JPH01200266A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic sensitive body having excellent characteristic of high sensitivity, small residual potential and excellent durability by the excellent carrier generatability of a bisazo compd. by incorporating the bisazo compd. expressed by special formula into the photosensitive layer formed on a conductive base of the electrophotographic sensitive body. CONSTITUTION:The bisazo compd. expressed by general formula I is incorpo rated into the photosensitive layer formed on the conductive base. In formula, R1 and R2 respectively denote a hydrogen atom, halogen atom, substd. or unsubstd. alkyl group, substd. or unsubstd. alkoxy group, nitro group, cyano group or hydroxy group. Z denotes an atom. group necessary for forming a carbocyclic arom. ring or heterocyclic arom. ring. Further, X and Y respectively denote a hydrogen atom, substd. or unsubstd. alkyl group, substd. or unsubstd. aryl group or substd. or unsubstd. heterocyclic group; (m) and (n) denote 1, 2 or 3 integer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having a photosensitive layer containing a specific bisazo compound.

[Prior Art] Conventionally, as electrophotographic photoreceptors, inorganic photoreceptors having a photosensitive layer containing as a main component a photoconductive compound such as selenium, zinc oxide, cadmium sulfide, silicon, etc. have been widely used. However, these are not necessarily satisfactory in terms of sensitivity, thermal stability, moisture resistance, durability, etc. for example,
When selenium crystallizes, its properties as a photoreceptor deteriorate, making it difficult to manufacture.Also, selenium crystallizes due to heat, fingerprints, etc., and its performance as a photoreceptor deteriorates.

Additionally, cadmium sulfide has problems with moisture resistance and durability, and zinc oxide has problems with durability.

In order to overcome these drawbacks of inorganic photoreceptors, research and development have been actively conducted in recent years on organic photoreceptors having photosensitive layers containing various organic photoconductive compounds as main components. For example, Japanese Patent Publication No. 50-10496 describes a photoreceptor having a photosensitive layer containing poly-N-vinylcarbazole and 2,4,7-dolinitro-9-fluorenone. However, this photoreceptor is not necessarily satisfactory in sensitivity and durability. In order to improve these drawbacks, attempts have been made to develop a higher-performance troweled photoreceptor by assigning carrier generation and carrier transport functions to different materials. In such so-called functionally separated photoreceptors, each material can be selected from a wide range.
Many studies have been conducted since it is possible to relatively easily create a photoreceptor with arbitrary performance.

[Problems to be Solved by the Invention] Many compounds have been proposed as carrier-generating substances in the functionally separated type photoreceptor as described above.

An example of using an inorganic compound as a carrier generating substance is, for example, amorphous selenium described in Japanese Patent Publication No. 43-16198, which is used in combination with an organic photoconductive compound. The disadvantage that the carrier generation layer crystallizes due to heat and deteriorates the characteristics as a photoreceptor has not been improved.

Furthermore, many electrophotographic photoreceptors using organic dyes or organic pigments as carrier-generating substances have been proposed. For example, as electrophotographic photoreceptors containing a bisazo compound in the photosensitive layer, JP-A-54-22834, JP-A-55-73057, JP-A-55-117151, and JP-A-56-46237 are already known. However, these bisazo compounds do not necessarily satisfy the characteristics of sensitivity, residual potential, or stability during repeated use, and the range of selection of carrier transport materials is also limited, which makes them difficult to meet the wide demands of electrophotographic processes. It does not fully satisfy.

[Object of the Invention] An object of the present invention is to provide an electrophotographic photoreceptor containing a specific bisazo compound having excellent carrier generation ability.

Another object of the present invention is to provide high sensitivity and low residual potential.
Furthermore, it is an object of the present invention to provide an electrophotographic photoreceptor with excellent durability whose properties do not change even after repeated use.

Still another object of the present invention is to provide an electrophotographic photoreceptor containing a bisazo compound that can effectively act as a carrier generating substance even in combination with a wide variety of carrier transporting substances.

[Means for Solving the Problems] As a result of extensive research to achieve the above objectives, the present inventors have discovered that a specific bisazo compound can act as an excellent active ingredient for electrophotographic photoreceptors. , has completed the present invention.

That is, the above object of the present invention can be achieved by using an electrophotographic photoreceptor having a photosensitive layer containing a bisazo compound represented by the following general formula [I] on an electrostatic support.

General Formula [I] [R+ and R2 each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a nitro group, a cyan group, or a hydroxy group. However, R1 and R2 may be the same or different.

Z represents an atomic group necessary to form a carbocyclic aromatic ring or a heterocyclic aromatic ring.

X and Y each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, X and Y may be the same or different, and may also work together to form a ring.

m and Qn each represent an integer of 1.2 or 3.

] [Specific structure of the invention] The halogen atoms represented by R+ R3 and R2 in general formula [1] include chlorine atom, bromine atom, fluorine atom, and iodine atom, among which chlorine atom or bromine atom Atoms are preferred.

The substituted/unsubstituted alkyl group represented by R1 and R2 is preferably a substituted/unsubstituted alkyl group having 1 to 4 carbon atoms, such as methyl group, ethyl group, isopropyl group, t-butyl group, trifluoro A methyl group or the like is preferred.

The substituted/unsubstituted alkoxy group represented by R1 and R2 is preferably an alkoxy group having 1 to 4 carbon atoms, such as methoxy group, ethoxy group, isobutoxy group, [-butoxy group, 2-chloroethoxy group] Examples include groups.

The group represented by each of R1 and R2 is preferably a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group.

In the general formula [I], Z represents an atomic group necessary to form a carbocycle or a heterocycle, and examples of carbocycles formed by such an atomic group include substituted and unsubstituted benzene rings. , naphthalene ring, etc. Examples of the heterocycle include substituted and unsubstituted dibenzothiophene rings and carbazole rings. Among these carbocycles or heterocycles, substituted or unsubstituted benzene rings are preferred. Furthermore, these carbocycles or heterocycles can have a substituent, and examples of the substituent include a halogen atom,
Examples include amine groups, alkyl groups, and hydroxy groups.

In general formula [I], X and Y each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Examples of substituted alkyl groups include methyl groups, etc.
Furthermore, examples of substituted alkyl groups include trifluoromethyl groups and the like. Furthermore, examples of unsubstituted aryl groups include phenyl group and naphthyl group. Examples of the heterocyclic group include a carbazole group and a bilysili group, and this heterocyclic group may have a substituent such as an alkyl group, a methoxy group, a halogen atom, a cyano group, and an amino group. , x and Y may be the same or different.

In general, X and Y may jointly form a ring, and specific examples of such a ring include substituted and unsubstituted quinoline rings and indoline rings.

The ring formed by X and Y may have a substituent.

- In the drinking price [I], m and n are 1 and 2, respectively.
or an integer of 3, preferably m=n=1. ■or when n is an integer of 2 or more, R1 or R2 is the same -
Or it may be a different group. R when m is an integer of 1
The substitution position of 1 can be the 1°2.3 or 4-position, with the 4-position being preferred. Similarly, n is 1
When R2 is an integer, the substitution position of R2 can be the 6.7- or 8-position, and among these, the preferred position is the 7-position.

Specifically, the bisazo compound represented by the general formula [I] of the present invention is as follows: [I[-A], [ll-8],
[I[IA], [I[[-B], [IV-A].

[rV-B], (V-A] or [V-BIF table is a joke.

- Shell formula [1l-Bl General formula [I[[-A] General formula [111-Bl General formula [1'l/-Bl χ General formula [V-A] General formula [V-B] Above - Drinking price [■-A], []] I-B ~ V-A],
[V-B] t:i T, R+, R2, X, Y.

m and n are R+, R2, and X of the above-mentioned -drink price [I].

Synonymous with Y, m and n.

More specifically, the bisazo compounds of the present invention represented by the above-mentioned -Drinking costs [■-ΔC and [■-B]] are the following -Drinking costs [II-A Co. 1 to [II-A]-9 and [ll-8
]-1 to [ll-8]-9.

1, Z, l C] r! ! -B]-1 [n-B]-2 [11-B]-3 [11-B]-6 In addition, the present invention represented by the general formula [I[[-A] and [I[[-B] More specifically, the bisazo compounds have the following general formulas [I[[-A]-1 to [I[IA]-9 and [I[[-8]-1 to [II[-B]- It is represented by 9.

[111-Bl-1 [111-Bl-3 [111-Bl-4 [1[! -B]-5 [1[1-Bl-7 [I[1-Bl-3 rTII-Bl-9 - Suazo compound of the present invention represented by [IV-A] and [rV-B] More specifically, below −
Drinking cost [IV-A]-1 to [IV-A]-9 and [rV-
8]-1 to [rV-Bl-9.

[IV-B]-1 [N-B1-2 [■-Bl-3 [IV-B]-4 [IV-Bl-5 [■-B]-6 [IV-Bl-7 [IV-Bl- 3 [IV-Bl-9 The bisazo compounds represented by the general formulas [V-Δ] and [V-Bl of the present invention are more specifically represented by the following - Drinking cost [V-A
l-1~[V-Al-9 and [V-8]-1~[V-8
]-9.

[V-Al-1 Su[V-Al-2 [V-Al-3 [V-Al-4 U [V-Al-5 Su[V-Al-6 [V-Al-7 [V-Al- 8 [V-Al-9 [V-Bl-2 [V-Bl-3 [V-Bl-4 X, [V-Bl-5 [V-Bl-6 [V-Bl-7 [V-Bl- 8
-B1-1 ~ [I[-Bl-9, [I[[-A
Co-1 ~ [III-A Co-9, [I
[[-8]-1~ [I[[-8]-9, [IV-AJ
-1 ~ IIV-AI -9, [IV-Bl -1 ~
[IV-8] -9, [V-AI-1 to [V-AI-
9 and [V-8]-1 to [V-8]-9 R+
, R2, X and Y are R+, R2,
Synonymous with X and Y.

Specific examples of the bisazo compound represented by the general formula [I] of the present invention are shown below, but the compounds of the present invention are not limited thereto.

lt--~.

The bisazo compound represented by the general formula [I] of the present invention is:
It can be easily synthesized by known methods.

Synthesis Example 1 (Synthesis of Exemplary Compound No. 217 Having the Structural Formula of -Drink [I[[-Al-2)] 2.5-Diamino-9
- 2.10 p (0.01 mol) of fluorenone in 10 g of hydrochloric acid
1j2. A solution of 1.4 g (0.02 mol) of sodium nitrite dissolved in 5 vQ of water was added dropwise while maintaining the temperature below 5°C. After continuing stirring at the same temperature for an additional hour, insoluble matter was removed by filtration, and a solution of 4.6 g of ammonium hexafluorophosphate dissolved in 50112 water was added to the filtrate.

The precipitated tetrazonium salt was collected by filtration and dissolved in N,N-dimethylformamide (DMF) 10'01j2.

2-Hydroxy-3-naphthoic acid benzylidene aminoanilide while keeping the temperature below 5°C 5.80! +(0,02
A solution prepared by dissolving mol) in 200 mffi of DMF was added dropwise.

While continuing to maintain the temperature below 5°C, 1 to 6q (0.04 mol) of reethanolamine was added to DMF 30 *
1 was added dropwise to the mixture, and the mixture was stirred at 5° C. or lower for 1 hour and at room temperature for 4 hours. After the reaction, the precipitated crystals were collected by filtration, washed with DMF, washed with water, and dried to obtain the desired product 6.02.

Calculated values: C-72, 4%, H-3, 94%, N-13
, 8% actual value; C = 70.9%, ) -1-4, 15%
, N-15,7% Synthesis Example 2 (-drinking cost [I[1-B] -
Synthesis of exemplary compound NO,217 having the structural formula of 3)
2.10 g of 2.5-diamino-9-fluorenone (0,
01 mol> of salt M 101 (1, dispersed in 201 g of water,
While keeping the temperature below 5℃, add 1.4g of sodium nitrite (0,
A solution of 0.2 mol) dissolved in 5 v (l) of water was added dropwise.

After continuing stirring at the same temperature for an additional hour, insoluble materials were removed by filtration, and a solution of 4.6 g of ammonium hexafluorophosphate dissolved in 50 g of water was added to the filtrate.

The precipitated tetrazonium salt was collected by filtration and dissolved in 100 d of N,N-dimethylformamide (DMF).

A solution dissolved in 2-hydroxy-5-(benzylideneaminocarbamoyl)benzo[a]-carbazole 7 2001Q was added dropwise while maintaining the temperature at 5°C or lower.

Subsequently, while maintaining the temperature below 5°C, a solution of 6 g (0.04 mol) of triethanolamine dissolved in 30% DMF was added dropwise, followed by stirring at below 5°C for 1 hour and at room temperature for 4 hours. After the reaction, the precipitated crystals were collected by filtration, washed with DMF, washed with water, and dried to obtain 7.25 g of the desired product.

Estimated value: C = 74.1%, l-1 = 4.05%, N
= 14.2% Actual value: C = 71.4%, l-1 = 3
．． 98%, N-15.5% Synthesis Example 3 (-drinking cost [V-Al
Synthesis of exemplified compound NO, 145 having the structural formula -5)
2.46 (1 (0.01 mol)) of 4,5-diamino-2,7-difluoro-9-fluorenone was dissolved in 10 i of hydrochloric acid.
R.

Disperse in water for 20 minutes, keep it below 5℃, and add nitrite to 1-
Lium 1.41; l (0.02 mol) to water 511
2 was added dropwise. After continuing stirring at the same temperature for another 1 hour, insoluble matter was filtered off and i! ! A solution of 4.6 g of ammonium hexafluoride phosphate dissolved in 50 m+2 of water was added to the liquid. The precipitated tetrazonium salt was collected by filtration and mixed with 100 N,N-dimethylformamide (DMF).
2-hydroxy-3-naphthoic acid benzylidene amino [3',
5'-dikuO90ro]anilide 1B+) (0.02
A solution of mol) dissolved in 200 d of DMF was added dropwise.

Triethanolamine 61J (0.04 mol) was added to DMF3 while continuing to maintain the temperature below 5°C.
The solution was added dropwise to the mixture and stirred at 5° C. or lower for 1 hour and at room temperature for 4 hours. After the reaction, the precipitated crystals were collected by filtration and [)M
F. Wash, wash with water, dry, and remove the target object G. 52 (l was obtained.

Calculated value; C=59.6%, H=2.64%, N=1
1.71% real 1! IIa: C = 61.3%. I-
(-3.15%, N-10.7% Synthesis Example 4
Exemplary compound N having the structural formula of (-drinking cost [V-B]-9
O. Synthesis of 429) 4,5-diamino-1,8-dicyano-9-fluorenone 2.60! I+ (0.01 mol) in hydrochloric acid 101j2.

A solution of 1.41 J (0.02 mol) of sodium nitrite dissolved in 5 d of water was added dropwise while maintaining the temperature below 5°C. After continuing stirring at the same temperature for another 1 hour, insoluble matter was removed by filtration, and a solution of 4.6 g of ammonium hexafluorophosphate dissolved in 50 ml of water was added to the filtrate. The precipitated tetrazonium salt was collected and treated with N,N-
It was dissolved in 100 g of dimethylformamide (DMF).

2-Hydroxy-3-[benzylideneamino(3'-iodo)carbamoyl]benzo[
a] - Rubazol 9.4H! (0.02 mol) as DM
A solution dissolved in F200112 was added dropwise.

While keeping the temperature at 5° C. or lower, 6 g (0.04 mol) of triethanolamine dissolved in DMF 301Q was added dropwise to the mixture, followed by stirring at 5° C. or lower for 1 hour and at room temperature for 4 hours. After the reaction, the precipitated crystals were collected, washed with DMF, washed with water, and dried to obtain the desired product 7.250.

Calculated values: C=58.4%, H=2.78%, N-1
3.0% actual value; C=55.4%, H=2.72%
, N-14,5% Synthesis Example 5 (Synthesis of Exemplary Compound No. 247 having the structural formula -drinkage [IV-A]-2) 3.5
-Diamino-4-iodo-9-fluorenone 3.37g
(0.01 mol) was dispersed in 10 parts of hydrochloric acid and 20 parts of water,
Sodium nitrite 1.4 (1 (0)
, 02 mol) dissolved in 5 parts of water ρ was added dropwise. After continuing stirring at the same temperature for another 1 hour, insoluble matter was removed by filtration, and a solution of 486 g of ammonium hexafluorophosphate dissolved in 50112 of water was added to the filtrate. The precipitated tetrazonium salt was collected by filtration and diluted with N,N-dimethylformamide (D
11 IF) Dissolved in 100-d. 2-Hydroxy-3-naphthoic acid benzylideneamino[4'-bromo]anilide while keeping the temperature below 5°C 7.3. IQ(0,
A solution in which 02 mol) was dissolved in DMF 200nfk was added dropwise.

Subsequently, 6 g (0.04 mol) of triethanolamine was added to DMF 30 while keeping the temperature below 5°C.
The solution dissolved in d was added dropwise, and the mixture was stirred at 5° C. or lower for 1 hour and at room temperature for 4 hours. After the reaction, the precipitated crystals were collected, washed with DMF, washed with water, and dried to obtain 6.63 (l) of the desired product.

Calculated values: Q-53, 6%, H-2, 65%, N=10
．． 2% actual value: C-56.5%, )-1-2,81%
, N = 955% Synthesis Example 6 (Synthesis of Exemplary Compound No. 340 having the structural formula of 6rV-8]-3) 3.5-
Diamino-4-hydroxy-9-fluorenone 2.26
(Disperse J (0.01 mol) in 10112 hydrochloric acid and 20 d water, and while keeping the temperature below 5°C, 1.4 C sodium nitrite.
A solution of I (0.02 mol) in 5112 ml of water was added dropwise. After continuing stirring for another hour at the same temperature,
Insoluble materials were removed by filtration, and a solution of 4.69 ammonium hexafluorophosphate dissolved in 501 g of water was added to the filtrate. The precipitated tetrazonium salt was collected by filtration and dissolved in 100 vQ of N,N-dimethylformamide (DMF). While keeping the temperature below 5°C, 9.41 (1 (0.02 mol)) of 2-hydroxy-3-[benzylideneamino(4'-iodo)carbamoyl]benzo[a]-carbazole was added to DMF.
A solution dissolved in 200 ml was added dropwise.

Continuing to keep the temperature below 5°C, a solution of triethanolamine 5 (00.04 mol) in DMF30112 was added dropwise and stirred at below 5°C for 1 hour and at air temperature for 4 hours. After the reaction, the precipitated product was collected, washed with DMF, washed with water, and dried to obtain 7.06 g of the target product.

Kei Wei (Direct: C=58.1%, @=3.0
2%, N=11.1% Actual value: C=58.4%,
1-1 = 2.72%, N-13,6% Other compounds of the present invention are also substituted with 5,<1.2.3 or 4)-diamino-substituted as in the above synthesis example. , unsubstituted -9-
A tetrazo compound is prepared using fluorenone, and then 2-hydroxy-3-(substituted methyleneaminocarbamoyl)-benzo[a]-substituted/unsubstituted It can be made by reacting with carbazole.

The bisazo compound of the present invention has excellent photoconductivity,
The electrophotographic photoreceptor of the present invention can be manufactured by providing a photosensitive layer in which the photoreceptor is dispersed in a binder on a conductive support. The bisazo compound of the present invention makes use of its excellent carrier generation ability, and by using it as a carrier generation substance and using a carrier transport substance that can effectively act in combination with this, the bisazo compound can be used as a so-called functionally separated photosensitive material. It can be a body. The functionally separated photoreceptor may be a mixed and dispersed type of both of the above substances, but it may be a carrier generation layer containing a carrier generation substance made of the bisazo compound of the present invention, and a carrier transport layer containing a carrier transport substance. It is more preferable to use a laminated type photoreceptor having an fI layer.

The electrophotographic photoreceptor of the present invention, for example, as shown in FIG. As shown in FIG. 2, there is provided a photosensitive layer 4 having a substantially separated laminated structure in which a carrier generating layer 2 containing a carrier-transporting substance and a binder resin is a lower layer and a carrier-transporting layer 3 containing a carrier-transporting substance and a binder resin is an evaporator. As shown in FIG. Examples include those provided with a photosensitive layer 14 having a single layer structure containing a substance, a carrier transport substance, and a binder resin.

In the case of a photosensitive layer with a laminated structure, most of the incident light is absorbed by the carrier generation layer, generating many charge generation carriers, and the generated charge carriers are recombined and captured (1~lap). ) It is preferable to make the film as thin as possible within a range of thickness sufficient to generate photocarriers in order to inject them into the carrier transport layer without being deactivated.

The carrier transport layer is electrically connected to the above-mentioned chyrelia generation layer, and receives charge carriers injected from the charge generation layer in the presence of an electric field, and also transports these charge carriers to the surface. It has R ability.

In addition, a single-layer structure is a surface-separated type photoreceptor! ! i
Since the layer is responsible for the generation and transport of photocarriers, the carrier generation substance and the gear transport substance are electrically connected within the layer, and/or the carrier generation substance also contributes to the transport of carriers.

Further, the carrier generation layer may contain both the carrier generation substance and a part of the carrier transport substance.

In either layer structure, a protective layer may be provided on the photosensitive layer as shown in FIGS. 7 to 9, and a protective layer may be provided on the photosensitive layer as shown in FIGS. 4 to 6. A subbing layer (intermediate layer) having barrier compensation and adhesive properties may be provided between the layers.

Examples of binder resins that can be used for the photosensitive layer, protective layer, and subbing layer include polystyrene, polyethylene, polypropylene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, polyurethane resin, and phenol. resin, polyester resin, alkyd resin, polycarbonate resin,
Addition polymer resins such as silicone resins and melamine resins, polyaddition resins, polycondensation resins, and copolymer resins containing two or more repeating units of these resins, such as vinyl chloride-vinyl acetate copolymers Examples include insulating resins such as composite resins, vinyl chloride-vinyl acetate-maleic anhydride composite resins, and leading semiconductors of polymers such as poly-N-vinylcarbazole.

Further, amines may be added to the photosensitive layer of the present invention for the purpose of improving the carrier-generating function of the carrier-generating substance, and it is particularly preferable to add a secondary amine.

Such secondary amines include, for example, dimethylamine, diethylamine, di-n propylamine, di-isopropylamine, di-butylamine, di-isobutylamine, di-0 amylamine, di-isoamylamine, di-n
Hexylamine, di-isohexylamine, di-n-pentylamine, di-isopentylamine, di-n-octylamine.

Di-isooctylamine, di-n nonylamine, di-isononylamine, di-n decylamine, di-isodecylamine, di-n monodecylamine, di-isomonodecylamine, di-n dodecylamine, di- Isododecylamine and the like can be mentioned.

The specific amines may be added in a molar amount of 1 times or less, preferably 0.2 to 0.005 times the amount of the carrier-generating substance.

Further, in the photosensitive layer of the present invention, an antioxidant may be added for the purpose of preventing ozone deterioration.

Typical examples of such antioxidants are shown below, but the invention is not limited thereto.

Group (1): Hindered phenols dibutylhydroxytoluene, 2.2'-methylenebis(6-t-butyl-4-methylphenol), 4.4
'-Butylidene bis(6-[-butyl-3-methylphenol>, 4,4'-thiobis(6-1-butyl-3
-methylphenol), 2,2'-butylidene bis(6
-t-butyl-4-methylphenol), α-1~cohuerol, β-1~copherol, 2,2,4-1-tumethyl-6-hydroxy-7-t-butylchroman, pentaerythyltetrakis [3 -(3,5-di[-butyl-4-hydroxyphenyl)propione-1~],
2.2'-thiodiethylenebis[3-(3゜5-di(-butyl-4-hydroxyphenyl)propionate]), 1.6-hexanediolbis[3-(3,5-di-t-butyl- 4-hydroxyphenyl)propionate], butylhydroxyanisole, dibutylhydroxyanisole, 1-[2-((3,5-di-tert)
-butyl-4-hydroxyphenyl)propionyloxy)ethyl] -4-[3-(3,5-di-tert-
butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-titramethylpiperidyl, and the like.

Group (II): paraphenylenediamines N-phenyl-
N'-isopropyl-p-phenylenediamine, N,N
'-5ec-butyl-p-phenylenediamine, N
-Phenyl-N-5ec-butyl-p-phenylenediamine, N.

N'-diisopropyl-〇-phenylenediamine, N,
N'-dimethyl-N,N'-di-t-butyl-p-
such as phenylenediamine.

(Group I
Octyl-5-methylhydroquinone, 2-(2-octadecenyl)-5-methylhydroquinone, etc.

Group (IV): organic sulfur compounds dilauryl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, ditetradecyl-3,3'-thiodipropionate, etc.

Group (V): d-phosphorus compounds such as triphenylphosphine, tri(nonylphenyl)phosphine, tri(dinonylphenyl)phosphine, tricresylphosphine, and tos(2,4-dibutylphenoxy)phosphine.

These compounds are known as antioxidants for rubber, plastics, oils and fats, and are easily available commercially.

These antioxidants may be added to any of the carrier generation layer, carrier transport layer, or retaining layer, but are preferably added to the carrier transport layer.

In that case, the addition of antioxidant 4 is the carrier transport substance 10
0.1 to 100 mR part, preferably 1
~50 parts by weight, particularly preferably 5 to 25 parts by weight.

Next, as a conductive support supporting the photosensitive layer, a metal plate such as aluminum or nickel, a metal drum or gold foil, a plastic film coated with aluminum, tin oxide, indium oxide, etc., or a conductive material coated. Paper, films such as Plus Deck, or drums can be used.

In the present invention, the carrier generation layer is typically formed by dip coating, spray coating, blade coating, etc., of a dispersion of the bisazo compound of the present invention as described above dispersed in a suitable dispersion medium or solvent alone or together with a suitable binder resin. It can be provided by a method of coating on a support or subbing layer or on a carrier layer by roll coating or the like and drying.

The bisazo compound of the present invention is made into fine particles of an appropriate particle size using, for example, a ball mill or a sand mill.
It can be dispersed in a dispersion medium.

A ball mill, homomixer, sand mill, ultrasonic disperser, attritor, etc. are used for dispersing the bisazo compound of the present invention.

Examples of the dispersion medium for the bisazo compound of the present invention include hydrocarbons such as hexane, benzene, toluene, and xylene;
Methylene chloride, methylene bromide, 1,2-dichloroethane, 5yn-te-1-lachloroethane, cis
-Halogenated hydrocarbons such as 1,2-dichloroethylene, 1,1.2-1-dichloroethane, 1,1.1-trichloroethane, 1,2-dichloropropane, chloroform, bromoform, and chlorobenzene, acetone, methyl ethylke 1- alcohols such as cyclohexanone, esters such as ethyl acetate and butyl acetate, methanol, ethanol, propatool, butanol, cyclohexanol, heptatool, ethylene glycol, methyl cellosolve, ethyl cellosolve, 1M cellosolve, etc. Alcohol and its derivatives, ethers such as tetrahydrofuran, 1,4-dioquiline, furan, ralfural, acetals, pyridine, n-butylamine, diethylamine,
In addition to nitrogen compounds such as amines such as ethylenediamine and isopropanolamine, amides such as N,N-dimethylformamide, fatty acids and phenols, sulfur and phosphorus compounds such as carbon disulfide and mono-ethyl phosphate, etc. It will be done.

When the photoreceptor of the present invention has a laminated structure, the weight ratio of the binder in the carrier generation layer: 1: 1: 1: 0: 1: 1: 500: 0: 5
It is 00.

If the amount of the carrier-generating substance is less than this, the photosensitivity will be low and the increase in residual potential will be suppressed, and if it is more than this, the dark decay and the received electric charge fi2 will be reduced.

The thickness of the chirelia generation layer formed as described above is:
Preferably 001-10μm, preferably 01-10μm for vT
It is 5 μm.

Further, the carrier transport layer can be formed by applying and drying a mixture of the Kyrelia transporting substance alone or in combination with the above-mentioned binder resin in an appropriate solvent or dispersion medium. As the dispersion medium used, the dispersion medium used in dispersing the carrier-generating substance can be used.

Carrier transport substances that can be used in the present invention include:
Although not particularly limited, examples include oxazole derivatives, oxadiazole derivatives, thiazole derivatives, thiadiazole derivatives, triazole derivatives, imidazole derivatives, imidasilone derivatives, imidazolidine derivatives, bisimidazolidine derivatives, styryl compounds, hydrazone compounds,
Pyrazoline derivatives, amine derivatives, oxacilone derivatives, benzothiazole derivatives, benzimidazole derivatives, quinazoline derivatives, benzofuran derivatives, acridine derivatives, phenazine derivatives, aminostilbene derivatives,
These include poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene, and the like.

The carrier transport substance used in the present invention is preferably one that has an excellent ability to transport holes generated during light irradiation to the support side and is suitable for combination with the bisazo compound of the present invention. Preferred carrier transport substances are the following: (A), (B) and (
Examples include those represented by C).

General formula (A) However, Ar1, Ar2, Ar4 each represent a substituted or unsubstituted 7-aryl group, Ar3 represents a substituted or unsubstituted arylene group, R1 is a hydrogen atom, a substituted or unsubstituted alkyl group, Or represents a substituted or unsubstituted aryl group.

Specific examples of such compounds are described in detail on pages 3 to 4 of JP-A-58-65440 and pages 3-6 of JP-A-58-198043.

General formula (B) 1(.

However, R1 is a substituted or unsubstituted aryl group, or a substituted.

It is an unsubstituted heterocyclic group, and R2 is a hydrogen atom and is substituted.

It represents an unsubstituted alkyl group, a substituted or unsubstituted aryl group, and n is an integer of 0.1 or 2.
It is described in the publications No. 8-134642 and No. 58-166354.

However, R1 is, in other words, an unsubstituted alkyl group or a substituted or unsubstituted aryl group, and R2 is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted.

They are an unsubstituted alkoxy group, a @-substituted, unsubstituted amino group, and a hydroxy group, and R3 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. Synthesis methods for these compounds and their illustrations are described in detail in Japanese Patent Publication No. 148150/1982, which can be incorporated into the present invention.

Other preferred chyrelia transport substances of the present invention include:
Examples include hydrazone compounds described in JP-A-57-67940, JP-A-59-15252, and JP-A-57-101844, respectively.

The amount of the carrier transport substance per 100 parts by weight of the binder resin in the carrier transport layer is preferably 20 to 200 parts by weight, particularly preferably 30 to 150 parts by weight.

The thickness of the carrier transport layer to be formed is preferably 5 to 5.
0 μm, particularly preferably 5 to 30 μm.

Further, in the case of a single FJu fat separation type electrophotographic photoreceptor using the bisazo compound of the present invention, the ratio of the binder (2) of the bisazo compound of the present invention to the carrier transport substance is 0 to 100:
1-500: 0-5oO is preferable, and the thickness of the photosensitive layer formed is preferably 5-50 μm, particularly preferably 5-50 μm.
30 tt m.

In the present invention, the carrier generation layer may contain one or more electron-accepting substances PT for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use.

'Electron acceptor 1 student E'lA p that can be used here
Examples of t include succinic anhydride, maleic anhydride, dibromaleic anhydride, phthalic anhydride, herachlorophthalic anhydride, te-1-bromalephthalic anhydride, and 3-bromaleic anhydride.
Nitrophthalic anhydride, 4-nitrophthalic anhydride, biromellitic anhydride, mellitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, 0-dinitrobenzene, m-dinitrobenzene, 1.3.5-trinitrobenzene , paranitrobenzonitrile, vicryl chloride, quinone chlorimide, chloranil, brumanil, dichlorodicyanobarabenzoquinone, anthraquinone, di-21-loanthraquinone, 2,7-sinitrofluorenone, 2,4.7-dolinitrofluorenone, 2゜4.5.
7-teI ranitrofluorenone, 9-fluorenylidene [dicyanomethylenemalonodinitrile], polynitro-9-fluorenylidene-[dicyanomethylenemalonodinitrile], picric acid, 0-21-benzoic acid, p-
21-lobenzoic acid, 3.5-dini-1-lobenzoic acid, pentafluorobenzoic acid, 5-21-herosalicylic acid, 3.5
- Gini! - Rosalicylic acid, phthalic acid, mellitic acid and other compounds with high electron affinity can be mentioned.

Further, the addition ratio of the electron-accepting substance is bisazo compound of the present invention:electron-accepting substance-10020.01 to
200, preferably 100:0.1-100.

This electron-accepting substance may be added to the carrier transport layer. The addition ratio of the electron-accepting substance to such a layer is the total carrier-transporting substance:electron-accepting substance=ioo:
o, oi~100, preferably 100:0.1~
It is 50.

In addition, the photoreceptor of the present invention may also contain, if necessary, an ultraviolet absorber, an antioxidant, etc. for the purpose of protecting the photosensitive layer, and may also contain a dye for color sensitivity correction.

The electrophotographic photoreceptor containing the bisazo compound of the present invention can be sensitive to visible light and near-infrared light, but preferably has an absorption maximum at a wavelength of about 400 to 850 μm.

Examples of light sources with such wavelengths include halogen lamps,
Fluorescent lamps, tungsten lamps, gas lasers such as argon lasers, helium-neon lasers, semiconductor lasers, and the like are generally used.

The electrophotographic photoreceptor of the present invention has the above structure,
As is clear from the Examples described below, it has excellent charging characteristics, sensitivity characteristics, and image forming characteristics, and especially shows little fatigue deterioration even when used repeatedly, and has excellent durability.

[Examples] Hereinafter, the present invention will be specifically explained using Examples, but the embodiments of the present invention are not limited thereby.

Example 1 Vinyl chloride-vinyl acetate-
Maleic anhydride copolymer [S-LEC MF-10]
(manufactured by Block Chemical Co., Ltd.) with a thickness of 0.05 μm is provided, and on top of that, 2 g of exemplified compound N0.438 having the structure of general formula [■-A]-1 and polycarbonate resin [
Panrai! -L -1250] (manufactured by Yondaikasei Co., Ltd.) 2
g was added to 110d of 1,2-dichloroethane and dispersed in a ball mill for 12 hours. This dispersion was applied to a dry film thickness of 0.5 μm to form a carrier generation layer,
Furthermore, on top of that, as a carrier transport layer, the following structural formula (C
T-1) 6a and polycarbonate resin [Panlite L-
1250] 10g of 1,2-dichloroethane 80iI2
A carrier transport layer was formed by applying a solution dissolved in the above to a dry film thickness of 15 μm, thereby producing a photoreceptor of the present invention.

The following characteristics were evaluated using an electrostatic paper tester manufactured by Seisakusho'@JEPA-8100. After charging with a charging voltage of -6 KV for 5 seconds, leave in the dark for 5 seconds, and then irradiate with halogen lamp light so that the illuminance on the photoreceptor surface is 35 lux -sec to attenuate the surface potential by half. The required exposure m (half exposure fit) E1/2 was determined. Also 3
The surface potential (residual potential) VR after exposure at an exposure time of Q luX ·sec was determined. 100 more similar measurements
I did it repeatedly. The results are shown in Table 1.

Comparative Example 1 A comparative photoreceptor was prepared in the same manner as in Example 1, except that the following bisazo compound (CG-1>) was used in place of the above-mentioned exemplified compound as a carrier generating substance.

(CG-1) Regarding this comparative photoreceptor, measurements were performed in the same manner as in Example 1, and results not shown in No. 18 were obtained.

As is clear from the results in Table 1 and above, the photoreceptor of the present invention is extremely superior in sensitivity, residual potential, and repetition stability compared to the comparative photoreceptor.

Examples 2 to 4 Exemplary compound No. 258 represented by the general formula [■-△]-6 as a carrier generating substance, -Drinking cost [111-A]-
Exemplary compound No. 8 represented by No. 8, -drinking cost [V-
A] Exemplary compound No. represented by -3.

A photoreceptor of the present invention was prepared in the same manner as in Example 1, using 73 as a carrier transport material, and the following compounds as carrier transport substances, respectively, and the same measurements were performed. Got the results.

(CT-2) (CT-3) (CT-4) From the results shown in Table 2 and above, the electrophotographic photoreceptor using the bisazo compound of the present invention as a carrier generating substance has high sensitivity as in Example 1. It can be seen that the residual potential is low and the repeatability is excellent.

Examples 5 to 9 Aluminum was vapor-deposited on a polyester film, the intermediate layer used in Example IM 1 was provided, and the exemplified compound [■-Δ]-2-239. [TI-Δ]-9-4
05, [111-Al-9-352, [V-A
29 of l-9-648 and [T[-8]-3-286, respectively, and polycarbonate resin (Panlite L-1250
] 20 was added to 1,2-dichloroethane 110v+Q and dispersed with a sand grinder for 8 hours. This dispersion liquid was applied so that the dry film thickness was 0.5 μI to form a carrier generation layer. Furthermore, as a carrier transport layer, 6tJ of the following structural formula (CT-5) is applied to 1 part polycarbonate resin [Panlite K-1300] (manufactured by Yojin Kasei Co., Ltd.).
0 g dissolved in 80 iffi of 1,2-dichloroethane was applied so that the film thickness after drying was 15 μm.
A carrier transport layer was formed, and each photoreceptor of the present invention was produced.

(CT-5) The same measurements as in Example 1 were performed on this photoreceptor, and the results are shown in Table 3.

Comparative Example 2 An electrophotographic photoreceptor was prepared in the same manner as in Examples 5 to 5, except that a bisazo compound represented by the following structural formula (CG-2>) was used as a carrier-generating substance.

The same measurements as in Example 1 were performed on this comparative photoreceptor, and the results are shown in Table 3.

(CG-2> Table 3 Examples 70 to 12 Vinyl chloride-vinyl acetate-
An intermediate layer with a thickness of 0.05 μm made of a maleic anhydride copolymer [S-LEC MF-101 (manufactured by Mikki Kagaku Co., Ltd.) was provided, and an exemplified compound [ll-A1-1-90-29] was provided thereon.
and polycarbonate resin [Panlite l-1250E
2 g was added to 110 i12 of tetrahydrofuran and dispersed in a ball mill for 12 hours. This dispersion was applied to a dry film thickness of 0.5 μm to form a carrier generation layer, and furthermore, a carrier transport layer was formed using the following structural formula (CT-
6).

6 g of each of the compounds represented by (CT-7) and (CT-8) and polycarbonate resin [Z-200] (
A carrier transport layer was formed by coating a solution prepared by dissolving 10 liters (manufactured by Mitsubishi Gas Chemical Co., Ltd.) in 1,2-dichloroethane 80i12 so that the film thickness after drying was 15 μm, thereby creating the photoreceptor of the present invention. did.

(CT-6) (CT-7) (CT-8> Measurement was carried out in the same manner as in Example 1 except that a fluorescent lamp was used instead of the halogen lamp in Example 1. The results are shown in Table 4. I yelled.

Table 4 Example 13 An intermediate layer with a thickness of 0.05 μI made of vinyl chloride-vinyl acetate-maleic anhydride copolymer [S-LEC MF-10] (manufactured by Block Chemical Co., Ltd.) was placed on the surface of an aluminum drum with a diameter of 601 nIIl. and the exemplified compound [r
V-A] -6-279, [IV-A] -9-331
and [I[[-A]-2-636 29 and polyester resin [Vylon 200] (manufactured by Toyo Vj Co., Ltd.) 2
and 100 coq of 1,2-dichloroethane,
A dispersion liquid dispersed in a ball mill for 24 hours was coated to a film thickness of 0.6 μm after drying to form a carrier generation layer.

Furthermore, on top of this, the following compound (CT-9>309 and polycarbonate fat [Nipiron S-1000] (Mitsubishi Gas Chemical Co., Ltd. U>5O) was added to 1,2-dichloroethane 40
(A carrier transport layer was formed by dissolving it in h12 and coating it so that the film thickness after drying was 18 μm.

(CT-9) Each of the photoreceptors thus prepared was placed on an electrophotographic copying plate [I
J-Bix1550M R] (manufactured by Konica), and when images were copied, both photoreceptors had high contrast, and a clear copy image that was faithful to the original image was obtained. Moreover, this did not change even after repeating 10,000 times.

Comparative Example 3 One of the exemplified compounds in Example 13 was represented by the following structural formula (C
A drum-shaped comparative photoreceptor was prepared in the same manner as in Example 13, except that the bisazo compound represented by G-3) was used, and the copied image was evaluated in the same manner as in Example 13.
Only images with a lot of fog could be uploaded. Moreover, as copying is repeated, the contrast of the copied image decreases, and after 10,000 repetitions, the copied image is hardly 1q.

