JPH03131664A - Water-insoluble monoazo dye - Google Patents

Abstract

NEW MATERIAL:A compound, expressed by formula I and having a crystal modification characterized by an X-ray diffraction pattern (CuKalpha) exhibiting strongest peaks at about 6.5 deg. and 24.7 deg. diffraction angles (2theta) and further three middle peaks at about 11.2 deg., 16.9 deg. and 26.6 deg. (2theta). USE:A red dye capable of homogeneously dyeing polyester fiber, etc. PREPARATION:A compound expressed by formula II is diazotized and then coupled with a coupler expressed by formula III in an aqueous medium, preferably at -5 to +5 deg.C temperature for 0.5-10hr.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a monoazo dye, and more specifically, a red color having a novel crystal modification that can uniformly dye polyester fibers etc. even under high temperature and harsh conditions. This relates to monoazo dyes.

[Conventional technology]

In recent years, various rationalizations have been made to dyeing methods in the dyeing industry.For example, when dyeing polyester fibers using disperse dyes, Ichikawa uses the liquid jet dyeing method, and for yarns, it uses the cheese dyeing method. Alternatively, there is a puff cage staining method, which is widely used.

In these dyeing methods, the dyeing dispersion is forcibly circulated in a dense interior where stationary fibers are wound in many layers, so the dye particles dispersed in the dyeing bath are They are required to be fine particles and have excellent dispersion stability in a dyeing bath. If the dye particles become large, the filtration phenomenon of the dye particles will occur through the fiber layer, resulting in poor penetration of the dye into the fibers, dyeing of the inner or outer layer in deep and light colors due to the adhesion of aggregates, or the dye adhering only to the fiber surface. Problems such as a decrease in fastness such as abrasion resistance occur.

Therefore, it is necessary for the dyes used in such dyeing methods to have good dispersion in the dye bath, and the dispersibility does not deteriorate over a wide temperature range from room temperature to the high temperature at which actual dyeing occurs. .

However, 6. - When the temperature is high in the dye bath during boat fishing, the dispersibility of the dye often tends to decrease, and as a result, the aggregated dye forms a filtration residue on the surface of the dyed object as described above. In the case of a dyed material that adheres to the dyed material and has many layers, the dye density differs between the outer layer and the inner layer, making it impossible to obtain a dyed product with a uniform density.

Particularly recently, from the viewpoint of saving resources and energy, the dyeing bath ratio has been reduced (the ratio of the dyed object:dying solution has been changed from 1:30 to 1:1).
10), ■ Decrease in the usage ratio of dispersant (reduced the ratio of dye cake dispersant from 1:3 to 1=1), and ■
Dyeing conditions are becoming more severe, such as higher dyeing conditions for short periods of time (from 1 hour at 130°C to 0.5 hours at 135°C), but all of these conditions are not sufficient to stabilize the dispersion of dyes. This has a disadvantageous effect on the properties of dyes, so even dyes that have relatively good dispersion stability in conventional dyeing methods often have poor dispersion stability in more severe modern dyeing methods.

For example, the structure of the pyridine-based monoazo dye represented by the following structural formula [1] is known from Japanese Patent Publication No. 61-39347, and its manufacturing method is to combine a diazo component and a coupling component according to a conventional method. Obtained by coupling reaction. This monoazo dye can uniformly dye polyester fibers under conventional mild dyeing conditions, and has excellent fastness properties. However, when dyeing is carried out at high temperatures and under harsh conditions as described above, the dispersibility of the dye is significantly reduced and it is extremely difficult to obtain a dyed product with uniform dye density.

In addition, this dye has problems in terms of compatibility with various dyeing aids, for example, its high-temperature dispersion stability is extremely poor in the presence of mirabilite (Na2S04), and therefore it is used in combination with reactive dyes etc. to dye polyesters. When dyeing cotton blend products in the presence of Glauber's salt, uneven dyeing occurs. Furthermore, when dyes are blended and used, there is a drawback that color blurring and uneven dyeing occur due to compatibility with the blended dyes.

[Problem to be solved by the invention]

The present invention solves the above-mentioned drawbacks and provides a dye that can perform good dyeing even under harsh conditions at high temperatures.

As a result of intensive studies regarding the above-mentioned drawbacks, the present inventors found that there are at least two types of crystal modifications in the pyridine-based monoazo compound represented by the above structural formula (1), one of which is high temperature. The dispersion stability is not very good under the dyeing conditions of the crystal modification, and the cake obtained in the conventional synthesis reaction is the crystal modification.The other is that the dispersion stability is not very good under the dyeing conditions of However, we have discovered that this is a new crystal modification that has very good dispersion stability. Furthermore, the stability of the dispersed state of a dye composition in a high-temperature dye bath has a significant relationship not only with the size of the dye particles but also with the crystal modification. The inventors have discovered that it is possible to achieve dispersion stability of a dye composition in a high-temperature dye bath, and have arrived at the present invention.

