JPS6177855A - Photosensitive body - Google Patents

Abstract

PURPOSE:To obtain a photosensitive body having superior electrophotographic characteristics such as charge retentivity, sensitivity and residual potential by using an azo compound represented by a specified formula as a photoconductive substance forming the photosensitive layer of a photosensitive body. CONSTITUTION:A photosensitive layer contg. an azo compound represented by general formula I is formed on an electrically conductive support. The photosensitive layer may be a laminate consisting of a carrier generating layer contg. said azo compound as the principal component and a carrier transferring layer contg. a carrier transferring substance as the principal component. The photosensitive layer may be formed on the support with an intermediate layer in-between. The photosensitive layer may be formed by dispersing said azo compound as a carrier generating substance in a layer contg. a carrier transferring substance as the principal component.

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 containing an inorganic photoconductive compound such as selenium, zinc oxide, cadmium sulfide, silicon, etc. as a main component have been widely used as electrophotographic photoreceptors. However, these are not necessarily satisfactory in terms of sensitivity, thermal stability, moisture resistance, durability, etc. 6 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 1 in terms of humidity and durability, and zinc oxide has problems in durability, etc.

In order to overcome these drawbacks of inorganic photoreceptors, research and development of organic photoreceptors having photosensitive layers mainly composed of various organic photoconductive compounds have been actively conducted in recent years. The publication 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 sensitivity and durability. Should carrier generation function and carrier transport be used to improve these shortcomings? Fi-performance is divided into different types of products, and a higher-performance organic photoreceptor is produced.
Attempts are being made to issue 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 any desired gender can be produced relatively easily. Ta.

[Problem to be solved by the invention]

A large number of compounds have been proposed as carrier-generating substances in the functionally separated photoreceptor described above.

An example of using an inorganic compound as a carrier generating substance is amorphous selenium described in Japanese Patent Publication No. 43-16198, which may be used in combination with an organic photoconductive compound or may be made of amorphous selenium. The disadvantage that the carrier generation layer crystallizes due to heat and deteriorates the characteristics as a photoreceptor has not been improved.

Furthermore, many electrophotographic photoreceptors using organic dyes or organic pigments as carrier-generating substances have been proposed. For example, as an electrophotographic photoreceptor containing a bisazo compound in the photosensitive layer, JP-A-53-95033, JP-A-53-13
JP-A No. 2347, JP-A-54-22834, 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 are limited in the selection range of carrier transport materials, which meet the wide demands of electrophotographic processes. It is not enough to fully satisfy.

Furthermore, in recent years, light sources for photoreceptors have been A.
Gas lasers such as lasers and semiconductor lasers are beginning to be used. A characteristic of these lasers is that they can be turned on and off in chronological order, making them particularly promising as light sources for copiers with image processing functions, such as Intelligent Covia, and printers for output from Funviewers. There is. 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 lower output power than a gas laser, and also has a longer wavelength than the oscillation wavelength (
(approximately 780 nm or more), the spectral sensitivity of conventional photoreceptors is higher on the shorter wavelength side, and as is, it is impossible to use them as photoreceptors using semiconductor lasers as light sources.

An object of the present invention is to solve the above-mentioned problems and provide a photoreceptor containing a specific azo compound that has carrier-generating 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.

A further object of the present invention is to provide a photoreceptor containing an azo compound that can be effectively used as a carrier generating material even in combination with a wide variety of carrier transporting materials.

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

Further objects of the present invention will become clear from the description in the specification.

[Complete means to solve the purpose]

As a result of intensive research to achieve the above object, the present inventors discovered that the azo compound represented by the general formula [I] can function as an active ingredient of a photoreceptor, and completed the present invention. This is what I did.

General formula [I] N [wherein, X is an oxygen atom or =C N Y, and VY2 is a hydrogen atom, a halogen atom, a 7-cya group,
It represents a hydroquine group, an alkyl group, or an alkoxy group, and n represents an integer of 0 or 1.

