DE2251706A1 - COLOR-STABLE MODIFICATIONS OF A DISPERSION COLORANT - Google Patents

Description

Color-stable modifications of a disperse dye

The invention relates to two new modifications of the dye of the formula . > ■ '■

CH ₂ -CH ₂ -OOOCH ₃ Χ ^Η 5

with X-ray diffraction diagrams (Cu K _a radiation) with the following line images:

a) Line of strong intensity at a diffraction angle 2 θ / "ο / from 25.3 *

Lines of medium intensity at diffraction angles 2 θ £ ° J of 7.3, 13.6, 13.9, 16.7, 21.1, 23.1 and 29.0 and lines of low intensity at diffraction angles 2 θ C ⁰ J of 14.3, 18.3, 19.8, 22.6 and 26.1 and

b) Line of strong intensity at a diffraction angle 2 θ C ⁰ J of 24.5,

Lines of medium intensity at diffraction angles 2θ C ⁰ J of 10.9, 18.3 and 22.3 and

Lines of low intensity at diffraction angles 2 θ Z ~ ° _7 of 9.0, 17.8, 20.8, 23.2, 26.2, 27.6 and 28.0.

The modification of the dye, referred to below as the α-modification, is known, its X-ray diffraction _{diagram (Cu K a} radiation) according to Figure 1 at a diffraction angle 2θ of 25.5 ° a line of strong intensity, with diffraction angles of 5.9 °, 12 , 1 °, 13.0 °, 14.2 °, 15.9 °, 17.8 °, 18.4 °, 24.1 °, 26.0 ° and 28.0 ° lines of medium intensity and at diffraction angles of 9.7 °, 11.0 ° and lines of low intensity. The dye is

533/72 -2-

409817/0970

- 2 - O. Z. 29 477

known as a disperse dye for dyeing and printing textile material, especially polyester-cellulose acetate and -triacetate fiber material. He can after that from the German patent specification 1,544,375 known method by coupling diazotized N-ethyl-N ~ ß-carbomethoxyethylaniline and 3-amino-5-nitro-2,1-benzisothiazole be prepared in acidic medium. The modification obtained in this way is under the conditions of Plot dyeing is not sufficiently stable to dye.

The new modifications of the present invention, hereinafter referred to as ß-modification (connection with the line of strongest intensity at 25.3 ° in the X-ray diffraction diagram) and γ-modification (connection with the line of strongest intensity at 24.5 in the X-ray diffraction diagram), are prepared by heating the α-modification in aqueous suspension. This is based on an aqueous suspension of the α-modification as it is obtained in the preparation of the dye after coupling or as it can be obtained from the dye by redispersion. The suspensions can additionally contain surface-active substances such as dispersants and wetting agents. For conversion of the "modification in the desired color-stable ß-γ and modifications can is eg so that the suspension is heated within 30 to 60 minutes under stirring to 60 ⁰ C, then the temperature at intervals of 30 to 60 minutes increases by 5 to 10 ⁰ C to a temperature of 70 to 75 ⁰ C and left at this temperature for a further one to two hours. This treatment converts the α-modification to a greater or lesser extent into the β-modification. Further heating to 85 to 10O ⁰ C leads to complete conversion into the ß-modification and further to the formation of the γ-modification. The conversion is all the more complete, the purer the starting material.

Following this temperature treatment, the suspension can be expediently after cooling to room temperature »if necessary after dilution with water, filter and obtain the dye pure in a manner known per se. Instead of purely aqueous suspensions can also be dye suspensions in mixtures of water with polar organic solvents,

409817/0970 ~ ³ ~

- 3 - O.Z. 29 477

such as alcohols, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone are subjected to the temperature treatment. In these cases, it is advantageous to work with strongly supersaturated solutions at temperatures of about 50 ^° C. and above.

