JPH09111143A - Monoazo pyridone dye mixture and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a yellow monoazo pyridone dye mixture which can dye well even under severe conditions at a high temp. SOLUTION: This dye mixture comprises a monoazo dye represented by the formula [I] wherein R is H and a monoazo dye represented by the same formula wherein R is Cl in a wt. ratio of (1:1)-(1:4), has a crystal modification characterized by an X-ray diffraction diagram (CuKα) having a strong peak at a diffraction angle (2θ) of 9.0 deg., medium peaks at diffraction angles of 7.4 deg., 10.1 deg., and 23.8 deg. and weak peaks at diffraction angles of 6.2 deg. and 15.1 deg.C, and is produced by diazotizing a mixture of 2-nitroaniline and 4-chloro-2-nitroaniline in a wt.ratio of (1:1)-(1-4) and coupling the resultant diazo compd. with 1-(2- ethylhexyl)-3-cyano-6-hydroxy-4-methylpyrrolidone.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a monoazo dye, and more specifically, a yellow pyridone monoazo dye having a novel crystal modification capable of uniformly dyeing polyester fibers and the like even at high temperature and under severe conditions. The present invention relates to a mixture and a manufacturing method thereof.

[0002]

2. Description of the Related Art In recent years, various rationalizations have been made in the dyeing process in the dyeing industry. For example, when polyester fibers are dyed with a disperse dye, a jet dyeing process is used for cloth and a cheese dyeing process is used for yarn. The method or package dyeing method is widely used.

These dyeing methods are methods in which a dense fiber layer in which a number of fibers are wound is made stationary and the dye dispersion is forcibly circulated in the fiber layer for dyeing. As described above, it is required that the dye particles dispersed in the dyeing bath are fine particles and that the dispersion stability in the dyeing bath is excellent. If the dye particles become large, the filter phenomenon of the dye particles occurs due to the fiber layer, 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. Therefore, problems such as deterioration in fastness such as abrasion resistance will occur.

Accordingly, the dye used in such a dyeing method has good dispersibility in a dyeing bath, and its dispersibility does not decrease in a wide temperature range from room temperature to a high temperature at which actual dyeing occurs. is necessary. However, in general,
When the dyeing bath is heated to a high temperature, the dispersibility of the dye tends to decrease, and as a result, the agglomerated dye adheres to the surface of the article to be dyed in the form of a filtration residue as described above, and also in many layers. Dyeing densities differ between the outer layer part and the inner layer part of the overlapped dyed products, and dyeing products of uniform density cannot be obtained.

Particularly, recently, from the viewpoint of resource saving and energy saving, (1) a low bath ratio of the dyeing bath (the ratio of the dyeing solution: the dyeing solution is reduced from 1:30 to 1:10), (2) the dispersant Lower usage ratio (dye cake: dispersant ratio 1: 3 to 1: 1
And (3) further increasing the temperature of the dyeing conditions for a shorter time (1 hour at 130 ° C. to 0.5 hour at 135 ° C.)
Although the dyeing conditions are shifting to harsh conditions, all of these conditions adversely affect the dispersion stability of the dye,
Even in the case of dyes which have relatively good dispersion stability by the conventional dyeing method, there are many cases where the dispersion stability becomes poor under more severe recent dyeing conditions.

For example, the pyridone type monoazo dye represented by the general formula [I] in which R is --H is:
Known by the Chemical Substances Control Law (5) -5289, the diffraction angle (2
θ) X-ray diffractogram (CuK) showing a strong peak at 7.4 ° and an intermediate peak at 8.1 °, 10.1 ° and 26.3 °.
It has a crystal modification characterized by α). Further, the pyridone-based monoazo dye represented by the general formula [I] in which R is —Cl is known by the Chemical Substances Control Law (5) -5933 and has a strong peak at a diffraction angle (2θ) of 9.6 °.
Furthermore, it has a crystal modification characterized by an X-ray diffraction pattern (CuKα) showing intermediate peaks at 7.2 °, 23.2 ° and 26.2 °. These dyes are obtained by diazotizing a diazo component and coupling reaction with the coupling component according to a conventional method. These dyes are
When used alone, the polyester fibers can be uniformly dyed under the conventional mild dyeing conditions, and the various fastnesses are excellent. However, when dyeing at high temperature as described above under severe conditions,
The dispersibility of the dye is markedly reduced, and it is extremely difficult to obtain a dyed product having a uniform dyeing density.

