JPH0136863B2 - - Google Patents

Description

[Detailed description of the invention] <Industrial application field> The present invention relates to fiber-reactive monoazo compounds.

<Prior Art> It is known that dyes having a β-sulfatoethylsulfonyl group can be applied to dyeing textile materials as so-called vinylsulfone type reactive dyes.
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 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.

Also, in Toba, Special Publication No. 39-18184,
Below formula The dyes shown are listed.

However, these dyes not only have low solubility and 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, so they have little practical value. .

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

<Problems to be Solved by the Invention> In order to solve the problems of the prior art, the present inventors have conducted intensive studies in search of an orange to scarlet vinyl sulfone type reactive dye that has particularly excellent chlorine fastness. As a result, it was found that a specific monoazo compound having a β-sulfatoethylsulfonyl group and a monochlorotriazinyl group as reactive groups gives an orange to scarlet dyeing with excellent chlorine fastness. It has also been found that the compounds of the present invention can overcome the drawbacks of reactive dyes having a monochlorotriazinyl group as described above.

<Means for Solving the Problems> The present invention provides the following general formula () in the form of a free acid: (In the formula, R ₁ is an acetyl group, a propionyl group,
benzoyl group, succinyl group, or maleinyl group, R ₂ is hydrogen or methyl group, R ₃ and R ₄ are each hydrogen, methyl group or ethyl group, X ₁ is hydrogen,
X ₂ each represents hydrogen, chlorine, methyl group, methoxy group or sulfonic acid group. ) is provided.

The compound of the present invention can be produced, for example, as follows. General formula () (In the formula, R ₁ and R ₂ have the above-mentioned meanings.) The aniline sulfonic acid represented by the formula is diazotized by a conventional method, and then the general formula () (In the formula, R ₃ has the above-mentioned meaning.) By coupling the compound represented by the formula with a neutral or alkaline compound, the general formula () A monoazo intermediate represented by the formula (wherein R ₁ , R ₂ , and R ₃ have the above-mentioned meanings) is obtained, and this is primarily condensed with cyanuric chloride to obtain a dichlorotriazinyl compound.

Then the general formula () (In the formula, R ₄ , X ₁ , and X ₂ have the above-mentioned meanings.) The monoazo compound 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 compound of the general formula () can also be obtained by condensing the alinine compound of the formula (2) and then secondarily condensing the monoazo intermediate of the general formula ().

Alternatively, a compound of general formula () and an aniline compound of general formula () can be condensed with cyanuric chloride in any order to form general formula (). (In the formula, R ₃ , R ₄ , X ₁ , and X ₂ have the above-mentioned meanings.) To obtain a monochlorotriazinyl compound,
Subsequently, the compound of general formula () can also be obtained by coupling with the diazo component of general formula ().

Alternatively, the compound of the general formula () is first condensed with cyanuric chloride, and then coupled with the diazo component of the general formula () to form a compound of the general formula (). (In the formula, R ₁ , R ₂ and R ₃ have the above-mentioned meanings.) A monoazo intermediate represented by the formula (wherein R 1 , R 2 and R 3 have the above-mentioned meanings) is obtained, and from this, an aniline compound of the general formula () can be obtained.

Or general expression () (In the formula, R ₄ , X _{1 ,} and A compound of the general formula () may be obtained by esterifying the compound in sulfuric acid.

Examples of the compound represented by the general formula () include the following compounds.

3-acetylaminoaniline-6-sulfonic acid 3-propionylaminoaniline-6-sulfonic acid 3-benzoylaminoaniline-6-sulfonic acid 3-succinylaminoaniline-6-sulfonic acid 3-maleynylaminoaniline-6-sulfone Acid 4-acetylaminoaniline-6-sulfonic acid 4-propionylaminoaniline-6-sulfonic acid 4-benzoylaminoaniline-6-sulfonic acid 4-succinylaminoaniline-6-sulfonic acid 4-maleynylaminoaniline-6- Sulfonic acid 3-acetylamino-4-methylaniline-6
-Sulfonic acid 3-propionylamino-4-methylaniline-6-sulfonic acid 3-benzoylamino-4-methylaniline-
6-sulfonic acid 3-succinylamino-4-methylaniline-
6-sulfonic acid 3-maleynylamino-4-methylaniline-
6-Sulfonic acid The monoazo compound represented by the general formula () thus obtained is useful for dyeing cellulosic fibers such as natural or regenerated cellulose fibers such as cotton, hemp, viscoel silk, and viscose sulfur. .

