JPS60191267A - Photosensitive body - Google Patents

Abstract

PURPOSE:To obtain a photosensitive body having high sensitivity particularly to laser light, small residual potential and excellent durability without changing said characteristics even after repeated use by incorporating a specific azo compd. as a carrier generating material into a photosensitive layer. CONSTITUTION:The compd. expressed by the formula I [Y1, Y2 are respectively alkyl, alkoxy, halogen, CN, NO2 or OH, l is 0 or 1, m, n are 0-3, A is the groups expressed by the formulas II-V, Z is the atom group necessary for constituting a (substd.) arom. or arom. heterocycle, Q is (substd.) carbamoyl or sulfamoyl, R1 is H, (substd.) alkyl, NH3, carbamoyl, COOH and the ester thereof or CN, A' is (substd.) aryl, R2, R3 are (substd.) alkyl, aralkyl, aryl] is incorporated into a single layer or into an electric charge generating layer in the case of the double-layered photosensitive layer. The photosensitive body having high sensitivity and substantial sensitivity to long wavelength light such as semiconductor laser or the like is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photoreceptor, and more particularly to a novel photoreceptor having a photosensitive layer containing a specific azo compound.

(Prior Art) Conventionally, inorganic photoreceptors having a photosensitive layer mainly composed of an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide, silicon, etc. have been widely used as photoreceptors. However, these are not necessarily satisfactory in terms of sensitivity, thermal stability, moisture resistance, durability, etc. For example, when selenium crystallizes, its properties as a photoreceptor deteriorate, making it difficult to manufacture.Also, heat can cause fingerprints to crystallize, and cadmium has poor moisture resistance, durability, and even zinc oxide. There's a problem.

In order to overcome these drawbacks of inorganic photoreceptors, research and development have been actively conducted in recent years on organic photoreceptors having photosensitive layers containing various organic photoconductive compounds as main components. For example, Japanese Patent Publication No. 50-10496 describes an organic photoreceptor having a photosensitive layer containing poly-N-vinylcarbazole and 2,4,7-dolinitro-9-fluorenone.

However, this photoreceptor is not necessarily satisfactory in terms of sensitivity and durability. In order to improve these drawbacks, attempts have been made to develop organic photoreceptors with higher performance by assigning the carrier generation function and the carrier transport function to different substances. Many studies have been conducted on such so-called function-separated type photoreceptors because each material can be selected from a wide range and a photoreceptor having arbitrary performance can be produced relatively easily.

Many compounds have been proposed as carrier generating substances for such functionally separated photoreceptors. Examples of using inorganic compounds as carrier generating substances include:
For example, there is amorphous selenium described in Japanese Patent Publication No. 43-16198, which is used in combination with an organic photoconductive compound, but the carrier generation layer made of amorphous selenium is crystallized by heat to form a photoreceptor. The drawback of deteriorating the characteristics of the device has not been improved.

Furthermore, many electrophotographic photoreceptors have been proposed that use growth dyes or organic pigments as carrier-generating substances. For example, as an electrophotographic photoreceptor containing a bisazo compound in the photosensitive layer, JP-A No. 54-22834 and JP-A No. 54-4.
6558, JP-A-56-46237, JP-A-58-194035, etc. are already known. However, these bisazo compounds do not necessarily satisfy the characteristics of sensitivity, residual potential, or stability during repeated use, and the range of carrier transport materials that can be selected is also limited. It does not fully satisfy.

Furthermore, in recent years Ar laser and He-N have been used as light sources for photoreceptors.
Gas lasers such as e-lasers and semiconductor lasers are beginning to be used. These lasers are characterized by being capable of 0N10FF in time series, and are particularly promising as a light source for copying machines with image processing functions, such as intelligent copiers, and printers for computer output. Among these, semiconductor lasers are attracting attention because their nature does not require electrical signal/optical signal conversion elements such as acoustic engineering elements, and they can be made smaller and lighter. However, this semiconductor laser has a low output power compared to a gas laser, and its oscillation wavelength is also long (
(approximately 780 nm or more), the spectral sensitivity of conventional photoreceptors is too high on the short wavelength side, and as is, it is impossible to use them as photoreceptors using semiconductor lasers as light sources.

(Objective of the Invention) An object of the present invention is to provide a photoreceptor containing a specific azo compound that is stable against heat and light and has excellent carrier generation ability.

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

Still another object of the present invention is to provide a photoreceptor containing an azo compound that can effectively act as a carrier generating substance even in combination with a wide variety of carrier transporting substances.

