JPS59204840A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To obtain the titled sensitive body having stability to heat and light and superior carrier generating power by forming a photosensitive layer contg. a specified bisazo compound on an electrically conductive support. CONSTITUTION:A photosensitive layer 4 is formed on an electrically conductive support 1 by laminating a carrier generating layer 2 contg. a bisazo compound of <=5mum particle size represented by formula I as the principal component and a carrier transferring layer 3 contg. a carrier transferring substance such as trinitrofluorenone as the principal component. In the formula I , each of Ar1 and Ar2 is an (un)substituted aromatic carbon ring; each of k and l is 0 or 1; each of X1-X4 is H or cyano; A is a group represented by formula II, III, IV or V; Y is (un)substituted carbamoyl or (un)substituted sulfamoyl; Z is an (un)substituted cyclic aromatic carbon ring or a group of atoms required to form the ring; Ar3 is (un)substituted aryl; R1 is (un)substituted amino; (un)substituted alkyl, (un)substituted carbamoyl or carboxyl (ester); and each of R2 and R3 is (un)substituted alkyl, (un)substituted aralkyl or (un)substituted aryl.

Description

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

(Prior Art) Conventionally, inorganic photoreceptors having a photosensitive layer containing an inorganic photoconductive compound such as selenium, zinc oxide, or cadmium sulfide as a main component have been widely used as electrophotographic photoreceptors. but,
These are not necessarily satisfactory in terms of sensitivity, thermal stability, heat resistance, durability, etc. For example, when selenium crystallizes, its sensitivity decreases, making it difficult to manufacture and crystallizing due to heat, fingerprints, etc., resulting in deterioration of performance as a photoreceptor. Additionally, cadmium sulfide has problems with moisture resistance and durability, and zinc oxide has problems with durability, etc.

In order to overcome the drawbacks of these 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-vinylcarbashield 2,4,7-dolinitro-9-fluorenone. However, this photoreceptor is not necessarily satisfactory in sensitivity and durability. In order to further improve these drawbacks, attempts have been made to develop organic photoreceptors with higher sensitivity by assigning different substances to the functions of carrier generation and transport. For a functionally separated electrophotographic photoreceptor, each material can be selected from a wide range, and a photoreceptor having arbitrary performance can be created.

Many compounds have been proposed as carrier generating substances for such functionally separated electrophotographic photoreceptors. An example of using an inorganic compound as a carrier generating substance is amorphous selenium described in Japanese Patent Publication No. 43-16198, which is used in combination with an organic photoconductive compound. This carrier generation layer has the disadvantage that it crystallizes due to heat, deteriorating the characteristics of the photoreceptor.

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-47-37543, JP-A-54-217
No. 28, JP-A-57-74746, JP-A-Sho 5
7-169756 and the like have already been proposed. However, these bisazo compounds are not necessarily satisfactory in terms of characteristics such as sensitivity, residual potential, and stability during repeated use, and the selection range of carrier transport substances is also limited, making them difficult to use in electrophotographic processes. It does not fully satisfy the wide range of demands of