Further, these dyes also have a problem in compatibility with various dyeing assistants. For example, Glauber's salt (Na ₂ SO ₄ )
The high temperature dispersion stability in the presence is extremely poor, and therefore when dyeing a polyester / cotton blend with a reactive dye or the like in the presence of Glauber's salt, uneven dyeing occurs. Furthermore, even when using a dye in combination, color blurring from the point of compatibility with the compounded dye,
There is a drawback that uneven dyeing occurs.

[0008]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks and provides a dye capable of excellent dyeing under high temperature and severe conditions. As a result of intensive studies aimed at eliminating the above-mentioned drawbacks, the present inventors have found that in the above-mentioned general formula [I], a mixture containing two types of pyridone-based monoazo dyes having different groups represented by R in a specific ratio is: It has been found that these two types of pyridone-based monoazo dyes have novel crystal modifications different from the respective crystal modifications, and that the dye mixture has good dispersion stability at high temperature and under severe dyeing conditions. Further, the stability of the dispersed state of the dye mixture in the high temperature dyeing bath has a significant relationship not only with the size of the dye particles but also with the crystal modification, and when the dye mixture having the above novel crystal modification is used, For the first time, the inventors have found that the dispersion stability of a dye mixture in a high-temperature dyeing bath can be achieved and reached the present invention.

[0009]

That is, the present invention relates to a monoazo dye represented by the general formula [I] in which R is --H, and
The weight ratio of the monoazo dye in which R is -Cl is 1: 1.
-1: 4 and a strong peak at a diffraction angle (2θ) of 9.0 °, an intermediate peak at 7.4 °, 10.1 ° and 23.8 °, and further at 6.2 ° and 15.1 °. Pyridone-based monoazo dye mixture with a crystalline modification characterized by a weak peak X-ray diffractogram (CuKα) and 1: 1 of 2-nitroaniline and 4-chloro-2-nitroaniline
~ 1: 4 (weight ratio) The mixture was diazotized to give 1-
The gist is a method for producing the pyridone-based monoazo dye mixture, which comprises coupling reaction with (2-ethylhexyl) -3-cyano-6-hydroxy-4-methylpyrrolidone.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. A dye mixture comprising two kinds of pyridone dyes represented by the above general formula [I] of the present invention and having a novel crystal modification is, for example, a diazo component such as 2-nitroaniline and 4-chloro-2-nitro. 1: 1 weight ratio with aniline
After mixing in a ratio of ˜1: 4, diazotization is carried out by a conventional method, and this is then subjected to a pyridone-based coupler at a temperature of −5 to 15 ° C., preferably 0 to 10 ° C. in a methanol aqueous medium for 0.5 to 15 hours. It is produced by a coupling reaction with certain 1- (2-ethylhexyl) -3-cyano-6-hydroxy-4-methylpyrrolidone. The cake of the dye mixture obtained by precipitation and separation from the reaction mixture after the coupling reaction is washed with water and dried by a conventional method.

