JPH08311364A - Water-insoluble blue monoazo dye - Google Patents

Abstract

PURPOSE: To obtain a new compound capable of uniformly dyeing a polyester fiber, etc., even under severe conditions. CONSTITUTION: This compound of the formula has a crystal structure having an X-ray diffraction pattern (CuKα) manifesting relatively strong peaks at 9.4, 25.6 and 26.6 deg. diffraction angles (2θ) and further medium peaks at 6.4, 13.1, 22.2 and 28.1 deg. diffraction angles. The compound of the formula is obtained by diazotizing a 2-amino-3-cyano-5-nitrothiophene, then coupling the resultant diazo compound with 3-methoxyacetylamino-N,N-dimethylaniline, dispersing the reactional product in an aqueous medium and treating the prepared dispersion at 60-130 deg.C for 0.5-30hr.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In recent years, various dyeing methods have been rationalized in the dyeing industry. For example, when dyeing polyester fibers with a disperse dye, a jet dyeing method is used for cloth and a cheese dyeing method is used for yarn. The dyeing method or the package dyeing method is widely used. 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, dye particles dispersed in a dyeing bath are fine particles. And that the dispersion stability in the dye bath is excellent. That is, when the dye particles become large, the filtration phenomenon of the dye particles occurs due to the fiber layer, and the dye does not permeate into the inside of the fiber, or the inner or outer layer is shaded due to the adhesion of aggregates, and the dye adheres only to the fiber surface. Problems such as a decrease in abrasion resistance will 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. Required. However, in general, when the temperature is raised in a dyeing bath at high temperature, the dispersibility of the dye is apt to decrease, and as a result, the agglomerated dye adheres to the surface of the dyed substance in the form of a filter residue, As for the object to be dyed, which has many layers, the dyeing density is different 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, JP-A-59
The following structural formula [I] described in JP-A-93971

[0005]

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When the dye represented by the formula (1) is produced by simply diazotizing and coupling reaction according to a conventional method as in Example 1 of the publication, it is possible to uniformly dye polyester fibers under the conventional mild dyeing conditions. It is possible and, in addition, various fastnesses can be satisfied to some extent. 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 As a result of intensive investigations by the present inventors regarding the above-mentioned drawbacks, the thiophene-based monoazo compound represented by the structural formula [I] can be obtained by conventional conventional synthetic reactions. We have found a compound having a novel crystal structure, which cannot be obtained with a fixed solid, and has good dispersion stability even under high temperature and severe dyeing conditions.

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 shows relatively strong peaks at diffraction angles (2θ) of 9.4 °, 25.6 ° and 26.6 °, and further 6.4 °, 13.1. ° 2
The following structural formula [I] having a crystal structure characterized by an X-ray diffraction diagram (CuKα) showing intermediate peaks at 2.2 ° and 28.1 °

[0011]

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The gist is a water-insoluble blue monoazo dye represented by: The monoazo compound having a novel crystal structure of the present invention is obtained as follows. For example, 2-amino-3-cyano-5-nitrothiophene is diazotized by a conventional method, and then it is -8-10 in a dilute sulfuric acid medium.
C, preferably -5 to 5 C for 0.5 to 15 hours,
3-methoxyacetylamino-N, N which is a coupler
-A monoazo compound of the structural formula [I] shown above is synthesized by a coupling reaction with diethylaniline.

