JPH0310670B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has one extremely strong peak at a diffraction angle of 2θ of 8.7°, three strong peaks at a diffraction angle of 2θ of 15.6°, 20.0° and 26.2°, and a diffraction angle of 2θ of 14.8°. ，18.4゜，
The following structural formula [ ] This relates to a monoazo compound represented by

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 inside the fiber. 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 chemical structural formula of the r-modified monoazo compound according to the present invention is known from Japanese Patent Publication No. 40-25431, but the monoazo compound obtained by the production method described in the above document can The dispersion decreases significantly when the temperature is increased, making it difficult to obtain dyed products with uniform dyeing density.

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 three types of crystal modifications, one of which is a thermally unstable crystal modification (hereinafter referred to as β-type modification), which It is considered to be a mixture of crystal modifications.)
It was discovered that the other two are crystal modifications (α-type modification and γ-type modification) that are extremely stable even under high-temperature heating, and that the stability of the dispersed state of the dye composition in a high-temperature dye bath is It is not determined only by the size of the dye particles, but 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 a compound with α-type crystal modification or the γ-type crystal modification of the present invention. , I discovered that I could achieve my purpose for the first time.

The novel γ-type modification of the present invention has the following structural formula, for example: Diazotize the compound [ ] by a conventional method, In an aqueous medium, the β-type modification obtained by coupling with the compound [] shown in [] may be prepared as a formaldehyde condensate of naphthalene sulfonic acid; in the presence of a dispersant or in organic solvents such as alcohols such as methanol, ethanol or butanol; ethers such as dioxane; glycols and glycol ethers such as ethylene glycol and ethylene glycol monoethyl ether from 15°C. It can be produced by processing at 140°C for 30 minutes to 30 hours.

Next, the γ-type modification and β-type modification of the monoazo compound represented by the above structural formula [] according to the present invention will be explained with reference to the drawings. Figures 1 and 2 show powder
It is based on a line diffraction method, and is a diagram in which the diffraction state due to CuKα rays is recorded using a proportional counter. The horizontal axis shows the diffraction angle 2θ, and the vertical axis shows the diffraction intensity. Figure 1 shows γ-type transformation, with one extremely strong peak at a diffraction angle of 2θ8.7°, three strong peaks at diffraction angles of 2θ15.6°, 20.0°, and 26.2°, and a diffraction angle of 2θ14.8°. It has five intermediate intensity peaks at , 18.4°, 23.2°, 24.4° and 27.8°. 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° for the same crystal form, and these drawings make clear the differences between each crystal modification.

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

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 17.489g and sodium sulfite 1.68g
Nitrosyl sulfate was prepared from g and 44% at 0-5℃.
Add 9 ml of sulfuric acid dropwise to 2-amino-5 at -2°C 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 3-N,
N-bis(2-ethylcarbonyloxyethyl)
4.6 g of amino-4-methoxyacetanilide
% sulfuric acid (400 ml). The mixture was stirred at 0-3℃ for 3 hours, filtered, washed with water, and dried to form the following structural formula. A dark green powder of a monoazo compound represented by was obtained. (Yield: 6.4 g) The obtained powder was of β type modification, and its X-ray diffraction pattern is shown in FIG. The obtained β
10 g of the transformed powder was dispersed in 10 g of water and 100 ml of methanol and stirred at 30° C. for 2 hours to effect crystal transition. After the crystal transformation was completed, it was filtered and dried to obtain a γ-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 γ-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, soaking, washing with water, and drying, a clear greenish-blue dyed fabric with good light fastness was obtained.

[Brief explanation of the drawing]

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

Claims (1)

[Claims] 1. One extremely strong peak at a diffraction angle of 2θ8.7°,
Three strong peaks at diffraction angles 2θ 15.6°, 20.0°, and 26.2° and diffraction angles 2θ 14.8°, 18.4°, 23.2°,
X showing five intermediate intensity peaks at 24.4° and 27.8°
The following structural formula has a crystal modification characterized by a line diffraction pattern (CUKα) A monoazo compound represented by