JPH0397760A - Bisazo compound and use thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I {Y is H, halogen, cyano, alkyl or alkoxy; R1 is H, halogen, alkyl or acyl; A is group shown by formula II to VII [Z is (substituted) aromatic hydrocarbon; Q is (substituted) carbamoyl or sulfamoyl; R2 is (substituted) alkyl, (substituted) aralkyl or aryl; Z is bifunctional aromatic hydrocarbon or heterocyclic ring containing N in the ring; R3 is (substituted) alkyl, amino, carbamoyl, etc.; X is (substituted) aryl]). USE:A photo-conductive material in a sensitized material for electrophotography. PREPARATION:A diamine shown by formula VII is tetrazotized and then the tetrazonium salt is coupled with a coupler corresponding to formula II to formula VII in the presence of an alkali.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel bisazo compound useful as a photoconductive material in an electrophotographic photoreceptor.

[Prior art]

Conventionally, photoreceptors used in electrophotography include selenium,
8 Electrophotography, which often uses inorganic photoconductive materials such as zinc oxide and cadmium sulfide, is a well-known process in which the surface of a photoreceptor is first charged by corona discharge, and then photoimage exposure is performed to separate the exposed areas. After neutralization of the surface potential by the transfer of charges,
This method forms a visible image by bringing toner into contact with the electrostatic latent image remaining in the unexposed area. In such electrophotography, the basic conditions required for the photoreceptor are (1) the ability to charge it to an appropriate potential in the dark, (2) the ability to generate little spontaneous charge in the dark, and (3) the ability to charge to an appropriate potential in the dark. ) Charges can be quickly erased by light irradiation.

The inorganic photoreceptor using an inorganic photoconductive material has the above-mentioned (1) to
Although condition (3) is satisfied, it lacks flexibility and is extremely harmful or toxic, so there are many environmental conservation problems, and the main points of thermal stability and durability are not necessarily satisfied. do not have. On the other hand, organic photoreceptors using organic photoconductive materials such as polyvinyl rubber, anthracene, etc. can be produced by coating by using an appropriate binder, so they are extremely productive and inexpensive. It has advantages that inorganic photoreceptors do not have, such as the ability to control the sensitive wavelength range due to the wavelength selectivity of the molecular structure of organic photoconductive materials.

[Problem to be solved by the invention]

An object of the present invention is to provide a novel bisazo compound useful as a photoconductive material for organic electrophotographic photoreceptors, which has the advantages described above.

[Means to solve the problem]

The above object can be achieved by a novel bisazo compound represented by the following general formula (1).

[However, Y represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an alkoxy group, R1 represents a hydrogen atom, a halogen atom, an alkyl group, or an acyl group, and A represents the following general formulas (II) to (■) represents the aromatic force of . (IN) (III) (IV) Lll1 (V) (VI) (■)
? However, in formula (+'I), Z represents a substituted or unsubstituted aromatic hydrocarbon group, Q represents a substituted or unsubstituted carbamoyl group or sulfamoyl group, and formulas (IIN) and (IV
), R■ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or an aryl group, and has the formula (
In V) and (VI), Z represents a divalent aromatic hydrocarbon group or a heterocyclic group containing a nitrogen atom in the ring, and in formula (■), R3 is a hydrogen atom, a substituted or unsubstituted alkyl group , an amino group, a carbamoyl group, a carboxyl group or an ester thereof, a cyano group, or a substituted or unsubstituted aryl group. )] The bisazo compound of the above general formula is useful as a photoconductive material in an organic electrophotographic photoreceptor, as described below.6 Specific examples of the bisazo compound of the present invention are shown below, but the present invention is not limited thereby. It's not something you can do.

(Leaving space below) Table 2 Notes: I is the position relative to the azo group These bisazo compounds can be easily produced by known methods. For example, general formula (■)? ■ (However, Y and R are as described above) A diamine represented by the formula (I
After coupling with couplers corresponding to I) to (■), or once the tetrazonium salt is isolated in the form of a borofluoride salt, it can be coupled with a suitable solvent such as N,N-dimethylformamide, dimethyl sulfoxide, etc. It can be easily produced by coupling with a coupler in a solvent in the presence of an alkali. The reaction formula at this time is as follows.

