JPS63132970A - Monoazo dye blend - Google Patents

Abstract

PURPOSE:To obtain the titled red dye blend having novel crystalline from, capable of uniformly dyeing polyester fibers, etc. even under high-temperature and severe conditions, by mixing respectively specific two kinds of dyes. CONSTITUTION:The objective dye blend consisting of two monoazo dyes of formulas I and II, respectively, in the weight ratio pref. 70/30-30/70 having a crystalline form characterized by such an X ray diffraction pattern (Cu-Kalpha) that two intense peaks are present at diffraction angles (2theta) ca. 22.8 deg. and 26.7 deg., respectively, and also two medium-intensity peaks at ca. 12.6 deg. and 15.6 deg., respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a monoazo dye mixture, and more particularly:
The present invention relates to a red monoazo dye mixture having a novel crystalline form that can uniformly dye polyester fibers etc. even under high temperature and harsh conditions.

(Prior Art) In recent years, various rationalizations of dyeing methods have been carried out in the dyeing industry. For example, when dyeing polyester fibers using disperse dyes, jet dyeing methods are often used to dye a large amount of fibers at once.Among these, widely used examples include beam dyeing, cheese dyeing, package dyeing, etc. There are several methods.

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, when the dye particles become large, a filtration phenomenon of the dye particles occurs through the fiber layer, resulting in poor penetration of the dye into the inside of the fiber, dark/light dyeing of the inner or outer layer due to adhesion of aggregates, or dye adhesion only to the fiber surface. Problems such as a decrease in fastness such as friction fastness occur. 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 will become.

However, in general, when the dye bath is heated to a high temperature, the dispersibility of the dye in the dye bath tends to decrease.

As a result, the agglomerated dye adheres to the surface of the dyed object in the form of filtration residue as described above, and in the case of a dyed object that has many layers, the dyeing concentration differs between the outer layer and the inner layer. A dyed product of uniform density cannot be obtained.

In particular, recently, from the perspective of saving resources and energy, reducing the dye bath ratio (for example, reducing the ratio of dyeing solution to dyeing material to 1:30)
(for example, reducing the dye cake to dispersant ratio from 1:3 to 1:0), reducing the proportion of dispersant used (e.g., reducing the dye cake to dispersant ratio from 1:3 to 1:0).
Furthermore, the dyeing conditions become harsher, such as (1) increasing the dyeing temperature to a higher temperature for a shorter time (for example, reducing the temperature from 130°C x 1 hour to 135°C x 5 hours). It is transitioning. Moreover, such harsher dyeing conditions have a disadvantageous effect on the dispersion stability of the dye.
Even if disperse dyes have relatively good dispersion stability according to conventional dyeing methods, many of them have poor dispersion stability when used in recent streamlined dyeing methods that are stricter than conventional dyeing methods.

For example, benzothiazole-based monoazo dyes represented by the following structural formulas (1) and CI) are included in the claims of Japanese Patent Publication No. 44-30628, and are combined with a diazo component in a conventional manner. Although it is manufactured by a method of coupling reaction with a ring component, when the diazo component is synthesized, products with different introduction positions of chlorine atoms are inevitably produced and mixed, so usually the front claw structural formula [I] It is obtained as a mixture of dyes indicated by and [position]. This monoazo dye mixture, when used under conventional mild dyeing conditions, can uniformly dye polyester fibers and the resulting dyed products have excellent solidity.

(Problems to be Solved by the Invention) However, when polyester fibers are dyed using the above-mentioned conventional monoazo dye mixture under the recent streamlined high-temperature and severe dyeing conditions as described above, the dye There was a problem in that the dispersibility was significantly reduced and it was extremely difficult to obtain a dyed product with uniform dye density. In addition, conventionally, this type of dye has had problems with its compatibility with various dyeing aids, such as extremely poor high-temperature dispersion stability in the presence of glauber's salt (Na2So4), and therefore reactivity with glauber's salt (Na2So4). 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 mixture capable of solving 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 benzothiazole-based monoazo compounds represented by the front nail structural formulas [I] and (1) have at least There are two types of crystal forms, one of which has poor dispersion stability under high-temperature dyeing conditions, and the other with dispersion stability even under high-temperature and more severe dyeing conditions. It has been found that the former is in a very good crystalline form, and that the cake obtained in a conventional synthesis reaction is a crystalline form in which the dispersion stability of the former is not very good. Furthermore, the stability of the dispersed state of the dye composition in a high-temperature dye bath is not determined only by the size of the dye particles, but is significantly related to the crystal form mentioned above, and it is important to obtain a stable dispersion system in the dye bath. The present invention was achieved based on the knowledge that the object could only be achieved by using the above-mentioned new crystal form, which was not available in the past. That is, the present invention is a mixture of dyes represented by the following structural formulas (1) and (1) J , and a diffraction angle (2θ)
Two strong peaks at about 228° and 26,7°, about 1
X showing two medium intensity peaks at 16° and 15.6°
The subject matter is a monoazo dye mixture having a crystalline form (hereinafter referred to as "α-type crystalline form") characterized by a linear diffraction pattern (Cu K& ).