In the case of the exhaust method, dyeing 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 soda carbonate, tribasic sodium phosphate, or caustic soda. Dyeing can also be carried out by a printing method, for example, by printing a colored paste containing an acid binder such as bicarbonate of soda, sodium carbonate, tribasic sodium phosphate, or caustic soda, urea, and a sizing agent, preferably sodium alginate, on the fiber.
After intermediate drying, it is carried out by steaming or dry heating at 100 to 200°C.

Furthermore, the staining may be carried out by a continuous method, or cold patch batch staining is also possible.

The dyed product thus obtained is particularly excellent in chlorine fastness, light fastness and sweat/sunlight fastness.

Chlorine fastness is 3rd or 4th grade according to ISO method.
In particular, considering that the use of chlorine bleach in laundry in general households has recently become widespread, the compound of the present invention, which has excellent chlorine fastness, is of high value as a dye. 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 or 4th grade, and from this point of view as well, the value of the compound of the present invention as a dye 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 compound of the present invention also solves this problem. There is. In other words, the acid stability of dyed products produced by the compound of the present invention (the test method is to immerse the dyed fabric in 1% acetic acid for 30 minutes and then treat it with 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 compound 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 possible to obtain dyed products with high density. figure,
At the same time, it has excellent wash-off properties and has the great advantage that unfixed dye can be easily removed.

Furthermore, the compound of the present invention has the unique ability to be hardly affected by changes in dyeing temperature, alkali agent, inorganic salt addition amount, and bath ratio in exhaust dyeing, and allows dyeing to be carried out with extremely high reproducibility.

The present invention will be explained in more detail by way of examples.
In the text, parts represent parts by weight.

Example 9.2 parts of cyanuric chloride is added to a solution of 0.1 part of a nonionic surfactant dissolved in 100 parts of water at 0 to 5°C and dispersed. To this, add 11.3 parts of J 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, 14.1 parts of 1-aminobenzene-3-β-hydroxyethylsulfone sulfate was added, and the pH was adjusted to 5 to 6 with a 20% aqueous sodium carbonate solution.
The mixture was heated to ℃ and stirred at the same temperature for 2 hours.

Then, after cooling again to 0-5°C, 12.6 parts of sodium bicarbonate are added. A solution obtained by diazotizing 11.5 parts of 4-acetylaminoaniline-6-sulfonic acid in a conventional manner is added to this at 0 to 5°C over 1 hour. After stirring at the same temperature for 2 hours, adjust the pH to 5 with hydrochloric acid.
6, and 20 parts of sodium chloride was added to precipitate crystals, which were filtered under suction, washed, and dried at 60°C to obtain a monoazo compound of the following formula ().

Monoazo compounds represented by the following formulas (2) to (12) were obtained in the same manner as above.

Reference Example 1 0.3 parts of the compound represented by formula (1) above is dissolved in 200 parts of water, 20 parts of Glauber's salt is added, 10 parts of cotton are added, and the temperature is raised to 50°C. 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.

Reference example 2 Color paste composition Compound of formula (1) 5 parts Urea 5 parts Sodium alginate (5%) Base paste 50 parts Boiling water 25 parts Baking soda 2 parts Balance 13 parts Color paste having the above composition was applied on mercerized cotton broadcloth. 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 of a free acid: (In the formula, R ₁ is an acetyl group, a propionyl group,
benzoyl group, succinyl group or maleinyl group, R ₂ is hydrogen or methyl group, R ₃ and R ₄ are each hydrogen, methyl group or ethyl group, X ₁ is hydrogen,
X ₂ represents hydrogen, chlorine, methyl group, methoxy group or sulfonic acid group. ) A monoazo compound represented by