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

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

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

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

(Structure of the invention) General formula CI) XI X2 X3 etc.) k and l: each an integer of O or 1, X+, X2
,Xs and・Unsubstituted aralkyl group, substituted/unsubstituted phenyl group, R11=hydrogen atom, substituted/unsubstituted alkyl group having 1 to 4 carbon atoms, substituted/unsubstituted aromatic/carbocyclic group (for example, substituted/unsubstituted Substituted phenyl group, substituted/unsubstituted +7-y-M
, a substituted or unsubstituted anthryl group, etc.), or a substituted or unsubstituted aromatic heterocyclic group (for example, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuryl 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 aralkyl group (e.g. benzyl group, phenethyl group, etc.), halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom), number of carbon atoms 1 to 4 substituted/unsubstituted alkoxy groups (e.g., methoxy group, ethoxy group, isoprobioxy group, tertiary butoxy group, 2-chloroethoxy group, etc.), hydroxy group, substituted/unsubstituted aryl IL'
Oxym (for example, p-chlorophenoxy group, 1-naphthoxy group, etc.), acyloxy group (for example, acetyloxy group, p-cyanobenzoyloxy group, etc.), carboxyl group, its ester group (for example, ethoxycarbonyl group) , m-bromophenoxycarbonyl group, etc.), carbamoyl group (e.g., aminocarbonyl group, tertiary butylaminocarbonyl group, aminosulfonyl group, etc.), acyl group (
For example, acetyl group, 0-nitrobenzoyl i, etc.),
Sulfo group, sulfamoyl group (e.g., aminosulfonyl group, tertiary butylaminosulfonyl group, p-tolylaminosulfonyl group?), 7mino group, acylamino group (e.g., 7 acetylamino groups, 7 benzoylamino groups, etc.), sulfonamide groups (e.g. methanesulfonamide M, p
-) luenesulfonamide group, etc.), cyano 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 atom (chlorine atom to bromine atom, fluorine atom, iodine atom), substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms (
For example, methoxy group, ethoxy group, impropoxy group,
tertiary butoxy group, 2-chloroethoxy group, etc.) cyano group,
There are four nido groups.

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 naphthalene ring, a substituted/unsubstituted indole ring, a substituted/unsubstituted carbazole ring, etc.

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

R8 is a hydrogen atom, a substituted/unsubstituted alkyl group, a substituted/unsubstituted alkyl group,
unsubstituted a, mino group, carboxy 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.

Ar 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 yama and crow. However, 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, tertiary butyl group) group, trifluoromethyl group, etc.), and substituted/unsubstituted alkoxy groups having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, isopropoxy group, tertiary butoxy group, 2-chloroethoxy group).

R2 and R8 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl group, preferably a substituted or 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.).

Furthermore, it is preferable that the bisazo compound of the present invention represented by the general formula [I] is a bisazo compound represented by the following general formula [■], [■], [Q] or [■].

X, XI3 [In the formula, Ar1, Ar2 and A are the same as in the general formula [■].

The element is a hydrogen atom or a cyano group. ] General formula l] CN CN [wherein Arl , Ar2 and A are the same as general formula [ID]. [7] [In the formula, Art, Art and A are the same as the general formula [ID].

X is a hydrogen atom or a cyano group. N This is the case where the bisazo compound represented by ] is a bisazo compound represented by the following general formula 01 [], l], [hill], [X] or addition].

X5 XI! [In the formula, A, X, and general formula (same as ID, A
r3 and Ar4 represent a substituted or unsubstituted 7-enylene group. ] CN CN [wherein A is the general formula [same as ID, Ar, and Ar
4 represents a substituted or unsubstituted 7-enylene group. [General formula family] X.

[In the formula, A and X7 are the same as in the general formula study], and ArB and A14 represent a substituted or unsubstituted 7-enylene group. ] Ar3 and Ar represent a substituted or unsubstituted 7-enylene group. ] General 2] A-N=N Ars”1”-Ara N=N-A [
In the formula, A is the same as in the general formula [■], and Ar and Ar4 represent a substituted or unsubstituted 7-enylene group. (Effects of the Invention) That is, according to the present invention, a bisazo compound represented by the general formula CI) is preferably used as a photoconductive substance constituting the photosensitive layer of an electrophotographic photoreceptor.
], [H], [■] or solid], more preferably a bisazo compound represented by the above general formula [■], l], (5)
By using a bisazo compound represented by It is possible to produce an excellent electrophotographic photoreceptor that has a high temperature and low fatigue change even after repeated use. In particular, in so-called functionally separated electrophotographic photoreceptors in which carrier generation and transport are performed using separate substances, the excellent carrier generation ability of the bisazo compound of the present invention is utilized exclusively, and other carriers are used. By combining it with a transport substance, even better electrophotographic photoreceptors can be created.