Still another object of the present invention is to provide a photoreceptor having sufficient practical sensitivity even to long wavelength light sources such as semiconductor lasers.

Other objects of the present invention will become apparent from the description in the specification.

(Structure of the Invention) As a result of intensive research to achieve the above object, the present inventors discovered that an azo compound represented by the following general formula [I] can act as an active ingredient of a photoreceptor, This completes the present invention.

General formula [1] In the formula, Yl and Y2 are each a group selected from an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, or a hydroxy group, l is an integer of O or 1, and m and n are 0 to an integer of 3, A is, Q is a substituted/unsubstituted alkyl group of a carbamoyl group, a substituted/unsubstituted 7-ralkyl group, a substituted/unsubstituted phenyl group, R7 is a hydrogen atom, and has a carbon number of 1 ~4 substituted/unsubstituted alkyl groups, substituted/unsubstituted aromatic carbocyclic groups (e.g., substituted/unsubstituted 7''enyl groups, substituted/unsubstituted ＼7tyl groups, substituted/unsubstituted anthryl groups) groups, etc.), or substituted/unsubstituted aromatic heterocyclic groups (e.g., substituted/unsubstituted carbazolyl groups, substituted/unsubstituted dibenzo7lyl groups, etc.)
represents.

Substituted/unsubstituted groups include, for example, carbon atoms of 1
~4 alkyl groups (e.g. methyl group, ethyl group, isopropyl group, tertiary butyl group, FIJ fluoromethyl group!), substituted/unsubstituted aralkyl groups (e.g. benyl group,
7enethyl group, etc.), halogen atoms (chlorine atom, bromine atom, fluorine atom, iodine atom), substituted/unsubstituted alkoxy groups having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group, impropoxy group, tertiary butoxy group) group, 2-chloroethoxy crystal), hydroxy group, substituted/unsubstituted aryloxy group (
For example, p-chlor727oxy group, 1-su7toxy group, etc.)
, acyloxy groups (e.g., acetyloxy, p-cyanobenzoyloxy, etc.), carboxy groups, ester groups thereof (e.g., ethoxycarbonyl, %11-bromophenoxycarbonyl, etc.), carbamoyl groups (e.g., ami7carbonyl, tertiary butylaminocarbonyl group, ami7carbonyl group, etc.) acyl group (e.g., acetyl group, 〇-nitrobenzoyl group, etc.), sulfo group, sulfamoyl group (e.g., aminosulfamoyl group, tertiary butylaminosulfonyl group, (p-) lylaminosulfonyl group, etc.), amine 7 group, acylami 7 group (e.g., acetyl amine 7 group, benzoylami 7 group, etc.), sulfonamide group (e.g., methanesulfonamide 4, p) luenesulfonamide group, etc. ), cya/group, nitro group, etc., but preferably substituted/unsubstituted alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, isopropyl group, 11
-butyl group, trifluoromethyl group, etc.), halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group, butoxy group, 2-chloroethoxy group, etc.) cyano group, nitro group.

Z is an atomic group necessary to form a substituted/unsubstituted aromatic carbocycle or a substituted/unsubstituted aromatic heterocycle,
Specifically, it represents an atomic group forming, for example, a substituted/unsubstituted benzene ring, a substituted/unsubstituted 7-ring, a substituted/unsubstituted indole ring, a substituted/unsubstituted carbazole ring, etc.

Examples of substituents for the atomic group forming these rings include a series of substituents such as those listed as substituents for R4+ Rs, but preferably halogen atoms (chlorine atoms,
bromine atom, fluorine atom, iodine atom), sulfo group, sulfamoyl i (for example, ami/sulfonyl M, p-)lylaminosulfonyl group, etc.).

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

A' is a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted phenyl group, and examples of substituents for these groups include a series of substituents such as those listed as substituents for R4-Rs. but preferably a halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), carbon number 1-4
Substituted/unsubstituted alkyl groups (e.g., methyl group, ethyl group, isopropyl group, tertiary butyl group, trifluoromethyl group, etc.), substituted/unsubstituted alkoxy crystals having 1 to 4 carbon atoms (e.g., methoxy group, ethoxy group, impropoxy group, tertiary butoxy group, 2-chloroethoxy group).

R2 and Ro represent a substituted/unsubstituted alkyl group, a substituted/unsubstituted aralkyl group, and a substituted/unsubstituted aryl group, preferably a substituted/unsubstituted alkyl group having 1 to 4 carbon atoms (for example, Methyl group, ethyl group, isopropyl group,
tertiary butyl group, trifluoromethyl group, etc.), substituted/unsubstituted phenyl group (eg, phenyl group, p-methoxyphenyl group, m-chlorophenyl group, etc.).

