JPH0210184B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for dyeing cellulose fibers in a strong red color. More specifically, the present invention provides the following general formula () in the form of a free acid: [In the formula, (also good). The sulfonic acid group of nucleus A is in the m- or p-position relative to the amino group. ] This is a method for dyeing cellulose fibers, which is characterized by using the dye shown below. It is known that dyes having a β-sulfatoethylsulfonyl group can be applied as so-called vinylsulfone type reactive dyes for dyeing textile materials.
However, there are few products dyed with azo-based red reactive dyes having β-sulfatoethylsulfonyl groups that have good discharge printability and good fastness, especially chlorine fastness. It was often a problem. Therefore, there has been a strong demand for a red reactive dye that has excellent chlorine fastness and discharge printability. Red 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 it also has the disadvantage of low acid stability of the dyed product, so it is never sufficient for practical use. I couldn't say it. For this reason, the present inventors have conducted intensive studies in search of a red vinyl sulfone type reactive dye with high fastness and good whiteout property, and have found that the dye represented by the general formula (), That is, it has been found that a monoazo dye having a β-sulfatoethylsulfonyl group and a monochlorotriazinyl group as reactive groups gives a red dyed product having both excellent fastness and whiteness. It has also been found that the dye of the present invention can overcome the drawbacks of reactive dyes having a monochlorotriazinyl group as described above. In the present invention, cellulose fibers include:
For example, natural or recycled cellulose fibers such as cotton, linen, viscose human silk, and viscose cotton can be used. In the case of the exhaust method, the dyeing of the present invention uses soda carbonate,
It is carried out at relatively low temperatures in a dye bath containing mirabilite or common salt in the presence of an acid binder such as tribasic sodium phosphate or caustic soda. It can also be dyed using a textile printing method. The dye of the present invention can be produced, for example, as follows. General formula in free acid form () (In the formula, X represents the above-mentioned meaning) A compound represented by the formula () is diazotized and converted into a free acid form of the general formula () (In the formula, Y represents the above-mentioned meaning.) By coupling with a compound represented by the following, a dye represented by the general formula () can be obtained. Alternatively, a free acid obtained by diazotizing a condensate of cyanuric chloride and m-phenylenediaminesulfonic acid and coupling it with a compound represented by the general formula () can be obtained in the form of a free acid obtained by the general formula (). (In the formula, Y represents the above meaning) and a compound represented by the general formula () (In the formula, X represents the above-mentioned meaning.) The dye represented by the general formula () can be obtained by condensing the aniline compound represented by the following. Or general expression () (In the formula, X represents the above meaning) A β-hydroxyethyl sulfone compound represented by the above general formula () is used in place of the above general formula (), and after performing the same reaction, it is finally esterified in sulfuric acid. It may also be a dye of general formula (). The thus obtained dye of the present invention is excellent in various fastness properties, particularly chlorine fastness, light fastness, and sweat/sunlight fastness, and has extremely good whiteout property. This has high utility value in the ground dyeing field of exhaust dyeing. Furthermore, the dye of the present invention exhibits extremely good performance in terms of wash-off properties, making it possible to shorten the rinsing step after dyeing. Furthermore, since the dye 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 the advantage of being advantageous in terms of wastewater treatment, since only a small amount of dye remains during the dyeing process. have As a dye similar to the present invention, for example,
Publication No. 39-18184 includes the following: The red reactive dye shown is described. However, the dye of the present invention has significantly better whiteout property than the above-mentioned dyes. Additionally, the same bulletin states the following: Also described are red reactive dyes represented by . However, the above dyes have poorer exhaust dyeing properties than the dyes of the present invention.
In particular, it is surprising that the solubility and fixing properties are poor and the practical value is small. Furthermore, the dye of the present invention has the unique ability to be hardly affected by changes in the dyeing temperature, alkali agent, inorganic salt addition amount, and bath ratio during exhaust dyeing, and allows dyeing to be carried out with extremely high reproducibility. Next, the method of the present invention will be explained with reference to examples. In the text, parts indicate parts by weight. Example 1 Formula (1) in free acid form Dissolve 0.3 parts of the dye shown in 200 parts of water and add 20 parts of mirabilite.
10 parts of cotton, and raise the temperature to 60℃. After 30 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing was completed, washing with water and sorbing were performed to obtain a red dyed product with good fastness properties and good white-out property. Similarly, when dyeing was carried out in the same manner as in Example 1 using dyes (2) and (3) obtained using the following general formula () in the form of free acid and general formula () in the form of free acid as components, the following results were obtained. A red dyed product with good color fastness and good white-out property was obtained.

