DD244349B1 - METHOD FOR PRODUCING NEW BLACK PENTAKISAZO DYES - Google Patents

Description

Field of application of the invention

The invention relates to a process for the preparation of novel black Pentakisazofarbstoffe of formula I (see formula Appendix) in which K is the radical of one of the coupling components acetoacetanilide, phenol, 3-hydroxy-2'-methyl-diphenylamine or 1,3-diaminobenzene and the one X is SO ₃ H and the other X is H. The new dyes are well suited for dyeing hydroxy- and nitrogen-containing natural or synthetic fiber materials, for example cellulose, cotton, regenerated cellulose, wool, half wool, silk and paper, but especially for dyeing leather.

Characteristic of the known state of the art

DD-PS 100486, 100730 and 112772 describe the preparation of tetrakisazo dyes which satisfy the general formula II, in which K, = the radical of optionally substituted 1,3-diaminobenzenes and / or hydroxydiphenylamines.

Dyes of this type dye natural fiber materials, especially leather, in black tones. But they have application-technical defects; especially the weak general acid resistance and the low solubility in water are mentioned here.

Object of the invention

The aim of the invention are new, natural fiber materials black dyes, the o.g. no longer have technical defects.

Explanation of the essence of the invention

The objective has been found to correspond to pentakisazo dyes which are obtained by coupling one mole of bis-diazotized 4,4'-diamino-diphenylamine-2-sulfonic acid to 2 mol of 2-amino-8-hydroxynaphthalene-6-sulfonic acid in an alkaline manner, the diaminodisazo compound obtained bisdiazotiert, with one mole of 1,3-diaminobenzene-4-sulfonic acid coupling, the resulting compound with one mole of diazotized 1-aminobenzene-4-sulfonic acid and finally to one mole of acetoacetanilide, phenol, 3-hydroxy-2'-methyl-diphenylamine or 1,3-diaminobenzene couples. The diazotizations and couplings are carried out in a conventional manner.

In addition to the improved acid resistance to formic acid and the high solubility in water, the Pentakisazofarbstoffe have a good balance on chrome leather, but also on combined tanned leather, and other leather ranges on.

Due to their excellent dyeing properties, the dyes achieve a high color depth and an excellent level of authenticity in scar and suede leather. For example, the dye of the formula I obtained according to the invention having acetoacetanilide as coupling component K has great application-technological significance. Its improved performance is compared to the obtained according to Example 1 of DD-PS 112772 dye in the table below:

Properties According to the Invention

Fastnesses obtained DD-PS112 772

Dye Example 1

2.2

Solubility 20 ° C / 60 ° C 5.5 acid resistance 3 Coloring (Velor) 4 rub fastness dry 4 wet 3

According to the invention Dye according to -2- 244 349 properties preserved DD-PS 112 772 fastness dye example 1 fastness to washing 5 5 hue 5.5 2.3 Bleeding BW / Wo water fastness 5 4 hue 5.5 5.5 Bleeding BW / Wo migrationfastness 5.5 3-4 / 4 Scar depth / flesh side - for all leathers - preferably for application width suitable species chrome leather - to reach - does not deliver rich, durchge by colored dyed black black leather leather

embodiments example 1

A bisdiazo compound prepared from 28 parts of 4,4'-diamino-diphenylamine-2-sulfonic acid, 400 parts of water, 40 parts of 32% hydrochloric acid and 14 parts of sodium nitrite at 10 ⁰ C runs within 90 minutes in one of 48 parts of 2-amino -8-hydroxynaphthalene-6-sulfonic acid, 400 parts of water and 34 parts of sodium carbonate existing coupling component solution. The temperature is 10 ⁰ C, the coupling is completed after stirring overnight. The resulting Diaminodisazofarbstoff is cooled to ^{0 0} C, treated with 100 parts of 32% hydrochloric acid and bisdiazotiert by addition of 14 parts of sodium nitrite in 30 minutes. Here, a solution quickly running, consisting of 19 parts of 1,3-diaminobenzene-4-sulfonic acid, 210 parts of water and 17 parts of sodium carbonate.

The half-sided coupling comes to an end quickly.

The temperature should not exceed 5 ° C.

The medium reacts slightly acidic. Is no longer a coupling component detectable approaches the Diazotrisazoverbindung one from 17.5 parts of sulfanilic acid, 120 parts of water, 20 parts of 32% hydrochloric acid and 7 parts of sodium nitrite diazonium compound prepared, with a temperature of 1O ⁰ C is established.

By adding 150 parts of 12.5% sodium carbonate solution within 60 minutes, the coupling is completed.

The suspension reacts weakly alkaline. If no diazotized sulphanilic acid is detectable, the final coupling takes place.

It is carried out by adding acetoacetanilide, which is dissolved to 17 parts in 180 parts of water and 24 parts of 30% sodium hydroxide solution. At 10 ° C, the clutch ends overnight. The dye is salted out with 180 parts of sodium chloride, heated to 60 ° C, filtered off with suction and dried at 100 ⁰ C.

He dyes chrome leather in greenish blacks. Use fastnesses are shown in the table above.

Example 2

If phenol is used instead of acetoacetanilide, then you get a dye that is obtained in a slightly bluish hue. The performance characteristics correspond to those of the dye of Example 1.

Example 3

If 3-hydroxy-2'-methyl-diphenylamine is used instead of acetoacetanilide, then a dye is obtained which is obtained in a slightly redder hue.

The performance characteristics correspond to those of the dye of Example 1.

Example 4

If 1,3-diaminobenzene is used instead of acetoacetanilide, a dye is obtained which dyes leather in a neutral black.

The performance characteristics correspond to those of the dye of Example 1.

Claims (3)

A process for the preparation of novel black Pentakisazofarbstoffe of formula (I), wherein K is the radical of one of the coupling components acetoacetanilide, phenol, 3-hydroxy-2'-methyl-diphenylamine or 1,3-diaminobenzene, and one X for SO3H and the other X stands for H, by alternating and repeated application of diazotization or coupling reaction steps in a conventional manner, characterized in that first the coupling of 2 moles of 2-amino-8-hydroxynaphthalene-6-sulfonic acid with 1 mole bisdiazoti2rter4,4'-diaminodiphenylamine-2-sulfonic acid, the renewed bisdiazotization of the resulting product and its subsequent coupling with one mole of 1,3-diaminobenzene-4-sulfonic acid , followed by the reaction of the resulting compound with one mole of diazotized i-aminobenzene-4-sulfonic acid followed by coupling with acetoacetanilide, phenol, 3-hydroxy-2'-methyl-diphenylamine or 1,3-diaminobenzene is made. For this 1 page formulas