Among the azo compounds represented by the general formula [1] used in the present invention, preferred compounds have the following general formula [11] or [I[ The horizontal side general formula [I[] represented by [] In the formula, YI' and Y2' are groups selected from an alkyl group or a halogen atom, and A, m and n are the same as in the general formula [I].

General formula [1 [1] In the formula, YZ + Y'21 A tm and n are general formula [
Same as I[].

Specific examples of the bisazo compound represented by the general formula [I] that are effective in the present invention include those having the following structural formula, but the bisazo compound of the present invention is not limited by this. General formula [IV] in formula [I]
], general formula [IV], general formula (■), general formula (■) (the number of the substituent represents the position on the mother nucleus), and others, B-@) B-( 93) The azo compound described above can be synthesized by a known method, for example, the method shown in the following synthesis example.

Synthesis Example (Synthesis of Exemplified Compound B-(1)) 21.0 g (0.1 mol) of 2.5-noamino-9-7luorenone was dispersed in concentrated hydrochloric acid 11, and the dispersion was stirred at a temperature of 5. ℃
13.8 g of sodium sulfite A (0,
An aqueous solution of 2 mol) dissolved in 200 ml F) water was added dropwise. After the dropwise addition was completed, stirring was continued under cooling for an additional hour, and then filtration was performed. 250 g of ammonium hexafluorochloride was added to the obtained m solution, the resulting crystals were collected by filtration, and the hexafluorofluoride of tetrazonium was collected. Obtained phosphate. This crystal is N.

It was dissolved in tonomethylformthiamide 51 to obtain a dropping solution [D] for the next coupling reaction.

2-Hydroxy-3-(4-methoxy-2-methylphenylcarbamoyl)-benzo[al-carnoxole (
Dissolve 78 g (0.2 mol) of S7Toll A S -S R) in 2.54 N,N-dimethylformamide,
To this, triethanolamine 62. was added, and this solution was cooled to a temperature of 5° C., and while stirring vigorously, the above-mentioned dropping solution [D] was added dropwise thereto. After the dropwise addition was completed, the mixture was stirred for 1 hour under cooling, and further stirred at room temperature for 2 hours, and the resulting crystals were collected by filtration. The crystals were washed 3 times with 11's N,N-methylformamide, 2 times with 11's water, and 171
After washing twice with acetone and drying, 42.0 g (yield 41%) of a black compound was obtained.

This black compound shows that in its infrared absorption spectrum, absorption due to the C=0 bond of the amide is observed at ν = 1690 cm', and in elemental analysis, the actual value (C = 73.77%) is observed. , N=10.
78%1H=4.52%) is the theoretical value (C=73.8
1%.

N = 10.93%, H = 4.33%), so it was confirmed to be the target exemplary compound B-(1).

The azo compound of the present invention has excellent photoconductivity, and when a photoreceptor is manufactured using the azo compound, a photosensitive layer in which the azo compound of the present invention is dispersed in a binder is provided on a conductive support. However, among the photoconductivity of the azo compound of the present invention, it can be used as a carrier-generating substance by taking advantage of its particularly excellent carrier-generating ability, and a carrier-transporting substance that can effectively act in combination with this. By using them together, particularly excellent results can be obtained when a so-called functionally separated photoreceptor is constructed. Although the functionally separated photoreceptor may be a separate type, it is more preferably a laminated photoreceptor comprising a carrier generation layer containing a carrier generation substance and a carrier transport layer containing a carrier transport substance.

Further, the azo compound used in the present invention has the general formula [I]
The azo compounds represented by can be used alone or in combination of two or more, and may also be used in combination with other azo compounds.

Various types of mechanical configurations of photoreceptors are known, and the photoreceptor of the present invention can take any of these forms.

Usually, the configuration is as shown in FIGS. 1 to 6. Figures 1 and 3
In the figure, a photosensitive layer 4 consisting of a laminate of a carrier generation layer 2 containing the aforementioned azo compound as a main component and a carrier transport layer 3 containing a carrier transport substance as a main component is provided on a conductive support 1. As shown in FIGS. 2 and 4, this photosensitive material N4 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, a photoreceptor having the most excellent electrophotographic properties can be obtained.

Further, in the present invention, as shown in FIGS. 5 and 6, a photosensitive layer 4 comprising the carrier-generating substance 7 dispersed in a layer 6 mainly composed of a carrier-transporting substance is provided on the conductive support 1. It may be provided directly or via the intermediate layer 5.

