JPS58152248A - Electrophotographic receptor - Google Patents

Abstract

PURPOSE:To obtain an electrophotographic receptor high in durability and sensitivity, and suitable for repeating uses, by adding a bisazo compd. to a photosensitive layer. CONSTITUTION:The photosensitive layer of an electrophotographic receptor contains a bisazo compd. of formulaIin which Ar1, Ar2 are each an optionally substd. aromatic hydrocarbon group; A is a group of formulae II-V; Y is H, OH, carboxy, sulfo, optionally substd. carbamoyl or sulfamoyl, or the like; Z is an atomic group needed to complete an optionally substd. aromatic or hetero ring; R1 is H, carboxy, or optionally substd. alkyl or carbamoyl, cyano, or the like; R2 is optionally substd. aryl; and R3 is optionally substd. alkyl or aralkyl or aryl. The obtained photoreceptor has high sensitivity, small residual potential, and superior durability, and these characteristics are not changed even after repeated uses.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrophotographic photoreceptor, and more particularly to a novel electrophotographic photoreceptor containing a bisazo compound. More specifically, the present invention relates to a highly durable electrophotographic photoreceptor that has high sensitivity and is suitable for repeated use.

Conventionally, in electrophotographic photoreceptors, selenium, zinc oxide,
No embrittlement of cadmium etc. 41! Those having a photosensitive layer containing a former conductor as a main component were widely used. However, these are not necessarily fully satisfactory in terms of sensitivity, heat resistance, moisture resistance, or printing durability, and are particularly difficult to manufacture and handle due to the properties of selenium and purified cadmium wafer. There were also restrictions.

On the other hand, electrophotographic photoreceptors having a photosensitive layer containing an organic photoconductive compound as a main component are relatively easy to manufacture, have low manufacturing costs, and can be formed into either a cylindrical drum shape or a sheet shape. be easy to handle,
In addition, it has many advantages such as excellent heat resistance, whereas selenium photoreceptors generally have poor heat resistance and crystallize under high temperature conditions, and have attracted much attention in recent years.

Poly-N-vinylcarbazole is known as such an organic photoconductive compound, and 2.4.7-
An electrophotographic photoreceptor having a photosensitive layer whose main component is a charge transfer complex formed with a Lewis acid such as dolinitro-9-fluorenone has already been put into practical use. However, this photoreceptor is not necessarily satisfactory in terms of sensitivity and printing durability.

On the other hand, there are known functionally separated electrophotographic photoreceptors of laminated or dispersed type in which the carrier generation function and the carrier transport function of the photoconductive function are respectively assigned to separate substances. Such functionally separated electrophotographic photoreceptors have a wide range of materials to choose from, making it relatively easy to achieve high performance in electrophotographic properties such as charging characteristics, sensitivity, residual potential, and printing durability. It has the advantage that it is easy to create an electrophotographic photoreceptor having the following characteristics. Various types of carrier-generating substances have been proposed in the past as carrier-generating substances that primarily perform carrier generation among the photoconductive functions of electrophotographic materials. Motoe is well known for its carrier generation layer formed from amorphous selenium as an inorganic substance.
This has the disadvantage that it crystallizes under high temperature conditions and its performance deteriorates.

In addition, various proposals have been made to use Hikari 4 as a carrier-generating substance among organic dyes of the f# family, which have particularly excellent ability to generate medial rays.
Perylene threads described in the specification of No. 1,882 or Japanese Patent Publications No. 48-30513, JP-A No. 53-95033, JP-A-54-12742, and JP-A-56-1
Azo compounds disclosed in Japanese Patent Application Laid-open No. 16040, Japanese Patent Application Laid-Open No. 54-20737, and US Pat. No. 4,052,210, V, are already known. However, these azo compounds are not necessarily satisfactory in terms of characteristics such as sensitivity, residual potential, or stability when used repeatedly, and the selection range of carrier transport substances is also limited. The reality is that nothing that satisfactorily satisfies the wide range of requirements of electrophotographic processes has yet to be obtained.

An object of the present invention is to provide an electrophotographic photoreceptor containing a bisazo compound that is stable to heat and light and has excellent carrier generation ability.

Another object of the present invention is to provide high sensitivity, low residual potential,
Another object of the present invention is to provide an electrophotographic photoreceptor with excellent durability whose properties do not change even after repeated use.

As a result of intensive research to achieve the above object, the present inventors discovered that a bisazo compound represented by the following general formula [1] can be used as an active ingredient of a photoreceptor, and completed the present invention. It's a running thing.

General formula (14% formula% In the formula, Ar, , Mur, Id, each represents a substituted or unsubstituted aromatic carbocyclic group, preferably a butterfly-substituted or unsubstituted phenyl group, or a naphthyl group, more preferably represents a substituted or unsubstituted phenyl group.Substituents for these groups include, for example, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkoxy groups, herogone atoms, cyano groups, carboxy groups, and esters thereof. group, sulfo group, azilamino group, carbamoyl group, acyl group, acyloxy group, sulfonamido group, sulfamoyl group, sulfone group, etc., preferably substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, Cyano group, halogen atom.

XI + 4 p xS p Each of X4 represents a hydrogen atom or an electron-withdrawing group, and -1 preferably represents a hydrogen atom, a cyano group, a halogen atom, a carboxy group, or a nitro group.

, Y is a hydrogen atom, a hydroxy group, a carboxy group, an ester group thereof, a sulfo group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted sulfamoyl group, preferably a substituted or unsubstituted carbamoyl group, Substituted/unsubstituted lower alkyl group having 1 to 4 carbon atoms and substituted/unsubstituted 7-enyl group, - is a hydrogen atom, and has 1 carbon number
to 4), or a substituted or unsubstituted aromatic carbocyclic group (for example, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuryl group, etc.). Substituents for these groups include, for example, those having 1 to 1 carbon atoms.
4. View alkyl group, #1 atom - bromine atom, halogen atom, lower alkoxy group having 1 to 4 carbon atoms, hydroxy group, phenoxy group, 7 aryl group such as naphthoxy group, acyloxy group, carboxy group, Examples thereof include ester groups, carboxylic groups, acyl groups, sulfo groups, sulfamoyl groups, amino groups, aclaramino groups, sulfonamide groups, cyano groups, nitro groups, etc., but preferably alkyl groups having 1 to 40 carbon atoms. group, a halogen atom such as a chlorine atom or a bromine atom, a lower alkoxy group having 1 to 4 carbon atoms, a cyano group, and a nitro group.

2 is an atomic group necessary to form a substituted/unsubstituted aromatic carbocycle or a t*/unsubstituted aromatic heterocycle, specifically, for example, a substituted *unsubstituted benzene ring, a substituted/unsubstituted Represents the atomic group forming substituted and unsubstituted indole, substituted and unsubstituted indole, and unsubstituted carbazolyl.

Examples of substituents for the atomic group forming these rings include a series of substituents such as those listed as substituents for -1-, but halogen atoms, sulfo groups, and sulfamoyl groups are preferred.

R1 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted 7-mino group, a carboxy group, an ester group thereof, a substituted or unsubstituted carbamoyl group, or a cyano group, preferably a hydrogen atom or a group having 1 to 1 carbon atoms. 4 is an alkyl group and a cyano group.

凰 is a substituted φ-unsubstituted orir group, preferably a substituted or unsubstituted phenyl group.

Examples of substituents for these groups include a series of substituents listed as substituents for 4s R1, but preferably a halogen atom, a carbon number of 1 to 4f) 44e
-Alkyl group, lower alkoxy group having 1 to 4 carbon atoms.

R1 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted 7-aryl group, preferably a C1-C4 alkyl group or a phenyl group.

The functional component #ffielectronic can be obtained by using only the excellent carrier@success of the bisazo compound of the present invention as a component of the F-containing material, or by using separate materials for carrier generation and transport. By using it as a carrier generation material for Photoreceptor A, it has excellent film properties, excellent electrophotographic properties such as charge retention, sensitivity, and residual potential, and has little deterioration due to stress even after repeated use, and is resistant to heat and light. The present invention can be enjoyed by creating a four-electronic photoreceptor that can exhibit stable characteristics in one cell.

Examples of the bisazo compound useful in the present invention represented by the above general formula include those having the following structural formula, but the bisazo compound of the present invention is not limited thereto.

