JPS6057348A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic sensitive body excellent in carrier generating performance, capable of combining with a wide range of carrier transfer substances, and to improve stability, sensitivity, durability, etc., by forming a photosensitive layer contg. a specified azo-substd. condensed polycyclic compd. on a conductive substrate. CONSTITUTION:A photosensitive layer 4 formed on a conductive substrate 1 contains one of azo-substituents of condensed polycyclic compds. represented by formulae I , II, and III and they have one or two azo substituents -N=N-A(A is one of formulae IV-VII; Z in an aromatic carbon ring, or the like; Q is carbamoly or sulfamoyl; R1 is H, alkyl, amino, or the like; A' is aryl; R2, R3 are each aryl, aralkyl, or the like), and they may be substd. by -Y1 and -Y2 each being H, halogen, cyano, alkyl, or the like. The photosensitive layer 4 contains a carrier transfer substance and a carrier generating substance, and as the carrier generating substance, one of said azo substituents of the compds. I , II, and III are used. The photosensitive body having such a photosensitive layer is superior in various characteristics of charging and sensitivity and image formation, free from deterioration due to fatigue in repeated uses, and good in durability.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photoreceptor, and more particularly to a novel electrophotographic photoreceptor having a photosensitive layer containing a photoconductive compound made of an organic radical conductor.

Conventionally, as electrophotographic photoreceptors, inorganic photoreceptors having photosensitive layers mainly composed of Ia-free conductive compounds such as selenium, zinc oxide, and cadmium sulfide have been widely used! ! the law of nature. However, these have poor sensitivity, thermal stability, moisture resistance, durability, etc.
6 is not necessarily satisfactory. For example, selenium photoreceptors are difficult to manufacture because their properties as a photoreceptor deteriorate when they crystallize, and they are susceptible to exposure to heat, fingerprints, etc.
! l! Crystallized.

The performance as a photoreceptor deteriorates. In addition, the cadmium sulfide photoreceptor is moisture resistant JP durability VCS, and the zinc oxide photoreceptor in the housing also has problems in durability.

In order to overcome these drawbacks of inorganic photoreceptors, research and development have been actively conducted in recent years on organic photoreceptors having nine layers of photoconductivity, which are mainly composed of various organic photoconductive compounds. For example, Japanese Patent Publication No. 50-10496 describes an organic photoreceptor having a photosensitive layer containing poly-h-vinyl carnosol and 2,4,7-dolinitro-9-fluorenone. However, this photoreceptor has a sensitivity of 3 and a durability of 8, which are not necessarily satisfactory. In order to improve these deficiencies, attempts have been made to develop a higher performance photoreceptor by assigning the carrier generation and carrier transport functions to different materials. Many studies have been conducted on such so-called function-separated type electrophotographic photoreceptors because each material can be selected from a wide range and photoreceptors with arbitrary performance can be produced relatively easily. A large number of compounds have been proposed as carrier-generating substances for functionally separated electrophotographic photoreceptors such as I. An example of using an inorganic compound as a carrier generating substance is 1, for example, amorphous selenium dust described in Japanese Patent Publication No. 43-16198, which is used in combination with an organic photoconductive compound. The disadvantage that the carrier generation layer crystallizes due to heat and deteriorates the characteristics as a photoreceptor has been improved, and C does not exist.

'17' (Organic dye-'P organic pigment) Many electrophotographic W& elements used as carrier generating substances have been proposed. -93157 Publication, JP-A-5
There are those disclosed in JP-A-5-126254, JP-A-56-143437, JP-A-57-196241, and the like. However, what do these organic compound photoreceptors have in terms of sensitivity, residual potential, or stability during repeated use? However, it does not necessarily satisfy the wide range of requirements of the electrophotographic process, such as limiting the selection range of the housing and carrier transport quality.

- In recent years, Ar laser, He
Gas lasers such as -Ne 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 light sources for copiers and computer output printers that have image processing functions, such as intelligent copiers. Among these, semiconductor lasers are attracting attention because their characteristics include that electrical signal/original signal conversion elements such as acousto-optic devices are not performing well, and that they can be made smaller and lighter. However, this semiconductor laser has a lower output than a gas laser, and its oscillation wavelength is also long (approximately 780 nm or more), so the spectral sensitivity of conventional photoreceptors is more on the short wavelength side. -1: It is impossible to use the photoreceptor as a light source for a V-zer or exposure source.

