metal equivalent, especially calcium. Preferably, hydrazine is hydrogen or sodium. Representative groups of Ζ1 capable of eliminating domains such as halogens, such as chlorine and bromine; organic carboxylic acids and ester groups of sulfonic acids, such as alkyl carboxylic acids, substituted or unsubstituted Benzoic acid and substituted or unsubstituted benzenesulfonic acid, especially -12- 200946600 is an alkanoyloxy group of 2 to 5 carbon atoms like ethoxylated oxy, phenyloxy, sulfophenoxy, benzene Sulfhydryloxy and tolylsulfonyloxy, and acidic ester groups of inorganic acids such as phosphoric acid, sulfuric acid and -thiosulfuric acid (phosphate, sulfate and thiosulfate groups) And a dialkylamino group having an alkyl group each having 1 to 4 carbon atoms, such as dimethyl And a diethylamino group. Zl preferably chlorinated, and more preferably sulfato is 0 preferred dye having the formula (I) to correspond to the formula (La) to (Ic)

The definitions of X, RG and Μ are given above. Particularly preferred dyes of formula (I) correspond to formulas (Ia) to (Ic)' wherein X, RG and hydrazine have the preferred meanings as defined above. An especially preferred dye having the formula (1) corresponds to the formulae (Ia) to (IC)' wherein X, RG and oxime have the preferred meanings as defined above. Therefore, an especially preferred dye having the formula (1) is, for example, a dye having the following formula (I d) to (1S) -13- 200946600

Wherein A1 is a group having the formula (Illf), (Illg), (Illh) or (Illi); A2 is a group having the formula (Illd) or (Ille); R1 (> is methyl, methoxy Or a group of -S03M; and the definition of hydrazine is as defined above. The dye of formula (I) can be prepared by a synthetic procedure known to the skilled person. In a preferred method, a compound of the formula (VI)

(VI) 200946600 wherein hydrazine is as defined above, diazotized and coupled to a compound of formula (VII) (VII)

-X-RG wherein X and RG are as defined above. Compounds of formula (VI) are known and can be prepared in accordance with what is taught in DE 629 257 257. Compounds of formula (VII) are also known and can be prepared by known methods. The dyes of the formula (I) of the invention have useful application characteristics' and can be used for dyeing and printing materials comprising formamidine and/or hydroxyl groups. The materials mentioned can be present in the form of, for example, a sheet-like structure (like paper and leather), in the form of a film (for example like a polyamide film), or in the form of a bulk composition (for example by Made up of polyamine or polyurethane). In particular, however, they are present in the form of fibers of the materials mentioned. Accordingly, the dyes of the invention having formula (I) are used to dye and print any type of cellulosic fibrous material. They are preferably also used for dyeing or printing polyamide fibers or blends of polyamide and cotton or with polyester fibers. It is also possible to use the dye of the formula (I) of the present invention to print a fabric or paper by an ink jet method. Accordingly, the present invention also provides the use of a dye of the formula (I) according to the invention for dyeing or printing a material comprising a carbenamide and/or a hydroxyl group, or, as the case may be, in a conventional manner The material is dyed or the method of printing -15-200946600, wherein one or more dyes of formula (I) according to the invention are used as a colorant. Advantageously, the thus-synthesized solution of the dye of formula (I) of the present invention (after appropriate addition of a buffer material, and optionally after concentration or dilution) can be used directly as a liquid product for dyeing. Fibrous materials or fibers herein especially refer to textile fibers which may be present as a braid, yarn or in the form of a skein or wrap. The meglumine-containing materials are, for example, synthetic and natural polyamines and polyurethanes, especially in the form of fibers, such as wool and other animal hair, silk, leather, nylon-6,6, nylon-6, Nylon-1 1 and nylon-4 〇 hydroxyl-containing materials are those of natural or synthetic origin, such as cellulosic fiber materials or their regenerated products, as well as polyvinyl alcohol. The cellulosic fiber material is preferably cotton, and other plant fibers such as linen, hemp, jute, and ramie fibers. Regenerated fibers of cellulose are, for example, staple fiber viscose fibers and filament viscose fibers. The dyes of the invention having the formula (I) can be applied and fixed to the materials mentioned, in particular by the use of techniques known for water-soluble dyes, in particular for fiber-reactive dyes, in particular On fibrous materials. Wool has been subjected to a final process without fluff or low shrinkage (see for example H. Rath, Lehrbuch der Textilchemie, Springer-Verlag, 3rd edition (1 972), pp. 295-299, in particular by the so-called Hercosett The final treatment of the method (ρ·298); J. Soc. Dyers and Colourists 1972, 93-99, and 1975, 33-44) can be dyed and 200946600 has very good fastness properties. The method of dyeing wool products is carried out here from an acidic medium in a conventional manner. For example, acetic acid and/or ammonium sulphate or acetic acid and ammonium acetate or sodium acetate can be added to the dyebath to obtain the desired pH. In order to obtain an acceptable degree of homogenization, it is preferred to add a conventional leveling agent, for example one based on cyanuric chloride and three times the molar amount of an aminobenzenesulfonic acid and/or an aminonaphthalenesulfonic acid. The reaction product, or based on, for example, a reaction product of stearylamine and ethylene oxide. For example, the dyes of the present invention preferably undergo a depletion dyeing process initially from an acid dyebath having a pH of about 3.5 to 5.5 under pH control conditions, and then convert the pH to neutral at the end of the dyeing time and optionally It is weakly basic (ranging to pH 8.5) to bring about complete active bonding between the dyes and fibers of the invention (especially for very deep shades). At the same time, the portion of the dye that is not actively bound is removed. The methods described herein are also suitable for dyeing on fibrous materials made from other natural polyamides or synthetic polyamides and polyurethanes. Such materials can be dyed using conventional dyeing and printing methods as described in the literature and known to those skilled in the art (see, for example, Η. - K. Rouette, Handbuch d e r T extil veredlung,