A is a substituted/unsubstituted carbamoyl group; R4 is a hydrogen atom; a substituted/unsubstituted alkyl group having 1 to ZO; phenyl group, R1 is a hydrogen atom, a substituted/unsubstituted furkyl group of carbons WL1 to 20, a substituted/unsubstituted aromatic carbocyclic group (for example, 11
Substituted/unsubstituted phenyl group, substituted/unsubstituted 7-tyl group,
Substituted/unsubstituted anthryl group, etc.), or! l! It represents a substituted/unsubstituted aromatic heterocyclic group (for example, a substituted/unsubstituted carbazolyl group, a former 1-unsubstituted nobenzofuryl group, etc.), a substituted/unsubstituted W1-substituted furkyldene 7 group.

Substituted/unsubstituted groups include, for example, carbon atoms of 1
~20 furkyl groups (e.g. methyl group, ethyl group, impupyl group, 3wk butyl group, trifluoromethyl group, etc.), substituted/unsubstituted 7-furkyl group ([Miba, benyl group, 7-ethyl group, etc.]), Halo Y71! Child A (chlorine atom,
bromine atom, fluorine atom, iodine atom), 'fl-substituted/unsubstituted alkoxy group of carbon XWL1-20 (e.g. metquine group,
Ethoxy group, impropoxy group, tertiary butoxy group, 2-
chloroethoxy group), hydroxy group, substituted/unsubstituted 7
lyloxy group (e.g. p-ral7/oxy group, 1-
7-toxy group, etc.), 7-yloxy group (e.g., 7-cetyloxy group, p-cyanobenzoyloxy group, etc.), carboxy group, its ester group (e.g., ethoxycarbonyl group, p-amophenoquine group, etc.), carbamoyl groups (e.g., 7-7-carponyl group, tertiary-butyl-7-mino-carponyl group, 7-nylino-carponyl group, etc.), 7-syl group (
(e.g., acetyl group, 0-nido-abenzoyl group, etc.), sulfo group, sulf-1 moyl group (e.g., aminosulfonyl group, tertiary butyl 7-mi/sulfonyl group, p-)lyl-7-minosulfonyl group, etc.), amine-7 group, 7syl7mi7 group (e.g., 77ylami7 group, benzoyl7mi7 group, etc.), sulfonamide group (e.g., methanesulfonamide group, 9-)
luenesulfonamide group, etc.), sia7 group, nitro group, etc., but preferably substituted or unsubstituted alkyl groups having 1 to 4 carbon atoms (e.g., 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. ethoxy group, ethoxy group, tertiary butoxy group) , 2-chloroethoxy group, etc.) Schiff 7 group, and nitro group.

Z is an atomic group necessary to form a substituted/unsubstituted aromatic carbocycle or a substituted/unsubstituted aromatic heterocycle,
For example, substitution/not! ! represents an atomic group forming a substituted benzene ring, a substituted or unsubstituted 7talene ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted carbazole ring, etc.

Examples of substituents for the atomic group forming the second ring include a series of substituents such as those listed as substituents for R1 and Rs, but halogen atoms (chlorine atoms, bromine atoms, fluorine atoms) are preferred. atom, iodine atom), a sulfo group, a sulfo moyl group (for example, an ami/sulfonyl group, a p-)lylaminosulfonyl group, etc.), and a carbamoyl group.

R+ is a hydrogen atom, li! Exchange/Vermilion! ! alkyl group,
r! IPA/unsubstituted ami7 group, carboxyl group, ester group thereof, substituted/unsubstituted carbamoyl group, cyano group, preferably hydrogen atom, substituted/unsubstituted alkyl group having 1 to 8 carbon atoms (e.g. methyl group, ethyl group, inpropyl group, tertiary butyl group, trifluoromethyl group, etc.),
They are a cyano group, a 3.2-pennolidene 7-minocarbamoyl group, and a 3.2-fulkylidene 7-minocarbamoyl group.

