JPS63210172A - Monoazo benzothiazole compound having crystalline structure, production thereof and method of dyeing hydrophobic fibrous material by using the same - Google Patents

Abstract

PURPOSE:To produce the title compd. which gives dyed articles having a uniform density, by heating a specified monoazo benzothiazole in an aq. medium or an org. medium. CONSTITUTION:A monoazo benzothiazole compd. obtd. by coupling a diazo product of 4,6-dibromo-2-aminobenzothiazole with N,N-di(acetoxyethyl)aniline by a conventional method is heated in the presence of optionally, a surfactant (e.g., lignosulfonic acid) and an inorg. salt (e.g., NaCl) in an aq. medium and/or an org. solvent (e.g., methanol) at 15-140 deg.C for 30min-4hr to transform its crystalline structure, thus obtaining 4,6-dibromo-2-[4-{N,N-di(acetoxyethylamino) phenylazo]benzothiazole having a crystalline structure characterized by an X-ray diffraction pattern with intense reflection at an angle of diffraction (2theta: Cu-Kalpha) of 5.65 deg. and 25.87 deg. and medium reflection at an angle of 10.74 deg., 16.89 deg., 18.91 deg., 21.68 deg. and 23.48 deg..

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a monoazobenzothiazole compound having a crystalline structure, a method for producing the same, and a method for dyeing hydrophobic fiber materials using the same.

(Prior Art) In recent years, the dyeing industry has widely used a jet dyeing method in which a hydrophobic fiber material is tightly wound into many layers and a dye dispersion is forcibly circulated therein. The dye used in this dyeing method is required to have good dispersibility in the dye bath, and the dispersibility does not deteriorate over a wide temperature range from room temperature to high temperatures during dyeing.

Japanese Patent Publication No. 45-7712 discloses a monoazobenzothiazole disperse dye for dyeing hydrophobic fiber materials.

(Problems to be solved by the invention) However, the compound obtained by the production method described in the same publication shows a significant decrease in dispersibility when exposed to high temperatures, and when used for dyeing, the concentration is uniform. There were problems such as not being able to obtain a dyed product and causing aggregates.

As a result of intensive studies aimed at solving the above-mentioned problems, the present inventors discovered a new monoazobenzothiazole compound having a specific crystal structure, and discovered that the above-mentioned problems could be solved by using this compound. The invention was completed.

(Means for Solving the Problems) The present invention provides (1) diffraction angle (2θ; Cu-Kα)5.
Strong reflections at 65° and 25.87°, 10.7
4,6-dibromo-2 with a crystal structure characterized by an X-ray diffraction diagram showing moderate reflections at 4°, 16, 89°, 18.91°, 2i, 68° and 23.48°
-[4-{N,N-di(acetoxyethyl)amino)phenylazo]benzothiazole, (2) diazotized 4,6-dibromo-2-aminobenzothiazole and N,
A monoazobenzothiazole compound obtained by coupling with N-di(acetoxyethyl)aniline is heated in an aqueous medium, an organic solvent, or a mixture of both, optionally in the presence of a surfactant or an inorganic salt. Provided is a method for dyeing sex fibers characterized by the following.

The monoazobenzothiazole compound having a specific crystal structure of the present invention can be obtained by combining 4,6-dibromo-2-aminobenzothiazole diazotized by a conventional method and N,N-di(acetoxyethyl)aniline by a conventional method. It can be produced by converting the crystal structure by heating the cake obtained by coupling in an aqueous medium, an organic solvent, or a mixture of both, if necessary in the presence of a surfactant or an inorganic salt. can.

The conversion of the crystal structure can be continued without removing the cake after neutralizing the mixture after the coupling reaction has been completed and preferably setting the pH within the range of 5 to 8. Alternatively, it is also possible to use a wet cake taken out after coupling.

Examples of organic solvents that can be used for heat treatment include lower alcohols such as methanol and ethanol, lower aliphatic carboxylic acids such as acetic acid and propionic acid, lower aliphatic ketones such as acetone and methyl isobutyl ketone, tetrahydrofuran, and dioxane. ethers such as ethylene glycol, ethylene glycol monoacetate, diethylene glycol dimethyl ether, etc.
Glycol esters or glycol ethers, aromatic solvents such as toluene, xylene, monochlorobenzene,
or a mixture thereof.

Heat treatment can be carried out as long as the amount of aqueous medium, organic solvent, or a mixture of both is at least enough to fully immerse the cake, but it is preferable to obtain sufficient stirring to avoid uneven heating. Therefore, it is best to use a culm that is at least 10 times the weight of the cake.

During the heat treatment, a dispersant such as a formalin condensate of naphthalenesulfonic acid, a formalin condensate of naphtholsulfonic acid and cresol, ligninsulfonic acid, or a surfactant such as polyethylene glycol or polyvinylpyrrolidone may be present. In some cases, excellent results such as improved dye dispersibility can be expected.

