JPH10183005A - Water-insoluble pyridone-base disazo dye and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an orange pyridone-base disazo dye which can perform good dyeing even at high temps. under severe conditions. SOLUTION: A water-insoluble pyridone-base disazo dye which has a crystal modification characterized in an X-ray diffraction diagram (CuKα) having strong peaks at diffraction angles (2θ) of about 6.9 deg., about 15.4 deg., about 18.8 deg., and about 25.7 deg. and medium peaks at diffraction angles (2θ) of about 12.2 deg. and about 26.7 deg.. This dye is produced by subjecting a coupling product of 4'-(4- hydroxyphenylazo)anilne and 6-hydroxy-1,4-dimethyl-2-oxo-1,2-dihydro-3- pyridinecarbonitrile to condensation with 2,4-difluoro-6-(di-n-butylamino)-1,3,5- triazine in acetone, dispersing the resultant cake in a water-base medium, and stirring the dispersion at 60-150 deg.C for 0.5-30hr to form a β-type crystal modification or by conducting the condensation in N,N-dimethylformamide and putting the resultant condensate in water to precipitate crystals of a β-type crystal modification.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pyridone disazo dye, and more particularly, to an orange pyridone dye having a novel crystal modification capable of uniformly dyeing polyester fibers and the like even under severe conditions at high temperatures. The present invention relates to a disazo dye and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, various dyeing methods have been streamlined in the dyeing industry. For example, when a polyester fiber or a polyester / polyamide mixed fiber is dyed using a disperse dye, a liquid flow dyeing method is used for fabrics. For yarn, cheese dyeing or package dyeing is widely used.

[0003] In these dyeing methods, a dense fiber layer in which a number of layers of fibers are wound is kept stationary, and a dye dispersion is forcibly circulated in the fiber layer for dyeing. As described above, it is required that the dye particles dispersed in the dye bath are fine particles and that the dispersion stability in the dye bath is excellent. If the dye particles become large, the fiber layer causes the dye particles to be filtered, which results in poor dye penetration into the interior of the fiber, or dyeing of the inner or outer layer due to the adhesion of aggregates, or the attachment of the dye only to the fiber surface. Problems such as a decrease in fastness such as rub fastness 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 often tends to decrease, and as a result, the aggregated dye adheres to the surface of the material to be dyed as described above, and in many layers. The overlapping dyeing materials have different dyeing densities in the outer layer portion and the inner layer portion, and a dyed product having a uniform concentration cannot be obtained.

[0005] Particularly recently, from the viewpoints of resource saving and energy saving, (1) lowering the bath ratio of the dyeing bath (reducing the ratio of the material to be dyed to dyeing solution from 1:30 to 1:10), and (2) dispersing agent (Dye cake: dispersant ratio is reduced from 1: 3 to 1: 2)
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 dyes having relatively good dispersion stability in the conventional dyeing method often have poor dispersion stability under severer recent dyeing conditions.

For example, pyridone disazo dyes represented by the structural formula (I) described in claim 1 are disclosed in JP-A-60-25.
No. 2660, which is generally obtained by performing a coupling reaction between a diazo component and a coupling component according to a conventional method. This disazo dye can uniformly dye polyester fibers under conventional mild dyeing conditions, and is also excellent in various fastnesses. However, when dyeing is performed under severe conditions at the high temperature as described above, the dispersibility of the dye is significantly reduced,
It is extremely difficult to obtain a dyed product having a uniform dyeing concentration.

Further, this dye also has a problem in compatibility with various dyeing assistants. For example, the high-temperature dispersion stability in the presence of sodium sulfate (Na ₂ SO ₄ ) is extremely poor, and therefore, it is difficult to use reactive dyes and the like. When dyed in combination with polyester / cotton blends in the presence of sodium sulfate, uneven dyeing occurs. Furthermore, when a dye is used in combination, there is a disadvantage that color blur and uneven dyeing occur due to compatibility with the compound dye.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks and to provide a dye which can perform good dyeing under severe conditions at high temperatures. We have:
As a result of intensive studies on the above disadvantages, the structural formula (I)
There are at least two types of crystal modifications of the pyridone-based disazo compound represented by formula (1), one of which is a crystal modification that does not have very good dispersibility under high-temperature dyeing conditions and is obtained by a conventional ordinary synthesis reaction. The dye cake obtained is of this crystal modification, whereas the other is a novel crystal modification which has very good dispersion stability at high temperatures and under severe dyeing conditions. Further, the stability of the dispersion state of the dye composition in a high-temperature dyeing bath is not only related to the size of the dye particles but also to the crystallinity, and the above-mentioned crystalline form of the compound having the novel crystallinity is used. It was found for the first time that the dispersion stability of the dye composition in a high-temperature dyeing bath could be achieved, and the present invention was reached.