The cake of the monoazo compound obtained by this synthesis has an amorphous structure, but in the present invention, the compound having the above crystal structure is obtained by further treating this cake under specific conditions. As this treatment method, for example, a dye cake having an amorphous structure is dispersed in an aqueous medium, and in some cases, a formaldehyde condensate of naphthalenesulfonic acid,
In the presence of a dispersant such as a concentrate of a sulfite pulp waste liquor containing sodium lignin sulfonate as a main component,
C., preferably at a temperature of 80 to 100.degree. C. for 0.5 to 30 hours, preferably 1 to 10 hours, by stirring, or methanol, ethanol, butanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether. Etc. are dispersed in an organic solvent such as alcohols such as, ethers such as dioxane and tetrahydrofuran, and stirred at a temperature of 15 to 100 ° C., preferably 20 to 80 ° C. for about 0.5 to 10 hours. It Alternatively, a coupling reaction between a diazotization reaction product of 2-amino-3-cyano-5-nitrothiophene and 3-acetoxymethyl-N, N-diethylaniline is carried out in the above organic solvent to give a reaction product of 5 to 5%. Three
The target compound having the above-mentioned crystal structure can also be obtained by stirring at 0 ° C. for about 1 to 10 hours.

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 CuK in the powder X-ray diffraction method.
FIG. 4 is an X-ray diffraction diagram in which a state of diffraction by α rays is recorded using a proportional counter, and the horizontal axis indicates the diffraction angle (2
θ), and the vertical axis represents the diffraction intensity. FIG. 1 shows a novel crystal form of the dye of the present invention, showing relatively strong peaks at 9.4 °, 25.6 ° and 26.6 °, and further 6.4.
Intermediate peaks are shown at °, 13.1 °, 22.2 ° and 28.1 °. FIG. 2 shows the amorphous structure of a conventional dye, 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 ± 0.2 ° if they are of the same crystal type, and these drawings clearly show the difference in crystal form. ing. The behavior of the monoazo compound at the time of dyeing is different due to this difference in crystal form, and in the case of the present invention, good dyeing can be performed even if a dyeing method is employed at high temperature and under severe conditions.

The fibers which can be dyed with the monoazo dye of the present invention include polyethylene terephthalate, polybutylene terephthalate, polyester fibers composed of a polycondensate of terephthalic acid and 1,4-bis- (hydroxymethyl) cyclohexane, or cotton. Examples include mixed-spun products and mixed-woven products of the above polyester fibers with natural fibers such as wool. In order to dye polyester fibers with the monoazo dye of the present invention, a condensate of naphthalenesulfonic acid and formaldehyde, a higher alcohol sulfate ester, a higher alkylbenzene sulfonate or the like is used as a dispersant by an ordinary method in an aqueous medium. Dyeing or printing can be carried out by preparing a dyeing bath or printing paste dispersed in the above. 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 satisfactorily dye polyester fibers or a blended product thereof. Specifically, polyester fibers are dyed at a temperature of 125 to 140 ° C., a dyeing bath ratio is 15 times or less, and the dispersant is used in an aqueous medium under severe conditions such that the dispersant is used in an amount of 3 times or less by weight. It is also possible to perform exhaust dyeing in the presence.

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) 11.8 g of 3-methoxyacetylamino-N, N-diethylaniline was dissolved in 350 ml of a 5% aqueous solution of sulfuric acid to obtain a coupling component. Next, 98% sulfuric acid 4
18.5 g of 43% nitrosyl sulfuric acid was added to 2.9 g,-
With stirring at 5 to 0 ° C., 8.45 g of 2-amino-3-cyano-5-nitrothiophene was gradually added to carry out diazotization to obtain a diazotized solution. This diazotized solution was added dropwise to the coupling component solution at 0 to 5 ° C., the mixture was stirred at the same temperature for 10 hours, the precipitated solid was separated by filtration, washed with water and dried, and represented by the structural formula [I] shown above. 11.7 g of a dark blue compound are obtained. When the powder of the monoazo dye obtained by this reaction was analyzed by an X-ray diffraction method, it was found to be a substance having an amorphous structure shown in the X-ray diffraction diagram of FIG. On the other hand, 11.7 after washing with water
g of the compound was resuspended in 30 times by weight of water, and
The temperature was raised to 0 to 85 ° C., the heat treatment was carried out for 8 hours at this time, the temperature was cooled to room temperature, the precipitated solid was separated by filtration and dried, and the obtained substance was analyzed by an X-ray diffraction method. It was a substance showing the crystal form of the X-ray diffraction pattern.