-3 to -4 to -5 to -6 to -8 to -9 to -10 to -11 to -12 to -13 K to -14 to -15 to -17 to - in addition to - to each of the exemplified compounds - 27 ni-ani-29 ni-(fund) K-31 ni-branch K -oni-ani-ani-aK -a -41 ni-42 ni-44 ni-45-46 ni-47 -48 -51 -52 -K -5, i -56 -57 - Guo K -'ω -61 K - - K -ω -64 -67 -73 -74 -75 K - closed 0N ON Br K - i.e. 00H The above bisazo compounds can be easily synthesized by known methods. For example, Synthesis Example 1 (Synthesis of Exemplary Compound -1) Makromol chem,
84, 64-79 (1965).
-Butadiene tful: 2-Reduced with tin and hydrochloric acid in the presence of l,4-bis-[p-7ξnophenyl)-1,3-
I am saddened by the loss of Butagene.

Thus obtained 91,4-bis-[p-aquinophenyl)-
1,3-butadiene 2.36 N (0.01 mol)
Dispersed in a mixture of 10117 concentrated hydrochloric acid and 101 water,
1.52 & (0,022 mol) of sodium nitrite dissolved in water S- was added dropwise to water cooling along f# while keeping the internal temperature between 0°C and 5°C, and stirred at the same temperature for 1 hour. .

After the reaction, a small amount of residue was separated, 1 g of 42% borofluoride water #20d was added to a P moat, and the precipitate was collected, washed with water, and thoroughly dried. The obtained tetrazodiwam salt was converted into N,N-
Dissolve dimethylformand 50 LIK and use the tetrazonium salt solution for the next reaction.

Next, 2-hydroxy-3-nattoic acid anilide (naphthol A 8 ) 5.27 & (0.02 mol),
5.4 g of triethanolamine was mixed with 400 d of N,N-
Dissolve in dimethylformamide and cool with water to an internal temperature of 10 to 1
While maintaining the temperature at 3°C, the tetofzonium salt solution which had been adjusted to have a gloss as described above was added dropwise, and the mixture was further stirred at the same temperature for 2 hours, and further stirred and reacted at room temperature for 2 hours. After that, the precipitate was mixed with 1M1
After washing with L,N,N-dimethylformamide and drying with acetone, the desired bisazo compound 4,5 is obtained.
I lost 9.

Melting point: 300℃ or higher Infrared absorption spectrum: Si=1680 (amide absorption)
The appearance of a molecular ion peak with C e = 784 in the FD-MA8B spectrum confirmed that the target substance had been synthesized.

Synthesis Example 2 (Synthesis of -25 to exemplified compound) Organi
91.4-bis-(p-
Ditrophenyl)-1-cyano-1,3-11 diene was reduced with tin and hydrochloric acid in the presence of alcohol, and 1,4-bis-1,3-11 diene was reduced with tin and hydrochloric acid in the presence of alcohol.
(p-aminophenyl)-1-cyano-1°3-butadiene/ was obtained.

2.61 1,4-bis-(p-aminophenyl)-1-cyano-1,3-butadiene thus obtained
Ii (0.01 mol) was added and dispersed in a mixture of 101 concentrated hydrochloric acid and 10 ml water, and a solution of 1.521 (0.022 mol) sodium nitrite dissolved in 5 ml 1C of water was cooled to 0. It was added dropwise while maintaining the temperature at ~5°C, and the mixture was stirred and reacted at the same temperature for 1 hour.

After the reaction, a small amount of the residue is filtered and added to P solution with 42% white fluorinated hydrogen acid water #! Jun. 201 was added, and the precipitate was collected, washed with water, and thoroughly dried for nine hours. Obtained tetrazonium salt
, was dissolved in N-dimethylformamide 50117 to obtain a tetrazonium salt solution to be used in the next reaction.

Next, 5.271 (0.02 mol) of 2-hydroxy-3-naphthoic acid anilide (naphthol A 8 ) and 5.41 mol of triethanolamine were added to 400 d of N,N-dimethylformamide Kil! Dissolve and reduce internal temperature to 0-5℃ under water cooling.
The tetrazonium salt solution prepared above was added dropwise while maintaining the temperature, and the mixture was stirred for 2 hours at the same temperature, and the mixture was further stirred and reacted at room temperature for 2 hours. After that, the precipitate was subjected to FEE
The desired bisazo compound 4.0 is washed with L,N,N-dimethylformamide and then acetone and dried.
I got it.

One point Infrared absorption spectrum above 300℃, ν = 2200CIl
(CN absorption), ν = 16801f' (adsorption absorption)
Since a molecular ion peak of ψ=809 appeared in the FD-mass spectrum, it was confirmed that the target substance was synthesized.

Synthesis Example 3 (Synthesis of -30 to compound 91) 2-hydroxy-3-naphthoic acid-2',4'-dimethylanilide (naphthol AS-MX) 5.83.9 (0,0
The tetrazonium salt (0, 01 mol) of N,N-dimethylformamide solution was gradually added. Further at the same temperature 2
The mixture was stirred for an hour, and the mixture was further stirred and reacted at room temperature for 2 hours. After the reaction, one precipitate was collected, washed with N,N-dimethylformamide, then water, and then acetone, and dried to obtain the desired V-sazo compound 4.59.

Infrared absorption spectrum with melting point of 300℃ or higher, ν = 2200 cm (
CN absorption), ν = 1680 ff1-” (amide absorption) and FD-MA8B spectrum A/ic m/@
: It was confirmed that the target substance was synthesized because a peak of 866 molecule io7+1 appeared.

Synthesis Example 4 (Synthesis of exemplified compound -73) Organi
3-bromo-1-cyano-1 obtained by combining m-nitro-α-bromocinnamaldehyde and p-nitropendylcyanite in alcohol in the presence of hyherizine according to the method described in c Reaction Vol. 15, 204. -(p-nitrophenyl)=4-
(m-nitrophenyl)-i,a-butadiene was reduced with tin and hydrochloric acid in the presence of alcohol, and 3-bromo-1-cyano-1-(TI+-7minophenyl)-4-(m-aminophenyl)- 1,3-butadiene was obtained.

3-bromo-1-cyano-1- thus obtained
(p-aminophenyl)-4-(m-7minophenyl)
-1,3-butadiene 4.0# (0.01 mol) was dispersed in a mixture of 15 salmon hydrochloric acid and 151 water, and 1.52
11 (o, 022 mol) of sodium nitrite in 51 LI of water
All of the chlorinated water was poured into the chest while keeping the internal temperature at 0 to 5° C., and the mixture was stirred and reacted at the same temperature for 1 hour.

After the reaction, a small amount of residue was separated and 42% was added to 1P111Il.
One part of the white fluoride water Ill aqueous solution (9) was added, and the resulting precipitate was subjected to PMR, washed with water, and then thoroughly dried. The obtained tetrazonium salt was dissolved in N,N-dimethylformamide 50wLtK.
This was dissolved to obtain a tetrazonium salt solution to be used in the next reaction.

Next, 2-hydroxy-3-naphthoic acid-3I-nitroanilide (naphthol As-88) 6.161 (0,02
mol), triethanolamine (5.49 mol) was dissolved in 400 ml of N,N-dimethylformamide, and the internal temperature was brought to 1.
Tetrazonium salt ff prepared as above while being maintained at 0 to 13°C! The mixture was added dropwise, stirred at the same temperature for 2 hours, and further stirred at room temperature for 2 hours.

Thereafter, the precipitate was collected, washed with N,N-dimethylformamide and then with acetone, and dried to obtain the target bisazo compound 6.29.

Melting point: 300℃ or higher Infrared absorption spectrum: C=22007111 (C
N absorption), ν = 1680 ff1-” (amide absorption) and molecular ion y M' in the FD-MA88 spectrum.
= 879 Since a group of isotope peaks attributed to K appeared, it was confirmed that the target substance had been synthesized.

The bisazo compound of the present invention has excellent photoconductivity, and when an electrophotographic photoreceptor is manufactured using the bisazo compound, the conductive support W! It can be produced by providing on a body a photosensitive layer in which the bisazo compound of the present invention is dispersed in a binder. In addition, as another method, among the photoconductivity of the bisazo compound of the present invention, it is used together with a carrier transporting substance that is rigid as a carrier generating substance and can act effectively in combination with the particularly excellent carrier generating ability. Especially laminated IJ
It is also possible to use a dispersion type so-called functionally separated type electrophotographic photoreceptor.