[0009]

The gist of the present invention is that a diffraction peak (2θ) has strong peaks at about 6.9 °, about 15.4 °, about 18.8 ° and about 25.7 °, and further has a peak at about 12 °. .2 ° and about 2
The following structural formula (I) having a crystal modification characterized by an X-ray diffraction diagram (CuKα) showing an intermediate peak at 6.7 °
And a water-insoluble pyridone disazo dye represented by the formula:

[0010]

Embedded image

Another gist of the present invention is to diazotize 4 '-(4-hydroxyphenylazo) aniline,
Hydroxy-1,4-dimethyl-2-oxo-1,2-
Coupling reaction with dihydro-3-pyridinecarbonitrile, followed by condensation reaction with 2,4-difluoro-6- (di-n-butylamino) 1,3,5-triazine in acetone, followed by filtration. The present invention resides in the method for producing a water-insoluble pyridone-based disazo dye described above, which comprises dispersing the cake in an aqueous medium and stirring at a temperature of 60 to 150 ° C for 0.5 to 30 hours.

A further gist of the present invention is to diazotize 4 '-(4-hydroxyphenylazo) aniline,
-Hydroxy-1,4-dimethyl-2-oxo-1,2
-Dihydro-3-pyridinecarbonitrile, followed by 2,4-difluoro-6- (di-n-
(Butylamino) 1,3,5-triazine and a condensation reaction in N, N-dimethylformamide, and then releasing the condensation reaction solution into water to obtain precipitated crystals. The present invention relates to a method for producing a pyridone-based disazo dye.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The disazo compound of the present invention represented by the above structural formula (I) and having a novel crystal modification (hereinafter referred to as β-type crystal modification) can be obtained as follows. For example,
4 '-(4-Hydroxyphenylazo) aniline is diazotized by a conventional method, and is then combined with 6-hydroxy-1,4-dimethyl-2-oxo-1,
2-Dihydro-3-pyridinecarbonitrile is reacted in a methanol medium with, for example, -5 ° C to 15 ° C, preferably 5 to 15 ° C.
The coupling reaction is performed at a temperature of 15 ° C. for 2 to 10 hours.
Further, the coupling reaction product and 2,4-difluoro-
6- (Di-n-butylamino) 1,3,5-triazine in acetone, for example at 30 to 55 ° C., preferably 45 to 55 ° C.
A condensation reaction is performed at 55 ° C. for 6 to 20 hours to synthesize a disazo compound of the structural formula (I) shown above.

The disazo compound cake obtained by precipitation and filtration from the reaction mixture after the condensation reaction has a diffraction angle (2.
θ) This is a crystal modification showing strong peaks at about 11.5 ° and about 17.3 ° (hereinafter referred to as α-form crystal modification). In the present invention, this cake is further treated under specific conditions. Transform to β-type crystal. As this treatment method, for example, (1) the cake of the α-type crystal modification is dispersed in an aqueous medium, and in some cases, a formaldehyde condensate of naphthalenesulfonic acid, a waste liquid of sulfite pulp containing ligninsulfonic acid sodium as a main component. In the presence of a dispersant such as a concentrate,
At a temperature of 150 ° C, preferably 80-100 ° C,
A method of stirring for 30 hours, preferably 1 to 10 hours is employed.

As another method for producing the disazo dye having a β-form crystal modification of the present invention, for example, the above 4′-
The coupling reaction product of (4-hydroxyphenylazo) aniline and 6-hydroxy-1,4-dimethyl-2-oxo-1,2-dihydro-3-pyridinecarbonitrile is converted to N, N-dimethylformamide 2,4-difluoro-6- (di-n-butylamino) 1,
A condensation reaction with 3,5-triazine is carried out at, for example, 30 to 80 ° C., preferably 45 to 55 ° C. for 2 to 6 hours, and then the condensation reaction product is released into water (room temperature), and the precipitated crystals are separated by filtration. Washing and drying may be mentioned. According to this method, it is possible to directly synthesize the disazo compound of the structural formula (I) having the β-type crystal modification.

Next, the α-form and β-form modifications of the disazo compound represented by the structural formula (I) will be described with reference to the drawings. 1 and 2 are X-ray diffraction diagrams obtained by recording the state of diffraction by CuKα radiation in a powder X-ray diffraction method using a proportional counter. The horizontal axis indicates the diffraction angle (2θ), and the vertical axis indicates the diffraction intensity. . FIG. 1 shows a β-type crystal modification which is a novel crystal type of the present invention, and in particular, diffraction angles (2θ) of about 6.9 °, about 15.4 °, about 18.8 ° and about 25.7 °. Peak at about 12.2 ° and about 2
It has an intermediate peak at 6.7 °. FIG. 2 shows a conventional α-type crystal transformation, showing strong peaks at diffraction angles (2θ) of about 11.5 ° and about 17.3 °, which is clearly different from the crystal transformation of FIG.

