JPS637224B2 - - Google Patents

Description

[Detailed description of the invention] The present invention produces characteristic reflections at the following glancing angle θ (CuK - line) and relative intensity: [θ] 6.0 8.6 9.5 12.1 12.7 13.4 14.8 Relative intensity 100 22 27 57 49 38 31 characterized by the X-ray diffraction diagram shown in FIG. The present invention relates to a new crystallographic modification (β-modification) of the dye represented by the formula, which is stable under dyeing conditions.

The dye of the above formula is 2-chloro-4 in aqueous hydrochloric acid solution.
It is obtained by diazotizing -nitro-aniline and coupling the resulting diazo compound solution with a solution of N-ethyl-N-cyanoethyl-m-toluidine in dilute hydrochloric acid. In this case, an α-transformation occurs which does not have sufficient stability under the conditions that occur when carrying out the staining. The diffractogram (Fig. 2) shows: [θ] 2.6 6.2 8.7 12.8 13.4 13.8 Relative intensity 38 100 26 45 52 27 The β-transformation, which is stable to staining under staining conditions such as high temperature and in the presence of dyeing aids, There is virtually no further variation in grain size and crystal shape. In this case, therefore, the dyeing properties and the stability of the dispersion are not adversely affected, unlike the α-transformation, which is unstable under the dyeing conditions.

The new β-modification, which is stable under the staining conditions, is produced by preparing an aqueous suspension of the α-modification at 80-130°C, optionally under pressure.
Preferably, it can be obtained by heating at 90 to 110°C for 2 hours.

The transformation to the β-modification, which is stable under the dyeing conditions, can also be achieved by heating the α-modification in the form of an aqueous suspension at temperatures between 80 and 130 °C with the addition of water-soluble organic solvents, such as ethanol or glycols. It will be done.

Furthermore, the β-modification, which is stable under dyeing conditions, can be obtained by heating an aqueous suspension of the α-modification at a temperature of about 80 to 100° C. with the addition of anionic, cationic or nonionic surface-active compounds. Suitable surface-active compounds for this are, for example, sodium diisobutylnaphthalene sulfonate, an addition product of 25 mol of ethylene oxide and 1 mol of stearyl alcohol, a mixture of alkyldimethylbenzylammonium chlorides, an addition product of 2 mol of ethylene oxide and 1 mol of lauryl alcohol. These are tertiary organic phosphate esters or fatty acid polyglycolic esters.

Furthermore, stable β-transformation can be obtained under staining conditions by the following method. That is, the α-modification can be carried out using conventional dispersants, such as alkylated naphthalene sulfonic acids, polyvinyl sulfonates, condensation products of naphthalene sulfonic acid and formaldehyde or of phenols and formaldehyde, alkali salts of lignin sulfonates or sulfite cellulose waste liquors. obtained by grinding at a temperature of about 80-90°C with the addition of

The β-modification, which is stable under the dyeing conditions, is separated after its preparation, for example by filtration of the liquid phase, and a known finish consisting of a dispersant, such as alkylated naphthalene sulfonic acid, polyvinyl sulfonate, naphthalene sulfonic acid and formaldehyde, is applied. or a condensation product consisting of phenol and formaldehyde,
It is carried out at normal temperatures with the addition of an alkali salt of lignin sulfonate or a sulfite cellulose waste solution. Customary equipment such as ball mills or sand mills are suitable for microdispersion.

Preparations of the β-transformation, stable under the dyeing conditions, obtained in this way in liquid or powder form have comparable α-
Unlike the modified preparations, they are suitable without any restrictions for dyeing textile materials consisting of cellulose esters or synthetic linear polyesters, such as polyethylene glycol terephthalate, at temperatures from 100 DEG to 220 DEG C. Preparations that are stable under these dyeing conditions do not aggregate in aqueous media and under the influence of high temperatures. This is particularly important for dyeing rolls, such as cheese rolls, and results in improved test results in various dyeing tests.

In the following examples, unless otherwise specified, "parts" and "%" are by weight.

