JPS60196770A - Photosensitive body - Google Patents

Abstract

PURPOSE:To obtain high sensitivity, low residual potential and excellent durability by providing a photosensitive layer contg. a specific azo compd. on a conductive base. CONSTITUTION:A photosensitive layer 4 contg. the azo compd. expressed by the formula I [Y1, Y2 are respectively alkyl, alkoxy, halogen, etc., l is 0, 1, m and n are 0-3. A is the formulas II, III, IV or V (Z is an arom. ring or heterocycle, Q is carbamoyl, sulfamoyl, R1 is H, alkyl, amino, carbamoyl, etc., A' is aryl, R2, R2 are alkyl, aryl, etc.)] is provided on a conductive base 1. A carrier transfer material (CTM) and carrier generating material (CGM) are incorporated into the layer 4 and the azo compd. expressed by the formula I is used as the CGM. The layer 4 may be the laminate of a charge generating layer 2 contg. the CGM and a charge transfer layer 3 contg. the CTM. Such azo compd. as the CGM is stable with heat and light and acts effectively as the CGM in a wide range of combination with the CTM, by which the photosensitive body having high sensitivity, low residual potential and excellent durability is obtd. and such photosensitive body is usable for a long wavelength light source such as a semiconductor laser 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 photoreceptor M containing a specific azo compound.

(Prior art) Conventionally, as a photoreceptor, the Kuroiso photoreceptor, which has a photosensitive layer mainly composed of photoconductive compounds such as selenium, zinc oxide, cadmium sulfide, and silicon, has been widely used. , these are not necessarily inferior in terms of sensitivity, thermal stability, moisture resistance, durability, etc. For example, when selenium crystallizes, its properties as a photoreceptor deteriorate, so it is difficult to manufacture. Also, heat, fingerprints, etc. cause crystallization, which deteriorates the performance as a photoreceptor. Cadmium sulfide also has problems with moisture resistance and durability, and zinc oxide has problems with durability, etc.

In recent years, research and development have been actively conducted on organic photoreceptors having a photosensitive layer containing a photoconductive compound as a main component to overcome these drawbacks of the Kuroiso photoreceptor. For example, Japanese Patent Publication No. 1983-00433 describes an organic photoreceptor having a photosensitive layer containing poly-N-vinylcarbazole and 2,4,7-)linitro-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. For such a flexible 8V type photoreceptor, various materials can be selected from a wide range, and a photoreceptor with arbitrary performance can be produced relatively easily40, so much research has been carried out. It was done well.

A large number of compounds have been proposed as carrier-generating substances for such (geometrically separated) type photoreceptors.

An example of using a Kuroiso compound as a carrier generating substance is the amorphous selenium described in Japanese Patent Publication No. 16198 (1978), which is used in combination with the Kuroiso conductive compound. The drawback that the carrier generation layer consisting of the above crystallizes due to heat and deteriorates the characteristics as a photoreceptor has not been improved.

Many photoreceptors have also been proposed that use growth dyes or organic pigments as carrier-generating substances. For example, as a photoreceptor containing a bisazo compound in the photosensitive layer,
No. 22834, JP-A-54-46553, 1
．． 4 Publication No. 56-46237, Japanese Patent Publication No. 58-1989]
No. 9940333 is already known. However, these bisazo or trisazo compounds have poor sensitivity,
It does not necessarily satisfy the characteristics of residual potential or stability during repeated use, and it sufficiently satisfies the wide range of requirements of electrophotographic processes, such as the range of selection of carrier transport materials. isn't it.

Furthermore, in recent years, lIr laser, 1i
Gas lasers such as e-Ne lasers and semiconductor lasers are beginning to be used. These lasers are characterized by the ability to be turned on and off in chronological order, making them ideal for image processing applications such as intelligent copiers. It is particularly promising as a light source for copying and computer output printers with +i capability. Among these, semiconductor lasers are attracting attention because their nature does not require an electrical signal/optical signal conversion element such as a trM optical element, and they can be made smaller and lighter. However, this semiconductor laser has a low output compared to a gas laser, and its oscillation wavelength is long (approximately 780 nm or more), so the spectral sensitivity of conventional photoreceptors is on the opposite side of the short wavelength spectrum. In this state, 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 stress 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 be effectively used as a carrier photobiomaterial 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.

