JPS60197764A - Photosensitive material - Google Patents

Abstract

PURPOSE:To provide a photosensitive material which is stable against heat and light, has excellent charging and image-forming characteristics and little fatigue deterioration, by providing a laminate layer composed of a carrier transporting layer and a carrier generating layer contg. a specified azo compd. as a photosensitive layer on an electrically conductive support. CONSTITUTION:A photosensitive material is obtd. by providing a photosensitive layer 4 composed of a laminate of a carrier generating layer 2 and a carrier transporting layer 3 on an electrically conductive support 1 such as a metallic sheet in such a manner that a soln. of an azo compd. of formula I [wherein Y1, Y2 are each alkyl, alkoxy, halogen, cyano, etc.; l is 0-1; m, n are each 0-3; A is an atom group required for forming a group of formula II, III or IV (wherein Z is an arom. or heterocyclic ring); Q is carbamoyl, sulfamoyl; R1 is H, alkyl, amino, etc.; A' is aryl; R2, R3 are each alkyl, aralkyl, etc.] is applied to the support 1 in such a quantity as to give a dry film of 0.01-20mum in thickness to form the layer 2 and a soln. of an electron-accepting material such as trinitrofluorene is then applied to the layer 2 to form the layer 3.

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, as a photoreceptor, a *m photoreceptor having a photosensitive layer mainly composed of an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide, or silicon has been widely used. However, these are not necessarily satisfactory in terms of sensitivity, thermal stability, moisture resistance, durability, etc. For example, when selenium crystallizes, its properties as a photoreceptor deteriorate, making it difficult to manufacture.Also, selenium crystallizes due to heat, fingerprints, etc., and its performance as a photoreceptor deteriorates. In addition, cadmium sulfide has problems with moisture resistance and durability, and zinc oxide has problems with durability, etc.

In order to overcome these drawbacks of inorganic photoreceptors, research and development have been actively conducted in recent years on organic photoreceptors having photosensitive layers containing various organic photoconductive compounds as main components. For example, Japanese Patent Publication No. 50-10496 discloses a photosensitive layer containing poly-N-vinylcarbazole and 2,4,7-)dinitro-9-fluorenone. There is a description of a photoreceptor. However, this photoreceptor is not necessarily satisfactory in sensitivity and durability. In order to improve these drawbacks, attempts have been made to develop organic photoreceptors with higher performance by assigning the carrier generation function and the carrier transport function to different substances. Much research has been done into such so-called function-separated photoreceptors because it is relatively easy to create light photoreceptors with desired performance by selecting materials from a wide range of materials. It's here.

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.

In addition, many photoreceptors have been proposed that use organic dyes or organic pigments as carrier-generating substances. For example, in JP-A-54
-22834 publication, JP-A-54-46558 publication,
JP-A-56-46237, JP-A-58-1940
Publication No. 35 and the like are already known. However, these bisazo compounds are not always satisfactory in terms of sensitivity, residual potential, or stability during repeated use, and the selection range of carrier transport materials is also limited. It does not fully satisfy the wide range of process requirements.

Furthermore, in recent years, ^r laser, He
Gas lasers such as Ne lasers and semiconductor lasers are beginning to be used. A characteristic of these lasers is that they can be turned on and off in time series, making them particularly promising as light sources for copiers 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 an electrical signal/optical signal conversion element such as an acousto-optic element, and because they can be made smaller and lighter. However, this semiconductor laser has a low output compared to a gas laser, and the oscillation wavelength is also long (approximately 780 nm or more), so the spectral sensitivity of conventional photoreceptors is too high on the short wavelength side. It cannot be used as a photoreceptor using a laser as a light source.

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

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

Still another object of the present invention is to 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.

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

(Structure of the Invention) As a result of intensive research to achieve the above object, the present inventors discovered that an azo compound represented by the following general formula (1) can be obtained as an active ingredient of a photoreceptor, This completes the present invention.