M is a substituted or unsubstituted 7-aryl group, preferably r!
A monosubstituted/unsubstituted phenyl group, and substituents for these groups include, for example, a series of Ii! Substituents are listed, preferably halogen atoms (chlorine atom, bromine atom, fluorine atom, iodine atom), substituted or unsubstituted alkyl groups having 1 to 4 carbon atoms (for example, methyl group, ethyl group, isopropyl group) group, tertiary butyl group, trifluoromethyl group (4), substituted/unsubstituted alkoxy group with 1 to 4 carbon atoms (e.g., methoxy group, ethoxy group, impropoxy group, 31&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 W1-substituted 7-aryl group, preferably a substituted or unsubstituted alkyl group with a carbon of 211 kl to 4 ( For example, methyl group, ethyl group, inpropyl group, tertiary butyl group, trifluoromethyl group, etc.), substituted/unsubstituted 7enyl group (for example, phenyl group, p-methoxyphenyl group, chlorophenyl group) eat.

Specific examples of the azo compound represented by the general formula (1) that are useful for completing the present invention include those having the following structural formula, which may be used to express the present invention. In 11, the following formula Ruruihi soup proboscis doki general formula (la
] A book expressed by .

CIa] Among the compounds represented by -class formula [I], those represented by the following general formula [Ib] 7 CIb ] ・47＼ Crucible 11 hook: 1 white ° - No-yield formula [I] Saruru Kajiru゛Ji Chuchoki General Formula〔IO3
Among the compounds represented by the general formula [I], those represented by the following general formula CId].

B-276 B-27g B-279 B-280 B-281 The above azo compounds can be easily synthesized by known methods. A specific example will be shown below.

Synthesis example (synthesis of exemplified compound B'-1), i.e., 2,6-
Noni Toro 11. II, 12.12-tetracyano-9
,10-Anthraquinotumethane 1 (JP-A-1983-105
53) was reduced with tin chloride to give Noamitsu compound 2, and this Noamitsu compound 2.33.4. (0.1 mol) was added to a mixture of 1 q~ of concentrated hydrochloric acid and 1 ml of water and dispersed at 13°8.
g (0.2 mol) of sodium nitrite dissolved in water] was added dropwise at 5°C under cooling with water. After the dropwise addition was completed, the reaction solution was filtered, and 50% sodium phosodide aqueous solution I was added to the IT solution.
The resulting precipitate was collected by filtration, washed with water, and thoroughly dried. The obtained salt was dissolved in 49% N,N-trimethylformthiamide (DMF) 1.511% to prepare a tetrazonium salt solution to be used in the next reaction.

Next, 52.6 g of 2-hydroxy-3-7enylcarbamoyl (su7tol AS-su7talene, manufactured by Hoechst)
(0.2 mol), 27 g (0.4 mol) of sodium acetate in H
, OO, 511, and while cooling with water, the tetrazonium salt 78 solution prepared above was added dropwise, and the mixture was further stirred for 2 hours to react. The resulting crystals were collected by filtration, washed twice with N,N-trimethylformamide (No. 511) and twice with water (No. 59), and then dried to obtain the target bisazo compound B.
-1,55,6 g (63%) was obtained. Melting point: 300° or higher, M” at m/z 882 in FD-MS spectrum
C=73.32 in elemental analysis.
% + N = 15.74 + H = 3.45% (calculated values are C = 7'3.46%, N = +5.88%, H =
3.43%), it was confirmed that the target substance was synthesized.

The azo compound of the present invention has excellent photoconductivity, and can be used to form a photoreceptor! ! In the case of manufacturing, it can be manufactured by providing a photosensitive layer in which the azo compound of the present invention is dispersed in a binder on a conductive support. Utilizing its excellent carrier generation ability, it can be used as a carrier generation substance, and by using it together with a carrier transport substance that can effectively act in combination with this substance, it is possible to create a variety of 8! Particularly impressive results are obtained when the photoreceptor is constructed as a photoreceptor of the photoreceptor type. The functionally separated photoreceptor may be of a dispersed type, but it is more preferably a laminated type photoreceptor in which a carrier generation layer containing a carrier generation substance and a carrier transport layer containing a carrier transport substance are laminated.

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 may include an electron-accepting substance that easily transports electrons, such as trinitrofluorene or tetranitrofluorenone. Polymers having a heterocyclic compound in the side chain as typified by Nobaka poly-N-vinylcarbazole, triazole derivatives, oxanoazole conductors, imiguzole derivatives, pyrazoline groove conductors, poly7-aryl alkane derivatives,
Examples include electron-donating substances that easily transport holes, such as phenylenenoamine derivatives, hydrazone derivatives, amino-substituted chalcone derivatives, triaryl 7-mine derivatives, carbazole derivatives, stilbene derivatives, and 7-7 thianone groove conductors. The carrier transport substance used in the present invention is not limited to these.

Typical examples of carrier transport substances useful in the present invention 1 are shown below. General formula CII) I3 [wherein Rl l Rl + and R13 are hydrogen atoms, alkyl groups, alkoxy groups, herodene atoms, hydroxy groups, cyano groups] , a noalkylamino group, )7lylami7 group, a noalkylamino group, or a nitro group.

] General formula (III) [wherein, RIIIR171RIIIR+, and R20
Ha, water X! y represents a child, an alkyl group, an alkoxy group, a herodene atom, a human axy group, a cya group, a noalkylamino group, a diaryl group, a )7ralkyl group, or a nitro group. 8 units represent a furkyl group, a 7enyl JE which may have a substituent, and a 7tyl group which may have a substituent, R16 is a hydrogen atom, an alkyl group, a cyano group, or a substituent represents a phenyl group which may have a general formula (fV) [wherein, Rx + * R2□, R2, and R2+ are a hydrogen atom, an alkyl group, an alkoxy group, an adenoid atom, a hydroxy R7 represents a hydrogen atom, a phenyl group which may have a substituent, a Schiff/ represents a group or a furkyl group,
Ar+ is a phenyl group which may have a substituent, a 7-tyl group which may have a substituent, and Ra3 is a furkyl group,
It represents a benyl group which may have a substituent, a phenyl group which may have a substituent, or a heptyl group which may have a substituent.

Ro represents a hydrogen atom, a furkyl group, an alkoxy group, a halogen atom, a hydroxy group, a noafurkyl 7mino group, or a nitro group] General formula (V) [wherein, Rxs+ Rzy+ Rxm and R2, are hydrogen atoms, llR2゜ representing a furkyl group, an alkoxy group, a halogen atom, a hydroxy group, a n7) group, a noaryl7mino group, a noarylami7 group, a noafrylmino group, or a nitro group may have a hydrogen atom or a substituent. A represents a good phenyl group, cyano group, or alkyl group
r, may have a substituent, and R11 is a furkyl group, a pennol group, which may have a substituent, a phenyl group, which may have a substituent, or
Represents a 7-tyl group which may have a substituent.

R74 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a noafurkyl 7mino group, or a nitro group] General formula (Vl) M2 [wherein, Rs+ + R32@Rz, is a hydrogen atom ,
Alkyl group, alkoxy group, halogen atom, hydroxy group, Schiff) group, nofurkyl7mino group, noaryl7mi7
group, noafurkyl7mino group, or nitro group
represents an integer of 1 or 2,] General formula [■] [In the formula, R3+tRzs, Rz*tRttrRis and C/Rss are water J! g, child, alkyl group, alkoxy group,) 10 dene atom, hydroxy group, cyano group, alkyl 7mino group, noaryl 7mino group, noafurkyl 7mino group, or nitro group, R1° is a hydrogen atom or Represents a 7enyl group] General formula [■] 84゜ [In the formula, R+l+R+i+R+3tk+R*i and C/
R4g is a hydrogen atom, an alkyl group, an alkoxy group, an island rodene atom, a human O4 crystal, a cyano group, a nofurkylreamino group, a noarylamine 7 group, a nofurkyl 7mino group,
or represents a nitro group, R1 represents a hydrogen atom or a phenyl group] General formula (I [wherein s R4*tR*I+Rso+Rs+1Rsz and Rsz are a hydrogen atom, a furkyl group, an alkoxy group,
/) 0 gene atom, hydroxy group, cyano group, noaryl7mino group, noaryl7mino group, di7ralkyl7Specific examples of the above carriers are as follows.

