JPH07168377A - Electrophotographic photoreceptor - Google Patents

Abstract

PURPOSE:To attain high sensitivity, low residual potential and satisfactory image characteristics by incorporating a specified compd. into a photosensitive layer on an electric conductive substrate. CONSTITUTION:When a photosensitive layer is formed on an electric conductive substrate to obtain an electrophotographic photoreceptor, a compd. represented by formula I is incorporated into the photosensitive layer. In the formula I, each of X1-X3 is an org. residue which may have a substituent and X1-X3 may be different from one another. The compd. represented by the formula I is especially preferably a compd. represented by formula II, wherein each of X1-X3 is 0, =N-CN, etc., each of R1 and R2 is alkyl, vinyl, ester, acyl, amido, H, cyano or nitro, each of the alkyl, vinyl, ester, acyl and amido may have a substituent. and each of (m) and (n) is an integer of 0-3. This compd. has electron transferring ability and the objective electrophotographic photoreceptor using the compd. as an electron transferring material has high sensitivity and stabilized characteristics of the photoreceptor at the time of repeated use.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an electrophotographic photosensitive member for forming an electrostatic latent image. More specifically, it relates to an electrophotographic photoreceptor having a layer containing a compound having an electron transporting ability.

[0002]

2. Description of the Related Art Conventionally, electrophotographic photoreceptors using organic photoconductors have been variously studied because of their advantages such as pollution-free, high productivity and low cost. It is put to practical use as a photoreceptor. These electrophotographic photoreceptors include a laminated type and a single layer type, but a photoreceptor using an organic photoconductor generally has a charge generation layer that generates a charge by light irradiation and a charge that transports the generated charge. It has a laminated structure consisting of a transport layer. In this case, as the charge transport material used in the charge transport layer, a polymer material such as poly-N-vinylcarbazole or a low molecular weight compound such as pyrazoline, hydrazone or triphenylamine derivative is used.

However, since all of these charge-transporting substances have a hole-transporting ability, most of the developing systems adopting a negative charge on the surface of the photoconductor are adopted.
For this reason, the toner that has been conventionally used in high-speed machines cannot be used, and there are few high-quality toners at present. Further, when the surface of the photoconductor is negatively charged as described above, there is a problem that not only the ozone is generated due to the reaction with oxygen in the air at the time of charging to harm the environment but also the surface of the photoconductor is deteriorated.

On the other hand, a positive charging laminated photoreceptor having an electron transport layer on the lower side and an electron generating layer on the upper side has been developed by reversing the layer structure of the photosensitive layer of the laminated photoreceptor. Since the charging potential is low and the printing durability is poor, a protective layer is further provided on the electron generating layer.

[0005]

In order to solve the above problems, a photoconductor in which a charge transport material having an electron transporting property is used in a charge transport layer and the surface of the photoconductor is positively charged. Should be configured. 2,4,7-Trinitro-9-fluorenone is known as such an electron-transporting material, but its solubility is poor and it is not possible to obtain practical sensitivity by combining it with an existing charge-generating substance. It was In addition, 2, 4,
As a result of improved studies on 7-trinitro-9-fluorenone, in recent years, an electron transporting substance having a solubilizing group introduced into an electron acceptor structure has been proposed. For example, Japanese Patent Laid-Open No. 1-206349
No. 2-135362, No. 2-214866, No. 3-290666 and “Japan Hardcopy '92” Proceedings, 173, (1992). However, in the present situation, when any of the compounds is combined with an existing charge generating substance to form a photoreceptor, the sensitivity is still insufficient in practical use, and a good image cannot be obtained.

In view of the above problems, it is an object of the present invention to provide an electrophotographic photosensitive member using a charge transporting substance having an electron transporting ability.

Another object of the present invention is to provide a laminate type electrophotographic photoreceptor for positive charging, which has excellent electrophotographic performance, that is, high sensitivity, low residual potential and good image characteristics.

[0008]

As a result of research, the present inventors have found that the object of the present invention can be achieved by any of the following electrophotographic photoreceptors. That is, (1) an electrophotographic photoreceptor having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula [A].