Deutscher Fachverlag GmbH, Frankfurt/Main). The dye liquor and the printed paste, together with the dye of formula (I), may comprise additional additives. Additives are, for example, wetting agents, antifoaming agents, leveling agents, and agents which affect the properties of the fabric material, such as softeners, for use in a fireproof final treatment as well as soiling, drainage and oil removal additives or water softeners. Printed pastes may also contain, in particular, natural or synthetic thickeners such as, for example, algae-17-200946600 acid salts and cellulose ethers. The amount of dye in the dye bath and the printed paste can vary widely depending on the depth of the desired hue. In general, the dyes of the formula (I) are present in an amount of from 0.01% to 15% by weight, based on the dyed material and the printed paste, and in particular from 0.1% to 10% by weight. The quantity exists. On cellulose fibers, they are made from a variety of acid-binding agents (and, if appropriate, neutral salts such as sodium chloride or sodium sulfate) using depleted dyeing from a high liquor, dyed products. Has a very good amount of color. The application of the dye is preferably at a pH of from 3 to 7, and the pH is particularly from 4 to 6 for the depletion process. The bath ratio can be selected within a wide range and is, for example, between 3:1 and 5:1, preferably between 5:1 and 3:1. The dyeing is preferably from 40 ° C to 105 ° C. (at a temperature between, suitably under pressure at a temperature of up to 130 ° C, and where appropriate in the presence of a conventional dyeing aid, in a water bath. To increase the moisture resistance of the dyed material 'Unfixed dyes can be removed in a post-treatment. This post-treatment is especially at pH 8 to 9 and the temperature is 75 ° C to 80. (Available in time.) A possible method here is to introduce the material. The warm water bath is gradually heated and the bath is gradually heated to the desired temperature and the dyeing process is completed at this temperature. It is also possible (if desired) to accelerate the dye-depleted neutral salt to the water bath only after the actual dyeing temperature has been reached. The padding method also provides excellent color yield on cellulose fibers and a very good color accumulation. The dye system is fixed in batches by a conventional method at room temperature or at the temperature of the rise, for example. Steam treatment or use of dry -18-200946600 heat up to about 60. (:. Similarly 'usual printing methods for cellulose fibers can be carried out in one step', for example by using one containing sodium bicarbonate or some of them The paste of the acid-binding agent is printed and subsequently steamed at 100 ° c to 103 ° C 'either in two steps, for example by using a neutral or weakly acidic printed color. Printing, and then by overprinting the printed material through a hot electrolyte-containing city bath or by using an alkaline electrolyte-containing padding solution and then over-staining the domain The material is fixed in batch or steam treatment or dry heat treatment, which produces a strong color print with a sharp outline and a clear white base. The result of the printing is affected by changes in fixing conditions. According to the conventional thermal fixation method, hot air of 120 ° C to 200 ° C is used for dry heat fixation. In addition to the conventional steam at l ° ° ° C to 103 ° C, it is possible to use The temperature is up to 160. (: superheated steam and high pressure steam.) Acid-binding agents that affect the fixing of dyes on cellulose fibers, such as water-soluble alkaline salts of alkaline earth metals, and likewise no organic or organic acids. Or release the city when heated Alkaline earth metal of the composition. Particularly suitable are alkaline earth metal hydroxides and alkali metal salts of weak to medium strength inorganic or organic acids, and preferred alkaline earth metal compounds are sodium and potassium compounds. Sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, sodium formate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium trichloroacetate, water glass or trisodium phosphate. The present invention has the formula (I) The dyes are noticed by the high activity, good -19-200946600 good fixing ability 'very good accumulation ability and high light fastness and perspiration fastness. Therefore, they can be exhausted The dyeing method is applied at low dyeing temperatures and requires only a short steam treatment time in the padding steam treatment. The degree of fixation is high and the unfixed parts are easily washed away, and between the consumption and the fixation The difference is very small, ie the loss in soaping is very low. They are also particularly useful for printing, especially on cotton, and also for the printing of nitrogen-containing fibers such as wool or silk or blended