JP3032591B2 - Water-insoluble dye mixture - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-insoluble dye mixture, and more particularly, it can uniformly dye polyester fibers and the like even under severe conditions at high temperatures.
The present invention relates to a red water-insoluble monoazo dye mixture having excellent H dependency.

[0002]

2. Description of the Related Art In recent years, a jet dyeing method, a cheese dyeing method or a package dyeing method has been widely adopted as a dyeing method for polyester fibers. In the case of these dyeing methods, a finely wound layer of a material to be dyed is used. Since it is necessary to forcibly circulate the dyeing dispersion liquid therein, the water-insoluble disperse dye used here is required to have various fastnesses and good dispersion stability. In particular, recently, since the dyeing conditions have become severe, such as a decrease in the dyeing bath ratio, a decrease in the amount of the dispersant used, and an increase in the dyeing temperature, regarding disperse dyes which have not been a problem with regard to dispersion stability. Can also be a problem. In the case of the monoazo dye represented by the formula [I] as well, although various fastnesses were excellent, the dispersion stability was poor under the above-mentioned dyeing conditions.

[0003]

DISCLOSURE OF THE INVENTION In view of the above circumstances, the present inventors have studied to improve the dispersion stability of monoazo dyes having two types of structures represented by the above formula [I]. In the case where a compound having a specific crystal form is used, it has been found that the dispersion stability is remarkably excellent, and a patent application has been filed. (Japanese Patent Application No. 1-3036
No. 09 and No. 1-303610) However, according to the subsequent studies, the monoazo dyes having the specific crystal form and having two types of structures represented by the above formula [I], when used alone, show a problem in dyeing. Was found to be slightly inferior in temperature dependency.

An object of the present invention is to improve the temperature dependency during dyeing of a monoazo dye having two types of structures represented by the formula [I], and the present inventors have further studied. As a result, it has been found that when two types of monoazo dyes represented by the above formula [I] and having a specific crystal form are mixed and used in a specific ratio, the temperature dependency is greatly improved.

[0005]

SUMMARY OF THE INVENTION The means for solving the problem] is a dye wherein in the formula [I] wherein R is -C ₃ H ₆ OCH _3, and diffraction angle (2 [Theta]) most about 6.6 ° Strong peak,
Further, a monoazo dye having a crystal modification characterized by an X-ray diffraction pattern (CuKα) showing three weak peaks at about 11.4 °, 31.6 ° and 33.8 °, and a compound represented by the formula [I] R is -C ₂ H ₄ OC ₂ H ₄ OH, and three strong peaks at diffraction angles (2θ) of about 6.2 °, 14.5 ° and about 25.2 °, and about 18 X-ray diffraction diagrams showing two intermediate peaks at 0.2 ° and 19.4 ° (C
a water-insoluble dye mixture of a monoazo dye having a crystalline modification characterized by uKα) in a weight ratio of 2: 8 to 8: 2.

Hereinafter, the contents of the present invention will be described in detail.
You. In the present invention, the monoazo compound represented by the formula [I]
As for the dye, R is -C_ThreeH₆OCH_ThreeAnd -C_TwoH_FourO
C_TwoH_FourIncluding two structures for OH, each dye is
Usually, 2-cyano-4-nitroaniline is prepared by a conventional method.
Azotization and then in an aqueous medium at −5 to 15 ° C.
Preferably at a temperature of -5 to 5C for about 0.5 to 10 hours,
Each has a corresponding pyridine-based coupler and coupling
It can be synthesized by responding. But here
Of the monoazo compound represented by the formula [I]
R is -C_ThreeH₆OCH_ThreeAnd -C_TwoH_FourO
C_TwoH _FourIn any case of OH, the crystal transformation is almost amorphous.
In the present invention, each cake is further subjected to specific conditions.
Need to be treated with the above-mentioned specific crystal type
There is. This processing method usually involves a coupling reaction.
The resulting cake is dispersed in an aqueous medium and
Formaldehyde condensate of naphthalenesulfonic acid,
Sulfite mainly composed of sodium lignin sulfonate
60 to 130 in the presence of a dispersant such as a pulp waste liquid concentrate
° C, preferably at a temperature of 80 to 100 ° C for 0.5 to 30 hours
For a period of time, preferably 1 to 10 hours, or
Alcohols such as methanol, ethanol or butanol
, Ethers such as dioxane, ethylene glycol
Dispersed in an organic solvent such as
0.5 to 100 ° C., preferably 20 to 80 ° C.
A method of stirring for about 10 to 10 hours is employed. Departure
In general, two types of structures represented by the formula [I]
The monoazo compounds are treated separately, but each
Mix and use each corresponding coupling component
Two types of structures represented by the above formula [I] by a ring reaction
Synthesis of monoazo dyes in the same system
And then treat this mixture simultaneously.
No.

