JPS6015460A - Dye crystal modification which is stable against heat and production thereof - Google Patents

Abstract

PURPOSE:To convert crystal modification into one which is stable against heat, by diazotizing p-nitroaniline, coupling the diazotized aniline with N-cyanoethyl- N-benzylaniline and heating the resulting dye, which is unstable against heat, in water. CONSTITUTION:p-Nitroaniline is diazotized and coupled with N-cyanoethyl-N- benzylaniline to produce the dye of the formula and having a crystal modification which is unstable against heat. The dye is heated at 40 deg.C or above in water, a water-soluble org. solvent or water contg. an anionic or nonionic surfactant to convert the crystal modification into one which is stable against heat. The crystal modification stable against heat is characterized by an X-ray diffraction pattern with very intensive peaks at angles of diffraction of 16.5, 20.3 and 26.5 and with slightly intensive peaks at angles of diffraction of 7.2, 14.4, 16.1, 24.8, 26.1, and 29.1 in powder X-ray diffractometry using Cu-Kalpha line.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to crystal modifications of dyes. For more details, see Cu
-Diffraction angle (2θ) in powder X-ray diffraction method using Kα rays
(Extremely strong peak at O1t6.s, zo, 3,265, diffraction angle (2θ) (:'] 7.2, 14=4.

A thermally stable crystal of a dye represented by formula (1) characterized by an X-ray diffraction diagram (Fig. 1) with rather strong peaks at 16.1, 24.8, 26.1, and 29.1. Metamorphosis (hereafter referred to as β-
type crystal) and its manufacturing method.

In the present invention, the formula (1
) The thermally unstable crystal modification of the dye (hereinafter referred to as α-type crystal) can be achieved by diazotizing p-nitroaniline and converting it into N-cyanoethyl-N-benzylaniline according to a known method. obtained by. This α-type crystal, for example, has a diffraction angle (2θ) of CO120,2,21,2 in powder X-ray diffraction using α-rays for Cu-.

A strong peak characteristic of 21.8 and a diffraction angle (2θ) ('1
It gives an X-ray diffraction diagram with somewhat strong peaks at 8.0, 13.2, 23.5, 27.0, and 28.5. This α-type crystal dye is mixed with a dispersant such as a sodium salt of a polymeric condensate of naphthalene sulfonic acid or a sodium lignin sulfonic acid salt using a sand mill or the like, using a machine, etc., to produce a blended fabric according to the usual method for manufacturing products. When used for dyeing, since the α-type crystals are unstable to heat, conversion or exchange of crystals occurs at the polyvarnish level, resulting in dye particles turning into tar or forming aggregates. Such tar compounds and coarse dye particles interfere with uniform dyeing. Particularly in Obermeyer dyeing, cheese dyeing, beam dyeing, jet dyeing, etc., aggregated particles are filtered through the fiber layer, causing clogging and
This causes poor internal penetration, casing spots, etc., which not only prevents uniform dyeing, but also causes inconveniences such as a decrease in the fastness of the dyed product. Particularly in recent years, the dyeing industry has streamlined dyeing methods and taken energy-saving measures, reducing the bath ratio, and methods such as the above-mentioned dyeing method, in which the dyed object is dyed in a stationary state, have become more popular. As a result, dyes with poor dispersion stability at high temperatures are heavily loaded.

The inventors of the present invention have made intensive studies to improve the above-mentioned drawbacks and to obtain a crystal transformation of the dye represented by formula (I) with excellent dispersion stability at high temperatures in order to meet market demands. The present invention was completed by discovering that β-type crystals, which are characterized by X-ray diffraction patterns, have extremely excellent dyeing stability at high temperatures.

Further, the present invention will be explained in detail.

β of the dye with the formula (Il) stable for dyeing at high temperatures
- type crystals are obtained by a known coupling method followed by diazotization. A wet cake or a dry cake of α-type crystals is heated at 40°C or higher in water or water containing a water-soluble organic solvent or an anionic or nonionic surfactant. Obtained by heating at temperature. When heating with only water, the treatment temperature is usually higher than when heating with water containing a water-soluble organic solvent or an anionic or nonionic surfactant.
Preferably, the treatment is carried out at 00° C. or higher, for example, 120 to 160° C., for about 3 hours.