((lηJ and of the invention) The present invention has achieved the above objects (as a result of extensive research, it has been found that the azo compound inertia '4 expressed by the following general formula [1])
The present invention was completed by discovering that it can act as an active ingredient in photoreceptors.

General formula CI) In the formula, y+ and Y2 are each selected from an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, or a hydroxy group, 9 is an integer of 0 or 1, and n is 0-3 (however, both integer and n are not O), A is R2Rs1H, Q is a substituted/unsubstituted carbamoyl group to 4 substituted/unsubstituted alkyl groups, and a substituted/unsubstituted 7-ralkyl group, a substituted/unsubstituted phenyl group, R1 is a hydrogen atom, a substituted/unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted/unsubstituted aromatic carbocyclic group (e.g. substituted or unsubstituted phenyl group, substituted or unsubstituted heptyl group, substituted or unsubstituted anthryl group, etc.), or substituted or unsubstituted aromatic polycyclic group (e.g. substituted or group, substitution/
(unsubstituted dibenzofuryl group, etc.).

Substituents for these groups include, for example, substituted or unsubstituted alkyl groups having a carbon number of ~4 (e.g., methyl group, ethyl group,
Isopropyl crystal, tertiary butyl crystal, tri7fluoromethyl group! ! p), substituted/unsubstituted aralkyl convex (e.g. benzyl group, 7enethyl group, etc.), halogen atom (chlorine atom,
Bromine atom, fluorine j≦(child, iodine atom), substituted/unsubstituted alkoxy group having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group, isopropoxy group, tertiary butoxy group, 2-chloroethoxy group, etc.) , hydroxy group, substituted/unsubstituted aryloxy group (e.g., p-chlorophenoxy group, 1-
7-toxy group, etc.), acyloxy group (e.g., acetyloxy group, p-cyanobenzoyloxy group, etc.), carboxyl group, ester thereof (e.g., ethoxycarbonyl group, lff-bromophenoxycarbonyl group, etc.)
, carbamoyl group (e.g. ami7carbonyl group, tertiary butylaminocarbonyl group, anilinocarbonyl group, etc.),
Acyl group (e.g. acetyl group, 0-nitrobenzoyl group, etc.), sulfo group, sulfamoyl JI! i (for example,
Ami 7/L, t, =L Q, 31 butyl amide/sulfonyl 4, p-tolylami/sulfonyl group, etc.), ami 7
group, acylamide/J', (e.g., 7 acetylamide groups, 7 benzoylamide groups, etc.), sulfonamide convex (e.g., methanesulfonamide group, p-toluenesulfonamide group, etc.), cyano group, di10 group, etc. Substituted/unsubstituted alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, isopropyl group, 11-butyl group, trifluoro, /thyl!+N%), halogen atoms (chlorine atoms) , bromine atom, fluorine atom, iodine atom), substituted or unsubstituted alkoxy L having 1 to 4 carbon atoms! ζ (for example,
Methoxy group, methoxy 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 Kung Group 6 heterocycle, specifically, for example, a substituted/unsubstituted benzene ring, a substituted・
unsubstituted 7tane ring, substituted/unsubstituted indole ring,
Atom If forming a substituted/unsubstituted carbazole ring, etc.
As the substituents for the atomic group forming these rings in Table 4, a series of substituents such as those listed as substituents for It < and It s are listed, but preferably it is f- (chlorine atom, bromine atom, fluorine atom f, iodine atom)
, sulfo group, sulfamoyl group (e.g. ami7 sulfonyl g, p -l tsurami/sulfonyl group'='j'
) There is T'.

R1 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or
Unsubstituted amino groups, carboxyl groups, their ester crystals,
Substituted/unsubstituted carbamoyl groups, sia/ranium, preferably hydrogen atoms, carbon fli1...4 substituted/unsubstituted alkyl groups (e.g., methyl group, ethyl group, isopropyl group, tertiary butyl group) (, trifluoromethyl group, etc.)・
, is a cyano group.

8' is a substituted or unsubstituted 16-substituted aryl group, preferably a substituted or unsubstituted 7enyl L (and examples of substituents for these groups include a series of substitutions such as R The group is preferably a halogen atom (
chlorine atom, bromine atom, fluorine atom f, iodine atom T-), substituted or unsubstituted alkyl group having 1-4 carbon atoms (e.g. methyl group, ethyl group, isopropyl group, tertiary bunal group, trifluoro methyl group, etc.), substituted/unsubstituted alkoxy groups having 1 to 4 carbon atoms (e.g.))oxy group, ethoxy group, impropoxy group, tertiary butoxy group, 2-chloroethoxy group)
It is.