During the long heat treatment, inorganic salts such as sodium sulfate, rooftop sodium, ammonium acetate, etc. may be present.
Good results such as easy crystal conversion are expected in some cases.

The temperature of the heat treatment in the present invention is 15°C to 140°C.
, preferably in the range of 50°C to 100°C at normal pressure. If the heat treatment temperature is lower than 50° C., a long time treatment is required to convert the crystal structure. Although it is possible to carry out the process at a temperature of 100° C. or higher, it is not advisable in terms of operation, as it requires a pressure-resistant container.

The heat treatment time is 80 minutes to 40 hours, and is preferably about 1 to 5 hours, although it depends on the temperature, the type and amount of the medium or solvent, and the type and amount of other additives.

The thus obtained monoazobenzothiazole compound having a specific X-ray diffraction pattern is pulverized into fine particles and dispersed in an aqueous medium together with a suitable dispersant such as formalin 18 compound of naphthalene sulfonic acid. A dye is made using the process and used as a paste or as a powder by spray drying. This dye is used to dye hydrophobic fiber materials, especially polyester fibers, in an aqueous medium under pressure.
Dyeing can be conveniently carried out by high-temperature dyeing methods, in which dyeing is carried out at 10 to 140 DEG C., or by carrier dyeing, in which dyeing is carried out at relatively low temperatures, for example in the boiling state of water, in the presence of a carrier such as 0-phenylphenol or trichlorobenzene.

By using the monoazobenzothiazole compound having the novel crystal structure of the present invention, dyeing problems such as decreased dispersibility and aggregates that occur in compounds having the crystal structure as obtained by the coupling reaction can be avoided. The occurrence of such problems is completely eliminated, and it is possible to obtain a clear, highly concentrated and uniformly dyed product.

Next, the crystal form of the monoazobenzothiazole compound in the present invention will be explained with reference to the drawings. These figures are based on the powder X-ray diffraction method, and are schematic illustrations of the figures in which the diffraction state due to Cu-Kd ray irradiation was recorded with a self-recording device using a Geiger counter.

The horizontal axis represents the diffraction angle (2θ; α for Cu−), and the vertical axis represents the relative intensity of the diffraction lines (R, 1,). Figure 2 shows the crystal structure obtained by coupling according to the method of Example 1, and Figure 1 shows the crystal structure of the monoazobenzothiazole compound of the present invention obtained by heat-treating the crystal in Figure 2. It shows the crystal structure.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the following Examples. In the examples, parts represent parts by weight.

Example 1 4.6-dibromo-2-aminobenzothiazole 15.
5 parts were suspended in 150 parts of 70% sulfuric acid, and 14.8 parts of 48% nitrosyl sulfuric acid was added dropwise to diazotize the suspension while maintaining the temperature at 0 to 5°C. Meanwhile, 14.0 parts of N,N-di(acetoxyethyl)aniline was dissolved in 200 parts of methanol, and 0 to 5
The diazo solution was added and coupled while maintaining the temperature at °C. After the reaction is completed, 4,6-dibromo-2 is filtered and washed.
-1:4-{N,N-di(acetoxyethyl)amino)
Phenylazo]benzothiazole wet cake 48
．． 8 parts (17.5 parts in terms of solid content) were obtained. After drying this cake at 20°C under vacuum, the melting point was measured to be 70-75°C. The X-ray diffraction diagram is shown in FIG.

48.8 parts of this wet cake was suspended in 500 parts of water, stirred at 80° C. for 8 hours, and heat-treated. After cooling, the mixture was filtered and washed to obtain 84.1 parts of a wet cake of the compound having a novel crystal structure (17.4 parts in terms of solid content). The melting point of the crystals thus obtained is 188-140℃
It is. The X-ray diffraction diagram is shown in FIG.

The maximum absorption wavelength λ of this compound in dimethylformamide solvent is 525 parts m.

Example 2 4 having a new specific crystal structure obtained in Example 1,
8 parts of 6-dibromo-2-[4-{N,N-di(acetoxyethyl)amino)phenylazo]benzothiazole and 8 parts of naphthalene-β-sulponic acid noformalin condensate;
Atomized and dispersed with 1.5 parts of sodium ligninsulfonate, and mixed with 8 parts of higher alcohol sulfate in water a, oo
A dyebath is prepared by uniformly dispersing it in the o parts.

100 parts of Tetoron spun yarn (polyester fiber; Toshisha product) was immersed in this dye bath and dyed at 130°C for 60 minutes. A light cleaning treatment is performed at 65° C. for 10 minutes using a treatment solution consisting of 8 parts of an amphoteric surfactant and 8,000 parts of water.

Thereafter, the dyed product was washed with water and dried to obtain a deep, vivid and durable scarlet dyed product.

This dyed product had a uniform density and no aggregates such as specks were observed.

