JPS60202444A - Photosensitive body - Google Patents

Abstract

PURPOSE:To provide photosensitive bodies acting effectively as a carrier generating substance even in combination with a wide variety of carrier transporting substances, and having sufficient practical sensitivity for a long wavelength light source such as semiconductor laser, etc. CONSTITUTION:Superior photosensitive bodies having high stability to heat and light, and superior photographic characteristics such as charge maintaining property, sensitivity, residual potential, etc. causing little deterioration due to fatigue even if it is used repeatedly, moreover, having sufficient sensitivity in a long wavelength region >=780nm, are provided by using azo compds. expressed by the general formula ( I ) for a photoconductive substance constituting a photosensitive layer 4 of a photoconductive body.

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, Japanese Patent Publication No. 50-10496 describes an organic photoreceptor having a photosensitive layer containing poly-N-vinylcarbazole and 2.4.7-)Lielow-9-fluorenone. However, this photoreceptor is not necessarily satisfactory in sensitivity and durability. In order to improve these shortcomings, the carrier generation function and carrier transport function are different from each other.
- Attempts are being made to develop organic photoreceptors with higher performance by assigning the burden to other materials. 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. As an example of using a free compound as a carrier generating substance,
For example, there is amorphous selenium described in Japanese Patent Publication No. 43-16198, which is used in combination with an organic photoconductive compound, but the carrier generation layer made of amorphous selenium is crystallized by heat to form a photoreceptor. The drawback of deteriorating the characteristics of the device 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-54-46,
558, JP-A-56-464-237, JP-A-58-194035, etc. are already known. However, these bisazo compounds do not necessarily have the characteristics of sensitivity, residual potential, or stability during repeated use, and
The selection range of carrier transporting substances is also limited, and the wide range of requirements of electrophotographic processes cannot be fully satisfied.

Furthermore, in recent years Ar laser and He-N have been used as light sources for photoreceptors.
Gas lasers such as e-lasers and semiconductor lasers are beginning to be used. These lasers are characterized by being capable of 0N10FF in time series, and are particularly promising as a light source for copying machines with image processing functions, such as intelligent copiers, and printers for computer output. Semiconductor lasers are attracting attention because their nature eliminates the need for 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 lower output power than a gas laser, and its oscillation wavelength is also longer (
(approximately 780 nm or more), the spectral sensitivity of the photoreceptor manufactured by Jumei is higher on the short wavelength side, and as it stands, it is impossible to use it as a photoreceptor using a semiconductor laser as a light source.

(Objective 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 substance even in combination with a wide variety of carrier transporting substances.

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 intensive research to achieve the above object, the present inventors discovered that an azo compound represented by the following general formula [11] can act as an active ingredient of a photoreceptor, and the present inventors have It is a completed invention.

General formula [I] However, in the formula, Q is a substituent or an unsubstituted benzene ring, an alkyl group, or a group selected from an alkoxy group, and Yl and Y2 are a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an alkoxy group, respectively. 0 and n are integers of O to 2, (wherein III and n are both 7-A is A' R2R:1 1 H, and Y3 is a substituted or unsubstituted carbamoyl group R1 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, R5 is a hydrogen atom, a substituted or unsubstituted group having 1 to 4 carbon atoms an alkyl group, a substituted or unsubstituted aromatic carbocyclic group (e.g., a substituted or unsubstituted phenyl group, a substituted or unsubstituted 7-tyl group, a substituted or unsubstituted anthryl group, etc.), or a substituted or
Unsubstituted aromatic heterocyclic groups (e.g., substituted/unsubstituted carbazolyl groups, substituted/unsubstituted dibenzofuryl groups, etc.) Examples of substituted/unsubstituted groups include, for example, alkyl groups having 1 to 4 carbon atoms ( For example, methyl group, ethyl group, isopropyl group, tertiary butyl group, trifluoromethyl group, etc.), substituted
Unsubstituted aralkyl groups (e.g. benzyl group, 7enethyl group, etc.), halogen atoms (chlorine atom, bromine atom, fluorine atom, iodine atom), substituted/unsubstituted alkoxy groups having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group, isopropoxy group, tertiary butoxy group, 2-chloroethoxy group), hydroxy group, substituted/unsubstituted aryloxy group (e.g. p-chlorophenoxy group, 1-7toxy group, etc.), Acyloxy groups (e.g. acetyloxy, p-cyanobenzoyloxy, etc.), carboxyne groups, and their ester groups (
(e.g., ethoxycarbonyl group, m-bromophenoxycarbonyl group, etc.), carbamoyl group (e.g., aminocarbonyl group, tertiary butylamine/carbonyl group, anilinocarbonyl group, etc.), acyl group (e.g., acetyl group, 0-
nitrobenzoyl group, etc.), sulfo group, sulfo77moyl group (e.g., aminosulfamoyl group, tertiary butylaminosulfonyl group, p-tolylaminosulfonyl group, etc.)
, amide 7 group, acylami 7 group (e.g., acetyl amide 7 group)
groups, benzoylamino groups, etc.), sulfonamide groups (e.g., methanesulfonamide groups, p-toluenesulfonamide groups, etc.), cyano groups, nitro groups, etc., but preferably substituted groups having 1 to 4 carbon atoms. Unsubstituted alkyl group (for example, methyl group, ethyl group, isopropyl group, n-butyl group, trifluoromethyl group, etc.), halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), carbon number 1-4
Substituted/unsubstituted alkoxy groups (e.g., methoxy groups,
ethoxy group, tertiary butoxy group, 2-chloroethoxy group, etc.) 7 group, and nitro group.

Z is an atomic group necessary to form a substituted/unsubstituted aromatic carbocycle or a substituted/unsubstituted aromatic polycyclic ring,
Specifically, it represents an atomic group forming, for example, a substituted/unsubstituted benzene ring, a substituted/unsubstituted naphthalene ring, a substituted/unsubstituted indole ring, a substituted/unsubstituted carbazole ring, etc.

Examples of substituents for the atomic groups forming these rings include a series of substituents such as those listed as substituents for R, and R5, but preferably halogen atoms (chlorine atom, bromine atom, fluorine atom) , iodine atom), sulfo group, sulfamoyl group (eg, aminosulfonyl group, p-)lylaminosulfonyl group, etc.).

R1 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or
Unsubstituted amine 7 group, carboxyl group, its ester group,
Substituted/unsubstituted carbamoyl group, cyano group, preferably hydrogen atom, substituted/unsubstituted alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, isopropyl group, 3
butyl group, trifluoromethyl group, etc.), and cyano group.

A' is a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted phenyl group, and the substituents for these =11- groups include a series of substituents such as those listed as substituents for R4gRs. halogen atoms, chlorine atoms, bromine atoms, fluorine atoms, iodine atoms)
, 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 alkoxy groups having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, impropoxy group, tertiary butoxy group, 2-chloroethoxy group).

R2 and R3 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, preferably a substituted or 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 (eg, phenyl group, p-methoxyphenyl group, m-chlorophenyl group, etc.).

Among the azo compounds represented by the general formula [I] used in the present invention, particularly preferred compounds are represented by the following general formula [II] in terms of sensitivity and stability against heat and light. It has a structure.

General formula [11] In the formula, A and Q are the same as in the general formula [I].

Specific examples of the azo compound useful in the present invention represented by the general formula [I] include those having the following structural formula, but the azo compound of the present invention is not limited thereto.

Those represented by the following general formula [ITI] in general formula [1],
General formula [I[[] Others.

A-(72)'A-(72)' That is, 2,7-sinitrofluorenone 1 (manufactured by Tokyo Kasei Co., Ltd.) is reacted with benzyl cyanide 2 to form the dinitro compound 3, which is reduced with iron. Diamino compound 4 30.9g (
Add and disperse 13.88 (0.1 mol) of thorium nitrite to a mixed solution of 11 (concentrated hydrochloric acid and 11) and dropwise add a solution of 13.88 (0.2 mol) of thorium nitrite dissolved in 0.11 of water at 5°C under water cooling. After the dropwise addition was completed, the reaction solution was filtered, 50% hexafluorin ammonium aqueous solution 11 was added to the filtrate, and the resulting precipitate was collected by filtration, washed with water, and thoroughly dried. The obtained salt was dissolved in 1.5 i 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)-ben V[a]-carbazole (Su7tol AS-8R, manufactured by Hoechst) 79.3
g (0.2 mol), triethanolamine 60g1 in N
, N-dimethylformamide, and the tetrazonium salt solution prepared above was added dropwise while cooling with water, and the mixture was further stirred for 2 hours to react. The resulting crystals were collected by filtration, and the crystals were diluted with 54% N,N-dimethylformamide twice.
After washing twice with acetone, the mixture was dried to obtain 37.1 g (33%) of the target bisazo compound A-(1). Melting point 3
00° and above, m/zl in FD-MS spectrum]
, 24 shows a peak of M, and elemental analysis shows that C
= 75.81%, N=11.1.7%, H=4.5
0% (calculated values are C=75.85%, N=11.21
%.

1 (=4°39%), the target substance was synthesized.36 The azo compound of the present invention has excellent photoconductivity. The azo compound of the present invention can be manufactured by providing a photosensitive layer on the body in which the azo compound of the present invention is dispersed in a binder. Particularly excellent results can be obtained when a so-called function-separated type photoreceptor is constructed by using it as a carrier-generating substance and using it together with a carrier-transporting substance that can effectively act in combination. 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 has the general formula [I]
The azo compounds represented by these may be used alone or in combination with two or more thereof, or may be used in combination with other azo compounds.

Various 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. Figures 1 and 3
In the figure, a photosensitive layer 4 consisting of a laminate 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 is provided on a conductive support 1. . As shown in FIGS. 2 and 14, 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 manner, a photoreceptor having the most excellent electrophotographic properties can be obtained.

Further, in the present invention, as shown in FIGS. 5 and 6, a photosensitive layer 4 formed by dispersing the carrier-generating substance 7 in WIG containing a carrier-transporting substance as a main component is directly deposited on the conductive support 1. , or : may be provided through the intermediate layer 5.

When the azo compound of the present invention is used as a carrier-generating substance, the carrier-transporting substance used in combination with the azo compound is an electron-accepting substance that easily transports electrons such as linitrofluorenone or tetranitrofluorenone. Polymers having polycyclic compounds in their side chains such as vinylcarbazole, triazole derivatives, oxadiazole derivatives, imiguzole derivatives, pyrazoline derivatives, polyarylalkane derivatives, phenylenediamine derivatives, hydrazone derivatives, amide 7-substitution power Examples include electron-donating substances that easily transport holes, such as lucon derivatives, triarylamine derivatives, carbazole derivatives, stilbene derivatives, and phenothiazine derivatives.
The carrier transport substance used in the present invention is not limited to these.

The carrier generation layer 2 constituting the two-layered photosensitive layer 4 may be applied directly to the conductive support 1 or the carrier transport layer 3, or if necessary, provided with an intermediate layer such as an adhesive layer or a single barrier layer, for example. It can be removed by forming it using 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 the azo compound is made into fine particles in a dispersion medium using a ball mill, a homomixer, etc., and a dispersion liquid is applied.

Examples of the solvent or dispersion medium used for forming the carrier generation layer include n-butylamine, noethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methylethylketone, cyclohexanone, Examples include benzene, toluene, xylene, chloroform, 1,2-dichloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, and the like.

When using a binder 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.

4O- 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-1
2) 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-1, 7) Poly-N-vinylcarbazole These binders may be used alone or in combination of two or more
1- Can be used as a mixture.

The thickness of the carrier generation layer 2 formed in this way is
It is preferably 0.01 μW to 20 μm, more preferably 0.05 μff1 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,
Examples include paper, plastic films, etc. that have been made conductive by coating, vapor depositing, or laminating a thin layer of a metal such as aluminum, palladium, or gold containing a conductive compound or alloy such as indium oxide. 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-mentioned structure, and as is clear from the examples described later, it has excellent charging characteristics, sensitivity characteristics, and image forming characteristics, and is particularly resistant to fatigue deterioration even after repeated use. It has excellent durability.

+J, Below, only one embodiment of the present invention will be described, but the embodiments of the present invention are not limited thereby.

(Example) Example 1 2 g of Exemplary Compound A-(21) and polycarbonate resin [
Panrye) L-1250J (manufactured by Ondai Kasei Co., Ltd.) (2 g) was added to 110 TllQ of 1,2-dichloroethane, and dispersed in a ball mill for 12 hours. This dispersion was applied onto a polyester film coated with aluminum to a dry film thickness of 1.
1-phenyl-(p
-Methystyryl)-5-(p-methoxyphenyl)pyrazoline (6 g of -(1)) is added to polycarbonate in the following bucket construction method) 1 (Panlite L-1250Jlog fat and 1
, 2-dichloroethane 110TIIQ was coated to form a carrier transport layer such that the film thickness after drying was 15 μm, thereby producing a photoreceptor of the present invention.

-1 The photoreceptor obtained in the above manner was subjected to the following characteristic evaluation using a new SP-428 type electrostatic paper test block manufactured by Kawaguchi Electric Co., Ltd. After being charged for 5 seconds with a charging voltage of -6KV, it was left in the dark for 5 seconds, and then the illuminance on the photoreceptor surface was 351.
The halogen lamp light was irradiated so that the surface potential became 11, and the exposure amount (half-reduced exposure amount) E% required to attenuate the surface potential by half was determined. Also, the surface potential (residual potential) VR after exposure at an exposure amount of 301 u/sec was determined. The same measurement was repeated 100 times and the following bisazo compound G-(1) was used as a carrier generating substance.
A comparative photoreceptor was prepared in the same manner as in Example 1, except that .

G-(1) Regarding this comparative photoreceptor, measurements were performed in the same manner as in Example 1, and the results shown in Table 2 were obtained.

45- As is clear from the results in Table 2 and above, the photoreceptor of the present invention is extremely superior in sensitivity, residual potential, and repetition stability compared to the comparative photoreceptor.

As Example 2-4, 6-methyl-1-(1-ethyl-4
-carbazolyl)methylideneamino-1,2,3゜4-
Tetrahydroquinoline (for the following compound -(2)), 1-
(1-ethyl-4-carbazolyl)methylideneamino-
1,2,3,4-tetrahydroquinoline (compound K below)
-(3)), and 4,4'-methyl-4"-(4-chloro)-styryltriphenylamine (compound K below)
A photoreceptor of the present invention was prepared in the same manner as in Example 1 using (4)), and the same measurements were performed to obtain the results shown in Table 4.

-2 ■ 2H5 to -3 ■ 2H5 to -4 Table 3 Example 5 Vinyl chloride-vinyl acetate-
A 0.05 μm thick intermediate layer made of a maleic anhydride copolymer “S-LEC MF-10J (manufactured by Antisui Kagaku Co., Ltd.) was provided, and 2 g of Exemplified Compound A-(11) was added thereon at 1,2-
Mix 110 ml of dichloroethane and mix with a ball mill for 24 ml.
The time-dispersed dispersion was applied so that the film thickness after drying was 0.5 μl to form a carrier generation layer. In this carrier generation layer, 6 g of 3.3',4-)limethyl-triphenylamine and 1.0 g of methacrylic resin "Acrivet" (manufactured by Mitsubishi Rayon 48-) were added to 70 IT of 1.2-dichloroethane.
A carrier transport layer was formed by applying a solution dissolved in IQ so that the film thickness after drying was 10 μm, thereby producing a photoreceptor of the present invention.

When the same measurement as in Example 1 was carried out on this photoreceptor, the first error was 1 and E'A = 2.6 lux.
- Obtained the result of 5ecsVB=Ov.

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 so that the film thickness after drying was 1.3μI11, A carrier generation layer was formed.

Next, 49-6 g of 4-methoxy-4'-styryltriphenylamine (the following compound K-(5)) and a polyester resin [Vylon 200J (manufactured by Toyobo Co., Ltd.) Log] were added on top of it. A photoreceptor of the present invention was prepared by dissolving the carrier transport layer in 2 dichloroethane, 7 oTnQ, and applying this solution so that the film thickness after drying was 12 μm.

The same measurements as in Example 1 were performed on this photoreceptor, and the results shown in Table 4 were obtained.

Comparative Example 2 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-(2) 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 4.

G-(2) Table 4 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-7toxyphenyl)carbazole and 10 g of polycarbonate "Panlite L-1250J (manufactured by Ondai Kasei Co., Ltd.) were added to 1.2-dichloroethane 70TII.
A carrier transport layer was formed by coating a solution dissolved in Q so that the film thickness after drying was 10 μm, thereby producing a photoreceptor of the present invention.

This photoreceptor was measured in the same manner as in Example 1 until the film thickness of the 400□O1 disoluble MI-1 gauze was 13 μm, and E'A = 1.91ux-s.
ec and V, =Ov.

Example 8 A layer of vinyl chloride-vinyl acetate-maleic anhydride copolymer "S-LEC MP-10J (manufactured by Block Chemical Co., Ltd.) with a thickness of 0.0 mm was coated on the surface of an aluminum drum with a diameter of 100 mm.
An intermediate layer of 05μ[n is provided, and exemplified compound A-
(36) 4 g of 1,2-dichloroethane was mixed with 400 mQ of 1,2-dichloroethane, and a dispersion solution was dispersed for 24 hours using a ball mill dispersion machine, and then applied so that the film thickness after drying was Q, 6μi11.
A carrier generation layer was formed.

Furthermore, on top of this, 3(+)-methoxystyryl)-9-
(p-methoxyphenyl)carbazole (compound K below)
- (6)) and 50 g of polycarbonate resin [Kneepilon S-1000J (manufactured by Mitsubishi Gas Chemical Co., Ltd.)]
．． 2-dichloroethane 53--2 was applied to the sea urchin to form a carrier transport layer, and a drum-shaped photoreceptor was prepared.

The photoreceptor produced in this way is used in an electrophotographic copying machine rU.
- When the image was copied using a modified Bix 1600 M RJ (manufactured by Konishiroku Photo Industry Co., Ltd.), a copy image with high contrast, faithful to the original image, and clear was obtained. Moreover, this did not change even after repeating 10,000 times.

Comparative Example 3 A drum-shaped comparative photosensitive material was prepared in the same manner as in Example 8, except that the exemplified compound A-(36) was replaced with a bisazo compound (G-(3)) 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 is repeated, the contrast of the copied image decreases, and the copying is repeated 2000 times.Example 9: Vinyl chloride-vinyl acetate-
Maleic anhydride copolymer [Sure Nku M F-10
An intermediate layer with a thickness of 0.05 μIn made of J (manufactured by Sekisui Chemical Co., Ltd.) was provided, and on top of that, 5 g of exemplary compound A-(17) and 3.3 g of polycarbonate resin [Panlite L-12504 (manufactured by Yotaikasei Co., Ltd.) Add to 100 liters of dichloromethane,
A photoreceptor was prepared by applying a dispersion solution dispersed in a ball mill for 24 hours to a dry film thickness of 10 μm.

E% and VR of the photoreceptor obtained as described above were measured in the same manner as in Example 1 except that the charging voltage was changed to 16 Kv. The first result was E%” 2.2 lux·sec and VR=5V.

Example 10 6 g of p-N,N-diethylami/)benzaldehyde-1,1-diphenylhydrazone and 10 g of polyester resin ``Vylon 200 J (manufactured by Toyobo Co., Ltd.) were added as a carrier transport layer to a polyester film deposited with aluminum. 1,2-dichloroethane 70rnQ1.l
This solution was applied so that the film thickness after drying was 10 μm.

Next, 1 g of exemplified compound A-(12) and A-
-(14)1. and 1,2-dichloroethane 110,
A dispersion liquid was mixed with Q and dispersed in a ball mill for 24 hours, and the dispersion liquid was applied so that the film thickness after drying was 0.5 μm to form a carrier generation layer, thereby forming a photoreceptor of the present invention.

The photoreceptor thus obtained was evaluated in the same manner as in Example 9, and found to be E'A==2,41ux-see and vR=+5v.

Example 11 A 2% ethylenediamine solution of the exemplified compound Compound A-(10) was applied onto a polyester film laminated with aluminum so that the dry film thickness was 0.5 μm to form a carrier generation layer. .

Furthermore, 1-methyl 3-(
p-diethylaminophenyl)-5 to (p-diethylaminophenyl)pyrazoline (to the following compound -(7)),
1-phenyl(p-methoxystyryl)-5-(p-diethylami77yonyl)pyrazoline to the following compound -(8
), or 1-phenyl-(1)-methylstyryl)
-5-(p-methylphenyl)pyrazoline (compound K-(9) below) was separately added to 56-K-(7) K-(8) K-(9) resin (manufactured by Yodai Kasei Co., Ltd., Panrai) L-1250)
A solution prepared by dissolving 4g of L in 140ml of 1,2-dichloromethane was coated and dried to give a film thickness of 12μm after drying.
I got 7-.

These three types of photoreceptors are each manufactured by Denki Seisakusho Co., Ltd.
The following characteristics were evaluated using an electrostatic paper tester model 5P-428 manufactured by Kogyo Co., Ltd. Charged with a charging voltage of -6Kv for 5 seconds, and then
After leaving it for a second, turn on the halogen light until the material surface illuminance is 35 lu.
x, and the exposure amount required to attenuate the surface potential by half (half-reduction exposure amount, E%) was measured. or,
Surface potential after exposure with an exposure amount of 301ux-see (
Residual potential) VR was measured. As shown in Table 6, the results were good in combination with any carrier transporting substance.

Table 5 Comparative Example 4 Exemplary compound A-(10) was converted into the following bisazo compound (G
A comparison photoreceptor was made with the same length as in Example 11 except that G -(4)) was used, and the characteristics were evaluated.
4) As shown in Table 6, the results varied depending on the carrier transporting substance.

Table 6 Example 12 2 g of Exemplified Compound A-(2) and 1,2-dichloroethane Lo were placed on the conductive support provided with the intermediate layer used in Example 5.
om(l) was well dispersed and mixed, and the film thickness after drying was 0.3μ.
[n] to create a carrier generation layer.

Then, 4-methyl-4'styryl-triphenylamine (compound K below) was added as a carrier transport substance thereon.
-(10)) 6 g and polycarbonate [Panlite L
-1250J (manufactured by Ondai Kasei Co., Ltd.) K - (10) 10g was dissolved in 1,2-dichloroethane 90Fi and applied to form a carrier transport layer so that the film thickness after drying was 10μ. , a photoreceptor of the present invention was prepared.

For this photoreceptor, room temperature 6
The electrophotographic properties at 0- were measured in the same manner as in Example 1.

The results are shown in Table 17.

As is clear from the results in Table 7 and above, the electrophotographic photoreceptor of the present invention has good sensitivity and residual potential characteristics even at high temperatures;
It can be seen that it is stable against heat.

Example 13 2 g of Exemplary Compound A-(1) and 1,2-dichloroethane were placed on the conductive support provided with the intermediate layer used in Example 5.
A carrier generation layer was prepared by thoroughly dispersing and mixing WIQ and applying the mixture to a dry film thickness of 0.3 μm.

61- 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 30cfn away, and the lamp was turned on for 10 minutes at 15oo'cd/c/cm.
UV light of L was irradiated. Next, 7 g of 4-methoxy-4' = (4-methylstyryl)-triphenylamine (compound K - (11) below) and polycarbonate [ Panrye) L-1250] (manufactured by Ondai Kasei Co., Ltd.) (10 g) was dissolved in 90 g of 1,2-dichloroethane.

