JPS6231029B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel monoazo compound and a method for producing the same. More particularly, the present invention relates to a monoazo compound suitable for dyeing fibrous materials, particularly cellulosic fibrous materials, yellow, and a method for producing the same. It is known that dyes having a β-sulfatoethyl sulfone group can be applied as so-called vinyl sulfone type reactive dyes for dyeing textile materials. However, dyeings made with azo-based yellow reactive dyes having a β-sulfatoethyl sulfone group generally have low chlorine fastness, and fading due to chlorine contained in tap water is often a problem. There has been a strong demand for a yellow reactive dye with excellent strength. Yellow dyes with a monochlorotriazinyl group as another typical reactive group different from the β-sulfatoethyl sulfone group are also known, but these reactive dyes generally require high dyeing temperatures. In addition, it is only used for textile printing because it lacks exhaust dyeing suitability, and furthermore, it has the disadvantage of low acid stability of the dyed product obtained, so it is never sufficient for practical use. I couldn't say it. For this reason, the present inventors conducted extensive research in search of a yellow vinyl sulfone type reactive dye with particularly excellent chlorine fastness. It has been found that certain monoazo compounds containing a lutriazinyl group give yellow dyeings of excellent chlorine fastness. It has also been found that such a specific monoazo compound can overcome the drawbacks of reactive dyes having a monochlorotriazinyl group as described above. That is, according to the present invention, in the form of a free acid, the following general formula (In the formula, R ₁ is a methyl group, phenyl group or amino group, R ₂ is hydrogen, methyl group, methoxy group or ethoxy group, X ₁ and X ₂ are hydrogen, chlorine,
Represents a methyl group, methoxy group, carboxyl group or sulfonic acid group. Moreover, the position of the sulfonic acid group on the naphthalene ring is the 1,5-position or the 4,8-position. ) in the form of a monoazo compound and free acid represented by the following general formula () (In the formula, the sulfonic acid group is at the 1,5 position or the 4,8 position
It is a positional substitution. ) 2-aminonaphthalene-disulfonic acid represented by the formula () is diazotized, and the general formula () is obtained. (In the formula, R ₁ represents a methyl group, phenyl group or amino group, and R ₂ represents hydrogen, methyl group, methoxy group or ethoxy group.) General formula in the form () (In the formula, R ₁ and R ₂ have the above-mentioned meanings.) An aminomonoazo compound represented by the formula (wherein R 1 and R 2 have the above-mentioned meanings) is obtained, and this is combined with cyanuric chloride and a free acid in the form of the general formula () (In the formula, X ₁ and X ₂ each represent hydrogen, chlorine, a methyl group, a methoxy group, a carboxyl group or a sulfonic acid group.) A method for producing a monoazo compound represented by formula () is provided. The monoazo compound represented by the general formula () has excellent dye properties and is useful for textile materials, especially cotton,
It is suitable for dyeing natural or recellulose fiber materials such as hemp, viscose human silk, and viscose cotton, and can provide yellow dyed products with excellent fastness to various types of fastness, especially fastness to chlorine. The monoazo compound represented by the general formula () can be produced by the method described below. 2-aminonaphthalene-disulfonic acid represented by the general formula () is diazotized according to a conventional method,
This is coupled with an m-phenylenediamine compound represented by the general formula () by a conventional method to obtain an aminomonoazo compound represented by the general formula (). It is possible to firstly condense this with cyanuric chloride to obtain a dichlorotriazinyl compound, and then to secondarily condense an aniline compound represented by general formula () to obtain a monoazo compound represented by general formula (). can. Alternatively, cyanuric chloride can be expressed by the general formula ()