After workup and drying, blue pigments compared to the previously known α-modification in the normal manner for disperse dyes, dyeing, ie aqueous medium at temperatures up to about 140 ⁰ C, if appropriate in the presence of customary dyeing auxiliaries, in particular after aging in liquid preparations , are stable in color, ie their crystal structure no longer adversely change under the specified conditions. They also show better rheological properties, which are expressed in particular in the perfect flowability of liquid preparations even after prolonged storage.

The conversion can be carried out by recording X-ray diffraction spectra, Infrared spectra (KBr) or by microscopic and electron microscopic observations of samples taken easily track.

The arcing diffraction diagrams according to Debye-Scherrer shown in Figures 1, 2 and 3 can be assigned to the modifications α, ß and γ. A counter tube goniometer was used for recording and an X-ray structure tube with Cu K _a radiation was used as the radiation source. The goniometer rotation speed was 1 ° per minute.

The indicated diffraction angles were measured using diffraction diagrams that were recorded with rotational speeds of 0.25 ° per minute. For each graph, the intensity of the strongest line was set equal to $ 100. In comparison, the lines of an intensity of more than 25 fo were called lines of medium intensity and the lines of an intensity of less than 25 <fo were called lines of low intensity.

'-4-409817 / 0970

- 4- - O.Z.29 477

In order to obtain technically suitable dye products for dyeing and printing, the novel modifications according to the invention can be used by customary mechanical processes, if necessary in the presence of suitable dispersants and other customary additives, such as antifreeze, buffer substances, protective colloids or small amounts of solvents, converted into a high degree of fine distribution will. Conventional devices, such as mills, for example, are suitable for the fine distribution which may be carried out Ball mills, rocking mills, sand mills or kneaders. Ale dispersant for example, condensation products of mono- or polynuclear aromatic compounds, such as naphthalene, Naphthols, phenols or their sulfonic acids, with formaldehyde or other substances that condense with aromatic rings can, such as urea, ethylene oxide or isocyanates, optionally with the addition of sodium sulfite, also lignosulfonates and nonionic and anionic surface-active compounds into consideration.

The new dyestuff modifications converted into high fine distribution are particularly suitable for dyeing textile materials made of synthetic linear polyesters, such as polyethylene glycol terephthalate or chemically analogous polymers, and semisynthetic fiber materials such as cellulose triacetate at temperatures of about 100 to 200 ^° C. The new dyestuff modifications are dispersion-stable under dyeing conditions and do not have the disadvantage of dyestuff flocculation in dyeing processes in which they are exposed to a relatively high temperature in an aqueous medium for a prolonged period. In particular when dyeing wound bobbins - for example cheeses - no agglomeration, flocculation and finally filtration of the dye on the bobbins occur even when the dye liquor is only slowly exhausted or when working with such a large excess of dye that the dyebath is never exhausted . This is why the new dye modifications are particularly suitable in apparatus dyeing for loose material and when dyeing bobbins or yarns.

In the following examples, data refer to parts and percentages, unless otherwise noted, on weight.

409817/0970 -5-

- 5 - 0.Z. 29 477

example 1

60 parts of the nach. DBP 1 544 375 dye of the α-modification obtained in the acidic coupling of diazotized 3-amino-5-nitro-2,1-benzisothiazole with N-ethyl-N-ß-carbomethoxyethylaniline are mixed with 30 parts of a ligninsulphonate with an average molecular weight of over 12,000 and an average content of 0.05 to 0.2 sulfo groups per phenylpropane unit in an aqueous dilution of 20 to 30 $ (dry content), stirred for ^{2 hours at 70 °} C., then for 8 hours at 90 ^{° C.} After this temperature treatment, the dye-dispersant mixture contains the stable dye modification γ.

The dye / dispersant mixture obtained in this way is finely divided after cooling without being filtered off and gives a liquid dispersion containing at least 20% dye with very good rheological properties.

The liquid preparation made from the new modification is very dispersion-stable even under dyeing conditions and is particularly suitable for dyeing synthetic textile materials and semi-synthetic fibers using modern dyeing processes. It does not lead to dye flocculation or filtration under the conditions of such dyeings, which are usually carried out at higher temperatures. That is particularly beneficial from when dyeing bobbins made of polyester or triacetate fibers.

