JPH07304990A - Monoazo dye compound - Google Patents

Abstract

PURPOSE:To obtain the compound which exhibits high dispersion stability even under severe dyeing conditions including high temperatures and has good color fastness to light and friction. CONSTITUTION:This dye is an insoluble monoazo dye compound represented by the formula and having a crystal form characterized by an X-rays diffraction pattern (CUKalpha) in which strong peaks appear at diffraction angles of about 5.0 deg., 22.8 deg., 23.5 deg., 24.9 deg. and about 25.1 deg. and middle peaks at about 6.5 deg., 8.0 deg., 11.3 deg., 14.4 deg., 17.0 deg., 18.0 deg. and about 19.6 deg..

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a monoazo dye compound. More specifically, the present invention relates to a blue-based monoazo dye compound having a novel crystal structure capable of uniformly dyeing polyester fibers and the like even under severe conditions at high temperatures.

[0002]

2. Description of the Related Art In recent years, various rationalizations have been made in dyeing methods in the dyeing industry. For example, when polyester fibers are dyed with a disperse dye, a jet dyeing method, a yarn dyeing method, and a yarn method are used for cloth. The cheese dyeing method and the package dyeing method are widely used for the purpose. Since these dyeing methods are methods in which a dye dispersion liquid is forcibly circulated in a dense layer in which stationary fibers are wound and dyeing is performed, dye particles dispersed in a dye bath more than ever before. Are fine particles and excellent dispersion stability in the dyeing bath. If the dye particles become large, the filtration phenomenon of the dye particles occurs due to the fiber layer, the dye does not permeate inside the fiber poorly, or the inner or outer layer is shaded due to the adhesion of aggregates, or the dye only adheres to the fiber surface. Problems such as deterioration of fastness such as abrasion resistance occur.

Therefore, the dyes used in such a dyeing method have good dispersibility in the dyeing bath, and the dispersibility is not lowered in a wide temperature range from room temperature to a high temperature at which actual dyeing occurs. is necessary. However, in general, when the dye bath is heated to a high temperature, the dispersibility of the dye tends to decrease, and as a result, the aggregated dye adheres to the surface of the dyed substance in the form of a filter residue as described above. However, in the case of a dyed material having multiple layers, the dyeing density differs between the outer layer part and the inner layer part, and a dyed product having a uniform density cannot be obtained.

Particularly, recently, from the viewpoint of resource saving and energy saving, the bath ratio of the dyeing bath is lowered (the ratio of the dyeing object: the dyeing solution is decreased from 1:30 to 1:10), and the use ratio of the dispersant is decreased ( The ratio of dye cake: dispersant was reduced from 1: 3 to 1: 1) and the dyeing conditions were raised for a shorter time (13
The dyeing conditions are shifting to severe conditions such as 0 ° C. for 1 hour to 135 ° C. for 0.5 hours). However, all of these conditions are disadvantageous to the dispersion stability of the dye. Even in the case of dyes having relatively good dispersion stability in the dyeing method, there are many cases where the dispersion stability becomes poor under more severe recent dyeing conditions. For example, the following structural formula [I]

[0005]

[Chemical 2]

The dye represented by the following formula is, for example, JP-B-39-
It is included in the claims described in Japanese Patent No. 14989. This dye is produced by simply subjecting the diazo component and the coupling component to a coupling reaction according to a conventional method. This monoazo dye is capable of uniformly dyeing polyester fibers under conventional mild dyeing conditions, and is also excellent in various fastnesses.
However, when dyeing is performed under severe conditions at the high temperature as described above, the dispersibility of the dye is remarkably reduced, and it is extremely difficult to obtain a dyed product having a uniform dyeing density.

This dye also has a problem in compatibility with various dyeing aids. For example, the high temperature dispersion stability in the presence of Glauber's salt is extremely poor. Therefore, polyester / cotton can be used in combination with a reactive dye or the like. When dyeing a blended product in the presence of Glauber's salt, uneven dyeing occurs. Further, even when a dye is blended and used, there is a drawback that color blurring and uneven dyeing occur due to compatibility with the blended dye.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a dye which solves the above-mentioned drawbacks and which can perform good dyeing under high temperature and severe conditions. As a result of diligent investigations by the present inventors regarding the above-mentioned drawbacks, in the thiophene-based monoazo compound represented by the structural formula [I], it is impossible to obtain an amorphous solid obtained by a conventional ordinary synthetic reaction, We have found crystals with a novel crystal structure that have good dispersion stability even under severe dyeing conditions at temperature.