(■) (IX) If necessary, react with R, 'W (however, R1' is the same as R except for H, and W is a halogen atom) in an organic solvent such as benzene to obtain an iminobibenzyl derivative (Off). Afterwards, it was nitrated with concentrated nitric acid in the presence of concentrated sulfuric acid to obtain the 2,8-dinitro compound (XII), which was then treated with NBS (N-promusuccinimide) and BPO in an organic solvent such as benzene.
(benzoyl peroxide) to bromate 10-bromo2
, 8-dinitro 00, which was debrominated with potassium hydroxide in an alcoholic solvent such as methanol to give 2.
,8-dinitrodibenzo(b,f) azepine derivative (X
N) and then convert these nitro groups into SnC 12 ,-
It can be obtained by reduction using a known reduction method such as HCD. (Space below) The diamine of general formula (■) can be synthesized by converting iminobibenzyl (X) (for example, according to the method of Japanese Patent Publication No. 32-6638) to (X) according to the following reaction formula.
(XI) (X[l) (XI[I
) (X!V) Reduction -→ (■) Since the bisazo compound of the present invention obtained as described above has charge generation ability and spectral sensitivity when irradiated with light, it can be used as a photoconductive material for electrophotographic photoreceptors. It is useful as a. In this type of photoreceptor, the photoconductive layer is either a single layer type (or dispersed type) or a laminated type (or functionally separated type), but in the case of a single layer type photoreceptor, the photoconductive layer is a charge-generating material. The bisazo compound of the present invention is dispersed in a solution containing a charge transport substance and a binder, and this is coated on a conductive support and dried to form a photoconductive layer. In the case of dispersing the bisazo compound in a binder solution,
This is coated on a conductive support and dried to form a charge-generating layer, and then a solution containing a charge-transporting substance and a binder dissolved therein is coated and dried to form a charge-transporting layer, or Conversely, it is manufactured by forming the charge transport layer as described above and then shaping the charge generation layer. In 2\, the charge transport substance is an oxadiazole derivative,
Examples of electron-donating substances that easily transport holes include oxazole derivatives, triazole derivatives, pyrazoline derivatives, hydrazone derivatives, enamine derivatives, stilbene derivatives, and triphenylamine derivatives. It is not limited. As the binder, a hydrophobic, highly dielectric, and electrically insulating film-type polymeric substance is usually used. Examples of such polymeric substances include polyester resins, phenol resins, polyvinyl butyral, polycarbonates, acrylic resins, methacrylic resins, vinyl chloride resins, styrene resins, silicone resins, and silicone resin-modified alkyd resins.

These binders may be used alone or in combination of two or more. In the case of a single-layer type photoconductive layer, the thickness is 2 to 100 μL, preferably 10 to 30 μm. The amount of bisazo compound is 1 to 200% by weight, preferably 10 to 200% by weight based on the binder.
100% by weight, and the amount of charge transport material is 10 to 200% by weight, preferably 30 to 12% by weight, based on the binder.
It is 0 heavy view%.

For stacked photoconductive layers, the thickness is 0 for the charge generating layer.
．． 01 to 5 μL, preferably 0.05 to 2 μL, and for the charge transport layer 2 to 100 μL, preferably 10 to 3
There is 0μ leakage. The amount of bisazo compound in the charge generating layer is 0.5 to 200% by weight, preferably 3% by weight based on the binder.
The amount of charge transport material in the charge transport layer is from 50 to 200% by weight, preferably from 60 to 150% by weight, based on the binder. For the purpose of flexibility, AQ is usually used as a conductive support.
A plastic film or paper coated with a metal such as is used. The present invention will be explained in more detail below using examples and application examples.

Example 19.0 g (97 mmol) of iminobibenzyl (X) synthesized by the method of Japanese Patent Publication No. 32-6638 was dissolved in 130 g of benzene in a N2 stream, and 11.5 g of acetyl chloride was dissolved under stirring at 76-78°C. g (146 mmol) was gradually added dropwise to react. After continuing stirring at the same temperature for 2 hours,
By cooling to room temperature, washing the reaction solution with water, and distilling off benzene, N-acetyliminobibenzyl (XIa) 2
2.8 g (96 mmol) (yield 99.3%) was obtained. Next, N-acetyliminobibenzyl (XIa) 22.8
g (96 mmol) was dissolved in 200 mQ of concentrated sulfuric acid, -5 to
Cool to 0°C. Add 60% to this solution under stirring at the above temperature.
22.2 g (211 mmol) of HN0 is slowly added dropwise. After continuing stirring at the same temperature for 2 hours, the reaction solution was poured into water, and the precipitated crystals were collected in a furnace, washed with water, and dried to obtain a crude product (30.5 g), which was further subjected to column chromatography. Isolated and purified pure 2,8-dinitro 5
-acetyliminobibenzyl (Xlla) 15.7 g
(48 mmol) ((yield 50.5%)) was obtained.

