JPH0314074B2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention has the following structural formula [] A monoazo compound with a diffraction angle (2θ) of
Characterized by an X-ray diffraction pattern (CuKα) showing four strong peaks at 9.2°, 17.4°, 18.4° and 25.7° and three intermediate intensity peaks at diffraction angles (2θ) of 14.1°, 14.8° and 27.3°. The present invention relates to a new crystal modification (hereinafter referred to as α-type modification).

In recent years, various rationalizations have been made to dyeing methods in the dyeing industry, and jet dyeing methods, in which a large amount of fibers are dyed at one time, are often adopted. Examples include beam staining, cheese staining, and package staining, which are widely used staining methods. These dyeing methods are dyed by forcibly circulating a dye dispersion liquid in a dense layer of stationary fibers, so the dye dispersion particles are fine particles and the dispersion system is If the dye particles are stable, they will circulate uniformly within the fiber layer and good dyeing results will be obtained, but if the dye particles become large, the fiber layer will cause the dye particles to overflow, causing the dye to penetrate into the fibers. Problems may occur, such as defects, dyeing of the inner or outer layer in deep and light colors due to adhesion of aggregates, and a decrease in fastness due to adhesion of dye only to the fiber surface. Therefore, it is necessary that the dye used in such a dyeing method has good dispersibility in the dye bath, and that the dispersibility does not deteriorate over a wide temperature range from room temperature to the high temperature at which actual dyeing occurs. However, when the temperature is raised in the dyebath, the dispersibility of the dye often tends to decrease, and as a result, as mentioned above, the aggregated dye adheres to the surface of the dyed object in the form of an excessive residue.
Furthermore, in the case of a dyed object having many layers, the dyeing concentration differs between the outer layer and the inner layer, making it impossible to obtain a dyed object with uniform density.

The monoazo compound represented by the above formula [] is, for example, the following structural formula [] The compound represented by is diazotized by a conventional method to form the following structural formula [] It can be obtained by coupling with a compound shown in It is difficult to obtain things.

The present inventors have conducted intensive studies regarding the above-mentioned points, and as a result, have arrived at the present invention. That is, the present inventors found that the monoazo compound has at least two types of crystal modification, one of which is a thermally unstable crystal modification (hereinafter referred to as β-type modification), which includes several types of crystal modification. It is considered to be a mixture of crystal modifications of
The other one is a crystal modification (α-type modification) that is very stable even when heated at high temperatures, and the stability of the dispersion state of the dye composition in a high-temperature dye bath is
It is determined not only by the size of the dye particles, but also has a significant relationship with the above-mentioned crystal modification, and in order to obtain a stable dispersion system for the dye bath, it is necessary to use the α-type crystal modification compound according to the present invention to achieve the objective. I found out that it can be achieved.

The novel α-type modification of the present invention is performed by converting the β-type modification obtained by the diazotization coupling described above in an aqueous medium into a formaldehyde condensate of naphthalene sulfonic acid; In the presence of a dispersant such as pulp waste liquid concentrate, or methanol,
Alcohols such as ethanol or butanol; ethers such as dioxane; organic solvents such as ethylene glycol, glycol ether, etc.
It can be produced by processing at 15°C to 140°C for 30 minutes to 30 hours.

Next, the α-type modification and β-type modification of the monoazo compound represented by the above general formula [] will be explained with reference to the drawings. Figures 1 and 2 are obtained by powder X-ray diffraction, and are diagrams in which the diffraction state of CuKα rays was recorded using a proportional counter. The horizontal axis shows the diffraction angle (2θ), and the vertical axis shows the diffraction intensity. Figure 1 shows the α-type transformation, with four strong peaks at diffraction angles (2θ) of 9.2°, 17.4°, 18.4°, and 25.7°, and diffraction angles of (2θ) of 14.1°, 14.8°, and
It has three intermediate intensity peaks at 27.3°.

Figure 2 shows β-type metamorphosis, and only gently undulating peaks can be seen. The diffraction angles determined by X-ray diffraction always match with an error of about ±0.1° if they are made of the same crystal, and these drawings are
The differences between each crystal modification are made clear.

Fibers that can be dyed with the monoazo compound of the present invention include polyester fibers made of polyethylene terephthalate, polycondensates of terephthalic acid and 1,4-bis(hydroxymethyl)cyclohexane, and natural fibers such as cotton, silk, and wool. Examples include blended products and mixed fiber products of fibers and the above-mentioned polyester fibers.

In order to dye polyester fibers using the monoazo compound of the present invention, a condensate of naphthalene sulfonic acid and formaldehyde, a higher alcohol sulfate ester, a higher alkylbenzene sulfonate, etc. are used as a dispersant in an aqueous medium by a conventional method. Dyeing or printing may be carried out by preparing a dyeing bath or printing paste in which the dye is dispersed. For example, in the case of dip dyeing, polyester fibers or their blends can be dyed with excellent fastness by applying ordinary dyeing methods such as high temperature dyeing, carrier dyeing, and thermosol dyeing. In this case, even better results can be obtained if an acidic substance such as formic acid, acetic acid, phosphoric acid or ammonium sulfate is added to the dyeing bath.

Further, the dye represented by the above structural formula [ ] used in the method of the present invention may be used in combination with dyes of the same type or dyes of other types, and good results such as improved dyeability can be obtained by combining the dyes with each other. There may be cases where

Next, the present invention will be explained in more detail with reference to Examples.

Example 97% sulfuric acid 17.48g and sodium nitrite 1.68g
Nitrosyl sulfate was prepared from g and 40% at 0-5℃.
Add 9 ml of sulfuric acid dropwise to 2-amino-5 at -2° to 0°C.
- 2.9 g of nitrothiazole were added. The mixture was stirred at -2°C for 2 hours, and the diazo solution was diluted with N-methyl-N-phenoxyethoxycarbonylethyl-
6.3 g of m-toluidine was added dropwise to a solution of 580 ml of 6.3% sulfuric acid. The mixture was stirred at 0-3℃ for 3 hours, filtered, washed with water, and dried to form the following structural formula. A brown powder of a monoazo compound represented by was obtained. (Yield: 8.5 g) The powder obtained was of β type modification, and its X-ray diffraction pattern is shown in FIG. Disperse 10g of this powder in 10g of water and 100ml of methanol and heat at 60°C for 2 hours.
The mixture was stirred for a period of time to effect crystal transformation. After the crystal transformation was completed, it was filtered and dried to obtain an α-type modification as shown in the X-ray diffraction pattern shown in FIG.

A dyeing bath was prepared by dispersing 0.5 g of the alpha-modified monoazo compound represented by the above structural formula [] in 3 water containing 1 g of naphthalene sulfonic acid-formaldehyde condensate and 2 g of higher alcohol sulfate ester. 100g of polyester fiber in this dye bath
After soaking and dyeing at 130°C for 60 minutes, soaping, washing with water, and drying, a brightly colored dyed fabric with good fire fastness was obtained.

[Brief explanation of the drawing]

FIGS. 1 and 2 are X-ray diffraction patterns of the α-type modification and β-type modification of the monoazo compounds obtained in the examples. In the drawings, the horizontal axis represents the diffraction angle (2θ), and the vertical axis represents the diffraction intensity.

Claims (1)

[Claims] 1. Four strong peaks at diffraction angles (2θ) of 9.2°, 17.4°, 18.4° and 25.7°, and diffraction angles (2θ) of 14.1°,
The following structural formula has a crystal modification characterized by an X-ray diffraction diagram (CuKα) showing three intermediate intensity peaks at 14.8° and 27.3° A monoazo compound represented by