Further, the stability of the dispersion state of the dye composition in a high temperature dyeing bath has a significant relationship not only with the size of the dye particles but also with the crystallinity, and the above-mentioned compound having a novel crystal structure was used. In this case, it was discovered for the first time that the dispersion stability of a dye composition in a high temperature dyeing bath can be achieved, and the present invention was reached.

[0010]

That is, the present invention provides a diffraction angle (2θ) of about 5.0 °, 22.8 °, 23.5 °, 24.
Strong peaks at 9 ° and about 25.1 °, then about 6.5 °,
8.0 °, 11.3 °, 14.4 °, 17.0 °, 1
The following structural formula [I] having a crystal structure characterized by an X-ray diffraction diagram (CuKα) showing moderate intensity peaks at 8.0 ° and about 19.6 °

[0011]

[Chemical 3]

A water-insoluble monoazo dye represented by: The monoazo compound having a novel crystal structure of the present invention is obtained as follows. For example, 2-chloro-
The diazotization of 4,6-dinitroaniline is carried out by a conventional method, and then it is 0 to 15 ° C. in an aqueous medium, preferably 0 to
Coupler at a temperature of 10 ° C for 0.5-10 hours 3
A monoazo compound represented by the above structural formula [I] is synthesized by a coupling reaction with-(N, N-diethylamino) -4-methoxyacetanilide.

The cake of the monoazo compound obtained by this synthesis has an amorphous structure, but in the present invention, the cake having the above crystal structure is obtained by further treating this cake under specific conditions. As this treatment method, for example, a cake having an amorphous structure is dispersed in an aqueous medium, and in some cases, a formaldehyde condensate of naphthalene sulfonic acid, a concentrate of a sulfite pulp waste liquid containing sodium lignin sulfonate as a main component, and the like. In the presence of a dispersant, a method of stirring treatment at a temperature of 60 to 130 ° C, preferably 80 to 100 ° C for 0.5 to 30 hours, preferably 1 to 10 hours, or alcohols such as methanol, ethanol or butanol, Disperse in ethers such as dioxane, organic solvents such as ethylene glycol and glycol ether,
0.5 to 100 ° C., preferably 20 to 80 ° C.
A method of stirring for about 10 hours is adopted.

Next, the amorphous structure and the crystal structure of the monoazo compound represented by the above structural formula [I] will be described with reference to the drawings. 1 and 2 show CuKα in the powder X-ray diffraction method.
FIG. 3 is an X-ray diffraction diagram in which the state of diffraction by rays is recorded using a proportional counter, the horizontal axis being the diffraction angle (
θ), and the vertical axis represents the diffraction intensity. FIG. 1 shows a novel crystal form of the present invention, which has a diffraction angle (2θ) of about 5.0.
°, 22.8 °, 23.5 °, 24.9 ° and about 25.
Strong peak at 1 °, about 6.5 °, 8.0 °, 11.
3 °, 14.4 °, 17.0 °, 18.0 ° and about 1
It has a medium intensity peak at 9.6 °. FIG. 2 shows a conventional amorphous structure, which is clearly different from the crystal form of FIG.

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

The fibers which can be dyed with the monoazo dye compound of the present invention include polyester fibers composed of polyethylene terephthalate, polybutylene terephthalate, polycondensates of terephthalic acid and 1,4-bis- (hydroxymethyl) cyclohexane, or the like, or Examples include a blended product and a blended product of natural fibers such as cotton and wool and the above polyester fibers. In order to dye polyester fibers with the monoazo dye of the present invention, a condensate of naphthalene sulfonic acid with formaldehyde, a higher alcohol sulfate ester, a higher alkylbenzene sulfonate, or the like is used as a dispersant in a conventional method in an aqueous medium. Dyeing or printing can be carried out by preparing a dyeing bath or printing paste dispersed in the above. Further, for example, in the case of dip dyeing, dyeing treatment methods such as the above-mentioned high temperature dyeing method, carrier dyeing method and thermosol dyeing method can be applied, and even if severe dyeing conditions are adopted in these methods. Since the monoazo dye of the present invention has excellent dispersion stability, it can dye polyester fibers or a blended product thereof well. Specifically, polyester fibers are dyed at a temperature of 125 to 140 ° C.,
It is also possible to perform exhaust dyeing in an aqueous medium in the presence of a dispersant under harsh conditions such as a dyeing bath ratio of 15 times or less and a use ratio of the dispersant to the dye of 3 times or less.

If desired, if an acidic substance such as formic acid, acetic acid, phosphoric acid or ammonium sulfate is added to the dyeing bath, further favorable results can be obtained. In addition, the structural formula [I] shown above of the present invention
The monoazo dye represented by (4) may be used in combination with other dyes, and when the dyes are mixed with each other, good results such as improvement in dyeability may be obtained in some cases.