fabrics containing wool or silk. © The dye of the formula (I) of the present invention, it is noted that the unfixed portion of the dye is easily washed away from the fibrous material after the dyeing operation, and the white portion which is included in the washing operation is not removed. Coloring or staining. This leads to some advantages for the dyeing operation, in which the washing cycle is saved and thus the cost is saved. The dyes and prints produced by the dyes of the invention having the formula (I) have a high color strength and a high fiber-dye bond stability in the acidic region as well as in the alkaline region, and also have good light. Fastness® and very good wet and firm properties such as wash, water, sea water, cross-dyeing and firmness of sweat as well as good fastness to pleating, hot pressing and frictional discoloration. The present invention also provides an ink for printing on a digital fabric by an ink jet method. The inks include the dye of the formula (I) of the present invention. The ink of the present invention comprises one or more dyes of the formula (1) of the invention based on the total weight of the ink, for example from 0.1% by weight to 50% by weight, preferably from 1% by weight. An amount of 30% by weight 'and more -20- 200946600 is preferably from 1% by weight to 15% by weight. For the ink used in the continuous flow method, the conductivity of 0.5 mS/m to 25 mS/m can be set by adding an electrolyte. Useful electrolytes include, for example, lithium nitrate and potassium nitrate. The ink of the present invention may include an organic solvent having an overall level of from 1% to 50% and preferably from 5% to 30% by weight. Suitable organic solvents are, for example, alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, tert-butanol, pentanol, polyols, for example: 1,2-ethanediol, hydrazine 1 , 2,3-propanetriol, butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, 2,3-propanediol, pentanediol, 1,4-pentane Glycol, 1,5-pentanediol, hexanediol, 0-Jiang-1,2-hexanediol, 1,6-hexanediol, 1,2,6-hexanetriol, 1,2-octane Alcohol, polyalkylene glycol, for example: polyethylene glycol, polypropylene glycol, alkylene glycol having 2 to 8 alkylene groups, such as: monoethylene glycol, diethylene glycol, triethylene glycol , tetraethylene glycol, thioglycol, thiodiglycol, butyl triethylene glycol, hexanediol, propylene glycol, dipropylene glycol, tripropylene glycol, a lower alkyl ether of a polyol, such as ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol mono-β-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triglyceride Alcohol monobutyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, propylene glycol Methyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, tripropylene glycol isopropyl ether 'polyalkylene ether ether, such as: polyethylene glycol monomethyl ether, polypropylene glycol glyceryl ether, polyethylene glycol tridecyl ether , polyethylene glycol nonylphenyl ether, amines such as: methylamine, ethylamine, triethylamine, diethylamine, dimethylamine, trimethylamine, dibutylamine, diethanolamine, triethanolamine, hydrazine _ Formamidine ethanolamine, ethylenediamine, urea derivative, such as: urea, thiourea, guanidine-methylurea, hydrazine, hydrazine, -ε -21 - 200946600 dimethyl urea, ethylene urea, 1,1,3 , 3-tetramethylurea, N-acetylethanolamine, guanamines, such as, for example, dimethylformamide, dimethylacetamide, acetamide, ketone or keto alcohol, such as: acetone, two Acetone, a cyclic ether such as, for example, tetrahydrofuran, trimethylolethane, trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol, γ-butyrolactone, ε-hexyl Indoleamine, additional cyclobutyl hydrazine, dimethylcyclobutyl hydrazine, methylcyclobutyl fluorene, 2,4-dimethylcyclobutyl milling, dimethylhydrazine, butadiene oxime, dimethyl hydrazine, dibutyl Chia Ν, Ν-cyclohexyl Pyrrolidone, Ν-methyl-2-pyrrolidone, Ν-ethylpyrrolidone, 2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone, 1-(3-hydroxypropyl)-2 -pyrrolidone, 1,3-dimethyl-2-iethylurea (l,3-dimethyl-2-imidazolidinone), 1,3-dimethyl-2-imidazolidinone (l,3-dimethyl- 2-imidazolinone), 1,3-dimethoxymethylimidazolidine, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-d-butyl) Oxyethoxyethoxy) Ethanol, 2-(2-propoxyethoxy)ethanol, pyridine, acridine, butyrolactone, trimethylpropane, 1,2-dimethoxypropane, dioxane Ethyl acetate, ethylenediaminetetraacetate ethylpentyl ether, 1,2-dimethoxypropane and trimethyl® propane. The ink of the present invention may further comprise a conventional additive such as a viscosity decelerating agent so as to be at a temperature of from 20. C to 50. The viscosity is set from 1.5 mPas to 40.0 mPas over the temperature range of C. The preferred ink has a viscosity of from 1.5 mPas to 20 mPas, and a particularly preferred ink has a viscosity of from 15 mPas to 15 mPas. Useful viscosity moderators include rheological