The mechanical structure of an electrophotographic photoreceptor is well known, and the electrophotographic S photoreceptor of the present invention can take any of these forms. Usually, they are in the form shown in Figures 1 to 6. 881 and 3, a carrier generation layer 2 containing the above-mentioned bisazo compound as a generating component and a carrier transport layer 3 containing a carrier transporting substance as a main component are formed on a conductive support l.
A photosensitive layer 4 made of a laminate of . 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, an electrophotographic photoreceptor having the most excellent electrophotographic properties can be obtained.

In addition, in the present invention, as shown in FIGS. 5 and 6, a photosensitive layer 4 comprising the carrier-generating substance 7 dispersed 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 layer 5.

When the bisazo compound of the present invention is used as a carrier-generating substance, carrier-transporting substances that can be used in combination with it include electron-transporting and t-accepting substances such as trinitrofluorenone or tetranitrofluorenone, as well as poly- Polymers with *** compounds in their side chains, such as N-vinylcarbazole, or triazole derivatives, oxadiazole derivatives, imidazole derivatives, pyrazoline derivatives, polyarylalkane fermentation 4K, and phenylenediamine derivatives. , hydrazone derivatives, amino-substituted chalcone derivatives, triarylamine derivatives, carbazole derivatives, stilbene # only, and other electron-donating substances that easily transport holes are included. Actually, these @
It is not determined.

The carrier generation layer 2 constituting the two-layer structure f and m4 is as follows:
Toden support l or carrier transport wI3 K ff
It can be formed by the following method, either directly or via an intermediate layer such as an adhesive layer or a barrier layer if necessary.

M-1 bisazo compound is dissolved in an appropriate solvent, or mixed and dissolved with a binder added as necessary, to form a 9 mm
How to apply.

A method in which the M-2 hisazo compound is made into fine particles in a dispersion medium using a ball-killer, a homomixer, etc., and a binder is added if necessary to mix and disperse the resulting dispersion.

Examples of the W4# and dispersant used for forming the carrier generation layer include n-butylamine, diethylamine, ethylenediamine, isofronolamine,
Triethanolamine, triethylenediamine, N, N
-dimethylformamide, acetone, methi, ruethyl ketone, cyclohexanone, pence/, toluene, xylene, chloroform, dichloroethane, dichloromethane,
Tetrahydrofuran, dioxane, methanol, ethanol, impropatol, ethyl acetate, butyl acetate, dimethyl sulfoxide, etc. are used.

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 conductivity, and is electrically insulating. Preferred examples of such a polymer electrolyte include the following σ], but the present invention is not limited thereto.

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 - to 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-fluid resin P-15 phenol -Formaldehyde resin P -1
6 Styrene Fluid Resin F-17 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 particle size of the carrier generating layer or photosensitive layer is preferably 0.01 pm to 20 m, more preferably 0.05 pm to 5 IJm, and the particle size of the bisazo compound is 5 pm. It is preferable that the following is true,
More preferably, it is l#w or less.

As the conductive support used in the electrophotographic photoreceptor of the present invention, the metal plate housing may be coated, vapor-deposited, or laminated with a conductive polymer, a conductive compound such as indium oxide, or a thin layer of a metal such as aluminum, palladium, or gold. Examples include paper, plastic film, etc. that have been made electrically conductive.

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, seratin,
Organic polymers such as casein, starch, polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, or aluminized aluminum are used.

The electrophotographic photoreceptor of the present invention has the above-mentioned structure, and as is clear from the examples described later, it has excellent charging characteristics, sensitivity characteristics, and #J shadow forming characteristics, and sometimes does not deteriorate due to fatigue when used repeatedly. The durability is poor due to the low amount of water.

Hereinafter, embodiments of the present invention will be specifically described, but the scope of the present invention is not limited thereby.

Vinyl chloride - vinyl acetate - is placed on a conductive support by laminating aluminum foil on a polyester film.
Maleic anhydride copolymer [A 0-thickness, U5#10 intermediate layer made of S-LEC MF-10J (Sekisui Chemical Co., Ltd. IR) was provided, and -12 parts by weight of the exemplified compound was added to 1.2-dichloroethane 140] A carrier generation layer was formed by dispersing and mixing the liquid in [i] so that the film thickness after drying was 0.5 μm.

Next, 6 parts by weight of l-phenyl-3-<p-diethylaminostyryl J-5-(p-diethylaminophenyl)-hirazoline and polyester [Pylon 200J (
(manufactured by Toyobo Co., Ltd.) and 10 parts by weight of 1,2-dichloroethane (manufactured by Toyobo Co., Ltd.) were dissolved in 1,2-dichloroethane. The film thickness after drying the liquid is 10
A carrier transport layer was formed by applying the coating to a thickness of .mu.m, and an electrophotographic photoreceptor of the present invention was prepared.

This electrophotographic photoreceptor was tested using an electrostatic copying paper tester "1".
3P-428111J (Kawaguchi Electric Seisakusho 11M) was used to measure the electrophotographic characteristics using the Guinamiak method.

The surface of the photoreceptor layer of the photoreceptor was charged for 5 seconds at a charging voltage of -6, OKV, and then the surface potential VA was determined when the photoreceptor surface was dead.Then, light from a tungsten lamp was irradiated so that the illuminance on the photoreceptor surface was 351 uX, and the surface potential VA was determined. 4 to reduce the quality by half! Exposure amount (half-reduced exposure amount) E −) (1uX
-seC) and 301uX-sea y) surface potential (residual potential) VR after exposure at an exposure dose of 301uX-sea y) was determined.

Further, similar measurements were repeated 100 times.

The result is the notification shown in Table 1.

Table 1 Ratio 112? IJ1 A comparative photoreceptor was prepared in the same manner as in Example 1 except for using the following bisazo compound as a carrier generating substance.

Measurements were carried out on this comparative electrophotographic photoreceptor 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 electrophotographic photoreceptor of the present invention is extremely superior in sensitivity, residual potential, and repetition stability compared to the comparative electrophotographic photoreceptor.

Example 2 An electrophotographic photoreceptor of the present invention was prepared in the same manner as in Example 1 except for using -2 as the exemplified compound as a carrier generating substance.

When this electrophotographic photoreceptor was measured in the same manner as in Example 1, the results shown in Table 3 were obtained.

Table 3 Aluminum wax was deposited on a polyester film, and then the intermediate layer used in Example 1 was provided, and on top of that, -32 parts by weight of the exemplified compound was dispersed and mixed in 140 parts by weight of 1,2-dichloroethane, and tiger liquid was added. The coating was applied so that the film thickness after drying was 0.5 #Ill to form a carrier generation layer.

Next, 6 parts by weight of p-(N,N-diethylamino)penzaltehyde 1,1-diphenylhydrazone and 10 parts by weight of polycarbonate "Panlite L-1250J (manufactured by Konjin Kasei Co., Ltd.) were mixed in 1.2 parts by weight. -dichloroethane 901
The electrophotographic photoreceptor of the present invention was prepared by coating a carrier transport layer by applying the solution dissolved in a certain amount to a film thickness of 12 pm after drying.

Measurements were carried out on this electrophotographic photoreceptor in the same manner as in Example 1, and the result was MA = -1050V, E 3A.
= 2.71 ux-sea, VR = OV.

Comparative Example 2 (vs. ohoJ stilbenzene) A comparative electrophotographic photoreceptor was prepared in the same manner as in Example 3, except that the following bisazo compound was used as a carrier generating substance.

When this comparative electrophotographic photoreceptor was measured in the same manner as in Example 1, VA = -1020V.

E 3A = 7.51ux-sea %VR = -80
It was V.

As is clear from the above results, the electrophotographic photoreceptor of the present invention has significantly superior initial characteristics than the comparative electrophotographic photoreceptor.

The electrophotographic photoreceptor of the present invention according to Example 4, , and Example H3 and the comparative electrophotographic photoreceptor according to Comparative Example 2 were each electrophotographically copied @ f U-biX.
2000 RJ (Konishi Roku Photo Industry Sharen), and after carrying out a durability test by repeating charging, exposure, and 1-no-nin operations for 2,000 times, Example IK was immediately used again.
The same ill determination was carried out. The results are shown in Table 4.

Table II4 As is clear from the results, the deterioration of the characteristics of the electrophotographic photoreceptor of Comparative Example 2 is severe and large, whereas the electrophotographic photoreceptor of the present invention of Example 913 can be used for 2,000 4-electrode exposures. It can be seen that even after repeated use, its characteristic strength remains stable with almost no change from the initial state.