However, the processing time can be made longer or shorter as necessary. When processing with water containing a water-soluble organic solvent or anionic or nonionic surfactant, heat at 40°C or higher, preferably 50°C or higher and 100°C or lower for about 3 hours.1
-, the α-type crystal is converted into the β-type crystal.

At this time, it is acceptable to maintain the temperature at 100° C. or higher or to extend the treatment time, but this is economically disadvantageous. The water-soluble organic solvents used are methanol,
Lower alcohols such as ethanol, inglobil alcohol, butyl alcohol, monoalkyl ethers of ethylene glycol such as butyl cellosolve, ethyl cellosolve, butyl cellosolve, glycols such as ethylene glycol, ketones such as acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, etc. Examples include cyclic ethers.

Examples of anionic surfactants used include β-7talinsulfonic acid (formalin condensate) salts, ligninsulfonate salts, and examples of nonionic surfactants include sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, Polyoxyethylene alkyl ethers, polyoxyethylene alkylphenols, polyoxyethylene alkyl amides, etc. are available. These can be used alone or in combination of two or more. The amount of water-soluble organic solvent or anionic or nonionic surfactant to be used is 1 to 70% (weight ratio) based on the water used, but when a dispersant is used as the surfactant, the crystals are separated after crystal conversion. If the dispersion process is carried out without the above, it is also possible to use more than the above-mentioned amount.

Crystal conversion from α-type crystals to β-type crystals is carried out after the coupling reaction using a wet cake obtained by filtration and washing with water, or by drying it, but it is difficult to do so without going through the filtration process. It can also be carried out by adding a required amount of a water-soluble organic solvent or an anionic or nonionic surfactant to the reaction solution after the coupling reaction and then heating it.

Also, if it does not adversely affect the coupling reaction, adding the solvent or surfactant before the coupling reaction and heat treatment after the coupling reaction can change the α-type crystal to the β-type crystal. Conversion is possible.

In the present invention, whether or not the desired crystal transformation has been completed can be confirmed by the I law of the X-ray diffraction spectrum.
- type crystals are orange in color, so they can also be determined by observing the powder appearance of the crystals.

Once the crystal conversion is completed, the crystals are generally separated and then dispersed using a known method, but without having to separate the crystals, the required amount of female agent 11 is added to the processing solution for dispersion. It is also possible to do this. The dye made into fine particles by the dispersion treatment is used for dyeing in the form of a paste or, if necessary, dried and powdered.

The present invention will be specifically explained below using Examples.

In the text, parts mean parts by weight.

Example 1 138 parts of p-nitroaniline, 600 parts of water, 270 parts of hydrochloric acid
Add 450 parts of ice to the mixture, lower the liquid temperature to below +5%℃, add 40% sodium nitrite 176I, and then
Hold at 3°C for 2 hours. The obtained diazo solution is added to a solution of 236 parts of N-cyanoethyl-N-benzylaniline dissolved in 1000 parts of a 70% aqueous sulfuric acid solution at 0 to 3°C. Thereafter, the mixture was kept at room temperature for 24 hours, filtered, and washed with water to obtain 1161 parts of a wet cake (dye content: 3465 parts).

When a part of this is dried in a dedicator, the dark red formula (I
A powder of α-type crystals of the dye represented by ) was obtained. The X-ray diffraction pattern is shown in Figure 2.

232 parts of the obtained α-type crystal wet cake (50 parts as dry dye), 20 parts of Demol N (manufactured by Kao Atlas Co., Ltd., an anionic surfactant), and Demol C (manufactured by Kao Atlas Co., Ltd., anionic surfactant).
9 parts of a mixture of 20 parts of anionic surfactant) and 400 parts of water.
The mixture was heated at 0 to 95°C for 3 hours, filtered, washed with water, and then dried under reduced pressure. The obtained orange β-type crystal powder gave an X-ray diffraction pattern as shown in FIG.

Staining Example 232 parts of β-type crystal powder obtained in the same manner as in Example 1 was sanded with 62 parts of Thymol N, 145 parts of Thymol 0, 2 parts of Lebenol DT400 (manufactured by Kao Atlas, a nonionic surfactant), and 559 parts of water. It was ground with a grinder to obtain 1000 parts of dye paste.

After dissolving 0.36 parts of this dye paste in 180 parts of water and adjusting the pH to -15 with acetic acid, 15 g of cloth made of polyester fiber was added and kept at 130°C for 60 minutes under pressure, then taken out and soaped. After washing, washing, and drying, a uniformly dyed orange cloth was obtained.

