MX2008000192A - Reactive dyes, a process for their preparation and their use - Google Patents

Abstract

Reactive dyes of formula (I), wherein D is a radical of formulae (II, IV, VI) or (VII), R1is hydrogen, acetyl, sulfo,α,β-dibromopropionylamino,α-bromoacryloylamino,β-chloroethylsulfonylbutyrylamino,β-sulfatoethylsulfonylbutyrylamino or vinylsulfonylbutyrylamino, R2is methyl or methoxy, X is halogen, Y is vinyl orβ-sulfatoethyl and Z is hydroxy, vinyl orβ-sulfatoethyl, are suitable especially for dyeing cotton and yield dyeings having good all-round fastness properties.

Description

REAGENT DYES, A PROCESS FOR ITS PRODUCTION AND ITS USE The present invention relates to novel reactive dyes, to a process for its production and to its use in the dyeing or printing of textile fiber materials. The practice of dyeing using reactive dyes has recently led to a greater demand on the quality of dyeing and the economic efficiency of the dyeing process. As a result, novel reagent dyes having improved properties, especially with respect to their application, continue to be a necessity. The current dyeing requires reactive dyes that have sufficient substantivity and, at the same time, have great ease of washing off the unfixed dye. In addition, they must exhibit good color, performance and high reactivity, the objective being especially to provide dyes that have a good degree of fixation. Known dyes do not meet these requirements in all properties. The dyes described in the prior art, such as, for example, the dyes of US Pat. No. 4,841,031, US 4 937 326 and JP 61-272 269, still have certain disadvantages, with respect to the required properties. The fundamental problem of the present invention is, therefore, to find improved reactive dyes for the dyeing and printing of fiber materials, improved reactive dyes possessing the aforementioned qualities to a high degree. The novel dyes must be distinguished especially by high fixing yields and high binding stability properties of the fiber and the dye, and in addition, it should be possible that those tientes that do not fix on the fibers, are easily separated by washing. It has been found that the problem possessed is largely solved by the dyes defined hereinafter. Therefore, the present invention relates to reactive dyes of the formula: in which D is a radical of the formula Ri is hydrogen, acetyl, sulfa, a, β-dibromopropionylamino, α-bromoarylolamino, β-chloro-ethylsulfonylbutyrylamino, β-sulfatoethylsulfonylbutyrylamino or vinylsulfonyl-butyrylamino; R2 is methyl or methoxy; X is halogen; And it's vinyl or sulfatoethyl; and Z is hydroxy, vinyl or β-sulfatoethyl.

Ri is preferably hydrogen, acetyl, α, β-dibromopropionylamino, α-bromoacyloylamino, β-chloroethyl-sulfonylbutyrylamino or vinylsulfonylbutyrylamino; Ri in particular is preferably hydrogen; D is preferably a radical of the formula (2), (3) or (4); D in particular is preferably a radical of the formula (2); for X, there are, for example, fluorine, chlorine or bromine, preferably fluorine or chlorine and especially chlorine; The dye of the formula (1) is preferably a dye of the formula: where d, X and Y each have the preferred definitions and meanings given above. The present invention also relates to a process for the preparation of reactive dyes, according to the invention, wherein (i) a compound of the formula: and another compound of the formula they are reacted, in any order, with a cyanuric halide and (ii) is coupled to the resulting compound of the formula to an amine of the formula D-NH2 (6) wherein D, X and Y each have the preferred definitions and meanings given above.

Since step (i) of the process, indicated above, can be carried out in any other order, two different process variables are possible.

Thus, for example, about one molar equivalent of a compound of the formula (6) is reacted with about one molar equivalent of the cyanuric halide, and the product obtained is then condensed with about one molar equivalent of a compound of the formula (5). ). In a variant of the preferred process, about one molar equivalent of a compound of the formula (5) is reacted with about one molar equivalent of the cyanuric halide and the obtained condensation product is then condensed with about one molar equivalent of a compound of the formula (6). Instead of the compound of the formula (5), it is also possible, for coupling, to use a product of the formula: in this case, step (ii) of the process is omitted. The compound of the formula (9) can be obtained by diazotizing an amine of the formula (8) and coupling the diazonium salt to a compound of the formula (5).