-62 on the exemplified compound on the conductive support used in Example 1
Weight parts and polycarbonate [) Kunlite L-125
0J (manufactured by Teijin Kasei Co., Ltd.) 2] parts were dispersed and mixed in 140 parts of 1,2-dichloroethane and applied to form a carrier-generating layer such that the film thickness after drying was 1 mmK.

Then, 3-(T)-methoxystyryl)-9-(p-
6 parts by weight of (methoxyphenyl)carbazole and 10 parts by weight of methacrylic resin "Acrivet" (manufactured by Mitsubishi Rayon Co., Ltd.) were added in 1. A carrier transport layer was formed by applying a solution of Q-dichloroethane (a) dissolved in parts by weight to a dry film thickness of 104 m, thereby producing an electrophotographic photoreceptor of the present invention.

This electrophotographic photoreceptor was measured in the same manner as in Example 1: E 3A = 311 uX, sec, VR =
It was OV.

7 → To the conductive support provided with the intermediate layer used in Example 1, a 2% ethylenediamine solution of -25 was applied to the indicated compound so that the film thickness after drying was 0.3 μm. ) forms a generation layer;

Furthermore, 6 parts by weight of P-(N,N-diethylamino)benzaldehyde-1,1-diphenylhydrazone and 1,2 parts by weight of polycarbonate [Nipiro/S-1000J (Mitsubishi Gas Chemical Co., Ltd.)] Dissolve ML in 1 ml of dichloroethane, dry! 1! The film thickness after is 14ρI
A carrier transport layer was formed by coating to give a coating composition of IIK, thereby producing an electrophotographic photoreceptor of the present invention.

When this electrophotographic photoreceptor was run for 1 m in the same manner as in Example 1, E 3y, = 2,31uX-8e
c, va=OV.

Further, this electrophotographic photoreceptor was used in an electrophotographic copying machine [U-bi
x 2000RJ (8th grade 6'4 x Kogyosha M'
) K fit, and when the image was copied, a clear copy th image that was faithful to the original image, had high contrast, and excellent gradation was obtained. Even if this was repeated continuously 000 times, a copy image similar to the initial one was obtained.

Comparative example 3.

A comparative electrophotographic photoreceptor was prepared in the same manner as in Example 6 except that the following bisazo compound was used as a carrier generating substance.

When images were copied using this comparative electrophotographic photoreceptor in the same manner as in Example 6, the initial images were good, but as copies were repeated, fog gradually increased, and after 1,000 copies. By repeating this process over and over again, only blurred images with large fog and low contrast can be obtained.

Φψ1 762 parts by weight of the indicated compound and 1 part of 1,2-dichloroethane were placed on the conductive support provided with the intermediate layer used in Example 1.
00 parts by weight are well dispersed and mixed so that the dry film thickness is 0.3
A carrier generation layer was formed by coating to a thickness of .mu.m.

Next, 4-6 parts by weight of the following hydrazone 84t as a carrier transport substance and polyester "Vylon 20" were added thereon.
0J (manufactured by Toyobo Co., Ltd.) dissolved in 10 parts by weight was applied so that the film thickness after line transfer was 12 pHJK to form a gear transport layer, thereby producing an electrophotographic photoreceptor of the present invention.

When this electrophotographic photoreceptor was defined in the same manner as in Example 1, the results shown in Table 5 were obtained.

Table 5 Comparative Example 5 Practical 8 and l! except that the following bisazo compound was used as the carrier generating substance. A child photographic photosensitive group for comparison was prepared in the same manner as y1.

Regarding this comparative electrophotographic photoreceptor, measurements were performed in the same manner as in Example 1, and the results shown in Table 6 were obtained.

As is clear from the results shown in Table 6, the electron 4 insensitive element of the present invention is superior to the comparative electron thick photoreceptor in terms of sensitivity, residual potential, and repetition stability.

Example 9 On the conductive support provided with the intermediate layer used in Example 1, 1,452 parts by weight of the exemplified compound and 1,2-dichloroethane were added.
00 parts by weight are well dispersed and mixed to obtain a dry film thickness of 0.3.
A carrier generation layer was prepared by applying the solution to a thickness of .mu.m.

Then, a carrier transport substance and L7 are added on top of the 3-(p
-methoxystyryl)-9-(1)-methoxyphenyl)carbazole and 10 parts by weight of polycarbonate [Panrye] L-1250J (manufactured by Konjin Kasei Co., Ltd.) were dissolved in 1.2-dichloroethane parts by weight. An electrophotographic photoreceptor of the present invention was prepared by coating a carrier transport layer such that the film thickness after drying was LO μm.

When this electrophotographic photoreceptor was measured in the same manner as the Hero fPJ1, z h = 2.4 xuz-aec
, VR=Ov.

Example IO~14 As a carrier generating substance, -3 and K-26 are used as exemplary compounds.
tl control example 9 using α, K-42, and K-ω in %
An electrophotographic photoreceptor of the present invention was prepared in the same manner as above, and the same measurements were carried out, and the results shown in Table 7 were obtained.

Table 7 2hμ--7 Samples An electrophotographic photoreceptor of the present invention was prepared in the same manner as in Example H3, except that -71 was used as the exemplified compound as a carrier-generating substance.

When this photoreceptor was measured in the same manner as in Example 1, E 34 = 2,41 uxaaec, VR = 2
V't"

Ratio &flJ 6 A comparison electron 4 photoreceptor was prepared in the same manner as in Fi Example IO except that the following bisazo compound was used as a carrier generating substance. When this comparative photoreceptor was subjected to pressure measurement in the same manner as in Example 1, it was found that E 34 =As is clear from the above results, the electrophotographic photoreceptor of the present invention has a higher sensitivity and residual potential than the comparative electrophotographic photoreceptor. It has excellent properties such as:

[Brief explanation of the drawing]

