JPS58154560A - Novel trisazo compound and its preparation - Google Patents

Abstract

NEW MATERIAL:A trisazo compound shown by the formulaI(R<1> is alkyl, alkoxy, nitro, dialkylamino, or halogen; n is integer of 1-3, and R<1> is either the same or different when n is 2 or 3; R<2> is alkyl, cycloalkyl, or aralkyl). USE:A photoconductive material for a sensitized material of electrophotography. Having high photosensitivity. PROCESS:A hexazonium compound shown by the formula II (X is functional group of anion) is reacted with a compound shown by the formula III, to give a compound shown by the formulaI. The hexazonium salt shown by the formula II is obtained by reacting a compound shown by the formula IV (Y is Br or I) with a p-nitrostyrene to give a novel compound shown by the formula V, which is reduced and diazotized.

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. An example is PoIJ. −． ll + vinyl force Rubazol and 2. 4. 7-Trinitrofluorene? A photoreceptor with a photoreceptor layer containing -on, a photoreceptor with a photoreceptor layer made of poly-N-vinyl rubazole sensitized with a pyrylium salt dye, a photoreceptor with a photoreceptor layer containing an organic pigment as a main component. , a photoreceptor having a photosensitive layer formed by laminating a charge generation layer and a charge transport layer, and a photoreceptor having a photosensitive layer containing a eutectic complex consisting of a dye and a resin as a main component.

Although the above photoreceptors 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. There is.

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 includes the general formula [■] (where Hl is an alkyl group, an alkoxy group, a nitro group,
dialkylamino group or halogen, n is an integer of 0.1.2 or 5, and when n is an integer of 2 or 6, κ is R1 may be the same or different group, R2 (
, 1 alkyl group, cycloalkyl group or aralkyl group.

) This is a novel trisazo compound represented by n.

The above trisazo compound CI) of the present invention can be produced by the following method. ν1] Another aspect of the present invention is the general formula [■] (where xVi is an anion functional group, R2 is an alkyl group,
Cycloalkyl group or aralkyl group. ) and a hexazonium salt represented by the general formula [■] (where RI J, l alkyl group, alkoxy group, nitro group, dialkylamino group, or norogen, n is an integer of 0.1.2 or 3) and when %n is an integer of 2 or 3, they may be the same or different groups.

The hexazonium salt is represented by the general formula [■] (where Y is bromine or iodine, and R2 is an alkyl group, cycloalkyl group, or aralkyl group (represented), for example, 9-1-5, 6- 9-mono-substituted-3,6-bis(p) of a new known compound represented by the general formula [■], which is produced by incubating Gino-Loh's 1-2tropolymer Rubazole and p-nitrostyrene endpage:2. -nitrostyryl)-1-nitrocarno《by reducing sol, the general formula [
(2)] It can be obtained by preparing 9-monosubstituted-3,6-bis(p-aminostyryl)-1-aminocarbazole represented by the formula and then diazotizing it.

The reaction of 9-monosubstituted-3,6-diha+:I-1-nitrorubazole with p-nitrosterene usually requires a catalyst and a hydrogen scavenger.

A suitable catalyst is a combination of a metal compound such as palladium acetate and a phosphorus compound such as triarylphosphine.

Triarylphosphines include triphenylphosphine, tri-101tolylphosphine, tris(2.5-
di-probylphenyl)bosphine, triα-naphthylphosphine, tris(2,5,4,s-
tetramethyl)phenylphosphine, tris(2-methyl-5-t-butylphenyl)phosphine, tris(p
Mention may be made of phosphines such as monocarpomethoxyphenyl)phosphine, and it is particularly preferred to use tris(2-#f-5-t-butylphenyl)phosphine.

The triarylphos7yne used in the present invention is a5 to IQ% 2) per mole of palladium acetate! Appropriate.

Also, the amount of palladium acetate used is 0.0% of the amount of styrene derivative used. 25 to 2 molti is suitable.

Suitable hydrogen halide scavengers include secondary amines, 6th class amines, and basic salts such as sodium bicarbonate and sodium carbonate. Such secondary amines and tertiary amines may be common amines such as diethylamine, di-n-butylamine, piperidine, morpholine, triethylamine, tri-n-butylamine, triamylamine, and tetramethylethylenediamine. The amount used is slightly in excess of the equivalent mole of hydrogen generated. Common reaction solvents include N,N-dimethylformamide, dimethylacetamide, toluene, xylene, chlorobenzene, 0-dichlorobenzene, trichlorobenzene, N-meth-2-pyrrolidone, and dimethylsulfoxide. is used.

