JPS6030787B2 - Dyeing method for cellulose fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dyeing cellulose fibers yellow.

More specifically, the present invention provides the following general formula (1) in the form of a free acid:
[Wherein, R is hydrogen or a lower alkyl group, R2 is a lower alkyl group, R3 is a sulfo-lower alkyl group, X,, X2
each represents hydrogen, a methyl group, a methoxy group, or a sulfonic acid group, and Y represents fluorine or chlorine.

] This is a method for dyeing cellulose fibers, which is characterized by using the dye shown below.

It is known that dyes having an 8-sulfate ethyl sulfone group can be used as so-called vinylsulfone type reactive dyes for dyeing textile materials.

However, dyeings made with azo-based yellow reactive dyes having an 8-sulfate ethyl sulfone group generally have low chlorine fastness, and fading due to chlorine contained in tap water has become a problem. There has been a strong demand for a yellow reactive dye with excellent strength. Yellow dyes with a monochlorotriazinyl group as a typical reactive group different from the 6-sulfatethylsulfone 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 dyeability, and it has the disadvantage of low acid stability of the dyed product, so it is by no means sufficient for practical use. I could not say it.

For this reason, the present inventors conducted extensive research in search of a yellow pinyl sulfone type reactive dye with particularly excellent chlorine fastness. It has been found that a monoazo dye containing a sulfatethylsulfone group and a monohalogenotriazinyl group gives yellow dyeings with excellent chlorine fastness. Furthermore, the inventors have 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, the cellulose fibers include natural or regenerated cellulose fibers such as cotton, linen, viscose human silk, and viscose cotton.

In the case of the exhaust method, the dyeing of the present invention is carried out at a relatively low temperature in the presence of an acid binder such as soda carbonate, tribasic sodium phosphate, or caustic soda, with the addition of ramie or common salt.

It can also be dyed using a textile printing method. The dye of the present invention can be produced, for example, as follows.

After primary condensation of 2,4-diaminobenzenesulfonic acid and cyanuric chloride or cyanuric fluoride, diazotization is performed by a conventional method to obtain a compound of the general formula (0) (including tautomers) [in the formula, R, , R2 and R3 have the meanings given above.

] Coupling with the pyridone derivative shown.

Then, the dye represented by the general formula (1) can be obtained by secondarily condensing the aniline compound represented by the general formula (m) [wherein X, , and X2 have the above-mentioned meanings].

Alternatively, cyanuric chloride or cyanuric fluoride and 2,4-
Diaminobenzenesulfonic acid and the aniline compound represented by the general formula (m) are condensed in any order to form the general formula (W
) [In the formula, X, dyes of general formula (1) can also be obtained.

Alternatively, the same reaction can be carried out using an 8-hydroxyethyl sulfone compound represented by the general formula (V) [wherein X, X2 have the above-mentioned meanings] in place of the aniline compound of the general formula (m). After this, the dye of general formula (1) may be obtained by finally esterifying it in sulfuric acid.

The dye of the present invention thus obtained is particularly excellent in chlorine fastness, light fastness, and sweat/sunlight fastness.

Especially considering that the use of chlorine bleach in household laundry has recently become widespread, the value of the dye of the present invention, which has 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 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
Since there is only a small amount of dye remaining in Liangyu, it is also advantageous in terms of wastewater treatment.

In addition, the dye of the present invention has excellent wash-off properties and whiteout properties, has a wide range of dyeing temperatures, and is less affected by the amount of inorganic salt added and the tolerance ratio, so it has good dyeing reproducibility. have. As a dye similar to the present invention, for example, the following yellow reactive dye is described in Samurai Publication No. 181 of 1983.

However, the chlorine fastness of these dyes is very low, being 1st class according to the ISO method, and their practical value is small. On the other hand, the yellow dye of the present invention has an excellent chlorine fastness of 3rd grade or 3rd to 4th grade according to the ISO method, and a light fastness of 6th grade to 4th grade according to the ISO method.
The sweat and sunlight rating is 4th grade or 4th to 5th grade, all of which are excellent. Furthermore, the acid stability of dyed products (the test method is to soak the beam cloth in 1% acetic acid for 30 minutes and then test it at 37±2℃ using a bar spirometer)
(processed at a temperature of 125 m/s for 6 hours) is also good at grade 4-5 or grade 5. Next, the method of the present invention will be explained with reference to examples.

In the text, parts represent parts by weight. Example 1 0.3 part of the dye represented by the formula 01 is dissolved in 20$ of water, 2 parts of sulfur is added, 1 part of cotton is added, and the temperature is raised to 50°C.

Then, after 3 minutes, add 4 parts of soda carbonate and boil at the same temperature.
Time staining. After dyeing, washing with water and soaping were performed to obtain a greenish-yellow dyed product with excellent fastness, especially fastness to chlorine. The above dye is synthesized, for example, as follows.

9.2 parts of cyanuric chloride is added to a solution containing 0.1 part of anionic surfactant dissolved in 10 parts of water and dispersed.

A solution prepared by dissolving 10.5 parts of sodium 2,4-diaminobenzenesulfonate in 100 parts of water is added dropwise to this at 0 to 5°C over 1 hour. After the dropwise addition is completed, a 20% aqueous sodium carbonate solution is added to adjust the pH to 7-8.

Next, 3.5 parts of sodium nitrite was added and dissolved, and the
Diazotization is carried out by injecting 12.7 parts of concentrated hydrochloric acid at 5°C. This diazo suspension was diluted with 1,4-dimethyl-6-hydride. Kissy 3
Add 10.5 parts of -sulfomethyl-2-pyridone to the solution containing 10 parts of IN caustic soda, add 5 parts of sodium bicarbonate, and stir until the coupling is complete. Then 1-amino/benzene-3-8-hydroxyethylsulfone sulfate ester16. Add the $ part and make the boat 5~
While adjusting the temperature to 40q0, raise the temperature to 40q0 and pitch for 5 hours at the same temperature.

Add 6 parts of sodium chloride to this solution to precipitate crystals, pass through a suction oven, wash, and dry at 60°C to obtain a dye {1
I got 1. Example 2 0.3 part of the dye represented by the formula (■) is dissolved in 20 $ of water, 2 parts of Sannitrate are added thereto, 1 $ of cotton is added, and the temperature is raised to 40 qC.

Then, after 20 minutes, 3 parts of tribasic sodium phosphate is added.
Dye for 1 hour at that temperature. After dyeing, washing with water and soaping were performed to obtain a greenish-yellow dyed product with excellent fastness, especially fastness to chlorine. Example 3 When dyeing was carried out using the following dyes in the same manner as in Example 1 or Example 2, greenish-yellow dyed products with excellent chlorine fastness were obtained.

Claims (1)

[Claims] 1 In the form of a free acid, there are the following general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 is hydrogen or a lower alkyl group, R_2 is a lower alkyl group, R_3 is a sulfo lower alkyl group, X_
1 and X_2 each represent hydrogen, a methyl group, a methoxy group, or a sulfonic acid group, and Y represents fluorine or chlorine. A dyeing method for cellulose fibers characterized by using the dye shown in ].