JPH05163443A - Dyestuff composition and method for dyeing hydrophobic fiber using the same - Google Patents

Abstract

PURPOSE:To provide a dyestuff composition containing a specific monoazo dyestuff and a specified benzoisothiazole monoazo dyestuff, excellent in the color value, build-up property, brilliance, light resistant fastness and sublimation fastness, and useful for dyeing hydrophobic fibers, etc. CONSTITUTION:The objective dyestuff composition contains (A) a compound of formula I preferably in an amount of 20-80wt.% and (B) a compound of formula II preferably in an amount of 80-20wt.%.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a dye composition and a dyeing method. More specifically, it relates to a dye composition containing two kinds of azo disperse dyes having a specific structure and a method for dyeing a hydrophobic fiber using the dye composition.

[0002]

2. Description of the Related Art Equation (1)

[0003]

[Chemical 3]

The monoazo dye represented by the formula, or the formula (2)

[Chemical 4]

The monoazo dye represented by the formula (1) is widely used because it gives a dyed product which is clear and has excellent fastness to sublimation when a hydrophobic fiber such as polyester fiber is dyed with these dyes.

However, these azo dyes have the drawback of being poor in dyeing property. Poor dyeability is preferable not only because it leads to quality problems of dyed products such as poor dyeing reproducibility and economical disadvantages, but also from the viewpoint of drainage pollution due to outflow of undyed dye at the time of dyeing. Not that.

[0007]

Problems to be Solved by the Invention Equations (1) and (2)
Sharpness, fastness to light, fastness to sublimation, p
It is strongly desired to improve their dyeability without losing properties such as H-dependence and thermal decomposability.

[0008]

Means for Solving the Problems The inventors of the present invention have achieved the present invention as a result of intensive research to solve the above-mentioned problems. That is, the present invention

Formula (1)

[Chemical 5]

The compound of formula (2)

[Chemical 6]

Dye composition containing a compound represented by the formula (2) Compound 5 of the formula (1) described in the above item (1)
95% by weight and 95 to 5% by weight of the compound of formula (2) represented by the above item (1) are contained in the dye composition. (3) In the above item (1) or (2) Provided is a method for dyeing hydrophobic fibers, characterized by using the dye composition shown. When the compound of formula (1) and the compound of formula (2) are mixed and used in the ratio as described above, the compound of formula (1)
Compared to the case where only the compound of formula (1) or the compound of formula (2) is used for dyeing, the dyeing rate is about 1.8 times (comparison of exhaustion rate by optical density value). It was confirmed that the color value was improved, and the build-up property was also good. Moreover, the hydrophobic fiber dyeing product dyed with the composition has the same sharpness and various fastnesses as the dyeing product dyed with the compound represented by the formula (1) or (2) alone, and is economical. Also from the viewpoint, the practical value of the dye composition and the dyeing method of the present invention is extremely high.

The present invention will be described in detail. The compounding ratio of the dye compounded in the present invention is 5 to 95% by weight, more preferably 20 to 80% by weight, of the compound represented by the formula (1).
When the compound represented by the formula (2) is mixed in an amount of 95 to 5% by weight, more preferably 80 to 20% by weight, particularly preferable results can be obtained in terms of dyeing amount and color tone.

The dye represented by the formula (1) is disclosed in JP-A-63-1.
89465 and the dye represented by formula (2) are known from JP-A-63-6057. The dye composition of the present invention may be prepared by mixing each of the dye bulk powders (compounds) and then subjecting it to a fine particle treatment to obtain a dye composition. Alternatively, the dye powders represented by the formulas (1) and (2) may be used. The powder may be separately subjected to fine particle treatment and then mixed in the above-described proportion to form a dye composition. Alternatively, in the latter case, individual finely divided dyes may be added to the dye bath to form the same composition as the dye composition of the present invention in the dye bath. Further, other dyes may be added within the range not impairing the gist of the present invention. The fine particles of the dye powder can be made into fine particles by a method known per se, for example, by mixing 15 parts of the dye powder with 35 parts of a formalin condensate of naphthalenesulfonic acid and 80 parts of water, and using a sand grinder to obtain a particle size of 5 μm. It is performed by processing until it becomes less than or equal to the level.

The dye composition of the present invention is used for dyeing as it is, in the form of paste, or after being dried, after being made into fine particles. Specific examples of the hydrophobic fiber which can be dyed by the method of the present invention include polyester fiber, polyamide fiber, diacetate fiber, triacetate fiber and their blended products, and these and cotton, silk, wool and other natural fibers. It may be a blended product.

The article to be dyed, which is mentioned as an example where the effect of the present invention is most effectively expressed, is a polyester ultrafine fiber product. In recent years, the technology for making fine fibers with a fineness of 1.0 denier or less has rapidly advanced, and its application to silk-like materials and raised knitted fabrics has become popular. (Processing Technology Volume 5, 1991,
Textile Co., Ltd.) The dyeing characteristics of products using these ultrafine fibers are quite different from the dyeing of products using fine fibers (1.0 denier or more), and the following problems occur. have.

(1) Since the dyeing speed is high, uneven dyeing is likely to occur. (2) Since the surface area is remarkably increased, the reflected light on the fiber surface is increased and the apparent color of the dyed product is lightened. That is, uneven dyeing tends to occur, and a fairly large amount of dye is usually required to obtain the same density as that of the fineness fiber dyed product, and the dyeing amount also increases, so that various fastnesses are often reduced.

When the dye composition of the present invention is used to dye hydrophobic fibers, especially polyester ultrafine fibers, the exhaustion is remarkably improved as compared with the case where each dye is used alone.
The surface density of the dyed product was improved, and uneven dyeing and deterioration of fastness were not observed.

According to the method of the present invention, for dyeing hydrophobic fibers with a dye composition containing a compound of formula (1) and formula (2), the fibers are immersed in an aqueous medium at 105 ° C. under pressure. As described above, it is advantageous to dye at 110 to 140 ° C. It is also possible to dye in the presence of a carrier such as O-phenylphenol or trichlorobenzene at a relatively high temperature, for example, boiling water. Alternatively, the dye dispersion may be padded on a cloth to give 150-230
It is also possible to carry out dyeing by a so-called thermosol method in which a dry heat treatment is carried out at a temperature of 30 seconds to 1 minute. On the other hand, the dye composition of the present invention and a natural sizing agent (for example, snow algin, starch, casein, gelatin, etc.), a synthetic sizing agent (for example, polyvinyl alcohol, polyvinyl acetate, etc.), an anti-reducing agent, a pH adjusting agent, a deep-dyeing agent, etc. At the same time, a printing paste may be prepared and dyeing may be carried out by a printing method according to a conventional method. It is also possible to dye from a dye bath mainly containing an organic solvent such as trichlorethylene or perchlorethylene. (Solvent dyeing)

In order to show that the dyeing method of the present invention is extremely excellent in improving the dyeing ratio, the formula (1) or the formula (2) is used.
Table 1 shows the results of comparison of the dyeability between the case of dyeing with the above compound alone and the case of dyeing with the dye composition of the present invention.

Table 1 Alone or Dyeing rate Amount of mixed dyes Polyester cloth (denier) surface concentration 3 0.3 3 Comparative Example 1 Formula (1) 1.0 part 59.5 77.4 100 Comparative Example 1 Formula ( 2) 1.0 part 53.5 65.5 100 Invention 1 Formula (1) 0.75 part + Formula (2) 0.25 part 76.2 97.1 111 Invention 2 Formula (1) 0.5 Part + Formula (2) 0.5 Part 94.6 99.7 119 Present Invention 3 Formula (1) 0.25 part + Formula (2) 0.75 part 78.3 98.1 111

The test dyes used are those obtained by subjecting 3 parts of the bulk powder of the dye to 7 parts of formalin condensate of naphthalene sulfonic acid and an appropriate amount of water for fine particle treatment with a sand grinder and drying by a vacuum drying method. did. In the "Inventions 1 to 3", the compounds of the formula (1) and the formula (2) which have been separately atomized are mixed in the ratios shown in Table 1.

The dyeing conditions are as follows. Dyeing object: Polyester processed yarn fabric (3 denier, 0.3 denier) Bath ratio: 1:30 Dyeing bath pH: 4.5 Dyeing temperature, time: 130 ° C, 60 minutes

The dyeing rate and surface density in Table 1 were measured or judged as follows. Dyeing ratio: A value obtained by subtracting the amount of dye remaining in the dye bath after dyeing from the amount of dye used for dyeing, divided by the amount of dye used first. The dye concentration was determined by a method of measuring the optical density using a 75% acetone aqueous solution. Surface density: The density of the dyed product was determined by visual judgment.

As is clear from the results in Table 1, the dyeing rate of the dye of the method of the present invention is extremely higher than that of the dye of the compound of the formula (1) or the compound of the formula (2) alone. It is recognized to be high. At the same time, the surface density also increased with the dyeing rate, and the effect of the blending was clearly recognized.

EXAMPLES The present invention will be described more specifically with reference to the following examples. In addition, "part" and "%" in an Example mean a weight part and weight%, respectively.

Example 1 2.25 parts of the compound of formula (1) and 0.7 of the compound of formula (2)
5 parts were made into fine particles together with 7 parts of a formalin condensate of naphthalenesulfonic acid to obtain a dye composition of the present invention. 3 parts of this dye composition was added to 3000 parts of water to form a dispersion, which was then adjusted to pH 4.5 with acetic acid, 100 parts of polyester white cloth (3 denier) was dipped, dyed at 130 ° C. for 1 hour, and then dyed cloth. The product was subjected to reduction washing and dried to obtain a clear deep blue dyed cloth. This dyed cloth had good fastness to sublimation and fastness to wetness.

