JP3212761B2 - Water-insoluble monoazo dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a monoazo dye, and more particularly to a blue monoazo dye having a novel crystal modification which can uniformly dye polyester fibers and the like even under severe conditions at high temperatures. .

[0002]

2. Description of the Related Art In recent years, various dyeing methods have been rationalized in the dyeing industry. For example, in the case of dyeing polyester fibers using disperse dyes, a liquid dyeing method, a yarn dyeing method and a yarn dyeing method are used for fabrics. For use, there are a cheese dyeing method and a package dyeing method, which are widely used.

[0003] In these dyeing methods, since a dyeing dispersion is forcibly circulated in a dense layer in which several layers of stationary fibers are wound to dye, the dyeing is more dispersed in a dyeing bath than before. It is required that the dye particles obtained are fine particles and have excellent dispersion stability in the dyeing bath. If the dye particles become large, the fiber layer causes the dye particles to be filtered, resulting in poor dye permeation into the fiber interior, or dyeing the inner or outer layer light and shade due to the adhesion of agglomerates, and the attachment of the dye only to the fiber surface. Problems such as a decrease in fastness such as rub fastness occur.

Accordingly, the dye used in such a dyeing method has good dispersibility in a dyeing bath, and its dispersibility does not decrease in a wide temperature range from room temperature to a high temperature at which actual dyeing occurs. is necessary. However, in general, when heated to a high temperature in a dyeing bath, the dispersibility of the dye often tends to decrease, and as a result, the aggregated dye adheres to the surface of the material to be dyed as described above. In addition, the dyeing density of the outer layer portion and the inner layer portion of the object to be dyed which is superimposed on any number of layers is different, so that a dyed material having a uniform density cannot be obtained.

In recent years, in particular, from the viewpoint of resource saving and energy saving, the bath ratio of the dyeing bath has been reduced (the ratio of the material to be dyed to the dyeing solution has been reduced from 1:30 to 1:10), and the use ratio of the dispersant has been reduced ( The ratio of dye cake: dispersant was reduced from 1: 3 to 1: 1, and the dyeing conditions were further increased in temperature for a shorter time (13
(1 hour at 0 ° C. to 0.5 hour at 135 ° C.), the dyeing conditions are shifting to harsh conditions. However, all of these conditions have a disadvantageous effect on the dispersion stability of the dye. Even dyes having relatively good dispersion stability in the dyeing method often have poor dispersion stability in more severe recent dyeing methods.

[0006]

DISCLOSURE OF THE INVENTION The present invention is to provide a dye which can perform good dyeing even under severe conditions at high temperature. I]

[0007]

Embedded image

The thiophene-based monoazo compound represented by the formula (1) has at least two types of crystal modifications, one of which is a crystal modification whose dispersion stability is not so good under high temperature dyeing conditions. It has been found that the cake obtained by the synthesis reaction of the above is the crystal modification, and the other one is a novel crystal modification that has a very good dispersion stability even at severe temperatures and under severe dyeing conditions. Furthermore, the stability of the dispersion state of the dye composition in a high-temperature dyeing bath is not only related to the size of the dye particles, but also has a significant relationship with the crystal transformation,
For the first time, it has been found that the use of a compound of the above-mentioned novel crystal modification can achieve the dispersion stability of a dye composition in a high-temperature dyeing bath, and reached the present invention.

[0009]

That is, the gist of the present invention is to provide a diffraction angle (2θ) of about 8.0 °, 11.5 ° and about 26.5 °.
3 strong peaks, about 15.4 °, 17.2 °,
SUMMARY OF THE INVENTION A water-insoluble monoazo dye represented by the above structural formula [I] having a crystal modification characterized by an X-ray diffraction pattern (CuKα) showing four intermediate peaks at 20.0 ° and about 27.0 °. And The novel crystal modification of the present invention (hereinafter, referred to as
A monoazo compound having an α-type crystal modification) can be obtained as follows. For example, 2-amino-3
-Cyano-5-nitrothiophene is diazotized in a conventional manner, and then is subjected to -5 to 15 ° C in a methanol medium.
A coupling reaction with N-ethyl-N-isopropylcarbonyloxyethyl-m-toluidine as a coupler is preferably performed at a temperature of -5 to 0 ° C for 0.5 to 3 hours to obtain a compound of the above-mentioned structural formula [I]. Synthesize a monoazo compound. The cake of the monoazo compound obtained in this synthesis is
The crystal modification (hereinafter referred to as β-type crystal modification) shown in the XD diagram of FIG. 2 is obtained. In the present invention, this cake is further treated under specific conditions to obtain α-type crystal modification. As this treatment method, for example, a cake of β-form crystal modification is dispersed in an aqueous medium, and in some cases, a formaldehyde condensate of naphthalenesulfonic acid, a concentrate of a waste sulphite pulp mainly composed of sodium ligninsulfonate, etc. 60 to 150 ° C., preferably 130 to 150 ° C. in the presence of a dispersant of
0.5 to 3 hours at a temperature of 140 ° C., preferably 0.5 to 3 hours.
1 hour, a method of stirring, or dispersing in alcohols such as methanol, ethanol or butanol, ethers such as dioxane, organic solvents such as ethylene glycol and glycol ether, and 15 to 100 ° C., preferably 20 to 80 ° C. A method of performing a stirring treatment at a temperature of about 0.5 to 10 hours is employed.