additives such as polyethylene caprolactam, polyvinylpyrrolidone, and polyethers of their copolymers-22-200946600 alcohols, associative thickeners, polyureas, polyurethanes, Sodium alginate, modified galactomannan, polyether urea, polyurethane, and nonionic cellulose ether. As a further additive, the ink of the present invention may include a surface active material to set a surface tension of 20 mN/m to 65 mN/m, which is suitable (if necessary) as the method used (heat or pressure technology) a function of ). Useful surface active materials include, for example, all surfactants, preferably nonionic surfactants, butyl diglycol, and 1,2-hexane diol. The ? ink may further include a conventional additive such as a substance which inhibits the growth of fungi and bacteria, and its amount is from 0.01% to 1% by weight based on the total weight of the ink. The ink of the present invention can be prepared by mixing various components in water in a conventional manner. The ink of the present invention is particularly useful for printing a wide variety of pretreatment materials such as silk, leather, wool, any kind of cellulosic fiber material, polyurethane, and polyamide fibers in an ink jet printing process. The Ink® of the present invention is also suitable for printing pretreated hydroxyl-containing and/or amino-containing fibers present in a mixture, examples of which are cotton, silk, wool and polyester or polyamide fibers. . Unlike conventional fabric printing, where the printing ink already contains all of the fixing chemicals and thickeners for a reactive dye, the auxiliaries must be applied to the inkjet printing process in a separate pretreatment step. Fabric substrate. Pretreatment of the fabric substrate, such as cellulose and regenerated cellulose fibers, as well as silk and wool, is carried out with an aqueous alkaline solution prior to printing. In order to fix the reactive dye, it is necessary to have 缄 'such as sodium carbonate, carbonic acid-23-200946600 sodium hydrogen, sodium acetate, trisodium phosphate, sodium citrate, sodium hydroxide, city donors, such as sodium chloroacetate, sodium formate, Hydrophilic substances such as, for example, urea, reduction inhibitors such as sodium nitrobenzene sulfonate, and also thickeners for preventing the flow of movable substances when printing ink is applied, such as sodium alginate, modified polyacrylates Or highly etherified galactomannan. The pretreatment reagents are applied uniformly to the fabric substrate in a defined amount using a suitable applicator, such as by means of a 2 or 3 roller ink roll, contactless spray technique, by foam coating or by suitably adapted Spray ink technology and then dry. After printing, the textile fiber material is dried at 120 ° C to 150 ° C and subsequently fixed. Fixation of inkjet prints prepared with reactive dyes can be carried out at room temperature or with saturated steam, with superheated steam, with hot air, with microwaves, with infrared radiation, with excitation light or with electron beams or with others Proper energy transfer techniques are carried out. There is a difference between the one-stage and two-stage fixation methods. In the one-stage solid beta process, the necessary fixing chemicals are already on the fabric substrate. This pretreatment is not necessary in the two-stage fixation method. Fixing only requires the domain (after ink jet printing) to be applied prior to the fixing process without an intermediate drying process. No additional additives such as urea or thickeners are required. Fixing is followed by post-printing treatment which is a prerequisite for good fastness, high brightness, and a flawless white substrate. The printed product produced by the ink of the present invention not only has high color strength in an acidic but alkaline region, but also has a high fiber-dye bond stability -24-200946600, as well as good light fastness and very good The wet and firm properties, such as washing, water, sea water, cross-dyeing, and the firmness of sweat, as well as good firmness for pleating, hot pressing, and frictional discoloration. [Examples] Example 1 2-Amino-4-trifluoromethylbenzenesulfonic acid (3.29 g, 0.014 mol) was added to water (50 ml) with stirring and mixed with a 1% sodium carbonate solution. The pH was adjusted to 7.0 to effect dissolution. Sodium nitrite (1.1 g, 0.016 mol) was added to the solution, and after stirring the solution for 10 minutes, it was added dropwise to a mixture of stirred ice (100 g) and concentrated HCl (15 ml). External cooling to ensure that the temperature is maintained at < 5 °C. After another 30 minutes, the re-nitridation was completed and the excess nitrite was broken by the addition of sulfamic acid. A monoazo dye having the following formula (12.09 g, ❹ 0 · 0 1 4 mol) prepared according to the prior art before partial addition of the diazonium salt solution over 15 minutes

