JPH0915881A - Electrophotographic photoreceptor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoreceptor high in sensitivity and low in residual potential using electron transport material with electron transport capacity, and excellent in durability without the change of specification even after repeated use by providing a photosensitive layer, containing a specific compound, on a conductive base body. SOLUTION: A photosensitive layer containing a compound expressed by a formula I or II is provided on a conductive base body. In the formula I, X represents O, S or Se, Q1 , Q2 represent =O, =C(CN)2 , =C(CO2 R5 )2 , =C(CN)(CO2 R5 ), =N-CNB, or =N-CO2 R5 . R1 -R4 represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an acyl group, respectively substitutive and nonsubstiutive alkyl groups, alkoxy group, aryl groups, sulfonyl groups or ester groups, R5 represents respectively substitutive and nonsubstitutive alkyl groups, aryl groups or heterocyclic groups. In the formula II, R1 -R4 represent respectively substitutive and nonsubstitutive aryl groups or heterocyclic groups, and R5 , R6 represent an hydrogen atom, respectively substitutive and nonsubstitutive alkyl groups or aryl groups.

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. 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, selenium has been used as an electrophotographic photoreceptor.
Inorganic photoreceptors having a photosensitive layer containing an inorganic photoconductive compound such as zinc oxide, cadmium sulfide and silicon as a main component have been widely used. However, these are not always satisfactory in sensitivity, thermal stability, moisture resistance, durability, etc.,
Further, some inorganic photoconductors have a problem in disposal because they contain substances harmful to the human body.

In order to overcome the drawbacks of these inorganic photoconductors, research and development of organic photoconductors having a photosensitive layer containing various organic photoconductive compounds as main components have been actively conducted in recent years. In particular, for the function-separated type photoconductor in which the charge generation function and the charge transport function are shared by different substances, the respective materials can be selected from a wide range. Therefore, many studies have been made because a photoreceptor having various performances can be produced relatively easily, and many technologies have been applied for patents.

For example, US Pat. No. 3,871,882, an electrophotographic photoreceptor using a perylene derivative as a charge generating layer and an oxadiazole derivative as a charge transporting layer, and JP-A-55.
No. 84943 discloses an electrophotographic photoreceptor using a distyrylbenzene bisazo compound as a charge generating substance and a hydrazone compound as a charge transporting substance. Compounds such as pyrazoline, hydrazone, and triphenylamine derivatives are known as typical substances having such a charge transporting ability.

However, all of these are substances having a hole transporting ability, and in the case of a function-separated type photoreceptor having a layer containing a charge generating substance as a lower layer and a layer containing a charge transporting substance as an upper layer, the surface of the photoreceptor is It is necessary to adopt a method of negatively charging. Therefore, it is not possible to use the negatively chargeable developer that has been widely used in the conventional inorganic photoconductors. Further, there is a defect that the amount of ozone generated when the photoconductor is charged by corona discharge is larger than that of the positive charge performed by the inorganic photoconductor. In particular, the large amount of ozone generated is a problem in terms of not only the deterioration of the photoconductor caused thereby but also the influence on the human body and environment.

As a positive charging type photoreceptor using an organic photoreceptor, a photoreceptor having a reverse layer structure in which a charge generating layer is an upper layer and a charge transporting layer is a lower layer using a conventional hole transport material, and a charge generating material is used. A single-layered photoreceptor containing a charge transporting material and a charge transporting material in the same layer has been studied. However, in terms of durability, environmental characteristics, etc., a product having sufficient performance for a high speed machine has not been obtained.

Therefore, in order to solve the above problems, a substance having an electron transporting ability is required as a charge transporting substance. To date, electron transport materials are 2, 4,
7-trinitrofluorenone is known, but this substance has insufficient solubility and compatibility with a solvent and a polymer used as a binder, and has sufficient properties for forming an actual photosensitive layer. Not only does it have a carcinogenic problem.

In addition, several electron transporting substances in which a soluble group is introduced into an electron accepting structure have been proposed in recent years. For example, JP-A-1-206349 and JP-A-2-13536.
No. 2, JP-A-2-214866, JP-A-3-2906.
No. 66, "Japan Hard Copy '92", Proc., P173 (1992) can be cited as examples. However, in the present situation, none of the compounds has sufficient sensitivity and potential characteristics when combined with existing charge generating substances, and presents practical problems.

[0009]

In view of the above problems, an object of the present invention is to use an electron transporting material having an electron transporting ability with high sensitivity and a small residual potential, and to change its characteristics even after repeated use. The object is to provide an electrophotographic photoreceptor having excellent durability.