1 (2 and R1 are substituted/unsubstituted alkyl groups, substituted/
It represents unsubstituted aralkyl (16) and substituted/unsubstituted aryl groups, but preferably substituted/unsubstituted alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, isopropyl group, tertiary butyl group) , trifluoromethyl group h+)
, substituted/unsubstituted phenyl group (e.g., phenyl group, p
-methoxyphenyl group, m-chlorophenyl group, etc.).

Among the azo compounds represented by the general formula [1] used in the present invention, particularly preferred compounds are Q=1, that is, the following general formula ( It has the structure shown in II).

General formula [11] In the formula, Yl', CI' and Y2' are groups selected from an alkyl group or a halogen atom, and A, It1 and the group are the same as in general formula [1].

Specific examples of the bisazo compound useful in the present invention represented by the general formula [1] include those having the following (1°4 formula, but the bisazo compound of the present invention is limited by this) It's not a thing.

Those represented by the general formula [■] in general formula (1).

General formula (ll[) CN (The number of the substituent represents the position on the mother nucleus) The following general formula (
5).

General Formula The azo compound as described above can be synthesized by a known method, for example, the method shown in the following synthesis example.

27.2 g (0.1 mol) of luorenone were dispersed in concentrated hydrochloric acid 19, the dispersion was cooled to a temperature of 5° C. with stirring, and 13.8 g of sodium nitrite was added. (0.2 mol)
An aqueous solution of 200 liters of water was added dropwise.

After the dropwise addition was completed, stirring was continued under cooling for an additional hour, and then filtration was performed to obtain hexafluoride in the resulting filtrate.

The crystals were dissolved in N,N-dimethylformamide 59.
A dropping solution (D) for the next coupling reaction was obtained.

2-Hydroxy-3-(4-methoxy-2-methylphenylcarbamoyl)-benzo[a) Carbazole (Cabutol AS-3R) 78 g (0.2 mol) with
Dissolved in 2.59% of N-methylformamide, added 62% of triethanolamine, and heated the solution to 5°C.
While stirring vigorously, add the above-mentioned dropping solution (
D) was added dropwise. After the dropwise addition was completed, the mixture was stirred for 1 hour under cooling, and further stirred for 2 hours at room temperature, and the resulting crystals were collected by filtration. The crystals were washed three times with N,N-dimethylformamide (No. 19), twice with water (No. 19), and twice with acetone (No. 19), and then dried to obtain a black compound 38.0° (yield 35%). .

This black compound shows that in its infrared absorption spectrum, absorption due to the C=0 concentration of amide is observed at beam=1680C-1, and in elemental analysis, the actual value (C=73.99%, N= 12.87%, H=4
．． 32%) is the theoretical value (C=74.02%, N=12.
89%, H=4.27%), and it was confirmed to be the target exemplary compound B-(1).

The azo compound of the present invention has excellent photoconductivity, and when an electrophotographic 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 possessed by the azo compound of the present invention, the azo compound of the present invention can be used as a carrier-generating substance by utilizing the carrier-generating ability that is more
By using it together with a carrier transporting substance that can effectively act in combination with this, particularly excellent results can be obtained when a so-called functionally separated photoreceptor is constructed. 1. The function-separated photoreceptor may be a dispersion type photoreceptor, but it is more preferably a laminated type photoreceptor in which a carrier generation layer containing a carrier generation substance and a carrier transport layer containing a carrier transport substance are laminated. .

Further, the azo compound used in the present invention has the above general formula [l]
The azo compounds represented by can be used alone or in combination of two or more, 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. 1rM and FIG. 3, the conductive support 1 is made up 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. A photosensitive layer 4 is provided. As shown in FIGS. 2 and 4, this photosensitive No.
You can also get it through . In this way, when the photosensitive layer 4 has an m:layer structure, 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 a layer 6 mainly composed of a carrier-transporting substance is formed on the conductive support 1. It may be provided directly or 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 is an electron-accepting substance that easily transports electrons, such as trinitrofluorenone or tetranitrofluorenone.
Polymers having a side chain of a heterocyclic compound such as poly-N-vinylcarbazole, triazole derivatives, oxanoazole derivatives, imidazole derivatives, pyrazoline derivatives, polyarylalkane derivatives, phenylenenoamine derivatives, Examples include electron-donating substances that easily transport holes, such as hydrazone derivatives, amino-substituted chalcone derivatives, triarylamine derivatives, carbazole derivatives, stilbene derivatives, and 7-7-thianone derivatives.
The carrier transport substance used in the present invention is not limited to these.