General formula [1] In the formula, Y and Y2 are each a group selected from an alkyl group, an alkoxy group, a halogen atom, a sia group, a nitro group, or a hydroxy group, Q is an integer of 0 or 1, and m and n are 0 An integer from 3 to 3 (however, both candy and n are not 0) A is H, Q is a substituted/unsubstituted carbamoyl group to 4 substituted/unsubstituted alkyl groups, and Substituted/unsubstituted 7-ralkyl group, substituted/unsubstituted phenyl group, R9 is a hydrogen atom, substituted/unsubstituted alkyl group having 1 to 4 carbon atoms, substituted/unsubstituted aromatic carbocyclic group (e.g., substituted・Unsubstituted phenyl group, substituted/unsubstituted s7tyl group, substituted/unsubstituted anthryl group, etc.), or substituted/unsubstituted aromatic heterocyclic group (for example, substituted/unsubstituted carbazolyl group, substituted/unsubstituted anthryl group, etc.) (unsubstituted dibenzo7lyl group, etc.).

Substituents for these groups include, for example, substituted/unsubstituted alkyl groups having 1 to 4 carbon atoms (e.g., methyl group, ethyl group,
isopropyl group, tertiary butyl group, trifluoromethyl group, etc.), substituted/unsubstituted 7-ralkyl group (e.g. benyl group, 7enethyl group, etc.), halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom) , substituted/unsubstituted alkoxy groups having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group,
isopropoxy group, tertiary butoxy group, 2-chloroethoxy group, etc.), hydroxy group, substituted/unsubstituted aryloxy group (e.g., p-chlorophenoxy group, 1-7toxy group, etc.), acyloxy group (e.g. , acetyloxy group, p-cyanobenzoyloxy group, etc.), carboxyl group, its ester group (e.g., ethoxycarbonyl group, seaweed-bromophenoxycarbonyl group, etc.), carbamoyl group (e.g., aminocarbonyl group, tertiary butylaminocarbonyl group) , aminocarbonyl group, etc.), acyl group (e.g.,
acetyl group, O-nitrobenzoyl group, etc.), sulfo group,
Sulfamoyl group (e.g., aminosulfonyl group, tertiary butylaminosulfonyl group, p-tolylamino/sulfonyl group, etc.), amino group, acylamino group (e.g., acetylamino group, benzoylamino group, etc.), sulfonamide group (e.g., Examples include methanesulfone 7mido group, p-)luenesulfonamide group, etc.), cyano group, di[0 group, etc., but preferably substituted or unsubstituted alkyl groups having 1 to 4 carbon atoms (for example, methyl group, Ethyl group, isopropyl group,
n-butyl group, trifluoromethyl group, etc.), halogen atoms (chlorine atom, bromine atom, fluorine atom, iodine atom), substituted/unsubstituted alkoxy groups having 1 to 4 carbon atoms (e.g. methoxy group, ethoxy group, tertiary butoxy group, 2-chloroethoxy 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 a substituted/unsubstituted benzene ring, a substituted/unsubstituted 7talene ring, a substituted/unsubstituted indole ring, a substituted/unsubstituted carbazole ring, etc.

Examples of substituents for the atomic groups forming these rings include a series of substituents such as those listed as substituents for R, and R5, but preferably halogen atoms (chlorine atom, bromine atom, fluorine atom) , iodine atom), sulfo group, sulfamoyl group (eg, aminosulfonyl group, p-)lylaminosulfonyl group, etc.).

R1 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or
unsubstituted amino group, carboxyl group, ester group thereof,
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 cyano group.

^' is a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted phenyl group, and the substituents for these groups include, for example, a series of substituents such as those listed as substituents for R, , R, Although listed, preferably halogen atom (a! elementary 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 groups having 1 to 4 carbon atoms (e.g., methoxy group) , ethoxy group, isopropoxy group, tertiary butoxy group, 2-chloroethoxy group).

R2 and R1 represent a substituted or unsubstituted furkyl group, a substituted or unsubstituted 7-ralkyl group, or a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms (e.g. , methyl group, ethyl group, isopropyl group, tertiary butyl group, trifluoromethyl group, etc.), substituted
Represents an unsubstituted phenyl group (eg, phenyl group, p-methoxyphenyl group, -chlorophenyl group, etc.).

Among the azo compounds represented by the general formula (1) used in the present invention, it is particularly preferred in that it has excellent sensitivity even in the wavelength region of F80 t+m or more.

The compound has Q:=1, that is, a structure represented by the following general formula (II).