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

<< ■ Z Z llll (be ■1
1 <1
< ) < ■l
l 1
(■ ■ < 5 Kazu＜ < ■＜
< 144 < 11 ■ < 7 <
＜■－＜
≦ ＜ ＜
■<<Riku Shizu・He1<The above bisazo compounds can be easily synthesized by known methods.

Synthesis Example 1' (Synthesis of Exemplary Compound A-(1)) Journal
al of American Chemical 5
ocietyVo1.70.3416, (1948)
2,5-2,5-bischloromethylthiophene HsONa 2,5-2,5-bischloromethylthiophene was synthesized according to the method described below using 2,5-bischloromethylthiophene as a starting material. ζChili→-naophene-bis-(4-aminostyryl)thiophene 320, l
i' (1 mo/I/) was added and dispersed in a mixture of 101 concentrated hydrochloric acid and 101 water, and a solution of 140.9 (2 mol) sodium nitrite dissolved in 1 liter of water was heated at 5°C under water cooling. After the dropwise addition was completed, the mixture was stirred and reacted for 1 hour.

After the reaction is completed, the reaction solution is filtered, and the filtrate is added with 42% bouf.

, 15 Il of hydrohydric acid were added, and the resulting precipitate was collected by filtration, washed with water, and thoroughly dried. The obtained salt was dissolved in 10 parts of N,N-dimethylformamide to prepare a tetrazonium salt solution to be used in the next reaction.

Next, 800 g (2 moles) of 2-hydroxy-3-naphthoic acid anilide (naphthol As) and 550.9 e5M of triethanolamine were dissolved in N,N-dimethylformamide, and the tetrazonium salt solution prepared above was added while cooling on ice. The mixture was added dropwise and further stirred for 2 hours to react.

Thereafter, the deposited precipitate was collected by filtration, washed with N,N-dimethylformamide and then with acetone, and dried to obtain 280 g (32.3%) of the target azo compound.

Melting point 300℃ or higher. Sea 1'5 in infrared absorption spectrum
Since a molecular ion peak of rry'z = 857 appeared in the D-mass spectrum, it was confirmed that the target substance was synthesized.

Synthesis Example 2 (Synthesis of Exemplified Compound A-(2)) (::oll
Ection Czechoslov Chemica
l ('orrmunicat -1on Vol,
Using 2-formyl-5-(4-nitrophenyl)thiophene synthesized according to the method described in 38.1809, (1978) as a starting material, 2 was synthesized according to the following method.
-(4-aminof,nil)-2-formyl-5-(4-
Nitrophene dust thiophene 2-(4-aminophene product →-
5-0-Aminostyryl→Thio7ene-(4-aminostyryl)-thiophene 290. ! 1 liter (1 mol) is 8.5
Add to the mixture of concentrated hydrochloric acid of No. 191 and water of No. 191 and disperse it.
A solution of 5 g (2 moles) of sodium nitrite dissolved in 5.8 mm of water was added dropwise at 5° C. under water cooling, and after completion of the dropwise addition, the mixture was stirred for 1 hour to react. After the reaction was completed, the reaction solution was filtered, 42% fluoroboric acid 13j51 was added to the filtrate, and the resulting precipitate was collected by filtration and diluted with water.

After washing, it was thoroughly dried. The obtained salt was dissolved in 19 volumes of N,N-dimethylformamide to prepare a tetrazonium salt solution to be used in the next reaction.

Next, 2-hydroxy-3-naphthoic acid anilide (naphthol AS) 520. ! i+ (2 mol) to 191 N
.

The tetrazonium salt solution dissolved in N-dimethylformamide and prepared above was added dropwise while cooling with ice, followed by dropwise addition of a solution of 250 g (3 mol) of sodium acetate dissolved in 91 parts of water, and the mixture was further stirred for 2 hours to react. I let it happen.