[0018]

EXAMPLES Next, the present invention will be described more specifically by way of examples. Example 1 (Production Example of Dye Crystal) 6-chloro-2,4-dinitroaniline 5.6 was added to a mixed solution of 98% sulfuric acid and nitrosyl sulfuric acid.
g was added and diazotized at 20 ° to 25 ° C. for 2 hours to prepare a diazo solution. On the other hand, 0.05 g of 3- (N, N-diethylamino) -4-methoxyacetanilide was added to 0.05
% To dissolve in sulfuric acid to prepare a coupling solution. The previously obtained diazo solution was added dropwise to this coupling solution together with a 25% aqueous sodium hydroxide solution so as to maintain pH 4, and the coupling reaction was carried out. After stirring at 0 ° C. for 1 hour, the precipitated solid was filtered off. Separately, washed with water and dried to give a green solid 10
g was obtained. The obtained powder of the compound solid represented by the general formula [I] was analyzed by an X-ray diffraction method and found to be an amorphous solid. The X-ray diffraction pattern is shown in FIG. Next, the obtained amorphous solid was dispersed in 20 volumes of water, stirred at 90 ° to 95 ° C. for 3 hours, and subjected to crystallization treatment. When the obtained crystal was analyzed by an X-ray diffraction method, it was a crystal having an X-ray diffraction pattern shown in FIG.

(Dyeing Example 1) (Dyeing under harsh conditions) 0.5 g of the monoazo dye having a crystal structure obtained in Example 1 above was mixed with 0.25 g of a naphthalenesulfonic acid-formaldehyde condensate and a higher alcohol sulfuric acid. A dyebath was prepared by dispersing 0.25 g of the ester in 1 liter of water. 100 g of polyester fiber was dipped in this dyeing bath, dyeing was carried out at 135 ° C. for 30 minutes, and then soaping, washing with water and drying were carried out. As a result, the dispersibility of the dye was good and the dyeing cloth was dyed uniformly. The obtained dyed fabric was blue and was excellent in light fastness grade 5 and abrasion resistance fastness grade 5. A similar dyeing test was conducted using a monoazo dye having an amorphous structure in the process of production in the above production example, and partial aggregation of the dye occurred in the dyeing bath, resulting in a non-uniform dyeing fabric and abrasion resistance. The degree was much worse than the first grade.

(Dyeing Example 2) (Dyeing under normal conditions) In Dyeing Example 1, the naphthalenesulfonic acid-formaldehyde condensate and the higher alcohol sulfate are each tripled to 0.75 g, and water is tripled to 3 times. Liter,
Dyeing was carried out by a slightly mild dyeing method in the same manner as Dyeing Example 1 except that the dyeing conditions were 130 ° C. for 60 minutes, and as a result, the dye having the crystal structure of the present invention was as good as Dyeing Example 1. Dyeing is possible, and the resulting dyed cloth is light fastness grade 5
The abrasion resistance was 5 and good. On the other hand, when the dye having the amorphous structure was used, a slight improvement was observed as compared with Dyeing Example 1, but the uneven dyeing only gave a dyed cloth.
Its abrasion resistance was 3rd grade.

[0021]

INDUSTRIAL APPLICABILITY The water-insoluble monoazo dye having a crystal structure of the present invention is remarkably excellent in dispersion stability as compared with conventional amorphous monoazo dyes, and at a high temperature, for example, in a dyeing solution: Dispersion stability can be maintained even under severe dyeing conditions such as a ratio of 1:10, a dye cake: dispersant ratio of 1: 1 and a dyeing condition of 135 ° C. for 0.5 hour, and therefore always good and uniform. Dyeing can be obtained, and the resulting dyed cloth has excellent light fastness and abrasion fastness. Therefore, the dye of the present invention is very useful from the viewpoint of resource saving and energy saving.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction diagram of a monoazo compound having a crystal structure obtained in an example of the present invention, in which 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 monoazo compounds having an amorphous structure obtained in Examples of the present invention, in which the horizontal axis represents the diffraction angle (2θ) and the vertical axis represents the diffraction intensity.

Claims (2)

[Claims] 1. A diffraction angle (2θ) of about 5.0 °, 22.8.
Strong peaks at 2 °, 23.5 °, 24.9 ° and about 25.1 °, and further about 6.5 °, 8.0 °, 11.3 °, 14.
The following structural formula [I] has a crystal structure characterized by an X-ray diffraction diagram (CuKα) showing medium intensity peaks at 4 °, 17.0 °, 18.0 ° and about 19.6 °. A water-insoluble monoazo dye compound represented by. 2. A method for dyeing polyester fibers, which comprises using the water-insoluble monoazo dye compound according to claim 1.