[0009]

[Chemical 8]

X ₁ , X ₂ or X ₃ is an organic residue which may have a substituent, and X ₁ , X ₂ or X ₃ may be different from each other.

(2) Particularly preferably, the above general formula [A]
The compound represented by the following general formula [a ₁ ], [a ₂ ], [a ₃ ]
An electrophotographic photoconductor characterized by being a compound represented by:

[0012]

[Chemical 9]

R ₁ and R ₂ may have an alkyl group which may have a substituent, a vinyl group which may have a substituent, an ester group which may have a substituent or a substituent. It represents an acyl group, an amide group which may have a substituent, a hydrogen atom, a cyano group or a nitro group.

M and n represent an integer of 0 to 3.

K, g, h, p, q and r represent an integer of 0-3.

Y _{1 to} Y ₉ are each a hydrogen atom, a cyano group, a nitro group, a halogen group, an ester group which may be substituted, an acyl group which may be substituted, an amide group which may be substituted, or a substituent. Represents a vinyl group which may be substituted or a phenyl group which may be substituted.

Z represents an oxygen atom, a sulfur atom, or ═C = 0.

Further, Y ₁₀ and Y ₁₁ are each a hydrogen atom, a halogen atom, a cyano group, a nitro group, an ester group which may be substituted, an acyl group which may be substituted, an amide group which may be substituted, or a substituent. Represents a vinyl group which may be substituted or a phenyl group which may be substituted.

[0019]

[Chemical 10]

In the formula, X ₁ , R ₁ and R ₂ are the same as in the general formula [a ₁ ].

[0021]

[Chemical 11]

In the formula, X ₁ , R ₁ and R ₂ are the same as in the general formula [a ₁ ].

However, Z ₂ is an oxygen atom, a sulfur atom, = C
= 0, = C = C ( Y 12) (Y 13). Y ₁₂ and Y ₁₃ are hydrogen atoms,
A cyano group, a nitro group, a halogen group, or an ester group which may be substituted, an acyl group which may be substituted, an amide group which may be substituted, a vinyl group which may be substituted, or a phenyl group which may be substituted. Represent

(3) In an electrophotographic photosensitive member having a photosensitive layer provided on a conductive support, the photosensitive layer has the following general formula [B].
An electrophotographic photoreceptor containing a compound represented by:

[0025]

[Chemical 12]

In the general formula [B], X and Y are = O, =
C (Z) (W), = N-CN, and Z and W are hydrogen atom, halogen atom or -CN, R ₃ -substituted phenyl group (R ₃ is alkyl, acyl, ester, methoxy, -CF ₃ , -CN, -NO ₂
Of each group or hydrogen atom) and an ester group.

R ₁ and R ₂ are alkyl, alkoxy, acyl, ester, phenyl, amide and sulfonamide groups. Further, m represents an integer of 1 to 4.

N ≧ 0, p ≧ 0 where either n or p is 2
In the above case, R ₁ and R ₂ may be different from each other.

(4) The electrophotographic photoreceptor of (3), wherein the compound represented by the general formula [B] is a compound represented by the following general formula [b].

[0030]

[Chemical 13]

In the general formula [b], X is = 0, = C
(Z) (W), = N-CN, and Z and W are hydrogen atoms,
Halogen atom or --CN, R ₃ -substituted phenyl group (R ₃ is alkyl, acyl, ester, methoxy, --CF ₃ , --CN, --N
O ₂ groups or hydrogen atoms) and ester groups.

R ₁ and R ₂ are alkyl, alkoxy, acyl, ester, phenyl, acid and sulfonamide groups.

N ≧ 0, p ≧ 0 However, if either n or p is 2 or more, R ₁ and R ₂ may be different from each other.

(5) In an electrophotographic photosensitive member having a photosensitive layer provided on a conductive support, the photosensitive layer has the following general formula [C].
An electrophotographic photoreceptor containing a compound represented by:

[0035]

[Chemical 14]

In the general formula [C], X and Y are = O =
C (Z) (W), a = N-CN, further, Z, W is a hydrogen atom, a halogen atom or -CN, R ₄ substituted phenyl group (R ₄ is an alkyl, acyl, ester, methoxy, -CF ₃ , -C
N, —NO ₂ groups or hydrogen atom) ester groups.