In Comparative Example Example 2, 4 having a novel time-determined crystal structure,
Instead of 6-dibromo-2-[4-{N,N-di(acetoxyethyl)amino)phenylazo]benzothiazole, the wet cake taken out after diazotization and coupling (the X-ray diffraction pattern of this is shown in Figure 2) When the same procedure was carried out as in Example 2 except for the same procedure as in Example 2, a scarlet dyed product with uneven density and dye aggregates adhering to the surface was obtained.

Example 8 4,6-dibromo-2-(4-(N) obtained by diazotization and coupling in the same manner as in Example 1.

43.8 parts of a wet cake of N-di(acetoxyethyl)amino)phenylazo]benzothiazole (solid content: IP-17.5m) was added to 100 parts of monochlorobenzene, and heated to 100°C for 8 hours while stirring for 8 hours. , remove monochlorobenzene by steam distillation, filter and wash to obtain 35.0 parts of wet cake (solid content: 17.5 parts).
Department) was obtained.

The X-ray diffraction pattern of the crystal thus obtained was the same as that in FIG. 1, and when it was dyed in the same manner as in Example 2, good dyeing results were obtained as in Example 2.

Example 4 4,6-dibromo-2-(4-(N) obtained by diazotization and coupling in the same manner as in Example 1.

48.8 parts of a wet cake of N-di(acetoxyether)amino)phenylazo]benzothiazole (17.5 parts in terms of solid content) was suspended in 500 parts of water, and 50 parts of acetic acid was suspended in 500 parts of water.
of the mixture was added and heat treated at 90° C. for 2 hours with stirring. After cooling, filter and wash to make wet cake 83.3
(solid content equivalent: 17.8 parts). The X-ray diffraction pattern of this product was similar to that shown in FIG.

When the thus obtained crystals were dyed in the same manner as in Example 2, good dyeing results were obtained as in Example 2.

Example 5 In Example 4, 15 parts of a formalin condensate of naphthalene sulfonic acid was added instead of 50 parts of acetic acid, and the other points were the same as in Example 8. The obtained crystal was the same as that shown in Figure 1. When this material was dyed in the same manner as in Example 2, good dyeing results similar to those in Example 2 were obtained.

Example 6 In Example 4, 5 parts of polyvinylpyrrolidone was added in place of 50 parts of acetic acid, and the other points were the same as in Example 8. shows,
When this material was used for dyeing in the same manner as in Example 2, good dyeing results were obtained as in Example 2.

Example 7 In the same manner as in Example 1, 4,6-dibromo-2-aminobenzothiazole was diazotized in sulfuric acid to obtain N.

After coupling by adding cold to a methanol solution of N-di(acetoxyethyl)aniline, 500 parts of water was added and the pH was set to 6.8 with an aqueous sodium hydroxide solution.
The mixture was stirred and heat-treated at ℃ for 4 hours. After cooling, filter and wash to obtain 4,6-dibromo-2 having a specific crystal structure.
-1:4-(N.

84.1 parts of a wet cake of N-di(acetoxyethyl)amino)phenylazo]benzothiazole (17.2 parts in terms of solid content) was obtained.

The X-ray diffraction pattern of the crystal thus obtained was the same as that shown in FIG. 1, and when it was dyed in the same manner as in Example 2, good dyeing results were obtained as in Example 2.

[Brief explanation of the drawing]

Figure 1 shows the X-ray diffraction diagram of the monoazobenzothiazole compound having the crystal structure of the present invention, and Figure 2 shows the X-ray diffraction diagram of the monoazobenzothiazole compound having 11 crystal structures obtained by coupling. This is what is shown. In the figure, the horizontal axis represents the diffraction angle (2θ; α for Cu−), and the vertical axis represents the relative intensity of the diffraction lines.

Claims (3)

[Claims] (1) Diffraction angle (2θ; Cu-Kα) 5.65° and 2
Showing strong reflection at 5.37°, 10.74°, 16.8
4,6-dibromo-2-[4-{N,N
-di(acetoxyethyl)amino}phenylazo]benzothiazole. (2) A monoazobenzothiazole compound obtained by coupling diazotized 4,6-dibromo-2-aminobenzothiazole and N,N-di(acetoxyel)aniline in an aqueous medium or an organic solvent. Or the diffraction angle (2θ; Cu-K
α) Shows strong reflections at 5.65° and 25.87°,
10.74°, 16.89°, 18.91°, 21.6
4,6-dibromo-2-[4-{N,N-di(acetoxyethyl)amino}phenylazo with a crystal structure characterized by an X-ray diffraction pattern showing moderate reflections at 8° and 23.48° ]Production method of benzothiazole. (3) Diffraction angle (2θ; Cu-Kα) 5.65° and 2
Showing strong reflection at 5.37°, 10.74°, 16.8
9°, 18.91°, 21.68° and 23.48°
4,6-dibromo-2-[4-{N,
A method for dyeing hydrophobic fiber materials, characterized in that N-di(acetoxyethyl)amino}phenylazo]benzothiazole is used.