DE1902475A1 - Basic azo dyes for polyacrylonitrile fibres - Google Patents

Abstract

Basic azo dyes for polyacrylonitrile fibres.. G2A. Are made by coupling aminobenzamidines of formula with coupling components of formula (in which R1, R2, R3 and R4 are alkyl, cyclo-alkyl or aralkyl, R5 and R6 are alkyl, hydroxy-alkyl, cyanoalkyl, halogen-alkyl, alkoxy-alkyl, carbalkoxy-alkyl or aryl groups and R7 is a hydrogen, halogen, alkyl, alkoxy or acetamido group. R3 and R4 may be connected by a ring consisting of (CH2)n where n is 4 or 5, -CH2CH2OCH2CH2-, or -CH2CH2SCH2CH2-). The coupling components may also be compounds with enolisable keto-groups, which contain no carboxylic or sulphonic acid radicals, such as pyrazolone-5 compounds or aceto-acetic arylides. The dyes are suitable for dyeing fibres of polyacrylonitrile or copolymers containing at least 50% polyacrylonitrile from acetic acid baths to give colours with very good general fastness.

Description

Process for the preparation of basic dyes The present invention relates to a process for the production of basic dyes.

In the West German Auslegeschriften 1011396 and 1014519, processes for dyeing acrylonitrite and similar fibers are described, which mention dyes of the following general formula: where R is a benzene ring, optionally with customary substituents, and A, B and a; Hydrogen or lower alkyls. However, these dyes do not always show adequate wet and perspiration fastness properties.

The aim and object of the invention was therefore to create new dyes, which showed better wet and perspiration fastnesses.

It has now been found that new basic dyes with good fastness properties can be produced by using the diazonium compounds of aminobenzamidines of the general formula with coupling components of the general formula couples, where R1, R2, R3 and R4, which can be identical or different, alkyl, cycloalkyl and aralkyl radicals, R5 and R6 alkyl, hydroxy # alkyl, cyanoalkyl, haloalkyl, alkoxylalkyl, carbalkoxyalkyl and acrylic radicals and halogen, alkyl, alkoxy and aoetamino groups and R3 and R4 can also be linked to one another by ring formation via (no 4 or 5), - CH2CH2-O-CH2CH2- or radicals.

Compounds with enolizable keto groups that are not carboxylic acid and contain sulfonic acid residues, e.g.

Pyrazolone-5, acetoacetic arylides and the like can also be used come as coupling components used.

The diazotization of the diazo components used according to the invention and the coupling with the coupling components can be carried out in a known manner.

With the dyes prepared according to the invention, polyacrylonitrile fibers or mixed polymer fibers with a minimum proportion of 50% polyacrylonitrile acetic acid bath with very good all-round fastness properties.

Compared to the dyes of the West German Auslegeschriften 1 011 396 and 1,014,519, the dyes according to the invention have better wet and perspiration fastness properties.

The p-aminobenzamidines used as diazo components are obtained by converting corresponding p-nitrobenzamides into the imide chlorides, reacting them with N, N ', N'-trisubstituted ethylenediamines of the formula where R1, R2 and R3 represent alkyl, cycloalkyl or aralkyl radicals and R2 and R3 can be linked to one another by ring formation via (n X 4 or 5), -CH2CH2-O-CH2CH2 or -CH2CH2-S-CH2CH2 radicals, and reduction of the p-nitrobenzamidines obtained.

The following examples are intended to explain the invention further without to limit them to that.

Example 1s 29 parts by weight of p-amino-N, N'-diethyl-N-diethylaminoethylbenzamidine is diazotized as known in hydrochloric acid solution at 0-5 ° a and the diazo solution coupled acidic with 16.5 parts by weight of N, N-diethyl-m-toluidine.

The dye is isolated from the solution as is known by salting out with common salt or alkali bromides or alkali iodides Way-obtained dye dyes polyacrylonitrile fibers orange at pH 4-5, with very good wet and perspiration fastness properties.

The following aminobenzamidines, for example, can also be used instead of the diazo component mentioned: Example 2: 27.6 parts by weight of p-amino-N-ethyl-N-diethylaminoethyl-N'-methylbenzamidine are diazotized as usual in a hydrochloric acid solution at 0-5 ° C.

The diazo solution is at 0-5 ° a with 12.1 parts by weight of dimethylaniline coupled and the dye isolated by salting out. The dye obtained is colored Polyacrylonitrile fibers in red-orange tones with good wet and white fastness properties at.

Example 3 29 parts by weight of p-amino-N, N'-diethyl-N-diethylaminoethylbenzamidine are diazotized in a known manner and with 15.6 parts by weight of m-chlorodimethylaniline coupled at 0-5 ° C. Polyacrylpitrile fibers turn orange with very good wet and dry properties Colored perspiration fastness.

Example 4: 34.4 parts by weight of p-amino-N-ethyl-N-diethylaminoethyl-N'-cyclohexyl-benzamidine are diazotized in hydrochloric acid solution at 0-50 o and with the solution of 17.4 parts by weight 1-Phenyl-3-methyl-pyrazolone-5 in 200 ml of O, 10 ml of concentrated sodium hydroxide solution, 20 parts by weight Sodium acetate and 20 parts by weight sodium carbonate are coupled at 0-5 ° C.

A yellow shade with good all-round fastness properties appears on polyacrylonitrile fibers achieved.

Example 51 29 parts by weight of p-amino-N, N'-diethyl-N'-diethylaminoethyl-benzamidine are as described in Example 1, diazotized.

For coupling, the diazo solution becomes an alkaline solution at 0-5 ° dropped from 17.7 parts by weight of acetoacetanilide. After stirring for several hours the dye is isolated. The dye obtained in this way dyes polyaryl nitride fibers in yellow nuances with good fastness properties.

Claims (2)

Claims 1. Process for the preparation of basic dyes, characterized in that diazonium compounds of aminobenzamidines of the general formula with coupling components of the general formula are coupled, where R1, R2, R3 and R4 are alkyl, cycloalkyl or aralkyl radicals, R5 and R6 are alkyl, hydroxyalkyl, cyanoalkyl, haloalkyl, alkoxy @ alkyl, carbalkoxyalkyl or aryl radicals and R7 H, halogen, alkyl, alkoxy or acetamino groups and R3 and R4 also by ring formation via - (CH2 @@ (n = 4 or 5), -CH2CH2-O-CH2-CH2- or -CH2CH2-S-CH2- CH2 residues can be linked to one another. 2. Modification of the method according to claim 1, characterized in that that as coupling components compounds with enolizable keto groups that do not have Contain carboxylic acid or sulfonic acid residues, such as pyrazolone-5 compounds or Acetoacetic arylides can be used.