JPS5818474B2 - 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 compounds of the following general formula (I) (wherein R1 represents a methyl group, a phenyl group, or an amino group, and R2 represents hydrogen, a methyl group, a methoxy group, or an ethoxy group, and X2 each represents hydrogen, chlorine, a methyl group, a methoxy group, a carboxyl group or a sulfonic acid group.

Further, the position of the sulfonic acid group on the naphthalene ring is the 1 and 5 positions or the 4 and 8 positions.

) 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-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 containing two β-sulfatoethyl sulfo groups 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 fastness.

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, and as a result, the dye represented by the general formula (I),
That is, it has been found that a monoazo dye having a β-sulfatoethyl sulfone group or a monochlorotriazinyl group as a reactive group gives a 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, examples of 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 relatively low temperatures in a dyebath containing Glauber's salt or common salt in the presence of an acid binder such as soda carbonate, 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.

2-aminonaphthalene-disulfonic acid is diazotized to give the general formula (1) (wherein, R1 and R2 have the above-mentioned meanings).

) is coupled with an m-phenylenediamine compound represented by the general formula (ffl) (wherein, R1 and R2 have the above-mentioned meanings).

) is obtained, and this is primary condensed with cyanuric chloride to obtain a dichlorotriazinyl compound.

Then, the general formula (Iv) (wherein, Xl and X2 have the above-mentioned meanings).

) The dye represented by general formula (I) can be obtained by secondarily condensing the aniline compound represented by formula (I).

(* means that the general formula (I ) can be obtained.

Alternatively, general formula (V) (In the formula, Xl and X2 have the above meanings.

) is used instead of the aniline compound of the general formula (■), the same reaction is carried out, and finally the dye of the general formula (I) is esterified in sulfuric acid. You can also use it as

The dye of the present invention thus obtained has particularly excellent fastness to chlorine, fastness to light, and fastness to sweat and sunlight.

In particular, considering that the use of chlorine bleach has recently become widespread in general households for washing at ℃, the value of the dye of the present invention, which has excellent chlorine fastness, is high.

In addition, the excellent fastness to needles, sweat, and sunlight makes 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 highly concentrated colored dyed products, but also to be advantageous in terms of wastewater treatment since only a small amount of dye remains in the dye bath. has advantages.

As a dye similar to the present invention, for example, Japanese Patent Publication No. 39-1
No. 8184 describes the yellow reactive dye shown below.

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 a chlorine fastness of ISO
The color fastness to light is 6-7, and the sweat and sunlight fastness is 4-4 to 4.
All of them are of excellent quality.

Furthermore, the acid stability of dyed fabrics (test method is 1% acetic acid 1 part 3
After soaking for 0 minutes, treat with 1251i/crj for 6 hours at a temperature of 37 ± 2°C using a bar spirometer).
-5 grade to 5 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 0.3 part of the dye represented by the formula (1) (λmax 390 nm, however, the same applies hereinafter in an aqueous solvent) was dissolved in 200 parts of water, and 20 parts of sodium sulfate was dissolved.
1 part, add 10 parts of cotton, and raise the temperature to 50°C.

Then, after 30 minutes, add 4 parts of soda carbonate and boil at the same temperature.
Time staining.

After dyeing, washing with water and soaping yielded a yellow dyed product with excellent fastness, especially fastness to chlorine.

? Dyes (2), (3), (
4) and (5) in the same manner as in Example 1, yellow dyed products with excellent chlorine fastness were obtained in both cases.

Reference Example 1 [Synthesis of Dye (1) of Example 1] 6.1 parts of 2-aminonaphthalene-4,8-disulfonic acid was added to 100 parts of water, and the mixture was adjusted to pH 8 with a caustic soda solution and dissolved.

After adding 1.4 parts of sodium nitrite to this solution,
After cooling to 6.1 parts of concentrated hydrochloric acid,
Stir for a minute.

After removing excess nitrous acid, this stock solution is added to a solution of 273,973.3 parts of m-acetyl chloride dissolved in 80 parts by volume of ice at 0 to 5°C.

Then, 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 washing this by suction r, redissolving it in 100 parts of water,
Adjust pH to 6-7.

Add 3.3 parts of cyanuric chloride to this solution and
Then, adjust the pH to 5-6 using 20% sodium carbonate aqueous solution.
Stir for 5 hours while adjusting the temperature.

Next, after processing 5.6 parts of l-aminebenzene-3-β-hydroxyethylsulfone sulfate, the temperature was raised to 40°C while adjusting the pH to 5 to 6 using a 20% aqueous sodium carbonate solution, and at the same temperature. Stir for 5 hours.

25 parts of sodium chloride was added to this solution to precipitate crystals, which were filtered by suction, washed, and dried at 60°C to form the dye (1).
I got it.

Example 2 A dye represented by formula (6) (m
- Obtained by using 3-aminophenyl urea instead of acetylaminoaniline) was dissolved in 200 parts of water, 20 parts of Glauber's salt was added, io parts of cotton was added, and the temperature was raised to 60°C. After 20 minutes, add 4 parts of soda.

Dye for 1 hour at that temperature.

After dyeing, washing with water and noping were performed to obtain a yellow dyed product with excellent chlorine fastness.

Similarly, the following general formula (II) and general formula (IV)
Or dyed glazes obtained using (V) as a component 7), (8),
When dyed using (9) and (10), a yellow dyed product with excellent chlorine fastness was obtained.

Dissolve 0.3 parts of the dye shown in 200 parts of water, add 20 parts of Glauber's salt, add 10 parts of cotton, raise the temperature to 50°C, and
After 0 minutes, add 4 parts of soda.

Dye for 1 hour at that temperature.

After dyeing, it was washed with water and soaped to obtain a yellow dyed product with excellent hardness, especially chlorine fastness.

Similarly, the following general formula (III) and general formula (IV)
Or dyes obtained using (V) as a component 02), 03)
A yellow dyed product with excellent chlorine fastness was obtained.

Claims (1)

[Claims] 1. In the form of a free acid, the following general formula (wherein R is a methyl group, a phenyl group or an amine group,
R2 is hydrogen, methyl group, methoxy group or ethoxy group,
Xl and X2 each represent hydrogen, chlorine, methyl group, methoxy group, carboxyl group or sulfonic acid group. Further, the position of the sulfonic acid group on the naphthalene ring is the 1.5-position or the 4-8 position. Selfie 1- characterized by using the dye represented by :
Dyeing method for Z-based fibers.