The compounds of formula (1) and formula (2) used here were synthesized as follows. 2.84 parts of 2-bromo-6-cyano-4-nitroaniline are gradually added to 30 parts of 96% sulfuric acid at 5 ° C or lower with stirring. Then at the same temperature, 30
After stirring for a minute, a mixture consisting of 14.8 parts of acetic acid and 3 parts of propionic acid is added below 10 ° C. Further, 6.2 parts of 43% nitrosyl sulfuric acid was added, and the mixture was stirred at 5 ° C or lower for 2 hours.

Thus, a transparent diazotized liquid was obtained. Then N
-Methyl-N-phenylpropyl-m-toluidine 4.
Ice is appropriately added to a solution consisting of 12 parts, 700 parts of water and 5 parts of 96% sulfuric acid, and the above diazotized solution is added dropwise while cooling to 5 ° C or lower. Next, heat treatment at 70 ° C. for 1 hour, then filter,
By washing with hot water and drying, 8.26 parts of crystals were obtained. 7 parts of this crystal, 15 parts of DMF and 1.5 parts of cuprous cyanide are added to a flask and heated and stirred at 100 ° C. for 3 hours. After that, crystals are precipitated with methanol, filtered, and the crystals are decopperized with aqueous ammonia to obtain the compound of formula (1) (dye bulk powder).
5.5 parts were obtained.

3-amino-5,7-dibromo-2,1-
6.16 parts of benzisothiazole was added to a 30% sulfuric acid aqueous solution 6
In addition to 0 parts, the mixture was stirred for 1 hour to sufficiently disperse it, and then cooled to -3 ° C, and 43% nitrosyl sulfuric acid 76. After being added dropwise at -3 ° C or below, the mixture was stirred at -3 to 0 ° C for 2 hours. The diazo solution thus obtained was dissolved in 2% sulfuric acid to give 3- (N, N-
Diethylamino) -propionylaminobenzene 4.5
Parts and 1 part of sulfamic acid were added dropwise to the solution at 0 to 5 ° C. while appropriately adding ice water, and the mixture was stirred at the same temperature for 30 minutes. Then, the reaction solution was heated to 70 ° C. and stirred at the same temperature for 1 hour, and then the product was filtered, washed with water and dried to obtain the compound of formula (2).
5.5 parts of a compound (dye bulk powder) was obtained.

Example 2 0.75 parts of the compound of formula (1) and 2.2 of the compound of formula (2)
5 parts was made into fine particles together with 7 parts of a formalin condensate of naphthalene sulfonic acid to obtain a dye composition of the present invention, and this was used to dye in the same manner as in Example 1. The polyester white cloth was made of 0.3 denier ultrafine fibers. As a result, a clear blue dyeing having a high density was obtained. This dyed cloth had good sublimation fastness and wet fastness.

Example 3 1.5 parts of the compound of the formula (1) and 1.5 parts of the compound of the formula (2) were microparticulated with 7 parts of a formalin condensate of naphthalenesulfonic acid to obtain a dye composition of the present invention. Dyeing was performed in the same manner as in Example 1. The polyester white cloth was made of 0.3 denier ultrafine fibers. As a result, a clear blue dyeing having a high density was obtained. This dyed cloth had good sublimation fastness and wet fastness.

Example 4 2 parts of the mixed dye obtained in the same manner as in Example 3 was added to 3000 parts of water to prepare a dispersion, and then the pH was adjusted to 4.5 with acetic acid, and 100 parts of polyester white cloth (3 denier) was dipped. Thirteen
Staining was performed at 0 ° C for 1 hour. Next, the dyed cloth was reduced and washed, and dried to obtain a clear blue dyed cloth. From the comparison of the dyeing densities of the dyed fabric (6% OWF dyed product) obtained by similarly dyeing 6 parts of the same mixed dye as this dyed fabric (2% OWF dyed product), the dye composition of the present invention was built. It was clear that the up-quality and color value were excellent.

Example 5 Dye composition obtained in Example 1 3 parts Carboxymethyl cellulose 20% aqueous solution 60 parts Sodium chlorate 0.5 parts Sodium tartrate 0.2 parts Leveling agent 2 parts Hot water 34.3 parts The following color paste was prepared, printed on a polyester white cloth (3 denier), intermediately dried at 80 ° C., held in superheated steam at 170 ° C. for 5 minutes, reduced and washed, and then washed with water and dried. A dyed product was obtained in which the portion printed with the color paste developed a vivid blue color. This dyed cloth had good sublimation fastness and wet fastness.

[0034]

EFFECT OF THE INVENTION Specific dicyanoazo dyes and isothiazo-
By using the dye composition containing the rumonoazo dye, it was possible to improve the drawback of low dyeing property (build-up property, color value) of each dye without losing the original properties of each dye.

Claims (3)

[Claims] 1. A formula (1): And a compound represented by the formula (2): A dye composition containing a compound represented by 2. A compound of formula (1) 5 as defined in claim 1
95% by weight and the compound 9 of the formula (2) according to claim 1.
Dye composition containing 5 to 5% 3. A method for dyeing a hydrophobic fiber, which comprises using the dye composition according to claim 1 or 2.