The monoazo compound of the general formula () can also be obtained by condensing the aniline compound represented by the formula (2) and then secondarily condensing the aminomonoazo compound of the general formula (). In the monoazo compound produced by the above method, the sulfatoethyl sulfone group can be easily changed by the action of an alkali to form a monoazo compound having a vinyl sulfone group. The monoazo compound of the present invention thus obtained is useful for yellowing dyeing of natural or regenerated cellulose fibers such as cotton, linen, viscose human silk, and viscose cotton. In the case of the exhaust method, dyeing is carried out at a relatively low temperature in a dye bath containing Glauber's salt or common salt in the presence of an acid binder such as sodium carbonate, tribasic sodium phosphate, or caustic soda. It can also be dyed using a textile printing method. At this time, by addition of an acid binder, the sulfate ethyl sulfone group becomes a vinyl sulfone group, which undergoes an addition reaction with the cellulose fibers to effect dyeing. By such a dyeing method, the monoazo compound of the present invention provides a yellow dyed product particularly excellent in chlorine fastness, light fastness, and sweat/sunlight fastness. In particular, considering that the use of chlorine bleach in household laundry has recently become widespread, the value of the monoazo compound of the present invention, which provides dyed products with excellent chlorine fastness, is high. In addition, its excellent light fastness, sweat fastness and sunlight fastness make it suitable for dyeing external wear such as sportswear. Furthermore, since the monoazo compound of the present invention exhibits a high exhaustion rate, it is possible not only to obtain dyed products with high density, but also to have a small amount of dye remaining in the dye bath, which is advantageous in terms of wastewater treatment. It has certain advantages. Furthermore, the monoazo compound of the present invention has excellent level dyeing properties, can be applied over a wide range of dyeing temperatures, and is less affected by the amount of inorganic salt added and the bath ratio, so it also has the characteristics of good dyeing reproducibility. As a dye similar to the present invention, for example,
Publication No. 39-18184 states the following: The yellow reactive dye shown is described. However, the chlorine fastness of these dyes is very low, being grade 1 according to the ISO method, and their practical value is small. On the other hand, the yellow dye of the present invention has excellent chlorine fastness of 3 to 4 or 4 according to the ISO method, light fastness of 6 to 7, and sweat/sunlight fastness of 4 to 4. - All of them are excellent as 5th grade.
Furthermore, the acid stability of the dyed product (test method is to soak the dyed fabric in 1% acetic acid for 30 minutes, then use a perspirometer to evaluate the acid stability at 37±
(treated at 125g/ ^cm2 for 6 hours at a temperature of 2℃) is also 4
-5th grade or 5th grade, which is good. Next, the method of the present invention will be explained with reference to examples. In the text, parts represent parts by weight. Example 1 2-aminonaphthalene-4,8- in 100 parts of water
Add 6.1 parts of disulfonic acid and adjust the pH to 8 with caustic soda solution.
Adjust to dissolve. After adding 1.4 parts of sodium nitrite to this liquid, the mixture was cooled to 0 to 5°C, and 6.1 parts of concentrated hydrochloric acid was added thereto, followed by stirring at the same temperature for 30 minutes.
After removing excess nitrous acid, the paste solution was m
- Add 3.3 parts of acetylaminoaniline dissolved in 80 parts by volume of water at 0 to 5°C. Next, the pH of this solution is adjusted to 3-5 to complete the coupling, and then the pH is raised to 8 to dissolve the product, and 40 parts of sodium chloride is added to reprecipitate the crystals. After suctioning this and washing it, add 100 ml of water.
and adjust the pH to 6-7. Add 3.3 parts of cyanuric chloride to this solution and heat to 20% at 20-25°C.
Stir for 5 hours while adjusting the pH to 5-6 using an aqueous sodium carbonate solution. Then, after adding 5.6 parts of 1-aminobenzene-3-β-hydroxyethylsulfone sulfate, the pH was adjusted to 5-5 using a 20% aqueous sodium carbonate solution.
The temperature was raised to 40°C while adjusting the temperature to 40°C, and the mixture was stirred at the same temperature for 5 hours. 25 parts of sodium chloride was added to this solution to precipitate crystals, which were filtered under suction, washed, and dried at 60°C to obtain a monoazo compound of the following formula (1). Similarly, diazo and coupling were performed to obtain the aminomonoazo compound [general formula ()] shown in the table below, and this and the aniline compound [general formula ()] shown in the table below.
were condensed in the same manner as above to obtain each monoazo compound.

