JPH039148B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has diffraction angles (2θ) of 9.1°, 15.7°, 23.6° and
Four strong peaks at 26.2° and diffraction angle (2θ)
The following structural formula has a novel crystal modification (hereinafter referred to as α-type modification) characterized by an X-ray diffraction diagram showing three intermediate-intensity peaks at 7.8°, 18.4°, and 21.3°. 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 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 pyridone azo compound according to the present invention is JP-A-56-129255 or JP-B-Sho.47-
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 two types of crystal modification, one of which is a crystal modification that is unstable to heat (hereinafter referred to as β-type modification); ), and the other one is a crystal modification (α-type modification) that is very stable even under high-temperature heating conditions. The stability of the dispersion state in the dyebath 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 in the dyebath, it is necessary to I discovered that I could achieve my goal for the first time by using The novel α-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 [] or [] Dispersion of a concentrate of sulfide pulp waste liquid whose main component is a formaldehyde condensate of naphthalene sulfonic acid; a formaldehyde condensate of naphthalene sulfonic acid obtained by coupling the β-type modification with a pyridone compound represented by the formula in an aqueous medium. 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 at It can be produced by processing at 140°C for 30 minutes to 30 hours. Next, the α-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 by CuKa 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 α-type transformation, with four strong peaks at diffraction angles (2θ) of 9.1°, 15.7°, 23.6°, and 26.2°, and
It has three intermediate intensity peaks at 7.8°, 18.4°, and 21.3°. Figure 2 shows β-type metamorphosis.
Only the peaks of gentle ups and downs can be seen. The diffraction angle by X-ray diffraction method is if the crystal form is the same.
These drawings, which always agree with an error of about ±0.1°, make clear 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 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 1 1.7 g of 3-cyano-6-hydroxy-1,4-dimethylpyrid-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 the 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 pH of the reaction solution was adjusted to 4 to 5, and the mixture was stirred at 0° to 5°C for 3 hours, washed with water, and dried under reduced pressure at 30°C to obtain 3.9 g of yellow crystals. The obtained powder was of β type modification, and its X-ray diffraction pattern is shown in FIG. 3 g of the obtained β-type modified powder was dispersed in 90 ml of water and stirred at 90° to 95° C. for 5 hours to effect crystal transformation. After the crystal transformation was completed, it was filtered and dried to obtain an α-type modification having the X-ray diffraction pattern shown in FIG. A dyeing bath was prepared by dispersing 0.5 g of the α-modified pyridone azo 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. Polyester fibers are dyed in this dye bath.
After immersing 100 g of the dye and dyeing it at 130°C for 60 minutes, soaping, washing with water and drying, a clear greenish-yellow dyed fabric with good light fastness was obtained. Example 2 16.4 g of 3-cyano-6-hydroxy-1,4-dimethylpyrid-2-one was added to 500 ml of 10% aqueous acetic acid, 10.0 g of formalin was added, and the mixture was reacted at 70°C for 10 hours, then heated to room temperature. The temperature was lowered, washed with water and dried to obtain 16.5 g of pale yellow crystals. As a result of performing mass spectrometry on this compound, the M ⁺ /e of the parent peak was
It was 340. The results of elemental analysis were as shown in the table below.

[Table] According to the above mass spectrometry and elemental analysis results, this compound is It was determined that Using 1.8 g of the above compound in place of 3-cyano-6-hydroxy-1,4-dimethylpyrid-2-one in Example 1, 4.1 g of β-type modified powder was obtained by the same diazotization and coupling reaction. 3g of the obtained β-type transformed powder was added to methanol.
The mixture was dispersed in 60 ml and stirred at 25° to 30°C for 8 hours to effect crystal transformation. After completion of crystal transformation, overdrying was performed to obtain α-type modification as in Example 1.

[Brief explanation of drawings]

FIGS. 1 and 2 are X-ray diffraction patterns of α-type and β-type modifications of the pyridone azo compounds obtained in 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 9.1°, 15.7°, 23.6° and 26.2° and three intermediate peaks at diffraction angles (2θ) of 7.8°, 18.4° and 21.3°. X indicating peak
The following structural formula has a crystal modification characterized by a line diffraction diagram. A pyridone azo compound represented by