(Dyeing Example) 0.2 g of the monoazo dye having a crystal structure obtained in the above Production Example was added to 1 liter of water containing 0.2 g of a naphthalenesulfonic acid-formaldehyde condensate and 0.2 g of a higher alcohol sulfate ester. A dispersion was prepared by dispersing. After immersing 100 g of polyester fiber in this dyeing bath and dyeing at 135 ° C. for 30 minutes,
When soaping, washing with water and drying were performed, the dispersibility of the dye was good, and the dyed cloth was dyed uniformly.
Further, the obtained dyed fabric has a Turkish blue color and has a light fastness of 4 to 5
The grade was good, and the abrasion resistance was grade 5. Comparative Example 1 When the monoazo dye having an amorphous structure synthesized in the production example of Example 1 was used to perform the same dyeing as in the dyeing example of Example 1, partial agglomeration of the dye occurred in the dyeing bath, resulting in unevenness. It was a dyed cloth, and the abrasion resistance was extremely inferior to Class 1.

Comparative Example 2 In Comparative Example 1, the naphthalenesulfonic acid-formaldehyde condensate and the higher alcohol sulfate were each tripled to 0.6 g, and water was tripled to 3 liters, and the dyeing condition was 130 ° C. for 60 minutes. As a result of dyeing with a slightly mild dyeing method in the same manner as in Comparative Example 1 except that
Although a slight improvement was observed as compared with Comparative Example 1, only uneven dyeing could be obtained only for the dyed cloth, and the abrasion resistance of the material itself was grade 3. With the dye having a crystal structure of the present invention, good dyeing was possible in the same manner as in Example 1, and the resulting dyed cloth was good in light fastness grade 4 to 5 and abrasion fastness grade 5.

[0021]

INDUSTRIAL APPLICABILITY The water-insoluble blue monoazo dye having a crystal structure of the present invention can be used at a high temperature and, for example, to be dyed:
The dyeing liquid has a very good dispersion stability even under severe dyeing conditions such as a dyeing solution ratio of 1:10, a dye cake: dispersant ratio of 1: 1 and a dyeing condition of 135 ° C. for 0.5 hours. The 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 (5)

[Claims] 1. A relatively strong peak at a diffraction angle (2θ) of 9.4 °, 25.6 ° and 26.6 °, and further 6.4.
The following structural formula [I] has a crystal structure characterized by an X-ray diffraction diagram (CuKα) showing intermediate peaks at °, 13.1 °, 22.2 ° and 28.1 °. A water-insoluble blue monoazo dye represented by. 2. A dyeing method for polyester fibers, which comprises using the water-insoluble blue monoazo dye according to claim 1. 3. 2-Amino-3-cyano-5-nitrothiophene is diazotized and then subjected to a coupling reaction with 3-methoxyacetylamino-N, N-diethylaniline, and the reaction product is dispersed in an aqueous medium. Then 60-130
The method for producing a water-insoluble blue monoazo dye according to claim 1, wherein the treatment is carried out at 0.5 ° C for 0.5 to 30 hours. 4. 2-Amino-3-cyano-5-nitrothiophene is diazotized and then subjected to a coupling reaction with 3-methoxyacetylamino-N, N-diethylaniline, and the reaction product is an alcohol or ether. The method for producing a water-insoluble blue monoazo dye according to claim 1, wherein the water-insoluble blue monoazo dye is dispersed in the solution and treated at 15 to 100 ° C. for 0.5 to 10 hours. 5. 2-Amino-3-cyano-5-nitrothiophene is diazotized and then subjected to a coupling reaction with 3-methoxyacetylamino-N, N-diethylaniline in alcohols or ethers, and further 5 30 ° C
The method for producing a water-insoluble blue monoazo dye according to claim 1, wherein the treatment is carried out for 1 to 10 hours.