Thereafter, the deposited precipitate was collected by filtration, washed with N,N-dimethylformamide and then with acetone, and dried to obtain the target azo compound 340F (40%). Melting point 3
00℃ or higher. In the infrared absorption spectrum, C=1680cI
n-1 (amide absorption) and r in the FD-mass spectrum.
Since a molecular ion peak of rV/z = 841 appeared, it can be understood that the target substance was synthesized.

The bisazo compound of the present invention has excellent photoconductivity, and when producing an electrophotographic photoreceptor using the same, a photosensitive layer in which the bisazo compound of the present invention is dispersed in a binder is formed on a conductive support. It can be manufactured by providing. Another method is to use the bisazo compound of the present invention as a carrier-generating substance that takes advantage of its particularly excellent carrier-generating ability among its photoconductivity properties, and to use it together with a carrier-transporting substance that can effectively act in combination with this. , laminated type,
Alternatively, it is also possible to use a dispersed so-called functionally separated electrophotographic photoreceptor. Furthermore, the bisazo compound used in the present invention can be used alone or in combination of two or more of the bisazo compounds represented by the general formula [I], or in combination with other bisazo compounds. It's okay.

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

Usually, the configuration is as shown in FIGS. 1 to 6. In FIGS. 1 and 3, the layer consists of a carrier generation layer 2 containing the above-mentioned bisazo compound as a main component and a carrier transport layer 3 containing a carrier transport substance as a main component on a conductive support l. A photosensitive layer 4 is provided.

As shown in FIGS. 2 and 4, this photosensitive material N4 may be provided via an intermediate layer 5 provided on a conductive support. When the photosensitive layer 4 has a two-layer structure in this manner, an electrophotographic photoreceptor having the most excellent electrophotographic properties can be obtained. 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 placed on a conductive support l. It may be provided directly or via the intermediate layer 5.

When the bisazo compound of the present invention is used as a carrier-generating substance, the carrier-transporting substance used in combination with the bisazo compound may include electron-accepting substances that easily transport electrons such as trinitrofluorenone or tetranitrofluorenone, as well as po'J-N. - Polymers having a heterocyclic compound in the side chain such as vinylcarbazole, triazole derivatives, oxydiazole derivatives, imidazole derivatives, pyrazoline derivatives, polyaryl almanol derivatives, phenylene diamine derivatives, hydrazone derivatives, amino Examples include electron-donating substances that easily transport holes, such as substituted chalcone derivatives, triarylamine derivatives, carbazole derivatives, and stilbene derivatives, but the carrier transporting substance used in the present invention is not limited to these.

The carrier generation layer 2 constituting the two-layered photosensitive layer 4 may be applied directly onto the conductive support 11 or the carrier transport layer 3, or after providing an intermediate layer such as an adhesive layer or a single barrier layer as required, for example, as follows. It can be formed by the following method.

M-1) A method of applying a solution in which a bisazo compound is dissolved in a suitable solvent, or a solution in which a binder is added and mixed as necessary.

M-2) A method in which a bisazo 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.

Examples of the solvent or dispersion medium used for forming the carrier generation layer include n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N,N-dimethylformamide, acetone, methyl ethyl ketone, Cyclohexanone, penzene, toluene, xylene, chloroform, 1,2-dichloroethane, dichloromethane, tetrahydrofuran, dioxane, methanol, ethanol,
Examples include isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoside, and the like.

When using a binder in the carrier generation layer or carrier transport layer, any binder can be used, but it is preferable to use a film-forming polymer that is hydrophobic, has a high dielectric constant, and is electrically insulating. . 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-acrylonitrile copolymer P-11) Vinyl chloride-vinyl acetate copolymer P-12)
Vinyl chloride-vinyl acetate-maleic anhydride copolymer P-13) Silicone resin P-14) Silicone-alkyd resin P-15) Phenol-formaldehyde resin P-16
) Styrene-alkyd resin P-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 preferably 0.01 μm to 20 μm, more preferably 0.05 μm to 5 μm. ~When the carrier generation layer or photosensitive layer is a dispersed layer, the particle size of the bisazo compound is preferably 5 μm or less, more preferably 1 μm or less.

