JPH0713199B2 - Water-soluble tetraazo dye and dyeing method using the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a brown-colored water-soluble tetraazo dye having a novel structure, and more specifically, two molecules of a disazo dye through a triazine group in the structure. The present invention relates to a tetraazo dye which is bonded to a cellulose and has one reactive group, and is particularly excellent in reaction fixing property to cellulose and nitrogen-containing fibers in a low pH region, and a dyeing method using the same.

[Prior art]

As a dye for dyeing cellulose or nitrogen-containing fibers, a water-soluble reactive dye is usually used,
Dyes with various structures have been proposed. Typically,
When the above-mentioned fibers are dyed by the dip dyeing method using this type of dye, a relatively low temperature of about 60 to 70 ° C. is adopted as the temperature of the dyeing bath.

In recent years, along with the diversification of fibrous materials, for example, mixed fibers of cellulose fibers and polyester fibers have been used. As a dyeing method for such mixed fibers, conventionally, a disperse dye is used in advance. At high temperature of ~ 140 ℃,
Dye polyester fiber, then with reactive dye
A so-called two-step method of dyeing cellulose fibers at a low temperature of about 60 to 70 ° C is adopted. Further, recently, a method has been proposed in which a reactive dye and a disperse dye are used in combination, and cellulose and polyester fibers are simultaneously dyed in a high temperature dyeing bath of 120 to 140 ° C. in a single bath.

However, when dyeing a cellulose fiber with a conventionally known reactive dye in such a high-temperature dyeing bath, the reaction fixation ratio of the dye to the fiber is low and a good dyed product is obtained. I couldn't do it.

Therefore, we have previously proposed a reactive dye composed of a tetraazo compound represented by the following structural formula [A] as a dye for improving such problems. (Japanese Patent Application Sho 60-8332
7) (In the formula, M represents a hydrogen atom or an alkali metal, and X
Is a halogen atom or R ¹ and R ² represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or —SO ₃ M, R ³ represents a hydrogen atom or an alkyl group, l represents 2 or 3, and m and n Represents 0 or 1.). However, in the case of this dye, a high dyeing ratio can be obtained in a pH range of 7 to 8 of the dyeing bath, but a pH range of 5 to 7 which is a pH particularly suitable for dyeing a mixed fiber of polyester fiber and cellulose fiber. However, there is a problem that the dyeing rate is not as high as expected.

[Problems to be Solved by the Present Invention]

In view of the above circumstances, the present invention has an object to provide a water-soluble dye having a further excellent reaction fixation ratio with respect to the cellulose fiber or the nitrogen-containing fiber even in the dyeing condition of the polyester fiber, particularly in the low pH region. To do.

[Means for solving problems]

 The present invention has the following general formula [I] in the form of a free acid.[In the formula, R¹And R²Is a hydrogen atom, alkyl group, hydro
Xyethyl group, sulfonic acid group, sulfamoyl group, cal
Represents a vamoyl group or a carboxyl group, and l is 2 or
Represents 3, m and n represent 0 or 1, and A
Represents an anion. ] Water-soluble tetraazo color represented by
The main point is the dyeing method using the dye and the dye.
is there.

Hereinafter, the present invention will be described in detail.

The water-soluble tetraazo dye represented by the general formula [I]
And A Is the positive charge and balun of the nitrogen atom of the pyridine nucleus.
Is a negative charge required to , Cl , Br
Etc.

The tetraazo dye represented by the general formula [I] shown above can be produced as follows. For example, the following general formula [II] (In the formula, l, m and n are the same as defined above) 1 mole ratio of the compound represented by the following general formula [III] (In the formula, l, m and n are the same as defined above) and 1 mol of the compound are condensed to give the compound represented by the following general formula [IV] (In the formula, l, m and n are the same as defined above).

Next, the tetraazo compound represented by the general formula [IV] is converted into the following general formula [V] The tetraazo dye of the general formula [I] shown above can be produced by condensing 1 mole ratio of the pyridine compound represented by the formula (wherein R ¹ and R ² are the same as defined above).

A normal salting-out method is used to obtain the desired product from the reaction solution, but the reaction solution may be directly spray-dried.

The tetraazo dye of the present invention can be widely used as a dye for dyeing fibers, cloths, papers, dyes for coloring synthetic resins, and further as a dye for inks for ink jet printers, but particularly as a dye. The suitability of is excellent.

When the tetraazo dye of the present invention is used as a dye,
The target fibers are cotton, viscose rayon,
Cellulosic fibers such as kypura ammonium rayon and hemp, and nitrogen-containing fibers such as polyamide, wool and silk are mentioned, and cellulose fibers are particularly preferable. Further, these fibers are, for example, polyester, triacetate,
Mixed fibers such as polyacrylonitrile may be used.

In the method for dyeing fibers using the tetraazo dye of the present invention, dyes necessary for dyeing fibers other than cellulosics, for example, disperse dyes described in Color Index (Third Edition) are simultaneously added to the dye bath. In addition, it can be dyed.

When the cellulosic fiber is dyed using the tetraazo dye of the present invention, for example, the tetraazo dye represented by the general formula [I] and the dye bath during dyeing are adjusted to pH 5 to 8, particularly preferably pH 5.5 to A buffer necessary to hold at 7, such as carbonic acid, phosphoric acid, acetic acid, citric acid and the like, and a sodium salt or potassium salt of these acids, usually alone or in a mixture of about 0.5 to 5.0 g / about; If necessary, use electrolyte (sodium chloride or sodium sulfate etc.
0 g /, particularly preferably 40-80 g /) is added to prepare a dye bath, and cellulosic fibers are added to this dye bath, and the temperature
Good dyeing can be performed by heating at 100 to 150 ° C. for 30 to 50 minutes.

Further, in order to dye a blended fabric, a blended knitted fabric or the like produced by mixing other fibers such as a polyester fiber with a cellulosic fiber, a tetraazo dye represented by the above general formula [I] of the present invention is used. By adding the disperse dye listed in the Color Index to the dye bath, the cellulosic fiber and the polyester fiber can be dyed simultaneously by the one-bath one-step method.

Further, in the case of dyeing a mixed-spun fabric, a mixed-woven knitted fabric, or the like as described above, a one-bath two-step method in which one fiber is dyed as is conventionally used and then the other fiber is dyed in the same bath May be applied, and further, a two-bath for dyeing cellulosic fibers and other fibers from separate baths by combining the dyeing method with the tetraazo dye of the present invention and the dyeing method for fibers other than cellulosic fibers It is also possible to adopt the law.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples and Dyeing Examples, but the present invention is not limited to the following Examples and the like.

Example 1 (a) Production Example The following structural formula 1 mole ratio of the disazo compound represented by 1 mole ratio of the disazo compound represented by
Condensed at ~ 40 ° C, the following structural formula The tetraazo compound represented by
After condensing 1 mole ratio of carboxypyridine at 90 ° C,
Salting out was performed with potassium chloride to produce a tetraazo dye having the following structural formula. The structural formula is expressed in the form of free acid.

(B) Dyeing Example: 0.2 g of the tetraazo dye of the present invention obtained in the above Production Example, 16 g of Glauber's salt, 0.4 g of Na ₂ HPO ₄ 12H ₂ O as a buffer and KH ₂ PO ₄ 0.1.
Add 200 g of water to 200 ml of water and add 10 g of unsilked cotton knitted fabric to a dyeing bath adjusted to pH = 7, raise the temperature to 120 ° C over 30 minutes, and dye at the same temperature for 60 minutes, then wash with water, soaping, washing with water, It was dried to obtain a reddish brown dyed product.

The dyeing rate of this dye was 81%, which was very good, and the dyed product obtained was extremely dense, and the fastness to light was excellent in the fifth grade.

Example 2 (a) Production Example Structural formula [a] below 1 mol ratio of the disazo compound represented by and 1 mol ratio of 2,4,6-trichlorotriazine are reacted at 0 ° C. pH 6 to 7, and the following structural formula A disazo compound represented by the following formula was produced, and further, the following tetraazo compound was produced by condensing the disazo compound represented by the above structural formula [a] with 1 mol ratio at 20 to 30 ° C. and pH 6 to 7.

