JPS6342943B2 - - 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 uses.

German patent applications no. 2620115 and no. 2554226
According to the specification, a device is known in which visible light can be concentrated onto a small surface by fluorescent centers interposed between layers in a synthetic resin plate. The compounds required as fluorescent centers in this device must have high light fastness, especially if light energy is to be converted into electrical energy, so that the device has a sufficient service life. That is, the compound used as the fluorescent center must have high light fastness in the synthetic resin used.

The object of the present invention is to find compounds suitable as fluorescent centers for light concentration devices, which exhibit strong fluorescence and at the same time have high light fastness in the medium used.
The aim was to provide something that would not have a detrimental effect on the medium.

The inventors have determined that the following formula (In the formula, A ¹ and A ² are hydrogen atoms, A ¹ is an isopropyl group and A ² is a hydrogen atom, or A ² is an isopropyl group and A ¹ is a hydrogen atom.) , 10-tetracarboxylic acid diimide has been found to have excellent properties as a fluorescent compound for light collection. This dye is particularly distinguished by very good fastness properties.

The compounds of formula a are extremely light-fast in synthetic resins (from which the synthetic resin plates used for future light collection are produced) and convert incident light into fluorescence with high efficiency. The wavelength of the fluorescence generated is 500 ~
It is 600nm.

The novel dye of formula a is prepared by mixing perylene-3,4,9,10-tetracarboxylic acid or its anhydride with 2-isopropylaniline, 2,4
- by condensation with diisopropylaniline or 2,5-diisopropylaniline in a solvent or diluent such as quinoline, naphthalene or trichlorobenzole, or in an excess of the aniline compound at elevated temperatures, such as temperatures from 180 to 230°C. It can be manufactured by folding. The reaction is preferably carried out in the presence of a condensation accelerator such as zinc chloride, zinc acetate, zinc propionate or hydrochloric acid.

The dye can be isolated from the reaction mixture in a conventional manner, for example by filtration. For example, if the temperature is exceeded
at 80 DEG -120 DEG C., optionally after diluting the reaction mixture with an inert solvent, such as a lower carboxylic acid amide such as formamide, an aromatic solvent such as toluene or chlorobenzole, or preferably an alkanol such as methanol, ethanol or isobutanol. is particularly advantageous. Trace amounts of perylene-3,4,
To remove the 9,10-tetracarboxylic acid, the dye can be boiled out with dilute caustic soda or soda solution.

The dye is optionally further purified, for example by fractional precipitation from concentrated sulfuric acid, recrystallization from an easily removable high-boiling solvent or boiling out with a solvent under grinding conditions. In order to obtain extremely pure compound (a), one purification operation is optionally repeated once or several times, or different purification operations are combined.

For use in light concentration, compound (a) is incorporated into synthetic resins suitable for use. For this purpose, the required amount of compound (a) is sprinkled onto the synthetic resin in the form of granules, and the granules are then extruded into flat structures. As the synthetic resin (medium), when used for concentrating light for solar cells, for example, polymethyl methacrylate, polymethyl acrylate, polystyrene,
Polydiethylene glycol-diallyl biscarbonate as well as suitable polyamides and polycarbonates are used.

The new dyes of the formula a are outstandingly suitable for coloring the raw materials of synthetic resins, especially thermoplastic synthetic resins. The dyestuff gives a very transparent, shiny and fluorescent orange coloration which exhibits very good lightfastness. The dyes can also be mixed with other dyes and used for the mixed coloring of synthetic resins, resulting in highly transparent and glossy colorings. Furthermore, the novel dyes are particularly suitable for the production of synthetic resins for light concentration as described in DE 26 20 115 A1, in which case the novel dyes serve as fluorescent centers.

