DE1140899B - Process for dyeing and printing cellulose-containing fibers with complex phthalocyanine intermediates containing heavy metals - Google Patents

Description

A process for dyeing and printing .. cellulnsehaltigex fibers with heavy-metal-containing complex Phthalocyaninzwischenprodukten additional patent 1,044,758 subject of the patent 1 044 758 is a process for dyeing and printing cellulose-containing fibers with heavy-metal-containing complex Phthalocyaninzwischenprodukten, which is characterized in that the fibers with tannin Tartar emetic or sulphurized chlorophenols pretreated and then colored or printed in the usual way.

In further processing of the process of the main patent is based Lying inventive idea it has now been found that one can do the pretreatment of fibers that are condensed with dye intermediates that are made from heavy metals IminQpyrroleninen exist, are to be colored, also containing sulfonic acid groups Compounds of the benzidine, N, N'-bis (p-aminophenyl) urea and stilbene series or use substantive organic dyes containing sulfonic acid gels.

The treatment of the fibers with the #f used the pretreatment Connections can be made in a simple manner so that the materials to be treated some time in an aqueous solution of the compounds used for the pretreatment leaves, expediently at a slightly elevated temperature, for. B. at temperatures around 40 to 90 ° C, although other temperatures can of course also be selected. Thereafter, the materials treated in this way are expediently rinsed and then colored with the heavy metal complexes of condensed iminopyrrolenines.

Heavy metal complexes of condensed iminopyrrolenines which are suitable for the new process and which are dye precursors are, in particular, the heavy metal complexes of condensed isoindolenines, which are built up from 4 to 6 1-amino-3-imino-isoind_olenine molecules and their presumed structures by F. Baumann, B. Bienert , G. Rösch, H. Vo 11 ma Rn and W. Wolf in "Angewandte Chemie", Vol. 68 (1956), p. 141. However, the heavy metal complexes of condensed 2-amino-5-imino-pyrrolene nerves which are substituted in the 3- and / or 4-position by alkyl or aryl radicals etc. and which are obtained by heat treatment of the 2-amino-5-imino are also suitable -pyrrolenine up to 65 ° C have been obtained in an organic solvent. Suitable heavy metals are especially copper, nickel and cobalt. The condensed Pyrrnlenine can be composed of those compounds that contain another exchangeable .Gruppe in place of the amino group, z. B. an alkoxy group. These connections can z.8. by the methods of German patent specifications 914250, 839939, 855710, 852588, 940164, the American patent specification 2683643 or the French patent specification 1ß23765. To produce the colorations, the heavy metal-containing complex phthalocyanine intermediates are dissolved in a solvent, e.g. B. in glycol, diethylene or polyethylene glycol or their monoethers, with the addition of an `acid, z. B. glacial acetic acid.

After the heavy metal complexes of the condensed imino-pyrrolenine has applied to the fiber pretreated according to the invention by subjecting it the fibers are advantageously an intermediate rinse and then developed Dye on the fiber. The development can either be carried out by conventional methods be e.g. B. by steam or dry heat, or particularly advantageously wet, by spending some time, e.g. B. 1/2 hour, at an elevated temperature in a liquor treated containing a reducing agent, e.g. IB. Hydrosulfite or sodium sulfoxylate, and the intermediate, neutral, basic, depending on the type of dye used or acidic can be adjusted to achieve the optimal tie% of the staining. The dyed fiber is then subjected to a customary aftertreatment by acidic aftertreatment and then alkaline soapy.

The method according to the invention has the advantage of 440 the heavy metal complexes condensed Pyrrolenines without impairing the fastness properties can be dyed on yarn, so that the production of colored fabrics is made possible with high authenticity. Furthermore, according to the method according to the invention can also be dyed on the jigger and especially on the reel. Farther The new process makes it possible to print fibers made from regenerated cellulose. In the previous processes with fibers that have not been pretreated according to the new process were made using materials made from viscose (rayon), has not yet achieved satisfactory results. Example 1 500 parts by weight of cotton cheeses are with the aqueous solution of 300 parts by weight of common salt and 5 parts by weight of the condensation product of 2 mol of cyanuric chloride with 1 1M1 of 4,4'-diaminodiphenyl-3,3'-disulfonic acid Sodium treated in 10,000 parts by volume of water at 20 to 25 ° C for 15 minutes. After this 50 parts by weight of soda are added to the solution and the cotton yarn is moved in it another 45 minutes. Then it is rinsed and then soaped at the boil for 15 minutes in a soap bath containing 30 parts by weight of soap and 20 parts by weight of soda in 10,000 parts by weight of water. The yarn is then rinsed well.