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive material which is stable against heat and gas and has excellent characteristics.

Another object of the present invention is to provide an electrophotographic 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 an electrophotographic photoreceptor having a photosensitive layer containing a specific condensed polycyclic compound that has excellent carrier-generating ability and a wide range of carrier transport materials to be combined with. There is a particular thing.

Still another object of the present invention is to provide an electrophotographic photoreceptor that has sufficient practical sensitivity even to long wavelength light sources such as cow body lasers. As a result of intensive research, we found that one or two azo substituents (-N, =N-
A), and also has substituents (-Yl) and (-Y2)'&
Having the general formula 0], @ or [II
It has been discovered that an azo-substituted fused polycyclic compound represented by [) can function as an active ingredient of an electron regenerating photoreceptor,
It was a misfire 94'x brother.

General formula (D General formula (n) General formula (III) where Yl and Y2 are each a hydrogen atom, a halogen atom, a cyano group,
Alkyl group or alkyl group? There are people.

A is H Na Omote Wa Ding.

R4 is a hydrogen atom, r#, a substituted or unsubstituted alkyl group having a prime number of 1 to 4, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted phenyl group.

R5 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aromatic carbocyclic group (for example, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted naphthyl group,
unsubstituted anthryl group, etc.).

-1! Substituted/unsubstituted aromatic heterocyclic group (for example, substituted/unsubstituted carbazolyl group, substituted/unsubstituted dipenzofuryl group, etc.).

When R4 and R5 have a substituent, the white eye substituent includes, for example, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms (
For example, methyl group, ethyl group, inzolovyl group, tertiary butyl group, trifluoromethyl group, etc.), substituted/unsubstituted aralkyl group (e.g. penzyl group, phenethyl group, etc.), halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), substituted φ unsubstituted alkoxy group having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group, impropoxy group, tertiary butoxy group, 2-chloroethoxy group, etc.), hydroxy group,
@substituted/unsubstituted -ruoxy group (e.g., p-chlorophenoxy group, l-naphthoxy group, etc.), acyloxy group, (e.g., acetyloxy group, p-cyanobenzoyloxy group, etc.), tJruIxyl group, its ester group (
For example, ethoxycarbonyl group, m-bromophenoxycarbonyl group, etc.), carbamoyl group (e.g. aminocarbonyl!, tertiary butylaminocarbonyl group, anilinocarbonyl group, etc.), acyl group (e.g. acetyl group, O-
nitrobenzoyl group, etc.), sulfo group, sulfamoyl group (e.g., aminosulfonyl group, tertiary butylaminosulfonyl group, p-)lylaminosulfonyl group, etc.), amine group, acylamino group (e.g., acetylamino group, benzoylamino group) etc.), sulfonamide groups (e.g., methanesulfonamide group, p-toluenesulfonamide group, etc.), cyano group, nitro group, etc.; Alkyl groups (e.g. methyl group, ethyl group, inpropyl group, n-butyl group,
trifluoromethyl group, etc.), chlorene 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), group, 2-chloroethoxy group),
They are cyan group and nitro group.

Z is an atomic group necessary to form a substituted or unsubstituted aromatic carbocyclic ring or a substituted or unsubstituted aromatic heterocyclic ring, specifically, for example, a substituted or unsubstituted benzene ring. , a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted carbazole ring, etc.

Examples of substituents for these ring-forming atomic groups include a series of substituents such as those listed as substituents for R4 and R5, but preferred are halogen atoms (chlorine, atoms,
bromine atom, fluorine atom, iodine atom), sulfo group, sulfamoyl group (for example, aminosulfonyl i, p-)lylaminosulfonyl group).

Kawa is a hydrogen atom, a substituted/unsubstituted alkyl group, a substituted/unsubstituted amino group, a carboxyl group, and its -t-steri
, a substituted/unsubstituted carbamoyl group, a cyano group, preferably a hydrogen atom, a substituted/unsubstituted alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, isopropyl group, tertiary butyl group, trifluoro methyl group) and cyano group.

A' is a substituted or unsubstituted oryl 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 R5. The groups are listed, preferably halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), carbon number 14-
Substituted/unsubstituted alkyl groups (e.g., methyl group, ethyl group, isopropyl group, 3R butyl group, trifluoromethyl group, etc.), substituted/unsubstituted alkoxy groups having 1 to 4 carbon atoms (e.g., methoxy group) , ethoxy group, impropoxy group, tertiary butoxy group, 2-chloroethoxy group).

