DE1569841B1 - Pigment dyes and processes for their preparation - Google Patents

Description

The invention relates to pigment dyes from the series of condensation products of perylene-3,4,9,10-tetracarboxylic acid and a process for their preparation.

Vat dyes of the perylene series have been used for dyeing textiles for a long time. The good lightfastness properties of these dyes have led to the use of perylene derivatives as pigment dyes. In particular, very special condensation products of perylene - 3,4,9,10 - tetracarboxylic acid were selected which are particularly suitable as pigments and have improved properties, "bbsonder", with regard to their. Resistance to solvents.

Processes are also known which improve the fastness properties of pigment dyes in the way to achieve. that in the manufacture of these dyes an enlargement of the molecule is carried out. In a method of this type, the Molecule enlargement brought about by an acid imide formation. In this procedure will be Dyes or dye intermediates that contain one or more pairs of carboxyl groups Contained in the ortho- or peri-position and capable of forming cyclic acid imides are, with ammonia or with any mono- or diamines or their substitution products implemented.

It has been shown that the - range DER previously known from -Konde 'lsaiionsp'todükten of perylene-3,4,9,10-tetracarboxylic acid built dyes can be expanded in progressive manner by the present invention perylene-3, 4,9,10-tetracarboxylic acid either - in free form or in the form of its anhydride or mixtures of the compounds mentioned with amines of the general formula in which R denotes a phenylene radical, a diphenylene radical or a 3,3-dimethyldiphenylene radical and R denotes the remainder of phthalic acid, naphthalic acid or 3-nitronaphthalic acid, is condensed in a manner known per se in a liquid reaction medium, optionally in the presence of a condensing agent , where pigment dyes of the general formula arise in which R and R, have the meaning given above.

Since the amines which can be used according to the invention are very easily mixed with perylenetetracarboxylic acid or their anhydride are condensable, are when carrying out the invention Process, the starting components are preferably used in an equivalent ratio. The amine can of course also be used in excess.

Among the applicable amines, N, N - naphthalylbenzidine, 3 - nitronaphthalic acid-N - (4 - aminophenylimide), NN - naphthalyl - (3,3'-dimethylbenzidine) and phthalic acid-N- (4-aminophenylimide) have proven to be particularly advantageous .

Although the condensation reaction can be carried out by all customary processes, for example under increased or reduced pressure, at temperatures between 50 and 200 ° C. and using ketones and water as the reaction medium, the process according to the invention is preferably carried out in such a way that the starting materials are in a high-boiling organic liquid as the reaction medium and be heated in the presence of a condensing agent.

Nitrobenzene is advantageous as the high-boiling organic liquid or ortho-dichlorobenzene and, as a condensing agent, those customary for this purpose Connections, e.g. B. zinc chloride, hydrogen chloride or glacial acetic acid is used.

The products which can be produced by the process according to the invention are red to bordeaux-red compounds, which are valuable after being converted into finely divided form Pigments represent and for coloring synthetic or natural high molecular weight Materials such as PVC, polystyrene, polyethylene, polyester or rubber are ideally suited -are. The new pigments can also be used for coloring paints, e.g. B. Nitro and stoving enamels, printing inks or for mass coloring paper or viscose use well.

The above-mentioned fine division of the carried out according to the invention Process resulting perylene derivatives in a form usable as a color pigment can be done in a variety of ways with comparable success. So z. B. reprecipitation from sulfuric acid, grinding with or without grinding aid, swelling in sulfuric acid or organic solvents such as aromatic hydrocarbons, chlorinated aromatic hydrocarbons, nitro hydrocarbons or dimethylformamide, good usable results.

The percentages given in the examples are percentages by weight.

Example 1 9.8 g of 3,4,9,10 - perylenetetracarboxylic dianhydride are first distilled anhydrous together with 2.65 g of zinc chloride and 2.65 g of sodium acetate in 150 cc of nitrobenzene. After cooling to 180 ° C. , a solution of 32.0 g of NN-naphthalenylbenzidine in 150 cc of nitrobenzene is added and the mixture is heated to boiling for 15 hours with stirring and reflux. The reaction product is filtered off while still hot, washed with hot nitrobenzene until no more amine can be detected, and washed out with ethanol and water. In order to remove any unreacted perylenetetracarboxylic acid, the crude product is boiled in about 5% potassium carbonate solution until it runs out on the filter paper - especially when looking under a UV lamp - no more fluorescence is visible. After filtering off with suction, washing neutral and drying, a bluish-tinged red pigment dye with very good lightfastness and excellent migrationfastness is obtained.