The carrier generation layer 2 constituting the two-layer photosensitive layer 4 is directly on the conductive support 1 or the carrier transport layer 3.
Alternatively, it can be formed, for example, by the following method, after providing an intermediate layer such as an adhesive layer or a barrier layer as required.

M-1) A solution of an azo compound dissolved in a suitable solvent,
Or, if necessary, add a binder and apply a mixed solution.

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 if necessary to mix and disperse the resulting dispersion and then applied.

Examples of the solvent or dispersion medium used for forming the carrier generation layer include I+-butylamine, diethylamine, ethylenenoamine, inpropaturamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methyl ethyl ketone, and cyclohexane. 7, benzene, toluene, xylene, chloroform, 1,2-dichloroethane, nochloromecne, tetrahydro 7, nooxane, methanol, ethanol,
Examples include isopropyl, ethyl acetate, butyl acetate, and trimethyl sulfoxide.

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>Silicon resin P-14) Silicone-alkyd resin P-1,5) Phenol-formaldeside resin P-16) Styrene-alkyd resin I)-171 Poly-N-vinylcarbazole These binders can be used alone or as a mixture of two or more.

The thickness of the carrier generation layer 2 formed in this way is
The thickness 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 dispersion system, the particle size of the azo compound is preferably 5 μm or less, more preferably 1 ui 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 and plastic films that have been made conductive by coating, vapor depositing, or laminating thin films of metals such as aluminum, palladium, and gold containing conductive compounds and alloys such as indium oxide. As an intermediate layer such as an adhesive or a 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 below, it has excellent electrical characteristics, sensitivity characteristics, and image forming characteristics, especially when used repeatedly. It also has less fatigue 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 2 g of Exemplary Compound B-(1B) and polycarbonate resin [
Panlite L-1250J (manufactured by Ondai Kasei Co., Ltd.) 2g and 1
, 2-dichloroethane 110-, and in a ball mill add 1
Dispersed for 2 hours. This dispersion was applied onto a polyester film on which aluminum had been vapor-deposited so that the film thickness after drying would be 1 μm to form a carrier generation layer, and further on top of this,
As a carrier transport layer, 4.4′-methyl-4″-(4
-chlor)-styryl-triphenylamine (in the following Mizozo formula-(1)) 6Fi polycarbonate resin RFRT [Panlite L-1250] 10g was dissolved in 1,2-dichloroethane 110- and the solution was dried. A carrier transport layer was formed by coating to a thickness of 15-1, thereby producing a photoreceptor of the present invention.

K-(1) The photoreceptor obtained as described above was subjected to the following characteristic evaluation using a new model SP-428 Seiden paper tester manufactured by Kawaguchi Electric Co., Ltd. After being charged for 5 seconds at a charging voltage of -6KV, it was left in the dark for 5 seconds, and then the illuminance on the surface of the photoreceptor was set to 35KV.
The halogen lamp light was irradiated so as to give a lux, and the exposure amount (half-reduced exposure amount) required to attenuate the surface potential by half was determined. In addition, the surface potential (residual potential) VR after exposure with an exposure amount of 301 ux-sec was determined. Further, similar measurements were repeated 100 times. 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) Regarding this comparative photoreceptor, measurements were performed in the same manner as in Example 1, and the results shown in Table 2 were obtained.