R2s and R3 are substituted/unsubstituted alkyl groups, substituted/unsubstituted aralkyl groups, ? and substitutedφ and unsubstituted oryl groups, but preferably substituted or unsubstituted alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, isopropyl group, tertiary butyl group, trifluoride group). 10,000 methyl base), substituted and unsubstituted phenyl! (For example, phenyl group % p-methoxyphenyl group, m-chlorophenyl group, etc.)

According to this invention, since the azo-substituted product of the fused polycyclic compound described above is used as the original tetraelectric substance constituting the photosensitive layer, l:9
It is stable against heat and light, and has a high charge retention ability.
It has excellent electrophotographic properties such as sensitivity and residual potential,
Moreover, it can provide excellent fc electrophotographic sensitization with little fatigue deterioration even when used repeatedly and has sufficient sensitivity even in the long wavelength region of 780 nm or more. Used in the present invention. Among the azo-substituted fused polycyclic compounds as described above, preferred are those represented by the following general formulas (IV) to [■].

General formula (IV) υ General formula EV) General formula (Vl) General formula [■] General formula (IX) (In the formula, A, Yl, and Y2 are the same as those in the general formula described above.) Among those represented by these general formulas, those represented by the following general formula [X] have particularly excellent sensitivity to elements in the long wavelength region of 780 nm or more and are easy to synthesize. is particularly preferred.

General formula (X) (In the formula, A is the same as in the general formula described above.

) Specific examples of the azo-substituted fused polycyclic compound used in the present invention include those having the following substituent formula, but the invention is not limited thereto. Furthermore, the compounds exemplified herein may be used in the form of salts, such as sulfates, hydrochlorides, and other forms.

Exemplary compounds (1-xa) to (1-38a:] and (
1-1b) to (r-asb) The columns rY1J, rY2J, rXJ, and rAJ in the boxes below represent Yl, Y2. Atoms ffc corresponding to X and A indicate groups, and the groups in the column rAJ are common to those with the same symbol except for the symbols raJ and rbJ of "compound w swallow". (Hereinafter) The same applies to the exemplified compounds described below.

Exemplary compounds (1-398) to (I-55a) and (1-
39b) to (1-55b), general formula exemplified compound (1-56) exemplified compound (l-57) exemplified compound (M-1a) to (II-4a) and = Il
-1b) to (II-4b)? General formula exemplified compounds ([-5a] ~ (II-8a) and (II-5b) ~
General formula exemplified compound (m-18) in (II-8b) 8
~Cm-4a, J & H (Il't-1b) ~[J
General formula exemplified compound (ll1-5a) in JI-4b)
)~(DI-8a) and (III-5b)~(■
-gb) The substances of the general formula above can be easily synthesized by known methods.

Synthesis Example (Synthesis of Exemplified Compound (1-1b:)) A summary of the synthesis route is shown below.

(AJ (IJ) [C] [DJ (, r-1b) Antoanthrone [A] was dinitrated with potassium nitrate in sulfuric acid according to the method of Industrial Chemistry Journal 60, 443 (1957). 4.10-diaminoanthanthrone (C) is obtained by firstly reducing it with thorium sulfide as lO-dinitroanthanthrone (H).
I got it. Next, this 4.10-noaminoantandrone (C, 33.6 g ((J, 1 mol)) and 800 g of a
Dissolve the nitrosyl sulfate N''- (sodium nitrite 13.8.9 (0,
A solution of 2 mol) dissolved in 400 g of concentrated sulfuric acid was added, and the mixture was stirred for 1 hour under ice and left for 2.1 night. After the reaction is completed, the reaction liquid KE P JIA L, Oki Chiriko concentration 42
% of fluoroboric acid was added, the resulting precipitate was collected, washed with water, thoroughly dried, and dissolved in 5 pieces of N-dimethylformamide to form a tetrazonium salt solution (CD). did. Next, 2-hydroxy-3-(4-methoxy-2-1f-penz[:a]carbazole (naphthol AS)
-8R) 79.3 g (0.2 mol), triethanolamine 60. Li[ToY54] was dissolved in N-dimethylformamide, and the above-mentioned tetrazonium salt solution CD) was added dropwise thereto while cooling on ice, and the mixture was further stirred for 2 hours to react.