A suitable compound of the formula (6) is preferably the compound of the formula: A suitable cyanuric halide is. for example, cyanuric chloride or cyanuric fluoride, especially cyanuric chloride. For example, the individual condensation reactions are carried out according to processes known per se, usually in an aqueous solution, at a temperature of, for example, 0 to 50 ° C, in particular 0 to 30 ° C. , and at a pH value of, for example, 2 to 10, especially 2 to 6. The diazotization of the amine of the formula (8) is carried out in a customary manner, for example using a nitrite, such as a nitrite of an alkali metal, such as sodium nitrite, in a mineral acid medium, for example, a hydrochloric acid medium, at temperatures of, for example, 5 to 40 ° C, preferably 0 to 25 ° C. The coupling to the coupling component of formula (5) or (7) is carried out in a manner known per se with acidic or neutral or weakly alkaline pH values, for example, at a pH of 1 to 10, advantageously to a pH of 3 to 7, and at temperatures of. for example, 5 to 40 ° C, preferably 0 to 35 ° C. The final product can, optionally, be further subjected to a conversion reaction, such conversion reaction is. for example, the conversion of a vinyl-reactive group present in Y, in its vinyl form, by treatment with a sodium hydroxide solution, such as the conversion of the β-sulfatoethylsulfonyl group to the vinylsulfonyl radical. These reactions are known per se. The compounds of the formula (5), (6) and (8) are known or can be prepared analogously to known compounds. The reactive dyes of the formula (1), according to the invention, are either in the form of the free acid or, preferably, in the form of a salt thereof Salts which come into consideration are, for example, salts of metals alkaline, alkaline earth metal and ammonium salts, and salts of organic amines The sodium, lithium, potassium and ammonium salts and salts of mono-, di- and tri-ethanolamine can be mentioned as examples. (1), according to the invention, are dyes for dyeing and printing an extremely wide variety of materials, such as fiber materials having hydroxyl groups or they contain nitrogen. Examples of nitrogen-containing fiber materials that may be mentioned are silk, leather, wool, polyamide and polyurethane fibers. The reactive dyes according to the invention are especially suitable for dyeing and printing cellulose-containing fiber materials of all kinds. These fiber materials containing cellulose are, for example, natural cellulosic fibers, such as cotton, linen and hemp, and also cellulose and regenerated cellulose, preferably cotton is preferred. The reactive dyes, according to the invention, are also suitable for dyeing or printing mixtures of cellulosic fabrics, for example mixtures of cotton and polyamide fibers, or especially fibers in cotton / polyester blend. The reactive dyes, according to the invention, can be applied to the fiber material and fixed to the fiber in a variety of ways, especially in the form of aqueous solutions of dyes and dye printing pastes. They are suitable both by the discharge method and by the dyeing, according to the cushion-dyeing method, according to which the products are impregnated with solutions of aqueous dyes optionally containing salts, and, after the treatment with alkali or the presence of alkali, the dyes are fixed, when appropriate, by the action of heat or by storing for several hours at room temperature. After fixing, the dyeings or prints are completely rinsed with cold or hot water, with the addition of an agent that binds a dispersion action and promotes diffusion of the dye without fixing. The reactive dyes, according to the invention, are distinguished by high reactivity, good color fixing capacity and a very good forming behavior. They can, therefore, be used according to the dyeing method of discharge, with low dyeing temperatures and require only very short vaporization times in the vapor-cushion method. The degrees of fixation are high and the unfixed dye can be easily separated by washing, the difference between the degree of discharge and the degree of fixation being markedly small, ie the loss of the action of the soap is very low. The dyes, according to the invention, are also particularly suitable for printing, more especially on cotton, but are also equally suitable for the printing of nitrogen-containing fibers, for example, wool or silk, or mixed fabrics including wool or silk. The dyes and prints produced using the reactive dyes, according to the invention, have a high dyeing strength and high fiber-dye binding stability, in both the acid and alkaline range, and also have a good firmness to light and very good properties in wet firmness, such as firmness to washing with water, seawater, cross-dyeing and transpiration, as well as Good resistance to chlorine, folding, hot pressing and rubbing. The reactive dyes according to the invention are suitable as colorants for use in recording systems. Such recording systems are, for example, commercially available inkjet printers, paper printers or textile printers or writing instruments, such as fountain pens or ballpoint pens, and especially inkjet printers. For that purpose, the reactive dye, according to the invention, is first carried in a form suitable for use in recording systems. A suitable form is, for example, an aqueous ink comprising the reactive dyes according to the invention, as a colorant. The inks can be prepared in a customary manner, by mixing together the individual components customary in inkjet printing in the desired amount of water. Substrates that come into consideration for inkjet printing include, in addition to paper and plastic films, for example materials of fibers containing the hydroxyl group or containing nitrogen, mentioned above, especially cellulose-containing fiber materials. These fiber materials are preferably textile fiber materials. The following examples serve to illustrate the invention. Unless stated otherwise, temperatures are given in degrees Celsius, parts are parts by weight and percentages are percentages by weight. The parts by weight are related to the parts by volume in a proportion of kilograms liters.