Industrially important from perylene-3,4,9,10-tetracarboxylic acid-bis-arylimides, such as p-aminoazobenzole, p-phenetidine, p-anisidine, 3,5-dimethylaniline or p-chloroaniline The arylimide provides a red coloration at normal processing temperatures, which does not fluoresce. In contrast, with the new dye, a glossy orange coloration is obtained which fluoresces in daylight in a transparent coloration. The new dyes are substantially better soluble in organic solvents or synthetic resins than, for example, the bisarylimides mentioned above. Due to this good solubility, a much better distribution of the new dye in the synthetic resin is obtained, so that special microdispersion and finishing treatments are not necessarily required before use.

Parts and percentages in the examples below relate to weight.

Example 1 Crystalline zinc acetate in 840 parts of quinoline at 100°C
40.8 parts, perylenetetracarboxylic acid 117 parts and 2,
Add 135 parts of 4-diisopropylaniline. Heat to 225-230°C while introducing a weak nitrogen stream,
The sample is then boiled with a dilute sodium carbonate solution and kept at this temperature until the finished sample shows no perylenetetracarboxylic acid. This was about 2 hours later. After cooling to about 100℃,
Wash sequentially with quinoline, methanol and water. The residue is stirred with about 1200 parts of a 2% aqueous sodium carbonate solution, heated to about 95°C, filtered and washed until neutral. Any traces of perylenetetracarboxylic acid that may still be present are removed during this process.
After drying, a dye of the following formula is obtained in very good yield.

Proceed as above, but instead of 2,4-diisopropylaniline, use the same amount of 2,5-isopropylaniline or 2-isopropylaniline99
When using parts, perylenetetracarboxylic acid-N,
N′-bis-(2′,5′-diisopropylanilide)
and -N,N'-bis-(2'-isopropylanilide) are obtained in extremely good yields.

Example 2 Mixed coloring of synthetic resin: Perylene-3,4,9,10-tetracarboxylic acid-bis-(2',4'-diisopropylanilide)
0.05 part is dry mixed in a high speed mixer with 100 parts of ground polystyrene block polymer. The mixture is melted and homogenized in a screw press at a cylinder temperature of 200-250°C. The colored plastic material is granulated either by expelling it hot from the nozzle head or by drawing it into a thread while cooling. The granules thus obtained are then either injected into a molded body at 200-250° C. in an injection molding machine or compressed on a press into any desired molded body.
Press-molded, orange-colored, glossy injection-molded bodies are obtained; these molded bodies emit fluorescence and exhibit very good light fastness.

Instead of polystyrene-block copolymer, polystyrene-emulsion polymer, suspension polymer,
Alternatively, a copolymer of styrene, butadiene, and acrylonitrile or acrylic ester can also be used.

Perylene 3,4,9,10-tetracarboxylic acid-
Perylene-3,4,9,10-tetracarboxylic acid-N,N'-bis-(2',5'-diisopropylanilide) was used instead of N,N'-bis-(2',4'-diisopropylanilide) anilide) or perylene-3,4,
9,10-tetracarboxylic acid-N,N'-bis-
(2'-isopropylanilide) gives exactly the same coloration with virtually the same properties.

Example 3 Perylene-3,4,9,10-tetracarboxylic acid-bis- was added to 1000 parts of polymethyl acrylate granules.
(Spread 0.05 part of 2',4'-diisopropylanilide evenly, and extrude this uniform mixture to make a fluorescent screen.

Claims (1)

[Claims] Linear formula (In the formula, A ¹ and A ² are hydrogen atoms, or A ¹ is an isopropyl group and A ² is a hydrogen atom, or A ² is an isopropyl group and A ¹ is a hydrogen atom.) 9,10-tetracarboxylic acid diimide dye. 2. The dye according to claim 1, characterized in that A ¹ or A ² is an isopropyl group. 3. A dye according to claim ¹ , characterized in that A 1 is an isopropyl group. Quaternary formula (In the formula, A ¹ and A ² are hydrogen atoms, or A ¹ is an isopropyl group and A ² is a hydrogen atom, or A ² is an isopropyl group and A ¹ is a hydrogen atom.) A method of coloring synthetic resin raw materials using 9,10-tetracarboxylic acid diimide dye.