When the azo compound of the present invention is used as a carrier-generating substance, the carrier-transporting substance used in combination with the azo compound is Bakapoly-N-vinyl, an electron-accepting substance that easily transports electrons, such as trinitrofluorenone or tetranitrofluorenone. Polymers having heterocyclic compounds in their side chains, such as carbazole, triazole derivatives, oxadiazole derivatives, imiguzole derivatives, pyrazoline derivatives, polyarylalkane derivatives, phenylenediamine derivatives, hydrazone derivatives, amino-substituted chalcone derivatives, tria Rylamine derivatives, carbazole derivatives, stilbene derivatives.

Examples include electron-donating substances that easily transport genuine tags, such as 7-carbohydrate/thiazine derivatives, but the carrier-transporting substances used in the present invention are not limited to these.

The carrier generation layer 2 constituting the two-layered photosensitive layer 4 may be applied directly to the conductive support 1 or the carrier transport layer 3, or if necessary, provided with an intermediate layer such as an adhesive layer or a single barrier layer, for example. It can be formed by the following method.

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

M-2) A method in which an azo compound is made into fine particles in a dispersion medium using a ball mill, a homomixer, etc., and a dispersion liquid is applied.

Examples of the solvent or dispersion medium used for forming the carrier generation layer include n-butylamine, diethylamine, ethylenediamine, invalylamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methylethylketone, and cyclohexanone. , benzene, toluene, xylene, chloroform, 1,2-dichloroethane, dichloromethane, tetrahydro7ran, dioxane', methanol, ethanol,
Examples include inpropyl, ethyl acetate, butyl acetate, dimethyl sulfoxide and the like.

When using a binder in the carrier generation layer or the carrier transport layer, any binder can be used, but it is preferable to use a film-forming polymer that is hydrophobic, has a high dielectric constant, and is electrically insulating.

Examples of such high molecular weight polymers include, but are not limited to, the following.

P-1) Polycarbonate P-2) Polyester P-3) Meccrylic resin P-4) Acrylic resin P-5) Polyvinyl chloride P-6) Polyvinylidene chloride P-7) Polystyrene P-8) Polyvinyl acetate P-9 ) Styrene-butadiene copolymer P-10)
Vinylidene chloride-acrylonitrile copolymer P-11) Vinyl chloride-vinyl acetate copolymer P-1
2) Vinyl chloride-vinyl acetate-maleic anhydride copolymer P-13) Silicone resin P-14) Silicone-alkyd resin P-15) 7
2/-formaldehyde resin P-16) Styrene-
Alkyd Resin P-17) Poly-N-vinylcarbazole These binders can be used alone or in a mixture of two or more.

The thickness of the carrier generation layer 2 formed in this way is
It is preferable that it is 0.0iμI11-20μI,
More preferably, it is 0.05 μm to 5 μm. Further, when the carrier generation layer or the photosensitive layer is a dispersed type, the particle size of the azo compound is preferably 5 μm or less, more preferably 1 μm or less.

Examples of the conductive support used in the electrophotographic photoreceptor of the present invention include metal plates including alloys, metal drums or conductive polymers, aluminum including conductive compounds and alloys such as indium oxide, palladium, gold, etc. Apply a thin metal layer of
Paper that has been made conductive by vapor deposition or lamination,
Examples include plastic films. As an intermediate layer such as an adhesive or barrier layer, in addition to the high molecular weight polymer used as the binder, a polymer material such as polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, or aluminum oxide is used.

The photoreceptor of the present invention has the above-mentioned structure, and as is clear from the examples described later, it has excellent charging characteristics, sensitivity characteristics, and image forming characteristics, and is particularly resistant to fatigue deterioration even after repeated use. It has excellent durability.

Hereinafter, the present invention will be specifically explained in Examples, 1: i
The embodiments of the present invention are not limited to 1.1 m and i.

(Example) Example 1 Exemplary compound B-<8) 2g and polycarbonate)? 15
Fat [Panlite L-1250J (manufactured by Ondai Kasei Co., Ltd.) 2g
was added to 110+J of 1,2-dichloroethane and dispersed in a ball mill for 12 hours. This dispersion was applied onto a polyester film coated with aluminum to a dry film thickness of 1.
μIfl, to form a carrier generation layer, and on top of that, as a carrier transport layer, 4,4-dimethyl-4-(4-methoxy)styryl-triphenylamine (-(1 )) A solution prepared by dissolving 6 g of polycarbonate resin "Panlite L-1250Jlog" in 110 mQ of 1,2-dichloroethane was applied to a dry film thickness of 15 μ to form a carrier transport layer. An electrophotographic photoreceptor of the invention was created.