The reaction is carried out at a temperature range of 75-150°C.

9-substituted-3,6 of the new compound obtained by K.
-Bis(p-nitrosteryl)-1-nitrocarbazole [■] is reduced to 9-monosubstituted 46-bis(p-aminostyryl)-1-aminocarbazole, which is diazotized to form a hexazonium salt. 91 substitution-5
．． 6-bis(p-aminostyryl)-1-aminocarbazole is added to a dilute inorganic acid such as dilute hydrochloric acid or dilute sulfuric acid,
Furthermore, add a sodium nitrite aqueous solution to this at -10 to 10
This is done by maintaining the temperature at ℃ and adding it. This diazotization is completed in 30 minutes to 2 hours. In this case, it is desirable that the reaction mixture is precipitated as a hexazonium salt by adding, for example, borofluoric acid, and then collected to obtain crystals.

Next, the compound [1] was added to the hexazonium salt (Il).
11] is added in an amount of 1 to 10 times the molar amount, preferably 2 to 5 times the molar amount of the hexazonium group, to cause a coupling reaction. In reality, this reaction is N. Dissolve the hexa7'=um salt and the coupling component in an organic solvent such as N-dimethylformamide or dimethyl sulfoxide, and dropwise add an alkaline aqueous solution such as a sodium acetate aqueous solution while maintaining the temperature at -10 to 10°C. This is done by doing this.

The novel trisazo endpage:3 compound r[ of the present invention thus obtained is particularly useful as a photoconductive material for electrophotographic photoreceptors. Therefore, for example, (1) a photosensitive layer made of a trisazo compound, (2) a photosensitive layer in which a trisazo compound is dispersed in a binder, (3) a photosensitive layer in which a trisazo compound is dispersed in a known charge transfer medium, (4) the above (1) Application examples of the novel trisazo compound include a photosensitive layer in which the photosensitive layer of () to (3) is used as a charge generation layer, and a charge transfer layer containing a well-known charge transfer medium is layered thereon.

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

Synthesis of Example 6. Fuming nitric acid (a...t52) in which 6.5 parts (by weight, same below) of 6-dipromocarbazole was dissolved in 80 parts of acetic acid, and dissolved in 10 parts of acetic acid with stirring. 1.33 parts were added dropwise at room temperature, and after the addition was completed, the mixture was heated to 70°C and reacted for 2 hours. A lot of the precipitate deposited after cooling was collected and recrystallized from chlorobenzene to obtain 5.17 parts of 46-dipromo-1-nitrocarpazole (yield: 70 yen) as yellow crystals. Melting point 2 6 7. 8℃.

After dispersing 50 parts of 46-dibromo-1-nitrocarbazole in 45 parts of dimethylformamide (hereinafter abbreviated as DMF), 08 parts of powdered KOH was added. DMF 5
2.15 parts of isoamyl bromide dissolved in 1 part was added dropwise at room temperature, and after completion of the dropwise addition, the reaction was carried out at 70°C for 5 hours and at 90°C for 3 hours. After cooling, the reactant was poured into 300 parts of water, the precipitate was collected, and after thoroughly washing with water,
By recrystallizing from ethanol, 9-yneamyl-3,6-dipromo-1-nitrocarbazole 4.00
(yield 67%) was obtained as yellow crystals.

9-yneamyl-3,6-dipromo-1-nitrocarpazole4. ODm, P-nitoasterene 512 parts, tri-n-butylamine! L88 parts, tri10-tolylphosphine 0. 1 1 1 part, palladium acetate 0. 0
4 1 part, N-methyl-2-pyrrolidone (hereinafter referred to as NM
A mixture consisting of 15 parts (abbreviated as P) was reacted at 100° C. for 10 hours with stirring under a nitrogen atmosphere. The reactant was added to a large amount of methanol, and the precipitate was collected as F. After thorough washing with methanol and recrystallization from NMP, 9-yneamyl-3,6-bis(p-nitrosteryl)-1-nitrorubazole 38
7 parts (yield: 74 cm) were obtained as orange crystals.