The monoazo dye targeted by the present invention has the front nail structural formula (1)
It is a mixture of monoazo compounds represented by It is determined by the mixing ratio of isomers. The present invention specifies the crystal form of such a dye mixture, which crystal form does not substantially differ even if the mixing ratio is varied within the above-mentioned range.

The monoazo dye mixture having the novel α-type crystal form of the present invention can be obtained as follows.

First, for example, an isomer mixture of dichlorobenzothiazol-2-amine represented by the following structural formulas (1) and [■] is diazotized by a conventional method, and then a compound represented by the following structural formula (V) (coupling component) and in aqueous medium,
By performing a coupling reaction at 0 to 15°C, preferably 0 to 10'C for 30 minutes to 10 hours,
) and (1) are synthesized. The cake of the conventional monoazo dye mixture obtained by this synthesis has a nearly amorphous crystal form (hereinafter referred to as the "β-type crystal form").
That's what it means. ).

On the other hand, in order to obtain the monoazo dye mixture of the present invention, the cake of the monoazo dye mixture having the β-type crystal form obtained above is further treated under specific conditions to transform it into the α-type crystal form. It is necessary to do so. In such a case, the treatment method under specific conditions includes dispersing the β-type crystal cake in an aqueous medium, and optionally dispersing the formaldehyde condensate of naphthalene sulfonic acid. In the presence of a dispersant such as a concentrate of sulfide pulp waste liquid containing lJ sodium geninsulfonate as a main component, at a temperature of 60 to 130°C, preferably 80 to 100°C, for 0.5 to 30 hours, preferably 1 to 10 hours. A method of stirring for a period of time, or (2) dispersing in an organic solvent such as alcohols such as methanol, ethanol or butanol, ethers such as dioxane, ethylene glycol, glycol ether, etc. at 15 to 100°C.
, preferably a method of stirring at a temperature of 20 to 80°C for about 5 to 10 hours at 0°C.

(Function) Next, the α-type crystal form of the present invention and the β-type crystal form of the conventional product in the monoazo dye mixture represented by the front nail structural formula [I] and (1) will be explained with reference to the drawings. Figures 1 and 2
The figure is an X-ray diffraction diagram recorded using a proportional counter to record the diffraction state of CuKw rays in powder X-ray diffraction method, sb, the horizontal axis shows the diffraction angle (2θ), and the vertical axis shows the diffraction intensity. Figure 1 shows the new crystal form α of the present invention.
It indicates a type crystal shape, especially a diffraction angle (2θ) of about 2Z8
It has two strong peaks at about 116° and 26.7°, and two moderate intensity peaks at about 116° and 15.6°. Second
The figure shows the conventional β type crystal form, which is clearly different from the α type crystal form shown in Figure 1. The diffraction angles determined by X-ray diffraction always match with an error of about ±0.1° if they are of the same crystal form, and these drawings clearly show the difference in crystal form. Due to this difference in crystal form, the behavior of the monoazo compound during dyeing differs, and in the case of the present invention, good dyeing can be achieved even if a dyeing method is employed at high temperatures and under harsh conditions.

Fibers that can be dyed with the monoazo dye mixture of the present invention include polyester fibers made of polyethylene terephthalate, polycondensates of terephthalic acid and 1,4-bis-(hydroxymethyl)cyclohexane, and natural fibers such as cotton and wool. Examples include blended products and mixed fiber products of fibers and the above-mentioned polyester fibers. In order to dye polyester fibers using the monoazo dye mixture 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, and an aqueous medium is dyed. Dyeing or printing can be carried out by adjusting the dyeing bath or printing paste dispersed therein. 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 even if harsh dyeing conditions are adopted with these methods, Since the monoazo dye mixture of the present invention has excellent dispersion stability, polyester fibers or blended products thereof can be dyed satisfactorily.

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

Furthermore, the monoazo dye mixture represented by the forenail structural formulas (1) and (1) of the present invention may be used in combination with other dyes, and good results such as improved dyeing properties can be obtained by combining the dyes with each other. There are cases.