Reference Example In Example 1, the temperature of the treatment solution containing β-type crystals after crystal conversion was lowered by shaking at room temperature, and after adding a dispersant to the treatment solution without going through the filtration and drying steps, it was treated with a sand grinder. did. Fine particle dyeing of the obtained β-type crystals; 1 paste uniformly dyed polyester fiber fabrics.

Example 2゜Dispersant Demol C for crystal conversion in Example 1,
Revenol J instead of Demol N) T400 40
A β-type crystal was obtained by carrying out the same treatment as in Example 1.

Example 3 Dispersant Thymol C1 for crystal conversion in Example 1
The same treatment as in Example 1 was carried out using 10 parts of Tween 80 (polyoxyethylene sorbitan nonionic surfactant) in place of Demol N to obtain β-type crystals.

Example 4 Dispersant Demol C for crystal conversion in Example 1,
Demol N was treated in the same manner as in Example 1 using ethylene glycol monomethyl ether to obtain β-type crystals.

Example 5 70% (t Ia! 802 parts of Tween is added to a mixture of 100 parts of aqueous solution and 23.6 parts of N-cyanoethyl-N-benzylaniline and stirred for 2 hours. To this liquid is added 13.8 parts of p-nitroaniline. After adding the diazotized solution at 0 to 3°C, it was kept at the same temperature for 3 hours and further stirred at room temperature for 20 hours.After that, caustic soda was added and the pH of the reaction solution was adjusted to 4-
After setting the temperature to 5, the temperature was raised to 50°C and kept at the same temperature for 2 hours. After filtering and washing with water, β-type crystals of the dye of formula (1) were obtained.

After adding caustic soda to bring the PL-1 to 4-5 and before stopping, a portion of the reaction solution was zumbling, filtered, and washed with water. The crystals obtained were α-type crystals.

Comparative Test Each dye paste was prepared from α-type crystals and β-type crystals of formula (I) in the same manner as in the dyeing example above.

Compare the stability of the obtained dye paste against heat.
In order to determine this, 1) a heat and L collection test, and 2) a casing spot test were conducted. (Table 1) Details of each test method are as shown in 9 below.

(1) Thermal flocculation test 0.36 parts of dye paste was dispersed in 100 parts of water, mixed with acetic acid and sodium acetate, and the pI-1 was adjusted to 4.5. Bath) F paper (manufactured by Toyo Kagaku Sangyo Co., Ltd.; No. 5 AP paper) was suction filtered at ℃ and judged from the amount and condition of the residue on the door paper. Based on a five-level scale from grade 5 (good) to grade 1 (poor).

(2) Casing spot test Disperse 0.73 parts of dye paste in 180 ml of water and add acetic acid,
Tetron Jersey 151 was immersed in a dye bath adjusted to pi-14.5 with sodium acetate, heated from 80°C for 40 minutes (using a color pet dyeing machine) to 130°C, and left at the same temperature for 10 minutes. After the temperature was maintained, it was cooled to 95° C. for 5 minutes, and the state of the aggregates adhering to the part where the dyed object was inscribed in the dyed object holder was judged. Based on a five-level scale from grade 5 (good) to grade 1 (poor).

Table 1

[Brief explanation of the drawing]

Figure 1 shows the X-ray radiation of a thermally stable β-type crystal. FIG. 2 is an X-ray diffraction diagram of a thermally unstable α-type crystal. Patent applicant Nippon Kayaku Co., Ltd.

Claims (1)

[Claims] (1) In the powder X-ray diffraction method using Cu-Kα rays, the diffraction angle (2θ) C6J16.5, 2'Q, 3, 26
．． 5K extremely strong peak, diffraction angle (2θ) C″17.
2゜14.4, 16.1, 24.8, 26.1.29.
(1) Crystal modification of the dye represented by formula (I) characterized by an X-ray diffraction pattern with a rather strong peak (2) Powder
In line diffraction method, diffraction angle (2θ) l:”II 6.5
, 20.3. Extremely strong peak at 26.5, diffraction angle (2θ) [7.
2, 14.4, 16.1, 24.8, 26.1
．． 29. A method for producing a crystal modification of a dye represented by formula (I) characterized by an X-ray diffraction diagram having a rather strong peak at 1.