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 B-(8), -(9) as carrier-generating substances
) and B-(10), and 6-methyl-1-(1-phenyl-4-
carbazolyl) methylideneamino-1゜2.3.4-tetrahydroquinoline (for the following compound -(2)), 1-(
1-722-4-carbazolyl)methylideneami/-
1,2,3,4-tetrahydroquinoline (compound K below)
-(3)), and 4,4'-trimethyl-4#-(4
-Methyl)styryl-triphenylamine (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. (2) K-(4) Table 3 Example 5 Conductive support made of polyester film laminated with aluminum foil Second, vinyl chloride-vinyl acetate-maleic anhydride copolymer M P -10
J (manufactured by Antisui Kagaku Co., Ltd.) with a thickness of 0.05 μm was provided, and 2 g of Exemplified Compound 13-(15) was added thereon.
. On this carrier generation layer, 6 g of 4-methyl-4'-styryrotriphenylamine and 108 g of methacrylic resin "7Clipets" (manufactured by Mitsubishi Rayon Co., Ltd.) were added to 70 g of 1,2-nochloroethane. The film thickness after drying of the solution dissolved in Q is 10
Coat 41 to form a carrier transport layer so that it becomes p1,
A photoreceptor of the present invention was prepared.

The same measurements as in Example 1 were performed on this photoreceptor, and the results were as follows: E 4- = 2,3 lux for the first IJ
・sec, \'R=OV result was obtained.

Example 6 On the conductive support provided with the intermediate J finish used in Example 5,
A 1% ethylenediamine solution of Exemplary Compound +3-(39) was applied so that the film thickness after drying was 0.3 In to form a carrier generation no.

Next, 1-(1-ethyl-4-carbazolyl)methylidene (compound K-(5) below) K-(5) "C2H.

6 g and polyester resin [Byron 200J (manufactured by Toyo Koketsu Co., Ltd.) 108] were dissolved in 1,2-nochloroethane 70-, and this solution was applied so that the length of the membrane I11 after drying was 124 m to form a carrier transport layer. Then, 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 2 A comparative photoreceptor was prepared in the same manner as in Example 6, except that exemplified compound B-(39) was replaced with bisazo compound G-(2) represented by the following structural formula.

This photoreceptor was subjected to 47 measurements similar to those in Example 1, and the results are shown in Table tjS4.

G-(2) Table 4 Example 7 A carrier generation layer was formed in the same manner as in Example 5 except that Exemplified Compound B-(15) was replaced with Exemplified Compound 13-(34). On top of this, 4-methoxy-4'-styryl-triphenylamine 6B and polycarbonate "Panlite L-1250J" were added.
A carrier transport layer is formed by coating a solution obtained by dissolving 1,2-dichloroethane 70- in 70-1,2-dichloroethane so that the film thickness after drying becomes Ion. A photoreceptor was created.

Measurements were performed on this photoreceptor in the same manner as in Example 1, and E+=2.21ux-see and VR=
It was ()■.

Example 8 A coating of vinyl chloride-vinyl acetate-maleic anhydride copolymer [S-LEC MP-10J (Sekisui Chemical Co., Ltd.!i2) with a thickness of 0 was coated on the surface of an aluminum drum with a diameter of 100+an.
．． 05- is provided, and exemplified compound B-(4
3) Mix 4g with 400ml of 1,2-dichloroethane,
A dispersion solution dispersed for 24 hours using a ball mill dispersion screw was coated to a dry film thickness of 0.6 μm to form a carrier generation layer.

Furthermore, on top of this, 3-(p-methoxystyryl)-9-
(p-methoxyphenyl)carbazole (compound K below)
-(6)) 3011 and polycarbonate resin [Corpilon S-1000J (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 50] were dissolved in 1,2-dichloroethane K-(6) 400-, and the film thickness after drying was 13 μm. A drum-shaped photoreceptor was prepared by applying the same to form a carrier transport layer.

The photoreceptor thus prepared is subjected to electrophotographic copying.
When it was attached to a modified U Bix 1000 M RJ (Konishi Roku Photo Industry Co., Ltd. 91) and an image was copied, 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 sample was prepared in the same manner as in Example 8, except that the exemplified compound B-(43) in Example 8 was replaced with a bisazo compound (G-(3)) represented by the following structural formula. When a photoreceptor was prepared and a copied image was evaluated in the same manner as in Example 8, only an image with a lot of fog was obtained. Furthermore, as copying is repeated, the contrast of the copied image decreases, and 2,000 times G-(3) −
Maleic anhydride copolymer “S-LEC MF-10J
An intermediate layer with a thickness of 0.05 ui made of Sekisui Chemical Co., Ltd. (Sekisui Chemical Co., Ltd.) was provided, and on top of that, an exemplified compound [1-(4)5B] and 3.3 g of polycarbonate resin [Panlite L 1250J (manufactured by Ondai Kasei Co., Ltd.)] was added to 100 nρ of dichloroethane,
The dispersion was dispersed in a ball mill for 24 hours and applied to a dry film thickness of 10 to form a photoreceptor.