R ₁ , R ₂ or R ₃ is an alkyl, alkoxy, acyl, ester, phenyl, amide or sulfonamide group. Further, m represents an integer of 1 to 2. m =
When 1, p ≧ 1. When m = 2, p ≧ 0.

Q ≧ 0, n ≧ 0 However, when either q or n is 2 or more, R ₁ , R ₂ and R ₃ may be different from each other.

The high performance of the present invention as an electron transport material is
It is considered that this is because the long-term compatibility with the binder is kept stable as compared with the conventional electron transport material.

Next, specific examples of the compounds represented by the above general formula and synthetic examples thereof will be shown.

(A) Compound represented by the general formula [A]: Exemplified compound:

[0042]

[Chemical 15]

[0043]

[Chemical 16]

[0044]

[Chemical 17]

[0045]

[Chemical 18]

[0046]

[Chemical 19]

[0047]

[Chemical 20]

[0048]

[Chemical 21]

[0049]

[Chemical formula 22]

[0050]

[Chemical formula 23]

[0051]

[Chemical formula 24]

[0052]

[Chemical 25]

[0053]

[Chemical formula 26]

[0054]

[Chemical 27]

[0055]

[Chemical 28]

[0056]

[Chemical 29]

[0057]

[Chemical 30]

[0058]

[Chemical 31]

[0059]

[Chemical 32]

[0060]

[Chemical 33]

[0061]

[Chemical 34]

[0062]

[Chemical 35]

[0063]

[Chemical 36]

[0064]

[Chemical 37]

[0065]

[Chemical 38]

[0066]

[Chemical Formula 39]

[0067]

[Chemical 40]

[0068]

[Chemical 41]

[0069]

[Chemical 42]

: Synthesis example:

[0071]

[Chemical 43]

In accordance with the above scheme, exemplary compound A-1
Was synthesized. That is, aluminum chloride 10g (0.075m
ol) and tetrachlorocyclopropene 13.4g (0.075mol)
Then, 10 ml of methylene chloride and 10 ml of methylene chloride were placed in a 300 ml four-headed flask, heated to reflux under a nitrogen stream, and stirred for 2 hours.

Thereafter, the reaction solution was cooled to -15 ° C,
10 ml of methylene chloride was added, and 30.9 g (0.15 m) of 2,6-tert-butylphenol dissolved in 75 ml of methylene chloride was further added.
ol) was added. The reaction temperature is kept between -10 ℃ and 5 ℃,
Stir for hours.

Then, 100 ml of pure water was added, the organic layer was separated, the methylene chloride layer was dried over Na ₂ SO ₄ , and methylene chloride was distilled off under reduced pressure to obtain crude crystals of 1 . This is ethyl ether
Recrystallization from 100 ml, 22.2 g of 1 in white crystals (Y64%)
Obtained.

Next, put 1 1.34 g and (2.9 mmol) phenyl malononitrile 0.75g and (5.3 mmol) beta-alanine 0.01g of acetic anhydride 3.5ml quadriceps flask 50 ml, stirred for 15 minutes at reflux temperature .

After that, the reaction was cooled to obtain orange crude crystals. The crude product was recrystallized in chlorobenzene, 2
Was obtained as orange crystals (1.27 g, Y74.7%).

Thereafter, the organic layer was separated, and the organic layer was washed with water and the benzene layer was dried with MgSO ₄ , and benzene was distilled off under reduced pressure to obtain blue-purple colored crystals as exemplified compound B.
-10.62 g was obtained with a yield of 91%. The melting point is 270 ° C.

The structure of Exemplified Compound A-1 was confirmed because the elemental analysis values agree with the calculated values.

Elemental analysis data C H N measured value 84.05 (%) 7.11 4.11 calculated value 84.16 7.07 4.09 (B) compound represented by general formula [B]: exemplified compound:

[0080]

[Chemical 44]

[0081]

[Chemical formula 45]

[0082]

[Chemical formula 46]

[0083]

[Chemical 47]

[0084]

[Chemical 48]

[0085]

[Chemical 49]

: Synthesis example:

[0087]

[Chemical 50]

In accordance with the above scheme, Exemplified Compound B-11
Was synthesized. That is, aluminum chloride 10g (0.075m
ol) and tetrachlorocyclopropene 13.4g (0.075mol)
And methylene chloride (10 ml) were placed in a 300 ml four-headed flask and stirred under a nitrogen stream at a reflux temperature for 2 hours.

