JPS5824461B2 - Bunsan Senriyou no Shikisai Anteina Hentai - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides the following line image (a) in an X-ray diffraction diagram (α-irradiation on Cu):
Diffraction angle 2θ(0)7.3, ■3.6.13.9.16.
Moderate intensity lines at 7.21, 1.23.1 and 29.0, diffraction angle 2θ(0) 14.3, ■8.3, ■9.8.22
．． 6 and 26.1 with lines of weak intensity.

As shown in Figure 1, the X-ray diffraction diagram (α-irradiation on Cu) shows an intense line at a diffraction angle of 2θ25.5°, a diffraction angle of 5.9°,
12.1°, 13.0°, 14.2°, 15.9°, 1
7.8°, 18.4°, 24.10.26.0° and 2
A dye modification, hereinafter referred to as the alpha modification, having a line of moderate intensity at 8.0° and lines of weak intensity at diffraction angles of 9.7° and 11.0° is known.

This dye is known as a disperse dye for dyeing or printing textile materials, especially polyester, cellulose acetate and triacetate.

This was done by converting the diazotized product of N-ethyl-N-β-carbomethoxyethylaniline into 3-amino-5-nitro-2.
1=Prepared by coupling with benzisothiazole in acidic medium.

The dye modifications thus obtained do not have sufficient color stability under the conditions of bath dyeing.

The novel modification according to the present invention is hereinafter referred to as the β modification (a compound with a strong line of intensity at 25.3° in the X-ray diffraction diagram),
This is produced by heating the alpha modification in an aqueous suspension.

In the preparation of the dye, the starting point is an aqueous suspension of the dye obtained either from the α modification obtained after coupling or from its redispersion.

The suspension may further contain surface-active substances such as dispersants and wetting agents.

In order to transform the α modification to the desired color-stable β modification, the suspension was heated to 60 °C for 30-60 minutes with stirring, and then the temperature was increased at intervals of 30-60 minutes, respectively.
~], the O'C is raised to 70-75°C and held at this temperature for an additional 1-2 hours.

By processing in this way, the α-transformation changes to the β-transformation in large quantities, even if there is a slight difference.

Further heating to 85-100° C. completes the transition to the β modification and further forms the γ modification.

The purer the starting material, the more completely the transition takes place.

The γ transformation is shown in the following line image (b) in the X-ray diffraction diagram (Cu, K (1-irradiation)): a line with strong intensity at diffraction angle 2θ (0,124,5, diffraction angle 2θ(0) 10.9. Moderate intensity lines at 18.3 and 22.3, diffraction angle 2θ(0) 9.0, ■7.8.20.8.23.
It has lines of weak intensity at 2.26, 2.27, 6 and 28.0.

The γ transformation is also novel and color stable.

The β-modification according to the invention may also be obtained in a mixture with the γ-modification, but the color stability is not adversely affected in this case either.

Following this heat treatment, the suspension, preferably after cooling to room temperature, is filtered, optionally after dilution with water, and the dye is purified in the usual manner.

Instead of a pure aqueous suspension, a dye suspension in a mixture of water and a polar organic solvent such as alcohol, acetone, methyl ethyl ketone, dimethyl formamide, dimethyl sulfoxide or N-methylpyrrolidone may be heat treated.

In this case, it is particularly advantageous to treat highly supersaturated solutions at temperatures of about 50° C. or higher.

After finishing and drying, a blue pigment is obtained, which, in contrast to the previously known α modification, requires the usual dyeing conditions for disperse dyes.
i.e. at temperatures up to about 140°C in an aqueous medium (
(optionally in the presence of customary dyeing auxiliaries), and in particular after maturation (possibly standing at elevated temperatures) in liquid preparations, i.e. under the conditions mentioned, the crystal structure is There's nothing to change.

They also exhibit improved rheological properties, which are manifested in particular in the faultless flowability of the liquid preparations even after long-term storage.

The transition can be easily tracked using X-ray diffraction spectra and external optical absorption spectra (KBr), or by observing the sample taken out using a microscope or an electron microscope.

The Debye-Scherrer X-ray diffraction patterns shown in Figures 1, 2 and 3 are for the α, β and γ modifications, respectively.

A counter goniometer is used for the imaging, and an X-ray structure tube with CuKα radiation is used as the radiation source.

The rotation speed of the goniometer is 1° per minute.

The measurement of a given diffraction angle is carried out by means of a diffractogram recorded at a rotation rate of 0.25° per minute.

In each figure, the intensity of the strongest line was taken as 100%.

In comparison, a line with an intensity greater than 25% was defined as a medium intensity, and a line with an intensity smaller than 25% was defined as a weak intensity line.

In order to obtain dye products suitable for industrial dyeing and printing, the novel transformation according to the invention can be carried out by conventional mechanical methods.
It is brought to a highly finely divided state, optionally in the presence of suitable dispersants and other customary additives such as antifreezes, buffer substances, protective colloids or small amounts of solvents.

For the optional comminution (ζ) customary equipment, such as grinders, such as ball mills, vibrating mills, sand mills or kneaders, are suitable.

Examples of dispersants include mononuclear or polynuclear aromatic compounds,
For example, condensation products of naphthalene, naphthols, phenols or their sulfonic acids with formaldehyde or other substances capable of condensation with aromatic rings, such as urea, ethylene oxide or isocyanates, optionally contain sodium sulfite and also lignin sulfonic acid. It is used with the addition of salts and nonionic or anionic surfactants.

