JPS58160358A - Novel trisazo compound and production thereof - Google Patents

Abstract

NEW MATERIAL:Trisazo compounds of formulaIIwherein R is alkyl, alkoxy, nitro, dialkylamino, halogen; n is 0, 1, 2, 3 with the proviso that when n is 2 or 3, Rs may be the same or different groups. USE:Photoconductive materials for electrophotographic photosensitive materials. For example, photosensitive layer (1) consisting of the trisazo compd., photosensitive layer (2) wherein the trisazo compd. is dispersed in a binder, photosensitive layer (3) wherein the trisazo compd. is dispersed in a charge transfer medium, and photosensitive layer (4) wherein the photosensitive layer of (1) to (3) is used as a charge generating layer, and a charge transfer layer contg. a charge transfer medium is laminated thereon. PREPARATION:A hexazonium salt of formula II (wherein X is an anionic functional group) is reacted with a compd. of formula III to obtain the desired compd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel trisazo compound and a method for producing the same.

In recent years, many electrophotographic photoreceptors using organic photoconductive materials have been proposed. For example, a photoreceptor provided with a photosensitive layer containing poly-N-vinylcarbazole 2.4.7-trinitrofluoren-9-one, a photosensitive layer made of poly-N-vinylcarbazole sensitized with a pyrylium salt dye. A photoreceptor with a photoreceptor layer containing an organic pigment as a main component, a photoreceptor with a photoreceptor layer consisting of a charge generation layer and a charge transport layer, and a photoreceptor with a photoreceptor layer consisting of a charge generation layer and a charge transport layer; There are photoreceptors that are provided with a photosensitive layer as a component.

Although the photoreceptors mentioned above have some excellent properties, one of their major drawbacks as electrophotographic photoreceptors is that they generally have lower photosensitivity than inorganic photoreceptors such as selenium. ing.

An object of the present invention is to eliminate the above-mentioned drawbacks and provide a novel trisazo compound having excellent properties as a photoconductive material and a method for producing the same.

That is, one of the present inventions is based on the general formula [I] (where R is an alkyl group, an alkoxy group, a nitro group, a dialkylamino group, or a halogen, n is an integer of 0, 1.2, or 6, and n is an integer of 2 or 6, R may be the same or different groups.)
This is a novel trisazo compound represented by

The above trisazo compound [I] of the present invention can be produced by the following method. That is, another aspect of the present invention is a hexazonium salt represented by the general formula [11] (where X is an anionic functional group) and a hexazonium salt represented by the general formula [III] (
However, R is an alkyl group, an alkoxy group, a nitro group, a dialkylamino group, or a halogen, n is an integer of 0, 1.2, or 3, and when n is an integer of 2 or 3, R is the same It may be any of different groups. ) is a novel method for producing a trisazo compound, which is characterized by reacting with a compound represented by:

The hexazonium salt is, for example, 1.2. '4-) Produced by reacting lyhalobenzene and nitrostyrene, 1, represented by the general formula [■], is produced by reducing tromethy1-nor)benzene to 2.4 -tris, and is produced by the general formula [■]. 1,2,4-)lis(aminoste-1-nor)benzene, and then diazotization.

1,2.4- The reaction between trichlorunzene and nitrostyrene usually requires a catalyst and a nitrogen-containing hydrocarbon. As a catalyst, a combination of a noble metal compound such as acetic acid/radium and a phosphorus compound such as triarylphosphine is suitable.

The nitrostyrene is preferably P-nitrostyrene.

Triarylphosphines include triphenylphosphine, tri-o-tolylphosphine, tris(2.5-
diyne-propylphenyl)phosphine, triα-naphthylphosphine, tris(2, 3, 4. 5-
Tetramethyl)phenylphosphine, Tris(2-methyl-5-t-butylphenyl)phosphine, Tris(P
Phosphines such as -carbomethoxyphenyl)phosphine can be mentioned, and use of tri-o-tolylphosphine and tris(2-methyl-5-t-butylphenyl)phosphine is particularly preferred.