<[rx lC High I7ζ What does it do General formula [1F structural component RIm Fb* B4-6 Formula [1~゛] Book with q Yusa - Makito [\”] The structure of the general formula [~'1] that has a denomination [do + - - V formula [■]
A photoreceptor having the structure f has the general formula [tlll] A photoreceptor having the general formula [tlll] *a of the general formula Based on which of those forms? )obtain.

Usually, it is in the form of Figure Il & 1 to factor 6. In FIGS. 1 and 3, a laminate of a carrier-17 generating layer 2 containing the above-mentioned 71 compounds as a main component and a carrier-transporting layer 3 containing a carrier-transporting substance as a main component on a conductive support 1 is shown. A photosensitive layer 4 is provided. As shown in FIGS. 2 and 4, this photosensitive layer 4 may be provided through an intermediate layer 5 provided on a conductive support. When the photosensitive layer 4 has a two-layer structure in this way, In addition, in the present invention, as shown in the aS diagram and FIG. The photosensitive layer 4 impregnated with the photosensitive layer 4 may be provided directly on the conductive support l or via an intermediate layer 5.

The carrier generation layer 2 constituting the two-layered photosensitive layer 4 can be applied directly onto the conductive support 11 or the carrier transport layer 3, or if necessary, on a Nakaoka layer such as an adhesive layer or barrier waste, etc. It can be formed by the following method.

A method of applying a solution in which the M-13 azo compound is dissolved in a suitable medium, or a solution in which a binder is added and mixed as necessary.

M-2) Grind the azo compound into fine particles in a dispersion medium using a ball mill, homomixer, etc., and add a binder (
A method of applying a mixed and dispersed fractional liquid.

The solvent or dispersion medium used to form the carrier generation layer includes n-1 thylamine, noethylamine, ethylenenoamine, impucvalamine, triethanolamine, triethylamine, and N=N-methylbenzene. , seven tons.

Methyl ethyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, 1,2-chloroethane% 1.1.2-) Lichloroethane, 1.1.1-
), lJria loethane, trichlorethylene, tetrachromitane, knock-a methane, tetrahydro-7ran, nooxane, methanol, ethanol, impropanol, ethyl acetate, butyl acetate, trimethyl sulfoxide, methyl hexasol, ethyl hexasol etc.

When using a binder in the carrier 177 generation layer or the carrier transport layer, any binder can be used, but it is recommended 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, which are preferably sized, include, for example, large-sized polymers, but they are not limited to #L-sized polymers.

P-1) Polycarbonate F P-2) Polyester P-3) Ivy resin P-4) 7Kutsuru resin P-5) Polyvinyl chloride P-6) Polyvinylidene chloride P-7) Polystyrene P-8) Polyvinyl acetate P -9) Styrene-butanoene copolymer p-to)
Vinylidene chloride-acrylic nitrile copolymer P-11> Vinyl chloride-vinyl acetate copolymer P-1
21 Vinyl chloride-vinyl acetate-maleic anhydride copolymer P, -13) Silicone resin P-14) Silicone-fluid resin P-15)
71 nor formaldehyde resin P-16)
Styrene Flukyd Resin P-17) Poly N-
Vinylcal/f-sol P-18) Merivinyl petitfour P-19) Polyvinyl 7-olmar 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
It is preferably from 0.01# to 20μ, more preferably from 0.05μ to 5μ. Also Kiya 17
7g & When the green layer or photosensitive layer is a dispersion system, the particle size of the azo compound is preferably 5 .mu.m or less, more preferably 1 .mu.m or less.

The conductive support used in the photoreceptor of the present invention includes a metal plate including an alloy, a metal drum, or a conductive salimer,
Examples include paper, plastic films, etc. that have been made conductive by spraying, vapor depositing, or laminating a thin layer of metal such as aluminum, parazoum, or gold containing a conductive compound or alloy such as innoum oxide. As an intermediate layer such as an IN adhesion layer or a barrier layer, in addition to the polymer used as the binder, organic polymer substances such as polyvinyl alcohol, ethyl cellulose, carboxyl methyl cellulose, or aluminum oxide are 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 even when used repeatedly. It has little deterioration and excellent durability.