Next, the α-form and β-form modifications of the monoazo compound represented by the structural formula [I] will be described with reference to the drawings. 1 and 2 are X-ray diffraction diagrams obtained by recording the state of diffraction by CuKα radiation in a powder X-ray diffraction method using a proportional counter. The horizontal axis indicates the diffraction angle (2θ), and the vertical axis indicates the diffraction intensity. . FIG. 1 shows an α-type crystal modification which is a novel crystal form of the present invention. In particular, three strong peaks at diffraction angles (2θ) of about 8.0 °, 11.5 ° and about 26.5 ° are shown. , And about 15.4 °, 17.2 °, 2
It has four intermediate peaks at 0.0 ° and about 27.0 °. FIG. 2 shows a conventional β-type crystal transformation.
Two strong peaks at 2.5 ° and 26.5 °, 22.5
° and 25.0 ° have two intermediate peaks.
This is clearly different from the α-type crystal modification.

The diffraction angles by the X-ray diffraction method always coincide with an error of about ± 0.1 ° for the same crystal type, and these drawings clearly show the difference of the crystal transformation. ing. The behavior of the monoazo compound at the time of dyeing is different due to the difference in the crystal type. In the case of the present invention, good dyeing can be performed even at a high temperature under severe conditions.

The fibers which can be dyed with the thiophene-based monoazo dye of the present invention include polyethylene terephthalate, polyester fibers composed of a polycondensate of terephthalic acid and 1,4-bis- (hydroxymethyl) cyclohexane, cotton, and the like. Blend products and blended products of natural fibers such as wool and the above-mentioned polyester fibers can be used. In order to dye polyester fiber using the monoazo dye of the present invention, a condensate of naphthalenesulfonic acid and formaldehyde, a higher alcohol sulfate, a higher alkylbenzene sulfonate, or the like is used as a dispersant in a conventional manner in an aqueous medium. Dyeing or printing can be performed by preparing a dyeing bath or printing paste dispersed in the above. Also, for example,
In the case of dip dyeing, a high temperature dyeing method as described above, a carrier dyeing method, a dyeing treatment method such as a thermosol dyeing method can be applied, and even if severe dyeing conditions are adopted in these methods, the present invention can be applied. Since monoazo dyes are excellent in dispersion stability, polyester fibers or their blends can be dyed well. Specifically, polyester fibers are dyed at a temperature of 125 to 140 ° C., and a dye bath ratio is 15 times or less,
It is also possible to perform exhaustion dyeing in an aqueous medium in the presence of a dispersant under severe conditions in which the use ratio of the dispersant to the dye is 3 times by weight or less.

[0013] In some cases, more favorable results can be obtained by adding an acidic substance such as formic acid, acetic acid, phosphoric acid or ammonium sulfate to the dyeing bath. In addition, the monoazo dye represented by the structural formula [I] used in the method of the present invention may be used in combination with other dyes, and good results such as improvement in dyeability may be obtained by blending the dyes.

[0014]

Next, the present invention will be described more specifically with reference to examples. Example 1 (Production Example of Dye Crystal) 50 g of N-ethyl-N-isopropylcarbonyloxyethyl-m-toluidine was added to 1 liter of methanol for 5 hours.
It was dissolved at 0 ° C. to obtain a coupling component. Then 80
83 g of 43% nitrosyl sulfuric acid was added to 216 g of sulfuric acid,
While stirring at -5 to 0 ° C, 2-amino-3-cyano-5-
34 g of nitrothiophene was gradually added to carry out diazotization to obtain a diazotized solution. The diazotized solution was added dropwise to the above-mentioned coupling component solution at -5 to 0 ° C, and the mixture was stirred at the same temperature for 3 hours, and the precipitated crystals were separated by filtration, washed with water and dried to give the structural formula [I 60 g of green crystals of the compound represented by the formula were obtained. When the powder of the monoaz dye obtained by this reaction was analyzed by an X-ray diffraction method, it was a β-type crystal modification shown in the X-ray diffraction diagram of FIG.