The resulting crystals were washed twice with hedimethylformamide and twice with acetone (51), and then dried to obtain 52.2 g (45%) of the compound. Analysis of this compound revealed that its melting point was over 300°C, and the peak in its infrared spectrum was at sea level 1690m-1.
(Amide absorption) K et al., and according to elemental analysis C=74
．． 45%, H=4.72%, H=9.60% (theoretical values are C=74.59%, H=4.70%.

N=9.67%), the target compound (1-t
It was confirmed that b).

The uninvented electrophotographic photoreceptor can be produced by providing on a conductive support a photosensitive layer in which an azo-substituted fused polycyclic compound is dispersed in a binder as described above. Another method is to utilize the particularly excellent carrier-generating ability of the azo-substituted fused polycyclic compound as described above and use it as a carrier-generating substance, and use it as a carrier-transporting substance that can effectively act in combination with this. By using them together, it is possible to obtain a type II electrophotographic photoreceptor or a so-called functionally separated type electrophotographic photoreceptor. 'f, 7c The azo-substituted product of the fused polycyclic compound used in the invention can be used as lal or in combination of two or more types.

Various types of mechanical configurations of electrophotographic photoreceptors are known, and the present invention may be configured in any of these configurations.

Usually, the configuration is as shown in FIGS. 1 to 6. 1 and 3, a carrier generation layer 2 containing an azo-substituted product of the above-mentioned condensed polycyclic compound and a carrier transporting material contained as a carrier-transporting material on a proprietary support 1 are shown. layer 3
A photosensitive layer 4 made of a laminate of . As shown in FIGS. 2 and 4, this photosensitive layer 4 may be provided through an intermediate layer 5 provided on a conductive support. When the photosensitive layer 4 has a two-layer structure in this manner, an electrophotographic photoreceptor having the most excellent electrophotographic properties can be obtained. Invention again? As shown in FIGS. 5-8 and 6.

A photosensitive layer 4 formed by dispersing a carrier-generating substance 7 made of an azo-substituted product of the fused polycyclic compound described above in a layer 6 mainly composed of a carrier-transporting substance is directly applied to the conductive support l.
Alternatively, it may be provided via the intermediate layer 5.

What if the electrophotographic photoreceptor is of a functionally separated type? Carrier transport substances used in combination include electron YM transporting substances such as trinitrofluorenone or tetranitrofluorenone, L'Pj electron accepting substances, and heterocyclic compounds such as poly-h-vinylcarbazole. Polymers in the chain, triazole derivatives, oxadiazole derivatives, imidazole derivatives, pyrazoline fatty acids, polyarylalkane salt conductors, phenylenediamine derivatives, hydrazone derivatives, amine-substituted chalcone derivatives, triarylamine 114' conductors, carbazole derivatives, Stilbene derivative, special hole transporter JPj
Examples include, but are not limited to, electron-donating substances.

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

(M-1) A method of applying a solution of a carrier-generating substance dissolved in a suitable solvent, or a solution prepared by adding and dissolving a binding agent as necessary.

(A4-2) A dispersion liquid in which a carrier-generating substance is made into fine particles in a dispersion medium using a ball mill, a homomixer, etc., and mixed and dispersed with a binder added as necessary? How to apply.

Solvents or dispersion media used to form the carrier generation layer include n-butylamine, diethylamine, ethylenediamine, isozolo/senolamine, triethanolamine, diethylenediamine, N,N-dimethylformamide, acetone, metheretherctone, and cyclohexanone. , benzene, toluene, xylene, chloroform, 1,2-dichloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol,
Examples include isopropanol, ethyl acetate, butyl acetate, and dimethyl sulfoxide.

When using N adhesive in the carrier generation layer or carrier transport layer, any material 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.

Polycarbonate polyester methacrylic resin acrylic resin polyvinyl chloride polyvinylidene chloride polystyrene polyvinyl acetate, butadiene copolymer vinylidene chloride-acrylonitrile copolymer vinyl chloride-vinyl acetate copolymer vinyl chloride-vinyl acetate-maleic anhydride copolymer silicone Resin Silicone Fluid resin Phenol Formaldehyde Resin Styrene Alkyd resin Polyvinylcarbazole These binders can be used alone or in combination of two or more.

The thickness of the carrier generation layer 2 formed by K in this way is:
It is preferably 0.01 μn′L to 20 μm,
More preferably, it is 0.05 μm to 5 μm. Also, when the carrier generation layer or photosensitive layer is a dispersed system.

The particle size of the azo substituted product is preferably 5 μm or less, more preferably 1 μm or less.