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

〔Example〕

Example 1 2 g of Exemplified Compound B-70 and 2 g of polycarbonate resin "Pamphui" L-12504 (manufactured by Maenin Kasei Co., Ltd.) were mixed in 1.
In addition to 110ml of 2-tsuk aa ethane, add 1
Dispersed for 2 hours. This dispersion was applied onto a polyester film coated with aluminum to a dry film thickness of 0.1 μm.
The above compound T-30.6g and polycarbonate resin "Hanhui"L-'1250 are coated to form a carrier generation layer, and on top of that, as a carrier transport layer.
J 1G, and 1,2-tsuk aa ethane 110id
The 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 dry film thickness of 20 .mu.m.

The photoreceptor obtained as described above was subjected to the following characteristic evaluation using an electrostatic paper tester model SP-428 manufactured by Kawaguchi Denki Shinsakusho Co., Ltd. 1lIl for 5 seconds at charged voltage -6KV? r
Surface potential V^ when applied with I, then left in the dark for 5 seconds,
Next, the photoreceptor surface was irradiated with heroden lamp light so that the illuminance was 35 lux, and the exposure amount (half-reduction exposure fi) E% required to attenuate the surface potential by half was determined.

In addition, the surface potential (residual potential) VR after exposure with an exposure amount of 30 Iux-sea was determined.

Further, similar measurements were repeated 100 times. The results are shown in Table 1.

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

When this comparative photoreceptor was measured in the same manner as in Example 1, the results shown in Table 2 were obtained.

As is clear from the results in Table 2 and above, the photoreceptor of the present invention of Example 1 has higher sensitivity, residual potential, and a9
It has excellent return stability.

Examples 2 to 4 Exemplary compounds B-23 and B-64 as carrier generating substances
, and B-132, and the compounds T-80, T-75 and VT-13, respectively, as carrier transport substances.
A photoreceptor of the present invention was prepared in the same manner as in Example 1 except that the photoreceptor was subjected to the same measurements as in Example 1, and the results shown in Table 3 were obtained. All exhibit excellent characteristics in terms of sensitivity, residual potential, and m-return stability.

Example 5 Vinyl chloride-vinyl acetate-
A 0.05μ thick intermediate layer made of maleic anhydride copolymer [S-LEC MF-10J (manufactured by Tanezu Kagaku Co., Ltd.) was provided, and 1.2-2 g of Exemplary Compound B-100° was placed thereon.
Jiku aoeta 7110ml! A dispersion liquid obtained by dispersing rgI in a ball mill for 24 hours was applied to form a carrier and a generation layer such that the film thickness after drying was 0.5 μ-. On this carrier generation layer, the above compound T-130,6 and methacrylic resin "Aku + 7 Peft" (manufactured by Mitsubishi Rayon Co., Ltd.) l-0 were added at 1.2-Tx aa.
The solution dissolved in 70 ml of ethane was added until the membrane 4 after drying was 10
A carrier transport layer was formed by coating the photoreceptor in an amount of μl to prepare a photoreceptor of the present invention.

Example 1 regarding this photoreceptor. When the same measurement was carried out, for the first time, E = 2.04ux・See,
A result of VR=OV was obtained, and both sensitivity and residual potential were excellent.

Example 6 A 1% ethylenenoamine solution of Exemplified Compound B-150 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 μm. , a carrier generation layer was formed. , and then the compound T
-101+ 6 g and polyester resin [Byron 2
00J (manufactured by Toyobo Co., Ltd.) 10° and 1,2-dichloroethane 70mQ l:tl! Then, this solution was coated to form a carrier transport layer so as to have a film thickness of 12 μm after drying, thereby producing a photoreceptor of the present invention.

When this photoreceptor was measured in the same way as Example 831, E % = 3,11ux-sea for the M1st measurement.
.

A result of V R = Ov was obtained, and the sensitivity and residual potential were excellent.

Example 7 In Example 5, Exemplified Compound B-100 was replaced with Exemplified Compound B
A carrier generation layer was formed in the same manner except that -51 was used. On top of this, 6g of the compound T-200 and polycarbonate [Panrai] L-125<IJ (manufactured by Ondai Kasei Co., Ltd.)10. A photoreceptor of the present invention was prepared by dissolving a solution of 1,2-chloroethane in 70 ml of 1,2-chloroethane and applying the solution to a dry film thickness of 10 .mu.m to form a carrier transport layer.