General formula [11] In the formula, Y S and Y2' are a group selected from an alkyl group or a halogen atom, ^, I11 and n are a group selected from the general formula (I
) is the same as

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

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

General Formula (III) The above azo compound 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)) 22.4 g (0.1 mol) of 2.7-diamitu-4-methyl-9-dicyanomethylidenefluorenone was dispersed in concentrated hydrochloric acid IQ, and the mixture was dissolved with stirring. The dispersion was cooled to a temperature of 5°C, and 200 g of sodium nitrite (13.8 g (0.2 mol)) was added to it.
An aqueous solution of - was added dropwise. After the dropwise addition, stirring was continued under cooling for another hour, and then filtration was performed, and 25 ammonium hexafluorophosphate was added to the obtained filtrate.
0 g was added, and the resulting crystals were collected by filtration to obtain tetrazonium hexafluorophosphate. This crystal is N.

Dissolved in N-dimethylformamide 59 to obtain the following drop solution CD) for the Cassilling reaction.

2-Hydroxy-3-(4-methoxy-2-methylphenylcarbamoyl)-benzo(a) carbazole (S71·-l AS-8R) 7B, (0.2 mol) with N
, was dissolved in 2.59 g of N-dimethylformamide, 62 g of triethanolamine was added thereto, and the solution was heated to a temperature of 5.
While cooling the mixture to 0.degree. C. and stirring vigorously, the above-mentioned dropping liquid CD) 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 12 hours, and the resulting crystals were collected by filtration. The crystals were washed three times with N,N-trimethylformamide (No. 19), twice with IQ water (IQ), and twice with acetatone (No. 19), and then dried to obtain a black compound No. 50.
9 g (yield 49%) was obtained.

In the infrared absorption spectrum of this black compound, absorption due to the C=O bond of the amide was observed at C=1690c11-1, and in elemental analysis, the actual value (C=73.82%, N=10 .71%, H=
4.52%) is the theoretical value (C=73.97%, N=10
．． 79%, H=4.46%), it was confirmed to be the target exemplary compound B-(1).

The azo compound of the present invention has excellent photoconductivity, and when an electrophotographic photoreceptor is manufactured using the azo compound, a photosensitive layer in which the azo compound of the present invention is dispersed in a binder is formed on a conductive support. However, among the photoconductivity of the azo compound of the present invention, the particularly excellent carrier generation ability is used as a carrier generation substance, and it acts effectively in combination with this. When used together with the obtained carrier transport material, a so-called functionally separated type photoreceptor is constructed, and particularly excellent results can be obtained in the case of iron. Although the function-separated photoreceptor may be a dispersion type photoreceptor, it is more preferably a laminated photoreceptor in which a carrier generation layer containing a carrier generation substance and a carrier transport layer containing a carrier transport substance are laminated.

Furthermore, the 7zo compound used in the present invention is represented by the general formula (1).
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. 11 to 6. In FIGS. 1 and 3, a laminate is formed of a carrier generation layer 2 containing the above-mentioned azo compound as a main component and a carrier transport layer 3 containing a carrier transport substance as a main component on a conductive support 1. A photosensitive layer 4 is provided. As shown in FIGS. 2 and 4, this photosensitive layer 4 may be provided via an intermediate layer 5 provided on a conductive support. When the photosensitive layer 4 has a two-layer structure in this manner, a photoreceptor having the most excellent electrophotographic properties can be obtained. Further, in the present invention, as shown in FIGS. 5 and 6, a photosensitive layer 4 formed by dispersing the carrier-generating substance 7 in a layer 6 mainly composed of a carrier-transporting substance is formed on the conductive support 1. It may be provided directly or via 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, imidazole derivatives, pyrazoline derivatives, polyarylalkane derivatives, phenylenediamine derivatives, hydrazone derivatives, amino-substituted chalcone derivatives, F Realylamine derivatives, carbazole derivatives, Stilbeku! Examples include electron-donating substances that easily transport holes, such as l conductors and fetchacin 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 binder is added if necessary to mix and disperse the resulting dispersion and then applied.

The dispersion medium used for forming the carrier generation layer includes n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, and methyl ethyl ketone. , toluene, xylene, aa form, 1,2-dichloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol, isopropanol, 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 low dielectric constant, and is electrically insulating. preferable. Examples of such high molecular weight polymers include the following:
It is not limited to these.

