DE1208022B - Process for the preparation of water-soluble phthalocyanine dyes containing reactive groups - Google Patents

Description

Process for the preparation of water-soluble phthalocyanine dyes containing reactive groups The invention relates to a process for the preparation of water-soluble dyes of the phthalocyanine series which contain the reactive group at least once contain. The process for the preparation of such dyes consists in reacting 1 mole of a phthalocyanine compound which contains two or more sulfonic acid chloride groups with at least 1 mole of ethyleneimine, whereby at most so much ethyleneimine is reacted that a sufficient number of sulfonic acid chloride groups remain free to to give the dye 'sufficient water solubility after hydrolysis has taken place.

The phthalocyanine compounds suitable for the process can be metal-free or contain a metal as a central atom, as is usually the case used copper, nickel or cobalt phthalocyanines. They can also be substituted be e.g. B. with chlorine atoms or phenyl groups, with the restriction that they still must be able to use the number of sulfonic acid chloride groups required for the process to record. The sulfonic acid chloride groups are introduced in a known manner, z. B. with chlorosulfonic acid, the starting materials already having sulfonic acid groups may contain.

The sulfonic acid chloride groups are directly on the benzene nucleus in 3- or 4-position or introduced into external residues.

The implementation of the Phthalocyaninsulfonsäurechloride with the ethyleneimine is preferably in an aqueous medium and with the addition of an acid-binding agent carried out, with the reaction mixture remaining so long after the condensation , stir until the excess sulfonic acid chloride groups are saponified. For protection the Äthyleniminringes, which must be retained for the dyeing process, is the Implementation under the mildest possible conditions, d. H. while avoiding high temperatures and large deviations of the pH value from the neutral point. One works advantageously at -5 to 50 ° C, preferably at 0 to 15 ° C, and in the pH range of 5 to B.

The new dyes are used for dyeing, padding and printing Fibers of vegetable and animal origin, from fibers made from regenerated cellulose, of casein fibers, of synthetic polyamide fibers and mixtures of these fibers and of leather. The dyeings obtained have very good light, washing, perspiration, Fastness to water, seawater, alkali, rubbing and ironing. Polyester fibers become very well reserved.

Compared to the next comparable, from the Belgian patent specification 560,033 known dyes are distinguished by the dyes obtainable according to the invention through a better fixation yield on cotton.

In the following examples, the parts mean parts by weight, the percentages by weight and the temperatures are given in degrees Celsius.

Example 1 A moist filter cake containing predominantly copper phthalocyanine disulfonic acid chloride, prepared by sulfochlorinating 57.6 parts of copper phthalocyanine in chlorosulfonic acid at 105 to 115 ° C. and subsequent precipitation on ice, is mixed with 200 parts of ice and 200 parts of water. The pH of the suspension is adjusted to 6 with sodium hydroxide solution. 4.4 parts of ethyleneimine are then added dropwise to the mass in the course of a few minutes. This is then stirred further at 0 °, the pH value being kept at 7 by the gradual addition of sodium hydroxide solution. As soon as no more sodium hydroxide solution is consumed, enough potassium chloride is added to the solution until the reaction product has completely precipitated. The dye is filtered off and dried at 30 to 35 ° in vacuo. It dyes cotton in light- and wet-fast turquoise-blue tones. Example 2 The procedure is as in Example 1 using a moist filter cake containing mainly copper phthalocyanine trisulfonic acid chloride, prepared by sulfochlorinating 57.6 parts of copper phthalocyanine in chlorosulfonic acid at 120 ° to 130 ° and then precipitating on ice and 8.6 parts of ethyleneimine, and holds the temperature during the reaction to 10 °. The new dye ' With phthalocyanine component sulfochlorination parts color shade game' temperature Ethylene imine on cotton 4 61 parts of 4-chloro copper phthalocyanine 145 to 150 ° 4.3 turquoise blue 5 89.6 parts of copper phthalocyanine-4,4 ', 4 ", 4"' - te-145 to 150 ° 8.6 the same. trasulfonic acid (100 ° / o) 6 57.2 parts cobalt phthalocyanine 125 to 135 ° 4.3 the same. 7 57.1 parts of nickel phthalocyanine 125 to 135 ° 4.3 the same. 8 73.9 parts of 4,4'-diphenyl copper phthalocyanine 140 ° 4.3 bluish green 9 88 parts 4,4 ', 4 ", 4"' - Tetraphenylkupferphthalo 20 ° with the addition of 4.3 yellowish green cyanine from Thionyl chloride 100 parts of a mercerized cotton fabric are impregnated at room temperature with a solution containing 20 parts of the dye prepared according to paragraph 1 of this example in 1000 parts of water and squeezed off on a padder to a dry weight increase of 70 to 800%. The dyed material is dried at 120 to 140 ° and then in 1000 parts of water containing 250 parts of calcined sodium sulfate, 30 parts of trisodium phosphate or 3 parts of sodium hydroxide and 5 parts of 3-nitrobenzene-1-sulfonic acid sodium, at 80 to 90 ° for 60 minutes Moving fixed. After it has been rinsed first cold and then hot, it is soaped at the boil for 20 minutes, then rinsed again and then dried.

A turquoise-blue dyeing is obtained, the washfastness of which is excellent is.

Claims (3)

Claims: 1. Process for the production of reactive groups containing water-soluble phthalo-When the notice of application is a Coloring table has been laid out with explanations. dyes cotton and fibers from regenerated Cellulose in wet-fast turquoise-blue tones. Example 3 If one proceeds according to the indications of Example 1, using a filter cake containing copper phthalocyanine tetrasulfonic acid chloride, produced by sulfochlorinating copper phthalocyanine in chlorosulfonic acid 145 to 150 ° C and subsequent precipitation on ice and 8.6 parts of ethyleneimine below Maintaining the reaction temperature at 15 °, a dye is obtained which Dyes cotton and wool in wet-fast turquoise-blue tones. The table below contains further reactive dyes containing ethyleneimide groups, which according to can be prepared according to the information given in the preceding examples. cyanine dyes, thereby gekennzeichn e t that one mole of a phthalocyanine compound which two or contains more sulfonic acid chloride groups, reacts with at least 1 mole of ethyleneimine, where one brings at most so much ethylene imine to the implementation that there is still a sufficient one Number of sulfonic acid chloride groups remain free to the dye after hydrolysis to give sufficient water solubility. 2. The method according to claim 1, characterized characterized in that the reaction is carried out in an aqueous medium. 3. Procedure according to claim 1, characterized in that the reaction in the presence of a acid-binding agent. Publications considered: Belgian Patent Nos. 560 033, 560 034.