JPS62220560A - Monoazo dye - Google Patents

Abstract

NEW MATERIAL:A monoazo dye in a crystal form, expressed by formula I and characterized by an X-ray diffraction pattern (CuKalpha) showing one strong peak at 25.0 deg. diffraction angle (2theta), two peaks of medium intensity at 7.2 deg. and 13.1 deg. and further two weak peaks at 6.4 deg. and 23.2 deg.. USE:A dye, capable of dyeing polyester fibers, etc., to yellow color and uniformly dyeing even at a high temperature and under severe condition and having improved color fastness to light and rubbing. PREPARATION:For example, a compound expressed by formula II is diazotized and subjected to coupling reaction with a coupling component expressed by formula III in an aqueous medium at 0-10 deg.C for 30min-10hr.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to monoazo dyes, and more specifically, to a novel crystalline form that can uniformly dye polyester fibers, etc. even under high temperature and harsh conditions. It is related to a yellow monoazo dye.

(Conventional technology) In recent years, various methods have been streamlined in the dyeing industry.1 For example, when dyeing polyester fibers using disperse dyes, the jet dyeing method, which dyes a large amount of hawk fibers at once, is often adopted. Examples of widely used methods include beam dyeing, cheese dyeing, and package dyeing.

These dyeing methods are dyed by forcibly circulating the dye dispersion in a dense layer of stationary fibers, so the dye particles dispersed in the dye bath are more concentrated than ever before. They are required to be fine particles and to have excellent dispersion stability in a dye bath. In other words, if the dye particles become large, the fiber layer may cause the dye particles to overflow, resulting in poor penetration of the dye into the interior of the fiber, dyeing the inner layer or outer layer darker or lighter due to adhesion of aggregates, or dyeing only the shallow part of the fiber. Problems such as a decrease in fastness such as friction fastness due to the adhesion of Therefore, the dye used in this dyeing method must have good dispersion in the dye bath and must not lose its dispersibility over a wide temperature range from room temperature to the high temperature at which actual dyeing occurs. It becomes.

However, in general, when the dye bath is heated to a high temperature, the dispersibility of the dye in the dye bath often tends to decrease, and as a result, the aggregated dye forms an excessive 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 dyeing density will be different between the outer layer and the inner layer, making it impossible to obtain a dyed product with a uniform density.

liquid ratio from l:30 to l:lo), ■reducing the dispersant usage ratio (for example, decreasing the dye cake to dispersant ratio from l:3 to l:l), and ■dying conditions. Further short-term temperature increase (e.g. from 3oC x 1 hour/
Jj℃×O0! Dyeing conditions are becoming more severe, such as 'shortening of time, high temperature, and shortening of time. Moreover, all of these harsher dyeing conditions have a disadvantageous effect on the dispersion stability of dyes, so even if disperse dyes have relatively good dispersion stability using conventional dyeing methods, Recent streamlined dyeing methods, which are more stringent, often result in poor dispersion stability.

That is, for example, the pyridone azo monoazo dye represented by the following structural formula [I], whose structure itself is included in the claims of British Patent No. 1216,093, is obtained by coupling a diazo component and a coupling component according to a conventional method. It is obtained by a manufacturing method that involves a ring reaction. Furthermore, when used under conventional, mild dyeing conditions, this monoazo dye dyes polyester fibers uniformly.
The dyed product obtained has excellent mystery fastness.

(Problems to be Solved by the Invention) However, when the conventional monoazo dye represented by the forefoot structural formula CD is used for dyeing polyester fiber under the recent streamlined high temperature and harsh dyeing conditions as described above, However, there was a problem in that the dispersibility of the dye was significantly reduced and it was extremely difficult to obtain a dyed product with uniform dye density. In addition, the conventional dyes have problems in compatibility with various dyeing aids, for example, they have extremely poor high-temperature dispersion stability in the presence of mirabilite (N-so4), and therefore have poor reactivity with mirabilite-containing dyes. When dyeing polyester/cotton blended products in combination with dyes, etc., not only will uneven dyeing occur, but also when blending and using dyes, there will be problems with color play and unevenness due to compatibility with the blended dyes. There was a problem that level dyeing occurred.

The present invention aims to provide a novel monoazo dye that can solve the above-mentioned conventional problems.

