DE3839459A1 - Azo disperse dyes - Google Patents

Abstract

The azo disperse dyes of the general formula I <IMAGE> where R1 and R2 are each independently of the other a halogen atom, R3 is methyl or else, if R5 is not ethoxy, hydrogen, R4 is hydrogen or methyl, and R5 is hydrogen, methyl, ethyl, chloromethyl, chloroethyl, vinyl, phenoxymethyl, C1-4-alkoxy, phenoxy, benzyloxy, allyloxy or unsubstituted or halogen- or C1-2-alkoxy-substituted C2-5-alkoxy, are highly suitable for dyeing hydrophobic, synthetic or cellulosic (semisynthetic) fibre material.

Description

It has been found that the azo emulsion paints differ from the general Formula I,

wherein
R₁ and R₂ independently of one another are a halogen atom,
R₃ is methyl or, if R₅ is not ethoxy, also hydrogen,
R₄ is hydrogen or methyl and
R₅ is hydrogen, methyl, ethyl, chloromethyl, chloroethyl, vinyl, phenoxymethyl, C _1-4 alkoxy, phenoxy, alyloxy, benzyloxy or C _2-5 alkoxy optionally substituted by halogen or C _1-2 alkoxy,

excellent for dyeing, block dyeing or printing on fibers or Fibrous material or materials made from full or half synthetic hydrophobic, high molecular weight organic substances, in particular also for rapid dyeing of polyester fiber suitable materials.

The dyes of the formula I can be used in a uniform form (only in 5-, or only in the 7-position of the benzothazole ring by a halogen atom substituted) or as a mixture of isomers. Generally receives one in the usual synthesis of 2-amino-dihalobenzthiazole Mixture, each in the 6-position and in the 5- or 7-position a halogen atom wearing.

In preferred compounds of the formula I, each independently of the other,
R₁ and R₂ fluorine, chlorine or bromine, preferably chlorine or bromine, especially chlorine,
R₂ methyl,
R₄ hydrogen and
R₅ is methyl, methoxy or ethoxy optionally substituted by a C _1-2 alkoxy group, preferably methyl or methoxy, in particular methyl.

The β modification of the disperse dye / isomer mixture of the formula Ia is particularly preferred

with characteristic lines in the X-ray diagram (Cu-k _α ₁ radiation) at grid spacings of 14.3 (strong), 9.5 (medium), 8.1 (medium), 7.3 (weak), 6.25 (strong), 5.0 (weak), 4.3 (weak), 3.9 (weak), 3.87 (weak), 3.6 (strong), 3.5 (strong), 3.38 ( strong) and 3.15 (weak) · 10 ^-10 m.

The new disperse dyes are produced by coupling a diazotized amine of formula II

with a compound of formula III  

The compounds of the formulas II and III are known or can be easy to produce in analogy to known methods. After the usual Manufacturing process for the amine of formula II always falls as Mixture of the 5,6- and 6,7-dihalogen compound. Diazotize and domes also take place in analogy to known work regulations.

The dye of the formula Ia is obtained by heating the amorphous α- modification (prepared by diazotization and coupling, according to Example 1) for about ½ to 2 hours, in the dry state or in aqueous suspension, at temperatures between 40 and 100 ° C. converted into the heat-stable β modification. The β modification is particularly suitable for dyeing, in particular for high-temperature dyeing, in accordance with all common methods.

The new dyes meet the needs of modern dye shops short dyeing time at the lowest possible temperature, good dye yield and excellent fastness properties, very contrary to the dyeing of polyester fiber materials (especially polyethylene terephthalate Fiber material) at temperatures above 120 ° C only a dyeing time between Requires 10 and 20 minutes.

The new dyes are characterized by high dyeing speed, good bath extract and good color yield (color depth), as well as high Degree of fixation and good consistency of shades over a wide temperature range out. The colorations obtained are perfectly irrelevant and so well fixed that subsequent reductive post-cleaning is largely unnecessary. Among the fastness properties of the dyeings obtained are the light, rubbing, Sweat, washing and pleating fastness are particularly worth mentioning.  

In the following examples, parts are by weight and Percentages by weight. The temperatures are in degrees Celsius specified.

example 1

21.9 parts of 2-amino- (5), 6, (7) -dichlorobenzothiazole mixture are in 46 Parts of glacial acetic acid, 5 parts of propionic acid and 82 parts of phosphoric acid (85%) dissolved at 45 to 50 °, cooled to 0 to 2 °, at this Temperature with 32 parts of nitrosylsulfuric acid (40%) and 3 Hours stirred. The diazonium salt solution obtained is always under Cooling to approx. 0 °, slowly to one that is also cooled to approx. 0 ° Solution of 20.7 parts of 1- (N-2'-acetoxyethyl-N-methyl) -amino-3-methyl-benzene in 2000 parts of glacial acetic acid, 50 parts of water, 150 parts of ice and 2 Parts of sulfamic acid are given. The fancy, red dye will filtered off, washed acid-free with water and dried in vacuo at 60 °. The dye obtained is a mixture of 5,6- and 6,7-dichloro- 2- (2'-methyl-N-acetoxyethylamino-phenylazo) benzothiazole. This dyes polyester fiber material in pure red tones with very good Fastness.