-1 The photoreceptor obtained as described above was subjected to the following characteristic evaluation using an electrostatic paper tester model SP-428 manufactured by Kawaguchi Electric Co., Ltd. After being charged for 5 seconds at a charging voltage of -6KV, it was left in the dark for 5 seconds, and then the illuminance on the surface of the photoreceptor was set to 35KV.
The film was irradiated with halogen lamp light so that the surface potential was halved, and the exposure amount (half-reduced exposure amount) El/2 was determined. Further, the surface potential (residual potential) VR after exposure with an exposure amount of 30 lux·see was measured. Further, similar measurements were repeated 100 times. The result is the first
As shown in the table.

Table 1 Example 2 Exemplified Compound B-(8) of Example 1 was converted to Exemplified Compound B-(
59) Create a photoreceptor with everything else being the same,
Characteristics were measured in the same manner as in Example 1, and the results shown in Table 2 were obtained.

Table 2 Comparative Example The following bisazo compound G-(1) was used as a carrier generating substance.
A comparative photoreceptor was prepared in the same manner as in Example 1, except that .

G-(1) Regarding this comparative photoreceptor, measurements were performed in the same manner as in Example 1, and the results shown in Table 3 were obtained.

As is clear from the results in Table 3 and above, the photoreceptor of the present invention is extremely superior in sensitivity, residual potential, and repetition stability compared to the comparative photoreceptor.

Example 3-5 Exemplary compounds B-(18) and B as carrier-generating substances
-(19) and B-(20) were used as carrier transport substances, respectively, 1-[4-(N, N-di(p
-tolyl) ami/benzylidene-aminocoindoline (
The following compound -(2)), 1-(1-phenyl-4-carbazolyl)methylideneamino-1,2,3,4-tetrahydroquinoline (the following compound K-(3)), and
A photoreceptor of the present invention was prepared in the same manner as in Example 1 except that 4-methoxy4-(4'-chloro)-styryl-triphenylamine (compound K-(4) below) was used. When the measurements were carried out, the results shown in Table tjS4 were obtained.

-2 to -3 to -4 Table 4 Example 6 Vinyl chloride-vinyl acetate-
An intermediate layer of ice-free maleic acid copolymer "S-LEC MF-10J (manufactured by Block Chemical Co., Ltd.) with a thickness of 0.05μIl+ was provided, and 2g of Exemplified Compound B-(10) was placed on top of it.
The dispersion was mixed with 110 μU of 2-dichloroethane and dispersed in a ball mill for 24 hours, and then applied to a dry film thickness of 0.5 μm to form a carrier generation layer.

On this carrier generation layer, 6 g of 4-methoxytriphenylamine and 10 g of methacrylic resin "Acrypet" (manufactured by Mitsubishi Rayon Co., Ltd.) were added to 70 g of 1,2-dichloroethane. Q
The photoreceptor of the present invention was prepared by applying a solution dissolved in the above to form a carrier transport layer so that the film thickness after drying was approximately 10 μm.

The same measurements as in Example 1 were carried out on this photoreceptor, and the first measurement showed that E%=2.2 lux・seC,
The result was VR=Ov.

Example 7 A photoreceptor was prepared in which Exemplified Compound B-(10) in Example 6 was replaced with Exemplified Compound B-(67), and the other conditions were the same as in Example 6, and the same measurements as in Example 1 were performed. Tokoro 1
Lie for the first time E ”A = 2.41 VR = Ov
I got the result.

Example 8 A 1% ethylenediamine solution of exemplified compound B-' (35) was applied onto the conductive support provided with the intermediate layer used in Example 6 so that the film thickness after drying was 1.3 μIll. , a carrier generation layer was formed.

Next, 6 g of 4-methoxy-4-styryltriphenylamine (compound K-(5) below) and 10 [+] of polyester resin "Vylon 200J (Toyobo Co., Ltd.'J)" 2 dichloroethane 70TI
The film thickness after drying this solution is 12 μI.
A carrier transport layer was formed by applying the photoreceptor to form a photoreceptor of the present invention.

The same measurements as in Example 1 were performed on this photoreceptor, and the results shown in Table 5 were obtained.

Example 9 A photoreceptor was prepared in the same manner as in Example 8 except that Exemplified Compound B-(35) in Example 8 was replaced with Exemplified Compound B-(81). The same measurements as in Example 1 were carried out on this photoreceptor, and the results shown in Table 5 were obtained.

