JPH042629B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to fiber-reactive compounds useful for dyeing and printing cellulose fibers, natural or synthetic polyamide fibers, polyurethane fibers or leather. More specifically, the present invention provides the following general formula (1) in the form of a free acid: (In the formula, X represents β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-chloroethyl or a vinyl group, and Y
represents a hydrogen atom, a chlorine atom, or a sulfonic acid group, and R represents an alkyl group having up to 4 carbon atoms. The compounds of the invention can exist both in the free acid form and in the form of their salts, preferably in the form of the alkali metal and alkaline earth metal, especially sodium and potassium salts. When the compounds of the invention are used for dyeing and printing textile materials, alkali metal salts are particularly preferred. The substituent represented by R is a linear or branched alkyl group, which may be substituted with, for example, a chlorine, bromine atom, or a nitro group, but from an industrial perspective, an unsubstituted linear alkyl group is preferred. . The compound of the present invention can be produced, for example, by the following method. That is, the compound of general formula (1) is the compound of general formula (2) (wherein, X and Y have the above meanings) in the form of a free acid obtained by condensing an aromatic amine of formula (3), cyanuric chloride and m- or p-phenylenediamine sulfonic acid. (In the formula, X and Y have the above-mentioned meanings.) A monochlorotriazine compound represented by the formula (4) is diazotized by a known method to form a free acid having the general formula (4). It can be produced by coupling with a naphthalene compound (wherein R has the above meaning). Depending on the reaction conditions, the starting compounds mentioned are present or used in the form of acids and/or salts, especially alkali salts. The naphthalene compound of general formula (4) has general formula (5) or
(6) R-COO-R (5) R-COO-Z (6) (in the above, R has the above meaning and Z means chlorine, bromine or fluorine atom) acid anhydride or acid Halide, 1-amino-8-
Hydroxynaphthalene-3,6- or -4,6-
It can be produced by reacting with disulfonic acid. The method for producing the compound of the present invention will be described in more detail. The monochlorotriazinyl compound of general formula (3) can be produced, for example, as follows. That is, cyanuric chloride and the aromatic amine represented by the general formula (2) are reacted in an aqueous solvent at pH 3 to 5 and 5 to 20°C, and then m
or p-phenylenediaminesulfonic acid and PH3~
It can be produced by reacting at 7.5 to 40°C. The acid binders used in this case are alkali metal salts of weak inorganic or organic acids, such as sodium carbonate, sodium bicarbonate or their potassium salts, primary or secondary sodium phosphates. The diazotization reaction can be carried out by a known method, for example, by using a small excess of sodium nitrite at 40° C. or lower under mineral acid conditions. The coupling reaction can also be carried out by a known method, for example, by adding the diazo compound to a solution containing the naphthalene compound represented by the general formula (4), or by the reverse method, and carried out at 0 to 30°C and pH 3 to 9. The naphthalene compound represented by the general formula (4) is 1-
An acid anhydride or acid chloride represented by general formula (5) or (6) is added to a neutralized aqueous solution of amino-8-hydroxynaphthalene-3,6- or -4,6-disulfonic acid, and the mixture is heated at 0 to 50°C. , by maintaining the pH at 3-8, and in some cases, subsequently at PH8-10,
It can be produced by hydrolyzing an O-acyl group at 40 to 110°C. Separation of the compounds from the reaction mixture is carried out in generally known manner by salting out the reaction medium with electrolytes, such as sodium or potassium chloride, or by evaporation of the reaction solution, for example by spray drying. When drying the salted-out product or the reaction solvent, in some cases, auxiliary agents such as stabilizers, such as primary or secondary sodium or potassium phosphates, dustless agents, solubilizing agents, dyeability improving agents, etc., may be added. It can also be added. The aromatic amine represented by the general formula (2) that can be used in the present invention includes, for example, aniline-2-
β-Sulfatoethylsulfone, 5-chloroaniline-2-β-sulfatoethylsulfone, 5-sulfoaniline-2-β-sulfatoethylsulfone, aniline-2-β-thiosulfon ethyl sulfonate, 5-chloroaniline-2-β-thiosulfate ethyl sulfonate,
5-Sulfoaniline-2-β-thiosulfatoethylsulfone, aniline-2-β-phosphatoethylsulfone, 5-chloroaniline-2-β
-Phosphatoethylsulfone, 5-sulfoaniline-2-β-phosphatoethylsulfone, aniline-2-vinylsulfone, 5-chloroaniline-2-vinylsulfone, 5-sulfoaniline-2-vinylsulfone , aniline-2-
