JPH0218353B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel bisazo compounds. More specifically, the present invention relates to bisazo compounds useful as fiber-reactive dyes, particularly for dyeing cellulosic 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 to produce blue or black dyes with good wet resistance and light resistance, but these dyes have various fastness properties. In particular, improvements are notable in terms of fastness to chlorine, exhaustion rate, fixation rate, and build-up performance. For example, the dye represented by the following formula described in Example 1 of the same publication had a chlorine fastness (ISO method) of grade 1 to 2, and was still unsatisfactory in terms of exhaustion rate, fixation rate, and build-up performance. Further, similar bisazo-reactive dyes are disclosed in Japanese Patent Publication No. 45-4337, but these dyes also have poor fastness properties other than light fastness and moisture fastness, such as fastness to chlorine in particular, as well as exhaustion rate and fixation rate. Alternatively, practical problems remain in terms of build-up performance. The present inventors conducted intensive studies to solve this problem, and as a result, the following general formula (1) 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. Z is a halogen atom, a nitro group, C ₁ −
It means a _C4 alkyl group or a _C1 - _C4 alkoxy group, and _R1 means a methyl group or an ethyl group. ] 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 (1), the alkali-removable group R is, for example, a halogen atom such as chlorine and bromine atom, an ester group of organic carboxylic acid and a sulfonic acid, such as an acetyloxy residue, etc. Alkanoyloxy residue, benzoyloxy residue or benzenesulfonyloxy residue or in the form of the free acid with the formula -OPO ₃ H ₂
Alternatively, it is an acidic ester group of phosphoric acid or sulfuric acid represented by _-OSO3H . 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 industrial interest have a residue Y of chlorine, bromine, methyl, ethyl,
A compound meaning a phenylene group optionally substituted with methoxy or ethoxy, or a phenylene group optionally substituted with two identical or different substituents selected from chlorine, bromine, methyl, ethyl, methoxy and ethoxy. It is. As the residue Y, mention may be made in particular of the 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 (1) can be produced as follows. General formula (2) The o-alkoxyaniline derivative represented by the formula (wherein Z and R ₁ have the above-mentioned meanings) is diazotized by a known method, and in the form of a free acid, the o-alkoxyaniline derivative represented by the general formula
(3) (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. Examples of the o-alkoxyaniline derivative represented by the general formula (2) include the following. 2,4 or 2,5-dimethoxyaniline, 4
or 5-methyl-2-methoxyaniline, 4 or 5-nitro-2-methoxyaniline, 4 or 5-chloro-2-methoxyaniline, 4 or 5-ethyl-2-methoxyaniline, 4 or 5
-bromo-2-methoxyaniline, 4 or 5-
Bromo-2-ethoxyaniline, 2,4 or 2,5-diethoxyaniline, 4 or 5-methyl-2-ethoxyaniline, 4 or 5-nitro-2-ethoxyaniline, 4 or 5-chloro-
2-ethoxyaniline, 4 or 5-ethyl-2
-ethoxyaniline, 4-n-propyl or n
-Butyl-2-methoxy or ethoxyaniline. 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 dyes prepared according to the invention are generally separated by 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 performance for dyeing (including printing) materials made of cellulose fibers, natural or synthetic polyamides, polyurethane fibers. Cellulose fiber materials are preferably exemplified by real 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. , 6-, polyamide-6, polyamide-11 or 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 soda carbonate, 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 drying 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. Although the compound of the present invention has only one fiber-reactive group in one molecule, it can dye cellulose fibers in a much darker color than CIReactive Black5, which has two fiber-reactive groups, and it also has better build-up properties. Moreover, the fastness of the dyed product obtained is even more 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, especially chlorine fastness. In other words, as stated in Japanese Patent Publication No. 43-15299 And as stated in Special Publication No. 45-4337 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, in the comparison of chlorine fastness, it was found that the known dyes were primary or 1-
In contrast to secondary compounds, the compounds of the present invention are secondary to 2-tertiary. Next, the present invention will be explained in more detail with reference to Examples. In the text, parts represent parts by weight. Examples 1-5 6.9 parts of P-cresidine, 15.6 parts of hydrochloric acid, and 150 parts of water
After mixing and dissolving 3.8 parts of sodium nitrite, diazotization was performed at 10°C or lower. 2 hours later
After removing excess nitrite with sulfamic acid,
Trisodium salt of 1-amino-2-(4-β-sulfatoethylsulfonylphenylazo)-8-hydroxynaphthalene-3,6-disulfonic acid
A neutral aqueous solution containing 33.85 parts was added. At 10-20°C, the pH was maintained at 5-8 for 3 hours by dropping a 15% aqueous sodium carbonate solution. 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. A predetermined amount of the above compound was dissolved in 200 parts of water, 20 parts of Glauber's salt was added, 10 parts of cotton was added, and the temperature was raised to 50°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, each compound represented by the following formulas (2) to (5) was obtained in the form of a free acid by the same method as above. Cotton was dyed using each of these dyes 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 above compounds (1) to (5) of the present invention with those of the following known dyes (A), (B) and (C).
Shown below. CIReactive Black5 Publication No. 43-15299 Listed in Special Publication No. 45-4337 The dye shown below was used. As a result, the compounds (1) to (5) of the present invention were compared to the comparative dye (A).
It has the property that it can be dyed in an extremely deep color in the entire range from low density dyeing to high density dyeing, and has extremely excellent build-up properties than any of (C).

[Table] This table shows the relative value of rudo.
Examples 6 to 21 Corresponding compounds are obtained in the same manner as in Example 1 using the raw material compounds listed in the table below.
Using each dye obtained, cotton was dyed in the same manner as in Example 1, and the compound of the present invention (1) described in Example 1 was obtained.
A dyed product having excellent properties similar to that obtained is obtained.

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[Table] Example 22 After mixing and dissolving 7.6 parts of 5-methyl-2-ethoxyaniline, 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)
A neutral aqueous solution containing 33.85 parts of the trisodium salt of -8-hydroxynaphthalene-3,6-disulfonic acid was added. At 10-20°C, the pH was maintained at 4-7 for 3 hours by dropping a 15% aqueous sodium carbonate solution. If the diazo compound is no longer detected, the pH will be 4~
6. Salting out at 30-40°C, filtering, and dissolving the obtained wet cake in water, adding equimolar amount of monosodium phosphate to pH 5-6, and drying to obtain the free acid in the form of the following formula (22 ) was obtained. A predetermined amount of the above compound was dissolved in 200 parts of water, 20 parts of Glauber's salt was 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. Examples 23 to 28 Corresponding compounds are obtained in the same manner as in Example 22 using the raw material compounds listed in the table below.
Using each of the obtained compounds, cotton is dyed in the same manner as in Example 20, and a dyed product having the same excellent performance as the compound (22) of the present invention described in Example 20 is obtained.

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Claims (1)

[Claims] 1 In the form of free acid, the following formula: [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. Z is a halogen atom, a nitro group, C ₁ −
It means a _C4 alkyl group or a _C1 - _C4 alkoxy group, and _R1 means a methyl group or an ethyl group. ] A bisazo compound represented by