Next, the crystal type specified in the present invention 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 the crystal form of the present invention in the case of a monoazo dye in which R in the formula [I] is -C ₃ H ₆ OCH ₃ , and FIG. 2 shows the crystal form in the formula [I]. It takes a crystalline form of the present invention where R is a monoazo dye is _{-C 2 H 4 OC 2 H 4} OH. It can be seen that each has a peak at a predetermined diffraction angle (2θ).
Note that the diffraction angles obtained by the X-ray diffraction method always coincide with each other with an error of about ± 0.1 ° for the same crystal type.

In the present invention, it is an essential requirement that two types of red monoazo dyes represented by the above formula [I] and having a specific crystal form be mixed and used. The mixing ratio is such that R in the formula [I] is -C ₃ H ₆ OC
H ₃ in which _{dye: -C 2 H 4 OC 2 H} 4 OH dye is 2: 8 to 8: 2 weight ratio, preferably 3: 7 to 7: 3 by weight. If the mixing ratio is too large or too small, the temperature dependency at the time of dyeing cannot be sufficiently improved. In the present invention, other various dyes may be appropriately blended and used in order to achieve a desired color tone.

The fibers which can be dyed with the pyridine-based monoazo dye mixture of the present invention are usually polyester fibers comprising polyethylene terephthalate, a polycondensate of terephthalic acid and 1,4-bis- (hydroxymethyl) cyclohexane, and the like. Or a blend of natural fibers such as cotton and wool and the above-mentioned polyester fibers, and a blended fabric.

To dye polyester fibers using the dye mixture of the present invention, a condensate of naphthalenesulfonic acid and formaldehyde, a higher alcohol sulfate, a higher alkylbenzene sulfonate, or the like is used as a dispersant in a conventional manner. A dye bath or printing paste dispersed in an aqueous medium can be prepared and dyed or printed. In the case of dip dyeing, for example, dyeing methods such as the high-temperature dyeing method, carrier dyeing method, and thermosol dyeing method described above can be applied. Since the monoazo dye mixture of the present invention is excellent in dispersion stability and pH dependency, it is possible to dye polyester fibers or their blends well.
Specifically, polyester fibers are dyed at a temperature of 125 to 1
Under severe conditions of 40 ° 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, in an aqueous medium,
Exhaustion dyeing in the presence of a dispersant is also possible. In some cases, more favorable results can be obtained by adding an acidic substance such as formic acid, acetic acid, phosphoric acid, or ammonium sulfate to the dyeing bath.

[0011]

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

Production Example 1 A coupling component solution was prepared by dissolving 3.0 g of 2-anilino-3-cyano-4-methyl-6- (γ-methoxypropylamino) -pyridine in 300 ml of 15% sulfuric acid at 0 to 3 ° C. And 1.6 g of 2-cyano-4-nitroaniline was added to a mixture of 3.3 g of 43% nitrosylsulfuric acid and 5 g of 80% sulfuric acid at 0 to 3 ° C. to perform diazotization to obtain a diazotized solution. This diazotized solution is added dropwise to the coupling component solution at 0 to 5 ° C., and then the pH is adjusted to pH 4 with sodium acetate.
5 and then, 1 hour, and stirred at the same temperature, crystals precipitated are collected by filtration, washed with water dried, the formula R is -C At a [I] ₃ H ₆
4.5 g of red crystals of the compound being OCH ₃ were obtained. Next, the obtained cake was dispersed in 10 times the volume of water,
The mixture was stirred at 90 to 95 ° C. for 3 hours to perform crystal transition. After the crystal transformation, filtration and drying were performed, and the obtained crystals were analyzed by an X-ray diffraction method. As a result, a crystal modification shown in the X-ray diffraction diagram of FIG. 1 was obtained.