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=OV.

Example 10 6 g of 1-phenyl-3-(1)-noenalami/styryl)5(p-noethylami7phenyl)pyrazoline and polyester 4Jf'fl[ Hyon 200J (Toyobo JiT Co., Ltd. Su) io++ was dissolved in 1,2-dichloroethane 7o-, and this solution was applied so that the film thickness after drying was 10p1.

Next, exemplified compound 13-(12) 1
[1 and B-(13) 1g tiger 1. 2-i) Rio
The film thickness after drying of the dispersion that was mixed with NOI and dispersed in a ball mill for 24 hours was 0. The photoreceptor of the present invention was formed by coating the photoreceptor in a uniform manner to form a carrier generation layer.

The photoreceptor thus obtained was evaluated in the same manner as in Example 9, and found to be E l =2.21 ux sec and VR = +5V.

Example 11 A 2% ethylenenoamine solution of Exemplary Compound E (-(19)) was applied onto a polyester film laminated with aluminum so that the film thickness after drying was 0.5 μl,
A carrier generation layer was formed. Furthermore, 1-[4-(N) is added as carrier transport Wr.

N-noethylamino)benrene]-amino-1
, 2, 3, /I-tetrahydroquinoline (1-(7)), 1-<1-ethyl-4-carbazolyl)methylideneami/-1, 2, 3,
4-tetrahydroquinoline (compound K-(8) below)
), or 4-7 toxic 4'-(4-chloro)-styryl-1rifenylamine (-<9 for the following compounds)
Separately each about 10cm and polycarbonate K-
(7) K-(8) C2H.

K-(9) (Il+fat (manufactured by Ondai Kasei Co., Ltd., Panlite L-125)
0) 14.

A solution of dissolved in 1,2-dichloroethane 140-
The photoreceptors were coated and dried so that the dry film thickness was 12 JJI, and photoreceptors with different carrier transport substances were obtained.

These three types of photoreceptors were each manufactured by Kawaguchi Deniso Seisakusho Co., Ltd. to SI)-4281! Using Seidenshi Test Iso, the following ′+co properties were evaluated. Charge the material with a charging voltage of -6 KV for 5 seconds, leave it in the dark for 5 seconds, and then irradiate the material with halogen light so that the illuminance of the material surface is 35 lux, which is necessary to halve the surface potential. Exposure (half-reduced exposure, E
+) was measured. Also, the surface potential (residual potential) \rR after exposure with an exposure amount of 30 lux·see was measured. As shown in Table 5, the results were good in combination with any carrier transport substance.

Table 5 Comparative Example-4 Exemplary Compound B-(19) was converted into the following bisazo compound (
Comparative G-(4) was prepared in the same manner as in Example 11 except that G-(4)) was used. As shown in Table 6, the results varied depending on the carrier transport substance.

Table 6 Example 12 On the conductive support provided with the intermediate layer used in Example 5, 2 g of Exemplified Compound B-(2) and 10 g of 1,2-dichloroethane were placed.
0- was well dispersed and mixed and coated so that the film thickness after drying was 0.3 μm to create an A/Yaria generation layer.

Next, 6 g of 4゜4'-dimethyl-4''-snaryltriphenylamine (compound K-(10) below) and polycarbonate "Panrai" L-12504 (manufactured by Yotaikasei Co., Ltd.) were added thereon as a carrier transport substance. K-(
10) A solution obtained by dissolving 10 g of 1,2-dichloroethane in 90 g of 1,2-dichloroethane was coated to give a film thickness of 10 noa after drying to form a carrier +77 transport layer, 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 7.

The results are shown in Table 7.

As is clear from the results shown in Table 7, the photoreceptor of the present invention has good sensitivity and residual potential characteristics even at high temperatures, and is stable against heat.

Example 13 The exemplified compound [! -(3) 28 and 1,2-dichloroethane 11
A carrier generation layer was prepared by thoroughly dispersing and mixing 0- and 0-, and applying the film to a thickness of 0.3- after drying.