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

The electrophotographic photoreceptor of the present invention has the above structure,
As is clear from the Examples described below, it has excellent charging characteristics, sensitivity characteristics, and image forming characteristics, and especially shows little fatigue deterioration even after repeated use, and is excellent in durability.

The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereby.

(Example) Example 1 2 g of exemplified fragrances A-Q) and 2 g of polycarbonate resin "Panlite L-1250J (manufactured by Yondai Kasei Co., Ltd.)
, 110 ml of 2-dichloroethane! In addition, it was dispersed in Ball Myrte for 12 hours. This dispersion was applied onto a polyester film coated with aluminum to a dry film thickness of 1 μm.
4,4'-dimethyl-4'' as a carrier transport layer.
-(4-methoxy)styrene 1) 6 g of phenylamine (-(+) in the following structural formula) was added to polycarbonate resin "Panlite L -1250J 10 & 1.2-
A carrier transport layer was formed by applying a solution dissolved in 110 mJ of dichloroethane so that the film thickness after drying was 15 μm, thereby producing an electrophotographic photoreceptor of the present invention.

The photoreceptor obtained as described above was subjected to the following characteristic evaluations using an electrostatic paper tester model SP-428 manufactured by Kawanichi Denki. After being charged for 5 seconds at a charging voltage of -6KV,
Leave it in the dark for 5 seconds, then increase the illuminance on the photoreceptor surface to 35+
A halogen lamp light was irradiated so that the surface potential became lux, and the exposure amount (half-reduced exposure amount) E% required to attenuate the surface potential by half was determined. Further, the surface potential (residual potential) VR after exposure with an exposure amount of 301 ux-sec was determined. Further, similar measurements were repeated 100 times. The results are shown in Table 1.

Comparative Example 1 The following bisazo compound G-(1
) was used, but in the same manner as in Example 1, comparison G −(1
) Regarding this comparative electrophotographic photoreceptor, measurements were performed in the same manner as in Example 1, and the results shown in Table 2 were obtained.

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

Example 2-4 Exemplary compounds A-(3) and A- as carrier generating substances
Using C31 and A-(711:), 1-(l-ethyl-4-carbazolyl)methylideneamino-1,2,3,4-tetrahydroquinoline (the following compound K-(2)) was used as a carrier transport substance, respectively. , 4,4'-dimethyl-4''-styryltriphenylamine (for the following compound -(3)), and 4-methyl-4'-(4-chloro)styryltriphenylamine (for the following compound -(4))
), and in the same manner as in Example 1, the electricity of the present invention,
A child photographic photoreceptor was prepared and the same measurements were carried out, and the results shown in Table 3 were obtained.

K-(4) Table 3 Example 5 Vinyl chloride-vinyl acetate-
A 0.05 μm thick intermediate layer made of maleic anhydride copolymer [S-LEC MF-10J (manufactured by Tanezu Kagaku Co., Ltd.) was provided, and 2 g of Exemplary Compound A-(25) was added to 110 mJ of 1,2-dichloroethane on top of it. The dispersion liquid was mixed and dispersed in a ball mill for U time and then applied to a dry film thickness of 0.5 μm to form a carrier generation layer. A solution prepared by dissolving Tory p-)lylamine 6I and 10 g of methacrylic resin "Acrivet" (manufactured by Mitsubishi Rayon Co., Ltd.) in 1,2-dichlorothane was poured onto this carrier generation layer until the film thickness after drying was 10 μm. A carrier transport layer was formed by coating as described above, and an electrophotographic photoreceptor of the present invention was prepared.

Regarding this electrophotographic photoreceptor, the same measurements as in Example 1 were performed, and E3A=2.011u for the first time.
x-sec, VR=OV results were obtained.

Example 6 On the conductive support provided with the intermediate layer used in Example 5, a 1% ethylenediamine solution of Exemplary Compound A-69 was applied so that the film thickness after drying was 0.3 μm, and carrier generation was performed. formed a layer.