The diffraction angles by the X-ray diffraction method always coincide with an error of about ± 0.1 ° for the same crystal type, and these drawings clearly show the difference of the crystal transformation. ing. Due to this difference in crystal form, the behavior of the disazo compound at the time of dyeing is different, and in the case of the pyridone-based disazo compound having the crystal modification of the present invention, at a high temperature, even if a dyeing method under severe conditions is adopted, Good dyeing can be achieved.

The fibers dyeable with the pyridone disazo dyes of the present invention include polyethylene terephthalate,
Polybutylene terephthalate, terephthalic acid and 1,4-
Polyester fibers such as polycondensates with bis- (hydroxymethyl) cyclohexane, anion-dyeable polyethylene terephthalate, and cation-dyeable polyethylene terephthalate, and polyester / cellulose mixed fibers are also included. Further, acetate fibers such as triacetate, diacetate, heat-resistant diacetate, silk, wool, polyurethane, polyamide (6-nylon, 6,6-nylon),
It is also applicable to nitrogen-containing fibers such as leather and wool, and also to the above-mentioned polyester fibers or mixed fibers of two or more selected from acetate fibers and nitrogen-containing fibers. The disazo dyes of the present invention are particularly suitable for polyester / polyamide microfiber fibers.

In order to dye polyester fibers or the like using the pyridone-based disazo dye of the present invention, a condensate of naphthalenesulfonic acid and formaldehyde, sodium ligninsulfonate, higher alcohol sulfate or the like is used as a dispersant in a conventional manner. Then, the dyeing can be carried out by a dye bath prepared by dispersing the dye in an aqueous medium. In the case of dip dyeing, dyeing methods such as the high temperature dyeing method, the carrier dyeing method, and the thermosol dyeing method described above can be applied, and the high temperature dyeing method is particularly preferable. Since the pyridone-based disazo dye of the present invention has excellent dispersion stability at high temperatures, it can dye polyester fibers and mixed fibers of these and other fibers satisfactorily. In particular,
Exhaustion of polyester fiber or the like in an aqueous medium in the presence of a dispersant under severe conditions of a dyeing temperature of 125 to 140 ° C., a dye bath ratio of 15 times or less, and a use ratio of a dispersant to a dye of 3 times or less. It is also possible to dye.

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. The pyridone-based disazo dyes represented by the structural formula (I) of the present invention may be used in combination with other dyes, and good results such as improvement in dyeability may be obtained by blending the dyes.

[0021]

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 Crystal) 6-hydroxy-1,4-dimethyl-2-oxo-1,
4.1 g of 2-dihydro-3-pyridinecarbonitrile
Was dissolved in 100 ml of methanol at 20 to 30 ° C. to obtain a coupling component. Next, 7.2 g of 35% hydrochloric acid and 6.0 g of 4 ′-(4-hydroxyphenylazo) aniline were added to 90 g of water, and 23 g of the mixture was added at 20 to 30 ° C. with stirring.
% Nitrite aqueous solution was gradually added, and diazotized to obtain a diazotized solution. The diazotized solution was dropped into the coupling component solution at 8 to 12 ° C., and the mixture was stirred at the same temperature for 2 hours, and the precipitated crystals were separated by filtration, washed with water, and dried.

8.4 g of the obtained crystals, 5.4 g of 2,4-difluoro-6- (di-n-butylamino) -1,3,5-triazine and 1.8 g of potassium carbonate were placed in 120 ml of a 97% acetone aqueous solution. The mixture was added and allowed to undergo a condensation reaction at 50 to 55 ° C. for 12 hours. After the completion of the reaction, 100 ml of methanol was added. Red crystal 1 of the compound shown
0.1 g was obtained. When the powder of the disazo dye obtained by this reaction was analyzed by an X-ray diffraction method, it was found to be an α-form crystal modification shown in the X-ray diffraction diagram of FIG.

Next, the obtained compound of the α-form crystal modification was dispersed in a 20% by volume of a 5% by weight aqueous solution of Reax 85A (a lignin dispersant manufactured by West Baco), and 9
The mixture was stirred at 0 to 95 ° C. for 8 hours to perform crystal transition. After the crystal transition, the crystals were separated by filtration and dried, and the obtained crystals were analyzed by X-ray diffraction.