It was dissolved in water (150 ml) and the pH was maintained at 5.0-6.0 throughout the process by the addition of 2N sodium carbonate solution. After stirring for an additional hour, the reaction mixture was dialyzed to remove the salt prior to evaporation in vacuo to give the desired product as a dark solid (20.02 g) which presented analytical data 200946600 consistent with the expected structure. Xmax is 592nm and smax is 38900°

Example 2 2-Amino-4-trifluoromethylbenzoic acid (5.0 g, 0.02 mol) was added to water (1 ml) with stirring, and the pH was adjusted to 6.0 with a sodium carbonate solution to effect dissolution. Sodium nitrite (1.4 g, 0.02 mol) was added to the solution, and after stirring the solution for 10 minutes, a mixture of stirred ice (25 g), water (25 g) and concentrated HCl (15 ml) was added dropwise. By using external cooling to ensure that the temperature is maintained at <5. (:. After another 30 minutes, the diazotization was completed, and the excess nitrite was destroyed by the addition of sulfamic acid before the addition of citric acid (8.09 g, 0.02 mol), and stirred while adding sodium bicarbonate. The pH was raised and maintained at 2.0. After 2 hours, the temperature had reached ambient temperature and chromatography indicated that the coupling was complete. The dye obtained had the following formula

The diazonium salt of 4-sulfatoethylsulfonanilide (〇·〇2 mol) was added portionwise to the solution according to step a) of the above step -26-200946600 before the pH was adjusted to 4.0 with sodium bicarbonate. Cold suspension. The mixture was then allowed to warm to ambient temperature and the pH was maintained at 4.0 overnight. Then, the solution was concentrated under vacuum before the product was precipitated by controlled addition of methylated alcohol. The solid was isolated by filtration and dried in a blast oven at 40 ° C to give the desired product as a dark solid (30.5 g) which presented analytical data consistent with expected product , Xmax is 601 nm, and smax is φ 45000.

