JPS6224558B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dyeing cellulose fibers scarlet to red. More specifically, the present invention provides the following general formula () in the form of a free acid: (In the formula, R represents hydrogen or a lower alkyl group having up to 4 carbon atoms, X ₁ represents hydrogen, a methoxy group or a sulfonic acid group, and X ₂ represents hydrogen. m represents 0 or 1.) This is a method for dyeing cellulose fibers.

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 reactive dyes having 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 reactive dye with excellent properties.

Dyes with a monochlorotriazinyl group as a 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 intensive studies in search of a scarlet vinyl sulfone type reactive dye with particularly excellent chlorine fastness. It has been found that monoazo dyes containing sulfatoethylsulfonyl and monochlorotriazinyl groups give scarlet dyeings of 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, hemp, 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. General formula () (In the formula, m has the above-mentioned meaning.) The aminonaphthalene sulfonic acid represented by the above formula is diazotized by a conventional method, and then coupled with a γ acid in a neutral or alkaline state to form the general formula (). (In the formula, m has the above-mentioned meaning.) A monoazo compound represented by the following is obtained, and this is primarily condensed with cyanuric chloride to obtain a dichlorotriazinyl compound.

Then the general formula () (In the formula, R, X ₁ and X ₂ have the above-mentioned meanings.) The dye of the general formula () can be obtained by secondarily condensing the aniline compound represented by the following.

Alternatively, cyanuric chloride can be expressed by the general formula ()
The dye of general formula () can also be obtained by condensing an aniline compound of formula (2) and then secondarily condensing a monoazo compound of general formula ().

Alternatively, a gamma acid and an aniline compound of the general formula () can be condensed with cyanuric chloride in any order to form a compound of the general formula (). (wherein R, X ₁ and X ₂ have the above-mentioned meanings) to obtain a monochlorotriazinyl compound,
Subsequently, the dye of the general formula () can also be obtained by coupling with the diazo component of the general formula ().

Alternatively, after primary condensation of γ-acid with cyanuric chloride, coupling with the diazo component of general formula () results in general formula (). The dye of the general formula () can also be obtained by obtaining a monoazo compound represented by (wherein m has the above-mentioned meaning) and condensing the aniline compound of the general formula () with the monoazo compound.

Or general expression () (In the formula, R, X ₁ , and X ₂ have the above-mentioned meanings.) Using the β-hydroxyethyl sulfone compound represented by A dye of general formula () may be obtained by esterification in sulfuric acid.

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

The chlorine fastness is 3rd grade or 3rd to 4th grade according to the ISO 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 the quantity of sportswear in recent years, is excellent at 3rd grade or 3rd to 4th grade, 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 has solved 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,
at a temperature of 37 ± 2 °C using a perspirometer.
(treated at 125 g/cm ² for 6 hours) is good at grade 4-5 or grade 5, and is of high value from this point of view as well.

In addition, the dye of the present invention has good alkali stability and shows a high exhaustion rate and fixation rate in exhaust dyeing, and also shows a high fixation rate in textile printing, so it is not only possible 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 dyeing temperature, alkali agent, amount of inorganic salt added, 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 dyes shown are listed.

However, these dyes not only have lower solubility than the dyes of the present invention and have poor build-up properties, making it impossible to obtain dyed products with high density, but also have the disadvantage of extremely poor wash-off properties. Its practical value is small.

Furthermore, the latter dyes are particularly poor in light fastness.

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 (1) Dissolve 0.3 parts of the dye shown in 200 parts of water and add 20 parts of mirabilite.
1 part, 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 and soaping were performed to obtain a scarlet dyed product with excellent chlorine fastness.

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 5°C. To this, add 11.3 parts of gamma acid to 100 parts of water, pH 7
The solution dissolved in step 8 is added dropwise at 0 to 5°C over 1 hour. After the addition is complete, 20% aqueous sodium carbonate solution is added to adjust the pH to 3, and the mixture is further stirred for 2 hours. Next, 14 parts of 1-aminobenzene-3-β-hydroxyethylsulfone sulfate was added, and the mixture was heated at 40°C while adjusting the pH to 5 to 6 with a 20% aqueous sodium carbonate solution.
and stir at the same temperature for 2 hours.

Then, after cooling again to 0-5°C, 12.6 parts of sodium bicarbonate are added. To this is added a diazotized solution of 15 parts of 2-aminonaphthalene-1,5-disulfonic acid in a conventional manner at 0 to 5°C over 1 hour. After stirring at the same temperature for 2 hours, adjust the pH to 5~5 with hydrochloric acid.
6, and 20 parts of latrium chloride was added to precipitate crystals, which were filtered under suction, washed, and dried at 60°C to obtain dye (1).

When dyeing was carried out using the following dyes (2) and (3) in the same manner as in Example 1, scarlet dyed products with excellent chlorine fastness were obtained.

Example 2 Formula (4) Dissolve 0.3 parts of the dye shown in 300 parts of water and add mirabilite.
Add 30 parts, add 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, washing and soaping were performed to obtain a scarlet dyed product with excellent solid fastness.

When the following dyes (5) and (6) were used in the same manner, scarlet dyed products with excellent chlorine fastness were obtained.

Example 3 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 scarlet print with excellent chlorine fastness was obtained.

Claims (1)

[Claims] 1. The following general formula in the form after release: (In the formula, R represents hydrogen or a lower alkyl group having up to 4 carbon atoms, X ₁ represents hydrogen, a methoxy group or a sulfonic acid group, and X ₂ represents hydrogen. m represents 0 or 1.) A dyeing method for cellulose fibers characterized by the use of the method.