The conductive support used in the electrophotographic photoreceptor of the present invention includes metal plates including alloys, metal drums or conductive polymers, 4-carbon compounds such as indium oxide @ aluminum including JF Kaikin, etc. Examples include paper, plastic film, etc. that have been made conductive by coating a thin layer of metal such as radium or gold, vaporizing N, or laminating. As an intermediate layer such as an adhesive layer or a barrier layer, in addition to the high molecular weight polymer used as the binder, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, and other polymers such as aluminum oxide are used.

The electrophotographic photoreceptor of the present invention has the above composition,
As is clear from the examples described below, it has excellent charging characteristics, custom sensitivity, and image forming characteristics, and particularly has excellent durability with little fatigue deterioration even after repeated use.

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

(Example) Example 1 2 g of exemplified compound (I-4b), 2 g of polycarbonate resin "Sonrai" L-1250J (Bujin Kasei Co., Ltd.), and 110 ml of 'kl, 2-dikuoo ethane V
C was added and dispersed in a ball mill for 12 hours. This fractional liquid-aluminum vaporized polyester film was coated to a dry film thickness of 1 μm to form a carrier generation layer, and on top of that, a carrier transport layer was formed using the following structural formula (K-1). 6 g of boss 4-methoxy-4'-steryl-triphenylamine and polycarbonate resin [
) A carrier transport layer was formed by dissolving the lOI of Tannrite L 1250J and 110g of 'kl, 2-dichloro, and loethane and applying the l'c solution to a dry film thickness of 15 μm. The invention of Ryuko's photographic photoreceptor was destroyed.

(K-1) Fabrication of a % machine for the photoreceptor obtained as described above/F
The following characteristics were evaluated using an electrostatic paper tester model 5P-428. After charging to a charging voltage of -6 for 5 seconds, leave it in the dark for 5 seconds, and then reduce the illuminance on the photoreceptor surface to 351.
The amount of exposure required to reduce the surface potential by 1,000 times by irradiating it with light and sound from a halogen lamp so that the surface potential becomes ux (half-reduced exposure amount)
I asked for ET. In addition, the surface potential (residual potential) after fc was determined by exposure at an exposure dose of 3Q 1uX-8ec. Further, similar measurements were repeated 100 times. The result is the first
As shown in the table.

Table 1 Comparative Example 1 A comparative photoreceptor was cracked in the same manner as in Example 1, except that a compound represented by the following structural formula (G-1) was used as a carrier-generating substance.

(G-1) Regarding this comparative electrophotographic 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 results in Table 2 and above, the non-inventive electrophotographic photoreceptor is extremely superior in sensitivity, residual potential, and repetition stability compared to the comparative electrophotographic photoreceptor.

Examples 2 to 4 Exemplary compounds (1-2b), (
I-10b) and (1-39b), and the following structural formulas (K-2) and (K-3)% (
K-4), respectively 4,4'-dimethyl-4''-
(4-Methyl)-steryl-triphenylamine, 4.
4'-Methyl-4"-(4-chloro)-steryl-triphenylamine, 4-methyl-4'-(4-methoxy)
-Using styryl-triphenylamine.

The electrophotographic photoreceptor 2 of the present invention was otherwise prepared in the same manner as in Example 1.
When it exploded and similar measurements were carried out, the results shown in Table 3 were obtained.

(K-2) (K-3) (K-4) Third Clothing Example 5 Vinyl chloride-vinyl acetate-
A 0.05 μm thick intermediate layer made of a maleic anhydride copolymer “Eslec MF-10J (manufactured by Tsukisui Kagaku Co., Ltd.) was provided, and 2 g of exemplified compound (II-zb) was added at 1.2 μm on top.
- A dispersion mixed with 110rnt of dichloroethane and dispersed in a ball mill for 24 hours.The film thickness after drying is 0.5μm.
A carrier generation layer was formed by applying the coating to form a carrier generation layer.

Like this carrier generation layer, a liquid solution containing 6 g of 4-methoxy-triphenylamine and 10 g of methacrylic resin "Acrivet" (manufactured by Mitsubishi Rayon Co., Ltd.) dissolved in 70 tnt of 1,2-dichloroethane was used, and the film after drying was prepared. Thickness is 10μm
An uninvented electrophotographic photoreceptor is formed by applying VC to form a carrier transport layer. It was torn.