[0010]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the inventors have found that the general formula [1]
The present invention has been completed by finding that the specific compound represented by [2], [3], or [4] can act as an excellent active ingredient of an electrophotographic photoreceptor. That is, the object of the present invention is achieved by adopting the following configuration.

(1) It is characterized in that a photosensitive layer containing a compound represented by the following general formula [1], [2], [3] or [4] is provided on a conductive support. Electrophotographic photoreceptor.

[0012]

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(In the formula, X represents O, S or Se. Q ₁ and Q ₂ are respectively = O, = C (CN) ₂ and = C (C
_{O 2 R 5) 2, =} C (CN) (CO 2 R 5), = N-CN,
= Represents the N-CO ₂ R _5. R _{1 to} R _{4 each} represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an acyl group, a substituted or unsubstituted alkyl group, an alkoxy group, an aryl group, a sulfonyl group or an ester group. R ₅ is each a substitution,
Represents an unsubstituted alkyl group, aryl group, or heterocyclic group. )

[0014]

[Chemical 6]

(In the formula, R _{1 to} R ₄ each represent a substituted / unsubstituted aryl group or heterocyclic group. R ₅ and R ₆ represent a hydrogen atom, a substituted / unsubstituted alkyl group, or aryl, respectively. Represents a group.)

[0016]

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(In the formula, R represents a hydrogen atom or an OH group, and Ar _{1 to} Ar ₄ each represent a hydrogen atom or a substituted or unsubstituted aryl group.)

[0018]

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(In the formula, Q ₁ and Q ₂ are respectively = O and = C (C
N) ₂ , = C (CO ₂ R ') ₂ , = C (CN) (CO
₂ R '), = NAr', or = NCN. R '
Represents a substituted or unsubstituted alkyl group, and Ar 'represents a substituted or unsubstituted aryl group. Ar ₁ and Ar ₂ represent a substituted or unsubstituted aryl group, R represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group or an aryl group, and n represents an integer of 1 to 4. (2) The photosensitive layer is formed by laminating a charge generation layer and a charge transport layer, and the compound represented by the general formula [1], [2], [3] or [4] is used in the charge transport layer. The electrophotographic photosensitive member according to (1), wherein the electrophotographic photosensitive member is contained.

Next, specific examples of the electron transporting material of the present invention will be described, but the electron transporting material of the present invention is not limited thereby.

[1] Compound Represented by General Formula [1] In the general formula, R ₅ is a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, and R _{1 to} R ₄ are hydrogen atoms. Those having a substituted or unsubstituted aryl group are preferable.

Among the compounds represented by the general formula [1], particularly desirable ones are as follows.

<Exemplified Compound>

[0024]

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[0025]

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[0026]

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[0027]

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The above electron transporting substance can be synthesized by a known method.

For example, the typical compounds are as follows.

(Synthesis example)

[0031]

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This compound is described in J. Amer. Chem.
Soc. , 67, 1643 (1945). Similarly, other compounds represented by the general formula [1] can be synthesized by changing the substituents and the like.

[2] Compound of General Formula [2] In the general formula, R ₁ and R ₄ are hydrogen atoms, R ₂ and R ₃ are substituted or unsubstituted aryl groups, and R ₅ and R ₆ have 1 carbon atoms. It is preferably a substituted or unsubstituted alkyl group of 4 to 4, or a substituted or unsubstituted aryl group.

Among the compounds represented by the general formula [2], particularly desirable ones are as follows.

[0035]

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[0036]

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The above compounds can be synthesized by a known method.

For example, typical compounds are as follows.

(Synthesis example)

[0040]

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This compound is described in J. Amer. Chem.
Soc. , 74, 4353 (1952), and other compounds represented by the general formula [2] can also be synthesized by changing the substituents.

[3] Compound Represented by General Formula [3] In the general formula, the aryl group of Ar _{1 to} Ar ₄ may have any substituent, but preferable substituents are alkyl, alkoxy, Aryl, aryloxy, acyl, acyloxy, carbamoyl, halogen, nitro, cyano and the like can be mentioned.

Next, specific examples of the compound represented by the general formula [3] of the present invention will be shown.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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The above-mentioned electron-transporting substance can be prepared by a known method, for example, J. Org. Chem. , 50, 5546 (1985)
And Ann, 462, 72 (1928). The typical compounds are as follows.

[0050]

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Other compounds can also be synthesized by changing the substituents and the like.

[4] Compound Represented by General Formula [4] In the general formula, the substituents of Ar ₁ , Ar ₂ and Ar ′ may have any substituents, but preferable substituents are alkyl,
Alkoxy, aryl, aryloxy, halogen, nitro, cyano and the like can be mentioned.