Next, the crystal modification of the dye mixture of the present invention and the dye represented by the formula (I) wherein R is --H and R
Each crystal modification of the dye represented by --Cl will be described with reference to the drawings. 1 to 3 are X-ray diffraction diagrams in which the state of diffraction by CuKα rays in the powder X-ray diffraction method is recorded using a proportional counter, the horizontal axis indicates the diffraction angle (2θ), and the vertical axis indicates the diffraction intensity. . FIG. 1 shows a novel crystal modification of the dye mixture according to the invention, in particular a strong peak at a diffraction angle (2θ) of 9.0 °, 7.4 °, 10.1.
Intermediate peaks at ° and 23.8 °, then at 6.2 ° and 1
It has a weak peak at 5.1 °. 2 shows the crystal modification of the dye represented by R in the general formula [I], and FIG. 3 shows the crystal modification of the dye represented by R in the general formula [I]. It is clearly different from the crystal modification of FIG. The X-ray diffraction diagram of the crystal modification of the dye mixture of the present invention shows that R in the general formula [I] is represented by -H and R in the general formula [I].
Is not obtained by mixing a dye represented by --Cl, and the mixture produced by subjecting the diazo compound obtained by mixing the diazo component in a specific ratio by the production method of the present invention to a coupling reaction has a unique characteristic. It is a characteristic.

The diffraction angles by the X-ray diffraction method are always the same with an error of about ± 0.1 ° if they are of the same crystal type, and these drawings clearly show the difference in crystal transformation. ing. The behavior of the monoazo dye at the time of dyeing is different due to this difference in crystal type, and in the case of the dye mixture having the crystal modification of the present invention, good dyeing can be achieved even if a dyeing method is employed at high temperature and under severe conditions. You can do it.

The fibers which can be dyed with the dye mixture of the present invention include polyethylene terephthalate, polyester fibers made of polycondensation of terephthalic acid and 1,4-bis- (hydroxymethyl) cyclohexane, cotton, wool, etc. Examples include a mixed-spun product and a mixed-woven product of the natural fiber and the polyester fiber. In order to dye polyester fibers using the dye mixture of the present invention, a dye can be prepared by a conventional method using a condensate of naphthalenesulfonic acid and formaldehyde, a higher alcohol sulfate ester, a higher alkylbenzene sulfonate, or the like as a dispersant. Dyeing or printing can be performed with a dyeing bath or a printing paste prepared by dispersing in a medium. Further, for example, in the case of dip dyeing, a dyeing treatment method such as the high temperature dyeing method, the carrier dyeing method, and the thermosol dyeing method described above can be applied,
Moreover, even if severe dyeing conditions are adopted by these methods,
Since the dye mixture of the present invention is excellent in dispersion stability, polyester fibers or a blended product of them and other fibers can be dyed well. Specifically, polyester fiber or the like is dyed at a temperature of 125 to 140 ° C. and a dye bath ratio of 15
It is also possible to perform exhaust dyeing in an aqueous medium in the presence of a dispersant under harsh conditions such that the dispersant is used in an amount of 3 times or less, and the use ratio of the dispersant to the dye is 3 times or less.

In some cases, if an acidic substance such as formic acid, acetic acid, phosphoric acid or ammonium sulfate is added to the dyeing bath,
Even better results are obtained. Further, the mixture of the dyes represented by the above-mentioned general formula [I] of the present invention may be used in combination with other dyes, and by blending the dyes with each other, good results such as improvement in dyeability may be obtained in some cases.

[0015]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 (Production Example of Dye Crystals) To 3.8 g of 98% sulfuric acid, 6.3 g of 43% nitrosylsulfuric acid was added, and 1.2 g of 2-nitroaniline and 4-chloro-under stirring at 20 to 30 ° C. 2.1 g of 2-nitroaniline
Was gradually added to carry out diazotization to obtain a diazotized solution.
Then, 1- (2-ethylhexyl) -3-cyano-6-
Hydroxyl-4-methylpyridone (5.2 g) was dispersed in 80% methanol water (210 ml) at 5-8 ° C., sodium acetate trihydrate (16.6 g) and urea (0.25 g) were added, and the diazotized solution was then added. Was added dropwise at 0 to 5 ° C., the mixture was stirred at the same temperature for 10 hours, and the precipitated crystals were separated by filtration, washed with water and dried, and in the general formula [I] shown above, R was —H and —Cl.
6.4 g of yellow crystals of a mixture of dyes represented by When the powder of the dye mixture obtained by this reaction was analyzed by the X-ray diffraction method, it was found to be the crystal modification shown in the X-ray diffraction diagram of FIG.