P-1) Polycarbonate P-2) Polyester P-3) Methacrylic resin P-4) Acrylic resin P-5) Polyvinyl chloride P-6) Polyvinylidene chloride P-7) Polystyrene P-8) Polyvinyl acetate P-9 ) Styrene-butadiene copolymer P-10)
Vinylidene chloride-7crylonitrile 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-Fluid If resin-P-15
) Phenol-formaldehyde t' If fat P-1
6) Styrene-alkyd resin P-17) Poly-N-vinylcarbazole These binders may be used alone or in combination with
The thickness of the carrier generation layer 2 thus formed is:
It is preferably 0.01-201 m, more preferably 0.05-5 Jjl. Carry again
□ When the azo-generating layer or the photosensitive layer is a dispersed type, the particle size of the azo compound is preferably 5 us or less, more preferably 1- or less.

The conductive support used in the photoreceptor of the present invention may be a metal plate including an alloy, a metal drum, or a conductive polymer, a conductive compound such as indium oxide, aluminum including an alloy, palladium, gold, etc. Examples include paper, plastic films, etc. that have been made conductive by coating, vapor depositing, or laminating a metal thin film. As an intermediate layer such as an adhesive or a barrier layer, in addition to the polymer used as the binder, an organic polymer material such as polyvinyl alcohol, ethyl cellulose, carboxymethyl cellulose, or aluminum oxide is used.

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

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

(Example) Example 1 2 g of Exemplary Compound B-(10) and polycarbonate resin [
2 g of Panlite L-1250J (manufactured by Ondai Kasei Co., Ltd.) was added to 1,2-dichloroethane 110- and dispersed in a ball mill for 12 hours. This dispersion was applied onto a polyester film on which aluminum had been vapor-deposited so that the film thickness after drying would be 1-1 to form a carrier generation layer, and further on top of this,
As a carrier transport layer, 6 g of 4-methoxy-4'-styryl-triphenylamine (the following structural formula K (1))
Polycarbonate resin [Panlite L-1250J
A carrier transport layer was formed by applying a solution prepared by dissolving IO, and 1,2-dichloroethane 110- to a thickness of 15- after drying, thereby producing a photoreceptor of the present invention.

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.
A halogen lamp light was irradiated so that the surface potential became lux, and the exposure amount E+ required to attenuate the surface potential by half (half-reduced exposure amount) was determined. Further, the surface potential (residual potential) VR after exposure with an exposure amount of 301 ux-see was determined. Further, similar measurements were repeated 100 times. The results were as shown in Table 1.

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

G-(1) Regarding this comparative photoreceptor, measurements were performed in the same manner as in Example 1, and the results shown in Table 2 were obtained.

As is clear from the results shown in Table 2 and above, the photoreceptor of the present invention is extremely superior in sensitivity, residual potential, and repetition stability compared to the comparative photoreceptor.

Example 2-4 Exemplary compounds B-(1) and B-( as carrier-generating substances)
2) and B-(3), and 1-(4-(N,N-noethylamino)
-benzylidene]-7minor 1,2゜3.4-tetrahydroquinoline (for the following compound -(2)), 4-methyl-
4'-styryl-triphenylamine (compound K below)
-(3)) and 4,4'-dimethyl-triphenylamine (-(4)) were used for the following compounds, and the rest were Example 1.
A photoreceptor of the present invention was prepared in the same manner as above, and the same measurements were performed, and the results shown in Table 3 were obtained.

K-(2) K-(3) K-(4) Example 5 Vinyl chloride-vinyl acetate-
Maleic anhydride copolymer [Eslec MP-10J (
An intermediate layer with a thickness of 0.05 kon (manufactured by M Suikagaku Co., Ltd.) was provided, and on top of that, 2 g of Exemplified Compound B-(5) was mixed with 110-1,2-dichloroethane and dispersed in a ball mill for 24 hours. The liquid was applied so that the film thickness after drying was 0.51 to form a carrier generation layer. On this carrier generation layer, 68 g of 3゜3't4-)limethyl-triphenylamine and 10 g of methacrylic resin "Acrivet" (manufactured by Mitsubishi Rayon Co., Ltd.) were added to 70 g of 1,2-dichloroethane.
A carrier transport layer was formed by applying a solution dissolved in - to a film thickness of 10 m after drying, thereby producing a photoreceptor of the present invention.