Example 1: a) 94.5 parts of cyanuric chloride were vigorously stirred in 750 parts of an ice-water mixture, with the addition of a wetting agent and 0.5 part of disodium hydrogen phosphate, and the mixture was adjusted to a pH of 2.6 , using 32% hydrochloric acid A neutral solution of 160 parts of 2-amino-5-naphthol-1,7-disulfonic acid in 600 parts of water, then added there, the temperature of the reaction mixture being maintained at 0 at 2 ° C and the pH value at 2.5. The pH of the reaction mixture was then increased to 4, using a solution of sodium hydroxide (30%). b) A neutral solution of 162 parts of the compound of the formula: in 800 parts of water was added at 8 ° C to the reaction mixture, obtained according to a) the pH was maintained at about 4.5 by the addition of a sodium carbonate solution (20%). After the addition, the reaction mixture was heated to 30 ° C and stirred overnight. c) 179 parts of the 4-aminoazobenzole-3, '-disulfonic acid were stirred in 750 parts of water and 170 parts of ice and 139.2 parts of 32% hydrochloric acid were added to the mixture. 113 parts by volume of a sodium nitrite solution were then added dropwise to the mixture and the stirring was subsequently carried out for a brief period, in order to complete the reaction. Excess sodium nitrite was destroyed using sulfamic acid. d) The suspension of the diazonium salt obtained, according to c), was dosed into the reaction mixture obtained according to b (, the pH of which was adjusted in 7 by the addition of a sodium carbonate solution (70%), the temperature of the reaction mixture being maintained at 16 ° C and the pH being maintained at 7, by the addition of a sodium carbonate solution (29). %). The pH value was then adjusted to 6.3 using hydrochloric acid and the obtained reaction mixture was filtered until clear, free of salt by dialysis and concentrated. 780 parts of a compound were obtained, which, in the free acid form, corresponded to the formula: (? jtóx 508 n) and which stain the cotton with a nuance that has good full properties of firmness.

Examples 2 to 11: The dyes, indicated below, which dye the cotton in red shades, which have good complete properties of firmness (? max: 48 © nm) (? max: 482 nm) (J 520 n) (ma. "512 nm) (- 502 n) (482 nm) C 482 nm) (630 nm) Dyeing procedure 1 100 parts of cotton cloth were introduced, at 60 ° C, into 1500 parts of a dye bath, containing 45 g / 1 of sodium chloride and 2 parts of the reactive dye obtained according to Example 1 After 45 minutes at 60 ° C, 20 g / 1 of anhydrous sodium carbonate was added. The dyeing was continued for 45 minutes at that temperature. The dyed products are then rinsed, soaped boiling for a quarter of an hour with a non-ionic detergent, rinsed again and dried.

