JPH0437106B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel bisazo compound and a method for dyeing cellulose fibers using the same. More specifically, the present invention relates to a novel fiber-reactive bisazo compound and a method for dyeing cellulose fibers navy color using the same. CIReactive Black5 is known as a reactive dye that dyes cellulose fibers blue or black, but despite having two vinyl sulfone-type fiber-reactive groups in one molecule, the dyeing rate for cellulose fibers is low. The problem is that there is insufficient For the purpose of solving this problem, the special public
Examples 13 and 14 of the publication contain dyes represented by the following formula.
(A) and (B) are listed. Furthermore, Example 17 of Japanese Patent Publication No. 45-4337 describes a dye (C) represented by the following formula. However, compared to CIReactive Black5, the dyeing rate is only about 60% for dye (A), about 50% for dye (B), and only about 60% for dye (C). However, the above-mentioned problems have not been solved. The present inventors have conducted intensive studies to solve these problems, and have found that a specific bisazo compound, in which a specific number of sulfonic acid groups are present in a specific position in the structure, solves these problems and is an excellent product. The present inventors have discovered that it is possible to obtain a dyed product with a high density of navy color having a high dyeing rate and build-up property, and have completed the present invention. That is, the present invention provides the following general formula () in the form of a free acid: [In the formula, R ₁ and R ₂ are each independently a hydrogen atom,
Indicates a methyl group or a methoxy group. However, R ₁ ,
When either one of R ₂ is hydrogen, the other represents a methyl group or a methoxy group. Q is the group −SO ₂ CH=
_{Indicates CH2} or _{-SO2CH2CH2R .} Here, R is a group that is eliminated with an alkali. n represents 0 or 1, and one of the sulfonic acid groups is located adjacent to the azo group bonded to the naphthalene ring. ] A bisazo compound represented by the following is provided. The present invention also provides a method for dyeing cellulose fibers, characterized by using a bisazo compound represented by the general formula (). Q in the general formula () is -SO ₂ CH ₂ CH ₂
When R, the alkali-removable group R includes, for example, halogen atoms such as chlorine and bromine atoms, ester groups of organic carboxylic acids and sulfonic acids, lower alkanoyloxy residues such as acetyloxy residues, benzoyloxy residues, etc. or in the form of benzenesulfonyloxy group or free acid with the formula -OPO ₃
These include acidic ester groups of phosphoric acid or sulfuric acid represented by H ₂ or -OSO ₃ H, and the like. Although the bisazo compounds according to the invention can exist both in the free acid form and in the form of their salts, they are preferably in the form of salts, especially alkali metal and alkaline earth metal, especially sodium, potassium and calcium salts. More preferred forms are alkali metal salts. The bisazo compound of the present invention represented by the above general formula has excellent properties as a fiber-reactive dye, such as dyeing rate, alkali stability, build-up property, wash-off property, etc., and has a navy-colored color with excellent various fastness properties. It is a useful compound that gives dyes. The novel bisazo compound represented by the general formula () can be produced as follows. That is, the general formula () [In the formula, R ₁ , R ₂ and Q have the above meanings. ] The aromatic amine represented by is diazotized by a known method, and mixed with equimolar amounts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid or its salt in an acidic medium, optionally with a reaction accelerator. coupling at -5 to 30°C under the addition of
Then the general formula () [In the formula, n and the positional relationship of the substituents have the above-mentioned meanings. ] It can be produced by adding equimolar amounts of the naphthylamine sulfonic acid derivative represented by the formula diazotized by a known method and coupling the mixture at -5 to 40°C under weakly acidic to weakly alkaline conditions. Depending on the reaction conditions, the starting compounds mentioned are present or used in the form of acids and/or salts, in particular alkali metal salts. The bisazo compounds produced according to the invention are generally separated by known methods, such as salting out with electrolytes such as sodium chloride or potassium chloride, or evaporation of the reaction solution, such as spray drying, optionally with the addition of auxiliaries such as stabilizers. and can be done. Examples of the aromatic amine represented by the general formula () include the following. 1-amine-2- or 4-methoxybenzene-
5-β-sulfatoethylsulfone, 1-amino-2-methoxy-5-methylbenzene-4-β-sulfatoethylsulfone, 1-amine-2,5-dimethoxybenzene-4-
β-sulfatoethyl sulfone, 1-amine-2,4-dimethylbenzene-5-β
-sulfatoethylsulfone, 1-amino-2,4-dimethoxybenzene-5-