The same measurements as in Example 1 were performed on this photoreceptor, and for the first time, E4 = 2.1 lux・see,
VR=OV cF) results were obtained.

Example 6 A 1% ethylenediamine solution of exemplified compound B-(43) was applied onto the conductive support provided with the intermediate layer used in Example 5 so that the film thickness after drying was 0.3 ul. , a carrier generation layer was formed.

Then 1-722-3-(p-diethylaminostyryl)-5-(p-diethylaminophenyl)
Pyrazoline (chemical compound K-(5) below) K-(5) 6.g and polyester resin [Pylon 200J (manufactured by Toyobo Co., Ltd.) 10g were dissolved in 1,2-dichloroethane 70-, and this solution was dried. A carrier transport layer was formed by coating to a film thickness of 127j1, thereby producing a photoreceptor of the present invention.

The same measurements as in Example 1 were performed on this photoreceptor, and the results shown in Table 4 were obtained.

Comparative Example 2 A comparative photoreceptor was prepared by replacing the exemplified compound B-(24) in Example 6 with a 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 4.

G-(2) Table 4 Example 7 A carrier generation layer was formed in the same manner as in Example 5 except that Exemplified Compound B-(5) was replaced with Exemplified Compound B-(35). On top of this, 3-(p-methoxystyryl)
6 g of -9-(p-methoxyphenyl)carbazole and 10 g of polycarbonate [Panlite L-1250J (manufactured by Ondai Kasei Co., Ltd.) were mixed with 70-g of 1,2-dichloroethane.
A photoreceptor of the present invention was prepared by coating a solution dissolved in the above to form a carrier transport layer so as to have a dry film thickness of 10 μs.

Measurements were performed on this photoreceptor in the same manner as in Example 1, and found that E −) = 1,91ux-sea and V
R=Ov.

Example 8 Vinyl chloride-vinyl acetate-maleic anhydride copolymer [
A 0.05-thick intermediate layer consisting of S-LEC MP-10J (manufactured by Tanezu Kagaku Co., Ltd.) was provided, and exemplified compound B-
(38) 4. 1.2 -:/Chloroethane 40〇-
A dispersion liquid was mixed with the following and dispersed for 24 hours using a ball mill dispersion machine, and the dispersion liquid was applied so that the film thickness after drying was 0.6 - to form a carrier generation layer.

Furthermore, on top of this, 30 g of p-(N*N-7ethylamino)benzaldehyde-1,1-diphenylhydrazone (compound K-(6) below) and polycarbonate resin "
Corpilon S-1000J (manufactured by Mitsubishi Chemical Corporation) 5
0g of 1,2-dichloroethane K-(6) was dissolved in 400wIQ of 1,2-dichloroethane K-(6) and coated to form a carrier transport layer such that the film thickness after drying was 13-1, thereby producing a drum-shaped photoreceptor.

The photoreceptor thus prepared is subjected to electrophotographic copying.
When it was attached to a modified U-Bix 1600M RJ (manufactured by Konishiroku Photo Industry Co., Ltd.) and an image was copied, a copy image with high contrast, faithful to the original image, and clear was obtained. Moreover, this did not change even after repeating 10,000 times.

Comparative Example 3 A drum-shaped comparative sample was prepared in the same manner as in Example 8, except that the exemplified compound B-(8) in Example 8 was replaced with a bisazo compound (G-(3)) represented by the following structural formula. When a photoreceptor was prepared and a copied image was evaluated in the same manner as in Example 8, only an image with a large amount of capri was obtained. Furthermore, as copying was repeated, the contrast of the copied image decreased, and after 2000 repetitions, hardly any copied image could be obtained.

G-(3) Example 9 Vinyl chloride was placed on a conductive support made of a polyester film laminated with aluminum foil.

-Vinyl acetate-maleic anhydride copolymer [S-LEC M
Made of F-10J (manufactured by Tanezu Kagaku Co., Ltd.) Thickness% 0.0
A 5 gm intermediate layer was provided, and exemplified compound B-(1
4) 1250J (manufactured by Ondai Kasei) 3.3. and dichloromethane (100 liters, 1 liter) and milled with a ball mill for 24 hours.
A photoreceptor was prepared by applying the time-dispersed dispersion to a dry film thickness of 10.