A novel highly finely dispersed dye modification makes synthetic linear polyesters such as polyethylene glycol terephthalate or polymers of similar chemical structure and semi-synthetic fibers such as cellulose triacetate as finely divided as about 100-200'
It is extremely suitable for dyeing at a temperature of C.

The new dye modification is dispersion stable under the dyeing conditions and does not suffer from the disadvantage of precipitation of dye aggregates, even in dyeing processes involving prolonged exposure to hot aqueous media.

Especially when dyeing scrolls, e.g. wound on cruciform bobbins, agglomerates also agglomerate when the liquor is consumed only slowly or even when operating with such a large quantity of dye that no consumption of the liquor occurs. No product is produced, and there is no P classification of the dye on the last bobbin.

The new dye modification is therefore highly suitable in machine dyeing, especially for loosely laid materials and in the dyeing of wound yarns or threads.

Parts and percentages in the examples below are by weight unless otherwise indicated.

Example 1 Acidic coupling of diazotized 3-amino-5-nitro-2,1-benziisothiazole with N-ethyl-N-β-carbomethoxyethylaniline as described in DE 1544375 60 parts of the α-modified dye obtained by
2 along with 30 parts of lignin sulfonate that is ~0.2
0-30% (dry matter content) aqueous dilution and none, 7″0℃
Stir at 90° C. for 2 hours and then at 90° C. for 8 hours.

After this heat treatment, the dye/dispersant mixture becomes stable β of the dye.
Contains metamorphosis.

After cooling, the dye/dispersant mixture thus obtained is finely dispersed without suction filtration, resulting in a liquid, low-density (20% dye-containing dispersion) with very good rheology.

The liquid preparations produced from the new dye modifications are extremely dispersion-stable under various dyeing conditions and are particularly suitable for dyeing fiber materials from synthetic and semi-synthetic fibers by modern dyeing methods.

It does not cause dye agglomeration or dye overflow under its dyeing conditions, which are carried out at almost high temperatures.

This is particularly effective when dyeing wraps from polyester fibers or cellulose triacetate fibers.

Proceed as above, except that the dye is heat treated at 70°C for 2
time and then at 90° C. for 8 hours, a dye/dispersant mixture containing a stable gamma modification of the dye is obtained.

This mixture exhibits similar dispersibility and dyeability.

Example 2 Pressure of a dye in the α modification obtained by coupling diazotized 3-amino-5-nitro-2·l-benziisothiazole with N-ethyl-N-β-carbomethoxyethylaniline 100 parts as a 10-15% aqueous suspension at 60°C for 2 hours and finally at 70°C for 2 hours at 80-15%.
Stir at 85°C for 4 hours.

After cooling, the dye obtained as a stable β-modified substance is suctioned and filtered.
Used as a wet press for dispersion.

After fine dispersion, a dispersion with a low dye content (both 50-70%) is obtained which is color stable and suitable for modern dyeing methods;
It is highly suitable for dyeing and printing textile materials.

Example 3 97 parts of an α-modified dye obtained by coupling diazotized 3-amino-5-nitro-2,1-benziisothiazole with N-ethyl-N-β-carbomethoxyethylaniline were , 7 as a 20-25% aqueous suspension with 3 parts of sodium diisobutylnaphthalene sulfonate.
1 hour at 0℃, 2 hours at 80℃, and finally 8 hours at 90-95℃.
Stir for an hour.

After cooling, new transformation (67% β transformation and 33% γ transformation)
Suction and wash the dye that has changed into .

After dispersion, this dye press yields a color-stable dispersion;
It is highly suitable for dyeing and decontaminating polyester and cellulose triacetate.

Example 4 100 parts of an α-modified dye obtained by coupling diazotized 3-amino-5-nitro-2,1-benziisothiazole with N-ethyl-N-β-carbomethoxyethylaniline were , water) and 60 parts of dimethylformamide, stirred at 60°C for 2 hours, then at 80°C for 5 hours, and then filtered under hot suction.

After fine dispersion, the dye thus transformed into the β modification has a low dye content suitable for modern dyeing methods with color stability; at least 50
resulting in a dispersion with ~70%.

It is highly suitable for dyeing and printing textile materials from polyester and cellulose triacetate.

Operating as above, but heat-treating the dye at 60° C. for 2 hours and then at 90° C. for 5 hours, a dye/dispersant mixture containing a rigidly color-stable γ modification is obtained.

[Brief explanation of drawings]

Figure 1 shows the α-modified dye, and Figure 2 shows the β-modified dye.
FIG. 3 is an X-ray diffraction diagram of each of the γ-modified dyes.

Claims (1)

[Claims] 1 In the X-ray diffraction diagram (Cu, Ka-irradiation), the following line image diffraction angle 2θ (line with strong intensity at 0,125,3, diffraction angle 2
θ[0]7.3.13.6, ■3.9, ■6.7.21
．． Moderate intensity lines at 1.23.1 and 29.0, diffraction angle 2θ(0) 14.3.18.3.19.8.22
．． A color-stable modification of a dye of the following formula, characterized by having lines of weak intensity at 6 and 26.1. 2 A dye of the following formula having an X-ray diffraction pattern as shown in FIG.
Characterized by heating at a temperature of 60°C or higher until a dye with a line diffraction pattern is formed, the line of strong intensity at the diffraction angle 2θ (0,125,3, the diffraction angle 2
θ(0)7.3, ■3.6.13, 9.16.7.21
．． Moderate intensity lines at 1.23.1 and 29.0, diffraction angle 2θ(0) 14.3, ■8.3.19, 8.22
．． 6 and 26.1 Preparation of color stable modifications of the above dyes having lines of weak intensity.