Example 1 2-chloro-4-nitro-aniline was diazotized in an aqueous hydrochloric acid solution, and the diazo compound obtained in the solution was coupled with a dilute hydrochloric acid solution of N-ethyl-N-cyanoethyl-m-toluidine. 100 parts of the dye are heated in the form of an aqueous suspension to 90-95° C. for 2 hours. At this time, the α-transformation, which is unstable under the staining conditions, changes to the β-transformation, which is stable under the staining conditions. The dyestuff is taken and ground with 110 parts of a condensation product consisting of cresol, formaldehyde and sodium bisulfite, the sodium salt of diisobutylnaphthalenesulfonic acid and water in a pearl mill at a temperature not exceeding 50°C until fine dispersion is achieved. . The preparation is then dried in a spray device. After drying, the desired content of pure dye is adjusted using the sodium salt of dinaphthyl methanesulfonic acid. The powder obtained satisfies all dyeing requirements.

Example 2 100 parts of the water-moistened monoazo dyestuff obtained according to Example 1 were prepared without after-treatment with 110 parts of a condensation product of cresol, formaldehyde and sodium bisulfite, diisobutylnaphthalenesulfonic acid, as described in Example 1. Grind in a ball mill with sodium salt and water at 80-90°C until fine dispersion is achieved. At this time, the α-transformation, which is unstable under the staining conditions, changes to the β-transformation, which is stable under the staining conditions. The preparation is dried in an atomizer and adjusted to the desired purity content as described in Example 1.

Example 3 100 parts of the monoazo dye obtained in Example 1 was added to Example 1.
It is converted to the β-modification, which is stable under the dyeing conditions, by heating in the form of an aqueous suspension at 90-95° C. for 2 hours as described in . The water-moistened percake is ground as described in Example 1 with 60 parts of a condensation product consisting of cresol, formaldehyde and sodium bisulfite, 60 parts of the sodium salt of ligninsulfonic acid and 20 parts of the sodium salt of diisobutylnaphthalenesulfonic acid. , dried and adjusted to the desired content of pure ingredients.
The powder preparation obtained satisfies virtually all dyeing requirements.

Example 4 100 parts of the monoazo dye obtained according to Example 1 were added in the form of an aqueous suspension containing 10% glycol for 2 hours.
Heat to ~95°C, cool and aspirate. The water-moist percake is ground with the dispersant given in Example 1 in a pearl mill at temperatures up to 50 DEG C. until well-finely dispersed. A liquid dye preparation with satisfactory dyeing properties and good stability is thus obtained.

Example 5 100 parts of the monoazo dye obtained according to Example 1 were stirred for 2 hours at 90° C. in the form of an aqueous suspension containing 0.5% by volume of the reaction product of the tertiary organophosphate ester of lauryl alcohol with 2 moles of ethylene oxide. do. The dye taken off is ground as described in Example 1. A liquid dye preparation with satisfactory dyeing properties is thus obtained.

[Brief explanation of the drawing]

Figures 1 and 2 are X-ray diffraction diagrams. X-rays are Cu-
In the K〓 line, the horizontal axis is the glancing angle and the vertical axis is the relative intensity.

Claims (1)

[Claims] 1. The X shown in FIG. 1 having characteristic reflections at the following glancing angles θ and relative intensities: [θ] 6.0 8.6 9.5 12.1 12.7 13.4 14.8 relative intensities 100 22 27 57 49 38 31 Characterized by a line diffraction diagram, Eq. The stable transformation (β
-transformation). 2 The X-ray diffraction diagram shown in Figure 1 is characterized by the characteristic reflections at the following glancing angles θ and relative intensities: [θ] 6.0 8.6 9.5 12.1 12.7 13.4 14.8 relative intensities 100 22 27 57 49 38 31 Equation (1) The stable transformation (β
When producing an α-modified dye expressed by the above formula (1) which is unstable under dyeing conditions and is characterized by the X-ray diffraction pattern shown in FIG. A process for producing the β-modification of the above dye, characterized in that it is heated as a suspension to a temperature of 80 to 130°C or (b) ground at 80 to 90°C in the presence of a dispersant. 3. The method according to claim 2, which comprises heating while adding a water-soluble organic solvent in the method (a) above. 4. The method according to claim 2, which comprises heating with the addition of an anionic, cationic or nonionic surfactant compound in the method (a) above.