JPS6224559B2 - - Google Patents

Description

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

More specifically, the present invention provides the following general formula () in the form of a free acid: (wherein A is a phenyl group having one sulfonic acid group or a naphthyl group having two sulfonic acid groups,
R is a hydroxyl group or an amino group, X ₁ is hydrogen, a methyl group, a methoxy group, or a sulfonic acid group, respectively;
X ₂ represents a hydroxyl atom. ) This is a method for dyeing cellulose fibers, which is characterized by using the dye shown in the following.

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, dyeings made with azo-based bright yellow reactive dyes containing a β-sulfatoethylsulfonyl 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 bright yellow reactive dye with excellent chlorine fastness.

Dyes with a monochlorotriazinyl group as another typical reactive group different from the β-sulfatoethylsulfonyl 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, so it is by no means sufficient for practical use. Ta. For this reason, the present inventors conducted extensive research in search of a bright yellow vinyl sulfone type reactive dye with particularly excellent chlorine fastness. It has been found that a monoazo dye having a β-sulfatoethylsulfonyl group and a monochlorotriazinyl group gives a bright yellow dyeing with excellent chlorine fastness. 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, 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 a dye bath containing Glauber's salt 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 patch batch dyeing is also possible.

The dye of the present invention can be produced, for example, as follows.

After primary bonding of 2,4-diaminobenzenesulfonic acid and cyanuric chloride, diazotization is performed by a conventional method to form the general formula () (In the formula, A and B have the above-mentioned meanings.) It is coupled with a pyrazolone derivative represented by the following formula. Then the general formula () (In the formula, X ₁ and X ₂ have the above-mentioned meanings.) The dye represented by the general formula () can be obtained by secondarily condensing the aniline compound represented by the following.

Alternatively, cyanuric chloride, 2,4-diaminobenzenesulfonic acid, and an aniline compound represented by the general formula () are condensed in any order, and the general formula (In the formula, X ₁ and X ₂ have the above-mentioned meanings.) It can also be obtained by obtaining a compound represented by the formula, diazotizing it by a conventional method, and coupling it with a pyrazolone derivative represented by the general formula (). Dyes of general formula () can be obtained.

Alternatively, the general expression () (In the formula, X _{1 and} A dye of the general formula () may be obtained by esterifying the compound in sulfuric acid.

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

The chlorine fastness is 3rd grade or 3rd to 4th grade according to the JIS method, and it has excellent chlorine fastness, especially considering that the use of chlorine-based whiteners in laundry in general households has recently become widespread. The value of the dye according to the invention is high. In addition, the sweat and sunlight fastness, which has become a problem with the expansion of sportswear in recent years, is excellent at grade 3-4 or grade 4, and from this point of view as well, the value of the dye of the present invention is high. Furthermore, with conventional reactive dyes, there was a phenomenon in which the dyed product was affected by acidic gases in the air and its fastness decreased over time, but the dye of the present invention solves this problem. There is. That is, the acid stability of the dyed product of the dye of the present invention (the test method is to immerse the dyed fabric in 1% acetic acid for 30 minutes, and then treat it at 125 g/cm ² for 6 hours at a temperature of 37 ± 2°C using a perspirometer. ) is good at 4th to 5th grade or 5th grade, and from this point of view as well, it is of high value.

In addition, the dye of the present invention has good alkali stability and exhibits a high exhaustion rate and fixation rate in exhaust dyeing, and also shows a high fixation rate in textile printing, making it possible not only to obtain dyed products with high density. At the same time, it has excellent wash-off properties and has the great advantage that unfixed dye can be easily removed.

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.

As a dye similar to the present invention, for example,
Publication No. 39-18184 contains the following formula The yellow reactive dye shown is described.

However, this dye has a low exhaustion rate and a low build-up property, so it has the disadvantage that dyed products with high density cannot be obtained. However, the dye of the present invention is superior to this dye in terms of exhaustion suitability.
A bright yellow dyed product with high density can be easily obtained.

Next, the method of the present invention will be explained with reference to examples.

In the text, parts represent parts by weight.

Example 1 Formula 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 30 minutes, 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 bright yellow dyed product with excellent fastness, especially fastness to sweat and sunlight.

The above dye is synthesized, for example, as follows.

To a solution in which 0.1 part of a nonionic surfactant is dissolved in 100 parts of water, 9.2 parts of cyanuric chloride is added and dispersed at 0 to 10°C. 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 complete, add a 20% aqueous sodium carbonate solution to adjust the pH to 7-8. Then sodium nitrite
Add 3.5 parts to dissolve and diazotize by injecting 12.7 parts of concentrated hydrochloric acid at 0 to 5°C. This diazo suspension
Add 19.5 parts of -(4'.8'-disulfo-2'-naphthyl)-3-carboxypyrazolone to 150 parts of water at pH 7-8 at 0-5°C. During this period, 20%
Adjust the pH to 5-6 with an aqueous sodium carbonate solution. After injecting the diazo suspension, stir at 0 to 5°C until coupling is completed.

Then, 16.9 parts of 1-aminobenzene-3-β-sulfatoethylsulfone was added, and the temperature was raised to 40°C while adjusting the pH to 5 to 6, and the mixture was stirred at the same temperature for 5 hours. 60 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 dye (1).

Example 2 Formula (2) 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 60℃.
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 yielded a bright yellow dyed product with excellent fastness, especially fastness to sweat and sunlight.

Examples 3 to 6 In the same manner as in Example 1 or Example 2, the following (3) to
When dyed using the dye (6), bright yellow dyed products with excellent fastness were obtained in all cases.

Example 7 Composition of colored paste 5 parts dye of formula (1) above 5 parts urea 5 parts sodium alginate (5%) Base paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts The colored paste having the above composition was mercerized Print on cotton broadcloth, and after intermediate drying, steam at 100℃ for 5 minutes, wash with hot water, soap, wash with hot water, and dry.

In this way, a bright yellow print with excellent color fastness was obtained.

Claims (1)

[Claims] 1 The following general formula in the form of a free acid: (wherein A is a phenyl group having one sulfonic acid group or a naphthyl group having two sulfonic acid groups,
R represents a hydroxyl group or an amino group, X ₁ represents hydrogen, a methyl group, a methoxy group or a sulfonic acid group, and X ₂ represents a hydrogen atom. ) A dyeing method for cellulose-based fiber materials characterized by using a dye represented by: