JPS58225156A - Monoazo dye and preparation thereof - Google Patents

Abstract

NEW MATERIAL:A monoazo dye, consisting of a crystalline compound of the formula, and having the following properties: X-ray diffraction peaks at diffraction angles (2theta): Strongest peaks at about 20.0 deg. and 7.5 deg. and the next strongest peaks at about 25.4 deg., 25.1 deg., 22.8 deg., 21.6 deg. and 11.6 deg.. USE:Dipping and printing polyester fibers or mixed fabrics thereof with cotton, silk, wool, etc. or combined filamentary yarn fabrics in blue color. PROCESS:2,4-Dinitro-6-bromoaniline is diazotized and then coupled with 3-acetylamino-N,N-diethylaniline to give a dye cake, which is then heat-treated preferably in an aqueous medium at 50-200 deg.C, preferably 60-130 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has a diffraction angle (:1θ) of approximately 20.0' and 7.0%.
This invention relates to a crystalline monoazo dye represented by the following structural formula characterized by an X-ray diffraction diagram showing the strongest peak at 3°, and a method for producing the same.

In recent years, various rationalizations have been carried out in dyeing methods in the dyeing industry. For example, jet dyeing methods, which dye large amounts of fibers at once using dyeing methods such as beam dyeing, cheese dyeing, or package dyeing, have been increasingly adopted. There is. These dyeing methods are dyed by forcing the dye dispersion to pass through a dense fiber layer wound in many layers, so it is difficult to confirm that the dye particles in the dye dispersion are stable signature particles. desirable.

If the dye particles become large during the dyeing process, the penetration of the dye particles into the inside of the fiber layer will be poor, resulting in a difference in shading between the inner and outer layers of the fiber layer, and also resulting in poor fastness. Problems such as deterioration may occur. Therefore, it is necessary that the dye used in such a dyeing method has good dispersibility in the dye bath, and that the dispersibility does not deteriorate over a wide temperature range from room temperature to the high temperature at which actual dyeing occurs. However, due to the nature of dyeing, the dispersibility of dyes in dye baths at high temperatures is generally unfavorable, and in some cases, dye particles may aggregate during dyeing, resulting in uneven dyeing.

The structural formula of the monoazo dye according to the present invention is known, for example, from No. 961 published by Tokugawa Sho I/-, but when this monoazo dye produced by a conventional method is used for dyeing at high temperatures, This method has the disadvantage that the dispersion state of the dye particles in the dye bath decreases, and therefore it is difficult to obtain a dyed product with uniform dyeing density.

In view of the above circumstances, the present inventors have conducted various studies on methods for improving the dispersion stability at high temperatures of monoazo dyes having the above structural formula. One of them is a transformation that is obtained by ordinary synthetic reactions but is unstable to heat (hereinafter referred to as α-type transformation), and the other is a transformation that is extremely stable even under high temperature heating. We discovered that the transformation is a stable transformation (hereinafter referred to as β-type transformation), and based on this knowledge, we confirmed that the β-type transformation is actually stable even in high-temperature dye baths, and we have developed the present invention. completed.

Hereinafter, one aspect of the present invention will be explained in detail.

The transformation of the monoazo compound having the above structural formula according to the present invention will be explained with reference to the attached drawings.
It is a diagram in which the diffraction state in the case of Ou-K# line radiation was recorded using a proportional counter by the line diffraction method, where the horizontal axis shows the diffraction angle (Jθ) and the vertical axis shows the diffraction intensity.

FIG. 1 shows the β-type modification of the present invention, which is clearly crystalline and has a diffraction angle (θ) of about 20.
It has the strongest peaks at θ0 and 7go, and about -!
, Da01.2! It has strong peaks following the strongest peaks at r, 101.2, za 0, comb 6° and / /, 4°. Even though it is a supplementary feature, the 1st diffraction angle (-〇)
Approximately ama, za 0, coda, 3°.

:tti, oo and -,? , 41' also has a weak peak.

It is clear from FIG. 1 that the dye of the present invention has a characteristic crystal structure. On the other hand, Figure 1 shows α-type transformation, but it has only gently undulating peaks and is not crystalline but amorphous. in this way,
As is clear from the diffractograms of α-type and β-type transformations obtained by X@ diffraction method, they can be distinguished by whether they are amorphous or crystalline.

As a method for obtaining the β-type transformation of the present invention, according to the company's conventional method,
Co, Dirzynitro 6-bromoaniline is cyazized,
Next, a monoazo compound of the above structural formula having an amorphous α-type modification obtained by a coupling reaction with 3-acetylamino-N,N-diethylaniline! θ〜koo o
C, preferably by heat treatment at a temperature of 60 to JOC. If the temperature of this heat treatment is lower than the above-mentioned temperature, #'i, the crystals of the monoazo compound cannot be favorably changed from the α-type modification to the β-type modification. The time for the heat treatment varies somewhat depending on the treatment method and treatment temperature, but is usually about 3 hours.

The heat treatment is usually carried out by: (1) a method in which the mixture obtained in the coupling reaction is subsequently treated; (2) the reaction mixture is once filtered to collect a cake, and then this cake is suspended in an aqueous medium for treatment; (2) the reaction A method of treating the cake separated from the mixture in the presence of a dispersant in the process of adding X% of the disperse dye composition, and a method of treating the cake separated from the reaction mixture in the gas phase can be adopted. It is possible, and the method (2) above is particularly preferred.

Examples of fibers that can be dyed with the monoazo compound of the present invention include polyester fibers such as polyethylene tere-7-thalerate, polycondensates of terephthalic acid and/or lI-bis-(hydroxymethyl)cyclohexane, or Examples include blended products and mixed fiber products of natural fibers such as cotton, silk, and wool and the above-mentioned polyester fibers.

To dye fibers using the monoazo compound of the present invention9, it is usually carried out in an aqueous medium in the presence of a dispersant such as a condensate of naphthalene sulfonic acid and formaldehyde, a higher alcohol sulfate, or a higher alkylbenzene sulfonate. A dye bath or printing paste is prepared by finely dispersing the dye cake, and the dyeing or printing process can be performed using this dye bath or printing paste. In the case of dip dyeing, it can be applied to dyeing methods such as high temperature dyeing, carrier dyeing, and thermosol dyeing. In the present invention, a monoazo compound having a receding structural formula and a dye having another structure may be used in combination, and various compounding agents may be added in the process of preparing the disperse dye.

As described above, when dyeing is performed using the monoazo compound having β-type modification of the present invention, the dye particles are uniformly and stably dispersed even in a high-temperature dye bath, so that the fiber is the uniform concentration, t', aiゎ, 8□, i Tsuruwa, 1
Two. D (Has the effect of being highly effective.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Example In a glass reactor equipped with a stirrer, Naza wt% sulfuric acid/
Prepare ff O, J f, add sodium nitrite/A
, A f is added and stirred at a temperature of 70'C to completely dissolve to prepare nitrosyl sulfuric acid, which is then added to,
2. Add lI-dinitroaniline 6θ, Of, so'
The diazotization reaction was carried out at a temperature of 6 ℃ for 3 hours.

On the other hand, 3-acetylamino-N,N-diethylaniline I7. The above diazotization reaction mixture was added dropwise to a solution of j f in a 1 coulometric aqueous solution of thiosulfuric acid at 200 V under stirring at an OC temperature over 2 hours to carry out a coupling reaction.

After the reaction is completed, the mixture is poured into a blue dye cake 104.
19 were recovered. When a part of this cake was analyzed for crystal modification by X# diffraction method, it was found to be an amorphous α-type modification having an X-ray diffraction pattern as shown in Figure 1.

Subsequently, this dye cake was divided into 100ml of water and heated under stirring at a temperature of 90 U for 3 hours. After the heat treatment, the cake was filtered and a part of it was analyzed for crystal modification by X-ray diffraction, as shown in Figure 1.
It was a β-type modification with an xa diffraction pattern.

<Thermal Stability Test> A thermal stability test was conducted on the dye cake having the Tokunen β-type modification or α-type modification using the same method as in the above example, and the results shown in Table 1 were obtained. Ta.

1st table diameter) High temperature dispersibility test dye crystal, naphthalene sulfonic acid-formaldehyde condensate, cresol sulfonic acid of naphthalene sulfonic acid
Tests were conducted on dye compositions obtained by dispersing a formaldehyde condensate and a ligninsulfonic acid condensate in CoV water, pulverizing them using a sand grind mill, and then spray drying them.

Dye composition/f and leveling agent (Nicca Chemical, trademark Sunsolt 700θ) 0.3 f are dispersed in water 3θθm/,
Adjust the pH to 3 with ammonium sulfate and acetic acid, /30Cx/,0
After heat treatment for 1 minute, the mixture was rapidly cooled with goC4, and suction filtrated using quantitative filter paper (Toyo Roshi, Shoulder & A), and the amount of aggregates on the surface of F paper was determined according to the following criteria.

[Brief explanation of the drawing]

Figures 1 and 2 are X-ray diffraction patterns of the β-type modification and α-type modification of the monoazo compounds obtained in the examples, where the horizontal axis shows the diffraction angle (, 2θ) and the vertical axis shows the diffraction intensity. show. Agent Patent Attorney Hase - (7 people), i. Procedural Amendment (Voluntary) Written by Kazuo Sugi, Commissioner of the Japan Patent Office / Display of the case Showa! 2 years patent M 1st theta 6! Name of the invention Monoazo dye and its manufacturing method 3 Relationship with the case of the person making the amendment Patent applicant Synthetic Dye Technology Research Association V agent No. 2, 12-chome, Maruno, Chiyoda-ku, Tokyo, 100! Table 1 subject to amendment [Table 1 1 and above]

Claims (5)

[Claims] (1) Structural formula below %formula% A monoazo dye that is more powerful than the crystalline compound represented by. (2) In the X-ray diffraction diagram of a crystalline compound, the diffraction angle (-
〇) The monoazo dye according to claim (1), which exhibits the strongest peaks at about θ, 0° and 7.3°. (3) When a crystalline compound has one diffraction angle (-
〇) About ko o, o0 and 7. ! The strongest peak is shown at r0, and about -s, 11O, koS, 10, ko, 2.
The monoazo dye according to claim 1 or 2, which exhibits a strongest peak followed by a strong peak at f0, edge 6°, and /1.6°. (4) Diazotization of J,41-dinitro-6-bromoaniline followed by 3-acetylamino-N. A method for producing a monoazo dye consisting of a crystalline compound represented by the following structural formula, which comprises heating a dye cake obtained by coupling with N-diethylaniline at a temperature of θ to 1001:. (5) The method according to claim (4), characterized in that the heat treatment is carried out in an aqueous medium at a temperature of 40 -/JOC.