When this electrophotographic photoreceptor was measured in the same manner as in Example 1, the first measurement yielded E±-L12 1ux-sec and VR-OV results of ya/a.

Example 6 Intermediate layer used in Example 5? On the provided conductive support, a 1% ethylenediamine solution of exemplary compound (III-2b) was applied so that the film thickness after drying was 0.3 μm VC,
A carrier generation layer was formed.

Then, 1 represented by the following structural formula (K-5) is added thereon.
6 g of -(l-ethyl-4-carbazolyl)methylideneamino-1,2,3,4-tetrahydroquinoline and 1 g of polyester resin "Pylon 200" (manufactured by Toyobo Co., Ltd.)
0. The electrophotographic photoreceptor of the present invention was prepared by dissolving the mixture in 70 rnL of 2-dichloroethane and applying the solution to a thickness of 12 μm after drying to form a carrier transport layer.

(K-5) 2B5 When the same measurements as in Example 1 were carried out on this electrophotographic photoreceptor, the lees shown in No. 4A were obtained.

Comparative Example 2 A comparative electrophotographic photoreceptor was prepared in the same manner as in Example 6 except that the exemplified compound (lIl-2b:]w was replaced with a compound represented by the structural formula (G-2) below. The same measurements as in Example 1 were carried out on this electrophotographic photoreceptor, and the results are shown in Table 4.

(-G-2) Table 4 Example 7 A carrier generation layer was prepared in the same manner as in Example 5, except that the exemplified compound (II-2b) YfU-containing gold compound Cl7b) was used instead. Formed. On top of this, 6 g of p-(N,N-diethylamino)benzaldehyde-1,1-diphenylhydrazone represented by the following structural formula (K-6) and polycarmenate resin "Kunzenlite L-1250J (large quantity chemical 704 of 1,2-dichloroethane
A carrier transport layer was formed by dissolving the 7c liquid and applying it to a film thickness of IO μmK after drying.

Measurements were carried out on this electrophotographic photoreceptor in the same manner as in Example 1.
.

and VR=OV.

(K-6) Example 8 Vinyl-vinyl acetate-canned water maleic n copolymer & copolymer [from Eslec M, F-104 (manufactured by Tanezu Kagaku Co., Ltd.) thickness of 0
．． An intermediate layer of 05 μm was provided, and the exemplified compound (x
-21b], 400- of 2-dichloroethane
The dispersion was mixed with a ball mill disperser for 24 hours and coated to form a carrier-generating layer with a film thickness of 0.6 μm after drying.

Furthermore, p- represented by the structural formula (K-6) above is added.
(NsN-diethylamino)benzaldehyde-1,1
-Diphenylhydrazone sol and de recarbonate resin [Corbilon S-1000J (manufactured by Mitsubishi Gas Chemical Co., Ltd.)
A drum-shaped electrophotographic photoreceptor was prepared by dissolving 50 g of the carrier transport layer in 1,2-dichloroethane 4004 and spreading the solution to a dry film thickness of 13 μm.

Photoreceptor electrophotographic copying machine "tJ" produced in this way
- When the Bix V2J (manufactured by Konishiroku Photo Industry Co., Ltd.) was installed on a modified machine and a single artist was copied, a clear one-step copy image -b1 with high contrast and faithful to the original painting was obtained. Moreover, this did not change even after repeating 10,000 times.

Comparative Example 3 Example 8 VcX Exemplified Compound (1'-21b) Y
A comparative electrophotographic photoreceptor in the form of a drum was prepared in the same manner as in Example 8, except that the compound '1I21 represented by the following structural formula ((3-3)) was used, and copies were made in the same manner as in Example 8. When the images were evaluated, only images with a lot of fog were obtained.Also, as the number of copies was repeated, the contrast of the copied image decreased, and even after 2000 copies, no copy image could be obtained. .

(G-3) Example 9 Vinyl chloride-vinyl acetate-
A 0.05 μm thick intermediate layer made of a maleic anhydride copolymer "S-LEC MF-10J (Sekisui Chemical Co., Ltd.) was provided, and on top of that, 3I of the exemplified compound (I-36b) and polycarbonate resin [Pan In addition to 3.3 g of Light L-1250J (manufactured by Kijin Kasei Co., Ltd.) and 100% of dichloromethane, a dispersion solution dispersed in a ball mill for 24 hours was coated so that the film thickness when dried was 10 μmVC, and an electrophotographic photoreceptor was prepared. Created.

