JPS6334904B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel perylene-3,4,9,10-
This invention relates to tetracarboxylic acid diimide and its use.

The new dye, which is distinguished by very good fastness properties, has the following formula: It is expressed as

This dye was prepared by known means such as perylene-3,
4,9,10-tetracarboxylic acid or its anhydride with 2,6-diisopropylaniline in a solvent or diluent such as quinoline, naphthalene or trichlorobenzole or a large excess of the aniline compound at a temperature of 180 to 230°C. It can be produced by condensation with The reaction is preferably carried out in the presence of a condensation promoter such as zinc chloride, zinc acetate, zinc propionate or hydrochloric acid.

The dyestuff is extracted from the reaction mixture in a conventional manner, for example after dilution with an inert organic solvent which does not dissolve the diimide, preferably an alcohol such as methanol, ethanol, isopropanol or isobutanol, and passing the hot reaction mixture between 20 and 80°C. Or isolated by centrifugation.

The dye can also be isolated as follows. An organic liquid having good solubility for the dye, such as N-methylpyrrolidone or a lower carboxylic acid amide such as dimethylacetamide or preferably dimethylformamide, is added to the entire reaction mixture.
Add at 50-150°C, preferably at 70-120°C to form a solution, pass through the solution and remove from the solution an organic liquid that does not dissolve or only slightly dissolves the dye, such as a lower alcohol, preferably methanol (optionally water The diimide is precipitated and isolated using a mixture of The dyes are often obtained in sufficiently pure form.

In order to remove any traces of perylene-3,4,9,10-tetracarboxylic acid still present, it may be boiled with dilute caustic soda solution or sodium carbonate solution. If necessary, the isolated dyestuff can be treated with a complexing agent such as ethylenediaminetetraacetic acid/tetrasodium salt in order to remove heavy metal ions that may be present. Both post-processing may be combined. The dye can optionally be further purified by reprecipitation from sulfuric acid or by recrystallization.

The new dyes are suitable for mixed coloring of synthetic resins, especially polystyrene and rigid polyvinyl chloride. This dye gives a very clear, shiny, fluorescent orange coloration and its lightfastness is very good. This dye can also be mixed with other dyes and used for mixed coloring of synthetic resins, in which case an extremely clear and glossy orange coloring is obtained.
Additionally, this new dye has been published in a German patent application.
It is suitable for the production of synthetic resin plates for light collection as described in No. 2620115, in which case the novel dye becomes the center of the fluorescence.

For the last mentioned purpose, the dye must be extremely pure. The product of the synthesis is therefore purified, for example, by fractional precipitation from sulfuric acid, recrystallization, etc., or by a combination of these operations.

For use in coloring synthetic resins, diimides can usually be used as they are synthesized.

Perylenetetracarboxylic acid-bisarylimides Industrially important arylimides from, for example, p-aminoazobenzole, p-phenetidine, p-anisidine, 3,5-dimethylaniline or p-chloroaniline can be prepared at customary processing temperatures. Gives a non-fluorescent red coloring. In contrast, with the new dyes, a bright orange coloration which fluoresces in sunlight is obtained in a transparent mixed coloration. The new dyes are essentially better soluble in organic solvents and synthetic resins than, for example, the bisarylimides mentioned above. As a result of the better solubility, the new dyes achieve a better distribution in the synthetic resin and therefore do not require special microdispersion and finishing treatments before use.

Parts in the examples below are parts by weight.

Example 1 750 parts of quinoline, perylene-3,4,9,10
-Tetracarboxylic acid dianhydride 98.4 parts, 2,
354 parts of 6-diisopropylaniline, zinc oxide
Add 13.6 parts and 40 parts of glacial acetic acid. Heat to 225-235° C. with a weak nitrogen stream and maintain this temperature until the sample boiled in dilute sodium carbonate solution shows no perylenetetracarboxylic acid. It is after about 10 hours in this case. After cooling to about 80°C, dilute with 1,000 parts of methanol, pour this suspension into 8,000 parts of methanol at room temperature, stir and filter. The residue is washed with methanol and then with water. This residue is added with stirring to 3500 parts of 2% sodium carbonate solution, heated to about 95° C., filtered, washed to neutrality and dried.
Traces of perylenetetracarboxylic acid, which were probably still present, are then removed and the dye is obtained in very good yield.

C ₄₈ H ₄₂ O ₄ N ₂ (molecular weight 710) C H O N Calculated value (%) 81.1 6.0 9.0 3.9 Actual value (%) 79.8 5.7 9.6 4.4 Example 2 Perylene-3,4,9, Ten
-Tetracarboxylic acid dianhydride 98.6 parts, 2,
Add 356 parts of 6-diisopropylaniline and 49 parts of zinc propionate (anhydrous). Heat to 225-235° C. with a weak stream of nitrogen and maintain this temperature until the sample boiled in dilute potassium carbonate solution shows no perylenetetracarboxylic acid. It is after about 10 hours in this case. After cooling to about 80° C., diluting with 1000 parts of methanol, the suspension is poured into 5000 parts of methanol at room temperature, stirred overnight and filtered. The residue is washed with methanol and then with water. This residue was dissolved in a 2% potassium carbonate aqueous solution.
Add to 3500 parts with stirring and heat to about 95℃.
Filter, wash until neutral, and dry. Traces of perylenetetracarboxylic acid, which were probably still present, are then removed and the dye is obtained in very good yields.

C ₄₈ H ₄₂ O ₄ N ₂ (molecular weight 710) C H O N Calculated value (%) 81.1 6.0 9.0 3.9 Actual value (%) 80.8 5.9 9.2 4.1 All of the compounds obtained in the above examples
It has a melting point of over 350℃.

Usage example Perylene-3, 4, 9, 10 using a high-speed mixer
0.05 part of -tetracarboxylic acid-bis-(2',6'-diisopropylanilide) (manufactured according to Example 1) was added to 100 parts of a pulverized polystyrene block polymer.
Dry mix into parts. Mixture cylinder temperature
Melt with a screw extruder at 200-250℃,
Homogenize. The plastic colored material is granulated by injecting it through a nozzle hole when hot or by drawing it out in the form of a thread while cooling. The thus obtained granules are then injection molded at 200 to 250° C. using an injection molding device to form a molded product, or compression molded to an arbitrary molded product using a compression molding machine. A bright orange injection molded or compression molded product that emits fluorescent light is obtained. This coloration has very good lightfastness.

Instead of polystyrene block polymers, polystyrene emulsion polymers, suspension polymers or copolymers of styrene with butadiene and acrylonitrile or acrylic esters may be used.

Claims (1)

[Claims] Linear formula Perylene-3,4,9,10-tetracarboxylic acid diimide represented by: Quadratic equation A method of using perylene-3,4,9,10-tetracarboxylic acid diimide represented by the formula for mixed coloring of synthetic resins. cubic formula A method of using perylene-3,4,9,10-tetracarboxylic acid diimide represented by: for concentrating light.