Thereafter, the reaction solution was cooled to -15 ° C,
10 ml of methylene chloride was added, and 30.9 g (0.15 m) of 2,6-tert-butylphenol dissolved in 75 ml of methylene chloride was further added.
ol) was added. The reaction temperature was between -10 ° C and 5 ° C, and the mixture was stirred for 1 hour.

Then, 100 ml of pure water was added, the organic layer was separated, the methylene chloride layer was dried over Na ₂ SO ₄ , and methylene chloride was distilled off under reduced pressure to obtain a crude crystal of 1 . This is ethyl ether
Recrystallization from 100 ml, 22.2 g of 1 in white crystals (Y64%)
Obtained.

[0091] Next, put 1 11.6 g (0.025 mmol) and benzene 1 liter of 1 liter 0.1MKOH potassium ferricyanide was dissolved in a solution 21.4g of (0.065 mol) in quadriceps flask 3 l and stirred for 1 hour at room temperature .

Thereafter, the organic layer was separated, washed more thoroughly with water, the benzene layer was dried with MgSO ₄ , and benzene was distilled off under reduced pressure to obtain 2 crystals of purple color.

Finally, the crude crystals of 2 and 500 ml of benzene are placed in a three-headed flask and stirred at 40 ° C. for 45 minutes. After standing still for several hours, benzene was distilled off under reduced pressure to obtain purple color crude crystals. This crude crystal was recrystallized in acetonitrile and pu
The yield of the exemplified compound P-11 9.06 g was obtained as rple-colored crystals.
Obtained at 4%.

Since the elemental analysis values agree with the calculated values,
The structure of Exemplified Compound B-11 was confirmed.

[0095] (C) Compound represented by general formula [C]: Exemplified compound:

[0096]

[Chemical 51]

[0097]

[Chemical 52]

[0098]

[Chemical 53]

[0099]

[Chemical 54]

[0100]

[Chemical 55]

[0101]

[Chemical 56]

: Synthesis example: Angewante Chemistry 75, 860
(1963) Exemplified Compound C-1 was synthesized according to the literature.

Since the elemental analysis values agree with the calculated values,
The structure of Exemplified Compound C-1 was confirmed.

[0104] In the electrophotographic photosensitive member of the present invention, as the conductive support, for example, a metal pipe, a metal plate, a metal sheet, a metal foil,
A conductive polymer film, a polymer film provided with a vapor deposition layer of a metal such as Al, a polymer film coated with a metal oxide, a quaternary ammonium salt, or the like, or paper is used.

In the electrophotographic photosensitive member of the present invention, the photosensitive layer is provided on the conductive support, but the photosensitive layer may have a single layer structure, or a laminated structure in which the charge generating layer and the electron transporting layer are functionally separated. It may be one. An adhesive layer may be provided between the conductive support and the photosensitive layer.

As shown in FIGS. 1 (a) and 1 (b), the photoreceptor of the present invention comprises a conductive support 1 on which a charge generating substance (CG
M) as the main component of the charge generation layer (CGL) 2 and the electron transport layer (CTM) as the main component of the electron transport layer (C)
A photosensitive layer 4 composed of a laminate with TL) 3 is provided. The photosensitive layer 4 may be provided via an intermediate layer 5 provided on the conductive support 1, as shown in FIGS. Thus, when the photosensitive layer 4 has a two-layer structure, a photoreceptor having the most excellent electrophotographic characteristics can be obtained. In addition, in the present invention, as shown in FIGS.
The photosensitive layer 4 in which the particulate CGM 7 is dispersed in the layer 6 containing as a main component may be provided directly on the conductive support 1 or via the intermediate layer 5.

Further, a protective layer (OCL) may be provided on the photosensitive layer 4 if necessary.