λ _max. of the dye mixture = 536 nm.

Example 1a

To convert to the heat-stable b modification, the reaction mixture is adjusted to pH <1 after coupling by adding alkali and stirred at 90 ° for ½ hour.

Example 2

21.9 parts of a-amino- (5), 6, (7) -dichlorobenzothiazole mixture are in 46 Parts of glacial acetic acid, 5 parts of propionic acid and 82 parts of phosphoric acid (85%) dissolved at 45 to 50 °, cooled to 0 to 2 °, at this temperature by dropping 32 parts of nitrosylsulfuric acid (40%) diazotized and stirred for 3 hours. The diazonium salt solution obtained is always with cooling to approx. 0 °, slowly to one also at approx. 0 ° cooled solution of 22.3 parts of 1- (N-2'-methoxycarbonyloxyethyl-N- methyl) amino-3-methylbenzene in 200 parts glacial acetic acid, 50 parts water, 150 parts of ice and 2 parts of amidosulfonic acid. The fancy The dye is filtered off, washed acid-free with water and in vacuo dried at 60 °. The dye obtained is a mixture of the Compounds 5,6- and 6,7-dichloro-2- (2'-methyl-4'-N-methyl-N-methoxy- carbonyloxyethyl-amino-phenylazo) -benzthiazole, it dyes polyester fiber material in pure red tones with very good fastness properties.

λ _max. of the mixture = 534 nm.

The following table shows further ones that can be produced according to Example 1 Dye mixtures of the formula I indicated, where R₁ and R₂ are always chlorine, R₃ is always methyl and R₄, with the exception of Examples 10 and 11, in which R₄, is methyl, always mean hydrogen. The nuances of the colors with these mixtures on polyester fiber material are always bluish red.  

table

Coloring example

1.0 part of the dye obtained according to Example 1 and conditioned as a powder preparation (the β- modification, with a coupon fraction of 63%) is mixed with 4000 parts of water at 60 ° and dispersed in a high-temperature dyeing machine. A little ammonium sulfate and formic acid are added to adjust the pH to 5, 100 parts of polyester fiber material (Dacron T 56) are introduced, the dyeing temperature is closed and the bath is warmed to 130 ° at 3 ° per minute, dyeing for 20 minutes , cools to a temperature below 100 °, removes the substrate, rinses it once hot and cold and dries it. The deep color obtained shows a clear, level bluish red shade and meets high fastness requirements. The remaining dye bath contains 5% residual dye (colorimetric determination).

Claims (7)

1. The azo disperse dyes of the general formula I, wherein
R₁ and R₂ independently of one another are a halogen atom,
R₃ is methyl or, if R₅ is not ethoxy, also hydrogen,
R₄ is hydrogen or methyl and
R₅ is hydrogen, methyl, ethyl, chloromethyl, chloroethyl, vinyl, phenoxymethyl, C _1-4 alkoxy, phenoxy, benzyloxy, allyloxy or C _2-5 alkoxy optionally substituted by halogen or C _1-2 alkoxy. 2. The isomeric azo disperse dye mixtures of the formula I, according to Claim 1. 3. The azo disperse dyes of the formula I as claimed in claim 2, in which R₁ and R₂ are fluorine, chlorine or bromine, preferably chlorine or bromine, in particular chlorine,
R₃ methyl,
R₄ hydrogen and
R₅ is methyl, methoxy or ethoxy optionally substituted by a C _1-2 alkoxy group. 4. The azo disperse dyes of the formula I according to claim 3 wherein R₅ is methyl or methoxy, especially methyl. 5. The β crystal modification of the isomeric disperse dye mixture of the formula Ia with characteristic lines in the X-ray diagram (Cu-k _α ₁ radiation) at grid spacings of 14.3 (strong), 9.5 (medium), 8.1 (medium), 7.3 (weak), 6.25 (strong), 5.0 (weak), 4.3 (weak), 3.9 (weak), 3.78 (weak), 3.6 (strong), 3.5 (strong), 3.38 ( strong) and 3.15 (weak) · 10 ^-10 m. 6. A process for the preparation of the azo disperse dyes of the general formula I, according to claim 1, characterized in that a diazotized amine of the formula II with a compound of formula III couples. 7. Use of the azo disperse dyes of the formula I, according to one of claims 1 to 5 for dyeing, pad dyeing or printing Fibers or threads or materials made from or semi-synthetic hydrophobic, high molecular weight organic Fabrics.