JPS62220561A - Monoazo dye - Google Patents

Abstract

NEW MATERIAL:A monoazo dye in a crystal form, expressed by formula I and characterized by an X-ray diffraction pattern (CuKalpha) showing two strong peaks at 7.3 deg. and 26.3 deg. diffraction angles (2theta) and two weak peaks at 10.3 deg. and 27.4 deg.. USE:A dye, capable of dyeing polyester fibers, etc., to yellow color and uniformly dyeing even at high temperatures under severe condition and having improved color fastness to light and rubbing. PREPARATION:For example, a compound expressed by formula II is diazotized and then subjected to coupling reaction with a coupling component expressed by formula III in an aqueous medium, preferably at 0-10 deg.C for 30min-10hr.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a monoazo dye, and more specifically, it has a novel crystal form that can uniformly dye polyester fibers etc. even under high temperature and harsh conditions. This relates to yellow monoazo dyes.

(Conventional technology) In recent years, various dyeing methods have been streamlined in the dyeing industry.1 For example, when dyeing polyester fibers using disperse dyes, jet dyeing methods, which dye a large amount of fibers at once, are often adopted. Examples of widely used methods include beam dyeing, cheese dyeing, and package dyeing.

These dyeing methods are dyed by forcibly circulating a dye dispersion liquid in a dense layer of stationary fibers, which are wound in many layers. It is required that the dye particles be fine particles and have excellent dispersion stability in the dyeing bath.In other words, when the dye particles become large, a filtration phenomenon of the dye particles occurs by 1 m of fibers, and the dye enters the inside of the fibers. Problems occur such as poor penetration of the dye, dyeing the inner layer or outer layer in shades due to the adhesion of aggregates, and a decrease in fastness such as abrasion fastness due to the adhesion of the dye only to the fiber surface.Therefore, such dyeing methods The dye used for this purpose has good dispersion in the dye bath.

is necessary.

However, in general, when the dye bath is heated to a high alpha degree, the dispersibility of the dye in the dye bath often tends to decrease, and as a result, the aggregated dye forms a filtration residue on the surface of the dyed object as described above. In the case of a dyed material that adheres to the dyed material and has many layers, the dyeing density will be different between the outer layer and the inner layer, making it impossible to obtain a dyed product with a uniform density.

Decrease the ratio of liquid from /:30 to /: / 0tlC), ■ Decrease the ratio of dispersant used (for example, lower the ratio of dye cake to dispersant from 7 = 3 to /:/), and further ■ Dyeing. Increasing the temperature further for a short period of time (e.g. /30℃×/
time to i3z”c×o,s time)
The dyeing conditions are becoming more severe. Moreover, all of these harsher dyeing conditions have a disadvantageous effect on the dispersion stability of the dye, so even if conventional dyeing methods have relatively good dispersion stability and specific dispersion dyes are used, However, the recent streamlined dyeing methods often result in poor dispersion stability.

That is, for example, the pyridone-based monoazo dye represented by the following structural formula [l], whose structure itself is included in the description in JP-A-30-27&:24, is prepared by combining the diazo component and the coupling component in accordance with a conventional method. It is obtained by a production method involving a Kuipling reaction). Furthermore, this monoazo dye can uniformly dye polyester fibers when used under conventional, mild dyeing conditions.
The dyed product obtained also has excellent fastness.

(Problems to be Solved by the Invention) However, the conventional monoazo dye represented by the above structural formula (1) cannot be used to dye polyester fibers under the recently streamlined high temperature and harsh dyeing conditions described above. When used, the dispersibility of the dye is significantly reduced and it is extremely difficult to obtain a dyed product with uniform dye density. There was a problem. Also, conventional dyes have problems in compatibility with various dyeing aids, for example, their high-temperature dispersion stability is extremely poor in the presence of mirabilite (Na180a), and therefore reactive dyes containing mirabilite, etc. When used in combination with poly□ ester/M blended products, it does not cause uneven dyeing, and when used in combination with dyes, color pre-setting is required from the viewpoint of compatibility with the blended dyes. There were problems in that it caused uneven staining.

The present invention aims to provide a novel monoazo dye that can solve 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 pyridone-based monoazo compound represented by the m-suizo construction formula [1] has at least one class. There are two crystalline forms, one of which has poor dispersion stability under high-temperature dyeing conditions, and the other with poor dispersion stability even under high-temperature and even harsher dyeing conditions. It has been found that in addition to being a crystalline form with good dispersion stability, the cake obtained in a conventional synthesis reaction is a crystalline form with poor dispersion stability. Furthermore, the stability of the dispersed state of a dye composition in a high-temperature dye bath is not determined only by the size of the dye particles.

There is a significant relationship between the above-mentioned crystal forms, and after creating a stable dispersion system for the dyebath, it is necessary to use a compound with the above-mentioned new crystal form that has not been seen before to achieve the desired purpose. It can be achieved. The present invention was arrived at based on the following knowledge.

That is, 1 the present invention has the following structural formula [1] OH, OHO,
H, (n) 01H@ 1 diffraction angle (,2θ) approximately 7.3° and 26.3°
4 strong peaks at about 1013° and J7.
! x5 diffraction diagram showing one weak peak at otl K
The gist of this invention is a monoazo dye that is a crystal form characterized by α) (hereinafter referred to as "α-type crystal form").

The monoazo compound having the novel α-type crystal form of the present invention is
It can be obtained as follows.

First, for example, a compound represented by the following structural formula [u] is υdiazotized by a conventional method, and then a compound represented by the following structural formula [O] 0H20HO,H,(n) 0,H5 (coupling component) and in aqueous medium,
O~is'c, preferably by coupling reaction at 0~10°C for 30 minutes~/θ hours, the curved water structural formula [I
Synthesize the monoazo compound of F. The cake of the monoazo compound obtained by this synthesis has a nearly amorphous crystalline form (hereinafter referred to as "β-type crystalline form"). In contrast, in the present invention, this cake is further treated under specific conditions to form an α-type crystal. In this case, the treatment method under specific conditions includes dispersing the β-type crystal cake in an aqueous medium, and optionally dispersing it with sulfide whose main component is a formaldehyde condensate of naphthalene sulfonic acid and sodium lignin sulfonate. In the presence of a dispersant such as a concentrate of pulp waste liquid, 10 to 30"C, preferably 10 to 100
"C for 0.j~30 hours, preferably 1~I
A method of stirring for Q hours, or.

■Alcohols such as methanol, ethanol or butanol, and ethers such as dioxane.

Dispersed in an organic solvent such as ethylene glycol, glycol ether, etc., from 15 to ioo'c, preferably from 10 to gθ
A method of stirring at a temperature of .degree. C. for about .times.a to IQ is adopted.

(Function) Next, the α-type crystal form of the product of the present invention and the β-type crystal form of the conventional product in the monoazo compound represented by the bent water structural formula [1] will be explained with reference to the drawings. Stripes 1 and 2 are powder X
This is an X-ray diffraction diagram obtained by recording the diffraction profile of the OuKa line in the ray diffraction method using a probone linear counter, where the horizontal axis shows the diffraction angle (-〇) and the vertical axis shows the l-refraction intensity. Figure 1 shows the α-type crystal form, which is a new crystal form of the present invention, in particular, the diffraction angle (-〇) is about 7.3°%,
1.7°IC, two strong peaks, approx. 10. , J.

and λ7. It has one weak peak at 0.

Figure 1 shows the conventional β-type crystal form.

It is clearly different from the α-type crystal form shown in Figure 1. The diffraction angle by X-ray diffraction method is ±007 if the crystal form is the same.
Consistently consistent with an error of about zero, these drawings clearly show the difference in crystal form. Due to this difference in crystal form, the behavior of the monoazo compound during dyeing is different.
), in the case of the present invention, good dyeing can be achieved even if the dyeing method is employed at high temperatures and under harsh conditions.

Fibers that can be dyed with the monoazo dye of the present invention include:
Polyethylene terephthalate, terephthalate/, lI
Polymer products such as polycondensates with -bis-(hydroxymethyl)cyclohexane and the like can be mentioned. K dyeing polyester fibers using the monoazo dye of the present invention is carried out using a conventional method! ) Condensates of naphthalene sulfone with FIR aldehyde, higher alcohol sulfates, high M alkylbenzene sulfonates, etc. are used as powders.
A dyeing treatment method such as a dyeing method can be applied by adjusting a dyeing bath or printing paste dispersed in an aqueous medium and performing dyeing or printing.

Moreover, even if harsh dyeing conditions are used with these methods, 1
Since the monoazo dye of the present invention has excellent dispersion stability,
Polyester fibers or blended products thereof can be dyed well.

At that time, if necessary, use formic acid, acetic acid, and phosphorus in the dye bath! Even better results can be obtained by adding an acidic substance such as ammonium sulfate or the like.