[Table] Example 2 A monoazo compound represented by the following formula (6) was obtained by carrying out the same operation as in Example 1 using 3-aminophenyl urea in place of m-acetylaminoaniline in Example 1. In the same manner, an aminomonoazo compound [general formula ()] shown in the table below was obtained, and this was similarly condensed with an aniline compound [general formula ()] shown in the table below to obtain each monoazo compound.

【table】

[Table] Example 3 2-aminonaphthalene-4 in Example 1,
The same operation as in Example 1 was carried out using 2-aminonaphthalene-1,5-disulfonic acid in place of 8-disulfonic acid and 2-methoxy-5-acetylaminoaniline in place of m-acetylaminoaniline. A monoazo compound represented by the following formula (11) was thus obtained. In the same manner, an aminomonoazo compound [general formula ()] shown in the table below was obtained, and this was similarly condensed with an aniline compound [general formula ()] shown in the table below to obtain each monoazo compound.

【table】

[Table] Reference Example 1 Dissolve 0.3 parts of the monoazo compound represented by formula (1) obtained in Example 1 in 200 parts of water, add 20 parts of Glauber's Salt, add 10 parts of cotton, and raise the temperature to 50°C. do. Then 30
After a few minutes have elapsed, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping yielded a yellow dyed product with excellent fastness, especially fastness to chlorine. Similarly, when dyeing was carried out using monoazo compounds represented by formulas (2), (3), (4) and (5), yellow dyed products with excellent chlorine fastness were obtained. Further, when a monoazo compound represented by formula (1) in which the sulfate ethyl sulfone group is a vinyl sulfone group was used for dyeing in the same manner, a similar yellow dyed product was obtained. Reference Example 2 0.3 part of the monoazo compound represented by formula (6) obtained in Example 2 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 4 minutes, add 4 parts of soda. Dye for 1 hour at that temperature. After dyeing, washing with water and soaping yielded a yellow dyed product with excellent fastness, especially fastness to chlorine. When similarly dyed using the monoazo compounds represented by formulas (7), (8), (9) and (10), a yellow dyed product with excellent chlorine fastness was obtained. Further, when a monoazo compound represented by formula (6) in which the sulfate ethyl sulfone group is a vinyl sulfone group was used for dyeing in the same manner, a similar yellow dyed product was obtained. Reference Example 3 0.3 part of the monoazo compound represented by formula (11) obtained in Example 3 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 4 minutes, add 4 parts of soda. Dye for 1 hour at that temperature. After dyeing, washing with water and soaping yielded a yellow dyed product with excellent fastness, especially fastness to chlorine. When similarly dyed using monoazo compounds represented by formulas (12) and (13), a yellow dyed product with excellent chlorine fastness was obtained. Further, when dyeing was carried out in the same manner using a monoazo compound represented by formula (11) in which the sulfate ethyl sulfone group was a vinyl sulfone group, a similar yellow dyed product was obtained.

Claims (1)

[Claims] 1 The following general formula in the form of a free acid: (In the formula, R ₁ is a methyl group, phenyl group or amino group, R ₂ is hydrogen, methyl group, methoxy group or ethoxy group, X ₁ and X ₂ are hydrogen, chlorine,
Represents a methyl group, methoxy group, carboxyl group or sulfonic acid group. Moreover, the position of the sulfonic acid group on the naphthalene ring is the 1,5-position or the 4,8-position. ) A monoazo compound represented by 2 The following general formula () in the form of free acid: (In the formula, the sulfonic acid group is at the 1,5 position or the 4,8 position
It is a positional substitution. ) 2-aminonaphthalene-disulfonic acid represented by the formula () is diazotized, and the general formula () is obtained. (In the formula, R ₁ represents a methyl group, phenyl group or amino group, and R ₂ represents hydrogen, methyl group, methoxy group or ethoxy group.) General formula in the form () (In the formula, R ₁ and R ₂ have the above-mentioned meanings.) An aminomonoazo compound represented by the formula (wherein R 1 and R 2 have the above-mentioned meanings) is obtained, and this is combined with cyanuric chloride and a free acid in the form of the general formula () (In the formula, X ₁ and X ₂ each represent hydrogen, chlorine, a methyl group, a methoxy group, a carboxyl group, or a sulfonic acid group.) A free acid characterized by condensing an aniline compound represented by the following in any order: General formula in the form () (In the formula, R ₁ , R ₂ , X ₁ , and X ₂ have the above-mentioned meanings, and the position of the sulfonic acid group on the naphthalene ring is as above.) A method for producing a monoazo compound represented by the following.