Example 3

a) The dye according to Example 2a) is isolated before its intensity is determined by combustion analysis. b) - a mixture of sulfonated anilines of the formula

Prepared according to the art by condensation of 2,4,6-trifluoropyrimidine and 2,4-diaminobenzenesulfonic acid and comprising a specified positional isomer of about -27-200946600 2:1 mixture. c) The aniline mixture (53.45 g, 0-70 mol) sulfonated according to the above step b) was dissolved in water (200 ml), and the pH was 6.0 by adding a 10% aqueous sodium hydrogencarbonate solution. To this solution was added sodium nitrite (4.82 g, 〇_70 mol) and the mixture was stirred for 1 Torr. This solution was then added dropwise to a mixture of stirred ice (50 g) and concentrated HCl (80 ml), using external cooling to ensure that the temperature was maintained at < 5 °C. After another 30 minutes, the diazotization was completed and the excess nitrite was destroyed by the addition of sulfamic acid before the dye was added as a solid (60.0 g, 0.58 mol) according to the above step a), and Stirring while raising the pH and maintaining at 6.0 by the addition of sodium bicarbonate. After stirring overnight at ambient temperature, the product had precipitated and was at 40 in a forced air oven. (: Separation by filtration before drying) to produce a black solid (36·6 g) which presents analytical data consistent with the expected mixture of isomeric products.

Xmax is 607nm ’ emax is 5 025 0 °

200946600 Examples 4 to 4 3 Consistent to the methods described in Examples 1 to 3, the dye structures according to Examples 4 to 43 were prepared Xmax 4 Na03S\^X^CF3 NH, OH "S-C^a Na03S/^/^^ xS03Na 603nm 5 Na〇3Sy^CF3 c, ' N 丫 丫 '^ N γΤν ^N^^V^N^V,^^s〇2CH2CHi〇s〇3Na Na03S^^^^S03Na HH 613nm 6 ^ν^νΥγιΓν HNyvVv 0H % f,c Everyone is called 8 NaOp^^^^^SCyja Ν·^Ν Cl 628nm 7 h ^^N^YifN /ΝννΝγγΝ 如叫印-^叫·NaOjS^^^^SOjNa U'^ti Cl 613nm 8 ^^S03Na f| ] nh2 oh 〇 / Na03S^^^^S03Na^^ S〇2CH2CH2〇S〇3Na 621 nm ❹ -29- 200946600 9 3 NH2 OH kvp'SO2CH2CH20S03Na 〆〇631 nm 10 SO2CH2CH20S0,Na ?H !<人人巳NaC^S^^^^^SC^Na 594nm 11 Γ Naow— ^ XJ, ^ NaOaS^^^^^^SOaNa 599nm 12 w;:nA J00C 608nm 13 V^Wyn f 619nm 14 f3 ϋ jrx OH HN^N^N/^=ii^S02CH2CH20S03Na k S〇3Nl〇3S^^/^i/^S03Na 512nm 15 ?H HN person VnV?i HS〇3Na03S/^/^:::^ ^S〇3Na S12nm 16 FC X^L F3.^^] ?HS〇2CH2CH2OS03Na γ^Νγ^γΝ S〇3K!03S^^^^^S〇aNa 595nm -30- 200946600

-31 - 200946600

-32- 200946600

Na Na 596 596 596 596 596 He 035 people 乂^^S03Na 515nm 35 Cl Na〇3S^p^CF3 νΛν Ding Ding l S02CH2CH20S03Na NaC^S^^^^^SC^Na 516nm 36 Na03S\jj^j/CF3 M Ηχ(Η HO 八γΝ 〇 CH CH CH CH CH ΝγΛγΛ^Ν S0»Na 612nm 39 NJ\N ^rN/S02CH2CH20S03Na U 613nm 40 ^ 〇H , 472nm 41 NaO^SOCHjCh^OjS^^^ Ua°>s'^r^^i XX. . ΛΡ3 X· U Also l! SOaNa 416nm 42 J\ ^x^S〇2CH2CH2〇S〇3Na ςχ...minutes sojNa SO,Na 407nm 43 ^WS〇,Na HO^ N\ S02CH2CH20S03Na 383nm -34- 200946600