Example 2 9.8 g of 3,4,9,1 0- ferylenetetracarboxylic dianhydride are first distilled anhydrous together with 2.65 g of zinc chloride and 2.65 g of sodium acetate in 150 ml of nitrobenzene. After cooling to 180 ° C. , a solution of 18.2 g of NN-naphthalenylbenzidine in 150 ml of nitrobenzene is added and the mixture is refluxed for 15 hours with stirring. After working up as indicated in Example 1 , the same pigment with the same fastness properties is obtained in the same yield.

Example 3 9.8. g 3,4,9,10 - perylenetetracarboxylic dianhydride are first distilled anhydrous together with 2.65 g zinc chloride and 2.65 g sodium acetate in 150 cc nitrobenzene. After cooling to 1800C thereto is added a solution of 29.1 g of 3-Nitronaphthalsäure-N - (4 - aminophenylimid) in 150 cc of nitrobenzene and heated for 15 hours while stirring under reflux to boiling. After working up as indicated in Example 1 , a bluish-tinged red pigment dye is obtained with excellent fastness, resistance to erosion and light.

Example 4 9.8 g of 3,4,9,10 - perylenetetracarboxylic dianhydride are first distilled anhydrous together with 2.65 g of zinc chloride and 2.65 g of sodium acetate in 150 cc of nitrobenzene. After cooling to 180 ° C. , a solution of 34.3 g of N, N-naphthalyl- (3,3-dimethylbenzidine) in 150 cc of nitrobenzene is added and the mixture is heated to the boil for 15 hours with stirring and reflux. After working up as indicated in Example 1 , a bright red pigment dye with very good migration fastness is obtained.

Example 5 9.8 g of 3,4,9,10 - perylenetetracarboxylic dianhydride are first distilled anhydrous together with 2.65 g of zinc chloride and 2.65 g of sodium acetate in 150 cc of nitrobenzene. After cooling to 180 ° C. , a solution of 20.9 g of phthalic acid N- (4-aminophenylimide) in 150 cc of nitrobenzene is added and the mixture is heated to boiling for 15 hours with stirring and reflux. After working up as indicated in Example 1 , a red-brown pigment dye with excellent migration fastness is obtained.

Claims (2)

Claims: 1. Pigment dyes of the general formula - wherein R denotes a phenylene radical, a diphenylene radical or a 3,3 # -dimethyldiphenylene radical and R denotes the remainder of phthalic acid, naphthalic acid or 3-nitronaphthalic acid. 2. pigment of the formula 3. pigment of the formula 4. Pigment dye of the formula 5. pigment of the formula 6. A process for the preparation of pigment dyes consisting of condensation products of perylene-3,4,9,10-tetracarboxylic acid, characterized in that perylene-3,4,9,10-tetracarboxylic acid either in free form or in the form of its anhydride or mixtures of the compounds mentioned with amines of the general formula in which R is a phenylene radical, a diphenylene radical or a 3,3'-dimethyldiphenylene radical and R is the radical of phthalic acid, naphthalic acid or 3-nitronaphthalic acid, in a manner known per se in a liquid reaction medium, optionally in the presence of one Condensing agent, is condensed, pigment dyes of the general formula are obtained in which R and R have the meanings given above. 7. The method according to claim 1, characterized in that NN-naphthalbenzidine is used as the amine. 8. The method according to claim 1, characterized in that the amine used is 3-nitronaphthalic acid-N- (4-aminophenylimide). 9. The method according to claim 1, characterized in that the amine used is NN-naphthalyl- (3,3'-dimethylbenzidine). 10. VerfahrennachAnspruch: 1, characterized in that phthalic acid-N- (4-aminophenylimide) is used as the amine. 11. The method according to any one of the preceding claims, characterized in that the amine component is used in an equivalent amount. 12. The method according to any one of the preceding claims, characterized in that a high-boiling organic compound is used as the liquid reaction medium. 13. The method according to claim 7, characterized in that nitrobenzene or o-dichlorobenzene is used as the reaction medium.