Comparative Example 2 A comparative photoreceptor was prepared in the same manner as in Example 8, except that exemplified compound B-(35) was replaced with bisazo compound G-(2) represented by the following structural formula.

The same measurements as in Example 1 were performed on this photoreceptor, and the results are shown in Table 5.

G-(2) (Table 5 Example 10 A carrier generation layer was formed in the same manner as in Example 6 except that exemplified compound B-(10) was replaced with exemplified compound B-(41). On top of this, 6-Methyl-1-(1-phenyl-4-carbazolyl)methylideneami/-1,2,3
,4-tetrahydroquinoline (compound -(6)) 6
g and polycarbonate [Panlite L-1250J
(manufactured by Ondai Kasei Co., Ltd.) 10g and 1,2-dichloroethane 7
A carrier transport layer was formed by coating a solution dissolved in 0 ml of 1 liter so that the film thickness after drying was 10 μm, thereby producing a photoreceptor of the present invention.

This compound was measured in the same manner as in Example 1, and found to be E%"2.11ux-see and ■R-Ov.

Example 11 A photoreceptor was prepared in the same manner as in Example 6 except that Exemplified Compound B=(10) in Example 6 was changed to Exemplified Compound B-(87). When the obtained photoreceptor was measured in the same manner as in Example 1, E% = 2,11 ux-sec +V R
” It was Ov.

Example 12 A vinyl chloride-vinyl acetate-maleic anhydride copolymer [S-LEC MF-10J (manufactured by Sekisui Chemical Co., Ltd.) with a thickness of 0.0 was coated on the surface of an aluminum drum with a diameter of 100I.
A 5 μm intermediate layer was provided, and exemplified compound B-(45
)4. was mixed with 400 + nfl of 1,2-dichloroethane and dispersed for 24 hours using a ball mill dispersion machine. A dispersion was applied to form a carrier-generating layer so that the film thickness after drying was 0.6 μm.

Furthermore, on top of this, 3-(p-methoxystyryl)-9-
(p-methoxyphenyl)carbazole (compound K below)
-(6)) 30Fi and polycarbonate resin "Nipilon S-1000J (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 50Fi were dissolved in 1,2-dichloroethane K = (6) 400 mu, and the film thickness after drying was 13 μW. A drum-shaped photoreceptor was prepared by applying the carrier transport layer to the photoreceptor.

Electrophotographic copying of the photoreceptor created in this way tmrU
When it was attached to a modified Bix 1600 M RJ (manufactured by Konishiroku Photo Industry Co., Ltd.) and an image was copied, a copy image with high contrast, faithful to the original, and clear was obtained. Also, this did not change even after repeating it 10,000 times. 1 Example 13 A drum-shaped photoreceptor was prepared in the same manner as in Example 12 except that Exemplified Compound B-(45) in Example 12 was replaced with Exemplified Compound B-(91), and U-B ix 1600
When a copying test was carried out by attaching it to a modified MR model, Example 1
A clear copy image with high contrast and high fidelity was obtained as in case 2, and there was no change even after 10,000 repetitions.

Comparative Example 3 A drum-shaped comparative photosensitive material was prepared in the same manner as in Example 12, except that the exemplified compound B-(45) in Example 12 was replaced with a bisazo compound (G-(3)) represented by the following structural formula. When a body was prepared and a copy image was evaluated in the same manner as in Example 12, only images with many capri were obtained. Furthermore, as copying was repeated, the contrast of the copied image decreased, and after 2000 repetitions, hardly any copied image could be obtained.

-3 3rbe Example 14 Vinyl chloride-vinyl acetate-
Maleic anhydride copolymer [S-LEC M F-10J
(manufactured by Sekisui Kasei Co., Ltd.) with a thickness of 0.05 μm, and on top of that, 5 g of exemplary compound B-(3) and a polycarbonate resin [Panlite L-1250J (manufactured by Kijin Kasei Co., Ltd.) 3. A photoreceptor was prepared by adding 3 g of the photoreceptor to 100 mQ of dichloromethane and dispersing it in a ball mill for 24 hours, and applying the dispersion to a dry film thickness of 10 μm.

E3A and VR of the compound obtained as described above were measured in the same manner as in Example 1 except that the charging voltage was changed to +6 Kv. The first result is E% = 2.2 lux” See
and VR=Ov.

Example 15 6 g of p-N,N-diethylamino)benzaldehyde-1,1-diphenylhydrazone and a polyester resin [Vylon 200 J (manufactured by Toyobo Co., Ltd.) were added as a carrier transport layer on a polyester film deposited with aluminum.
10g and dissolved in 70mQ of 1,2-dichloroethane,
This solution was applied so that the film thickness after drying was 10 μm.