Examples include β-chloroethylsulfon, 5-chloroaniline-2-β-chloroethylsulfon, and 5-sulfoaniline-2-β-chloroethylsulfon. The novel compounds according to the invention are fiber-reactive and have very good properties for dyeing and printing materials consisting of cellulose fibers, natural or synthetic polyamide phosphor fibers, polyurethane fibers and leather. Cellulose fibers are preferably exemplified by cotton and regenerated cellulose, but also include other vegetable fibers such as linen, hemp, and jute. Polyamide fibers include natural and synthetic fibers such as wool and other animal hairs, silk, polyamide 6,6, polyamide
Examples include polyamide-6, polyamide-11, and polyamide-4. The compounds of the invention are particularly useful for dyeing and printing cellulose fibers, and dyeing and printing are carried out by conventional methods used for conventional reactive dyes. That is, in the case of the exhaust method, it is carried out at a relatively low temperature in a dye bath containing mirabilite or common salt in the presence of an acid binder such as soda carbonate, tribasic sodium phosphate, or caustic soda. Dyeing can also be carried out by a printing method, for example, by printing a colored paste containing an acid binder such as bicarbonate of soda, sodium carbonate, tribasic sodium phosphate, or caustic soda, urea, and a sizing agent, preferably sodium alginate, on the fiber.
After intermediate drying, it is carried out by steaming or dry heating at 100 to 200°C. Furthermore, the dyeing of the present invention may be carried out by a continuous method, or cold pad batch dyeing is also possible. The novel compound according to the invention exhibits excellent physical and chemical stability in dyeing stocks and printing pastes and in the presence of alkalis, and has very good affinity and excellent stability in conventional dyeing and printing. It has excellent build-up properties. In exhaust dyeing, it is relatively unaffected by the bath ratio, dyeing temperature, etc., and produces dyed products with good reproducibility and excellent level dyeing properties. The dyed or printed material obtained using the compound of the present invention has high tinting strength and excellent gloss.
It is excellent in various fastnesses, especially chlorine fastness, light fastness, perspiration and sunlight fastness, and has extremely good discharge printing properties. Next, the present invention will be explained with reference to examples. In the text,
Parts indicate parts by weight. Example 1 After adding 9.5 parts of cyanuric chloride and a small amount of nonionic surfactant to 50 parts of water and thoroughly dispersing the mixture, aniline-2-β-sulfatoethylsulfone was added at about 5°C
14.1 parts were added, and the pH was maintained at 3 to 4 for about 3 hours while adding 15% aqueous sodium carbonate solution. When the reaction was completed, 9.4 parts of m-phenylenediaminesulfonic acid was added, and the mixture was stirred overnight at pH 4-7 and 20-30°C. During this time, the pH was maintained with a 15% aqueous sodium carbonate solution. Then cool to 0-5℃ and add sodium nitrite.
Add 3.7 parts and 13.0 parts of concentrated hydrochloric acid, and stir at the same temperature for 1 hour. Excess nitrous acid is removed to obtain a diazotized liquid. On the other hand, 16.0 parts of H acid was neutralized and dissolved at pH 7 in 70 parts of water, and 20.5 parts of butyric anhydride was added at 20 to 30°C.
After stirring for 3 hours at 7-7.5, 90-95℃, PH8-
Keep warm at 8.5 for 1 hour. After cooling to room temperature,
In addition to the diazotization solution, coupling is performed at pH 5-7 and 0-5°C. After the reaction is complete, the following formula (1) is obtained by salting out with sodium chloride, filtering and drying. An electrolyte-containing red powder was obtained which contained a new reactive dye of , mainly in the form of its sodium salt. A red dyed product having excellent properties such as build-up properties, various fastnesses, level dyeing properties, and discharge printing properties was obtained by a normal usage method. Examples 2 to 17 In the same manner, new dyes corresponding to the following diazo components and coupling components were obtained respectively, and when dyed using these in the same manner as in Example 1, all of them exhibited the excellent condition described in Example 1. Indicated.

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1 The following general formula in the form of a free acid: (wherein, X represents β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl, β-chloroethyl or vinyl, Y represents a hydrogen atom, a chlorine atom or a sulfonic acid group,
R represents an alkyl group having up to 4 carbon atoms. ) A bifunctional reactive compound represented by