DE1064661B - Process for the preparation of basic phthalocyanine dyes - Google Patents

Description

A process for the preparation of basic phthalocyanine Zuatz for Patent Application F 13521 IV b / 22 e (Auslegeschrift 1,061,010) subject of the patent application F 13521 IV d / 22 e is a method for preparing basic phthalocyanine dyestuffs, which consists in that one phthalocyanine with mobile halogen atoms with aliphatic tertiary amines containing at least one primary or secondary amino group.

In further processing of the one on which the main patent application is based The idea of the invention has now been found that the basic phthalocyanine dyes also arise when sulfonic or carboxylic acid halides are used in a first reaction stage of phthalocyanine dyes with aliphatic primary or secondary halogen amines converts and the halogen compounds thus obtained in a second reaction stage can react with secondary aliphatic amines.

The reactions taking place in the two reaction stages according to the present invention can be illustrated by the following equations, in which F stands for the radical of a phthalocyanine dye, RI is hydrogen or a monovalent radical, R2 is a divalent radical, R3 and R4 are monovalent radicals and X is halogen : Halogenamines which can be used for the conversion of the stilfon and carboxylic acid halides of phthalocyanine dyes are primary and secondary aliphatic amines which contain one or more halogen atoms bonded in the alkyl radicals. As representatives of such halogenamines are z. B. ß-chloroethylamine, ß-,; -Dibromopropylamine, 1-amino-4-chlorobutane and ß, ß-dichlorodiethylamine called.

Secondary amines can be used as components for the second reaction stage of any kind, such as B. dimethylamine, diethylamine, diethanolamine and piperidine, Find use.

Both reaction stages can be carried out in an aqueous medium as well as in an inert organic solvent. To bind the at the Reaction liberated hydrogen halide is used either in excess of the amines or are additionally acid-binding agents, such as. B. caustic alkali or alkali carbonate, added. The reaction temperatures are generally temperatures in the range from 0 to 100 ° C proved to be suitable for both reaction stages.

The basic dyes prepared according to the invention can in the form of their salts in dilute acidic solution for dyeing fiber materials of all kinds, paper, wood, etc. m., serve. Particularly easily soluble products can can also be used for coloring foils or in rubber printing.

EXAMPLE 1 5 parts by weight of copper phthalocyanine (3) di- and / or tri- (β-chloroethyl) sulfamide in the form of 25% paste are added to 40 parts by weight of dimethylamine solution (−50%). After adding 6 parts by weight of 15% sodium hydroxide solution, the mixture is stirred at room temperature for 20 hours. The resulting reaction product is precipitated by brief heating and addition of sodium acetate solution, filtered off with suction and washed. The yield of the dye, which is soluble in dilute acetic acid with a clear blue color, is approximately quantitative.

The diethylamine derivative is produced in a similar manner with diethylamine solution obtain.

The copper phthalocyanine (3) di and / or tri (ß-chloroethyl) sulfamide obtained as follows: 14.6 parts by weight of copper phthalocyanine- (3) -di and / or tri-sulfochloride are finely divided in 80 parts by weight of water at 5 to 10 ° C. In this suspension, 7 parts by weight of chloroethylamine chlorohydrate, dissolved in 10 parts by weight of water, pour in with stirring. You give within 4 hours 39 Parts by weight of 10% sodium hydroxide solution are added, while the temperature is gradually reduced Rise to 18 ° C and stir for a further 20 hours at room temperature. The reaction product is suctioned off and washed. The yield is quantitative.

Example 2 In 45 parts by weight of 1-amino-3-dimethylaminopropane (- # - 50%) 5 parts by weight of copper phthalocyanine- (3) -di and / or -tri- (ß-chlorethylene) sulfamide entered in the form of 20 to 25% paste. After adding 6 parts by weight 15% sodium hydroxide solution, the reaction mixture is stirred for 20 hours at room temperature. To isolate the reaction product, after addition of saline solution with hydrochloric acid neutralized and extracted. The dye obtained in very good yield dissolves in dilute acetic acid with a clear blue color.

