JPH0220975B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a photoreceptor, and more particularly to a novel photoreceptor having a photosensitive layer containing a specific azo compound. (Prior Art) Conventionally, inorganic photoreceptors having a photosensitive layer mainly composed of an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide, silicon, etc. have been widely used as photoreceptors. 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, it crystallizes when exposed to heat or fingerprints, while cadmium has poor moisture resistance, durability, and even zinc oxide. There's a problem. 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, in Japanese Patent Publication No. 50-10496, poly-N-vinylcarbazole and 2,4,7-
There is a description of an organic photoreceptor having a photosensitive layer containing trinitro-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 organic photoreceptors with higher performance by assigning the carrier generation function and the carrier transport function to different substances. Many studies have been conducted on such so-called function-separated type photoreceptors because each material can be selected from a wide range and a photoreceptor having arbitrary performance can be produced relatively easily. Many compounds have been proposed as carrier generating substances for such functionally separated photoreceptors. Examples of using inorganic compounds as carrier generating substances include, for example, Japanese Patent Publication No. 43-16198.
There is an amorphous selenium described in the publication, which is used in combination with an organic photoconductive compound, but the carrier generation layer made of amorphous selenium crystallizes due to heat and its properties as a photoreceptor deteriorate. The shortcoming of storing it away has not been improved. Furthermore, many electrophotographic photoreceptors using organic dyes or organic pigments as carrier generating substances have been proposed. For example, as an electrophotographic photoreceptor containing a bisazo compound in the photosensitive layer, JP-A-54-22834, JP-A-54-46558, JP-A-56-46237, and JP-A-58-194035 are published. No. 2, etc. are already publicly known. However, these bisazo compounds do not necessarily satisfy the characteristics of sensitivity, residual potential, or stability during repeated use, and the range of carrier transport materials that can be selected is also limited. It does not fully satisfy. Furthermore, in recent years, Ar laser has been used as a light source for photoreceptors.
Gas lasers such as He-Ne lasers and semiconductor lasers are beginning to be used. A characteristic of these lasers is that they can be turned on and off in chronological order, making them particularly promising light sources for copiers with image processing functions, such as intelligent copiers, and printers for computer output. Among these, semiconductor lasers are attracting attention because their nature does not require electrical signal/optical signal conversion elements such as acoustic engineering elements, and they can be made smaller and lighter. However, this semiconductor laser has a low output compared to a gas laser,
Furthermore, since the oscillation wavelength is long (approximately 780 nm or more), the spectral sensitivity of conventional photoreceptors is higher on the short wavelength side, and as it is, it is impossible to use them as photoreceptors using semiconductor lasers as light sources. (Object of the Invention) An object of the present invention is to provide a photoreceptor containing a specific azo compound that is stable against heat and light and has excellent carrier generation ability. Another object of the present invention is to provide a photoreceptor with high sensitivity, low residual potential, and excellent durability whose characteristics do not change even after repeated use. Still another object of the present invention is to provide a photoreceptor containing an azo compound that can effectively act as a carrier generating material even in combination with a wide variety of carrier transport materials. Still another object of the present invention is to provide a photoreceptor having sufficient practical sensitivity even to long wavelength light sources such as semiconductor lasers. Still other objects of the present invention will become apparent from the description in the specification. (Structure of the Invention) As a result of extensive research to achieve the above objectives, the present inventors have discovered that an azo compound represented by the following general formula [] can act as an active ingredient of a photoreceptor, and the present inventors have It is a completed invention. General formula [] However, in the formula, Q is a substituent or a group selected from an unsubstituted benzene ring, an alkyl group, or an alkoxy group, Y ₁ and
_Y2 is a group selected from a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an alkoxy group, m and n are integers of 0 to 2 (however, m, n
are never both 0. ) A is

【formula】

【formula】

【formula】 or

[Formula], Y ₃ is a substituted or unsubstituted carbamoyl group (

[Formula]), substituted and unsubstituted sulfamoy group (

[Formula]), R ₄ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted phenyl group, R ₅ is a hydrogen atom, or a carbon number 1 to 4 substituted/unsubstituted alkyl groups, substituted/unsubstituted aromatic carbocyclic groups (e.g., substituted/unsubstituted phenyl groups, substituted/unsubstituted naphthyl groups, substituted/unsubstituted anthryl groups, etc.), or a substituted/unsubstituted aromatic heterocyclic group (e.g., a substituted/unsubstituted carbazolyl group, a substituted/unsubstituted dibenzofuryl group, etc.). Alkyl groups (e.g. methyl group, ethyl group, isopropyl group, tertiary butyl group, trifluoromethyl group, etc.),
Substituted/unsubstituted aralkyl groups (e.g. benzyl group, phenethyl group, etc.), halogen atoms (chlorine atom,
Bromine atom, fluorine atom, iodine atom), carbon number 1-4
substituted/unsubstituted alkoxy groups (e.g. methoxy group, ethoxy group, isopropoxy group, tertiary butoxy group, 2-chloroethoxy group), hydroxy group,
Substituted/unsubstituted aryloxy groups (e.g., p-chlorophenoxy group, 1-naphthoxy group, etc.), acyloxy groups (e.g., acetyloxy group, p-cyanobenzoyloxy group, etc.), carboxy groups, and their ester groups (e.g., ethoxycarbonyl) , m-
bromophenoxycarbonyl group, etc.), carbamoyl group (e.g., aminocarbonyl group, tertiary butylaminocarbonyl group, anilinocarbonyl group, etc.)
Acyl group (e.g., acetyl group, o-nitrobenzoyl group, etc.), sulfo group, sulfamoyl group (e.g., aminosulfamoyl group, tertiary butylaminosulfonyl group, p-tolylaminosulfonyl group, etc.), amino group, Examples include acylamino groups (e.g., acetylamino groups, benzoylamino groups, etc.), sulfonamide groups (e.g., methanesulfonamide groups, p-toluenesulfonamide groups, etc.), cyano groups, nitro groups, etc., but preferably carbon number 1 to 4 substituted/unsubstituted alkyl groups (e.g.
methyl group, ethyl group, isopropyl group, n-butyl group, trifluoromethyl group, etc.), halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), substituted/unsubstituted alkoxy group having 1 to 4 carbon atoms (For example, methoxy group, ethoxy group, tertiary butoxy group,
2-chloroethoxy group, etc.) cyano group, nitro group. Z is an atomic group necessary to form a substituted/unsubstituted aromatic carbocycle or a substituted/unsubstituted aromatic heterocycle, and specifically, for example, a substituted/unsubstituted benzene ring, a substituted/unsubstituted aromatic heterocycle, etc. Represents a group of atoms forming an unsubstituted naphthalene ring, a substituted/unsubstituted indole ring, a substituted/unsubstituted carbazole ring, etc. Examples of substituents for the atomic group forming these rings include a series of substituents such as those listed as substituents for R ₄ and R ₅ , but halogen atoms (chlorine, bromine, fluorine, etc.) are preferred. atom, iodine atom), a sulfo group, and a sulfamoyl group (for example, an aminosulfonyl group, a P-tolylaminosulfonyl group, etc.). R ₁ is a hydrogen atom, a substituted or unsubstituted alkyl group,
Substituted/unsubstituted amino group, carboxyl group, ester group thereof, substituted/unsubstituted carbamoyl group, cyano group, preferably hydrogen atom, carbon number 1-4
Substituted/unsubstituted alkyl groups (e.g., methyl group, ethyl group, isopropyl group, tertiary butyl group,
trifluoromethyl group, etc.) and cyano group. A' is a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted phenyl group, and examples of substituents for these groups include a series of substituents such as those listed as substituents for R ₄ and R ₅ . are listed, but preferably halogen atoms (chlorine atom, bromine atom, fluorine atom, iodine atom), substituted/unsubstituted alkyl groups having 1 to 4 carbon atoms (for example, methyl group, ethyl group, isopropyl group, tertiary butyl group, trifluoromethyl group, etc.), and substituted/unsubstituted alkoxy groups having 1 to 4 carbon atoms (for example, methoxy group, ethoxy group, isopropoxy group, tertiary butoxy group, 2-chloroethoxy group). R ₂ and R ₃ represent a substituted/unsubstituted alkyl group, a substituted/unsubstituted aralkyl group, and a substituted/unsubstituted aryl group, preferably a substituted/unsubstituted alkyl group having 1 to 4 carbon atoms ( For example, methyl group,
ethyl group, isopropyl group, tertiary butyl group, trifluoromethyl group, etc.), substituted/unsubstituted phenyl group (for example, phenyl group, p-methoxyphenyl group, m-chlorophenyl group, etc.). Among the azo compounds represented by the general formula [] used in the present invention, particularly preferable compounds in terms of sensitivity and stability against heat and light are those having the structure shown by the following general formula []. General formula [] In the formula, A and Q are the same as in the general formula []. Specific examples of the azo compound useful in the present invention represented by the general formula [] include those having the following structural formula, but the azo compound of the present invention is not limited to this. . Those represented by the following general formula [] in general formula [], general formula []

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] Items represented by the general formula [], General formula []

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] Other items. The above azo compounds can be easily synthesized by a known method, for example, the method shown in the following synthesis example. Synthesis Example 1 (Synthesis of Exemplary Compound A-(1)) First, an outline of the synthesis route is shown below. That is, 2,7-dinitrofluorenone 1~ (manufactured by Tokyo Kasei Co., Ltd.) is reacted with benzyl cyanide 2~ to form the dinitro form 3~, which is then reduced with iron to form the diamino form 4~30.9g (0.1 mol). with 1 part concentrated hydrochloric acid and 1 part
A solution of 13.8 g (0.2 mol) of sodium nitrite dissolved in 0.1 of water was added dropwise to the mixed solution at 5°C under ice cooling, and after the dropwise addition was completed, the reaction solution was filtered.
Add 50% hexafutucarin ammonium aqueous solution 1 to the filtrate.
was added, and the resulting precipitate was collected by filtration, washed with water, and thoroughly dried. The obtained salt was dissolved in 1.5 ml of N,N-dimethylformthiamide (DMF) to prepare a tetrazonium salt solution to be used in the next reaction. Next, 2-hydroxy-3-(4-methoxy-
2-methylphenylcarbamoyl)-benzo[a]
-Carbazole (Naphthol AS-SR, manufactured by Hoechst) 79.3g (0.2mol), triethanolamine
60 g was dissolved in N,N-dimethylformamide, and the tetrazonium salt solution prepared above was added dropwise while cooling with ice, and the mixture was further stirred for 2 hours to react. The resulting crystals were collected by filtration and treated with 5N,
After washing twice with N-dimethylformamide and twice with acetone (5), it was dried to obtain 37.1 g (33%) of the target bisazo compound A-(1). Melting point over 300°, M ⁺ at m/z 1124 in FD-MS spectrum
It is shown in the peak of C=
75.81%, N=11.17%, H=4.50% (calculated values are
C = 75.85%, N = 11.21%, H = 4.39%), which confirmed that the target substance was synthesized. The azo compound of the present invention has excellent photoconductivity, and when a photoreceptor is manufactured using the azo compound, a photosensitive layer in which the azo compound of the present invention is dispersed in a binder is provided on a conductive support. Among the photoconductivity possessed by the azo compound of the present invention, it can be used as a carrier-generating substance by taking advantage of its particularly excellent carrier-generating ability, and a carrier-transporting substance that can effectively act in combination with this. By using them together, particularly excellent results can be obtained when a so-called functionally separated photoreceptor is constructed. Although the functionally separated photoreceptor may be a separate type, it is more preferably a laminated photoreceptor comprising a carrier generation layer containing a carrier generation substance and a carrier transport layer containing a carrier transport substance. Further, the azo compound used in the present invention can be used alone or in combination of two or more of the azo compounds represented by the above general formula [], and may also be used in combination with other azo compounds. . Various types of mechanical configurations of photoreceptors are known, and the photoreceptor of the present invention can take any of these forms. Usually, the configuration is as shown in FIGS. 1 to 6. In FIGS. 1 and 3, a laminate is formed of a carrier generation layer 2 containing the above-mentioned azo compound as a main component and a carrier transport layer 3 containing a carrier transport substance as a main component on a conductive support 1. A photosensitive layer 4 is provided. As shown in FIGS. 2 and 4, this photosensitive layer 4 may be provided via an intermediate layer 5 provided on a conductive support. When the photosensitive layer 4 has a two-layer structure in this way, a photoreceptor having the most excellent electrophotographic properties can be obtained. In addition, in the present invention, FIGS.
As shown in the figure, a photosensitive layer 4 in which the carrier generating substance 7 is dispersed in a layer 6 containing a carrier transporting substance as a main component may be provided directly on the conductive support 1 or via an intermediate layer 5. good. When the azo compound of the present invention is used as a carrier generating substance, examples of the carrier transporting substance used in combination with the azo compound include electron-accepting substances that easily transport electrons such as trinitrofluorenone or tetranitrofluorenone, as well as poly-N-vinyl Polymers having a side chain of a heterocyclic compound such as carbazole, triazole derivatives, oxadiazole derivatives, imidazole derivatives, pyrazoline derivatives, polyarylalkane derivatives,
Phenylene diamine derivatives, hydrazone derivatives,
Examples include electron-donating substances that easily transport holes, such as amino-substituted chalcone derivatives, triarylamine derivatives, carbazole derivatives, stilbene derivatives, and phenothiazine derivatives, but the carrier transport substance used in the present invention is limited to these. isn't it. The carrier generation layer 2 constituting the photosensitive layer 4 having a two-layer structure is the conductive support 1 or the carrier transport layer 3.
It can be formed directly thereon or, if necessary, with an intermediate layer such as an adhesive layer or a barrier layer provided thereon, for example, by the following method. M-1 A method of applying a solution in which an azo compound is dissolved in a suitable solvent, or a solution in which a binder is added and mixed as necessary. M-2 A method in which an azo compound is made into fine particles in a dispersion medium using a ball mill, a homomixer, etc., and a dispersion liquid is applied. Solvents or dispersion media used for forming the carrier generation layer include n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, benzene, and toluene. , xylene, chloroform,
Examples include 1,2-dichloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, and the like. When a binder is used in the carrier generation layer or the carrier transport layer, any binder can be used, but it is preferable to use a film-forming polymer that is hydrophobic, has a high dielectric constant, and is electrically insulating. Examples of such high molecular weight polymers include, but are not limited to, the following. P-1 Polycarbonate P-2 Polyester P-3 Methacrylic resin P-4 Acrylic resin P-5 Polyvinyl chloride P-6 Polyvinylidene chloride P-7 Polystyrene P-8 Polyvinyl acetate P-9 Styrene-butadiene copolymer P- 10 Vinylidene chloride-acrylonitrile copolymer P-11 Vinyl chloride-vinyl acetate copolymer P-12 Vinyl chloride-vinyl acetate-maleic anhydride copolymer P-13 Silicone resin P-14 Silicone-alkyd resin P-15 Phenol Formaldehyde resin P-16 Styrene-alkyd resin P-17 Poly-N-vinylcarbazole These binders can be used alone or in a mixture of two or more. The carrier generation layer 2 formed in this way preferably has a thickness of 0.01 μm to 20 μm,
More preferably, it is 0.05 μm to 5 μm. Further, when the carrier generation layer or the photosensitive layer is a dispersed type, the particle size of the azo compound is preferably 5 μm or less, more preferably 1 μm or less. The conductive support used in the photoreceptor of the present invention includes a metal plate including an alloy, a metal drum, a conductive polymer, a conductive compound such as indium oxide, and a metal thin film such as aluminum, palladium, and gold including an alloy. Examples include paper, plastic film, etc. that have been made conductive by coating, vapor depositing, or laminating layers. As an intermediate layer such as an adhesive or barrier layer, in addition to the polymer used as the binder, an organic polymer material such as polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, or aluminum oxide is used. The 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 has little fatigue deterioration even after repeated use.
It has excellent durability. Hereinafter, the present invention will be specifically explained in Examples,
This does not limit the embodiments of the present invention. (Example) Example 1 2 g of exemplified compound A-(21) and polycarbonate resin "Panlite L-1250" (manufactured by Teijin Chemicals) 2
g was added to 110 ml of 1,2-dichloroethane and dispersed in a ball mill for 12 hours. This dispersion was applied onto a polyester film deposited with aluminum to a dry film thickness of 1 μm to form a carrier generation layer, and then a 1-phenyl-(p-methyl Styril)-5-
6 g of (p-methoxyphenyl)pyrazoline (the following structural formula K-(1)) was mixed with 10 g of polycarbonate resin "Panlite L-1250" in 1,2-dichloroethane.
A carrier transport layer was formed by coating a solution dissolved in 110 ml so that the film thickness after drying was 15 μm, thereby producing a photoreceptor of the present invention. The photoreceptor obtained as described above was subjected to the following characteristic evaluation using an electrostatic paper tester SP-428 manufactured by Kawaguchi Electric Seisakusho Co., Ltd. After charging with a charging voltage of -6KV for 5 seconds, leave in the dark for 5 seconds, then irradiate with halogen lamp light so that the illuminance on the photoreceptor surface is 35 lux, and calculate the amount of exposure required to attenuate the surface potential by half. (Half-reduced exposure amount) E1/2 was determined. Also
The surface potential (residual potential) V _R after exposure with an exposure amount of 30 lux·sec was determined. Furthermore, similar measurements were repeated 100 times. The results are shown in Table 1.

[Table] Comparative Example 1 The following bisazo compound G was used as a carrier generating substance.
A comparative photoreceptor was prepared in the same manner as in Example 1 except that -(1) was used. When this comparative photoreceptor was measured in the same manner as in Example 1, the results shown in Table 2 were obtained.

[Table] As is clear from the above results, the photoreceptor of the present invention is extremely superior in sensitivity, residual potential, and repetition stability compared to the comparative photoreceptor. Example 2-4 Exemplary compounds A-(5) and A as carrier generating substances
-(6) and A-(7) as carrier transport substances, respectively.
4-carbazolyl)methylideneamino-1,2,
3,4-tetrahydroquinoline (compound K- below)
(2)), 1-(1-ethyl-4-carbazolyl)methylideneamino-1,2,3,4-tetrahydroquinoline (compound K-(3) below, and 4,4′-methyl-4″-(4 -Chlor)-styryltriphenylamine (compound K-(4) below) was used to prepare a photoreceptor of the present invention in the same manner as in Example 1, and the same measurements were performed. The following results were obtained.

[Table] Comparative Example 2 The following bisazo compound G was used as a carrier generating substance.
A comparative photoreceptor was prepared in the same manner as in Example 4, except that -(2) was used. Measurements were performed on this comparative photoreceptor in the same manner as in Example 4, and the results shown in Table 4 were obtained.

[Table] As is clear from the above results, the photoreceptor of the present invention is extremely superior in sensitivity, residual potential, and repetition stability compared to the comparative photoreceptor. Example 5 A layer of vinyl chloride-vinyl acetate-maleic anhydride copolymer "Eslec MF-10" (manufactured by Sekisui Chemical Co., Ltd.) was placed on a conductive support made of aluminum foil laminated on a polyester film.
A 0.05 μm intermediate layer is provided, and exemplified compound A is placed on top of the intermediate layer.
2 g of -(11) was mixed with 110 ml of 1,2-dichloroethane and dispersed in a ball mill for 24 hours. A dispersion was coated to a dry film thickness of 0.5 μm to form a carrier generation layer. On this carrier generation layer, 6 g of 3,3',4-trimethyl-triphenylaminone and 10 g of methacrylic resin "Acrypet" (manufactured by Mitsubishi Rayon Co., Ltd.) were added to 70 g of 1,2-dichloroethane.
A carrier transport layer was formed by applying the solution dissolved in 100 ml to a dry film thickness of 10 μm, thereby producing a photoreceptor of the present invention. The same measurements as in Example 1 were carried out on this photoconductor, and the first measurement was E1/2=2.6lux・
sec, V _R =0v was obtained. Example 6 On the conductive support provided with the intermediate layer used in Example 5, a 1% ethylenediamine solution of Exemplary Compound A-(40) was applied to a dry film thickness of 1.3 μm, and a carrier was applied. A generation layer was formed. Then, 4-methoxy-4'-styryltriphenylamine (compound K-(5) below) is added thereon. 6 g and 10 g of polyester resin "Vylon 200" (manufactured by Toyobo Co., Ltd.) were dissolved in 70 ml of 1,2 dichloroethane, and this solution was applied so that the film thickness after drying was 12 μm to form a carrier transport layer. A photoreceptor of the present invention was prepared. The same measurements as in Example 1 were performed on this photoreceptor, and the results shown in Table 4 were obtained. Comparative Example 3 A comparative photoreceptor was prepared in the same manner as in Example 6 except that exemplified compound A-(40) was replaced with bisazo compound G-(3) represented by the following structural formula. The same measurements as in Example 1 were performed on this photoreceptor, and the results are shown in Table 5.

[Table] Example 7 A carrier generation layer was formed in the same manner as in Example 5 except that Exemplified Compound A-(11) was replaced with Exemplified Compound A-(37). On top of this, 6 g of 3-(p-methoxystyryl)9-(p-methoxyphenyl)carbazole and polycarbonate "Panlite L-
1250 (manufactured by Teijin Chemicals) in 70 ml of 1,2-dichloroethane, the film thickness after drying is
A carrier transport layer was formed by coating to a thickness of 10 μm, and a photoreceptor of the present invention was prepared. Measurements were carried out on this photoreceptor in the same manner as in Example 1, and E1/2 = 1.9 lux・sec and V _R = 0v.
It was hot. Example 8 An intermediate layer with a thickness of 0.05 μm made of vinyl chloride-vinyl acetate-maleic anhydride copolymer “Eslec MF-10” (manufactured by Sekisui Chemical Co., Ltd.) was provided on the surface of an aluminum drum with a diameter of 100 mm. Add 4 g of Exemplified Compound A-(36) to 400 ml of 1,2-dichloroethane.
The dispersion liquid was mixed with the following and dispersed for 24 hours using a ball mill dispersion machine, and the dispersion liquid was applied so that the film thickness after drying was 0.6 μm to form a carrier generation layer. Furthermore, on top of this, 3-(p-methoxystyryl)
-9-(p-methoxyphenyl)carbazole (compound K-(6) below) 30g and polycarbonate resin "Iupilon S-1000" (manufactured by Mitsubishi Gas Chemical Co., Ltd.)
50g and 1,2-dichloroethane A carrier transport layer was formed by dissolving the solution in 400 ml and applying it to a film thickness of 13 μm after drying, thereby producing a drum-shaped photoreceptor. The photoreceptor created in this way was attached to a modified electrophotographic copying machine "U-Bix1600MR" (manufactured by Konishiroku Photo Industry Co., Ltd.), and the image was copied with high contrast, faithful to the original image, and clear copy. Got the image. Moreover, this did not change even after repeating this 10,000 times. Comparative Example 4 A drum-shaped comparative photosensitive material was prepared in the same manner as in Example 8, except that the exemplified compound A-(36) in Example 8 was replaced with a bisazo compound (G-(4)) represented by the following structural formula. When a body was prepared and a copy image was evaluated in the same manner as in Example 8, only images with a lot of fog were obtained. Furthermore, as copying was repeated, the contrast of the copied image decreased, and after 2000 repetitions, almost no copied image could be obtained. Example 9 A layer of vinyl chloride-vinyl acetate-maleic anhydride copolymer "Eslec MF-10" (manufactured by Sekisui Chemical Co., Ltd.) was placed on a conductive support made of a polyester film laminated with aluminum foil.
A 0.05 μm intermediate layer is provided, and exemplified compound A.
(17) Add 5 g and 3.3 g of polycarbonate resin "Panlite L-1250" (manufactured by Teijin Chemicals) to 100 ml of dichloromethane, disperse in a ball mill for 24 hours, and apply the dispersion so that the dry film thickness is 10 μm. Then, a photoreceptor was created. The photoconductor obtained in the above manner is charged with a +
E1/2 and E1/2 in the same manner as in Example 1 except that 6Kv was used.
_VR was measured. The first result is E1/2=2.2lux・
sec and V _R =5v. Example 10 6 g of p-N,N-diethylamino)benzaldehyde-1,1-diphenylhydrazone and polyester resin "Vylon" were added as a carrier transport layer on a polyester film deposited with aluminum.
200" (manufactured by Toyobo Co., Ltd.) in 70 ml of 1,2-dichloroethane, and the film thickness after drying this solution.
It was applied to a thickness of 10 μm. Next, 1 g of exemplified compound A-(12) and A--
(14) 1 g of 1,2-dichloroethane was mixed with 110 ml of 1,2-dichloroethane, and the dispersion was dispersed in a ball mill for 24 hours. The dispersion was applied to a dry film thickness of 0.5 μm to form a carrier generation layer. was formed. The thus obtained photoreceptor was evaluated in the same manner as in Example 9, and found that E1/2=2.4lux・sec.
V _R = +5V. Example 11 A 2% ethylenediamine solution of the exemplified compound Compound A-(10) was applied onto a polyester film laminated with aluminum to a dry film thickness of 0.5 μm to form a carrier generation layer. Furthermore, 1-methyl-
3-(p-diethylaminophenyl)-5-(p-
diethylaminophenyl)pyrazoline (compound K-(7) below), 1-phenyl(p-methoxystyryl)-5-(p-diethylaminophenyl)pyrazoline compound K-(8) below, or 1-phenyl(p-methoxystyryl)-5-(p-diethylaminophenyl)pyrazoline -Methystyryl)-5-(p-methylphenyl)pyrazoline (compound K-(9) below), about 10 g each, and polycarbonate. Resin (manufactured by Teijin Chemicals, Panlite L-1250) 14
A solution prepared by dissolving G in 140 ml of 1,2-dichloroethane was coated and dried to give a film thickness of 12 μm after drying, thereby obtaining photoreceptors containing three different carrier transport substances. These three types of photoreceptors were manufactured by Kawaguchi Electric Manufacturing Co., Ltd.
The following characteristics were evaluated using an electrostatic paper tester model SP-428 manufactured by Co., Ltd. Charged for 5 seconds at a charging voltage of -6Kv,
After leaving this for 5 seconds, halogen light is irradiated so that the material surface illuminance is 35 lux, and the exposure amount required to attenuate the surface potential by half (half-reduction exposure amount, E
1/2) was measured. In addition, the surface potential (residual potential) V _R after exposure with an exposure amount of 30 lux·sec was measured.
As shown in Table 6, the results were good in combination with any carrier transport substance.

[Table] Comparative Example 5 Exemplary compound A-(10) was mixed with the following bisazo compound (G
A comparison photoreceptor was prepared in the same manner as in Example 11 except that -(5)) was replaced, and the characteristics were evaluated. As shown in Table 7, the results varied depending on the carrier transport substance.

[Table] Example 12 On the conductive support provided with the intermediate layer used in Example 5, 2 g of Exemplified Compound A-(2) and 100 ml of 1,2-dichloroethane were well dispersed and mixed, and the membrane after drying was prepared. A carrier generation layer was created by coating to a thickness of 0.3 μm. 4- is then added thereon as a carrier transport material.
6 g of methyl-4'styryl-triphenylamine (compound K-(10) below) and polycarbonate "Panlite L-1250" (manufactured by Teijin Chemicals) A carrier transport layer was formed by coating a solution prepared by dissolving 10 g of 1,2-dichloroethane in 90 g of 1,2-dichloroethane so that the film thickness after drying was 10 μm, thereby producing a photoreceptor of the present invention. The electrophotographic properties of this photoreceptor at room temperatures of 25° C. and 60° C. were measured in the same manner as in Example 1. The results are shown in Table 8.

[Table] As is clear from the above results, the electrophotographic photoreceptor of the present invention has good sensitivity and residual potential characteristics even at high temperatures, and is stable against heat. Example 13 2 g of Exemplified Compound A-(1) and 110 ml of 1,2-dichloroethane were well dispersed and mixed on the conductive support provided with the intermediate layer used in Example 5, and the film thickness after drying was
A carrier generation layer was created by coating to a thickness of 0.3 μm. In order to test the durability of this carrier generation layer against UV light, an ultra-high pressure mercury lamp (manufactured by Tokyo Shibaura Electric Co., Ltd.) was placed 30 cm away from the carrier for 10 minutes.
UV light of 1500 cd/cm ² was irradiated. Next, 4-methoxy-4'-(4-methylstyryl)-triphenylamine (compound K-(11) below) is applied as a carrier transport substance onto this carrier generation layer that has been irradiated with UV light.
7g and polycarbonate [Panlite L-1250]
(manufactured by Teijin Chemicals) was dissolved in 90 g of 1,2-dichloroethane. A carrier transport layer was formed by applying the liquid to a film thickness of 12 μm after drying, thereby producing a photoreceptor of the present invention. The same measurements as in Example 5 were performed on this photoreceptor. The results are shown in Table 8. Example 14 A photoreceptor of the present invention was prepared in the same manner as in Example 13, except that UV light was not irradiated after the carrier generation layer was formed, and the same measurements as in Example 5 were performed. 9th result
Shown in the table.

[Table] As is clear from the above results, the photoreceptor of the present invention has excellent sensitivity and residual potential characteristics against UV light irradiation, has small fluctuations in acceptance potential, and is stable against light. can. Comparative Example 6 Compound A-(1) was converted into the following bisazo compound (G-
Same as Example 13 and Example 14 except that (6)) was changed. A photoreceptor was prepared, and the same measurements as in Example 5 were performed. The results are shown in Table 10.

[Table] As is clear from the above results, the sensitivity and residual potential characteristics of the compounds prepared using the above compounds deteriorate upon UV light irradiation, and the amount of variation in acceptance potential is large. Example 15 A drum-shaped photoreceptor was prepared in the same manner as in Example 5 except that exemplified compound A-(11) was changed to A-(3). The spectral sensitivity of this photoreceptor at 790nm is
It was 0.42 μJ/cm ² (half exposure amount). The photoreceptor of the present invention has a laser beam intensity on the surface of the photoreceptor.
A live photo test was conducted using an experimental machine equipped with a semiconductor laser (790nm) that outputs 0.85mW. After the surface of the photoreceptor was charged to -6 KV, it was exposed to laser light and reverse development was performed at a bias voltage of -250 V. A good image without fogging was obtained. Comparative Example 7 A comparative photoreceptor was obtained in the same manner as in Example 15, except that the following Comparative Example bisazo compound was used in place of Exemplified Compound A-(3). The spectral sensitivity of this photoreceptor at 790nm is
It was 8.0 μJ/cm ² (half exposure amount). Using this comparative photoreceptor, an actual photographic test using a semiconductor laser was conducted in the same manner as in Example 15, but there was a lot of fog and no good images could be obtained. As is clear from the results of the above Examples and Comparative Examples, the photoreceptor of the present invention is significantly superior to the comparative photoreceptor in properties such as stability, sensitivity, durability, and compatibility with a wide range of carrier transport materials. It is something. (Effects of the Invention) According to the present invention, by using an azo compound represented by the general formula [] as a photoconductive substance constituting the photosensitive layer of a photoreceptor, heat and light It also has excellent electrophotographic properties such as charge retention, sensitivity, and residual potential. It also shows little fatigue deterioration even after repeated use, and has sufficient sensitivity even in the long wavelength region of 780 nm or more. It is possible to create an excellent photoreceptor with

[Brief explanation of drawings]

FIGS. 1 to 6 are cross-sectional views showing examples of the mechanical structure of the photoreceptor of the present invention.
~7 represents the following, respectively. 1... Conductive support, 2... Carrier generation layer,
3... Carrier transport layer, 4... Photosensitive layer, 5... Intermediate layer, 6... Layer containing a carrier transport substance, 7
...Carrier generating substance.

Claims (1)

[Scope of Claims] 1. A photoreceptor comprising a photosensitive layer containing an azo compound of the following general formula [] on a conductive support. General formula [] [Wherein, Q is a substituted or unsubstituted benzene ring,
Represents an alkyl group or an alkoxy group, Y ₁ and Y ₂
are a hydrogen atom, a halogen atom, a cyano group, and
Represents an alkyl group or an alkoxy group, m and n
Each represents an integer from 0 to 2, but m and n are never 0 at the same time. A is [Formula] [Formula] [Formula] or [Formula], where Z is necessary to constitute a substituted or unsubstituted aromatic carbocycle, or a substituted or unsubstituted aromatic heterocycle atomic group, Y ₃ is a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted sulfamoyl group, R ₁ is a hydrogen atom, a substituted or unsubstituted alkyl group, an amino group, a substituted or unsubstituted sulfamoyl group, amino group,
Substituted or unsubstituted carbamoyl group, carboxyl group and its ester group or cyano group, A' is substituted or unsubstituted aryl group, R ₂ and R ₃ are substituted or unsubstituted alkyl group, substituted or unsubstituted Represents a substituted aralkyl group or a substituted or unsubstituted aryl group. 2. The photoreceptor according to claim 1, wherein the photosensitive layer contains a carrier transporting substance and a carrier generating substance, and the carrier generating substance is an azo compound of the general formula []. 3. The photoreceptor according to claim 1 or 2, wherein 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.