9-inoamyl-3,6-bis(p-nitrostyryl)
-1-Nitrocarbazole & 87 parts, iron powder 7. 3 8
1 part, concentrated hydrochloric acid 2. 5 8 (volume) parts, 12.3 parts of water,
While stirring a mixture consisting of 150 parts of NMP, 9
The reaction was carried out at 0°C for 13 hours. A 20% aqueous sodium carbonate solution was added to the reaction mixture to adjust the pH to 8. After filtering the reaction mixture while hot, Ffi was poured into a large amount of water, the deposited precipitate was collected, thoroughly washed with water, and dried to obtain 9-yneamyl-3,6-bis(p -aminostyryl)-1-aminolupazole & 13 parts (yield: 96 buns)
was obtained as a yellow solid. 1.50 parts of 6-bis(p-aminostyryl)-1-aminocarbazole was added to dilute hydrochloric acid consisting of 17 parts of concentrated hydrochloric acid and 77 parts of water, and the mixture was stirred at 60°C for 30 minutes. The mixture was then cooled to 0°C, and 65 parts of sodium nitrite α was added to 2 parts of water.
．． A solution of 6 parts was added dropwise. After dropping, at the same temperature
Stir for 0 minutes, remove insoluble matter, add 2 parts of 42% borohydrofluoric acid aqueous solution A to solution F, collect precipitated crystals from F,
After washing with water and drying, endpage:4 hexazonium trifluoroborate was obtained as dark brown crystals.

2. Hexazonium salt thus obtained and 2-hydroxy-5-naphthoic acid anilide (naphthol AS) as a coupling component. 6 s part and D
Dissolved in 200 parts of MF, and added 7 parts of sodium acetate to this.
．． 5 An aqueous solution consisting of 9 parts and 50 parts of water was heated at 4 to 8°C.
The mixture was added dropwise at a temperature of about 1 hour, and after dropping, the mixture was stirred at room temperature for 5 hours. The generated precipitate was collected and washed five times with 200 parts of water, three times with 500 parts of DMF, and once with acetone. This was dried to obtain 156 parts of the indicated trisazo compound (yield: 59%).

The infrared absorption spectrum of the trisazo compound is shown in FIG.

Structural formula elemental analysis value C H N actual value (
Support)) 76.78 5.01 1[184
Calculated value (%) 77.05 4, 95 1α7
0 Application Example Trisazo pigment synthesized in Example and polyester resin (
Toyobo Co., Ltd.: Byron 200)
1 (volume ratio) was dissolved in a mixed solvent to obtain a solution with a weight of A4.

This solution was applied onto an aluminum substrate using an ablifier and dried to form a charge generation layer with a thickness of about 1 μm. On top of this, p-diethylaminopenzaldehyde N
．． N-diphenylhydrazone and polycarbonate resin (Panrai L, manufactured by Teijin) were blended in a weight ratio of 1=1 and dissolved in tetrahydrofuran to make a solution of 18% by weight, and the film thickness after drying was approximately 10μ. Apply it with an applicator so that it is dry, form a charge transfer layer, and
An electrophotographic photoreceptor having a photosensitive layer consisting of layers was obtained.

This feeling? Using an electrostatic copying paper tester (manufactured by Kawaguchi T-ki Seisakusho, SP-428 model), the light body was negatively charged by -6KV corona discharge for 15 seconds, and then left in a dark place for 20 seconds. , measure the surface potential Vo (V) at that time, and then irradiate the surface with light using a tungsten lamp so that the illumination intensity is 20 lux, and the surface potential becomes V
The time (seconds) it takes for the sample to turn into a duck was measured, and the half-exposure (iAE'A Clux Φ seconds) 1t was determined.

The result is V. =-740V, F! 1,4-42 lux·sec, and both charge retention in the dark and photosensitivity were κ large.

[Brief explanation of the drawing]

FIG. 1 shows the infrared absorption spectrum of the trisazo compound of the present invention produced in the example. endpage:

Claims (2)

[Claims] (1) General formula Cl) (However, R1 is an alkyl group, an alkoxy group, a nitro group,
R is an alkylamino group or an integer of 0, 1.2 or 3, and when n is an integer of 2 or 3, Rl may be the same or different groups; R2 is Alkyl group, cycloalkyl group or aralkyl group. ) A novel trisazo compound. (2) A hexazonium salt represented by the general formula (Il) (wherein, X is an anionic functional group and % R'' alkyl group, cycloalkyl group, or aralkyl group) and a hexazonium salt represented by the general formula [111] (however, R' u
Alkyl group, alkoxy group, nitro group, dialkylamino group or halogen, n is an integer of 0.1.2 or 3, and when n is an integer of 2 or 3, it may be the same or different groups. good. ) When reacting with a compound represented by Production method.