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

Reference Example 1 (Manufacturing example of dye mixture crystals represented by front nail structural formulas (1) and (1)) Mass, 5,6-dichloro-2-aminobenzothiazole 2.2f and 6,7-dichloro-2- A mixture of aminobenzothiazole Z2f was diazotized using nitrosyl sulfuric acid in 65% sulfuric acid at 0° C. for 2 hours to produce a diazo solution.

Also, N-ethyl-N-acetoxyethylaniline 4.
1f was dissolved in 2% sulfuric acid to prepare a coupling component solution.

The previously obtained diazo liquid was added dropwise to this coupling component solution at 0 to 2°C to cause a coupling reaction, and
After the reaction was completed by stirring for a period of time, the precipitated crystals were washed with water and dried to obtain red crystals of 7.92%. When the powder of the monoazo dye mixture obtained in this reaction was analyzed by X-ray diffraction, it was found to be in the β-type crystal form. The X-ray diffraction diagram is shown in FIG.

The resulting red dye mixture with the β-type crystal form was then dispersed in 20 times the volume of water and incubated at 90-95°C for 30 minutes.
The mixture was stirred for a period of time to transform the crystals. 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 (Dyeing test under high temperature and harsh conditions) 0.5 f of the monoazo dye mixture having the α-type crystal form of the present invention obtained in Reference Example 1 above was mixed with 0.252 f of the naphthalene sulfonic acid-formaldehyde condensate and A dyeing bath was prepared by dispersing it in water 11 containing 0.25 t of higher alcohol sulfate. 10 polyester fibers in this dyeing bath
When 0 g of the dye was immersed and dyed at 135° C. for 30 minutes, followed by noping, washing with water, and drying, the dispersibility of the dye was good, and the dyed fabric was uniformly dyed.

In addition, the obtained dyed fabric exhibited a bright red color and its fastness was extremely good, with a light fastness of grade 5 and a friction fastness of grade 5.

In addition, when a similar dyeing test was conducted using the monoazo dye mixture having the β-type crystal form in the process of production in Reference Example 1, partial aggregation of the dye occurred in the dye bath, resulting in unevenly dyed fabric. , and the friction fastness was significantly inferior to grade 1.

Example 2 (Conventional dyeing test under somewhat mild conditions) In Example 1, the naphthalene sulfonic acid-formaldehyde condensate and the higher alcohol sulfate were each 0.7 times as large.
59, water was tripled to 32, and the dyeing temperature was 6 at 130℃.
The dyeing was carried out in the same manner as in Example 1, except that a slightly milder dyeing method was used for 0 minutes. .

As a result, when the mixed dye having the α-type crystal form of the present invention was used, good uniform dyeing could be achieved as in Example 1, and the color fastness of the dyed fabric obtained was 5th class light fastness. It had an extremely good friction fastness of grade 5.

On the other hand, when using the mixed dye having the conventional β-type crystal form in the process of production in Reference Example 1, Example 1
Although a slight improvement was seen compared to the case of , a dyed fabric with uneven dyeing was still obtained, and its abrasion resistance remained at a slightly inferior level of grade 3.

(Effects of the Invention) As is clear from the above results, the benzothiazole-based monoazo disperse dye mixture of the present invention, which is novel in that it has an α-type crystal form, is superior to the conventional benzothiazole-based monoazo disperse dye mixture having a β-type crystal form. It has much better dispersion stability than monoazo disperse dye mixtures, and if used for dyeing polyester fibers, for example, it can maintain dispersion stability under any of the recent streamlined high-temperature and harsh dyeing conditions. Therefore, 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, abrasion fastness, etc. can be obtained.

[Brief explanation of the drawing]

FIG. 1 is an X-ray diffraction diagram of the α-type crystal form of the present invention obtained in Reference Example 1, and FIG. 2 is an X-ray diffraction diagram of the same conventional β-type crystal form, in which the horizontal axis represents the diffraction angle (2θ), and the vertical axis represents the diffraction intensity.

Claims (2)

[Claims] (1) For the dye shown by the following structural formulas [I] and [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] consisting of a mixture and diffraction angle (20)
A crystal characterized by an X-ray diffraction pattern (CuKα) showing two strong peaks at about 22.8° and 26.7° and two moderately intense peaks at about 12.6° and 15.6°. A monoazo dye mixture with a shape. (2) The monoazo dye according to claim 1, characterized in that the mixing ratio of the monoazo dyes represented by the structural formulas [I] and [II] is 70:30 to 30:70 by weight. dye mixture.