1 to 6 are cross-sectional views showing examples of the mechanical configuration 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 carrier transport substance 7...Carrier generating substance agent Yoshimi Kuwahara Figure 1 $2 Figure p, Figure 5 F! This figure procedural amendment document June 14, 1980 Patent Office Commissioner Island 1) Spring Book 1, Indication of the case 1982 Patent Application No. 85! $30 No. 2 Name of the invention Electrophotographic photoreceptor 3 Relationship to the case of the person making the amendment Address of the patent author 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (127) Konishiroku Photo Industry Co., Ltd. 4 Agent address: 191 Address: Konishiroku Photo Industry Co., Ltd., 1 Sakura-cho, Hino-shi, Tokyo 6, Full text of the specification to be amended 7, Engraving of the specification of the contents of the amendment (no change in content) Specification 1, Title of the invention: Electrophotography, S photoform 2, Claims (1) An electrophotographic photosensitive material comprising a photosensitive layer containing a bisazo compound represented by the following general formula (1) on a conductive support. body. General formula 〇〕 A kJ””N Ar, cxl ri x, -α-α4-mu →-←A [In the formula, ArI-1 represents a substituted or unsubstituted aromatic carbocyclic group, x, , x,, x,,
x4 each represents a hydrogen atom or an electron-withdrawing group, A
is Teatte, Y: hydrogen atom, hydrogen atom, *ruboxy group, its ester group, sulfo group, substituted/unsubstituted carbamoyl group or substituted/unsubstituted sulfamoyl group, 2: substituted/unsubstituted aromatic group Atom groups necessary to constitute a carbocyclic ring or a branched substituted/unsubstituted aromatic heterocycle, R8: hydrogen atom, substituted/unsubstituted alkyl group, substituted/unsubstituted amino group, carboxy group, ester group thereof, Substituted/unsubstituted carbamoyl group, cyano group, R1: Substituted/unsubstituted 7-aryl group, R3: Substituted/unsubstituted alkyl group, Substituted/unsubstituted aralkyl group Mat, -kLi Substituted/unsubstituted aryl represents a group. ] (2) The photosensitive layer contains a carrier-generating substance and a carrier-transporting substance, and the carrier-generating substance has the general formula [
vI Claims S which are bisazo compounds rewarded with 0
The electrophotographic photoreceptor according to item (1). 3. Invention f)llP! Al Description The present invention relates to an electrophotographic photoreceptor, and more specifically, a novel electrophotographic photoreceptor 'KIl'1'' containing a bisazo compound.
Ru. More specifically, the present invention relates to a highly durable electrophotographic photoreceptor that has high sensitivity and is suitable for repeated use. Conventionally, in electrophotographic photoreceptors, selenium, zinc oxide,
A photosensitive layer mainly composed of an inorganic photoconductor such as cadmium oxide was widely used. However, these are not necessarily fully satisfactory in terms of sensitivity, Jl resistance, humidity resistance, or printing durability III.
Due to the toxicity of IK selenium and cadmium sulfide, there were restrictions in the construction and handling of KII. On the other hand, electrophotographic photoreceptors having a photosensitive layer containing an organic photoconductive compound as a main component are relatively easy to manufacture, have low manufacturing costs, and can be formed into either a cylindrical drum shape or a sheet shape. be easy to handle,
In addition, it has many advantages such as excellent heat resistance, whereas selenium photoreceptors generally have poor heat resistance and crystallize under high temperature conditions, and have attracted much attention in recent years. Poly-N-vinylcarbazole is known as such an organic photoconductive compound, and 2.4.7-
Electrophotographic photoreceptors having a photosensitive layer containing as a main component a charge transfer complex formed with a Lewis acid such as dolinitro-9-fluorenone have already been put to practical use. However, this S
The light body is not always satisfactory in terms of sensitivity and printing durability. On the other hand, there are known functionally separated electrophotographic photoreceptors of laminated or dispersed type in which the carrier generation function and the carrier transport function of the photoconductive function are respectively assigned to separate substances. Such a functionally separated electrophotographic photoreceptor has a wide range of materials to choose from, and it is relatively easy to achieve high performance in electrophotographic properties such as charging characteristics, sensitivity, residual potential, and printing durability. It has the advantage that it is easy to create an electrophotographic photoreceptor with specific characteristics. Various types of carrier-generating substances have been proposed in the past as carrier-generating substances that primarily perform carrier generation among the photoconductive functions of electrophotographic photoreceptors. For example, a carrier generation layer formed from amorphous selenium as an inorganic material is well known, but this has the drawback that it crystallizes under high temperature conditions and its performance deteriorates. In addition, various proposals have been made to use photoconductive organic dyes and pigments with particularly excellent carrier-generating properties as carrier-generating substances, such as U.S. Pat. No. 3,871,
Perylene pigments described in the specification of No. 882 or Iisha Special Publication No. 18
48-30513, JP 53-95033, JP 54-12742, JP 56-11
No. 6040, JP-A-54-20737, Lf
Azo compounds such as those described in fllll#HI4.052.2xo4ijflJ specifications are already known. However, these azo compounds are not necessarily satisfactory in terms of characteristics such as sensitivity, residual potential, and stability when used repeatedly, and the selection range of carrier transport substances is also limited. The reality is that nothing that satisfactorily satisfies the wide range of demands of electrophotographic processes has yet to be obtained. An object of the present invention is to provide an electrophotographic photoreceptor containing a bisazo compound that is stable to heat and light and has a carrier generation ability K11t'. Another object of the present invention is to provide high sensitivity, low residual potential,
Another object of the present invention is to provide an electrophotographic photoreceptor with excellent durability whose properties do not change even after repeated use. As a result of intensive research to achieve the above object, the present inventors have discovered that a bisazo compound represented by the following general formula El) can function as an active ingredient of a photoreceptor, and have completed the present invention. General formula (1) A N trap 1'-rs CxlriXx-hekuXa Arc
-Oka A In the formula, Arl and Arl are respectively substituted and
It represents an unsubstituted aromatic carbocyclic group, preferably a substituted or unsubstituted phenyl group or a naphthyl group, and more preferably a substituted or unsubstituted phenyl group. Substituents for these groups include, for example, substituted or Unsubstituted alkyl group, substituted/unsubstituted alkoxy group, nor\rogen atom, cyano group,
Examples include a carboxy group, an ester group thereof, a sulfo group, an acylamino group, a carbamoyl group, an acyl group, an acyloxy group, a sulfonamide group, a sulfamoyl group, a sulfone group, but preferred are substituted/unsubstituted alkyl groups, substituted/unsubstituted alkyl groups, etc.
These are unsubstituted alkoxy groups, cyano groups, and herogen atoms. x, , x, , x, , x each represents a hydrogen atom or an electron-withdrawing group, preferably a hydrogen atom, a cyano group, a halogen atom, a carboxy group, or a nitro group. H , and Y is a hydrogen atom, a hydroxy group, a carboxy group, an ester group thereof, a sulfo group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted sulfamoyl group, preferably a substituted or unsubstituted carnoyl group. , a substituted/unsubstituted lower alkyl group having 1 to 4 carbon atoms, and a substituted/unsubstituted phenyl group, , hydrogen atom, substituted/unsubstituted lower alkyl group having 1 to 4 carbon atoms, substituted/unsubstituted aromatic group carbocyclic groups (e.g., substituted/unsubstituted phenyl groups, substituted/unsubstituted heptyl groups, substituted/unsubstituted anthryl groups, etc.), or substituted/unsubstituted aromatic heterocyclic groups (e.g., ff-substituted・Reward unsubstituted carbazolyl groups, substituted/unsubstituted dibenzofuryl groups, etc.). As a substituent of the group of Nit et al., for example, a group having 1 to 4 carbon atoms
alkyl groups such as chlorine atoms and bromine atoms, lower alkoxy groups having 1 to 4 carbon atoms, hydroxy groups, aryloxy groups such as phenoxy groups and naphthoxy groups, acyloxy groups, carboxy groups, ester groups thereof, Carno (
Examples include a moyl group, an acyl group, a sulfo group, a sulfamoyl group, an amine group, an acylamine group, a sulfonamide group, a cyano group, a nitro group, and preferably one or more carbon atoms.