[Means to solve the problem]

That is, the gist of the present invention is that the strongest peak is at a diffraction angle (2θ) of about 6.5° and about 24.7'', and furthermore, about 11.216.9
The subject matter is a water-insoluble monoazo dye represented by the following structural formula CI), which has a crystal modification characterized by an X-ray diffraction pattern (CuKα) showing three intermediate peaks at 10° and 26.6″′.

Novel crystal modification of the present invention (hereinafter referred to as α-type crystal modification)
A monoazo compound having the formula can be obtained as follows. For example, a compound represented by the following structural formula (n) is diazotized by a conventional method, and then it is diazotized in an aqueous medium at a temperature of -5 to 15°C, preferably -5 to 5°C to give a 0.5 to 1
A monoazo compound of the above structural formula (1) is synthesized by coupling reaction with a coupler shown by the following structural formula (CDI) for 0 hours.

The monoazo compound cake obtained by this synthesis has an almost amorphous crystal modification (hereinafter referred to as β-type crystal modification), but in the present invention, this cake is further treated under specific conditions to transform it into α-type crystal modification. shall be. This treatment method includes, for example, dispersing β-type crystal modified cake in an aqueous medium, and optionally concentrating sulfide valve waste liquid whose main components are a formaldehyde condensate of naphthalene sulfonic acid and sodium lignin sulfonate. In the presence of a dispersant such as
0 at a temperature of 60-130℃, preferably 80-100℃
．． A method of stirring for 5 to 30 hours, preferably 1 to 10 hours, or (2) alcohols such as methanol, ethanol or butanol, ethers such as dioxane,
Dispersed in an organic solvent such as ethylene glycol or glycol ether, and heated to 15 to 100°C, preferably 20 to 80°C.
A method of stirring at a temperature of about 0.5 to 10 hours is adopted.

Next, α of the monoazo compound represented by the above structural formula CI)
The type crystal modification and the β type crystal modification will be explained with reference to the drawings. Figures 1 and 2 show Cu in the powder X-ray diffraction method.
This is an XM diffraction diagram in which the diffraction state due to Kα rays was recorded using a proportional counter, and the horizontal axis is the diffraction angle (2
θ), and the vertical axis shows the diffraction intensity. FIG. 1 shows the α-type crystal modification, which is a new crystal type of the present invention. In particular, the strongest peak is at a diffraction angle (2θ) of about 6.5° and about 24.76°, and the strongest peak is at a diffraction angle (2θ) of about 6.5° and about 24.76°. 2”, 16.9’ and 26.
It has three intermediate peaks at 6°. FIG. 2 shows the conventional β-type crystal modification, which is clearly different from the α-type crystal modification shown in FIG.

The diffraction angles determined by X-ray diffraction always match with an error of about ±0.1e if they are of the same crystal type, and
These figures clearly show the differences in crystal modifications. Due to this difference in crystal type, the behavior of the monoazo compound during dyeing differs, and in the case of the present invention, it is possible to
Even if dyeing methods are used under harsh conditions, good dyeing can be achieved.

Examples of fibers that can be dyed with the pyridine-based monoazo dye of the present invention include polyester fibers made of polyethylene terephthalate, polycondensates of terephthalic acid and 1,4-bis-(hydroxymethyl)cyclohexane, and cotton, wool, etc. Examples include blended products and mixed fiber products of natural fibers and polyester fibers. In order to dye polyester fibers using the monoazo dye of the present invention, a condensate of naphthalene sulfonic acid and formaldehyde, a higher alcohol sulfate ester, a higher alkylbenzene sulfonate, etc. are used as a dispersant in a conventional manner in an aqueous medium. Dyeing or printing can be carried out by preparing a dyeing bath or printing paste in which the dye is dispersed. In addition, for example, in the case of dip dyeing, dyeing methods such as the above-mentioned high temperature dyeing method, carrier dyeing method, thermosol dyeing method, etc. can be applied, and furthermore,
Even if harsh dyeing conditions are employed in these methods, the monoazo dye of the present invention has excellent dispersion stability, so polyester fibers or blends thereof can be dyed satisfactorily. Specifically, polyester fibers are dyed at a temperature of 12
It is also possible to perform exhaust dyeing in the presence of a dispersant in an aqueous medium under harsh conditions where the dye bath ratio is 15 times or less and the ratio of dispersant to dye is 3 times or less by weight at 5 to 140°C. .