Next, specific examples of the compound represented by the general formula [4] of the present invention will be shown.

[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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The above electron-transporting substance can be prepared by a known method, for example, Chem. Ber. It can be synthesized by the method described in 99.2675 (1966). Typical compounds are as follows.

[0061]

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Other compounds can also be synthesized by changing the substituents and the like.

[0063]

The above-mentioned compound of the present invention has an excellent electron-transporting property, and a photosensitive layer having the compound dispersed in a binder is provided on a conductive support to produce the electrophotographic photosensitive member of the present invention. Can be done.

The compound of the present invention takes advantage of its excellent electron-transporting ability, and is used as a charge-transporting substance for an electrophotographic photoreceptor, and is used in combination with a charge-generating substance to form a so-called function-separated photoreceptor. Can be done. The function-separated type photoreceptor may be a photoreceptor having a mixed dispersion single layer structure of both substances, but is a laminated type having a charge generation layer as a lower layer and a charge transport layer made of the charge transport material of the present invention as an upper layer. It is more preferable to use a photoreceptor. In any layer structure, an undercoat layer (intermediate layer) having a barrier function and adhesiveness may be provided between the support and the photosensitive layer, or a protective layer may be provided on the photosensitive layer.

The charge transport layer may be formed by coating and drying an electron transport material of the present invention alone or in a solvent dissolved and dispersed with a binder resin using an applicator, bar coater, dip coater or the like. it can.

Examples of the binder resin usable in the charge transport layer include polystyrene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, polyurethane resin, phenol resin, polyester resin and alkyd resin. , A polycarbonate resin, a silicone resin, a melamine resin, and a copolymer resin containing two or more of these repeating units.

In addition to these insulating resins, polymer organic semiconductors such as polyvinyl-N-carbazole may be mentioned.

Examples of the dispersion medium of the electron transport material include hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane;
Ketones such as methyl ethyl ketone and cyclohexanone;
Esters such as ethyl acetate and butyl acetate; methanol,
Alcohols and their derivatives such as ethanol, propanol, butanol, methylcellosolve, ethylcellosolve; ethers such as tetrahydrofuran and 1,4-dioxane; amines such as pyridine and diethylamine; N,
One or more nitrogen compounds such as amides such as N-dimethylformamide; other fatty acids and phenols; sulfur such as carbon disulfide and triethyl phosphate, phosphorus compounds and the like can be used.

The electron transport material is preferably 20 to 200 parts by weight, and particularly preferably 30 to 150 parts by weight, per 100 parts by weight of the binder resin in the charge transport layer. The thickness of the formed charge transport layer is preferably 5 to 30 μm. In the case of a single-layer function-separated electrophotographic photoreceptor, the ratio of binder: electron transport material: charge generation material is 1 to 10.
0: 1 to 500: 1 to 500 are preferable, and the film thickness of the formed photosensitive layer is 5 to 50 μm.

Next, for the charge generating layer, a dispersion liquid obtained by dispersing the charge generating substance in a suitable solvent alone or with the same binder resin as used in the above charge transporting layer is dip coated, spray coated, blade coated, What is provided by the method of apply | coating on a support body or an undercoat layer by roll coating etc., and drying, or what vapor-deposited the charge generation substance on the support body or an undercoat layer is used. In the case of dispersion coating, the solvent used may be the dispersion medium used in the molecular dispersion of the electron transport material. A ball mill, homomixer, sand mill, ultrasonic disperser, Atlanta, or the like is used for dispersion.

Any known charge generating substance can be used, and examples thereof include selenium type inorganic semiconductors, various phthalocyanine compounds, azo compounds, pyrylium compounds, perylene type compounds, cyanine type compounds, squalium compounds, Polycyclic quinone compounds can be used.

When the photoreceptor of the present invention has a laminated structure, the weight ratio of the binder to the charge generating substance is 0 to 1 in the charge generating layer.
It is 0: 1 to 50. The thickness of the charge generation layer formed as described above is preferably 0.01 to 10 μm, particularly preferably 0.1 to 5 μm.

Next, as a conductive support for supporting the photosensitive layer, a metal plate of aluminum, nickel or the like, a metal drum, or a plastic film deposited with aluminum, tin oxide, indium oxide or the like, or a conductive substance is applied. You can use scrap paper, plastic film, and drums.

In the photosensitive layer of the present invention, the following antioxidants may be added for the purpose of preventing deterioration due to ozone.

(1) Hindered phenols (2) Hindered amines (3) Paraphenylenediamines (4) Hydroquinones (5) Organophosphorus compounds These compounds are used as antioxidants for rubber, plastics, oils and fats. It is known and is easily available as a commercial product.