Next, exemplified compound B-(23)Ig and B-(2
4) IFi and 1,2-dichloroethane 110. Ω and dispersed in a ball mill for 24 hours, the dispersion was applied to a dry film thickness of 0.5 μm to form a carrier generation layer, thereby forming the photoreceptor of the present invention.

The compound thus obtained was evaluated in the same manner as in Example 9, and found that E%=2.3 lux·sec and V%
=+5■.

Example 16 A 2% ethylenediamine solution of the exemplified compound Compound B-(16) was applied onto a polyester film laminated with aluminum to a dry film thickness of 0.5 μIll to form a carrier generation layer.

Furthermore, 1-phenyl-3 is added as a carrier transport layer thereon.
-(p-diethylami 7styryl)-5, (p-diethylami/phenyl)pyrazoline (for the following compound -(7)
), 1-(1-ethyl-4-carbazolyl)methylideneami/-1,2,3,4-tetrahydroquinoline The following compound K -(8), or 4-methoxy-4-(4
-methyl)styryltriphenylamine (compound K below)
-(9)) and polycarbonate K-(7) K-(8) 2H5 K-(9) resin (manufactured by Kijin Kasei Co., Ltd., Panlite L-1250) 1
A solution prepared by dissolving 4 g of the carrier transport substance in 140 Tll+1 of 1,2-dichloroethane was coated and dried to give a film thickness of 12 μm after drying, thereby obtaining photoreceptors each containing three different carrier transport substances.

The following characteristics were evaluated for each of these three types of photoreceptors using an electrostatic paper test block SP-428 manufactured by Kawaguchi Electric Seisakusho Co., Ltd. After charging for 5 seconds with a charging voltage of -6Kv and leaving it for 5 seconds, halogen light was applied to the material surface at an illuminance of 35 l.
ux, and the exposure amount required to attenuate the surface potential by half (half-reduced exposure amount, E K ) was measured. Further, the surface potential (residual potential) VR after exposure with an exposure amount of 3o1ux-8ec was measured. As shown in Table 6, the results were good in combination with any carrier transporting substance.

Table 6 Comparative Example 4 Illustrated compound B-(16) was converted to the following bisazo compound (G
A comparative photoreceptor was prepared in the same manner as in Example 11 except that G -(4)) was used, and the characteristics were evaluated.
4) As shown in the vS7 table, the results varied depending on the carrier transport substance.

tIS7 Table Example 17 On the conductive support provided with the intermediate layer used in Example 6, 2 g of Exemplified Compound B-(1) and 10 g of 1,2-dichloroethane were added.
0 mil, and the film thickness after drying is 0.3.
A carrier generation layer was created by applying the coating to a thickness of .mu.m.

1-[4-
(N,N-diethylamino)benzylidene]-7 minnow 14.3.4-tetrahydroxyphosphorus (the following compound Ig-(10) > 6 g and polycarbonate "Panrai")
A carrier transport layer was formed by applying a solution obtained by dissolving 10 g of L-1250J (manufactured by Ondai Kasei Co., Ltd.) K-(10) in 90 g of 1,2-dichloroethane so that the film thickness after drying was 10 μm, A photoreceptor of the present invention was prepared.

The electrophotographic properties of this photoreceptor at room temperatures of 25° C. and 60° C. were measured in the same manner as in Example 1.

The results are shown in Table 8.

As is clear from the results in Table 8 and above, the electrophotographic photoreceptor of the present invention has good sensitivity and residual potential characteristics even at high temperatures;
It can be seen that it is stable against heat.

Example 18 Exemplary compound B-(6)2Fi and 1,2-dichloroethane 11 were placed on the conductive support provided with the intermediate layer used in Example 6.
A carrier-generating layer was prepared by thoroughly dispersing and mixing the following materials and applying the mixture so that the film thickness after drying was 0.3 μm.

In order to test the durability of this carrier generation layer against UV light, an ultra-high pressure mercury lamp (manufactured by Tokyo Niura Denki Co., Ltd.) was placed at a distance of 30 cIrL out-of-plane at 1500 cd/e for 10 minutes.
RA UV light was irradiated. Next, 4.4-
Methyl-4-(4-chloro)-styryl-triphenylamine (7 g of the following compound -(11)) and 10 g of polycarbonate [Panlite L-1250] (manufactured by Ondai Kasei Co., Ltd.)
g was dissolved in 90 g of 1,2-dichloroethane.

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

The same measurements as in Example 6 were performed on this photoreceptor.

The results are shown in Table 9.

Example 19 A photoreceptor of the present invention was prepared in the same manner as in Example 18 except that UV light was not irradiated after the carrier generation layer was formed.
The same measurements were carried out. The results are shown in Table 9.

As is clear from the results in Table 9 and above, the photoreceptor of the present invention
It can be seen that it has excellent sensitivity and residual potential characteristics to light irradiation, has small fluctuations in acceptance potential, and is stable to light.

Comparative Example 5 Compound B-(6) was converted to the following bisazo compound (G-(5)
) in the same manner as in Example 18 and Example 19 except that G
-(5) A photoreceptor was prepared, and the same measurements as in Example 5 were performed. The results are shown in Table 10.

As is clear from the results in Table 10 and above, the sensitivity and residual potential characteristics of the compounds prepared using the above compounds deteriorate upon irradiation with UV light, and the amount of variation in acceptance potential is large.

Example 20 In Example 6, exemplary compound B-(10) was converted to B-(
A drum-shaped photoreceptor was produced in the same manner except that step 2) was changed. The spectral sensitivity of this photoreceptor at 790 nm is 0.4
It was 2 μJ/i (half exposure amount). The photoreceptor of the present invention was subjected to a photo-photographing test using a semiconductor laser (790 Old 1) which provided a laser beam intensity of 0.85 mW on the surface of the photoreceptor.

After charging the surface of the photoreceptor to -(3KV), it was exposed to laser light and reversely developed at a bias voltage of -250V.
A good image without fogging was obtained.

Comparative Example 6 A comparative photoreceptor was obtained in the same manner as in Example 20, except that the following Comparative Example bisazo compound was used in place of Exemplified Compound B-(2).

2 The spectral sensitivity of this photoreceptor at 790 nm is 7.24μ
J/crl (half exposure amount). Using this comparative photoreceptor, a photo-taking test using a semiconductor laser was conducted in the same manner as in Example 20, but there was a lot of fog and good images could not be obtained.

As is clear from the results of the above Examples and Comparative Examples, the photoreceptor of the present invention is significantly superior to the comparative photoreceptor in properties such as stability, sensitivity, durability, and combination with a wide range of carrier transport substances. It is something that

(Effects of the Invention) According to the present invention, by using the azo compound represented by the general formula [1F] as a photoconductive substance constituting the photosensitive layer of a photoreceptor, It is stable and has excellent electrophotographic properties such as charge retention, sensitivity, and residual potential. It also shows little fatigue deterioration even after repeated use, and has sufficient sensitivity even in the long wavelength region of 780 nm or more. It is possible to create a photoreceptor with

[Brief explanation of the drawing]

1 to 6 are cross-sectional views showing examples of mechanical groove formation in the photoreceptor of the present invention, and 1 to 7 in the figures represent the following, respectively. 1... Conductive support 2... Carrier generation layer 3... Carrier transport layer 4... Photosensitive layer 5... Intermediate layer 6 ...Layer 7 containing a carrier transport substance...
... Carrier-generating substance agent Patent attorney No 1) Parent bird 1 figure plot? Aku 5th diagram Sujito diagram

Claims (3)

[Claims] (1) A photoreceptor characterized by having a photosensitive layer containing an azo compound of the following general formula [1] on a conductive support. General formula [1] [wherein Y and Y2 each represent an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, or a hydroxyl group, l is an integer of 0 or 1, in and n
represents an integer from 0 to 3. A is 2R3 1 H, where Z is a substituent or an unsubstituted aromatic carbocyclic ring, or a substituent or an atomic group necessary to constitute an unsubstituted aromatic polycyclic ring, and Q is a substituent or an unsubstituted aromatic ring. An unsubstituted carbamoyl group, a substituent or an unsubstituted sulfamoyl group, R1 is a hydrogen atom, a substituent or an unsubstituted alkyl group, an amide group, a substituted or unsubstituted amino group, a substituent or an unsubstituted carbamoyl group , a carboxyl group and its ester group or a cyano group, A' is a substituted or unsubstituted aryl group, R2, R is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aralkyl group. Represents an unsubstituted aryl group. ] (2) The photosensitive layer contains a carrier transporting substance and a carrier generating substance, and the carrier generating substance has the general formula [
The photoreceptor according to claim 1, which is an azo compound of [I]. (3) The photoreceptor according to claim 1 or 2, wherein the photosensitive layer is formed of a laminate of a carrier generation layer containing a carrier generation substance and a carrier transport layer containing a carrier transport substance. .