El and VRy were measured in the same manner as in Example 1, except that the photoreceptor obtained as described above was replaced with an imperial voltage of +6 KV. The first result is E 1 = 3.51ux-se
c? and VR--1-30V.

Example 10 1-phenyl-3-(p-diethylaminosteryl)-5-(p-diethylaminophenyl)pyrazoline 61 and polyester resin "Pylon 20" were used as a carrier transport layer on an aluminium-deposited polyester film.
0J (Toyobo Co., Ltd.) was dissolved in 1,2-dichloroethane (70%) and applied so that the film thickness after drying of this solution was 10 μmfc.

Next, iI! of exemplified compound (1-36b) is added on top of this! and (1-9b) 1.9ton 1.2-dichloroethane 1
The electrophotographic photoreceptor of the present invention was prepared by mixing the dispersion solution with 10-10% and dispersing it in a ball mill for 24 hours, and twisting the dispersion so that the film thickness after drying was 0.5 μm VC to form a carrier generation layer.

The photoreceptors thus obtained were evaluated in the manner described in Examples 9 and 1 and were found to have an E knee of 3.61 ux-acc and a VR-+5v.

Example 11 A 2% ethylenediamine solution of exemplified compound Cl-4ob) was laminated with aluminum and then coated on a polyester film to a dry film thickness of 0.5 μm to form a carrier generation layer. Furthermore, on top of that, as a carrier transport layer, 1-(4-(N, N-G(p-1-lyl)
about 10% each of amino)henzylidene-amino]indoline, 4-methoxy-4'-(4-methyl)steryl-triphenylamine, and 4,4'-dimethylidene-amino]indoline, respectively. 14. Sl and polycarbonate resin "Nosonrai" L-1250J (manufactured by Kijin Kasei Co., Ltd.)
! A solution of 9YL2-diquaaa ethane dissolved in 1401 nt was coated and dried to give a dry film thickness of 12 μm to obtain electrophotographic photoreceptors containing three different carrier transport substances.

(K-7,) (K-8) (K-9) These three types of photoreceptors were each
The following characteristics were evaluated using a P-428 RLPT paper tester. Suspended for 5 seconds at a charged voltage of -5KV.

After leaving it in the dark for 5 seconds, irradiate it so that the halogen material surface illuminance is 351 uxvc, and the exposure i required to attenuate the surface roughness to 2 half (beam reduction -'h original foot, El)
measured. In addition, the second surface level (residual potential) after fc after exposure with an exposure source of 301 ux-sec is Vitτllt+J
Vshi1ko.

As shown in Table 5, the results were good for all combinations of carrier transport substances.

5th Optical Comparative Example 4 Comparative electrophotograph W and element Y were produced in the same manner as in Example 11 except that the exemplified compound [1-40b) was replaced with the compound represented by the following structural formula (G-4). ! ! ! As a result of the characteristic evaluation, as shown in Table 6, the results vary depending on the carrier transport material.

(G-4) Table 6 Example 12 To the tetraelectric support soil provided with the intermediate layer used in Example 5, 2 g of the exemplified compound (1-ib) and 100-ton of 1,2-dichloroethane were added. Well dispersed and mixed, film thickness after drying is 0.3
The carrier generation layer was coated to a thickness of 7 μm.

Next, the following structural formula (
6 g of 4-methoxy-4'-steryl triphenylamine shown by K-10) and polycarmenate resin "
/Zonlight L-1250J (manufactured by Kijin Kasei Co., Ltd.) 10
11? , 1,2-dichloroethane dissolved in 90 g was coated to form a carrier transport layer so that the film thickness after drying would be IO μmK, thereby producing an uninvented electrophotographic photoreceptor. Created.

(K-10) Regarding this electrophotographic property, what is the indoor width at 25℃ and 60℃? The electrophotographic properties of the film were measured in the same manner as in Example 11. In addition, VA is the acceptance potential when charged for 5 seconds. It is shown in Table 7 of Kaoru Raika.

Challenge 7 As is clear from the results in the table above, the uninvented electrophotographic material has good sensitivity and residual potential characteristics even when exposed to high temperatures.
It can be seen that it is stable against heat.

Example 13 On the 4#@order carrier provided with the intermediate layer used in Example 5,
2 g of Exemplified Compound (II-6b) and 110 yd of 1,2-dichloroethane were well dispersed and mixed until the film thickness after drying was 0.
, 3 μmK to form a carrier generation layer.