Next, the obtained β-form crystal was dispersed in 40 times the volume of water, and the mixture was stirred at 135 ° C. for 0.5 hour to transfer the crystal. After the crystal transformation, filtration and drying were performed, and the obtained crystals were analyzed by an X-ray diffraction method.
It was an α-type crystal modification showing a line diffraction pattern.

Test Example 1 (Dyeing Example) 0.2 g of the monoazo compound of the α-form crystal modification obtained in the above Example 1 was combined with 0.2 g of a naphthalenesulfonic acid-formaldehyde condensate and a higher alcohol sulfate ester.
A dye bath was prepared by dispersing in 1 liter of water containing 2 g.

100 g of polyester fibers are immersed in the dyeing bath and dyed at 135 ° C. for 30 minutes.
After washing with water and drying, the dispersibility of the dye was good and uniform dyeing on the dyed fabric was performed. The obtained dyed fabric is blue, and has a light fastness of 5 to 6 grades and a rub fastness of 5 classes.
The class was good. When a similar dyeing test was performed using the monoazo compound of the β-form crystal modification in the course of the production of the above production example, partial aggregation of the dye occurred in the dye bath, resulting in an unevenly dyed fabric, and abrasion resistance. The fastness was as low as 1st grade.

Test Example 2 (High-Temperature Filtration Test) 24 g of the monoazo compound of the α-form crystal modification obtained in the above-mentioned Example 1 was subjected to ligninsulfonic acid-formalin condensate 50.
g, 10 g of a naphthalenesulfonic acid-formalin condensate and 300 g of water were wet-ground with a sand grinder for 5 hours and spray-dried to obtain a powdery disperse dye composition. 1.6 g of the obtained dye (bath ratio 1: 10,4 /
1N), 200 ml of liquid, pH 5 (prepared with ammonium sulfate and acetic acid), and a dyeing bath prepared with a leveling agent of 1 g / 1 was air-cooked at 130 ° C. for 60 minutes, cooled, and then separated at 90 ° C. by 100 ml each. Cotton Broad # 40 (70φ), Toyo Filter Paper No. 5
The mixture was suction-filtered with -A (70φ), and the remaining amount of the dye on the filter medium was visually judged according to the following criteria.

Class 3 (good)-no residual pigment on the filter medium. Secondary (slightly poor)-residual pigment on the filter medium. Primary (poor) 残 residual pigment on the filter medium. On the other hand, when a similar test was carried out using the monoazo compound in the β-form modification, only a first-class result was obtained.

[0020]

The water-insoluble monoazo dye having a specific crystal modification according to the present invention can be used at a high temperature and, for example, in the following manner.
The dispersion stability is very good even under severe dyeing conditions such as a dyeing liquid ratio of 1:10, a dye cake: dispersant ratio of 1: 1, and a dyeing condition of 135 ° C. for 0.5 hour. The dyed fabric is excellent in light fastness and rub fastness. Therefore, the dye of the present invention is very useful from the viewpoint of resource saving and energy saving.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction diagram of an α-type crystal modification of a monoazo compound obtained in an example of the present invention. In the figure, the horizontal axis represents the diffraction angle (2θ), and the vertical axis represents the diffraction intensity.

FIG. 2 is an X-ray diffraction diagram of a β-type crystal modification obtained in an example of the present invention, in which the horizontal axis represents the diffraction angle (2θ);
The vertical axis represents the diffraction intensity.

Continuation of the front page (72) Inventor Yoshitaka Hayashida 1-1, Kurosaki Joishi, Yahata-nishi-ku, Kitakyushu-shi, Japan Mitsui Kasei Hoechst Co., Ltd. (56) References JP-A-5-105817 (JP, A) JP-A-2- 233766 (JP, A) JP-A-1-153755 (JP, A) JP-A-63-137965 (JP, A) JP-A-61-57649 (JP, A) JP-A-59-93752 (JP, A) JP-A-59-93751 (JP, A) JP-A-59-96165 (JP, A) JP-A-59-96166 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09B 67/48 C09B 29/09 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A diffraction angle (2θ) of about 8.0 °, 11.5 °
And 3 strong peaks at about 26.5 °, and about 15.4
The following structural formula [I] having a crystal modification characterized by an X-ray diffraction diagram (CuKα) showing four intermediate peaks at °, 17.2 °, 20.0 ° and about 27.0 °. A water-insoluble monoazo dye represented by the formula: