JPS60176046A - Photosensitive body - Google Patents

Abstract

PURPOSE:To obtain a photosensitive body high in sensitivity, small in residual potential, and superior in durability by forming a photosensitive layer contg. an azo compd. represented by specified general formula on a conductive substrate to prepare a photosensitive body. CONSTITUTION:A photosensitive body is obtained by laminating on a conductive substrate 1 a photosensitive layer 4 consisting of a carrier transfer layer 3 composed essentially of a carrier transfer material and a carrier generating layer 2 composed essentially of an azo compd. represented by formula I in which Y1- Y4 are each H, halogen, cyano, or alkoxy; n1-n3 are each 0, 1, or 2; A is one of formula II-V; Z is an aromatic C ring; Q is carbamoyl or sulfamoyl; R1 is H, alkyl, amino, or the like; A' is aryl; and R2, R3 are each alkyl, aralkyl, or the like.

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 an azo compound.

(Prior Art) Conventionally, as electrophotographic photoreceptors, inorganic photoreceptors having a photosensitive layer mainly composed of photoconductive compounds such as selenium, zinc oxide, cadmium sulfide, and silicon 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, heat, fingerprints, etc. cause crystallization, which deteriorates its performance as a photoreceptor. In addition, cadmium sulfide has problems with moisture resistance and durability, and zinc oxide has problems with durability, etc.

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 G;ibo1J-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 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, 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 photoreceptors using organic dyes or organic pigments as carrier-generating substances have been proposed. For example, as a photoreceptor containing a bisazo compound or a trisazo compound in the photosensitive layer, JP-A-54-22834, JP-A-54
-46558 publication, JP-A-56-46237 publication,
JP-A-57-196241 and the like are already known. However, these bisazo compounds or trisazo compounds are not necessarily satisfactory in terms of sensitivity, residual potential, or stability during retightening use.
In addition, the selection range of gear transport substances is limited, etc.
It does not fully satisfy the wide range of demands of electronic imaging processes.

Furthermore, in recent years Ar laser, i(e
Gas lasers such as -Ne lasers and semiconductor lasers are beginning to be used. These lasers have a characteristic that they can be turned on and off in time series, and are particularly promising as light sources for copiers with image processing fronts, such as intelligent copiers, and printers for computer output. Among these, semiconductor lasers are attracting attention because their nature does not require an electrical signal/optical signal conversion element such as an acousto-optic element, and because they can be made smaller and lighter. However, this semiconductor laser has a low output compared to a gas laser, and the oscillation wavelength is also long (approximately 780 nm or more), so the spectral sensitivity of conventional photoreceptors is too high on the short wavelength side. 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 to 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 effectively act as a gear 9f generating substance even in combination with a wide range of carrier transport substances. The object of the present invention is to provide a photoreceptor containing an azo compound that has the following properties.

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 [I] can act as an active ingredient of a photoreceptor, and the present invention It is a completed invention.

In the above formula, Yl, Y2, Y3 and Y4 are groups selected from a hydrogen atom, a halogen atom, a cyano group, an alkyl group or an alkoxy group, and n, , n and n are integers of 0, 1 or 2, and - R4 is a hydrogen atom, a substituted/unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted/unsubstituted aralkyl group, 1i'i
Substituted/unsubstituted phenyl group, R6 is a hydrogen atom, substituted/unsubstituted alkyl group having 1 to 4 carbon atoms, substituted/unsubstituted aromatic carbocyclic group (for example, substituted/unsubstituted phenyl group, substituted/unsubstituted alkyl group) (un16-substituted nonaphthyl group, substituted/unsubstituted anthryl group, etc.), or substituted/unsubstituted aromatic heterocyclic group (such as substituted/unsubstituted carbazolyl group,
(substituted/unsubstituted dibenzofuryl group, etc.).

Substituents for these groups include, for example, substituted/unsubstituted alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group,
isopropyl group, tertiary butyl group, trifluoromethyl group, etc.), substituted/unsubstituted aralkyl group (e.g. benzyl group, phenethyl group, etc.), halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), carbon Substituted/unsubstituted alkoxy groups of numbers 1 to 4 (e.g. methoxy group, ethoxy group,
isopropyl group, tertiary butoxy group, 2-ritalyl ethoxy group, etc.), hydroxy group, substituted/unsubstituted aryloxy group (e.g., p-chlorophenoxy group, l-naphthoxy group, etc.), acyluo, oxy group, ( For example, acetyloxy group, p-cyanobenzoyloxy group, etc.), carboxyl group, its ester group (for example, ethoxycarbonyl group,
n-bromophenoxycarbonyl group, etc.), carbamoyl group (e.g., ami7carbonyl group, tertiary butyl ami/carbonyl group, ami/sulfonyl group, etc.), acyl group (e.g., acetyl group, 0-nitrobenzoyl group, etc.), sulfo group , sulfamoyl group (e.g. ami/sulfonyl group, 3
butylaminosulfonyl group, p-tolylaminosulfonyl group, p-tolylamino/sulfonyl group, etc.), amide 7 group, acylaminosulfonyl group (e.g., acetylamide 7 group, benzoylamif group, etc.), sulfonamide group (e.g., methanesulfonamide group, p-toluene group, etc.) sulfonamide group, etc.), cyano group, nitro group, etc., but preferably substituted/unsubstituted alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, isopropyl group, lobethyl group, trifluoromethyl 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, tertiary butoxy group, 2-chloroethoxy groups, etc.) cyano group, nitro group.

Z is an atomic group necessary to form a substituted/unsubstituted aromatic carbocycle or a substituted/unsubstituted aromatic heterocycle,
Specifically, it represents an atomic group forming 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 group forming these rings include a series of substituents such as those listed as substituents for R4 and R5, but halogen atoms (chlorine atom, bromine atom, fluorine atom, iodine atom), sulfo group, sulfamoyl group (e.g. aminosulfonyl group, p-tolylamine/
sulfonyl group, etc.).

R1 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or
Unsubstituted ami7 groups, carboxy groups, ester groups thereof, substituted/unsubstituted carbamoyl groups, and cyano groups, preferably hydrogen atoms, substituted/unsubstituted alkyl groups having 1 to 4 carbon atoms (for example, methyl groups, ethyl group, isopropyl group, tertiary butyl group, trifluoromethyl group, etc.), and sia/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 R4 and Rs. However, preferably halogen atoms (chlorine atom, bromine atom, fluorine atom, iodine atom), substituted or unsubstituted alkyl groups having 1 to 4 carbon atoms (for example, methyl group, ethyl group, isopropyl group, tertiary butyl group) , a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms such as a trifluoromethyl group (
For example, methoxy group, ethoxy group, isopropoxy group,
tertiary butoxy group, 2-chloroethoxy group).

R2 and R3 do not represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, but 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
An unsubstituted phenyl group IM represents a phenyl group, p-methoxyphenyl group, m-chlorophenyl group, etc.).

Among the Bodhisattva + Azo compounds represented by the general formula [I] used in the present invention, particularly preferred compounds are the following general formula [1] in terms of sensitivity and stability against heat and light.
r].

General formula [111] where A is the same as general formula [I] - Specific examples of the azo compound useful in the present invention represented by the above general formula [■] include those having the following structural formula. However, this does not limit the ~ azo compounds of the present invention.

2 characters ii having the structure of general formula [IV'] Other 13' CHs B - (63) B - (64> B - (65) ) 3- ((i6) The above azo compounds can be easily synthesized by known methods. Specific examples thereof will be shown below.

Synthesis Example 1 (Synthesis of Exemplary Compound B-(1)) α(.

That is, 2,7-sinitrofluorenone (manufactured by L-Kyo Kasei Co., Ltd.) was reacted with triphenylphosphine fluorenylidenide 2 to form a dinitroform, which was then reduced with iron to form a diamidium/depletion. .

(Journal of American Cbem
ical 5ociety! 69 +723 (1
947)) 435.8 g (0.1 mol) of this diamino compound was added and dispersed in a mixture of dissolved hydrochloric acid (11) and water (14), and 13.8 g (0.2 mol) of sodium nitrite was dissolved in water 0.947)). .14 was added dropwise at 5°C under cooling with water. After the addition, the reaction solution was filtered. To the filtrate was added 1/2% aqueous solution of ammonium phosphorus hexafluoride. The resulting precipitate was collected by filtration and washed with water. , thoroughly dried. The obtained salt was dissolved in 1.5 mm of N,N-dimethylformamide (DMF) to prepare a tetrazonium salt solution to be used in the next reaction.

Next, 2-hydroxy-3-(4-methoxy-2-methylphenylcarbamoyl)-benz[a]carbazole (naphthol As-8R, manufactured by Hoechst) 79.3
g (0.2 mol), triethanolamine ωg, 47
The tetrazonium salt solution prepared above was added dropwise to the solution dissolved in N,N-dimethylformamide and cooled with ice, and the mixture was further stirred for 2 hours to react. The resulting product was collected by filtration and the crystals were diluted with 5/N.

2 times with N-dimethylformamide and 2 times with 51 a7tons.
After washing twice and drying, the desired bisazo compound B-(
1) 53.3,! ? (45%). Melting point 30
0 or more, the Ml peak is shown at 1173 in the Fl)-MS spectrum, and 1670 in the infrared spectrum.
cm-+ (ami'1-=absorption)' peak, and elemental analysis shows that C=77.60%, N=9
．． 48%, H = 4.52% (calculated value is C = 77
．． 80%, N=9.55%, H=4.47%), it is understood 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 formed on a conductive support. Among the photoconductivity of the azo compound of the present invention, the particularly excellent carrier generation ability is used as a carrier generation substance, and a carrier transport material that can effectively act in combination with the photoconductivity of the azo compound of the present invention. Particularly excellent results can be obtained when a so-called functionally separated type photoreceptor is constructed by using it together with other substances. The functionally separated photoreceptor may be a dispersed type photoreceptor, but it is more preferably a laminated type photoreceptor in which a carrier generation layer containing a carrier-generating substance and a carrier transport layer containing a carrier transporting substance are laminated. .

Furthermore, the azo compound used in the present invention has the general formula [■]
The azo compounds represented by can be used alone or in combination of two or more, or 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. 1.1 to 6. In FIGS. 1 and 3, a small layered structure consisting 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 is shown. 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 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 Wi 4 in which the carrier generating substance 7 is dispersed in a layer 6 containing a carrier transporting substance as a main component is directly applied onto the conductive support 1. , or may be provided via an intermediate M5.

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 may include electron-accepting substances that easily transport electrons such as 6-inch trinitrofluorenone or tetranitrofluorenone, as well as boron IJ-N. - Polymers having a heterocyclic compound in the side chain, such as vinylcarbazole, triazole derivatives, mexadiazole derivatives, imidazole derivatives, etc.
Examples include pyrazoline derivatives, polyarylalkane derivatives, phenylenediamine derivatives, hydrazone derivatives, amino-converted chalcone derivatives, triarylamine derivatives, carbazole derivatives, stilbene derivatives, phenothiazine derivatives, and other electron-donating substances that transport holes easily. However, the carrier transport substances used in the present invention are not limited to these.

The carrier generation layer 2 constituting the two-layered photosensitive layer 4 may be formed directly on the conductive N-body 11 or the carrier transport layer 3, or on an intermediate layer such as a photosensitive layer or a barrier layer if necessary, for example. It can be formed 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 binder is added thereto if necessary, and a mixed and dispersed dispersion is applied.

Examples of the solvent or dispersion medium used for forming the carrier generation layer include n-butylamine, diethylamine, ethylenediamine, isopronylamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methylethylketone, cyclohexanone, Benzene, toluene, xylene, chloroform, 1,2-dichloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol,
Examples include inpropatol, ethyl acetate, butyl acetate, dimethylforpogicide, and the like.

When using a binder in the carrier generation layer or 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 the following:
It is not limited to these.

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 F resin p-1
6) Styrene-alkyd resin p-17) Poly-N-vinylcarbazole These binders can be used alone or in a mixture of two or more.

The thickness of the carrier generation layer 2 formed in this way is
It is preferably 0.01 μm to 20 μm, more preferably 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,
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. Ti? As an intermediate layer such as a bonding layer or a barrier layer, in addition to the polymer used as the binder, organic polymer substances such as polyvinyl alcohol, ethyl cellulose, and carboxymethyl cellulose, or aluminum oxide are used.

The photoreceptor of the present invention has the above-described 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 when used repeatedly. It has little deterioration and excellent durability.

The present invention will be specifically explained below using Examples, but the embodiments of the present invention are not limited thereto.

(Example) Example 1 Exemplary compound B- (1012 g and polycarbonate resin [
Panlite I, -1250J (manufactured by Kijin Kasei Co., Ltd.) 29tf
1:1,2-dichloroethane was added to 110+++ liters, and the mixture was 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 layer, and on top of this a carrier transport layer was formed using 4-methoxy-4
'-(4-methoxy)styryl-triphenylamine (
The following structural formula K-(1)) 6.9' is a polycarbonate resin [Panlite L-1250j10g2 is 1,2-
Dichloroethane 110m7! A carrier transport layer was formed by applying a solution dissolved in water so as to have a dry film thickness of 15 μm, thereby producing a photoreceptor of the present invention.

K-(1) The photoreceptor obtained as described above was subjected to the following temporal evaluation using an electrostatic paper tester model 5P-428 manufactured by Gekka Denki Seisakusho. After charging with a charging voltage of -6 KV for 5 seconds, leave it in the dark for 5 seconds, then irradiate with halogen lamp light so that the illumination intensity on the photoreceptor surface is 351 ux, and the amount of exposure required to attenuate the surface potential by half. (Half exposure ft) E
Achieved %. In addition, the surface potential (residual potential) VR after exposure with an exposure amount of 301 ux-see was measured. Further, similar measurements were repeated 100 times with 9 repetitions. The results are shown in Table 1. Table 1 Comparative Example 1 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) This comparative photoreceptor was measured in the same manner as in Example 1, and the results shown in Table 2 were equal.

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.

Example 2-4 Exemplary compounds B-01) and B-0 as carrier generating substances
2) and B-(131) and 1-[4-(N, N-di(p-tolyl)) as carrier transport substances, respectively.
amino) benzylidene-aminocoindoline (compound K-(2) below), 4,4'-dimethyl-4"-(
4-methi)styryl-triphenylamine (the following compound -(3)), and 4-methyl-4'-(4-chloro)-styryl-triphenylamine (the following compound K
-(4)), and in the same manner as in Example 1, a photoreceptor of the present invention was prepared, and the same measurements were carried out.
The results shown in the table were obtained.

K-(2) K-(3) K-(4) Table 3 Example 5 Aluminum 9i on polyester film! A vinyl chloride-vinyl acetate-maleic anhydride copolymer [S-LEC MF-1
0J (manufactured by Tanezu Kagaku Co., Ltd.) with a thickness of 005 μm was provided, and exemplified compound B-(512,9 was added at 1,2
- Mix with 110 m/dichloroethane and use a ball mill to
A dispersion solution dispersed for 4 hours was coated to a film thickness of 0.5 μm after drying to form a carrier generation layer. On this carrier generation layer, 6 g of 4-medylene triphenylamine and methacrylic resin 1-Acrybet' (manufactured by Mitsubishi Raymin Co., Ltd.)'10fI were added to 70 m of 1,2-dichloroethane.
A carrier transport layer was formed by applying a solution dissolved in 1 to form a carrier transport layer so that the film thickness after drying was 10 μm, and the photoreceptor of the present invention was prepared. The same measurements as in Example 1 were performed on this photoreceptor. However, for the first time, E% = 2゜O1ux-s
ee.

The result was VR=OV.

Example 6 On the conductive support provided with the intermediate layer used in Example 5, a 1% ethylenediamine solution of Exemplary Compound B-(251) was applied so that the film thickness after drying was 0.3 μm, and the carrier A generation layer was formed.

Then on top of that, 3-(p-methoxystyryl)-9-
Dissolve 6 g of ('p-methoxyphenyl)carbazole (compound K-(5) below) and polyester Ishiba "Pylon 200J (Toyobo Co., Ltd. 1 (L9)" in 70 ml of 1,2-dichloroethane, and dry this solution. A carrier transport layer was formed by coating the film to a film thickness of 12 μm, thereby producing a photoreceptor of the present invention.

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 B-(25) was replaced with bisazo compound G-(2) represented by the following structural formula.

The same measurements as in Example 1 were carried out on this photoreceptor, and the results are shown in Table 4.

G-(2) Example 7 In Example 5, Exemplified Compound B-(5) was replaced with Exemplified Compound B
A carrier generation layer was formed in the same manner except that -C31)) was used. On top of this, 6 g of p-(N+ N-diethylamino)benzaldehyde-1,1-diphenylhydrazone (compound -(6)) and 10 g of polycarbonate [Panlite L-12504 (manufactured by Kijin Kasei Co., Ltd.) were added.
, 2-dichloroethane (70 ml) was applied to form a carrier transport layer so that the film thickness after drying was 10 μm, thereby producing a photoreceptor of the present invention.

Regarding this photoreceptor, measurements were performed in the same manner as in Example 1, and E54=2. O1ux-sec and VR=
It was OV.

Example 8 A 0.05μ thick film made of vinyl chloride-vinyl acetate-maleic anhydride copolymer [S-LEC MP-10J (manufactured by Rusui Kagaku Co., Ltd.)] was coated on the surface of an aluminum drum with a diameter of 100 mm.
A 7n intermediate layer is provided, and exemplified compound B-(2n4
fl into 400 ml of 1,2-dichloroethane,
A carrier-generating layer was formed by applying a dispersion solution that had been dispersed in a ball mill disperser for a while to give a film thickness of 0.6 μm after drying.

Furthermore, on top of this, 30 g of p-(N,N-diethylamide/)benzaldehyde-1,1-diphenylhydrazone (the following compound K-(6)')' and polycarbonate resin [-Corbilon S-1000J (Mitsubishi Gas Chemical A drum-shaped photoreceptor was prepared by dissolving 50 g of 1,2-dichloroethane K-(6) in 400 ral of 1,2-dichloroethane K-(6) and applying the solution to a film thickness of 13 μm after drying to form a carrier transport layer. .

The photoreceptor produced in this way was used in the electrophotographic copying machine "U-
When I installed it on a modified BIx1600MRJ (manufactured by Konishi Rokushado Kogyo Co., Ltd.) and copied the image, I was able to print a clear copy with high contrast and faithfulness to the original. Moreover, this did not change even after repeating 10,000 times.

Comparative Example 3 A drum-shaped comparative photoreceptor was produced in the same manner as in Example 8, except that exemplified compound B-(2η in Example 8 was replaced with a bisazo compound (G-(3)) represented by the following structural formula. When the copied image was #P-valued in the same manner as in Example 8, only images with many capri were obtained.
As copying was repeated, the contrast of the copied image decreased, and after 2000 repetitions, hardly any copied image could be obtained.

G-(3) Example 9 Vinyl chloride-vinyl acetate-maleic anhydride copolymer [S-LEC MF-10J
(manufactured by Katsusui Kagaku Co., Ltd.) with a thickness of 0.05 μm was provided, and on top of that an intermediate layer consisting of exemplified compound B-(1615,9) and polycarbonate resin “Panlite L-1250J (Kijinka Gasha!') 3.3 N and dichloroethane】00
In addition to M1, a dispersion liquid dispersed for another time using a ball mill was applied so that the film thickness when dried was 10 μm to prepare a photoreceptor.

The photoreceptor obtained as above was charged with a voltage of -4-6x.
E3A and VR were measured in the same manner as in Example I except that v was used instead. The first result was E%=2.11 ux-sec and VR=+6V.

Example 10 As a carrier transport layer on a polyester film deposited with aluminum, 6 g of 4-methoxy-4'-sudilylutriphenylamine and 10 g of a polyester resin [Vylon 200J (manufactured by Toyobo Co., Ltd.) were mixed at 1.2-g. It was dissolved in 70 ml of dichloroethane, and this solution was applied so that the film thickness after drying was 10 μm.

Next, exemplified compound B-(8)1. ! it and B
-(9) 1.9 and 1,2-dichloroethane 110ml
A dispersion liquid was mixed with the following materials and dispersed in a ball mill for U time, and the dispersion liquid was coated so as to have a dry film thickness of 05 μm to form a carrier generation layer, thereby forming a photoreceptor of the present invention.

The thus obtained photoreceptor was evaluated in the same manner as in Example 9, and the results showed that E%=2.31ux-see and VR
= +5V.

Examples] A 2% ethylenediamine solution of Exemplified Compound 13-(3) was applied onto a polyester film laminated with aluminum to a dry film thickness of 05 μm to form a carrier generation layer. Furthermore, carrier transport f
(j is 6-methyl-1-(l-ethyl-4-carbazolyl)methylideneamino-1,2,3,4-tetrahydroquinoline (compound K-(7) below), 4-methyl-47-styryl-tri Approximately 10 g of each of phenylamine (compound below - (8)) or 4-methoxy-triphenylamine (compound K - (9) below) and polycarbonate resin (manufactured by Yudai Kasei Co., Ltd. (Panlite L- A solution of 14 g of 1250) K-(9) dissolved in 140 ml of 1,2-dichloroethane was coated and dried to give a dry film thickness of 12 μm. Obtained.

These three types of photoreceptors are each made by Rodenki Seisakusho 5P.
The following characteristics were evaluated using a -428 type electrostatic paper tester. Charged to -6'V for 5 seconds, and then
After leaving it in the dark for a few seconds, turn on the halogen light until the material surface illuminance is 351u.
x, and the exposure amount required to attenuate the surface potential by half (half-reduction exposure amount, E3A') was measured.

In addition, the surface potential (residual potential) VR after exposure at an exposure amount of 301ux-see (7) was measured. As shown in Table 5, the results were good in combination with any carrier transport substance.

Table 5 Comparative Example 4 “Illustrated compound B-(3) was mixed with the following bisazo compound (G-(
4) Photoreceptors were prepared using fil (Comparative 11) in the same manner as in Example 11, and the characteristics were evaluated. As shown in Table 6, results varied depending on the carrier transport material.

G-(4) Table 6 Example 12 Exemplary compound B-(2) 29 and 1,2-dichloroethane 10 were placed on the conductive support provided with the intermediate layer used in Example 5.
(1+J was well dispersed and mixed, and the film thickness after drying was 0.3 μm.
A carrier-generating layer was created by applying the following coating to form a carrier-generating layer.

Then, 1-(1-ethyl-4-carbazolyl)methylidene amide/-1,2,
3,4-tetrahydroquinoline (compound K -QO below)
I) 6 g and 1 polycarbonate Panlite L-12
A carrier transport layer was formed by dissolving 10 g of 50J (manufactured by Ondai Kasei Co., Ltd.) in 1,2-dichloroethane 90F so that the film thickness after drying was 10 μm. Created.

The electronic imaging characteristics of this photoreceptor at room temperatures of 5° C. and α)° C. were measured in the same manner as in Example 7.

The results are shown in Table 7.

As is clear from the results in Table 7 onwards, the 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 B-(1) and 110 g of 1,2-dichloroethane were placed on the conductive support provided with the intermediate layer used in Example 5.
A carrier-generating layer was prepared by thoroughly dispersing and mixing the mixture with m1 and applying the film to a thickness of 0.3 μm after drying.

In order to test the durability of this carrier generation layer against UV light, an ultra-high pressure mercury lamp (manufactured by Tokyo Shibaura↑η1ki Co., Ltd.) was placed 30 crn away, and 1500 cd UV light was irradiated for 10 minutes. Next, 1-phenyl-(p-methylstyryl)-5-(p-methylphenyl)pyrazoline (compound K-011 below)) 7 was added as a carrier transport substance onto this gear generation layer that had been irradiated with UV light.
g and 10 g of polycarbonate [Panrye L-125o'' (manufactured by Ondai Kasei Co., Ltd.), 90 g of 1,2-dichloroethane
A photoreceptor of the present invention was prepared by applying a solution dissolved in I to form a carrier transport layer such that the thickness of the dried film K-(I11 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 16 photons of the present invention have excellent sensitivity and residual potential characteristics to UV light irradiation, have small fluctuations in acceptance potential, and are stable to light. It can be understood.

Compound B-(1) was converted into the following hisazo compound CG-(5
)) A photoreceptor was prepared in the same manner as in Example 13 and Example 14, except that 1)), and the same measurements as in Example 5 were carried out.

The results are shown in Table 9.

G-(5) Table 9 As is clear from the results shown above, the sensitivity and residual potential characteristics of the photoreceptor prepared using the above compound deteriorate due to UV light irradiation, and the fluctuation U of the acceptance potential is large.

Example 14 In Example 5, exemplary compound B-(5) was replaced with B-(6
) A drum-shaped photoreceptor was produced in the same manner except that The spectral sensitivity of this photoreceptor at 790 nm is 03
It was 7 μJ/c (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) which produced a laser light intensity of 0.85 mW on the surface of the photoreceptor.

After the surface of the photoreceptor was charged to 16 KV, it was exposed to laser light and reverse development was carried out at a bias voltage of 1250 volts, and a good image without fog was obtained.

Comparative Example 6 A comparative photoreceptor was obtained in the same manner as in Example 14, except that the following comparative bisazo compound was used in place of Exemplified Compound B-(6).

The spectral sensitivity of this photoreceptor at 790 nm is 92μ.
:J/crl (half-reduced exposure amount). Using this comparative photoreceptor, a photo-taking test using a semiconductor laser was conducted in the same manner as in Example 14, but there was a lot of fog and good images could not be obtained.

As is clear from the results of the above Examples and Comparative Examples, the photoreceptor of the present invention has better characteristics such as stability, sensitivity, durability, and combination with a wide range of carrier transport substances than the comparative booklet 4-child photoreceptor. It is extremely superior in terms of performance.

(Effects of the Invention) By using the azo compound represented by the general formula [I] as a photoconductive substance constituting the photosensitive layer of a photoreceptor according to the present invention, It is stable, has excellent electronic properties such as charge retention, sensitivity, and residual potential, and has little fatigue change even after repeated use, and has sufficient sensitivity even in the long wavelength region of 780 nm or more. It is possible to create a photoreceptor with

[Brief explanation of the drawing]

1 to 6 are cross-sectional views showing practical examples of the photoreceptor of the present invention, and 1 to 7 in the figures represent the following, respectively. ■... Conductive support, 2... Carrier generation layer, 3... Gear transport layer, 4... Photosensitive layer, 5... - Intermediate layer, 6... Layer containing a carrier transport substance -7...
... Gearia generated substances. Horse 1st muscle 2nd muscle 5th muscle diagram

Claims (3)

[Claims] (1) A photoreceptor comprising a photosensitive layer containing an azo compound represented by the following general formula CI) on a conductive support. General formula [I] [In the formula, Y5, ¥2, Y8, and ¥4 represent hydrogen, an atom, a halogen atom, a cyano group, an alkyl group, or an alkoxy group, ni, n2, and ns represent 011 or 2, and A represents Here, Z is a substituted or unsubstituted aromatic heterocycle, or a group of atoms necessary to constitute the substituted or unsubstituted aromatic heterocycle, and Q is a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted aromatic heterocycle. An unsubstituted sulfamoyl group, R is a hydrogen atom, a substituted or unsubstituted alkyl group, an irt-substituted or unsubstituted amyl group, a substituted or unsubstituted carbamoyl group, a carboxyl group and its Nisder group or sia/group, A ' represents a substituted or unsubstituted aryl group, R,, ns represents 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 〇)
The photoreceptor according to claim 1m, which is an azo compound represented by: (3) The photoreceptor according to claim 1 or 2, wherein the photosensitive layer is constituted by a laminate of a carrier-generating layer containing a carrier-generating substance and a carrier-transporting layer containing a carrier-transporting substance. . ′