Then 6-methyl-1-(1-phenyl-4-
6 g of (carbazolyl) methylideneamino-1,2゜3.4-tetrahydroquinoline (compound K-(5) below) and 10 g of polynisder resin "Vylon 200 J (manufactured by Toyobo Co., Ltd.) were dissolved in 70 mJ of 1,2-dichloroethane, This solution was applied to form a carrier transport layer such that the film thickness after drying was 12 μm, thereby producing an electrophotographic photoreceptor of the present invention.

The same measurements as in Example 1 were carried out on this electrophotographic photoreceptor.
After repeating the test 5000 times, the test was repeated 4 times, and the results shown in Table 4 were obtained.

Comparative Example 2 A comparative electrophotographic photoreceptor was prepared in the same manner as in Example 6 except that exemplified compound A-69 was replaced with bisazo compound G-(2) represented by the following structural formula.

The same measurements as in Example 1 were carried out on this electrophotographic photoreceptor.
The results obtained after the 5000th repetition are shown in the fourth
Shown on the back.

G-(2) Table 4 Example 7 A carrier generation layer was formed in the same manner as in Example 5 except that Exemplified Compound A-C251 was replaced with Exemplified Compound A-α0. On top of this, 6-methyl-1-(i-phenyl-4-
Carbazolyl) methylideneamino-1,2,3,4-tetrahydroquinoline (compound -(6))6. ! i' and 10 g of polycarbonate [Panlite L-1250J (manufactured by Yotaikasei Co., Ltd.), and 70 TL of l,2-dichloroethane.
The electrophotographic photoreceptor of the present invention was prepared by coating a carrier transport layer by applying a solution dissolved in 100 μm to a dry film thickness of 10 μm.

When this electrophotographic photoreceptor was strained and measured in the same manner as in Example 1, it was found that E3A = 2.41 ux-sec and VR = OV.

Example 8 An intermediate layer with a thickness of 0.05 μm made of vinyl chloride-vinyl acetate-maleic anhydride copolymer “S-LEC MF-10J (manufactured by Tanezu Kagaku Co., Ltd.) was provided on the surface of an aluminum drum with a diameter of 100 tax. Exemplified compound A
42514g 1,2-shikuooxtan 400ml=
A dispersion liquid was mixed with the above and dispersed for u hours using a ball mill dispersion machine, and the dispersion liquid was coated so that the film thickness after drying was 0.6 μm to form a carrier generation layer.

Further, on top of this, 30 g of 4-methoxy-4'-styryl-triphenylamine (the following compound - (6)) and 50 g of polycarbonate resin [Corpilon S-1000j (manufactured by Mitsubishi Gas Chemical Co., Ltd.)] were added in t,2-dichloroethane. 400- and coated to form a carrier transport layer so as to have a dry film thickness of 13 μm, thereby producing a drum-shaped electrophotographic photoreceptor.

The photoreceptor produced in this way was used in the electrophotographic copying machine "U-
When it was attached to a modified Bix V2J (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 photoreceptor was prepared in the same manner as in Example 8, except that exemplified compound A-α29 was replaced with bisazo compound G-(3) represented by the following structural formula. When the copied image was evaluated in the same manner as in Example 8,
Only images with a lot of fog 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.

G-(3) Example 9 Vinyl chloride-vinyl acetate-
An intermediate layer with a thickness of 0.05 μm made of maleic anhydride copolymer [S-LEC MF-10J (manufactured by Tanezu Kagaku Co., Ltd.) was provided, and 5 g of Exemplary Compound A-(10) and polycarbonate resin “Nogunlite L” were provided on the intermediate layer. -1250J (manufactured by Yotaikasei Co., Ltd.) 3.3g was added to dichloromethane 100TLe,
The film thickness when drying the dispersion that was dispersed for another time in a ball mill was 1
The coating was applied to a thickness of 0 μm to prepare an electrophotographic photoreceptor.

