JPH0218352B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel bisazo compounds. More particularly, the present invention relates to bisazo compounds useful as fiber-reactive dyes, particularly for dyeing cellulose fibers black. Conventionally, 2 moles of 1-aminobenzene-4-β-sulfatoethylsulfone were diazotized and 1 mole of 1-amino-8-hydroxy was used as a reactive dye for dyeing cellulose fiber materials blue to black to gray. CIReactive Black5 obtained by coupling with naphthalene-3,6-disulfonic acid is known. However, the fastness of dyed products using this dye is not sufficient, and improvements in texture are also desired. Japanese Patent Publication No. 43-15299 discloses bisazo-reactive dyes that dye cellulose fibers and give blue or black dyes with good wet resistance and light resistance, but these dyes have a low exhaustion rate. Improvements are expected in terms of adhesion rate or build-up performance. For example, the dye represented by the following formula described in Example 1 of the same publication was still unsatisfactory in terms of exhaustion rate, fixation rate, and build-up ability. Further, similar bisazo reactive dyes are disclosed in Japanese Patent Publication No. 4337/1982, but these dyes also have practical problems in terms of exhaustion rate, fixation rate, and build-up property. The present inventors conducted intensive studies to solve this problem, and as a result, the following general formula () was obtained in the form of a free acid. [In the formula, X is -CH=CH ₂ or -CH ₂ CH ₂ R (R
means a group that can be removed with an alkali), Y means a phenylene group or a naphthylene group, and the phenylene group is a C ₁ -C ₄ alkyl group, a C ₁ -
The naphthylene group may be substituted with 1 to 3 same or different substituents selected from _C4 alkoxy groups, chlorine atoms, and bromine atoms, and the naphthylene group may be substituted with 1 to 3 sulfonic acid groups. It's okay. Moreover, n means an integer of 2 to 3. ] It was discovered that the bisazo compound represented by the following is suitable for the purpose, and the present invention was completed. In the bisazo compound of the present invention represented by the general formula (), the alkali-removable group R is, for example, a halogen atom such as a chlorine and bromine atom, an ester group of organic carboxylic acid and a sulfonic acid, and a lower alkanoyl group such as an acetyloxy residue. oxy residue, benzoyloxy residue or benzenesulfonyloxy residue or in the form of the free acid of the formula -
These include acidic ester groups of phosphoric acid or sulfuric acid represented by OPO ₃ H ₂ or -OSO ₃ H. The bisazo compounds of the invention can exist both in the form of the free acid and in the form of its salts, but the salts, especially alkali and alkaline earth metal salts, especially sodium,
Preferably it is in the form of potassium and calcium salts. More preferred forms are alkali metal salts. Among the compounds of the present invention, representative compounds of particular industrial interest are phenylene groups in which the residue Y may be substituted with chlorine, bromine, methyl, ethyl, methoxy or ethoxy, or chlorine, bromine, methyl, ethyl It is a compound meaning a phenylene group which may be substituted with two same or different substituents selected from , methoxy and ethoxy. Further, the substitution position of the chlorine atom in the general formula () is particularly preferably the ortho position and the para position with respect to the azo group from the viewpoint of build-up property. As residue Y, mention may be made in particular of residues of the following formula:

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[Formula] (The bond indicated with an asterisk in the formula is − in the coupler.
N = a bond leading to the N- group). Among the novel compounds according to the invention, in particular the residue Y
is an optionally substituted phenylene residue,
A bisazo compound in which the residue X is a β-sulfatoethyl residue or a vinyl residue is preferred. The novel bisazo compound of general formula () can be produced as follows. General formula (2) (In the formula, n has the above-mentioned meaning) A polychloroaniline derivative represented by the formula (3) is diazotized by a known method, and in the form of a free acid, the polychloroaniline derivative represented by the general formula (3) is (In the formula, X and Y have the above-mentioned meanings.) It can be produced by coupling with a monoazo compound according to a known method. The monoazo compound of the general formula (3) is obtained by diazotizing the amine of the general formula (4) X-SO ₂ -Y-NH ₂ (4) (wherein, , PH3 or less, at -10° to 30°C, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and 2-
It can be manufactured by coupling for 10 hours. As the polychloroaniline derivative represented by the general formula (2), 2,4-, 2,5-, 3,5-, 2,3- or 3,4-dichloroaniline, 2,4,5-trichloroaniline Examples include. As the amine represented by the general formula (4), JP-A No. 55
Compounds described in Japanese Patent No.-12187 can be mentioned. Depending on the reaction conditions, each of the abovementioned starting compounds is present or used in the form of acids and/or salts, in particular alkali metal salts. The compounds prepared according to the invention are separated off by generally known methods, by salting out with electrolytes, such as sodium or potassium chloride, or by evaporation of the reaction solution, for example by spray drying. The novel compounds according to the invention are fiber-reactive and have very good properties for dyeing (including printing) materials made of cellulose fibers, natural or synthetic polyamides, polyurethane fibers. Cellulose fiber materials are preferably cotton and regenerated cellulose, or other vegetable fibers such as linen, hemp, jute, and polyamide fiber materials include natural or synthetic fibers such as wool and other animal hairs, silk, polyamide-6, Examples include polyamide-6, polyamide-6, polyamide-11, and polyamide-4. The application of the compounds of the invention is particularly excellent in cellulose fiber materials. In the case of the exhaust method, cellulose fiber materials are dyed at relatively low temperatures in a dyebath containing mirabilite or common salt in the presence of an acid binder such as carbon soda, tribasic sodium phosphate or caustic soda. Dyeing can also be done by a textile printing method. For example, a color paste containing an acid binder such as bicarbonate of soda, soda carbonate, tribasic sodium phosphate, or caustic soda, urea, and a sizing agent, preferably sodium alginate, is printed on the fiber, and after intermediate drying, 100% This is done by steaming or dry heating at ~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. Dyeing of polyamide fibers, polyurethane fibers and leather can be carried out in an acidic medium by conventional methods. For example, ammonium acetate or the like can be added to the dye bath to obtain the desired pH value. In order to obtain level dyeing properties, common leveling aids such as cyanuric chloride and 3
Preference is given to adding leveling aids based on reaction products with double molar amounts of aminobenzenesulfonic acid and/or aminonaphthalenesulfonic acid and/or reaction products of, for example, stearylamine and ethylene oxide. Dyeing is done at a temperature of 60℃ or above 60℃,
For example, at the boiling temperature of an aqueous bath, possibly under pressure.
It can be carried out at temperatures up to 120°C. The compound of the present invention has only one fiber-reactive group in one molecule.
Compared to CIReactive Black5, which has two of them, it can dye cellulose fibers in an extremely deep color, has excellent build-up properties, and has a higher fastness of the dyed product. It is excellent. Furthermore, the compound of the present invention can be dyed with superior exhaustion rate, fixation rate, and build-up property compared to the dyes described in Japanese Patent Publication No. 43-15299 and Japanese Patent Publication No. 45-4337. The product has excellent fastness such as light resistance and sunlight resistance. In other words, as stated in Japanese Patent Publication No. 43-15299 And as stated in Special Publication No. 45-4337 as well as Compared to other dyes, the compound of the present invention has the characteristic that it dyes extremely well not only in light colors but also in extremely dark colors, and as a result, the amount of dye required to be used is significantly smaller. . Furthermore, when the compound of the present invention is toned to produce a full black odor, it is economical since only a small amount of toning dye is required. Next, the present invention will be explained in more detail with reference to Examples. In the text, parts represent parts by weight. Examples 1-2 8.1 parts of 2,5-dichloroaniline, Emulgen
After mixing and dissolving 0.3 parts of 930, 11.3 parts of hydrochloric acid, and 150 parts of water, 3.8 parts of sodium nitrite was added and diazotization was performed at 10°C or lower. After 2 hours, excess nitrous acid was removed with sulfamic acid, and 1-amino-
2(4-β-sulfatoethylsulfonylphenylazo)-8-hydroxynaphthalene-3,6
- A neutral aqueous solution containing 33.85 parts of the trisodium salt of disulfonic acid was added. Adjust the pH to 4-7 by dropping a 15% aqueous solution of sodium carbonate at 10-20℃.
It kept time. When the diazo compound is no longer detected, salt out at pH 4-6 and 30-40°C, filter, dissolve the resulting wet cake in water, add equimolar amount of sodium phosphate to pH 5-6, and then dry. A compound represented by the following formula (1) was obtained in the form of a free acid. Dissolve the specified amount of the above dye in 200 parts of water, and
20 parts were added, 10 parts of cotton was added, and the temperature was raised to 60°C.
After 30 minutes, 4 parts of soda carbonate was added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were performed to obtain a greenish-black dyed product with excellent fastness. In addition, by the same method as above, a compound represented by the following formula (2) was obtained in the form of a free acid. Using this dye, cotton was dyed in the same manner as above to obtain a greenish-black dyed product with excellent color fastness. Table 1 shows the results of comparing the dyeing properties of the compounds (1) and (2) of the present invention described above with those of the following known dyes (A), (B), (C) and (D). CIReactive Black5 Publication No. 43-15299 Listed in Special Publication No. 45-4337 as well as As a result, the compounds (1) and (2) of the present invention were compared to the comparative dyes.
Compared to any of (A) to (D), it can be dyed in an extremely deep color in the entire range from low concentration staining to high concentration staining, and has the characteristics of extremely excellent build-up properties.

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[Table] Examples 3 to 21 Corresponding dyes are obtained in the same manner as in Example 1 using the raw material compounds listed in the table below. Using each of the obtained dyes, cotton was dyed in the same manner as in Example 1, and the compound of the present invention described in Example 1 was dyed.
A dyed product having excellent performance similar to (1) can be obtained.

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Claims (1)

[Claims] 1 The following formula in free acid form: [In the formula, X is -CH=CH ₂ or -CH ₂ CH ₂ R (R
means a group that can be removed with an alkali), Y means a phenylene group or a naphthylene group, and the phenylene group is a C ₁ -C ₄ alkyl group, a C ₁ -
The naphthylene group may be substituted with 1 to 3 same or different substituents selected from _C4 alkoxy groups, chlorine atoms, and bromine atoms, and the naphthylene group may be substituted with 1 to 3 sulfonic acid groups. It's okay. Further, n means an integer of 2 or 3. ] A bisazo compound represented by