(CG-3) C.F.

Examples 14 to 17 Vinyl chloride-vinyl acetate-
Maleic anhydride copolymer [S-LEC MF-10]
(manufactured by Blockchain Chemical Co., Ltd.) with a thickness of 1.05 μm is provided, and on top of that, as a chemical carrier transport material, the following structural formula (C
69 of T-10), 10 g of polycarbonate resin [Panlite L-1250], and 8 g of 1,2-dichloroethane.
A carrier transport layer was formed by applying a solution dissolved in 0.01 g to a dry film thickness of 15 μm.

(CT-10') Furthermore, exemplified compound [V-B] -5-3°[11
1-B] -4-268, [ff1-8] -7-35
4.

Add 2 J of each of [rV-8] -]7-63, 1.5 J of the above carrier transport substance (1, polycarbonate 1 to resin [Panlite L-1250] 2 J) to 30 i12 of 1,2-dichloroethane, The dispersed liquid was coated using a ball mill for 24 hours, and a carrier generation layer having a thickness of 4 μm after drying was provided to prepare photoreceptors of the present invention.

Table 5 Example 18 Exemplary compound No. 0.1 having the structure of general formula [V-8]-9 was prepared in the same manner as in Example 1 for these photoreceptors.
2g of 502 and 1~resin of polycarbonate [Panlite L
-1250J (manufactured by Yojin Kasei Co., Ltd.) 20 was added to 110d of 1°2-dichloroethane and dispersed in a ball mill for 12 hours. This dispersion was applied onto a polyester film on which aluminum was vapor-deposited so that the dry film thickness was 1 μm to form a carrier generation port, and on top of this a carrier transport layer was formed using the following structural formula (CT-11). 6 (I is polycarbonate 1 to resin [Panlite L-1250J 10 (
1 dissolved in 1,2-dichloroethane 110d was applied so that the dry film 1 would be 15 μl to form a carrier transport layer, thereby forming an electrophotographic photoreceptor of the present invention.

(CT-11) This photoreceptor was measured in the same manner as in Example 1, and the results were not shown in Table 6 (q).

Comparative Example 4 The following bisazo compound (CG-4
), a comparative photoreceptor was prepared in the same manner as in Example 18.

(CG-4) Regarding this comparative photoreceptor, measurements were carried out in the same manner as in Example 1, and the results shown in Table 6 were obtained.

Table 6 Examples 19 to 21 Illustrative compound NO, 181, -Balance [■-Bl] having the structure of the general formula [111-B]-9 as a carrier generating substance
Exemplary compound No. 322 having the structure -6, -drink price [V-8 Exemplary compound No. 0.98 having the structure A photoreceptor of the present invention was prepared in the same manner as in Example 18, and the same measurements were performed. The results are shown in Table 7 (CT-12) (CT-13>(CAT-14> Table 7) Example 22 The surface of an aluminum drum with a diameter of 100 μl was coated with vinyl chloride-vinyl acetate-maleic anhydride copolymer "Eslec MF-104 (manufactured by Shimizu Chemical Co., Ltd.) with a thickness of 1.05 cm.
A 1,2-
A dispersion solution was mixed with 400 d of dichloroethane and dispersed in a ball mill dispersion Akebono for 24 hours, and then applied to a film thickness of 0.6 μm after drying to form a carrier generation layer.

Furthermore, the structural formula already described (CT-9>300 and polycarbonate resin [Nipiron S-1000J
(manufactured by SanN Gas Chemical Co., Ltd.) 50oW1 was dissolved in 2-dichloroethane 40011 and coated to form a carrier transport layer such that the film thickness after drying was 13 μm, and a drum-shaped photoreceptor was prepared.

The photoreceptor created in this way can be printed on an electrophotographic printer.
When installed on a modified LP-3010J (manufactured by Konica), a copy image with high contrast, faithful to the original, and clear was obtained. Moreover, this did not change even after repeating 10°000 times.

Comparative Example 5 A drum-shaped comparative photoreceptor was prepared in the same manner as in Example 22, except that the kill relief generating substance in Example 22 was replaced with a bisazo compound (CG-5> represented by the following structural formula). When the copied image was evaluated in the same manner as in 22,
Only images with a lot of fog were obtained. Also, as copying is repeated, the contrast of the copied image decreases,
When the process was repeated 2,000 times, hardly any duplicate images were obtained.

(CG-5) As is clear from the results of the above Examples and Comparative Examples, the photoreceptor of the present invention has better stability, sensitivity, durability, and combination with a wide range of carrier transport substances than the comparative photoreceptor. It has extremely excellent properties.

As is clear from the results of the above examples, the photoreceptor of the present invention is significantly superior to the comparative photoreceptor in terms of stability, sensitivity, durability, and compatibility with a wide variety of carrier transport substances.

[Brief explanation of the drawing]

1 to 9 are sectional views showing the layer structure of the photoreceptor of the present invention, and 1 to 6 in the figures represent the following, respectively.

Claims (3)

[Claims] (1) An electrophotographic photoreceptor comprising a photosensitive layer containing a bisazo compound represented by the following general formula [I] on a conductive support. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [R_1 and R_2 are hydrogen atoms, halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, nitro groups, and cyano groups, respectively. Or represents a hydroxy group. However, R_1 and R_2 may be the same or different. Z represents an atomic group necessary to form a carbocyclic aromatic ring or a heterocyclic aromatic ring. X and Y each represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, X and Y may be the same or different, and may also work together to form a ring. m and n each represent an integer of 1, 2 or 3. ] (2) The photosensitive layer contains a carrier-generating substance and a carrier-transporting substance, and the carrier-generating substance has the general formula [
The electrophotographic photoreceptor according to claim (1), which is a bisazo compound represented by I]. (3) Claim (1) or (2) characterized in that the photosensitive layer is constituted by a laminate of a carrier generation layer containing a carrier generation substance and a carrier transport layer containing a carrier transport substance. The electrophotographic photoreceptor described above.