Example 2

100 parts of pressed material of the α-modification of the dye obtained by coupling dlazotierter 3-amino-5-nitro-2,1-benzisothiaz'ol with N-ithyl-N-β ~ carbomethoxyethylaniline are obtained as a 10 to 15% aqueous suspension for 2 hours at 60 ^° C., then at 70 ^° C. for 2 hours and finally at 80 to 85 ^° C. for 4 hours. After cooling, the dye obtained in the stable β-modifications is filtered off and used as a moist pressed material for dispersion. After fine division, a color-stable dispersion is obtained that is suitable for modern dyeing processes and has a dye content of at least $ 50 to $ 70,

409817 / 0970-

- 6 - O.Z. 29 477

those for dyeing and printing polyester textile material and cellulose triacetate is eminently suitable.

Example 3

97 parts of the α-modification of the dye obtained by coupling diazotized 3-amino-5-nitro-2,1-benzisothiazole with N-ethyl-N-ß-carbomethoxyäthy! Anilin with 3 parts of the sodium salt of diisobutylnaphthalenesulfonic acid as a 20 to 25 #ige aqueous suspension stirred for 1 hour at 70 ⁰ C for 2 hours at 80 ⁰ C and finally for 8 hours at 90 to 95 ⁰ C. After cooling, the dye converted into the new modifications (67 $> ß- and 33 $> γ-modification) is filtered off and washed. After dispersion, the dyestuff pressed material results in a dye-stable dispersion which is excellently suited for dyeing and printing textile material made of polyester and cellulose triacetate.

Example 4

100 parts of the dye obtained in the α-modification by coupling diazotized 3-amino-5-nitro-2,1-benzisothiazole with N-ethyl-N-ßcarbomethoxyätnylanilin are as a suspension in a mixture of 530 parts of water and 60 parts of dimethylformamide 2 Stirred for hours at 60 ^° C., then for 5 hours at 90 ^° C. and then filtered off while hot. The dyestuff thus converted into the γ-modification gives, after distribution, a color-stable dispersion, suitable for modern dyeing processes, with a dyestuff content of at least 50 to 70,56, which is excellently suited for dyeing and printing textile material made of polyester and cellulose triacetate.

-7-409817 / 0970

Claims (3)

- 7 - O.Z. 29 477 Claims
1. Color-stable modifications of the dye of the formula ^s / T ^ OH ₉
N = N- / VN ^ NO characterized by X-ray diffraction diagrams (Cu K _a radiation) with the following line images: a) Line of strong intensity at a diffraction angle 2 θ £ ⁰ J of 25.3, Lines of medium intensity at diffraction angles 2 θ £ ⁰ J of 7.3, 13.6, 13.9, 16.7, 21.1, 23.1 and 29.0 and lines of low intensity at diffraction angles 2 θ £ ⁰ J of 14.3, 18.3, 19.8, 22.6 and 26.1 and b) Line of strong intensity at a diffraction angle 2 θ C ⁰ J. of 24.5, Lines of medium intensity at diffraction angles 2θ £ ⁰ J of 10.9, 18.3 and 22.3 and Low intensity lines at diffraction angles 2θ £ ° J of 9.0, 17.8, 20.8, 23.2, 26.2, 27.6, and 28.0. 2. Process for the preparation of the dye modifications according to Claim 1, characterized in that the dye of the formula which has the X-ray diffraction diagram shown in Fig. 1, in, optionally polar organic solvents containing, aqueous suspension heated to temperatures of over 60 C until the dye products are formed have the X-ray diffraction diagrams shown in Fig. 2 and Fig. 3. -8- '409817/0970 - 8 - O. Z. 29 477 3. Use of the dye modifications according to claim 1 for dyeing textile material made of polyester and cellulose triacetate. Badische Anilin- & Soda-Fabrik AG Sign. 409817/0970