As an alternative to the above procedure, the dyeing can be carried out at 80 ° C, instead of at 60 ° C.

Dyeing procedure 2 0.1 part of the dye, according to Example 1, was dissolved in 200 parts of water and 0.5 part of sodium sulfate. 0.1 part of a leveling aid (based on the condensation product of a major aliphatic amine and ethylene oxide) and also 0.5 part of sodium acetate, were added. The pH is then adjusted to a value of 5.5, using acetic acid (80%). The staining bath was encouraged at 50 ° C for 10 minutes and then 10 parts of a wool cloth were added. The heating was then carried out, in the course of about 50 minutes, at a temperature of 100 ° C and the dyeing was carried out at that temperature for 60 minutes, after which the dye bath was allowed to cool to 90 ° C and the dyed products were removed. The wool fabric was washed with hot water and cold water, and then twisted and dried.

Printing process 3 parts of a dye, obtained according to Example 1, were irrigated, with rapid stirring, in 100 parts of a thickening agent, containing 50 parts of sodium alginate, 27.8 parts of water, 20 parts of urea, 1 part sodium m-nitrobenzenesulfonate and 1.2 parts hydrogen sodium carbonate. The printing paste, thus obtained, was used to print cotton cloth and the resulting printed material was dried and treated with saturated steam for 2 minutes at 102 ° C. The printed fabric was then rinsed, if desired soaped to a boil and rinsed again, and then dried.

Claims (9)

1. A reactive dye, of the formula: in which D is a radical of the formula Ri is hydrogen, acetyl, sulfo, a, β-dibromopropionylamino, α-bromoarylolamino, β-chloro-ethylsulfonylbutyrylamino, β-sulfatoethylsulfonylbutyrylamino or vinylsulfonylbutyrylamino; R2 is methyl or methoxy; X is halogen; And it's vinyl or sulfatoethyl; and Z is hydroxy, vinyl or β-sulfatoethyl.

2. A reactive dye according to any of claim 1, wherein: R is preferably hydrogen, acetyl, α, β-dibromopropionylamino, α-bromoacyloylamino, β-chloroethylsulfonylbutyrylamino or vinylsulfonylbutyrylamino;

3. A reactive dye, according to any of claim 1 or claim, wherein Ri is hydrogen;

4. A reactive dye according to one of claims 1 to 3, wherein D is a radical of the formula (2), (3) or (4);

5. A reactive dye according to one of claims 1 to 5, wherein D is a radical of the formula (2);

6. A reactive dye according to one of claims 1 to 5, wherein X is chlorine.

7. A process for the preparation of a reactive dye, according to claim 1, wherein (i) a compound of the formula: and another compound of the formula they are reacted in any order, with a cyanuric halide and (ii) is coupled to the resulting compound of the formula an amine of the formula D-NH2 (6) wherein D, X and Y are as defined in claim 1.

8. The use of a reactive dye, according to any one of claims 1 to 6, or a reactive dye, prepared according to claim 7, in the dyeing or printing of a fiber material containing a hydroxyl group or a fibers containing nitrogen.

9. The use, according to claim 8, in which the cellulose-containing fiber material, especially the cotton-containing fiber material, is dyed or printed. Summary of the Invention Reactive dyes of the formula: in which D is a radical of the formula Ri is hydrogen, acetyl, sulfo, a, β-dibromopropionylamino, α-bromoarylolamino, β-chloro-ethylsulfonylbutyrylamino, β-sulfatoethylsulfonylbutyrylamino or vinylsulfonylbutyrylamino; R2 is methyl or ethoxy; X is halogen; And it's vinyl or sulfatoethyl; and Z is hydroxy, vinyl or β-sulfatoethyl.