When this photoreceptor was measured in the same manner as in Example 1, jE x == 1.8 lux 7 s,
ea and v, = Ov, which was a good result.

Example 8 An intermediate layer with a thickness of 0.05 μl made of vinyl chloride-vinyl acetate-maleic anhydride copolymer [Eslenok MF, -1, OJ, manufactured by Sekisui Chemical Co., Ltd.] was coated on the surface of an aluminum drum with a diameter of 100 m5+. and exemplified compound B on it.
31+Fg was mixed with 400% of 1,2-dichloroethane and dispersed for 24 hours using a bottle mill dispersion machine. A dispersion solution was applied so that the film thickness 6 after drying was 0.6 μl to form a carrier generation layer. did.

Furthermore, on top of this, 30 g of the compound T-81 and a bottle were added.
7 Car Ho+-FtJINrnee Hihan S-1
000J (manufactured by Mitsubishi TTS Chemical Co., Ltd.) and 50g were dissolved in 400g of 1,2-dichloroethane, and the film thickness after drying was 18μm.
A carrier transport layer was formed by coating the powder to form a drum-shaped electrophotographic photoreceptor.

The photoreceptor produced in this way is used in an electrophotographic copying machine rU.
- When I attached it to a modified Bix 1600 M RJ (manufactured by Konishi Roku Photo Industry Co., Ltd.) and copied the image, the contrast was very good (I got a copy image that was faithful to the original and clear. Also, this is to, No matter how many times I repeated it, nothing changed.

Comparative Example 2 A drum-shaped comparative photoreceptor was prepared in the same manner as in Example 8, except that exemplified compound B-31 was replaced with bisazo compound G-3 represented by the following structural formula, and Example 8
When the copied W image was evaluated in the same manner as above, only images with many capri were obtained.

Further, as copying was repeated, the contrast of the copied image decreased, and after 2000 repetitions, hardly any copied image could be obtained.

G-ball O Example 9 Vinyl chloride-vinyl acetate-
Maleic anhydride copolymer “S-LEC MF-104
(A 0.05μ-thick intermediate layer made of Sekisui Chemical Co., Ltd. resin was provided, and 3.3 g of polycarbonate resin "Panlite L-1250J (manufactured by Kijin Kasei Co., Ltd.) and to 100 mu of nochloromethane,
A photoreceptor was prepared by applying a dispersion that had been dispersed in a ball mill for 24 hours to a dry film thickness of 10 μm.

E and R 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 was good: E number = 1.9111X sea and V p: + 6 v.

Example 10 ゛ 6 g of the compound T-77゜ and polyester resin "Vylon Zoo J (manufactured by Toyobo Co., Ltd.)" were added as a carrier transport layer on a polyester film on which aluminum was vapor-deposited.
10 g of 70I of 1,2-nochloroethane was dissolved in 1 g of 1,2-nochloroethane 70I, and this solution was applied so that the film thickness after drying was 10 + lj m.

Next, 1 g of Exemplified Compound B-13 and 1 g of B-3 were mixed with 110 g of 1,2-nochloroethane and dispersed in a ball mill for 24 hours. A photoreceptor of the present invention was formed by applying ka to a film thickness of 0.5 μm after drying to form a carrier generation layer.

The thus obtained photoreceptor was evaluated in the same manner as in Example 9. E% = 2. Olux·see and V R = +10v, showing good results.

Example 11 Vinyl chloride-vinyl acetate-
Maleic anhydride copolymer “S-LEC MF-104
An intermediate layer with a thickness of 0.05 μm made of ' (Sekisui Chemical Co., Ltd. A photoreceptor was prepared by adding 3 g of the photoreceptor (manufactured by Kijin Kasei Co., Ltd.) to 100 ml of nochloroethane and dispersing it with sand grating for 24 hours, and applying the dispersion to a dry film thickness of 10 μm.