CGL which constitutes the photosensitive layer 4 having a two-layer structure
2. The CTL 3 may be formed by the following method depending on the characteristics of CTM and CGM, directly or on the conductive support 1 which is the lower layer surface, or when an intermediate layer such as an adhesive layer or a barrier layer is provided if necessary. it can.

(1) Vapor deposition method (2) Coating method a) Method of coating a solution coating prepared by dissolving CGM and CTM in a suitable solvent.

B) A method in which CGM and CTM are made into fine particles in a dispersion medium by a ball mill, a homomixer or the like, and if necessary, mixed and dispersed with a binder to apply a dispersion coating material.

Examples of the vapor deposition method include a vacuum vapor deposition method, a sputtering method, an ion plating method, a CVD method, and the like, and a paint coating method includes a dipping method, a spray method, an air doctor method, a doctor blade method, and a reverse method. An appropriate method is selected according to the physical properties of the coating material such as the roll method.

The adhesive layer is formed of resin alone, coated with a low resistance compound such as tin oxide, indium oxide, or titanium oxide dispersed in resin, or coated with aluminum oxide, zinc oxide, silicon oxide, or the like. The vapor deposition film of
The resin used for the adhesive layer is not particularly limited, and examples thereof include vinylidene chloride-vinyl chloride copolymer, water-soluble polyvinyl butyral resin, alcohol-soluble polyamide resin, vinyl acetate-based resin, polyvinyl alcohol, nitrocellulose, and polyimide resin. To be

The thickness of the binder layer is preferably about 0.01 to 10 μm, and particularly preferably 0.01 to 1 μm.

When the photosensitive layer is a single layer, the compound represented by the above general formulas [A] to [C] is contained as a sensitizer in the photosensitive layer composed of a known material such as polyvinylcarbazole. Or a photosensitive layer containing a known charge generating substance containing the compounds represented by the above formulas [A] to [C] as an electron transporting substance.

On the other hand, when the photosensitive layer is a laminated type,
The charge generation layer may be obtained by vapor deposition of an electron generation substance on a conductive support, or may be formed by applying a coating liquid containing a charge generation substance and a binder resin as main components.

Any known charge generating substance and binder resin can be used.

For example, as the charge generating substance, an inorganic semiconductor such as Te-Se, an organic semiconductor such as polyvinylcarbazole, a bisazo compound, a trisazo compound, a metal-free phthalocyanine compound, a metal phthalocyanine compound,
Organic pigments such as pyrylium compounds, squarylium compounds, cyanine compounds, perylene compounds and polycyclic quinone compounds can be used. Among them, preferable charge generating substances include, for example, Y-type titanyl phthalocyanine pigments having an X-ray diffraction peak at 27.2 ° in JP-A-64-17066,
A having an X-ray diffraction peak at 26.3 ° in JP-A-62-67094
Type titanyl phthalocyanine pigment, B type titanyl phthalocyanine pigment having an X-ray diffraction peak at 28.7 ° of JP-A-61-239248, metal-free phthalocyanine pigment of JP-B-49-4338, and copper phthalocyanine of JP-A-57-163239. Pigments, vanadyl phthalocyanine pigments of JP-A-57-148747, perylene pigments of JP-A-49-128734, condensed polycyclic pigments of JP-A-47-18544, bisazo pigments of JP-A-1-150145, etc. is there. As the binder resin, polystyrene, silicone resin, polycarbonate resin, acrylic resin, methacrylic resin, polyester, vinyl polymer, cellulose resin, butyral resin, silicone modified butyral resin, alkyd resin and the like can be used.

The thickness of the electron generating layer is preferably about 0.01 to 10 μm, and particularly preferably 0.05 to 2 μm.

An electron transport layer is formed on the charge generation layer. The electron transport layer is composed of the compounds represented by the above general formulas [A] to [C] and a binder resin,
A coating solution containing the compounds represented by the above general formulas [A] to [C], a binder resin, and a suitable solvent as main components is applied onto the charge generation layer by an applicator, a bar coater, a dip coater, or the like. Formed by. In this case, the mixing ratio of various compounds and the binder resin is preferably 1: 100 to 100: 1, and particularly preferably 1:20 to 20: 1.