(Means for Solving the Problems) As a result of intensive studies to achieve the above object, the present inventors found that the pyridone azo monoazo compound represented by the forefoot structural formula (1) has at least the following types of crystal forms. exists,
One is a crystalline form that does not have very good dispersion stability under high-temperature dyeing conditions, and the other is a crystalline form that has very good dispersion stability even at high temperatures and even under harsh dyeing conditions. In addition, the dispersion stability of the cake obtained by ordinary synthesis reactions is not determined solely by the size of the dye particles, but is significantly related to the crystal form mentioned above. The present invention was achieved based on the knowledge that in order to obtain a stable dispersion system for the bath, the objective could only be achieved by using the above-mentioned new compound with a new crystalline form that had not been seen before. It is something. That is, the present invention has a lower He structural formula (1'1), a diffraction angle (,2θ) of about 2 j, one strong peak at about 7.2° and two peaks at 13.10. An X-ray diffraction diagram showing an intensity peak and two weaker peaks at approximately The main theme is dyes.

The monoazo compound having the novel α-type crystal form of the present invention is
It can be obtained as follows.

First, for example, a compound represented by the following structural formula [■] is diazotized by a conventional method, and then a compound represented by the following structural formula [old]
+SIO time coupling reaction to synthesize a monoazo compound of the forefoot structural formula [I]. The monoazo compound cake obtained by this synthesis has a nearly amorphous crystal form (hereinafter referred to as "β-type crystal form"). On the other hand, in the present invention, this cake is further treated under specific conditions to form α-type crystals. In this case, the treatment method under specific conditions is to disperse the β-type crystal cake in, for example, an aqueous medium, in which the main ingredients are a formaldehyde condensate of diysinaphthalene sulfonic acid and sodium lignin sulfonate. 60 to 130°C, preferably 10 to 130°C in the presence of a dispersant such as a concentrate of certain sulfide pulp waste liquid
100°C f) temperature for 0.3r to 30 hours, preferably /-10 hours, or (ii) methanol;
Dispersed in alcohols such as ethanol or butanol, ethers such as dioxane, organic solvents such as ethylene glycol, glycol ether, etc., at 75 to 100 °C,
Preferably, a method of stirring at a temperature of λO to rO<0>C for approximately o, r-io hours is employed.

(Function) Next, the α-type crystal form of the present invention and the β-type crystal form of the conventional product in the monoazo compound represented by the forefoot structural formula (1) will be explained with reference to the drawings. Figures 1 and 2 are nine X-ray diffraction diagrams obtained by recording the diffraction state of CuKq rays in powder X-ray diffraction using a proportional counter.
The horizontal axis shows the diffraction angle (λθ), and the vertical axis shows the diffraction intensity.

FIG. 1 shows the α-type crystal form, which is a new crystal form of the present invention, and in particular, the diffraction angle (2θ) is about 2 to θ.

It has one strong peak at about 7.2', /J, two strong peaks at 10 degrees, and two weak peaks at about 0,23.2 degrees. FIG. 2 shows a conventional β-type crystal form, which is clearly different from the α-type crystal form shown in FIG. X
The diffraction angle by line diffraction method is, if the crystal form is the same,
±0. The drawings clearly show the difference in crystal form, although they always agree with an error of ./'. Due to this difference in crystal form, the behavior of the monoazo compound during dyeing is different, 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.

Fibers that can be dyed with the monoazo dye of the present invention include polyethylene terephthalate, terephthalic acid (!:/
, 4'-bis-(hydroxymethyl)cyclohexane, and other polycondensates. 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. Dipping or printing can be carried out by adjusting a dyeing bath or printing paste dispersed in an aqueous medium. In addition, for example, in the case of dip dyeing, dyeing processing methods such as high temperature dyeing, carrier dyeing, thermosol dyeing, etc. as described above can be applied.
Moreover, even if these methods use harsh dyeing conditions,
Since the monoazo dye of the present invention has excellent dispersion stability,
Polyester fibers or blended products thereof can be dyed well.

In this case, even better results can be obtained by adding an acidic substance such as formic acid, acetic acid, phosphoric acid, or ammonium sulfate to the dyeing bath.

Furthermore, the monoazo dye represented by the forefoot structural formula (1) of the present invention may be used in combination with other dyes, and good results such as improved dyeing properties may be obtained by combining the dyes with each other.