Example 45 φ A textile consisting of mercerized cotton was padded with a liquid containing 35 g/1 of anhydrous sodium carbonate, 100 g/Ι of urea, and 150 g/Ι of low viscosity sodium alginate solution (6%). And then dried. The moisture absorption rate is 70%. The thus pretreated fabric and an aqueous ink were printed using a drop-on-demand (bubble jet) inkjet print head comprising 2% of the dye obtained according to Example 1, 20% of cyclobutene, and hydrazine. 〇 1% of 1^^&11^91^ and 77.99% of water. The printed product is sufficiently dried. The fixation was carried out via saturated steam at 10 ° C for 8 minutes. After printing, it is rinsed with warm water and subjected to φ with 95. The hot water of C is washed with a firmness, rinsed with warm water, and then dried to obtain a printed product having excellent usability. -35-

Claims (1)

.200946600 VII. Patent application scope: 1. Dye with the following formula (I) Mo3s wherein x is an aromatic or heteroaromatic divalent group; RG is a reactive group capable of forming a covalent bond to cellulose under dyed conditions, or a group, the group Including a reactive group capable of forming a covalent bond to cellulose under dyeing conditions; or a group having the following formula (VIII) Wherein B is 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene, which are unsubstituted or substituted by -S03M, -COOM or R1; or (C2_c6)_# Ordinary or (C^-C4)-alkylene-phenylene groups, which are unsubstituted or substituted by Ri; each R is AL, ammonia, (Ci-C6)-hospital, thio-(Ci C6) -院-36- 200946600 base, base * or by (C1-C4) - hospital base, (Ci_C4)_house oxygen, warp group, -S03M, halogen, -COOM, ethylamino, or urea Substituted phenyl; Q3 is chlorine, fluorine, cyanoamino, hydroxy, (Ci-Ce)-alkoxy., phenoxy, thiophenoxy, fluorenyl, alkyl fluorenyl, pyridyl, carboxypyridine Or a carbamic pyridyl group; and an equivalent of lanthanide hydrogen, a soil test metal or a soil test metal. 2. The dye according to claim 1, wherein the X system has one of the following formulas (Ila) to (Ilj) (lla) (lib) Ν' R' (llh) (Nj) wherein Ar is a phenyl group or a phenyl group substituted by 1, 2 or 3 substituents, and the -37-200946600 substituent is selected from the group consisting of: (CrCd-alkyl group) , (CrCU)-alkoxy, and -so3m; E1 has one of the meanings of Ar; a naphthyl group or a naphthyl group substituted by !, 2 or 3 substituents selected from the group consisting of the group below, the group Including: (Ch-C4)-alkyl, (CrCd-alkoxy, -S03M, amino, acetylamino, or thiol; or a 5- or 6-membered heterocyclic residue including one or two heteroatoms The 'a hetero atom is selected from the group consisting of nitrogen, oxygen, and sulfur; or ❹ is a 5- or 6-membered heterocyclic residue including one or two heteroatoms selected from the group consisting of 'This group includes: nitrogen, oxygen, and sulfur, which are substituted by 1, 2 or 3 substituents selected from the group consisting of ·_(Κ4)-alkyl and ( ^ + alkoxy; Ε 2 is a phenylene or naphthylene group which is unsubstituted or substituted by 1, 2 or 3 substituents selected from the group consisting of: (Ci -c4)-alkyl'(c丨·C4)_alkoxy, _ 〇 3M, amino, ethyl hydrazine, or a thiol group; or a divalent 5- or 6-membered heterocyclic residue comprising one or two heteroatoms selected from the group consisting of The group includes: nitrogen, oxygen, and sulfur; or a divalent 5- or 6-membered heterocyclic residue comprising one or two heteroatoms selected from the group consisting of nitrogen. , oxygen and sulfur, the residue is substituted by 1% 2 or 3 substituents selected from the group consisting of: (cμc4)-alkyl and (Cl-C4)-decyloxy; Or a group having the following formula (VIII) (VIII) 200946600 wherein R5 is (Κ4)-alkyl, (CrD-alkoxy'-S03M, or hydroxy; - R1 is as defined in claim 1; R2 is alkyl or -COOM; R3 is