4 alkyl groups, 710 gene atoms such as chlorine atoms and bromine atoms, lower alkoxy groups having 1 to 4 carbon atoms, cyano groups, and nitro groups. Za is a group of atoms necessary to form a substituted or unsubstituted aromatic carbocycle, or a substituted or unsubstituted aromatic heterocycle. Specifically, Il is a substituted or unsubstituted benzene ring, a substituted or Represents a group of atoms forming an unsubstituted naphthalene ring, a substituted or unsubstituted indole ring, or a substituted or unsubstituted carnoxole ring. Examples of substituents for the atomic group forming these rings include a series of substituents such as those listed as substituents for R4 and R1, but halogen atoms, sulfo groups, and sulfamoyl groups are preferred. R8 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted amide group, a carboxy group, an ester group thereof, a substituted or unsubstituted carbamoyl group, or a sia/group, preferably a hydrogen atom and a carbon number of 1 -4 alkyl group and cyano group. R1 is a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted phenyl group. Examples of substituents for these groups include a series of substituents such as those listed as substituents for R4, but preferably halogen atoms, alkyl groups having 1 to 4 carbon atoms, and all to 4 carbon atoms. It is a lower alkoxy group. Substituted or unsubstituted alkyl groups, substituted or unsubstituted aralkyl groups, or substituted or unsubstituted aryl groups, preferably an alkyl group having 1 to 4 carbon atoms, or a phenyl group. Namely, in the present invention, the bisazo compound represented by the general formula rI)t is used as a photoconductive substance constituting the emotional layer of an electrophotographic photoreceptor. This is used as a carrier generating substance for a secondary photographic photoreceptor, which has the function of generating and transporting carriers using separate substances (thereby, it has excellent coating properties, such as charge retention, sensitivity, It is possible to produce an electrophotographic photoreceptor that has excellent electrophotographic properties such as residual potential, shows little deterioration even after repeated use, and can exhibit robust and stable properties in the presence of heat, light, etc. Examples of the bisazo compound useful in the present invention represented by formula (1) include those having the following structural formula, but the bisazo compound of the present invention is not limited by this K. Exemplary compounds include - 2 -3 -4 -5 -6 -g -9 -10 K -11 -12 -13 -14 -22 -24 L -27 -4 -4 - (Capital) -31 -33 -34 -35 -36 -37 -41 -42 -44 -46 -47 -48 -51 -52 -53 -54 -55 K - Audience -57 -58 K -59 -ω -61 -62 -63 -64 -65 -66 -67 - Rui -69 -73 K" Cool (C00HK- 75 K -80ON K -81CN Br K"' C0OH The above bisazo compound can be reduced to 1 volume by a known method.
tK synthesis is possible. For example, Synthesis Example 1 (Synthesis of Exemplary Compound -1) Makromol Chew,
, 84.64N79 (1965), 1,4-bis-[p-nitrophenyl)-1,
3-Butadiene was reduced with tin and hydrochloric acid in the presence of alcohol to give 1,4-bis-[p, thus obtained 1,4-bis-(
p-aminophenyl)-1,3-butadiene 2.36
, lid (0.01 mol) with 10-concentrated hydrochloric acid and 10
- dispersed in a water mixture of 1.52! A solution of I (0,022 mol) of sodium sulfate dissolved in water was added dropwise under water cooling while keeping the internal temperature between 0°C and 5°C.
Allow to stir for an hour. After the reaction, a small amount of residual liquid was separated from Pfl, and 20% of borohydrogen fluoride was added to Pfl, and the precipitate was collected, washed with water, and thoroughly dried. The obtained tetrazonium salt was mixed with N,N
-dimethylformamide 50- to prepare a tetrazonium salt solution to be used in the next reaction. Next, 2-hydroxy-3-naphthoic acid ani IJ F (naphthol A 8 ) 5.2711 (0.02 mol)
, Torie 1 /- Lua i n 5.4 j' v400
'') N t N ') l f Dissolved in fluorformamide, and while keeping the internal temperature of a water-cooled tube at 10 to 13°C KfM, the tetrazonium salt solution prepared above was added dropwise, stirred for 2 hours at the same temperature, and further cooled to room temperature. The reaction was stirred for 2 hours.Then, the precipitate precipitated was collected to obtain 4.5 g of a bisazo compound of N,N-dimethylformad.The melting point was 300°C or higher, and the infrared convergence spectrum showed ν = 1680 m. -' (amide absorption) and FD-MAS8 spectrum K 5/;
, = 784 molecular ion peaks appeared, confirming that the target substance was synthesized. Synthesis Example 2 (Synthesis of -25 to exemplified compound) Organi
c R@aotion Vow 15, 204 1,4-bis-(p-
Nitrophenyl)-1-cyano-1,3-butadiene was reduced with tin and hydrochloric acid in the presence of alcohol to produce 1,4-bis-1,3-butadiene.
(p-aminophenyl)-1-cyano-1,3-butadiene was obtained. 1,4-bis-(p-aminophenyl)-1-cyano-1,3-ptadiene obtained in this manner.
619 (0.01 mol) with 10-concentrated hydrochloric acid and lQmI
1.52II (0,022
A solution prepared by dissolving 5 WdK of sodium nitrite (mol) in water was added dropwise to an ice-cooled solution at an internal temperature of vO to 5°C, and the mixture was stirred and reacted at the same temperature for 1 hour. After the reaction, a small amount of the residue was filtered, 42-hydrofluoric acid aqueous solution 201117 was added to the P solution, and the precipitated acid was collected by L1.
After washing with water, it was thoroughly dried. Obtained tetrazonium salt v
It was dissolved in N,N-dimethylformamide 50- to prepare a tetrazonium salt solution to be used in the next reaction. Next, 5.27 p (0.02 mol) of 2-hydroxy-3-naphthoic acid anilide (naphthol A 8 ) and 5.41 p of triethanolamine were dissolved in 400-N,N-dimethylformamide, and the mixture was heated in an indoor bath under water cooling. The tetrazonium salt solution prepared above was added dropwise while maintaining the temperature at 0 to 5°C, and the mixture was further stirred at the same temperature for 2 hours, and further stirred and reacted at room temperature for 2 hours. After that, the deposited precipitate was collected, N, N
The desired bisazo compound 4.0 was obtained by washing with -dimethylformamide and then with acetone and drying. Melting point: 300°C or higher Infrared IIs @ collection, k' = 220-OC
II-” (CN absorption), ν=1680cm+-”
(amide absorption) and FD-mass spectrum K”/,
Since a molecular ion peak of =809 appeared, it was confirmed that the target substance was synthesized. Synthesis Example 3 (Synthesis of exemplified compound -30) 5.83.9 (0.02 mol) of 2-hydroxy-3-naphthoethyl-2',4'-dimethylanilide (naphthol A8-MX) was mixed with N,N -Dissolve 70031K of dimethylformamide and add 20.9% of sodium chloride. N, N- of the tetrazonium salt (0.01 mol) prepared in Synthesis Example 2 while keeping the internal temperature at 10 to 13°C under water cooling.
50ml+7 dimethylformamide solution was gradually added. The mixture was further stirred at the same temperature for 2 hours, and further stirred and reacted at room temperature for 2 hours. After the reaction, the precipitate precipitated was collected, washed with N,N-dimethylformamide, then water, and then acetone, and dried to obtain the target bisazo compound 4.51. Melting point: 300°C or higher Infrared absorption spectrum: Si = 2200 cm - CN absorption), ν = 168 billion - 1 (amide absorption) and FD
-MA8B spectrum! Since a peak of molecular ion +1 of ICw'.=866 appeared, it was concluded that the target substance was synthesized. Synthesis Example 4 (Synthesis of exemplified compound -73) Organi
e R@action Mol Is, 3-promo 1- obtained by condensing Oboro-nidrow α-bromocinnamaldehyde and p-nitrobenzyl cyanide in the presence of piperidine in alcohol according to the method of 204 Kisen. Cyano-1-(P-nitrophenyl)-4
-(vm-nitrophenyl)-1,3-butadiene,
3-promo 1 was reduced with tin and hydrochloric acid in the presence of alcohol.
-cyano-1-(P-aminophenyl)-4-(■-7
Minophenyl)-1,3-butadiene was obtained. The 3-promo 1-cyano-1- obtained by K.
(p-aminophenyl)-4-(va-aminophenyl)-1,3-butadiene 4.01i (0.01 mol) was dispersed in a mixture of 15m#) hydrochloric acid and 15-water,
．． 52g (0,022mol) of sodium nitrite in 511ml of water
An aqueous solution dissolved in No. 4 was added dropwise while keeping the temperature at 0 to 5° C. under water cooling, and the mixture was further stirred and reacted at the same temperature for 1 hour. After the reaction, a small amount of the residue was separated, 30% of a 42% hydrogen fluoride aqueous solution was added to F*, and the precipitate was collected, washed with water, and thoroughly dried. The obtained tetrazonium salt was mixed with N,N
-Dissolved in dimethylformamide 501 to prepare a tetrazonium salt solution used in the next reaction. Next, 2-hydroxy-3-naphthoethyl-3'-nitroanilide (naphthol As-BS) 6.16Ii (0,
02 mol), triethanolamine 5.49 to 400-
was dissolved in N,N-dimethylformamide and cooled with water. While keeping the internal temperature at 10 to 13°C, the tetrazonium salt solution prepared above was added dropwise, and the solution was further stirred at the same temperature for 2 hours, and further stirred at room temperature for 2 hours. Made it react. Thereafter, the precipitate precipitated was collected, washed with N,N-dimethylformamide, then with a7ton, and dried to obtain 6.2 g of the target bisazo compound. = 22001-1 (C
N experimental yield), ν = 16801-1 (amide absorption) and molecular ion needle = 879 in the FD-MA8B spectrum
Since the isotope peak group caused by K was eclipsed, it was concluded that the target substance had been synthesized. The bisazo compound of the present invention has excellent photoconductivity, and when it is used for electrophotographic Mjt body t'l1iIL, a photosensitive layer in which the bisazo compound of the present invention is dispersed in a binder is formed on a conductive support. It is possible to construct II from trial and K. In addition, as another method, among the photoconductivity possessed by the bisazo compound of the present invention, IIK can be used as a carrier generating substance that takes advantage of its excellent carrier generating ability, and in combination with *1 a carrier generating substance that can act as IIK. From the usage K, the so-called functional component si of the laminated type or dispersion layer