A photoreceptor of the present invention was prepared by applying liquid K-(11) to form a carrier transport layer such that the film thickness after drying was 12 μm.

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. The results are shown in Table 8.

As is clear from the results in Table 8 and above, the photoreceptor of the present invention
It can be seen that it has excellent sensitivity and residual potential characteristics to light irradiation, has small fluctuations in acceptance potential, and is stable to light.

Comparative Example 5 Compound A-(1) was converted into the following bisazo compound (G-(5
)) in the same manner as in Example 13 and Example 14 except that G
-(5) A photoreceptor was prepared, and the same measurements as in Example 5 were performed. The results are shown in Table 9.

As is clear from the results in Table 9 and above, the sensitivity and residual potential characteristics of the compounds prepared using the compounds listed in Table 2 are degraded by UV light irradiation, and the amount of variation in acceptance potential is large.

64-5 Example Ume In Example 5, exemplified compound A-(11) was converted to A-(
A drum-shaped photoreceptor was produced in the same manner except that step 3) was changed. The spectral sensitivity of this photoreceptor at 790 nm is 0.4
It was 2 μJ/i (half exposure amount). This photoreceptor of the present invention was subjected to an actual photographic test using an experimental machine equipped with a semiconductor laser (790 nm) that produced a laser beam intensity of 0.85+nW on the surface of the photoreceptor.

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 6 5 A comparative photoreceptor was obtained in the same manner except that the following Comparative Example bisazo compound was used in place of Exemplified Compound A-(3) in the Example frame.

H8C0NHCOOH 6ji6, -C:6H8 65- The spectral sensitivity of this photoreceptor at 790 nm is 8. Oll
, T/i (half exposure amount). Using this comparative photoreceptor, a photo-taking test using a semiconductor laser was conducted in the same manner as in the example frame, 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 combination with a wide range of carrier transport substances. It is something that

(Effects of the Invention) According to the present invention, by using an azo compound represented by the general formula [1] as a photoconductive substance constituting the photosensitive layer of a photoreceptor, the object of the present invention can be achieved by: Construction: 5 = Knee tightness, and less fatigue deterioration even after repeated use. H
It is possible to produce an excellent photoreceptor having sufficient sensitivity in a wavelength range of not less than 3 and even more than 780 cm.

[Brief explanation of drawings]

1 to 6 are sectional views showing examples of mechanical implantation of the photoreceptor of the present invention, and 1 to 7 in the figures represent the following, respectively. 1... Conductive support 2... Carrier generation layer 3... Carrier transport layer 4... Photosensitive layer 5... Intermediate layer 6 ...Layer 7 containing a carrier transport substance...
... Carrier-generating substance agent Patent attorney No 1) Father-in-law 68- Horse 1 Figure Island? evil y7y diagram muscle diagram

Claims (3)

[Claims] (1) A photoreceptor characterized by having a photosensitive layer containing an azo compound of the following general formula [I] on a conductive support. General formula [11 [In the formula, Q represents a substituted or unsubstituted benzene ring, an alkyl group, or an alkoxy group, and Yl and Y2 are each a hydrogen atom, /'% rogen atom, a cyano group, an alkyl group, or an alkoxy group. , m and n are both integers between 0 and 1 and 2, and A is R2R. 1, where 2 + is a group of atoms necessary to constitute a 1-substituted or unsubstituted aromatic R ring, or a substituted or unsubstituted aromatic polycyclic ring, and Y3 is a substituted or unsubstituted aromatic ring. A substituted carbamoyl group, or a substituted or unsubstituted sulfamoyl group, R1 is a hydrogen atom, a substituted or unsubstituted alkyl group, an amine 7 group, a substituted or unsubstituted amine 7 group, a substituted or unsubstituted sulfamoyl group, carbamoyl group,
Carboxyl group and its ester group or cyano group, A
' represents a substituted or unsubstituted aryl group, R2 and R3 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group. ] (2) The photosensitive layer contains a carrier transporting substance and a carrier generating substance, and the carrier generating substance is of the general formula [I
] The photoreceptor according to claim 1, which is an azo compound. (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.