The triarylphosphine used in the present invention is suitably used in an amount of 05 to 10 moles per mole of palladium acetate. In addition, the amount of palladium acetate used is 0% of the amount of styrene derivative used.
．． 25 to 2 molti is suitable.

- As the hydrogen halogenide scavenger, secondary amines, tertiary amines, sodium bicarbonate, basic salts with sodium carbonate, etc. are suitable. Such secondary amines, 3
Examples of class amines include diethylamine, di-n-butylamine, piperidine, morpholine, triethylamine,
Commonly used amines such as tributylamine, triamylamine, and tetramethylethylenediamine may be used, and the amount used is slightly in excess of the equivalent mole of hydrogen halogenide generated. Common reaction solvents are used, such as N. N-dimethylformamide, dimethylacetamide, toluene, xylene, chlorobenzene,
O-dichlorobenzene, trichlorobenzene, N-methyl-2-pyrrolidone, and dimethyl sulfoxide are used. The reaction is carried out at a temperature range of 75-150°C.

1, 2 obtained in this way. 4-) Trostyryl) benzene [■] is reduced to 1,2.

4-tris(aminosteryl)benzene is diazotized to form a hexazonium salt, but diazotization is performed using 1, 2.
4-) Lis(aminostyryl)benzene is added to a dilute inorganic acid such as dilute hydrochloric acid or dilute sulfuric acid, and then an aqueous sodium nitrite solution is added thereto while maintaining the temperature at -10 to 10°C. . This diazotization is 60
It can be completed in minutes to 2 hours. In this case, it is desirable to precipitate the reaction mixture as a hexazonium salt by adding, for example, borofluoric acid, and then repeat the reaction several times to obtain crystals.

Next, the compound [■] is added to the hexazonium salt [■].
1] is added in an amount of 1 to 15 times the molar amount, preferably 3 to 8 times the molar amount of the hexazonium group, to cause a coupling reaction. In practice, this reaction is carried out by dissolving the hexazonium salt and the coupling component in an organic solvent such as N,N-dimethylformamide or dimethyl sulfoxide, maintaining the temperature at -10 to 10°C, and adding an aqueous solution such as sodium acetate. This is carried out by dropping an alkaline aqueous solution.

The novel trisazo compound of the present invention thus obtained is
It is particularly useful as a photoconductive material for electrophotographic photoreceptors.

Therefore, for example, (II photosensitive layer (2) consisting of a trisazo compound)
(3) A photosensitive layer in which a trisazo compound is dispersed in a binder; (4) a photosensitive layer in which a trisazo compound is dispersed in a known charge transfer medium; (4) the photosensitive layer of (1) to (3) above is used as a charge generation layer;
Examples of applications of the new trisazo compound include a photosensitive layer containing a well-known charge transport medium: a charge transport layer, an entire charge transport layer, and the like.

EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.

Example 1, 2.4-t! J-bromobenzene 31” parts (t
parts, hereinafter the same), 492 parts of P-nitromethyleff, 6.11 parts of tri-n-butylamine, 0.182 parts of tri-n-tolylphosphine, 0.067 parts of palladium acetate, N-
After reacting a mixture of 7 parts of methyl-2-pyrrolidone (hereinafter abbreviated as NMP) at 100°C for 10 hours, it is poured into methanol, the precipitated product is separated and recrystallized from chlorobenzene. 1°2 of orange crystals
, 4-) IJs(p-nitrostyryl)benzene 6
．． 29 parts (63% yield) were obtained.

697 parts of iron powder, 244 parts of concentrated hydrochloric acid, 11 parts of water, 6 parts, NMP
1.2.4-Tris (p
-2l-rostyryl)benzene329'1tlJ.

After stirring at 90 to 100°C for 5 hours, the pH was adjusted to 8 with a 20% aqueous sodium carbonate solution while hot, and insoluble matter was separated off while hot. By pouring the P solution into water, the precipitate that precipitates out is separated and recrystallized from chlorobenzene to obtain 1.58 parts of 1.2.4-tris(P-aminosteryl)benzene as dark yellow crystals. (yield 58%).