It is also possible to use it as an electrophotographic photoreceptor. Although various functional configurations of electrophotographic photoreceptors are known, the electrophotographic mjt body of the present invention can take any of them. The transition is the 1st W to 6th aU shape layer. In FIG. 81 and FIG. 3, a carrier generation layer 2 mainly composed of the bisazo compound mentioned above is formed on a conductive support 1;
A photosensitive layer 4 made of a laminate with a carrier transport 3 containing a carrier transport substance as a main component is provided. As shown in FIGS. 2 and 4, the photosensitive layer 4 may be provided via an intermediate layer 5 provided on a conductive support. Like this [4i
When the optical layer 4 has a two-story structure, an electrophotographic photoreceptor having the most excellent electrophotographic properties can be obtained. In addition, in the present invention, as shown in FIGS. 5 and 6, a photosensitive layer 4 formed by dispersing #-marked carrier generating substance 7 in a layer 6 mainly composed of a carrier transport substance is attached to a conductive support. Upper Kl [I! Alternatively, it may be provided via the company intermediate layer 5. When the bisazo compound of the present invention is used as a carrier-generating substance, examples of carrier-transporting substances that can be used in combination include electron-accepting substances that easily transport electrons, such as trinitrofluorenone and tetranitrofluorenone; Heterocyclic compounds such as poly-N-vinylcarbazole, polymers with diagonal chain KW, triazole derivatives, oxadiazole derivatives, imidazole S* bodies, pyrazoli 211311 bodies, polyarylalkane S conductors, phenylene diamines. Examples include electron-donating substances that transport holes such as derivatives, hydrazone derivatives, amino-substituted chalcone S* forms, triarylamine derivatives, carbazole derivatives, and stilbene derivatives. Kl
It is not determined. The two carrier generation layers constituting the two-layer photosensitive layer 4 are applied directly to the conductive support 1 or the carrier transport layer 3 or via an intermediate layer such as an adhesive layer or a barrier layer as necessary. , can be formed by the following method. A solution of M-1 bisazo compound dissolved in a suitable solvent,
Or 111 mixed and dissolved with a binder added as necessary.
Method of applying Il[. M-2 bisazo compound in ball mill, homomixer 11
A method in which the particles are made into fine particles in a dispersion medium, mixed and dispersed with a binder added if necessary, and then applied as a dispersion. Examples of the solvent or powder used for forming the carrier generation layer include n-butylamine, diethylamine,
Ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, dichloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, inglobanol, Examples include ethyl acetate, butyl acetate, dimethyl sulfoxide, 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 conductivity, and is electrically insulating. preferable. Examples of such high molecular weight polymers include, for example, the following, but are not limited thereto. P-1 Polycarbonate P-2 Polyester P-3 Methacrylic resin P-4 Acrylic resin P-5 Polyvinyl chloride P-6 Polyvinylidene chloride P-7 Polystyrene P-8 Polyvinyl acetate P-9 Styrene-butadiene copolymer P - 10 Vinylidene chloride-acrylonitrile copolymer P-11 Vinyl chloride-vinyl acetate copolymer P-12
Vinyl chloride-vinyl acetate-maleic anhydride copolymer P-13 Silicone resin P-14 Silicone-alkyd resin P-15 Phenol-formaldehyde resin P-16 Styrene-alkyd resin p-y Poly-N-vinylcarbazole These The binder can be used alone or as a mixture of two or more. The thickness of the carrier generation layer 2 formed by K in this way is:
The thickness is preferably 0.01 μm to 20 μm, more preferably F! It is 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 bisazo compound 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 a metal plate, a conductive polymer, a conductive compound such as indium II ride, aluminum, palladium,
Examples include paper and plastic films that have been made conductive by coating, vapor depositing, or laminating a thin layer of metal such as gold. 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, gelatin,
Organic polymer substances such as casein, starch, polyvinyl alcohol, ethyl cellulose, and carboxymethyl cellulose, or aluminum oxide are used. The electrophotographic 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 does not suffer from fatigue deterioration when used repeatedly. It is small and has excellent durability. Hereinafter, the embodiments of the present invention will be specifically described as Km, but the solid line embodiment of the present invention is not limited to Km. Example 1 Vinyl chloride-411 vinyl-maleic anhydride 11 copolymer "Esrec MF-10J" was deposited on a conductive support made of a polyester film laminated with aluminum foil.
(manufactured by Tanezu Kagaku Co., Ltd.) with a thickness of 0.05 μm is provided, and on top of this, a film obtained by drying a solution prepared by dispersing -12 parts by weight of the exemplary compound in 140 parts by weight of 1,2-dichloroethane. A carrier generation layer was formed by applying Km cloth to a thickness of 0.5 μm. Next, 6 parts by weight of 1-phenyl-3-(p-diethylaminostyryl)-5-(p-diethylami/phenyl)-pyrazoline and 10 parts by weight of polyester "Vylon 200J (manufactured by Toyobo Co., Ltd.) were added to 1.2- dichloroethane 9
0 parts by weight, and the film thickness after drying this solution is 10 μm.
A carrier transport layer is formed by applying Kf/ to a thickness of 5.
An electrophotographic photoreceptor of the present invention was prepared. Regarding this electrophotographic photoreceptor, the electrostatic copying paper tester "B"
The electrophotographic characteristics were measured using a dynamic method using "Model P-428" (newly manufactured by Kawaguchi Denki Seisaku). The surface potential VA when the surface of the photosensitive layer of the photoreceptor is charged at a charging voltage of -6.0 KV for 5 seconds, and then the light from a tungsten lamp is applied to S! Illuminance on the surface of the original pot body is 35 lux
The exposure amount required to attenuate the surface potential VA by half (half-reduced exposure amount) E4 (1 uz・
ssa ) and the surface potential (residual potential) VR after exposure at an exposure dose of 301 uz·ssa were determined. In addition, the same measurement was repeated 100 times.
1 Table Comparative Example 1 A comparative photoreceptor was prepared in the same manner as in Example 1, except that the following bisazo compound was used as a carrier generating substance. C,H. When measurements were carried out on this comparison electrophotograph and the S light body in the same manner as in Example 1, results were obtained as shown in Table 2.
As is clear from the results shown in the table, the electrophotographic photoreceptor of the present invention is extremely superior in #lB degree, residual potential, and repetition stability compared to the comparative electrophotographic photoreceptor. Example 2 An electrophotographic WB light body of the present invention was produced in the same manner as in Example 1, except that -2 was used as the exemplified compound as a carrier generating substance. When this electrophotographic photoreceptor was measured in the same manner as in Example 1, the results are shown in Table 3. (Additionally, -32 parts by weight of the exemplified compound was added to 140 parts by weight of 1,2-dichloroethane.
The IK dispersion-mixed liquid was coated with a cloth so that the film thickness after drying was 0.5 μIIK to form a carrier generation layer. , 10 parts by weight of polycarbonate U Panlite L-1250J (manufactured by Jyojin Kasei Co., Ltd.) and 90 parts by weight of 1,2-dichloroethane.
The electrophotographic photoreceptor of the present invention was prepared by applying a liquid containing 1K dissolved therein so that the film thickness after drying would be 12μIIK to form a transport layer. When this electrophotographic photoreceptor was measured in the same manner as in Example 1, VA=-1osov, mV
2=2.71ux-seo, VR=OV Comparative Example 2 A comparative electrophotographic photoreceptor was prepared in the same manner as in Example 3 except that the following bisazo compound was used as a carrier generating substance. When this comparative electrophotographic photoreceptor was measured in the same manner as in Example 1, VA=-1020V. E % = 7.51ux・seo, VR = -8
It was 0V. As is clear from the above results, the electrophotographic photoreceptor of the present invention has significantly superior initial characteristics than the comparative electrophotographic photoreceptor. Example 4 The electrophotographic photoreceptor of the present invention according to Example 3 and the comparative electrophotographic photoreceptor according to Comparative Example 2 were each used in an electrophotographic copying machine j.
tJ-Bix 2000 RJ (manufactured by Konishiroku Photo Industry Co., Ltd.) K equipment is used to perform charging, exposure, and cleaning operations at 2.0
Immediately after carrying out the durability test 00 times, the same measurements as in Example IK were carried out again. It is as shown in Table 4 of Keikisha. 41st! As is clear from these results, the deterioration of the characteristics of the electrophotographic photoreceptor of Comparative Example 2 is extremely large, whereas the electrophotographic photoreceptor of Example 30 of the present invention can be repeatedly charged and exposed for 2,000 m. It can be seen that the characteristics are stable with almost no change from the initial stage. Example 5 -62 was applied to the exemplified compound on the conductive support used in Example 1.