20 parts by weight of the complex copper-containing condensed pyrrolenine, that according to the method of German Patent 914 250, Example 18; obtain was by mixing phthalonitrile with alcoholic sodium methylate solution in the presence of benzene heated to 35 ° C for some time and then copper acetate some at 20 ° C Stirred time at this temperature, are made into a paste with 60 parts by weight of diethylene glycol and carefully dissolved with 100 parts by volume of glacial acetic acid. After 15 minutes you fill with cold water to 10,000 parts by volume. This solution is used to dye for about 30 minutes the pre-pickled material at 20 to 25'C. Then it is rinsed and then in a 50 to 60 ° C hot bath, containing 50 parts by volume of sodium hydroxide solution (38 ° B6) and 20 parts by weight of sodium hydrosulfite in 10,000 parts by volume of water, treated for 20 minutes. After rinsing, soap at the boil again with 30 parts by weight of soap and 20 parts by weight of soda in 10,000 parts by volume of water. The yarn is then blue colored.

Instead of the condensed pyrrolenine described above, you can the compounds obtained as follows can also be used: a) 25 parts by weight Methoxy-phthalonitrile in 116 parts by volume of methanol are at 20 ° C until saturation mixed with gaseous ammonia. Then 8 parts by volume of sodium methylate (containing 3.8% sodium) was added and the reaction mixture was slowly added while passing in ammonia heated to 55 ° C until a sample taken is soluble in 5% acetic acid. Thereon 130 parts by volume of methanol are added and the methanol is then added for removal of the ammonia distilled off. The same amount of methanol is then added again and 4.2 parts by weight of anhydrous copper chloride, dissolved in 50 parts by volume of methanol, added dropwise. Then again 25 parts by volume of sodium methylate solution (6%) added dropwise and then 2 hours at 20 ° C, 3 hours at 35 ° C and then 10 hours stirred at room temperature. After evaporation of the solvent 24 parts by weight are obtained from the yellow olive colored pyrrolenine.

b) 520 parts by weight of 4-aza-1,3-dümino-isoindolenine nitrate are stirred with 1.5 parts by volume of methanol and 125 parts by weight of sodium hydroxide in the form of a 10% methyl alcoholic solution are added. 91 parts by weight of copper acetate are then added and the temperature gradually increases , within 3 hours, increased to 65 ° C. The mixture is then heated to a gentle boil for a further 3 hours. The reaction mixture is then dissolved in 6000 parts by volume of water, and the precipitated portions are washed with water and dried. The copper complex obtained forms a yellow-olive-colored powder that dissolves in formamide to about 90% at room temperature. When the formamide solution is briefly heated, dark brown tetraaza copper phthalocyanine precipitates out of the solution. c) 40 parts by weight of 2-amino-5-imino-3,4-dimethylpyrrolenine nitrate are dissolved in 400 parts by volume of methanol by adding 1 to 2 parts by volume of concentrated aqueous ammonia. Then 9 parts by weight of nickel chloride (NiC12-6H20) are added and the mixture is heated to boiling for 1/2 hour, filtered hot and the filtrate is evaporated to dryness at low temperature. The residue is digested with 200 to 300 parts by volume of water and the red-brown nickel complex obtained is separated off. A bluish green is obtained.

It can also be used in place of the condensation product of cyanuric chloride with sodium 44'-diaminophenyl-3,3'-disulfonic acid, for example, the condensation products from cyanuric chloride with 4,4'-diaminodiphenylurea-3,3'-disulfonic acid sodium, 4,4'-diaminodiphenylamine-3,3'-disulfonic acid sodium or corresponding condensation products from cyanuric chloride and substituted aromatic sulfo-containing mono- or Use diaminoverbin boys.

Condensation products of this type can, for. B. obtained by one dissolves cyanuric chloride in acetone and at temperatures around 0 ° C in an equivalent aqueous solution of the corresponding amine can run in. Holds with alkaline agents the reaction is weakly acidic to neutral. Once through diazotization and coupling can no longer detect any free amino groups, the condensation product precipitated by acidification or sawing, filtered and carefully dried. Example 2 Yarns made of cotton or regenerated cellulose are with a 1% strength aqueous solution of 4,4'-diamidobenzoyldiphenylurea-3,3'-disulfonic acid or their salts (liquor 1:20) at room temperature for some time, e.g. B. for 30 minutes, if desired, in the presence of salts, such as. B. table salt treated. After Dehydration is dyed as described in Example 1.

Instead of 4,4'-diamidobenzoyldiphenylurea, 3,3'-disulfonic acid, 4,4'-diamidotoluyldiphenylurea-3,3'-disulfonic acid, 4,4'-diacetoacetylamino-3,3'-dimethyl-diphenyl, N, N'-dibenzoyl-benzidine-3,3'-disulfonic acid, the 1,3,5-triazines known from British patent 495479, which are described in German patent 640 908 on pages 1 and 2 under the numbers 1 to 19 Use the compounds listed below or the following compounds, among others:

Claims (1)

PATENT CLAIM: Further development of the process of patent 1 044 758 for dyeing and printing cellulosic fibers with heavy metal-containing complex phthalocyanine intermediates, characterized in that the fibers are here with compounds of benzidine, N, N'-bis (p-aminophenyl) containing sulfonic acid groups. - pretreated urea or stilbene series or substantive organic dyes containing sulfonic acid groups.