Further, 1 mol ratio of the tetraazo compound and 1 mol ratio of 3-carbamoylpyridine were condensed and then spray-dried to produce a tetraazo dye having the following structural formula. The structural formula is expressed in the form of free acid.

(B) Dyeing Example 0.2 g of the tetraazo dye obtained in the above Production Example, 16 g of Glauber's salt,
As a buffer, 0.1 g of Na ₂ B ₄ O ₇ · 10H ₂ O and 0.4 g of KH ₂ PO ₄ were added to water.
Unbleached cotton knit 1 in a dye bath prepared in addition to 200 ml
0 g was added, the temperature was raised to 130 ° C. over 30 minutes, and dyeing was carried out at the same temperature for 30 minutes, followed by washing with water, soaping, washing with water and drying to obtain a reddish brown dyed product.

The dyeing bath had a pH of 6.0 before and after dyeing.

The dyed product obtained is extremely dense and the dyeing rate of this dye is 77%.
It was also very good, and the light fastness was 5th grade.

Example 3 The following structural formula in the form after release In the following structural formula known as a tetraazo dye 0.2g and disperse dye Using a mixed dye consisting of 0.2 g of a monoazo dye represented by
To this, 12 g of Glauber's salt, 0.1 g of Na ₂ B ₄ O ₇ · 10H ₂ O and 0.4 g of KH ₂ PO ₄ as a buffer were added to 200 ml of water, and 10 g of a polyester / cotton = 50: 50 mixed-spun cloth was added to a dyeing bath prepared. It takes 30 minutes to put in 13
The temperature was raised to 0 ° C., and after dyeing at the same temperature for 60 minutes, washing with water, soaping, washing with water and drying were carried out to obtain a reddish brown dyeing product having good color uniformity. Before and after dyeing with this dye, pH6
It was.

The dyeability in this dyeing test was very good, and the obtained dyed product was extremely dense, and the light fastness was also excellent at grade 5.

The tetraazo dye used in this example was produced according to the method described in Example 1.

Example 4 The tetraazo dyes of the invention shown in Table 1 (expressed in the form of the free acid) were prepared according to the method described in Example 1 or Example 2 and described in Example 2. When a cotton cloth was dyed according to the method, the dyeing rate of each dyeing cloth was 70% or more, and the light fastness was grade 5, which was good.

The color tone and λmax of the obtained dyed fabric are the results as shown in Table 1.

[Advantages of the Invention] The tetraazo dye of the present invention is a novel water-soluble tetraazo compound having two disazo dye molecules bound to each other through a triazine group in the structure and having a reactive group consisting of a pyridine ring. It is useful as a dye for the system. In particular, when this compound is used for dyeing fibers containing cellulose or nitrogen-containing fibers, various fastnesses are excellent and dyeing properties are excellent. And, this effect is conventionally used as a dyeing condition of polyester, for example, at a high temperature of 120 to 140 ° C, and
It can be obtained under staining conditions in the pH range. The compounds of the invention are therefore particularly suitable as reactive dyes for simultaneous dyeing in a single bath with, for example, polyester / cellulose or mixed fibers with nitrogen-containing fibers together with water-insoluble disperse dyes.

Claims (2)

[Claims] 1. The following general formula [I] in the form of a free acid.[In the formula, R¹And R²Is a hydrogen atom, alkyl group,
Ciethyl group, sulfonic acid group, sulfamoyl group, carba
Represents a moyl group or a carboxyl group, 1 is 2 or
3, m and n represent 0 or 1, and A Is
Represents an anion]. 2. A fiber containing cellulose or nitrogen-containing fiber.
In the method for dyeing textiles, the following general formula in the form of free acid is used.
[I][In the formula, R¹And R²Is a hydrogen atom, alkyl group,
Ciethyl group, sulfonic acid group, sulfamoyl group, carba
Represents a moyl group or a carboxyl group, 1 is 2 or
3, m and n represent 0 or 1, and A Is
Represents an anion. ] Water-soluble tetraazo dye
A dyeing method characterized by using.