El- and VR of the photoreceptor obtained as described above were measured in the same manner as in Example 1, except that the charging voltage was changed to +6 KV. The first result is E f = 2,2 It+x-s
ee and VR=OV.

Example 10 6-Methyl-1-(1-ethyl-4
-carbazolyl)methylideneamino-1,2,3,4-
Tetrahydroquinoline 6I? and polyester resin "Pylon 200J (manufactured by Toyobo Co., Ltd.) Og" were dissolved in 1,2-dichloromethane 0-, and the film thickness after drying the second solution was 1.
It was applied so that it became 0-.

Next, exemplified compound B-(11)Ig and 3-(
12) Ig and 1,2-dichloroethane 110 were coated so that the film thickness after drying was 0.57j1 to form a carrier generation layer, thereby forming a photoreceptor of the present invention.

The thus obtained photoreceptor was evaluated in the same manner as in Example 9, and found that E±=2', O1ux-see, and VR=+10V.

Example 11 A 2% ethylenediamine solution of Exemplified Compound B-(15) was applied onto a polyester film laminated with aluminum so that the film thickness after drying was 0.5 Ara to form a carrier generation layer. Furthermore, 1-(4-(N) is added thereon as a carrier transport layer.

N-no(p-tolyl)aminobenzylidene-7mino]
Indoline (-(7) in the following compound), 4-methoxy-4'-(4-methyl)styryl-triphenylamine (-(8) in the following compound), or p(N+N-diethylamino)benzaldehyde-1, Separately about 10 g of 1-diphenylhydrazone (the above compound -(6)) and polycarbonate -K-(8) resin (manufactured by Ondai Kasei Co., Ltd., Panrai L-1250)
A solution prepared by dissolving 14 g of 14 g of 1,2-dichloroethane in 1,2-dichloroethane was coated and dried to give a film thickness of 12 tones upon 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 tester model SP-428 manufactured by Kawaguchi Electric Seisakusho Co., Ltd. After charging with a charging voltage of -6KV for 5 seconds and leaving it in the dark for 5 seconds, the material surface illuminance was 35.
lux, and the amount of exposure required to destroy the surface potential in half (destructive exposure amount, E+) was measured. Further, the surface potential (residual potential) VR after exposure with an exposure amount of 301 ux-sea was measured. As shown in Table 5, the results were good in combination with any carrier transport substance.

Table 5 Comparative Example-4 A comparative photoreceptor was prepared in the same manner as in Example 11 except that G-(4)
) As shown in Table 6, the results varied depending on the carrier transport substance.

Table 6 Example 12 On the conductive support provided with the intermediate layer used in Example 5, 2 g of Exemplified Compound B-(9) and 1,2-dichloroethane to
o J and (dispersed and mixed, the film thickness after drying is 0.3 j
A carrier generation layer was created by applying the coating to give a carrier generation layer.

Next, 6 g of 4゜4'-tumethyl-4''-(4-methyl)styryl-triphenylamine (compound K (9) below) and polycarbonate [Panlite L-1250J (Odai Kasei) were added as a carrier transport substance thereon. A carrier transport layer is formed by coating a solution obtained by dissolving K-(9) 10 and 1,2-dichloroethane in 90 g of 1,2-dichloroethane so that the film thickness after drying becomes 10-. created a body.

The electrophotographic properties of this photoreceptor at room temperatures of 25° C. and 60° C. were measured in the same manner as in Example 7.

The results are shown in Table 7.

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

Example 13 2 g of Exemplary Compound B-(6) and 110 g of 1,2-dichloroethane were placed on the conductive support provided with the intermediate layer used in Example 5.
- A carrier generation layer was prepared by dispersing and mixing and coating so that the film thickness after drying was 0.3 JjI.

In order to test the durability of this carrier generation layer against UV light, 30. Place a Jll11! 6-pressure mercury lamp (manufactured by Tokyo Shibaura Electric Co., Ltd.) in the closed position, and apply 1500 cd for 10 minutes.
/c112 UV light was irradiated. Next, as a carrier transporting substance,
1-(1-ethyl-4-carbazolyl)methylideneamino-indoline (for the following compound -(10)) 7 g
and polycarbonate [Pan 2ite L-1250] (10 g of Ondai Kasei Co., Ltd. 1F) were dissolved in 1,2-dichloroethane K-(10) 90%, and the solution was dried so that the film thickness after drying was 12%. A carrier transport layer was formed by coating to produce a photoreceptor of the present invention.