Any known binder resin can be used as the binder resin for the electron transport layer. For example, as the binder resin, acrylonitrile-butadiene copolymer, styrene-butadiene copolymer, vinyltoluene-styrene copolymer, styrene-modified alkyd resin, silicone-modified alkyd resin, soybean oil-modified alkyd resin, vinylidene chloride-vinyl chloride Resin, polyvinyl butyral, nitrated polystyrene, polymethylstyrene,
Polyisoprene, polyester, phenol resin, Kent resin, polyamide, polycarbonate, polythiocarbonate, polyacrylate, polyhaloacrylate,
Examples thereof include vinyl acetate resin, polystyrene, polyallyl ether, polyvinyl acrylate, polysulfone, polymethacrylate and the like. Among them, biphenyl Z type polycarbonate is particularly preferable. Further, an electron-donating substance may be added to the electron-transporting layer to prepare an ambipolar photoreceptor.

Further, an antioxidant or a radical trapping agent may be added to the electron transport layer.

The thickness of the electron transport layer is preferably 2 to 100 μm, particularly preferably 5 to 50 μm.

In the electrophotographic photosensitive member of the present invention,
A barrier layer may be provided on the conductive support. The barrier layer is
It is effective in preventing the injection of unnecessary charges from the conductive support and has the effect of improving the image quality. Materials for forming the barrier layer include metal oxide such as aluminum oxide, acrylic resin, phenol resin, polyester resin, polyurethane and the like. The barrier layer may be provided on the adhesive layer or may be provided on the upper side.

[0124]

EXAMPLES Next, the present invention will be specifically described by way of examples. In this embodiment, "part" means "part by weight".

(I) Sensitivity Evaluation Examples 1 to 30 A 0.5 μm-thick intermediate layer made of polyamide resin “CM8000” (manufactured by Toray Industries, Inc.) was provided on a PET film on which aluminum was vapor deposited, and “Chemical 57” was formed thereon. Perylene pigment G-shown in
l 1 part, polyvinyl butyral resin "ESREC BM
S "(manufactured by Sekisui Chemical Co., Ltd.) and 50 parts of methyl ethyl ketone as a dispersion medium dispersed in a sand mill were applied using a wire bar to form a charge generation layer having a thickness of 0.3 μm. Next, 1 part of the exemplified compounds shown in Tables 1 to 3 and 1.5 parts of a polycarbonate resin "Iupilon Z-200" (manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 10 parts of tetrahydrofuran (THF), and blade-coated on the charge generation layer to form a film. An electron transport layer having a thickness of 20 μm was formed.

Comparative Example 1 A comparative sample was prepared in the same manner as in Example 1 except that Comparative Compound 1 shown in "Chemical Formula 57" was used in place of the exemplified compound.

Evaluation 1 Electrophotographic Photosensitive Samples Obtained in Examples 1 to 30 and Comparative Example 1 Electrostatic Copy Paper Testing Apparatus EPA-8100
(Kawaguchi Electric Co., Ltd.) is used to charge to + 800V and 10 lu
The white light of x was exposed, and the exposure amount until the surface potential was halved was determined and used as the sensitivity. The results are shown in Tables 1 to 3.

(II) Durability Evaluation Examples 31 to 60 A 0.5 μm-thick intermediate layer made of polyamide resin “X-1874M” (manufactured by Daicel Hüls) was provided on a PET film on which aluminum was vapor deposited. 1 part of pigment X type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.), 0.4 part of polyvinyl butyral resin "ESREC BX-1" (manufactured by Sekisui Chemical Co., Ltd.), and 50 parts of methyl isopropyl ketone as a dispersion medium are dispersed using a sand mill. The obtained liquid was applied using a wire bar to form a charge generation layer having a thickness of 0.3 μm. Then, 1 part of the exemplified compounds of Tables 4 to 6 and 1.5 parts of a polycarbonate resin "Iupilon Z-200" (manufactured by Mitsubishi Gas Chemical Co., Inc.)
It was dissolved in 10 parts of HF and was blade-coated on the charge generation layer to form an electron transport layer having a thickness of 20 μm.