Example 3 In 40 parts by weight -, - 50% dimethylamine solution 5 parts by weight of copper phthalocyanine- (3) -di- and / or -tri- (β.y-dibromopropyl) sulfamide entered in the form of - 25% paste and the reaction mixture after addition of 9 parts by weight of 15% sodium hydroxide solution for 20 hours at room temperature. The excess dimethylamine is used to isolate the resulting dye largely driven off and the dye by adding saline solution (and possibly some hydrogen chloride) precipitated, filtered off with suction and washed. The reaction product, which is soluble in dilute acetic acid with a clear blue color, becomes very good Yield obtained.

The copper phthalocyanine- (3) -di and / or -tri- (ß.y-dibromopropyl) sulfamide is obtained as follows 14.6 parts by weight of copper phthalocyanine- (3) -di and / or tri-sulfochloride are finely divided in 50 parts by weight of water at 5 to 10 ° C. 19 parts by weight of 2,3-dibromopropylamine bromohydrate are dissolved in this suspension pour in 50 parts by weight of water with stirring. You give within 4 hours 4.2 parts by weight of caustic soda in the form of 10% lye added, whereby the temperature allowed to rise to 15 ° C, and then stirred for a further 20 hours at room temperature. That The reaction product is filtered off with suction and washed. The yield is very good.

Example 4 In 50 parts by weight of dimethylamine solution (--- 50%) 5 parts by weight of tetraphenyl copper phthalocyanine tetra (ß-chloroethyl) sulfamide in paste form registered. Now is 20 hours at room temperature. stirred, 1 part by weight of sodium hydroxide d, dissolved in a little water, added and, after the conversion has ended, the excess Removed dimethylamine, optionally added sodium acetate solution, the reaction product vacuumed and washed. The yield of the clear green color in acetic acid soluble dye is practically quantitative.

The tetraphenyl copper phthalocyanine tetra (ß-chloroethyl) sulfamide was obtained as follows: 14.5 parts by weight of tetraphenyl copper phthalocyanine tetrasulfochloride are entered in paste form in 80 parts by weight of ice / ice water and at 0 to 5 ° C with 7 parts by weight of chloroethylamine chlorohydrate dissolved in 10 parts by weight Water, added. At the same temperature, 4.2 are added within 11/2 hours Parts by weight of sodium hydroxide in the form of 10% lye are added with stirring. so the temperature is allowed to rise to 20 ° C. and stirred until the reaction has ended is. The reaction product is filtered off with suction and washed with water. The yield is quantitative.

The copper phthalocyanine (4) tetra (β-chloroethyl) sulfamide can be prepared in a similar manner (made from copper phthalocyanine- (4) -tetrasulfochloride and chloroethylamine analogously Paragraph 2) convert into a clear blue dye in good yield.

Example s In 25 parts by weight of diethanolamine and 20 parts by weight 5 parts by weight of copper phthalocyanine- (3) -di and / or -tri- (ß-chloroethyl) sulfamide are pyridine in paste form and 1 part by weight of sodium hydroxide, dissolved in 6 parts by weight of water, registered. Now is 20 hours at room temperature and 2 hours at 80 to 90 ° C stirred, the reaction product precipitated by adding sodium chloride solution, filtered off with suction and washed with water. The reaction product soluble in acetic acid with a clear blue color is obtained in good yield.

Claims (1)

PATENT CLAIM: Modification of the process for the production of basic Phthalocyanine dyes according to patent application F 13521 IVd / 22e, characterized in that that sulfonic or carboxylic acid halides of phthalocyanine dyes are used in a first reaction stage with aliphatic primary or secondary haloamines and the resulting Halogen compounds in a second reaction stage with secondary aliphatic Can react amines. When the registration is announced, there is a coloring board has been laid out.