Production Example 2 Production Example 1 was the same as Production Example 1 except that 3.2 g of 2-anilino-3-cyano-4-methyl-6-hydroxyethoxyethylaminopyridine was used as the coupling component.
Performs coupling reaction and crystal transition in the same manner as in the formula [I] Te at R is _{-C 2 H 4 OC 2 H 4} OH compounds, and the red crystals having a X-ray diffraction diagram of Figure 2 Obtained.

EXAMPLE 1 0.2 g of a dye obtained by mixing 60 parts by weight of the dye obtained in Preparation Example 1 and 40 parts by weight of the dye obtained in Preparation Example 2 was mixed with 0.6 g of a naphthalenesulfonic acid-formaldehyde condensate and a higher alcohol. The dyeing bath was prepared by dispersing in 1 liter of water containing 0.6 g of sulfate ester. After 100 g of polyester fiber was immersed in this dyeing bath and dyed at 130 ° C. for 60 minutes, soaping, washing and drying were performed. As a result, in each case, the dispersibility of the dye was good, and the dyed cloth was uniformly dyed. The obtained dyed cloth was bluish red, light fastness class 6 and rub fastness class 5 were obtained. And it was good. Next, to investigate the temperature dependence of the dye used,
In the above-mentioned dyeing, dyeing was carried out in the same manner except that the dyeing temperature was set to 120 ° C.
The temperature dependency in the case of dyeing was determined by comparing the dyeing rates of both dyed fabrics, and the temperature dependency was 85%.

Comparative Example 1 In Example 1, the dye used was 0.2% of the dye obtained in Production Example 1.
When dyeing was carried out in the same manner except that g was used, the temperature dependency was 60%.

Comparative Example 2 The dye used in Example 1 was replaced with the dye 0.2 obtained in Production Example 2.
When dyeing was carried out in the same manner except that g was used, the temperature dependency was 50%.

[0017]

The mixture of the water-insoluble monoazo dyes having a specific crystal form according to the present invention can be used at a high temperature and, for example, the ratio of the material to be dyed to the dyeing liquid is 1:10, and the ratio of the dye cake to the dispersant is 1%. 1: The dispersion stability is very good even under severe dyeing conditions such as 135 ° C. for 0.5 hour at a dyeing condition, and the temperature dependency at the time of dyeing is excellent.
The dyed fabric obtained is excellent in light fastness and rub fastness. Therefore, the dye mixture 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 monoazo compound obtained in Production Example 1.

FIG. 2 is an X-ray diffraction diagram of a crystal modification of the monoazo compound obtained in Production Example 2.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09B 67/22 C09B 67/48 C09B 29/42 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] (1) R in the following formula (I) is -C ₃ H ₆
A dye that is OCH ₃ and a diffraction angle (2θ) of about 6.6 °
X-ray diffractogram (Cu) showing the strongest peak at about 11.4 °, 31.6 ° and 33.8 °
A monoazo dye having a crystal modification characterized by Kα), wherein R in the following formula [I] is -C ₂ H ₄ OC ₂
H ₄ OH dye and diffraction angle (2θ) of about 6.2
3 strong peaks at °, 14.5 ° and about 25.2 °,
Further, a monoazo dye having a crystal modification characterized by an X-ray diffraction pattern (CuKα) showing two intermediate peaks at about 18.2 ° and 19.4 ° is mixed in a weight ratio of 2: 8 to 8: 2. Water-insoluble dye mixture. Embedded image (Wherein, R -C ₃ H ₆ OCH ₃ or -C ₂ H ₄ OC ₂
Represents H ₄ OH. )