Next, 2,8-dinitro-5-acetyliminobibenzyl (X[la)15. 7 g (48 mmol), N-
Promosuccinimide (N B S ) 10.3 g
(58 mmol) and benzoyl peroxide (B P O) 0
．． 1 g (0.5 mmol) was added to benzene 200@Q, stirred and reacted at 75-76°C for 2.5 hours, and then cooled to room temperature. The precipitated crystals were collected in a furnace, washed with ethyl acetate, and dried to give pure 10-bromo-2,8-dinitro-5.
-acetyliminobibenzyl (Xla) 15.4 g
(: lm mol) (yield 78.8%) was obtained.

Next, 10-bromo 2,8-dinitro-5-acetyliminobibenzinole Qla) 1 5.4 g (38 m
Monole) was dissolved in 150 aQ of methanol, and O~3
℃, and at this temperature add 20% KOH aqueous solution 1 under stirring.
0.7 g (38 mmol) was gradually added dropwise to react.

After continuing stirring at the same temperature for 1 hour, the precipitated crystals were collected in a furnace and recrystallized from a mixed solvent of ethyl acetate and cyclohexane to obtain pure 2,8=dinitro-5-acetyldibenzo (b, f).
7 Zepi: / (XNa) IL. 4 g (35 mmol) (
A yield of 90.8%) was obtained.

Next, 2,8-dinitro-5-acetyldibenzo (b,f
) Add 1.4 g (35 mmol) of azepine (XNa) L to 120 d of glacial acetic acid, and while stirring at 24-25°C, add 60.2 g (245 mmol) of stannous chloride dihydrate to 150 mQ of concentrated hydrochloric acid. Gradually add the solution dissolved in the solution dropwise and react. The mixture was further stirred and reacted at a temperature of 40 to 41° C. for 2 hours, and then cooled to 8 to 10° C. in an ice water bath, and the precipitated crystals were collected in a furnace. This is dissolved in water and passed through a furnace to remove impurities.

5% until this furnace liquid shows weak alkalinity (field = 8 to 9).
A NaOH aqueous solution was added, and the precipitated crystals were collected in a furnace, washed with water, and dried to give 5.3 g (20 mmol) of pure 2,8-diamino-5-acetyldibenzo(b,f) azevin (■a) (collection chamber). 55.8%).

Synthesis of bisazo compound of NQ 3 2.8-diamino-5-acetyldibenzo(b,f)azepine (■a) 5.0 g (19rnmol) was dispersed in a mixture of 5mQ of concentrated hydrochloric acid and 50% of water, After cooling to 0-2°C, a solution of 2.7 g (39 mmol) of sodium nitrite dissolved in 8 lIIIQ of water was added dropwise to react with stirring over 20 minutes, and the mixture was further stirred at the same temperature for 1 hour. Tetrazotization (IXa) was performed. Next, naphthol AS (3-hydroxy-2-naphthoic acid anhydride H0.
5 g (40 mmol) in 5% NaOH aqueous solution 30
0 After dissolving in IfiQ, the above tetrazotization solution (tetrazonium salt-containing solution) was added dropwise at 0 to 5°C for 30 minutes with stirring to react. After further stirring and reacting at the same temperature for 2 hours, the mixture was stirred and reacted at room temperature. Stir overnight. The reaction solution was filtered, the residue was washed with water, and then washed with acetone, tetrahydrofuran (THF) and dimethylformamide (DMF) in order, and the remaining D
The MF was washed away with acetone and dried to give 6.8 g (8.4 mmol) of the bisazo compound of Na3 (yield 4460
%) was obtained.

0 Purple-black crystals 0 Decomposition point: 300°C or above 0 Elemental analysis calculated value (%) Actual value (%) C 73.79 73.900 12
．． 05 12.15N 4.33
4.30o IR absorption spectrum (KBr
Tablet method) The absorption spectrum is shown in Figure 1.

o UV absorption spectrum λwax: 555 nm, [solvent is dimethylform t1
Mixture of amide/n-butylamine = 4/1 (weight ratio)] The absorption spectrum is shown in FIG.