[Table] Reference Example 1 Synthesis of dye (1) of Example 1 m-phenylenediaminesulfonic acid in 50 parts of water
Dissolve 9.4 parts and adjust the pH to 2.8±0.5 with hydrochloric acid.
Then cool to 0-5°C. Add 9.5 parts of cyanuric chloride to this solution and keep warm for 1 hour while adjusting the pH to 2-3 at 0-5°C. Thereafter, the temperature was raised to 30 to 35°C, 16.9 parts of 1-aminobenzene-3-β-sulfatoethylsulfone was added, and the mixture was kept at a pH of 4 to 5 for 4 hours. After that, cool to 0-5℃, add 3.5 parts of sodium nitrite and 8.8 parts of concentrated hydrochloric acid, and
Stir for an hour. After eliminating excess nitrous acid, this paste solution was added to a solution of 21.1 parts of 1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid dissolved in 200 parts of water and 4 parts of sodium bicarbonate at 0 to 5°C. Add. Next, the pH of this solution was adjusted to 5.5-6.5 to complete the coupling, and the temperature was adjusted to 30-35℃.
50 parts of sodium chloride was added for salting out, filtered under suction, washed, and dried to obtain dye (1). Example 2 Formula (4) in free acid form Dissolve 0.3 parts of the dye shown in 200 parts of water and add mirabilite.
Add 20 parts, add 10 parts of cotton, and raise the temperature to 50℃.
After 20 minutes, add 4 parts of soda. Dye for 1 hour at that temperature. After dyeing was completed, washing with water and soaping were carried out to obtain a red dyed product with good fastness properties and excellent white spotability. Similarly, dyeing was carried out in the same manner as in Example 2 using dyes (5) and (6) obtained using the following general formula () in the form of free acid and general formula () in the form of free acid as components. A red dyed product with good color fastness and excellent white-out property was obtained.

[Table] Reference Example 2 Synthesis of the dye of Example 2 In the same manner as Reference Example 1, m-phenylenediaminesulfonic acid and cyanuric chloride were condensed, and this condensation liquid was
Add 3.5 parts of sodium nitrite and 8.8 parts of concentrated hydrochloric acid at -5°C, and stir at the same temperature for 1 hour. After eliminating excess nitrous acid, this paste solution was added to a solution of 21.1 parts of 1-benzoylamino-8-hydroxynaphthalene-4,6-disulfonic acid dissolved in 200 parts of water and 4 parts of sodium bicarbonate at 0 to 5°C. Add. Next, the pH of this solution is
After adjusting the temperature to 5.5-6.5 to complete coupling, raise the temperature to 30-35°C, add 16.9 parts of 1-aminobenzene 3-β-sulfatoethyl sulfone, and keep warm at PH4-5 for 4 hours. Thereafter, 50 parts of sodium chloride was added at the same temperature for salting out, filtered under suction, washed, and dried at 60°C to obtain dye (4).

Claims (1)

[Claims] 1 The following general formula in the form of a free acid: [In the formula, X represents a hydrogen atom, a methyl group, a methoxy group, or a carboxyl group, and Y represents a hydrogen atom, a nitro group, or an amino group (this amino group may be substituted with a methyl group). The sulfonic acid group of nucleus A is in the m- or p-position relative to the amino group. ] A method for dyeing cellulose fibers, characterized by using the dye shown in the following.