The photoconductor obtained as described above was charged with a charging voltage of +6 K.
E% and VR were measured in the same manner as in Example 1 except that V was used. The first result was E! A= 3.91 ux・se
e and VR = 10k.

Example 10 6 g of l-phenyl-3-(p·-diethylaminostyryl)-5-(p-diethylaminophenyl)pyrazoline and polyester resin [Byron 20] were used as a carrier transport layer on a polyester film deposited with aluminum.
Dissolve 10 g of 0j (manufactured by Toyobo Co., Ltd.) in &1,2-dichloroethane 7 Qml, and dry this solution to a film thickness of 10 μm.
It was applied so that the thickness was m.

Next, exemplified compound A-(6)1. ! i' and A
- (7) 1g and 1,2-dichloroethane 110mJ &
The dispersion was mixed and dispersed in a ball mill for a while and then coated to give a film thickness of 0.51 tm after drying to form a carrier generation layer, thereby forming an electrophotographic photoreceptor of the present invention.

The photoreceptor thus obtained was evaluated in the same manner as in Example 9, and found to be E3A=3.61 ux-see and VR2+10■.

Example 11 A 2% ethylenediamine solution of Exemplified Compound A was coated on a polyester film laminated with aluminum so that the dry film thickness was 0.5 μm to form a carrier generation layer. Furthermore, as a carrier transport layer thereon, l-phenyl-3-(p-diethylaminostyryl)-5-(1)-diethylaminophenyl)virazo 1
) (the following compound K -(7)), 3-(p-methoxystyrene)-9-(p-methoxyphenyl)carnocy/V (the following compound -(8)), or p-
(N,N-diethylamino)benzaldehyde-1,1
- Diphenylhydrazone (separately add (9) to the following compound) - Approximately 10 g and polycarbonate K - (7) K - (8) K - (9) Resin (X Panrai manufactured by Kijin Kasei Co., Ltd.) L - 1250)1
A solution prepared by dissolving 4 g of 1,2-dichloroethane in 140 ml of 1,2-dichloroethane was coated and dried to give a dry film thickness of 12 μm to obtain photoreceptors containing three different carrier transport substances.

These three types of photoreceptors were each made by Kawaguchi Electric Seisakusho S
The following characteristics were evaluated using a P-428 electrostatic paper tester. Charged with a charging voltage of -6KV for 5 seconds, and then
After leaving it in the dark for a few seconds, turn on the halogen light until the material surface illuminance is 351u.
x, and the exposure amount required to attenuate the surface potential by half (half-reduced exposure amount, E3A) was measured. In addition, the surface potential (residual potential) VR after exposure at 301 ux-see (D exposure amount) was measured. As shown in Table 5, the results were good in combination with any carrier transport substance.

° Table 5 Comparative Example 4 Exemplary compound And was replaced with the following bisazo compound (G-(4)
) A comparative photoreceptor was prepared in the same manner as in Example 11 except that G-(4) was replaced, and the characteristics were evaluated. As shown in Table 6, results varied depending on the carrier transport material. .

Example 12 On the conductive support provided with the intermediate layer used in Example 5, 2 g of Exemplified Compound A-67) and 10 g of 1,2-dichloroethane were added.
0ml well dispersed and mixed, and the film thickness after drying is 0.3μm.
A carrier-generating layer was created by applying the following coating to form a carrier-generating layer.

Then, 1-(l-phenyl-4-carbazolyl)methylideneamino-1,2 is added thereon as a carrier transport substance.
,3,4-tetrahydroquinoline (compound K -Q below)
O)) 6.9 and polycarbonate "Panlite L -
1250J (manufactured by Ryotai Kasei Co., Ltd.) dissolved in 90 g of l,2-dichloroethane was applied to form a carrier transport layer such that the film thickness after drying was 10 μm. created a body.