The same measurements as in Example 5 were performed on this photoreceptor. The results are shown in Table 8.

Example 14 After forming the carrier generation layer (■v Except for not irradiating light,
A photoreceptor of the present invention was prepared in the same manner as in Example 13, and the same measurements as in Example 5 were performed. The results are shown in Table 8.

As is clear from the results in Table 8 and above, the photoreceptor of the present invention
It is easy to understand 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)
G-(5) A photoreceptor was prepared in the same manner as in Example 13 and Example 14 except that G-(5) was changed to G-(5), and the same measurements as in Example 5 were performed. The results are shown in Table 9.

As is clear from the results shown in Table 9, the photoreceptor prepared using the above compound was significantly affected by LIv light irradiation.

Example 14 In Example 5, Exemplary Compound B-(5) was replaced with B-(4)
A drum-shaped photoreceptor was produced in the same manner except that .

The spectral sensitivity of this photoreceptor at 780 no+ is 0.
It was 47 μJ/Cl2 (half exposure amount). The photoreceptor of the present invention has a laser beam intensity of 0.85 m on the photoreceptor surface.
A live photo test was conducted using an experimental machine equipped with a semiconductor laser (790 nm).

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

Comparative Example 6 A comparative photoreceptor was obtained in the same manner as in Example 14, except that the following comparative bisazo compound was used in place of Exemplified Compound B-(1).

The spectral sensitivity of this photoreceptor at 780 nm is 7.24.
It was μJ/ci2 (half exposure amount). Using this comparative photoreceptor, a photo-taking test using a semiconductor laser was conducted in the same manner as in Example 14, but there was a lot of fog and good images could not be obtained.

As is clear from the results of the above Examples and Comparative Examples, the photoreceptor of the present invention is significantly superior to the comparative photoreceptor in properties such as stability, sensitivity, durability, and combination with a wide range of carrier +77 transport materials. It is something that

(Effects of the Invention) According to the present invention, by using an azo compound represented by the general formula (1) as a photoconductive substance constituting the photosensitive layer of a photoreceptor, heat and light, which is the object of the present invention, can be used. It also has excellent electrophotographic properties such as charge retention, sensitivity, and residual potential, and has little fatigue change even after repeated use, and has sufficient sensitivity even in the long wavelength region of 780 na or more. It is possible to create an excellent photoreceptor.

[Brief explanation of drawings]