1,2.4- 1.00 parts of tris(P-aminostyryl)benzene was added to dilute hydrochloric acid prepared from 5.8 parts of concentrated hydrochloric acid and 5.8 parts of water, stirred at 60°C for 60 minutes, and then heated to 0°C. After cooling, a solution of 0.49 parts of sodium nitrite dissolved in 2 parts of water was added dropwise.

After that, it was stirred at the same temperature for 60 minutes, a small amount of insoluble matter was removed, and 642 parts of a 42-hydrofluoric acid aqueous solution was added to the p solution, and the precipitated crystals were removed, washed with water, and then dried. Hexazonium trifluoroborate was obtained as dark brown crystals.

As a coupling component to the hexazonium salt thus obtained, 2-hydroxy-6-naphthoic acid anilide (
Naphthol As) 2.02 parts and cooled N, N
-Dimethylformamide (hereinafter abbreviated as DMF) 200
5.73% of sodium acetate hexahydrate
and 40 parts of water was added dropwise at 4 to 8°C over about 1 hour, and then stirred at room temperature for 3 hours. The generated precipitate was collected and washed 6 times with 100 parts of water, then DM
It was washed three times with 150 parts of F and once with acetone. This is dried to form the trisazo compound 124 shown below.
(yield: 42).

Melting point: 269°C (decomposition) The infrared absorption spectrum of the trisazo compound is shown in FIG.

Structural formula elemental analysis value (measured value) O: 77.47 H: 4.62
) J: 1 [1,15 calculated value same) C near 7.
68 H: 4.59 N: 10.07 Application Example Trisazo pigment synthesized in Example and polyester resin (
Toyobo 42) Kuiron 200) is mixed at a weight ratio of 1:2, and this is mixed with
．． A solution of 84 volumes was prepared by dissolving it in a mixed solvent of 1 (volume ratio).

This solution was applied onto an aluminum substrate with an applicator and dried to form a charge generation layer with a thickness of about 1 μm.

On top of this, P-diethylaminobenzaldehyde-N,
N-diphenylhydrazone and polycarbonate resin (Panrai L manufactured by Tijin) were blended at a weight ratio of 1:1 and dissolved in tetrahydrofuran to make an 18 weight solution, so that the film thickness after drying was approximately 10μ. It was applied with an applicator, dried and allowed to form a charge transport layer.

In this way, an electrophotographic photoreceptor having a two-layer photosensitive layer was obtained.

This photoreceptor was negatively charged by performing a corona discharge of 16 KV for 15 seconds using an electrostatic copying paper tester (new model 5P-428 manufactured by Kawaguchi Electric), and then left in a dark place for 20 seconds. The surface potential Vo(v) of the surface was measured, and then the surface was irradiated with light using a Gesten lamp at an illuminance of 20 lux, and the surface potential was V.

Measure the time (seconds) until it becomes a bar, and measure the half-reduced exposure amount E!
A (looks/seconds) was calculated.

The results are: Vo = -820v, El/2 = 2
flux seconds, and both charge retention in the dark and light sensitivity were excellent.

[Brief explanation of the drawing]

FIG. 1 shows the infrared absorption spectrum of the trisazo pigment of the present invention produced according to the examples.

Claims (2)

[Claims] (1) General formula [I] (wherein R is an alkyl group, an alkoxy group, a nitro group, a dialkylamine group or) rogene, n is an integer of 0, 1.2 or 6, and n is 2 or 6 R may be the same or different groups. ) is a novel trisazo compound. (2) Hexazonium salt represented by the general formula [■] (where X is an anionic functional group) and the general formula [ff1) (where R is an alkyl group, an alkoxy group, a nitro group, a dialkylamino group, or a halogen, n 1.2 or 2, and when n is an integer of 2 or 3, it may be the same or different groups.) , general formula [I
] (However, R represents the above-mentioned group, and n is the above-mentioned integer.) A method for producing a novel Hiko trisazo compound represented by the following.