In order to test the durability of this carrier generation layer against UV light, an ultra-high pressure mercury lamp (Tokyo Shibaura Den (manufactured by Bosha)) was placed 30 cTll away, and the lamp was heated at 1500 cd/c for 10 minutes.
m2 of LIV light was irradiated. Next, 1 as a carrier transport substance is placed on the carrier generation layer that has been irradiated with UV light.
-(1-ethyl-4-carbazolyl)notylideneami/
-1,2,3,4-tetrahytomyquinoline (1: Compound K -(11)) 7 g and polycarbonate (Panrai) L-1250) (manufactured by Yotaikasei Co., Ltd.) 10F1,
A carrier transport layer was formed by applying a solution dissolved in 90 g of 1,2-dichloroethane K-(11) to a dry film thickness of 17 ms to form a photoreceptor of the present invention.

The same measurements as in Example 5 were performed on this photoreceptor. The results are shown in the rjSB table.

Example 14 Except for not irradiating UV light after forming the carrier generation layer,
A photoreceptor of the present invention was prepared in the same manner as in Example 13, 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 onwards, the photoreceptor of the present invention
(1) It can be seen that the sensitivity and residual potential characteristics are excellent against irradiation, the amount of fluctuation in acceptance potential is small, and it is stable against light.

Comparative Example 5 Compound B-(3) was converted into the following bisazo compound (G-(5
)) Same as Example 13 and Example 14 except that G
-(5) 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 photoreceptor prepared using the above-mentioned compound deteriorate due to extensive UV irradiation, and the amount of variation in acceptance potential is large.

Example 4 In Example 5, exemplified compound B-(15) was converted into 13-(
A drum-shaped photoreceptor was produced in the same manner except that step 1) was replaced. The spectral sensitivity of this photoreceptor at 780 nm is 0.
．． It was 55 μJ/cm' (half exposure amount). The photoreceptor of the present invention has a laser beam intensity of 0.5 on the surface of the photoreceptor.
A live photo test was conducted using an experimental rock equipped with a 5+nW semiconductor laser (780 nm).

After charging the surface of the photoreceptor to 16 KV, it was exposed to laser light and subjected to repulsion development at a bias voltage of 1250 V, 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-(1).

The spectral sensitivity of this photoreceptor at 78011111 is 7.
It was 24 μJ/CWI2 (half 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 is twice as 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.

(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, heat and light, which is the object of the present invention, can be used. It also has excellent photochromic properties such as charge retention, sensitivity, and residual potential, with little fatigue change even after repeated use, and has sufficient sensitivity even in the long wavelength range of 780 r+m or more. It is possible to create an excellent photoreceptor with

[Brief explanation of the drawing]