The reaction formula in this example is as follows. (X) (XIa) (XIla) (XTIIa) (XIVa) (■a) Examples 2 to 32 The reagents used in Example 1 were changed to correspond to the bisazo compounds in Table 1 excluding the bisazo compound of Oni 3. The bisazo compounds Nα1, 2, and 4 to 32 (Examples 2, 3, and 4 to 32, respectively) in Table 1 were combined in the same manner as in Example 1, except that they were used differently, except for the Na3 bisazo compound. ．． The melting points of these bisazo compounds are all 300°C or higher (decomposition), and the results of elemental analysis indicate that C. H. All differences between the calculated values and the measured values of O were within 0.4%. Further I
The R spectrum and UV absorption spectrum were measured, and based on these measurement results, they were identified as the corresponding bisazo compounds. Application example I 2 g of bisazo compound of Ha 3 and polyester resin (
2 g of Byron 200 (trade name, manufactured by Toyobo Co., Ltd.) was added to 100 g of cyclohexanone, and dispersed in a ball mill for 12 hours. This dispersion. A charge generating layer was formed by coating the polyester film on which AQ had been vapor-deposited so that the film thickness after drying would be 0.1 .mu.m and drying it. Next, the formula is shown in the same table. - C2H, hydrazone compound Log and polycarbonate resin (
A photoreceptor for electrophotography is formed by applying a solution of Teijin Ltd. product name K-1300) dissolved in 50 g of THF to a film thickness of 20 μm after drying and drying to form a charge transport layer. Created.

Next, this photoreceptor is charged to a surface potential of -500V using a charger, and halogen lamp light is irradiated onto the photoreceptor, and the amount of exposure required to attenuate the surface potential by half (half-reduction exposure amount E
1/2) was calculated. The result is E 1/2 =5.6(
Qux/see).

Application Examples 2 to 32 Laminated photoreceptors were prepared in the same manner as in Example 2 using the bisazo compounds shown in Table 2, and the half-decrease exposure amount E1/2 was measured. Obtained Results (See the margins below) Table 2 [Operations and Effects of the Invention] As can be seen from the above description, the novel bisazo compound of the present invention is useful as a new type of photoconductive material for electrophotographic photoreceptors.

[Brief explanation of drawings]

Figures 1 and 2 show the bisazo compound Na of the present invention, respectively.
FIG. 3 is an infrared absorption spectrum diagram and an ultraviolet absorption spectrum diagram of No. 3.

Claims (1)

[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) [However, Y represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an alkoxy group, and -R_1 is hydrogen represents an atom, a halogen atom, an alkyl group or an acyl group, and A
represents an aromatic coupler of the following general formulas (II) to (VII). ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VI) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VII) (However, in formula (II), Z is a substituted or unsubstituted aromatic hydrocarbon group, and Q is It represents a substituted or unsubstituted carbamoyl group or a sulfamoyl group, and in formulas (III) and (IV), R_2 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or an aryl group, and formulas (V) and In (VI), Z represents a divalent aromatic hydrocarbon group or a heterocyclic group containing a nitrogen atom in the ring, and in formula (VII), R_3 is a hydrogen atom, a substituted or unsubstituted alkyl group, or an amino group. , a carbamoyl group, a carboxyl group or an ester thereof, or a cyano group, X represents a substituted or unsubstituted aryl group)]. 2. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [However, Y represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an alkoxy group, and R_1 represents a hydrogen atom, a halogen atom, or an alkyl group. group or acyl group, and A
represents an aromatic coupler of the following general formulas (II) to (VII). ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VI) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VII) (However, in formula (II), Z is a substituted or unsubstituted aromatic hydrocarbon group, and Q is represents a substituted or unsubstituted carbamoyl group or sulfamoyl group, and in formulas (III) and (IV), R_2 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or an aryl group; In (VI), Z represents a divalent aromatic hydrocarbon group or a heterocyclic group containing a nitrogen atom in the ring, and in formula (VII), R_3 is a hydrogen atom, a substituted or unsubstituted alkyl group, or an amino group. , a carbamoyl group, a carboxyl group or an ester thereof, or a cyano group, and X represents a substituted or unsubstituted aryl group.