This carrier generation layer was placed at a distance of 30 ann from an ultra-high pressure mercury lamp (manufactured by Tokyo Shibaura Electric Co., Ltd.), and irradiated with UV at 1500 Cd/c1n2 for 10 minutes for 7 c.

Next, 1-(l-phenyl-4-carnozolyl)methylideneamino-1, which is represented by the following formula (K-11), is added as a carrier transport substance on the carrier generation layer that has been irradiated with UV ℃. 7 of 2,3,4-tetrahydroquinone
g and polycarbonate resin [Kunrite L-1250
J (manufactured by Banjin Kasei Co., Ltd.) dissolved in 90 g of 1,2-dichloroethane was coated so as to have a film thickness of 12 μm after drying and carrier transport polishing was performed. The photoreceptor exploded.

(K-11) Is this electrophotographic photoreceptor measured in the same manner as in Example 11? I did it. result? Shown in No. 8.

Example 14 An electrophotographic photoreceptor of the present invention was prepared in the same manner as in Example 13, except that 07 element was not irradiated after the carrier generation layer was formed, and the same measurements as in Example 11 were carried out. The results are shown in Table 8.

No. 8 As is clear from the above results, the uninvented electrophotographic photoreceptor has excellent sensitivity and residual potential characteristics against U-C irradiation, has small fluctuations in acceptance potential, and has excellent I understand that it is stable.

Comparative Example 5 Example 13 and Example 14 except that the exemplified compound [ll-6b) was changed to a compound represented by the following formula ((f-5))
An electrophotographic photoreceptor was prepared in the same manner as above.

The same measurements as in Example 11 were carried out. The results are shown in Figure 9.

(G-5) Table 9 As is clear from the results above, the electrophotographic photoreceptor produced using the above compound deteriorates in sensitivity and residual potential due to UV source heat irradiation, and changes in acceptance potential occur. The portions are also large.

Example 14 To Example 5? The exemplified compound [H, -2b, ) is [l
A drum-shaped electrophotographic tile was produced in the same manner except that 1-9b] was replaced. The spectral sensitivity of the photoreceptor at 790 nm was LOμJ/cIn2 (destructive exposure amount). This photoreceptor of the present invention? Semiconductor laser (790 nm) with a laser source intensity of 0.85 mW at the bottom of the photoreceptor
T2r: A live-action test was carried out using the equipped experimental machine.

After each side 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 A comparative electrophotographic photoreceptor was obtained in the same manner as in Example 141c'i6, except that a compound represented by the following structural formula (G-6) was used in place of the exemplified compound [■-9b].

(G-6) The spectral sensitivity of this photoreceptor at 790nm is 12.2μ
J7. ．． 2 (half-reduced exposure amount). Using this comparative photoreceptor, a live-photography test using a semiconductor laser was carried out in the same manner as in Example 14, but a good image was not obtained due to a large amount of capri.

As is clear from the results of the above Examples and Comparative Examples, the electrophotographic 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 electrophotographic photoreceptor. It is extremely excellent in terms of performance.

[Brief explanation of drawings]

1 to 6 are sectional views showing examples of the mechanical structure of the electrophotographic photoreceptor of the present invention, respectively. l... Conductive support 2... Carrier generation layer 3...
Carrier transport layer 4... Photosensitive layer 5... Intermediate layer 6... Layer containing a carrier transport substance 7... Carrier originating material science IN Part 3 Figure 2m 4th calendar

Claims (1)

[Scope of Claims] 1) It has one or two azo substituents (-N-he A), and may have substituents (-Yl) and (-Y2)Y. At least one azo-substituted product of the fused polycyclic compound represented by the following general formula (1), (II) or [''■]
An electrophotographic photoreceptor characterized in that it has a photosensitive layer containing seeds on a conductive support. General formula [I] General formula (n) General formula (I [[) % formula % Yl, Y, 2 are each a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an alkoxy group, A is H Z represents an atomic group necessary to constitute a substituted/unsubstituted aromatic carbocycle or a substituted/unsubstituted aromatic heterocycle, and Q represents a substituted/unsubstituted carbamoyl group or a substituted/unsubstituted aromatic heterocycle. Sulfamoyl group, R1 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted carbamoyl group, a carzexyl group or its ester group, or a cyan group. A' is a substituted/unsubstituted aryl group 'P! :Representation, R2
1R3 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a 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-substituted product of a fused polycyclic compound represented by general formula (1). The electrophotographic photoreceptor described in '.