1 to 6 are sectional views showing examples of the mechanical structure of 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 having a carrier transport substance 7... Carrier generation Substance agent Patent attorney No. 1) Step-parent procedure amendment March 20, 1985 Manabu Shiga, Commissioner of the Patent Office, Patent Application No. 111 of 1989! I (l No. 2 Name of the invention Light body Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Konishiroku Photo Industry Co., Ltd., 1 Sakura-cho, Hino-shi, Tokyo (Telephone: 0425-83 = 152)
1) Contents of Patent Part 6, Pressure Testing 1) The following sentence is added between the first line of page 13 of the specification and the first line of page 14, ``Furthermore, the above general formula used in the present invention (1)
Among the azo compounds represented by the general formula
Even more particularly preferred compounds are those having the structures shown in the general formulas. In addition, the compounds represented by the general formulas are much easier to synthesize the diamino form (general formula (l)), which is the raw material for their synthesis, than the compounds represented by the general formulas [12], p. Add the following text between lines 8 and 9, [In the general formula, Yr and Yr are selected from an alkoxyl group, a hydroxy group, an alkyl group, or a hydrogen atom (electron donating group)] group, provided that Yr and Yr are not both hydrogen atoms. A is the same as general formula (1). General formula [■] (Diamino compound serving as a raw material for the compound of general formula (V)) In the formula, Yr and Yr are the same as in the general formula. "l) Add the following text next to the table on page 1, and furthermore, as specific examples of bisazo compounds useful in the present invention shown between the above general formulas, those having the following structural formulas may be mentioned. However, the bisazo compound of the present invention is not limited thereby. Something expressed by the general formula [■] in general 2 concavities. General formula [■] (Z is a single substituent) 4) Add the following text between lines 17 and 18 of the same page, ``Synthesis Example 2 (Example Compound B - Synthesis of (99)) First,
The diamino body 7 used as a raw material is He1v. Chim, Acta, 29, 761-9 (19
46) It can be easily synthesized by a known method such as German et al. (Scheme 1) Yo 2, H 70% See Next, add diamino compound 8 23.8 # (0.1 mol) to 10% salt WI31! While stirring, this dispersion was cooled to 7115°C, and an aqueous solution of sodium nitrite 13.8 Ii (0.2 mol) dissolved in 200 ml of water was added dropwise to the dough. Ta. After the dropwise addition, stirring was continued under cooling for an additional hour, and then filtration was performed. 250 g of ammonium hexafluorophosphate was added to the obtained filtrate, the resulting crystals were counted, and the tetrazonium salt hexafluoro Obtained phosphate. This crystal was dissolved in N,N-dimethylformamide 51 to obtain a dropping solution (D) for the next coupling reaction. Dissolve 2-hydroxy-3-(4-methoxy-2-methylphenylcarbamoyl)-benzo(a)carbazole (naphthol A3-8R) 78# (0.2 mol) in N,N-dimethylformamide 2.51 , to which sodium acetate trihydrate (Cl, COONa・3) 1.0)
541 dissolved in 0.51 of water was added, and the solution was cooled to a temperature of 5° C., and the above-mentioned dropping solution [D] was added dropwise thereto while stirring vigorously. After the completion of the dropwise addition, 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 5/N,N-dimethylformamide, 2 times with 5/water, and 2 times with 5/acetone, and then dried to form a black compound 8.
4.519 (yield 65%) was obtained. In the infrared absorption spectrum of this μ-colored compound, absorption due to the C=0 bond of amide is observed at ν = 1680 (m), and in elemental analysis, the actual value (C = 74.05%. N = 10.57%, ) I = 4.58%), but the theoretical value (C = 74.13%, N = 10.64%, H
= 4.59%), which confirmed that it was the desired example compound B-(99). ”5)
The following sentence will be added between the 12th and 13th lines of page 69, after ``Not obtained.'' [Examples 15 to 26 In Example 5, Exemplified Compound B-(15) was replaced with CGM in Table 9, and 4-methyl-41-styryl-triphenylamine as CTM was replaced with CTM (Exemplified Compound in Table 9). Drum-shaped photoreceptors were produced in the same manner except that K-(12) to (23)) were used. 780 of this photoreceptor
The spectral sensitivity in nm was as shown in Table 9. The photoreceptor of the present invention was heated using a semiconductor laser (780 nm) with a laser beam intensity of 0.85 rdW on the surface of the photoreceptor.
) A live-action test was conducted using an experimental machine equipped with a. After the surface of the photoreceptor was charged to -700V, a laser beam was applied and an inverted YI image was obtained at a bias voltage of -200V, and a good image without capri was obtained. Exemplary compounds K-(12) to (23) KK-(1
2) K - (13) K - (14) K - (15) - (16) - (17) - (18) -r19)

Claims (1)

[Scope of Claims] (1) A photoreceptor comprising a photosensitive layer containing a 7zo compound represented by the following general formula (1) on a conductive support. General formula [1] [In the formula, Yl and Y2 each represent an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, or a hydroxy group, p is an integer of 0 or 1, a ring and n are 0 to 3 represents an integer. A is H, Z is a substituted or unsubstituted aromatic carbocycle, or a group of atoms necessary to constitute a substituted or unsubstituted aromatic heterocycle, Q is a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted aromatic heterocycle; unsubstituted sulfamoyl group, R1 is a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted amino group, substituted or unsubstituted carbamoyl group, carboxyl group and its ester group or cyano group,
A' represents a substituted or unsubstituted aryl group, R2J3 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted 7-ralkyl group, or a substituted or unsubstituted aryl group. (2) The photoreceptor according to claim 1, wherein the photosensitive layer contains a carrier transporting substance and a carrier generating substance, and the carrier generating substance is an azo compound of the general formula (1). (3) The photoreceptor according to claim 1 or 2, wherein the photosensitive layer is constituted by a laminate of a carrier-generating layer containing a carrier-generating substance and a carrier-transporting layer containing a carrier-transporting substance. .