1 to 6 are sectional views showing examples of the mechanical structure of the photoreceptor of the present invention, and numerals 1 to 7 in the figures represent the following, respectively. 1... Electrocardiographic support 2... Carrier generation layer 3... Carrier transport layer 4... Photosensitive stage 5... Intermediate layer 6... Layer 7 having a carrier transport substance...・Career generation qkJ trade agent Patent attorney No 1) Yoshi Parent bird 1 Figure 2 Figure A 5 Line drawing procedure amendment document March 20, 1985 Director General of the Special Communications Agency Shiga Gakudon 1 Incident display Suitable Showa Is9 patent Wish number! 13211B No. 2 Name of the invention Photoreceptor 3 The old days of correction! Relationship between 1 and 1 Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo 1 Sakura-cho, Hino-shi, Tokyo Konishiroku Photo Industry Co., Ltd. (Telephone: 0425-83-152)
1) Special Fraud Section 6, Contents of Amendment 1) Insert the following sentence between the last line of page 13 to the first line of page 14 of the specification, [Furthermore, the above general formula [IJ
Among the azo compounds represented by the general formula (1), it has particularly excellent sensitivity even in the wavelength region of 780 nm or more.
A compound even more particularly preferable than 3 is one having a structure represented by the general formula EV). In addition, the general formula (Vl
It is much easier to synthesize the diamino compound (general formula (10)), which is the raw material for its synthesis, than the compound represented by the general formula (Ell).''2) Ibid., page 14, line 8. ~ between lines 9 and 9, insert the following sentence after "They are the same." electron donating group)
A group selected from the following, provided that both Y7 and Yr are not hydrogen atoms. A is the general formula (same as I+. General formula (diamino compound that is a raw material for the compound of general formula Vl). In the formula, Yr and Yr are the same as the general formula [V. has been corrected to the following sentence.Furthermore, specific examples of the bisazo compound represented by the general formula (V) that are useful in the present invention include those having the following structural formula; The bisazo compound is not limited.General formula (in Vl, represented by the general formula source.General formula (■ 4), page 40, between lines 17 and 18, insert the following sentence: "Synthesis Example 2 (Synthesis 1 of Exemplary Compound B-(99)) First, the diamino compound 8 as a raw material was prepared as He1v. Chim, Acta, 29, 761-9 (19
46) Easily synthesized by a known method such as German et al. ″ 2 x 70% ω% Next, 1 diamino compound 8 28.69 (0.1 mol)
0% in hydrochloric acid 31, cooled the dispersion to a temperature of 5°C with stirring, and added 13.8% sodium nitrite.
An aqueous solution of F (0.2 mol) in 200 ml of water was added dropwise. After the dropwise addition, the tank was kept cooled for an additional hour, stirring was continued, and then 250 g of ammonium hexafluorophosphate was added to the filtrate obtained by filtration. Kisaflumerophosphate was obtained. This crystal was converted into N,N-dimethylforamide 51! 2-Hydroxy-3-(4-methoxy-2-methylphenylcarbamoyl)-benzo(aJ carbazole (naphthol As-8R) 78.9 (0.2 mol) N, N-
Dimethylformamide2. se was dissolved, and sodium acetate trihydrate (CH, C00Na-3I (20)
549 for water 0.51! This solution was cooled to a temperature of 5° C., and while stirring vigorously, the above-mentioned dropping solution CD) was added dropwise thereto. After the addition was completed, the mixture was stirred under cooling for 1 hour, and then heated to room temperature for 2 IF! After stirring for a while, the crystals formed were collected by filtration. 51 of these crystals! N, N-
The residue was washed three times with dimethylformamide, twice with 5/1 water, and twice with 51 a7ton, and then dried to obtain 71.6 g (yield: 72%) of a black compound. In the infrared absorption spectrum of this black compound, absorption due to the C-0 bond of the amide is observed at ν = 1680 cm, and in elemental analysis, the actual value (C = 74.00%, N, -12 ,65%,H=
4.42%), but the theoretical value (C = 74.17%, N
= 12.72%, H = 4.39%), it was confirmed to be the target exemplary compound B-(99). 5) Add the following sentence next to "R ('Jv '+ 41 was not found.") on page 70, line 11. was replaced with CGM in Table 9, and 4-methyl-41-styryl-triphenylamine as CTM was replaced with CTM (exemplary compounds K -<12) to (Z3) in Table 9, but in the same manner. A drum-shaped photoreceptor was created.
The spectral sensitivity in nm was as shown in Table 9. The photoreceptor of the present invention was heated using a semiconductor laser (800 nm
) We conducted a live-action test using an experimenter wearing a camera. After charging the surface of the photoreceptor to -700V, the laser
When Y-transfer development was performed at a bias voltage of -200 V, a good image with no fog was obtained. - The following margin exemplified compounds K - (t2) to (23) K - (12) K - (13) K - (14) K - (15) K - (16) K - (17) K - (18) K −(19) K −(20) K −(21) K −(22) Above”

Claims (1)

[Scope of Claims] (1) A photoreceptor characterized by having a photosensitive layer containing an azo compound of the following general formula CI) on a conductive support. General formula [1] [In the formula, Yl and Y2 each represent an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, or a hydroxy group, 9 is O or an integer of 1, ■ and 11 are 0
Represents an integer between 3 and 3. However, export and 11 cannot be O at the same time. A is υH, Z is a substituted or unsubstituted aromatic carbocycle, or an atomic group necessary to support the substituted or unsubstituted aromatic carbocycle, Q is a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted sulf77 moyl crystal, R1 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted carbamoyl group, a carboxyl group and its ester group or a sia7 group,
Δ' represents a substituted or unsubstituted aryl group, R2 and R* represent a substituted or unsubstituted alkyl crystal, a substituted or unsubstituted 7-ralkyl group, or a 16-substituted or unsubstituted aryl group. (2) 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 [1].
Photoreceptor described in section. (3) Claim 1 or )ll's 2, wherein the photosensitive layer is auxiliary with a laminate of a carrier-generating layer containing a carrier-generating substance and a carrier-transporting layer containing a carrier-transporting substance. Photoreceptor as described.