Example 2 (Production Example of Dye Crystal) 8.4 g of a disazo compound represented by the following structural formula

[0026]

Embedded image

5.5 g of 2,4-difluoro-6- (di-n-butylamino) -1,3,5-triazine, 1.6 g of potassium carbonate and 2.7 g of triethylamine were added to 24.5 ml of N, N-dimethylformamide. And subjected to a condensation reaction at 50 ° C. for 3 hours. This condensation reaction solution was discharged into 92 ml of water, cooled to 5 ° C., and the precipitated crystals were separated by filtration, washed and dried to obtain 11.8 g of a disazo dye represented by the structural formula (I). When this crystal was analyzed by an X-ray diffraction method, it was a β-type crystal modification shown in the X-ray diffraction diagram of FIG.

Test Example 1 (Dyeing Example) 1.0 g of the pyridone-based disazo dye of the β-form modification obtained in Example 1 was used in an amount of 1.0 g of a naphthalenesulfonic acid-formaldehyde condensate and 1.0 g of sodium ligninsulfonate. To obtain a fine dispersion of the dye. The total amount of this dye dispersion and 1 g of Nikka San Salt RM-340 (manufactured by Nika Chemical Co., Ltd.) were diluted with water to make the total amount 1 liter, and a dyeing bath was prepared. 100% polyester fiber cloth
g, and dyed at 135 ° C. for 30 minutes, followed by soaping, washing with water and drying. As a result, the dispersibility of the dye was good and the polyester fiber cloth was dyed a uniform orange color. The light-fastness of the obtained dyed fabric was good at class 5, and the fastness to rubbing was good at class 4-5. When a similar dyeing test was conducted using the disazo dye of the α-type crystal modification in the course of the production in Example 1 described above, the dyed cloth was unevenly dyed, and the fastness to rubbing was extremely inferior to class 2. .

Test Example 2 (Dyeing Example) The same operation as in Test Example 1 was conducted except that the polyester fiber cloth was changed to a polyester / polyamide conjugate fiber cloth. As a result, the dyed fabric was dyed in a uniform orange color, and also had good washing fastness and rub fastness.

Test Example 3 (Dyeing Example) In Test Example 1, 1.0 g of the disazo dye of the β-form crystal obtained in Example 2 was used, and 1.8 g of sodium ligninsulfonate and 0.2 g of higher alcohol sulfate were used. A polyester fiber cloth was dyed in the same manner as above except that the dispersion was made fine. The obtained polyester fiber cloth was dyed in a uniform orange color, and had a light fastness of class 5 and a rub fastness of class 4-5.

[0031]

The water-insoluble pyridone disazo dye having the β-form crystal modification of the present invention can be used at a high temperature and, for example, at a ratio of dye to dye of 1:10 and dye cake to dispersant of 1 at a high temperature. : 2, the dispersion stability is very good even under severe dyeing conditions of 135 ° C. for 0.5 hour, and the resulting dyed fabric is excellent in light fastness and rub 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 β-type crystal modification of a pyridone-based disazo compound 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 an α-type crystal modification of a pyridone-based disazo compound 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. .

Claims (3)

[Claims] 1. A diffraction angle (2θ) of about 6.9 °, about 15.4.
The following has a crystalline modification characterized by X-ray diffraction (CuKα) showing strong peaks at ゜, about 18.8 ° and about 25.7 °, and also intermediate peaks at about 12.2 ° and about 26.7 °. A water-insoluble pyridone disazo dye represented by the structural formula (I). Embedded image 2. 4 '-(4-hydroxyphenylazo)
The aniline is diazotized, and this is combined with 6-hydroxy-1,4
-Dimethyl-2-oxo-1,2-dihydro-3-pyridinecarbonitrile, followed by 2,4-difluoro-6- (di-n-butylamino) 1,2
After a condensation reaction with 3,5-triazine in acetone,
The cake obtained by filtration is dispersed in an aqueous medium, and 60 to 150
The method for producing a water-insoluble pyridone-based disazo dye according to claim 1, wherein the mixture is stirred at a temperature of 0.5C for 30 hours. 3. 4 '-(4-hydroxyphenylazo)
The aniline is diazotized, and this is combined with 6-hydroxy-1,4
-Dimethyl-2-oxo-1,2-dihydro-3-pyridinecarbonitrile, followed by 2,4-difluoro-6- (di-n-butylamino) 1,2
2. A water-insoluble pyridone according to claim 1, wherein the condensation reaction is carried out in 3,5-triazine and N, N-dimethylformamide, and then the condensation reaction solution is discharged into water to obtain precipitated crystals. A method for producing a disazo dye.