Comparative Example 2 A comparative sample was prepared in the same manner as in Example 31 except that Comparative Compound 2 shown in "Chemical Formula 57" was used in place of the exemplified compound.

Evaluation 2 The electrophotographic photosensitive member samples obtained in Examples 31 to 60 and Comparative Example 2 were evaluated by the "U-Bix1017" remodeling machine (manufactured by Konica Corporation) at the initial measurement and after the actual measurement after copying 10,000 sheets. did. The results are shown in Tables 4-6.

Vb: Black part potential, Vw: White part potential,
Vr: Residual potential (III) Image quality evaluation Examples 61 to 90 A 0.5 μm thick intermediate layer made of polyamide resin “CM8000” (manufactured by Toray Industries, Inc.) was provided on a cylindrical aluminum substrate, and a Bragg in X-ray diffraction was provided thereon. Angle 2θ 9.5 °, 24.1 °, 27.
1 part of titanine phthalocyanine having a peak at 2 °, 0.5 part of silicone-butyral resin, 50 parts of methyl isopropyl ketone as a dispersion medium were dispersed using a sand mill to form a charge generation layer having a thickness of 0.3 μm by dip coating. . Next, 1 part of the exemplified compounds shown in Tables 7 to 9 and 1.5 parts of a polycarbonate resin “UPILON Z-200” (manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 10 parts of THF, and dip-coated on the charge generation layer to form an electron having a thickness of 20 μm. A transport layer was formed.

Comparative Example 3 A comparative sample was prepared in the same manner as in Example 61 except that Comparative Compound 3 shown in "Chemical Formula 57" was used in place of the exemplified compound.

Evaluation 3 With respect to the electrophotographic photosensitive member samples obtained in Examples 61 to 90 and Comparative Example 3, images were output by a digital copying "Konica 9028" remodeling machine (manufactured by Konica) (charge polarity: positive, reverse development). I went. These samples were then placed at low temperature (10
(° C.) environment, left for 1 month, and then imaged again under the same conditions. The black spots on the white background portion of these copied images were evaluated. The results are shown in Tables 7-9.

[0134] The evaluation of the black spots, image analyzer to measure the size and number of black spots with "Omunikon 300 Model" (manufactured by Shimadzu Corporation), 1 cm ² of black spots or more in diameter 0.05mm
It was performed by judging how many there are. The criteria for evaluating the black spots are as shown below. It should be noted that if the result of the black spot determination is ⊚ or ◯, it is practical, but if it is Δ, it is not suitable for practical use, and if it is ×, it is not suitable for practical use.

Number of black spots having a diameter of 0.05 mm or more (pieces / cm ² ) Black spot determination 0 ◎ 1-3 ○ 4-10 △ 11 or more ×

[0136]

[Chemical 57]

[0137]

[Table 1]

[0138]

[Table 2]

[0139]

[Table 3]

[0140]

[Table 4]

[0141]

[Table 5]

[0142]

[Table 6]

[0143]

[Table 7]

[0144]

[Table 8]

[0145]

[Table 9]

As is clear from the above-mentioned tables, the electrophotographic photosensitive member using the electron transporting material of the present invention has higher sensitivity and repeatability than the conventional charge photographic photosensitive member using the charge transporting material. The characteristics of the photoconductor during use are stable, and
It can be seen that the occurrence of image defects is extremely small even after storage at low temperature.

[0147]

EFFECT OF THE INVENTION The compound of the present invention has an electron transporting ability, and can provide a positive charging laminated type photoreceptor having high sensitivity, low residual potential and good image retention.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of an exemplary embodiment of a photoconductor of the present invention.