The electrophotographic properties of this electrophotographic photoreceptor at room temperatures of 5° C. and ω° 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 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 13 Exemplified compound A-6712g and 110 g of 1,2-dichloroethane were placed on the conductive support provided with the intermediate layer used in Example 5.
A carrier-generating layer was prepared by thoroughly dispersing and mixing the mixture with m1 and applying the film to a thickness of 0.3 μm after drying.

For this carrier generation layer, an ultra-high pressure mercury lamp (manufactured by Tokyo Shibaura Electric Co., Ltd.) was placed 30 m away, and
UV light of 500 cd/7 was irradiated. Next, this UV
■-41-(p-anisoyl)-4-carbazolyl]methylideneamino-indoline (10% of the following compound
1V) 7g and polycarbonate (Panlite L-12
50) (manufactured by Ryotaikasei Co., Ltd.) 10g dissolved in 1,2-dichloroethane 909 was coated to form a carrier transport layer so that the film thickness after drying was 12 μm. An electrophotographic photoreceptor of the invention was created.

Regarding this electrophotographic photoreceptor, measurement 1 was performed in the same manner as in Example 5. The results are shown in Table 8.

Example 14 An electrophotographic photoreceptor of the present invention was prepared in the same manner as in Example 13, except that UV light was not irradiated after the carrier generation layer was formed, 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 electrophotographic photoreceptor of the present invention has excellent sensitivity and residual potential characteristics to UV light irradiation, has small fluctuations in acceptance potential, and is stable to light. I can understand.

Comparative Example 5 Compound A-67) was converted into the following bisazo compound G-(5)
Electrophotographic photoreceptors were prepared in the same manner as in Examples 13 and 14, except that G-(5) was changed, and the same measurements as in Example 5 were performed. The results are shown in Table 9.

As is clear from the above results, the lightning photoreceptor prepared using the above compound can be improved in sensitivity by UV light irradiation.
The residual potential characteristics deteriorate and the amount of fluctuation in the accepted potential is large.

As is clear from the results of the above Examples and Comparative Examples, the electrophotographic photoreceptor of the present invention has a higher thermal resistance than the comparative electrophotographic photoreceptor.
It is stable to light and has excellent stability, and has outstanding characteristics such as sensitivity, residual potential, durability, and combination with a wide range of carrier-generating substances.

[Brief explanation of the drawing]

1 to 6 are sectional views showing examples of the mechanical structure of the electrophotographic photoreceptor of the present invention, and 1 to 7 in the figures represent the following, respectively. l... Conductive support, 2... Carrier generation layer,
3...Carrier transport layer, 4...Photosensitive layer, 5...
Intermediate layer, 6...carrier transport substance 7.
...Carrier generating substance Containing layer, agent Yoshimi Kuwahara Figure 1 Figure 6 Closing chrysanthemum 2 Sengiku 4 review

Claims (2)

[Claims] (1) An electrophotographic photoreceptor comprising a photosensitive layer containing at least one bisazo compound represented by the following general formula [I] on a conductive support. X, X, X3X. [Wherein, Ar and Ar2: substituted and unsubstituted aromatic carbocycles, k and l = integers of 0 or l, respectively, X2, X2,
A and x4: each hydrogen atom or cyano group, Y: substituted/unsubstituted carbamoyl group or substituted/unsubstituted sulfamoyl group, z: ゛substituted/unsubstituted carbocyclic aromatic ring or substituted/unsubstituted Atom group necessary to constitute a heterocyclic aromatic ring, Ars: substituted/unsubstituted aryl group, R1: hydrogen atom, substituted/unsubstituted amine group, substituted/unsubstituted alkyl group, substituted/unsubstituted carbamoyl group or carboxyl group or ester group thereof, Ru and 'Rs: substituted and unsubstituted alkyl groups, respectively;
Represents a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aralkyl group. (2) The electrophotography according to claim 1, wherein the photosensitive layer contains a carrier transporting substance and a carrier generating substance, and the carrier generating substance is a bisazo compound represented by the general formula CI). Photoreceptor.