Weight parts and polycarbonate [) Gunlite L-125
A carrier generation layer was formed by dispersing and mixing 2 parts by weight of 0J (manufactured by Ryotai Kasei Co., Ltd.) in 140 parts by weight of 1,2-dichloroethane and applying the solution to a dry film thickness of 1 μymK. Next, 6 parts by weight of 3-(p-methoxystyryl)-9-(p-methoxyphenyl)carbazole and 10 parts by weight of methacrylic resin "Acrivet" (Mitsubishi Rayon Co., Ltd. 1 [)] were added to 90 parts by weight of 1.2-dichloroethane. The electrophotographic photoreceptor of the present invention was prepared by applying a solution dissolved in the above to form a carrier transport layer so as to have a film thickness of 10 μm after drying. When this electrophotographic photoreceptor was measured in the same manner as in Example 1, E station = 311uxaaeo %VR = OV
Met. Example 6 On the conductive support provided with the intermediate layer used in Example 1, a 2% ethylenediamine solution of -25 was applied to the exemplified compound so that the film thickness after drying was 0.3 AIImK to form a carrier generation layer. Formed. Furthermore, K p (N+ N-diethylamino)benzaldehyde-1,l-diphenylhydrazone 6
parts by weight, polycarbonate [Niepilon 8-1000
J (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 10 parts by weight were dissolved in 90 parts by weight of 1,2-dichloroethane, and the film thickness after drying was 14.
The electrophotographic photoreceptor of the present invention was prepared by applying the same to form a carrier transport layer. When this electrophotographic photoreceptor was measured in the same manner as in Example 1, F! 1/2: 2.31ux**so
, VR=QV. Further, this electrophotographic photoreceptor was used in an electrophotographic copying machine [U-Bi
When the image was copied using a x 2000 RJ (manufactured by Konishiroku Photo Industry Co., Ltd.) K device, a clear copied image faithful to the original INK, with high contrast, and excellent gradation was obtained. Even when this was repeated 10,000 times, the same duplicated images as the initial one were obtained. Comparative Example 3 A comparative electrophotographic photoreceptor was prepared in the same manner as in Example 6 except that the following bisazo compound was used as a carrier generating substance. When this comparison electrophotographic photoreceptor was copied in the same manner as in Example 6, the initial image quality was good, but with repeated copying, fog gradually increased and After repeating the process several times, it was no longer possible to obtain an unclear lil*L with large fog and low contrast. Example 7 A 0.05 tm thick intermediate layer made of vinyl chloride-vinyl acetate-maleic anhydride copolymer [Eslec MF-10J (manufactured by Block Chemical Co., Ltd.)] was provided on a polyester film on which aluminum was vapor-deposited. 1,423 parts by weight of the exemplified compound, 6 parts by weight of 1,1-bis(4-N,N-diethylano-2-methylphenyl)-1-phenylmethane, and polycarbonate [Panlite L-12].
Add 10 parts by weight of 50J (manufactured by Konjin Kasei Co., Ltd.) to 100 parts by weight of 1,2-dichloroethane, mix well with a ball mill, and apply the liquid so that the film thickness after drying is 10 μm. An electrophotographic photoreceptor of the present invention was prepared. Regarding this electrophotographic photoreceptor, the electrostatic copying paper tester "BP"
Electrophotographic characteristics were measured using a dynamic method using -42811J (newly manufactured by Kawaguchi Denki Seisakusho). The surface of the S light layer was charged at +6 KV for 5 seconds, and then the light from a tungsten lamp was applied to the surface of the light layer until the illuminance at INIK was 351.
When we calculated the exposure amount (1!q) by setting K so that uz[
Furthermore, the surface potential (residual potential) when an exposure amount of 301 ux-sea was applied was VR=+4V. Comparative Example 4 An electrophotographic photoreceptor for comparison was prepared in the same manner as in Example 7 of Tasha Co., Ltd., using the following bisazo compound as a carrier generating substance. When this comparative electrophotographic m light body was measured in the same manner as in Example 7, RV2 = IZ 4 xux・
8θa and VR=84 V, and both sensitivity and residual potential were significantly inferior to that of the electrophotographic photoreceptor of the present invention in Example 70. Example 8 On the conductive support provided with the intermediate layer used in Example 1, -762 parts by weight of the exemplified compound and 1 1,2-dichlorop-ethane were added.
00 parts by weight are well dispersed and mixed, and the film thickness after drying is 0.3
A carrier generation layer was formed by applying the coating to a thickness of μra11c. Next, 6 parts by weight of the following hydrazone derivative as a carrier transport substance and polyester [Vylon 200J] were added thereon.
(manufactured by Toyobo Co., Ltd.) was dissolved in 10 parts by weight of KII11 cloth so that the film thickness after drying was 12 μIIK to form a carrier transport layer, thereby producing an electrophotographic photoreceptor of the present invention. When this electrophotographic photoreceptor was measured in the same manner as in Example 1, the results were shown in Table 115. Table 5 Comparison Example 5 An electrophotographic photoreceptor for comparison was prepared in the same manner as in Example 8 of Takara Co., Ltd. using the following bisazo compound as a carrier generating substance. Regarding this comparative electrophotographic photoreceptor, K
When measurements were carried out, the results shown in Table 6 were obtained. As is clear from the results shown in Table 6, the electrophotographic photoreceptor of the present invention is superior to the comparative electrophotographic S photoreceptor in terms of sensitivity, residual potential, and repetition stability. Example 9 452 parts by weight of Exemplary Compound K and 100 parts by weight of 1,2-dichloroethane were well dispersed and mixed on the conductive support provided with the intermediate layer used in Example 1, and the film thickness after drying was 0.
A carrier generation layer was prepared by coating the sample in an amount of 371111. Then, 3-(p-
6 parts by weight of methoxystyryl)-9-(p-methoxyphenyl)carbazole and 10 parts by weight of polycarbonate [Panlite L-1250J (e-Jin Kasei Co., Ltd. II)
．． A carrier transport layer 11- was formed by applying a solution dissolved in 90 parts by weight of 2-dichloroethane so that the film thickness after drying was 10 μwafc, thereby producing an electrophotographic photoreceptor of the present invention. Regarding this electrophotographic photoreceptor, measurement L
Tato C mouth, IQ=! 41uz-s@c, VR=
It was OV. Example 1 ON14 As a carrier generating substance, -3 and K-26 were used as exemplary compounds.
, K-39, I got good results. Seventh! ! Practical Example 15 Electrophotographic mj of the present invention was prepared in the same manner as in Example 3 except that exemplified compound 41K-71 was used as the carrier generating substance.
t, the body was created. Regarding this photoreceptor, [measurement was made in the same manner as in Example 1, E noise = 2.41ux・meo, VR = -
It was 2V. Comparative Example 6 A comparative electrophotographic photoreceptor was prepared using the following bisazo compound as a carrier-generating substance by combining Hakahiro Solid Line Example 1O and Oka@K. When this worn photoconductor was measured in the same manner as in Example 1, gQ-8, g 1ux-ssa
, VR=-85V. As is clear from the above results, the electrophotographic S photoreceptor of the present invention is significantly superior in characteristics such as sensitivity and residual potential compared to the comparative electrophotographic photoreceptor. 4. Brief Description of the Drawings Figures 1 to 6 are WIF views showing examples of the mechanical configuration of the electrophotographic photoreceptor of the present invention. 1... Conductive support 2... Carrier generation layer 3
... Carry transport layer 4 ... Photosensitive layer 5 ... Intermediate layer 6 ... Layer containing carrier transport substance 7 ... Carrier generating substance agent Yoshimi Kuwahara

Claims (1)

[Scope of Claims] (IJ An electrophotographic photoreceptor characterized by having a photosensitive layer containing a bisazo compound represented by the following general formula on a nwt support. General formula (IJ A-N=N- Ar, -Cx, =ex, -0XFOX, A
r2-N=N-A [In the formula, Ar, , Ar, /d are each substituted. Represents an unsubstituted aromatic R18m group, "1
1 or a substituted sulfamoyl group. 2: Substituted or unsubstituted aromatic carbon method or atomic group necessary to constitute a substituted or unsubstituted aromatic heterocycle, R1: Water bulk atom, substituted or unsubstituted alkyl group, substituted or unsubstituted amino group , carboxy group, ester group thereof, substituted or unsubstituted carbamoyl group, cyano group, R2: substituted or unsubstituted 7-aryl group, Rs: substituted or unsubstituted alkyl group, substituted or unsubstituted 72 alkyl group represents a substituted or unsubstituted aryl group. ] (2) The oriented photosensitive layer contains a carrier-generating ring and a carrier-transporting substance, and the carrier-generating substance has the general formula (
An electrophotographic photoreceptor according to claim 1, which is a bisazo compound represented by IJ.