DE1125879B - Process for dyeing and printing fibers made from polymers or copolymers made from acrylonitrile or asymmetric dicyanaethylene - Google Patents

Description

Process for dyeing and printing fibers made from polymers or copolymers made from acrylonitrile or asymmetrical dicyanethylene Additive to patent 1011396 The subject of patent 1011 396 is a process for dyeing polymers or copolymers made from acrylonitrile or asymmetric dicyanethylene using sulfonic acid and carboxylic acid groups-free Monoazo dyes which have at least one non-aromatically bound tertiary amino group or quaternary ammonium group.

In further processing of this inventive concept it has now been found that there are also disazo and trisazo dyes free of sulfonic acid and carboxylic acid groups, which contain external basic, tertiary amino or quaternary ammonium groups, suitable for dyeing and printing polyacrylonitrile fibers.

The disazo and trisazo dyes to be used according to the invention can for example the benzolazobenzene series, the benzolazonaphthalene series or the benzolazo-arylpyrazolone series belong. They are made using known methods by coupling dianotized diamines or aminoazo dyes made with azo components. Here it cannot aromatic, d. H. externally bonded basic group either in the diazo or in the azo component be included. Quaternary ammonium groups can be used both before and also after the coupling reaction by conventional reaction of tertiary amino groups with Alkylating agents are introduced into the dye molecule.

Such dyes can also be used that have more than one have non-aromatically bound basic group in the molecule. On the other hand you can even two dyes share a common, preferably quaternary external basic Group included. In this way, uniform dye mixtures, for example, are obtained achieved, in which not necessarily both components need to be azo dyes. In addition to these groups, the dyes can also contain other groups that are customary in azo chemistry Substituents, with the exception of sulfonic acid and carboxylic acid groups, have.

The disazo and trisazo dyes used in the present process with a non-aromatically bound tertiary amino group are in the form of their salts or readily soluble in water as quaternary ammonium bases. For the most part show they also have a good drawability on polyacrylonitrile fibers, if the corresponding Dyes without the tertiary amino group or quaternary ammonium group on the Fibers not or only poorly.

The dyes are used in a conventional manner, e.g. B. dyed or printed from acidic solution on polyacrylonitrile fiber. The dyeings or prints obtained in this way are distinguished by good fastness properties. For example, in a dye bath, the 10 /, dye of the following composition calculated on the fiber weight, contains 5 g of polyacrylonitrile fibers without further additives in a liquor ratio of 1:40. The goods are shrunk at 40 to 50 ° C., brought to a boil within 20 to 30 minutes and boiled for 1 hour. It is then rinsed and dried. A corinth with good wet fastness properties, in particular good sublimation and ironing fastness and very good light fastness, is obtained. Example 2 In a dye bath containing 10 /, dye of the following composition calculated on the fiber weight, contains 3 g of polyacrylonitrile fibers with the addition of 3% acetic acid (based on the weight of the material to be dyed) in a liquor ratio of 1:40. The goods are received at 40 to 50 ° C, brought to a boil within 20 to 30 minutes and cooked for 1 hour. It is then rinsed and dried. An orange color is obtained. Example 3 In a dye bath containing 1% dye of the following composition calculated on the fiber weight, contains 5 g of polyacrylonitrile fiber with the addition of 2% soda (based on the weight of the material to be dyed) in a liquor ratio of 1:40. The goods are shrunk at 40 to 50 ° C., brought to a boil within 20 to 30 minutes and boiled for 1 hour. It is then rinsed and dried. An orange color is obtained.

With those in the. The dyes listed in the following table also give valuable dyeings on polyacrylonitrile fibers: is dissolved as the chloroacetic acid salt in 3 l of water to give a clear solution and 3 g of 30% acetic acid are added to the solution. 100 g of polyacrylonitrile fibers are then placed in the dyebath at 40 to 50.degree. C., the bath is brought to 100.degree. C. within 40 minutes and boiled for 1 hour: a bordo-colored dye is obtained. In the same way, with the oxalic acid salts of the dyes in the table below, dyeings with good fastness properties are obtained on polyacrylonitrile fibers Example 5 16.3 parts of 2-cyano-4-nitroaniline are introduced into 120 parts of nitrosylsulfuric acid with a content of 6.9 g of NaNOZ below 20 ° C. Stirring is continued until the amine is completely dissolved. The diazotization solution is then poured onto ice. The clear diazo solution is added to an aqueous-methanolic solution of 28 parts of 5-oxy-1-f-trimethylammonium chloride-ethylaminonaphthalene. The dye disengages immediately. The pH is reduced to 6 by adding sodium acetate. A diazo solution prepared by diazotizing 19.6 parts of 1-amino-4-chloro-2-trifluoromethylbenzene in 50 parts of 30% hydrochloric acid with 7 g of Na N 02 with the addition of ice is then added to the reaction mixture. The decoupled and precipitated dye is filtered off with suction and dried.

The dye dyes polyacrylonitrile fibers from a weakly acidic bath in blue-green shades with good fastness properties. In an analogous manner, diazo dyes can be prepared from the same coupling component and the first and second diazo components listed in the table below, which dye polyacrylonitrile fabrics in the shades given below. Example 6 14.3 parts of 2,4-dicyananiline are dissolved in 120 parts of nitrosylsulfuric acid containing 7 g of NaNO 2 below 20 ° C. and diazotized. It is then poured onto ice and the resulting solution is added to an aqueous solution of 30 parts of coupling base of the following formula: After the solution has been truncated to pH 3.5 with sodium hydroxide solution at O 'C , the precipitated dye is filtered off with suction and dried. It colors polyaeryl nitrile from weakly acidic baths in real yellow-tinged red tones. Example 7 With a printing paste of 30 g of dye from 2 moles of diazotized 2-chloro-4-nitroaniline and 1 mole of 1- (β-trimethylammonium chloride-ethyl) -amino-5-oxynaphthalene, 50 g of thiodiglycol, 30 g of cyclohexanol, 50% g acetic acid (30%), 280 g water, 30 g zinc nitrate (50%), 30 g printing oil, 50 g resorcinol or another phenol is printed on fabric made of polyacrylonitrile fiber; Then it is steamed in a continuous machine steamer or star steamer for 10 to 30 minutes at about 100 to 103 ° C and finally soaped at 40 to 60 ° C and dried. A greenish black print with good fastness properties is obtained.

Claims (1)

PATENT CLAIM: Further development of the process for the dyeing of fibers from polymers or copolymers of acrylonitrile or asymmetric Dicyanäthylens according to Patent 1011 396, characterized in that colored with sulfonic acid and carboxylic acid group-free disazo or trisazo dyes or printed, at least one non aromatically bound tertiary Have amino group or quaternary ammonium group.