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

Reference Example 1 Example of forming dye crystals represented by the forefoot structural formula (1) A: First, using 3-nitro-Hiro-I minobenzoic acid-(n) troglu sulfate, diazotization was carried out at 0°C for 2 hours to form a diazo solution. Manufactured.

Also, l, Hiro-dimethyl-3-cyano-6-hydroxycopyridone! ,,j f f water J 00 td
After dispersing K, it was dissolved using 2t% sodium hydroxide and sodium acetate to prepare a coupling solution.

Add the previously obtained diazo liquid to this coupling solution at 0.
pH ψ~ with hydrochloric acid and sodium hydroxide solution at −J°C! The coupling reaction was carried out by dropwise addition while maintaining the temperature at
%! , 2f was obtained. Analysis of the monoazo dye powder obtained in this reaction by X-ray diffraction revealed that it was in the β-type crystal form. The X-ray diffraction pattern of the sheep is shown in Figure 2.

Next, the obtained β-type crystal form was dispersed in 20 times the volume of water and stirred at 0-1t°C for 3 hours to effect crystal transformation. After completion of the crystal transition, the crystals were filtered and dried, and the obtained crystals were analyzed by X-ray diffraction, and were found to be α-type crystals as shown in the X-ray diffraction pattern shown in FIG.

Example 1 Monoazo compound 0 in the α-type crystal form obtained in Reference Example 1
．． j f, naphthalenesulfonic acid-formaldehyde condensate 0.21! ? and water ltK containing 0.2 j f of higher alcohol sulfate ester were dispersed to prepare a dyeing bath. When 100f of polyester fibers were immersed in this dyeing bath and dyed at 131°C for 30 minutes, soaping, washing and drying were performed, the dispersibility of the dye was good.
Uniform dyeing of the dyed fabric was achieved. In addition, the obtained dyed fabric was extremely good, with a greenish yellow light fastness of grade A and a friction fastness of grade J.

When a similar dyeing test was conducted using the β-type crystalline monoazo compound in the process of production in Reference Example 1, partial aggregation of the dye occurred in the dye bath, resulting in unevenly dyed fabric. Moreover, the friction fastness is significantly inferior to grade 1.

Example In Example 1, the naphthalene sulfone e-formaldehyde condensate and higher alcohol sulfate were each tripled to 0.7 j f, the water was tripled to 3t, and the dyeing temperature was 130°C for 6Q minutes. , except that it was done using a slightly milder staining method.

It was carried out in the same manner as in Example 1.

As a result, when the α-type crystal form of the present invention was used, good uniform dyeing was achieved as in Example 1, and the resulting dyed fabric had a light fastness of class 6 and a friction fastness! It was in very good condition.

On the other hand, when the conventional β-type crystal form was used, although a slight improvement was observed compared to Example 1, uneven dyeing was still obtained, and the abrasion fastness of the fabric was still unevenly dyed. It was also ranked at a slightly inferior level of 3rd grade.

(Effects of the Invention) As is clear from the above results, the pyridone-based monoazo disperse dye of the present invention, which is novel in that it has an α-type crystal form, is different from the conventional pyridone-based monoazo disperse dye that has a β-type crystal form. Compared to dyes, it has much better dispersion stability, and if it is used to dye polyester fibers, for example, it can maintain dispersion stability under any of the recent streamlined high-temperature and harsh dyeing conditions. It has a remarkable effect of industrial value, in that good uniform dyeing is always carried out, and dyed products with extremely good light fastness/lurk fastness, abrasion fastness, etc. can be obtained.

This is an X-ray diffraction diagram, in which the horizontal axis represents the diffraction angle (2θ) and the vertical axis represents the diffraction intensity.

Patent applicant: Mitsubishi Chemical Industries, Ltd. Representative patent attorney - (1 person) Hot water amazing

Claims (1)

[Claims] (1) The following structural formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] It has one strong peak at a diffraction angle (2θ) of about 25.0°, and one strong peak at a diffraction angle (2θ) of about 7.2° and A monoazo dye that is a crystalline form characterized by an X-ray diffraction pattern (CuKα) showing two moderately intense peaks at 13.1° and two weaker peaks at approximately 6.4° and 23.2°. .