Test Example 1 (hot filtration test) 0.5 g of the crystal modification dye mixture obtained in Example 1 above
Was refined with 0.5 g of a naphthalene sulfonic acid-formaldehyde condensate and 0.5 g of a higher alcohol sulfuric acid ester, which was then added to water 20 containing 0.4 g of ammonium sulfate.
Dispersed in 0 ml. The dispersion was heated, treated at 130 ° C. for 1 hour, then allowed to cool, and suction filtered at 90 ° C.
The residue on the filter cloth (cotton broad) was judged and the high temperature dispersibility was evaluated. In addition, the same test was carried out by using the dye represented by the general formula [I] in which R represents —H alone, and the test results obtained when the dye represented by R represents —Cl alone were classified into the second grade. And both were inferior.

Use Example 1 (Dyeing Example) 1.5 g of the novel crystal modification dye mixture obtained in Example 1 above, 1.5 g of naphthalene sulfonic acid-formaldehyde condensate and 1.5 of higher alcohol sulfate ester
The dyeing bath was prepared by pulverizing with g and dispersing this in 700 ml of water. 100g polyester fiber in this dyeing bath
Was dipped, dyed at 135 ° C. for 30 minutes, and then soaped, washed with water and dried. As a result, the dispersibility of the dye was good and the dyed cloth was dyed uniformly. The obtained dyed fabric is yellow and has a light fastness grade of 5 to 6 and a rub fastness of 4
It was a good grade of -5. The above general formula [I]
In the above, when a dye represented by R is —H and a dye represented by R is —Cl are used alone and dyed in the same manner, a slightly uneven dyeing fabric is obtained, and the abrasion resistance is 4 -It was class.

[0019]

The pyridone-based monoazo dye mixture having a specific crystal modification of the present invention has a high temperature, and for example, the ratio of the dyeing material to the dyeing liquid is 1: 7 to 10, and the ratio of the dye cake to the dispersant is. Even under severe dyeing conditions such as 1: 1 and dyeing conditions of 135 ° C. for 0.5 hours, the dispersion stability is very good, and the obtained 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 the drawings]

FIG. 1 is an X-ray diffraction diagram of a crystal modification of a pyridone-based monoazo dye mixture 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 a crystal modification of a dye represented by the general formula [I] where R is —H, in which the horizontal axis represents the diffraction angle (2θ) and the vertical axis represents the diffraction intensity. .

FIG. 3 is an X-ray diffraction diagram of a crystal modification of a dye represented by the general formula [I] in which R is —Cl, wherein the horizontal axis represents the diffraction angle (2θ) and the vertical axis represents the diffraction intensity. .

Claims (2)

[Claims] 1. A monoazo dye in which R is —H and a monoazo dye in which R is —Cl in the following general formula [I] has a weight ratio of 1: 1 to 1: 4 and a diffraction angle. (2θ) Strong peak at 9.0 °, 7.4 °, 10.1 °
And intermediate peaks at 23.8 °, and further 6.2 ° and 15.
A pyridone-based monoazo dye mixture having a crystal modification characterized by an X-ray diffractogram (CuKα) showing a weak peak at 1 °. Embedded image 2. 2-Nitroaniline and 4-chloro-2-
It is characterized in that a mixture of nitroaniline of 1: 1 to 1: 4 (weight ratio) is diazotized, and this is subjected to a coupling reaction with 1- (2-ethylhexyl) -3-cyano-6-hydroxy-4-methylpyrrolidone. The method for producing the pyridone-based monoazo dye mixture according to claim 1.