JPH039149B2 - - Google Patents

Description

[Detailed description of the invention] The present invention has diffraction angles (2θ) of 11.4°, 12.1°, 13.2°,
A novel crystal modification (hereinafter referred to as This is called the γ-type transformation) and has the following structural formula [] This relates to a pyridone azo compound represented by

In recent years, various rationalizations have been made to color washing methods in the color washing industry, and jet dyeing methods that dye a large amount of fiber at once are often adopted. Examples of these are beam dyeing, cheese dyeing, and package dyeing. These staining methods are widely used. 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 firmness 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 structure of the pyridone azo compound according to the present invention is JP-A No. 56-129255 or JP-A No. 47-Sho.
It can be obtained by the usual manufacturing method described in documents such as No. 18549. However, when the dye bath is heated to a high temperature, the dispersion of this compound is significantly reduced, making it difficult to obtain a dyed product with uniform dye 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 pyridone azo 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 includes several types of crystal modifications. ), and the other two are very stable crystal modifications (α-type modification and γ-type modification) even under high-temperature heating conditions. The stability of the dispersion state of the composition in a high-temperature dye bath is not determined only by the size of the dye particles, but is significantly related to the above-mentioned crystal transformation. Alternatively, the inventors discovered that the objective could be achieved only by using a compound with the γ-type crystal modification (for the α-type modification, a patent application has been filed as Japanese Patent Application No. 32,680/1983).

The novel γ-type modification of the present invention has the following structural formula, for example: The compound [] represented by is diazotized by a conventional method to form the following formula [] After coupling with a pyridone compound represented by The β-type modification obtained by methylation at the − position is optionally carried out in an aqueous medium in the presence of a dispersant of a concentrate of sulfide pulp waste liquid whose main component is a formaldehyde condensate of naphthalene sulfonic acid; sodium lignin sulfonate. , or alcohols such as methanol, ethanol or butanol;
It can be produced by treating at 15°C to 140°C for 30 minutes to 30 hours in an organic solvent such as ethers such as dioxane; glycols and glycol ethers such as ethylene glycol and ethylene glycol monoethyl ether.

Next, the γ-type modification and β-type modification of the pyridone azo compound represented by the above structural formula [] according to the present invention 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 γ-type transformation, with diffraction angles (2θ) of 11.4°, 12.1°, 13.2°,
It has five strong peaks at 25.2° and 27.6° and three intermediate intensity peaks at diffraction angles (2θ) of 16.6°, 18.2° and 19.9°. 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 clearly show the differences between each crystal modification.

Fibers that can be dyed with the disazo 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 natural fibers such as cotton, silk, and wool with the above-mentioned polyester fibers.

In order to dye polyester fibers using the disazo compound of the present invention, a dispersant such as a condensate of naphthalene sulfonic acid and formaldehyde, a higher alcohol sulfate ester, a higher alkylbenzene sulfonate, etc. is used as a dispersant in an aqueous medium. 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 firmness 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 1 1.5 g of 3-cyano-6-hydroxy-4-methylpyrid-2-one was added to 200 ml of 2% hydrochloric acid, and 200 g of ice was further added to prepare a coupling component solution.

Add 2.6 g of p-(phenoxyethoxycarbonyl)aniline to 300 ml of 5% hydrochloric acid, and add 200 g of ice.
A solution consisting of 0.8 g of sodium nitrite and 20 ml of water was added dropwise thereto, and after stirring for 2 hours, 0.2 g of sulfamic acid was added to decompose excess sodium nitrite to prepare a diazo solution. This diazo solution was dropped into the coupling component solution, and 3.0% of sodium acetate was added.
The reaction solution was stirred at 0 to 5°C for 3 hours, washed with water, and dried under reduced pressure at 30°C to obtain 3.7 g of yellow crystals.

The obtained crystals were dissolved in N,N-dimethylformamide.
The mixture was dissolved in 37 ml of water, 1.0 g of sodium carbonate and 1.7 g of dimethyl sulfate were added, and a methylation reaction was carried out at 30°C for 10 hours. After the reaction was completed, the mixture was poured into 370 ml of water and the precipitated yellow cake was collected.

The obtained powder was of β type modification, and its X-ray diffraction pattern is shown in FIG.

The obtained β-type modified powder was dispersed in 60 ml of methanol and stirred at 25 to 30° C. for 8 hours to effect crystal transition. After the crystal transformation was completed, it was filtered and dried to obtain a γ-type modification having the X-ray diffraction pattern shown in FIG.

A dyeing bath was prepared by dispersing 0.5 g of a γ-modified pyridone azo compound represented by the above structural formula [] in 3 water containing 1 g of a naphthalene sulfonic acid-formaldehyde condensate and 2 g of higher alcohol sulfate. Polyester fibers are dyed in this dye bath.
After immersing 100 g of the fabric and dyeing it at 130°C for 60 minutes, soaping, washing with water and drying, a clear greenish-yellow dyed fabric with good light resistance 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 pyridone azo compound 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. Five strong peaks at diffraction angles (2θ) of 11.4°, 12.1°, 13.2°, 25.2° and 27.6° and diffraction angles (2θ)
The following structural formula has a crystal modification characterized by an X-ray diffraction diagram (CuKα) showing three intermediate intensity peaks at 16.6°, 18.2° and 19.9° A pyridone azo compound represented by