[Explanation of symbols]

 1 Conductive Support 2 Charge Generation Layer (CGL) 3 Electron Transport Layer (CTL) 4 Photosensitive Layer 5 Intermediate Layer 6 Layer Containing Electron Transport Material 7 Charge Generation Material

Claims (5)

[Claims] 1. An electrophotographic photoreceptor having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula [A]. [Chemical 1] X ₁ , X ₂ or X ₃ is an organic residue which may have a substituent, and X ₁ , X ₂ or X ₃ may be different from each other. 2. The compound according to claim 1, wherein the compound represented by the general formula [A] is a compound represented by the following general formula [a ₁ ], [a ₂ ], [a ₃ ]. Electrophotographic photoreceptor. [Chemical 2] R ₁ and R ₂ are each an alkyl group which may have a substituent, a vinyl group which may have a substituent, an ester group which may have a substituent, an acyl group which may have a substituent, It represents an amide group which may have a substituent, a hydrogen atom, a cyano group and a nitro group. m and n represent the integer of 0-3. k, g, h, p,
q and r represent the integer of 0-3. Y _{1 to} Y ₉ are a hydrogen atom, a cyano group, a nitro group, a halogen group, or an ester group which may be substituted, an acyl group which may be substituted, an amide group which may be substituted, or a vinyl which may be substituted. Represents a phenyl group which may be substituted. Z is an oxygen atom, a sulfur atom, = C =
Represents 0. Further, Y ₁₀ and Y ₁₁ are a hydrogen atom, a halogen atom, a cyano group, a nitro group, or an ester group which may be substituted, an acyl group which may be substituted, an amide group which may be substituted, or a vinyl which may be substituted. Represents a phenyl group which may be substituted. [Chemical 3] In the formula, X ₁ , R ₁ and R ₂ are the same as in the general formula [a ₁ ]. [Chemical 4] In the formula, X ₁ , R ₁ and R ₂ are the same as in the general formula [a ₁ ]. However,
Z ₂ is an oxygen atom, a sulfur atom, ═C = 0, ═C═C (Y ₁₂ ).
(Y ₁₃ ). Y ₁₂ and Y ₁₃ are a hydrogen atom, a cyano group, a nitro group,
It represents a halogen group, an optionally substituted ester group, an optionally substituted acyl group, an optionally substituted amide group, an optionally substituted vinyl group, or an optionally substituted phenyl group. 3. An electrophotographic photoreceptor having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula [B]. [Chemical 5] In the general formula [B], X and Y are = O 2 = C (Z) (W),
= N-CN, and Z and W are hydrogen atom, halogen atom or -CN, R ₃ -substituted phenyl group (R ₃ is alkyl, acyl, ester, methoxy, -CF ₃ , -CN, -NO ₂ Each group or hydrogen atom) and an ester group. R ₁ and R ₂ are alkyl, alkoxy, acyl, ester, phenyl, amide, and sulfonamide groups. Further, m represents an integer of 1 to 4. n ≧ 0, p ≧ 0 However, when either n or p is 2 or more, R ₁ and R ₂ may be different from each other. 4. The electrophotographic photosensitive member according to claim 3, wherein the compound represented by the general formula [B] is a compound represented by the following general formula [b]. [Chemical 6] In the general formula [b], X is ═O, ═C (Z) (W), ═N
--CN, and Z and W are hydrogen atom, halogen atom or --CN, R ₃ -substituted phenyl group (R ₃ is alkyl, acyl,
Ester, methoxy, -CF _3, -CN, each group or a hydrogen atom -NO _2), an ester group. R ₁ and R ₂ are alkyl, alkoxy, acyl, ester, phenyl, amide, and sulfonamide groups. n ≧ 0, p ≧ 0 where n and p
When any of the above is 2 or more, R ₁ and R ₂ may be different from each other. 5. An electrophotographic photoreceptor having a photosensitive layer provided on a conductive support, wherein the photosensitive layer contains a compound represented by the following general formula [C]. [Chemical 7] In the general formula [C], X and Y are = O, = C (Z) (W),
= N-CN, and Z and W are hydrogen atom, halogen atom, or -CN, R ₄ -substituted phenyl group (R ₄ is alkyl, acyl, ester, methoxy, -CF ₃ , -CN, -NO ₂ Each group or hydrogen atom) is an ester group. R ₁ , R ₂ or R ₃ is an alkyl, alkoxy, acyl, ester, phenyl, amide or sulfonamide group. Further, m represents an integer of 1 to 2. When m = 1, p ≧ 1. When m = 2, p ≧
0. q ≧ 0, n ≧ 0 However, when either q or n is 2 or more, R ₁ , R ₂ and R ₃ may be different from each other.