The photoconductor obtained as described above was charged with a voltage of 16'v.
E and ■R were defined in the same manner as in Example 1 except that . The first result was good performance with E=1.31u'x·Se'e and VH=Ov.

Example 12 Exemplary compound B-7, 2g was added to 10% of 1,2-nochloroethane.
The liquid dispersed at 0mR was placed on a polyester film laminated with 7luminium so that the dry film thickness was 0.5 μm.
A carrier-generating layer was formed by coating the powder to form a carrier-generating layer. Further thereon, as a carrier transport layer, the compound T-6,
A solution of 10 g of polycarbonate resin (manufactured by IP Jinkasei Co., Ltd., Pan 2ite L-1250>14 g dissolved in 140 ml of 1°2-tsuku aa ethane) was prepared so that the film thickness after drying was 12 μm.
The photoreceptor of the present invention was obtained by coating the photoreceptor in an amount of m and drying.

This photoreceptor was subjected to the same measurements as in Example 1. The results were good as shown in Table 4.

Table 4 Example 13 A drum-shaped photoreceptor was prepared in the same manner as in Example 5 except that B-22 was used instead of Exemplary Compound B-100. The sensitivity of this photoreceptor to 790 ns semiconductor laser light is 630 vofl-as * u W −' ・5e
An actual photographic test was conducted using an experimental machine equipped with a Naro semiconductor laser (790 na), in which the laser light intensity on the surface of the photoreceptor of the present invention was 0.85 mW, and the laser beam intensity was e-' (light decay rate).

Set the surface of the photoreceptor to -6 vl:? rI? After IK printing, I exposed it to laser light and developed it at a bias voltage of 1250cm, which resulted in a good l! The image was obtained.

Comparative Example 3 A comparative photoreceptor was obtained in the same manner as in Example 13, except that the following Comparative Example Bisazo Compound G-6 was used in place of Exemplified Compound B-22.

The sensitivity of the photoreceptor in G- is 60 voH-a at 79 on-
m''・μW−1・5ea−′ (light attenuation rate).Using this comparative photoreceptor, we conducted an actual photographic test using a semiconductor laser in the same manner as in Example 13, but there were many capri (good images were I couldn't get it.

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

Examples 14 to 27 In Example 5, exemplary compound B-100 (charge generating substance) and compound T-130 (charge transporting substance) are shown in Table 5.
A drum-shaped photoreceptor was prepared in the same manner except for the pond. The light sensitivity of this photoconductor at 79On+s is as shown in Table 5, and in the same photo-taking test as Example 16 using this photoconductor (Examples 14 to 27), PIS 5 table (effect of the invention) According to the present invention, by using the azo compound represented by the general formula (1) as a photoconductive substance constituting the photosensitive layer of a photoreceptor, the object of the present invention such as charge retention, sensitivity, residual potential, etc. can be improved. It has excellent electrophotographic properties, has little fatigue deterioration even after repeated use, and has 78
It is possible to produce an excellent photoreceptor having sufficient sensitivity even in the long-wave fkgIA range of 0n- or more.

[Brief explanation of the drawing]

1 to 6 are sectional views showing examples of the mechanical structure of the photoreceptor of the present invention, and 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 Figure 1 Figure 2 Figure 3 Figure 4

Claims (3)

[Claims] (1) A photoreceptor characterized by having a photosensitive layer containing an azo compound represented by the following general formula [I] on a conductive support. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, It represents an alkyl group or an alkoxy group, and m represents an integer of 0 or 1. A has ▲mathematical formulas, chemical formulas, tables, etc.▼ ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ where Z is a substituted or unsubstituted aromatic carbon ring, or a substituted or unsubstituted aromatic carbon ring. Atom group necessary to constitute a substituted aromatic heterocycle, G is a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted sulfamoyl group, R_1 is a hydrogen atom, a substituted or unsubstituted alkyl group, substituted or unsubstituted amino group, substituted or unsubstituted carbamoyl group,
Carboxyl group and its ester group or cyano group, M is substituted or unsubstituted aryl group, R_2 and R_3 are substituted or unsubstituted alkyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aryl represents a 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 represented by I]. (3) The photosensitive layer 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. body.