In addition, the photoreceptor of the present invention may further contain an ultraviolet absorber or a dye for correcting color sensitivity for the purpose of protecting the photosensitive layer, if necessary.

Polymers useful as binders for the charge generation layer, intermediate layer and protective layer include, for example, polystyrene, acrylic resins, methacrylic resins, vinyl chloride resins,
Vinyl acetate resin, polyvinyl butyral resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, silicone resin, melamine resin and copolymer resin containing two or more of these repeating units Can be mentioned. In addition to these insulating resins, polymer organic semiconductors such as polyvinyl-N-carbazole may be mentioned.

Examples of the dispersion medium for the charge generating substance and the charge transporting substance include hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane; ketones such as methyl ethyl ketone and cyclohexanone; acetic acid. Esters such as ethyl and butyl acetate;
Methanol, ethanol, propanol, butanol,
Alcohols and derivatives thereof such as methyl cellosolve and ethyl cellosolve; ethers such as tetrahydrofuran and 1,4-dioxane; amines such as pyridine and diethylamine; nitrogen compounds such as amides such as N, N-dimethylformamide; Other fatty acids and phenols; one or more of carbon disulfide, sulfur such as triethyl phosphate, and phosphorus compounds can be used.

[0079]

EXAMPLES Next, the present invention will be described in detail with reference to Examples, but the present invention is not of course limited thereto. In the examples of the present invention, "part" means "part by weight".

Example [1] [Examples [1] -1 to 20] P vapor-deposited with aluminum.
An intermediate layer made of polyamide resin "CM8000" (manufactured by Toray Industries, Inc.) and having a thickness of 0.5 μm was provided on the ET film. In addition, the Bragg angle 2θ in X-ray diffraction of 9.5 °,
Using a wire bar, apply a liquid prepared by dispersing 1 part of titanyl phthalocyanine having peaks at 24.1 ° and 27.2 ° and 0.5 part of silicone-butyral resin as a dispersion medium and 50 parts of methyl isopropyl ketone using a sand mill. Then, a charge generation layer having a film thickness of 0.3 μm was formed. Then Table 1
1 part of the exemplified compound shown in 1 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). this,
Coating on the charge generation layer using a doctor blade to a film thickness of 2
A charge transport layer having a thickness of 0 μm is formed, and the photoreceptor of Example [1]-
1-20 were produced.

[0081]

[Table 1]

[Comparative Example [1] -1] A comparative sample was prepared in the same manner as in Example [1] -1 except that the comparative compound represented by the chemical formula (K-1) described below was used instead of the exemplified compound A-2. did.

[0083]

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Evaluation 1 For the electrophotographic photoreceptor samples obtained in Examples [1] -1 to 20 and Comparative Example 1, an electrostatic copying test apparatus EP was used.
A-8100 (manufactured by Kawaguchi Electric Co., Ltd.) was charged to +800 V, white light of 10 lux was exposed, and the exposure amount E1 / 2 (lux · sec) until the surface potential was halved was determined as the sensitivity. Table 2 shows the results.

[0085]

[Table 2]

[Examples [1] -21] 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 an intermediate layer was formed thereon by X-ray diffraction. Bragg angle 2θ of 9.5 °, 24.1 °, 2
Titanyl phthalocyanine 1 having a peak at 7.2 °
And 0.5 parts of silicone-butyral resin as a dispersion medium and 50 parts of methyl isopropyl ketone dispersed using a sand mill were dip-coated to form a charge generation layer having a thickness of 0.3 μm. Exemplified Compound [1] -A-21
1 part and polycarbonate resin "Iupilon Z-20"
0 "(manufactured by Mitsubishi Gas Chemical Co., Inc.) was dissolved in 10 parts of THF and dip-coated on the charge generation layer to form a charge transport layer having a film thickness of 20 µm. It was made.

[Embodiment [1] -22] Embodiment [1] -2
The exemplified compound [1] -A-21 in 1 is converted to [1] -A-
Example Photoconductor [1] -22 was prepared in the same manner as Example [1] -21, except that the number was changed to 30.

[Example [1] -23] Example [1] -2
The exemplified compound [1] -A-21 in 1 is converted to [1] -C-
Example Photoconductor [1] -23 was prepared in the same manner as Example [1] -21, except that the number was changed to 69.

[Example [1] -24] Example [1] -2
The exemplified compound [1] -A-21 in 1 is converted into [1] -B-
Example Photoconductor [1] -24 was prepared in the same manner as Example [1] -21, except that the number was changed to 74.