In addition, 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 in some cases.

Furthermore, the monoazo dye represented by the above structural formula CI) used in the method of the present invention may be used in combination with other dyes, and good results such as improved dyeability may be obtained by combining the dyes with each other.

(Example) Next, the present invention will be explained in more detail with reference to Examples.

Example 1 [Example of dye crystal molding] 3.2 g of 2-anilino-3-cyano-4-methyl-6=(γ-methoxypropylamino)-pyridine was mixed with 200 I! of methanol. i' at 0 to 3°C to obtain a coupling component solution.

1.7 g of 2-chloro-4-nitroaniline was dispersed in 201 IIl of a 5% aqueous hydrochloric acid solution, and 5 ml of a 15% aqueous sodium nitrite solution was added at 0°C to perform diazotization to obtain a diazotized solution. This diazotized solution was added dropwise to the coupling component solution at 0 to 5°C, stirred at the same temperature for 1 hour, and the precipitated crystals were separated, washed with water, and dried to form a crystalline product represented by the structural formula (1). 4.0 g of red crystals of the compound were obtained. When the monoazo dye powder obtained in this reaction was analyzed by X-ray diffraction, it was found to be a β-type crystal modification as shown in the X-ray diffraction diagram of FIG.

Next, the obtained β-type crystals were dispersed in 10 times the volume of water and stirred at 90 to 95° C. for 3 hours to effect crystal transition. After the crystal transition, the obtained crystals are passed through and dried.
When analyzed by a ray diffraction method, it was found to be α-type crystal modification as shown in the X-ray diffraction diagram of FIG.

Test Example 1 [Staining Example] 0.2 g of the α-type crystal modified monoazo compound obtained in Example 1 was mixed with 0.2 g of naphthalene sulfonic acid-formaldehyde condensate and 0.2 g of higher alcohol sulfate ester.
A dyeing bath was prepared by dispersing it in 1 liter of water containing 2 g.

100g of polyester fiber was immersed in this dyeing bath,
After dyeing at 5° C. for 30 minutes, soaping, washing with water, and drying were performed, the dispersibility of the dye was good, and the dyed fabric was uniformly dyed.

Furthermore, the obtained dyed fabric had a bluish red color, and had good light fastness of 6th grade and abrasion fastness of 5th grade.

In addition, when a similar dyeing test was carried out using the monoazo compound of β-type crystal modification in the middle of production in the above production example, partial aggregation of the dye occurred in the dye bath, resulting in unevenly dyed fabric and poor abrasion resistance. The fastness was grade 1, which was significantly inferior.

Test Example 2 [Dyeing Example] In Test Example 1, the naphthalene sulfonic acid-formaldehyde condensate and higher alcohol sulfate were each tripled to 0.75 g, the water was tripled to 31 g, and the dyeing conditions were 130°C and 60 g. Dyeing was carried out in the same manner as in Test Example 1, except that the dyeing was carried out using a slightly milder dyeing method. As a result, in the α-type crystal modification of the present invention, good dyeing was achieved in the same manner as in Test Example 1. The dyed fabric was also good, with a light fastness of 6th grade and a rub fastness of 5th grade. On the other hand, when β-type crystal modification was used, a slight improvement was observed compared to Test Example 1, but uneven dyeing was still obtained, and the abrasion fastness was grade 3. there were.

〔Effect of the invention〕

The water-insoluble monoazo dye having a specific crystal modification of the present invention can be used at high temperatures and under dyeing conditions such as a dyeing material:dying solution ratio of 1:10, a dye cake:dispersant ratio of 1:1, and dyeing conditions of 135%. The dispersion stability is very good even under severe dyeing conditions such as 0.5 hours at °C, and the dyed fabric obtained has excellent light fastness and abrasion fastness. Therefore, the dye of the present invention is very useful from the viewpoint of resource and energy saving.

[Brief explanation of the drawing]

Figure 1 is an X-ray diffraction diagram of the α-type crystal modification of the monoazo compound obtained in the example of the present invention, and Figure 2 is an X-ray diffraction diagram of the β-type crystal modification of the monoazo compound obtained in the examples of the present invention. (2θ
), and the vertical axis represents the diffraction intensity.

Claims (1)

[Claims] (1) The strongest peaks are at diffraction angles (2θ) of approximately 6.5° and 24.7°, and further at approximately 11.2°, 16.9°, and 26°.
．． X-ray diffraction diagram showing three intermediate peaks at 6° (CuKα
) has the following structural formula [
I 〕 ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ Water-insoluble monoazo dye indicated by 〔I〕.