hydrogen, -CN, or -CONH2; L has one of the meanings of B; Μ is as defined in Patent Application No. 1; and * is attached to the bond of the group RG. 3. As claimed in the second item The dye, wherein X corresponds to one of the following formulas (Ilk) to (11 The definitions of Μ and * are given in item 1 of the patent application. The dye according to any one of claims 1 to 3, wherein RG is -S02-CH = CH2, -S02-CH2CH2Z1 or a group having the following formula (III) ^-NCR ^-A (III) wherein 0 Z1 is a group capable of eliminating the domain; R1 is as defined above; A is a group having the following formula (Ilia), (Illb), or (IIIc) © V is fluorine or chlorine; U1 and U2 are independently fluorine, chlorine or hydrogen; and Q1 and Q2 are independently chlorine, fluorine, cyanoamino, hydroxyl, (Ci-Cs)-alkoxy, phenoxy, sulfur Phenoxy group, mercapto group, (Ci-Ce)-alkylindenyl group, pyridyl group, carboxypyridyl 'aminomercaptopyridinyl group or a group having the following formula (IV) or (V)—N, W-so2z2 (IV) (V) -40- 200946600 wherein R0 has one of the meanings of R1; R and R8 independently have the meaning of R1- or a combination thereof to form a group having the formula (2)j' or a formula, wherein a 3 5,β1 is an oxygen, sulfur, sulfonium, or _NR9· and is a (4) plant c6)-alkyl; a group of phenyl 'which is unsubstituted or substituted by 1 or .2 substituents, The substituents are selected from the group consisting of (Ci_C4)-alkyl, 0 (Ci-C4)-alkoxy, carboxyl, sulfo-chloro and bromo; or (Ci_c4)-sub-compartment Phenylene, (C2_C0)-alkylene' which may be interrupted by oxygen, sulfur, sulfonyl, amino, carbonyl, or formamidine; or phenylene_c〇nh_phenylene' which is a group Unsubstituted or substituted by 1 or 2 substituents selected from the group consisting of: (Cl-C4)-hospital, (CrC4)·alkoxy, hydroxy, sulfo, Carboxy, amino, ureido, and cyclin; or naphthylene, which is unsubstituted or substituted by one or two extended groups, and ❹ Z2 is -CH = CH2 or -CH2CH2Z1. 5. The dye according to claim 4, wherein the RG {systemic stomach has one of the following formulas (Illd) to (ΙΙΠ) groups -41 - 200946600 -S〇2_CH=CH2 (Hid) -SO2-CH2CH2OSO3M (llle) H (lllh) (mi) wherein the definition of R6 is given in item 3 of the patent application, and the definition of M is as given in item 1 of the patent application. 6. The dye according to any one of claims 1 to 3, wherein the hydrazine dye corresponds to a dye having the following formulas (la) to (Ic) - Among them. The definitions of X, RG and Μ are as given in the first section of the stomach sputum patent range. For example, the patent scope 1 corresponds to the dye 42 of the formula (I d) to 3 (Ig) of the following formula (I d) to 3 - the dye described in the item 200946600 Wherein A1 is a group having the formula (Illf), (Illg), (Illh) or (ΙΙΠ); A2 is a group having the formula (Illd) or (Ille); R1Q is a methyl group, a methoxy group, Or - S03M; and the definition of Μ is given in item 1 of the patent application. A method for producing a dye of the formula (I) as described in claim 1, wherein the compound of the formula (VI) is mo3s -43- (VI) 200946600 wherein Μ is defined as given in the first paragraph of the patent application, is diazotized and coupled to a compound of the following formula (VII) (VII) -X-RG wherein X and RG The definition is as in the scope of claim 1 to give $ ° 9. The dye of formula (I) as described in claim 1 is used for φ dyeing or printing of materials containing methionine and/or hydroxyl groups. Use. 10. An ink for use in digital textile printing by an ink jet method comprising the dye of formula (I) as described in claim 1 of the patent application. ❹ -44 - 200946600 IV. Designated representative map: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: None 200946600 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: (I) mo3s (I) -4-