In place of the sulfate ester group in β-sulfatoethylsulfone and the above compounds, examples include a phosphate ester group, acetyloxy group, propionyloxy group, n- or iso-butyryloxy group, benzoyloxy group, or benzenesulfonyloxy group. . The following compounds can be exemplified as naphthylamine sulfonic acid derivatives of general formula () that can be used in the present invention. 2-naphthylamine-1-sulfonic acid, 2-naphthylamine-1,5-disulfonic acid, 2-naphthylamine-3,6-disulfonic acid, 2-naphthylamine-1,6-disulfonic acid, 1-naphthylamine-2-sulfonic acid , 1-naphthylamine-
2,7-disulfonic acid. The bisazo compounds of the invention can dye cellulosic fiber materials, such as natural or regenerated cellulose, such as cotton or viscose rayon materials, according to the customary methods practiced with water-soluble reactive dyes. For example, in the case of cellulosic fibers, dyeing is carried out using the bisazo compounds of the invention and acid binders such as caustic soda, sodium carbonate, phosphates or baking soda. The dyeing method can be selected depending on the nature and physical properties of the fibers, and may be, for example, an exhaust method, a printing method, or a continuous dyeing method including a cold pad batch up method. When dyeing cellulosic fiber materials with the bisazo compounds of the invention, the dyeings obtained have good fastness properties, e.g. good rubfastness, good sunlight fastness and good wet fastness, e.g. washfastness, It has excellent water resistance, acid and alkali fastness, and fastness to peroxide-containing chemicals. Among these, preferred are bisazo compounds in which the azo group bonded to the naphthalene ring is at the β position in the general formula (), and furthermore, in the following formula [In the formula, R ₁ , R ₂ and Q have the above meanings.] ] The bisazo compound shown by is extremely excellent in color value and build-up property,
Moreover, it has excellent sweat fastness and sunlight fastness and chlorine fastness. These compounds of the present invention can be used in the above-mentioned Japanese Patent Publication No. 43-
Not only can it overcome the problems of the dyes described in Japanese Patent Publication No. 15299 and Japanese Patent Publication No. 45-4337, but surprisingly it has only one fiber-reactive group in one molecule. CI with two
Compared to Reactive Black5, it has superior characteristics in terms of color value, dyeing rate, and build-up property of the dyed product obtained. Next, the present invention will be explained in more detail with reference to Examples. In the text, parts represent parts by weight. Example 1 1-amine-2-(2,5-dimethoxy-4-
A suspension containing 33.55 parts of β-sulfatoethylsulfonylphenylazo)-8-hydroxynaphthalene-3,6-disulfonic acid at a temperature of 0 to 10°C and a pH of 0.5 to 2 (this is 1-amino-2, (obtained by diazotizing 5-dimethoxybenzene-4-β-sulfatoethylsulfone by a conventional method and coupling it with a neutral solution of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid)
of 2-naphthylamine-1-sulfonic acid.
After diazotizing 11.15 parts by a conventional method, add a solution in which excess nitrous acid has been removed with sulfamic acid, and heat at 5 to 15°C.
The pH was adjusted to 6 by adding sodium hydrogen carbonate over a period of about 1 hour, and the mixture was stirred until the diazo compound was no longer detected. The resulting dye solution is adjusted to pH 4.5 to 5.5 and then dried to form a free acid according to the following formula (1). [λmax 620 nm (water solvent)] A bisazo compound was obtained. 0.6 part of the above dye 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. Then, after 30 minutes, add 4 parts of soda soda and boil at the same temperature.
Time stained. After dyeing, washing with water and soaping were carried out to obtain a dyed navy color with excellent color fastness and rich build-up properties. Examples 2 to 8 Similar to Example 1, 1-amino-
Using 8-hydroxynaphthalene-3,6-disulfonic acid and the diazo component compound listed in the table below,
The corresponding bisazo compounds were obtained. Using each of the obtained bisazo compounds, cotton was dyed in the same manner as in Example 1 to obtain a navy colored dyed product having excellent performance similar to that of the compound represented by formula (1).

【table】

【table】

Claims (1)

[Claims] 1 The following general formula () in the form of a free acid: [In the formula, R ₁ and R ₂ are each independently a hydrogen atom,
Indicates a methyl group or a methoxy group. However, R ₁ ,
When either one of R ₂ is hydrogen, the other represents a methyl group or a methoxy group. Q is the group −SO ₂ CH=
_{Indicates CH2} or _{-SO2CH2CH2R .} Here, R is a group that is eliminated with an alkali. n represents 0 or 1, and one of the sulfonic acid groups is located adjacent to the azo group bonded to the naphthalene ring. ] A bisazo compound represented by 2 General formula () [In the formula, R ₁ and R ₂ are each independently a hydrogen atom,
Indicates a methyl group or a methoxy group. However, R ₁ ,
When either one of R ₂ is hydrogen, the other represents a methyl group or a methoxy group. Q is the group −SO ₂ CH=
_{Indicates CH2} or _{-SO2CH2CH2R .} Here, R is a group that is eliminated with an alkali. n represents 0 or 1, and one of the sulfonic acid groups is located adjacent to the azo group bonded to the naphthalene ring. ] A method for dyeing cellulose fibers, characterized by using a bisazo compound shown in the following.