Furthermore, the monoazo dye represented by the shaved ice structural formula [1] of the present invention may be used in combination with other dyes, and good results such as improved dyeing properties may be obtained by combining the dyes with each other.

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

Reference example/Example for producing dye crystals shown in Zensuizozo 2: Mass, Cornitrog-chloroaniline (3.5y) was diazotized with nitrous acid in hydrochloric acid by the usual method at 0°C for 2 hours. A diazo liquid was prepared by performing the following steps.

ti''-coethylhexyl-3-cyano-gumethyl-6-hydroxy-hyridon, water 300-
After dispersing in 25% sodium hydroxide and sodium acetate, a coupling solution was prepared.

Add the previously obtained diazo solution to this coupling solution.
pHII~! with hydrochloric acid and sodium hydroxide solution at 2°C!
After reacting at 0° C. for 3 hours, the precipitated crystals were separated from P, washed with water and dried to give yellow crystals G and J J I. The monoazo dye obtained in this reaction was analyzed by powder t-X-ray diffraction and found to be in the β-type crystal form. The X-ray diffraction diagram is shown in FIG.

Next, using the obtained β-type crystal form, it was dispersed in 20 times the volume of water and stirred at 90 to 9 k"C for 3 hours to effect crystal transformation. After completion of the crystal transformation, filtration and drying were performed. When the resulting crystal was analyzed by X-ray diffraction method, it was found that
It was an α-type crystal form showing a line diffraction pattern.

Example/ Monoazo compound 0 of the following α-type crystal form obtained in the above reference example/
・! f9, naphthalenesulfonic acid-formaldehyde condensate 0.2! A dye bath was prepared by dispersing water/lK containing 1 and higher alcohol [Ii 1 acid ester 0.2 j F'AHL7t. This dyeing bath contains 100% polyester fiber.
Soak JI, /, 3! ;' After staining with C for 30 minutes,
When the dye was soaked pink, washed with water, and dried, the dispersibility of the dye was good, and the dyed fabric was uniformly dyed. In addition, the obtained dyed fabric had a greenish-yellow color with extremely good needle fastness of grade 6 and Jll rub fastness of grade J.

In addition, when a similar dyeing test was carried out using the β-type crystalline monoazo compound that was being produced in the above reference example, partial aggregation of the dye occurred in the dye bath, resulting in unevenly dyed fabric. Moreover, the friction fastness was significantly inferior to grade 7.

In the working example/, the naphthalene sulfonic acid-formaldehyde condensate and the higher alcohol sulfate ester were each treated with 3 times the amount of O, ? j To J, the water is tripled to 3t, and the dyeing temperature is i, yo ℃ for 40 minutes. Except I used a slightly milder staining method.

It was carried out in the same manner as in Example 1.

As a result, 1) When using the α-type crystal form of the present invention, good uniform dyeing was achieved in the same way as in Example 1, and the dyed fabric obtained also had a light fastness of grade 6 and abrasion fastness of grade 3. It was extremely good.

On the other hand, when the conventional β-type crystal form was used, although there was a slight improvement compared to Example 1, a dyed fabric with uneven dyeing was still obtained, and its resistance was 1J! The scratch resistance was also only 3rd grade, which was a little inferior.

(Effects of the Invention) As is clear from the above results, the pyridone-based monoazo disperse dye of the present invention, which is novel in that it has an α-type crystal form, is different from the conventional pyridone-based monoazo disperse dye that has a β-type crystal form. It has much better dispersion stability compared to other dyes, and if it is used for dyeing polyester fibers, it can maintain dispersion stability under any of the recent streamlined high-temperature and harsh dyeing conditions. Good uniform dyeing and needle base fastness.

A dyed product with extremely good abrasion fastness etc. can be obtained. This has a remarkable effect of industrial value.

[Brief explanation of drawings]

Figure 1 shows α of the following monoazo compound obtained in Reference Example 1.
Figure 2 shows the X-ray diffraction diagram of the β-type crystal form.
This is a line diffraction diagram, in which the horizontal axis represents the diffraction angle (-0) and the vertical axis represents the diffraction intensity. 〉 Descendant

Claims (1)

[Claims] (1) Structural formula below [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I
], with two strong peaks at diffraction angles (2θ) of approximately 7.3° and 26.3°, and two strong peaks at approximately 10.3° and 27.4°.
A monoazo dye that is a crystalline form characterized by an X-ray diffractogram (CuKα) showing weak peaks.