Evaluation 2 The electrophotographic photosensitive drums obtained in Examples [1] -21 to 24 were mounted on a digital copying machine "Konica-9028" modified by Konica Corporation (charge polarity: positive, reverse development). When the image was mounted and copied, a high-contrast and clear copy image that was faithful to the original image was obtained. Also 5
Even when it was repeated 10,000 times, a clear copy image with high contrast was obtained.

As described above, the electrophotographic photosensitive member using the electron transporting material of the present invention has higher sensitivity than the conventional electrophotographic photosensitive member using the electron transporting material, and the photosensitive member after repeated use. You can see that the characteristics are stable.

Example [2] [Example [2] -1 to 10] P vapor-deposited with aluminum.
An intermediate layer made of polyamide resin "CM8000" (manufactured by Toray Industries, Inc.) and having a thickness of 0.5 μm was provided on the ET film. In addition, the Bragg angle 2θ in X-ray diffraction of 9.5 °,
Using a wire bar, apply a liquid prepared by dispersing 1 part of titanyl phthalocyanine having peaks at 24.1 ° and 27.2 ° and 0.5 part of silicone-butyral resin as a dispersion medium and 50 parts of methyl isopropyl ketone using a sand mill. Then, a charge generation layer having a film thickness of 0.3 μm was formed. Then Table 3
1 part of the exemplified compound shown in 1 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). this,
Coating on the charge generation layer using a doctor blade to a film thickness of 2
A charge transport layer having a thickness of 0 μm is formed, and the photoreceptor of Example [2]-
1 to 10 were produced.

[0093]

[Table 3]

[Comparative Example [2] -1] Exemplified Compound [2]-
A comparative sample was prepared in the same manner as in Example [2] -1, except that the comparative compound represented by the chemical formula (K-1) was used in place of 1.

Evaluation 1 With respect to the electrophotographic photosensitive member samples obtained in Examples [2] -1 to 10 and Comparative Example [2] -1, an electrostatic copying tester EPA-8100 (manufactured by Kawaguchi Electric Co., Ltd.) was used. +80
Exposure to white light of 10 lux by charging to 0 V, exposure amount E1 / 2 (lux · se) until the surface potential becomes half
c) was determined and used as the sensitivity. Table 4 shows the results.

[0096]

[Table 4]

[Example [2] -11] 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 an intermediate layer was formed thereon by X-ray diffraction. Bragg angle 2θ of 9.5 °, 24.1 °, 2
Titanyl phthalocyanine 1 having a peak at 7.2 °
And 0.5 parts of silicone-butyral resin as a dispersion medium and 50 parts of methyl isopropyl ketone dispersed using a sand mill were dip-coated to form a charge generation layer having a thickness of 0.3 μm. Next, 1 part of Exemplified Compound [2] -2 and 1.5 parts of a polycarbonate resin "Iupilon 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 give a film thickness of 20 μm. The charge transporting layer of No. 1 was formed to prepare Example photoconductor [2] -11.

[Example [2] -12] Example [2] -1
Example Photoconductor [2] -12 was prepared in the same manner as Example [2] -11, except that Exemplified Compound [2] -2 in Example 1 was changed to [2] -9.

[Example [2] -13] Example [2] -1
Example Photoconductor [2] -13 was prepared in the same manner as Example [2] -11 except that Exemplified Compound [2] -2 in Example 1 was changed to [2] -10.

[Example [2] -14] Example [2] -1
Example Photoconductor [2] -14 was prepared in the same manner as in Example [2] -11, except that Exemplified Compound [2] -2 in Example 1 was changed to [2] -14.

Evaluation 2 The electrophotographic photosensitive drums obtained in Examples [2] -11 to 14 were mounted on a digital copying machine "Konica-9028" modified by Konica Corporation (charge polarity: positive, reverse development). When the image was mounted and copied, a high-contrast and clear copy image that was faithful to the original image was obtained. Also 5
Even when it was repeated 10,000 times, a clear copy image with high contrast was obtained.

As described above, the electrophotographic photosensitive member using the electron transporting material of the present invention has higher sensitivity than the conventional electrophotographic photosensitive member using the electron transporting material, and the photosensitive member after repeated use. You can see that the characteristics are stable.

Example [3] [Example [3] -1] 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. On top of that, the Bragg angle 2θ for the CuKα characteristic X-ray is 9.5.
1 part of titanyl phthalocyanine having peaks at 2 °, 24.1 ° and 27.2 °, silicone-butyral resin 0.
A liquid in which 5 parts and 50 parts of methyl isopropyl ketone were dispersed using a sand mill was applied using a wire bar to form a charge generation layer having a film thickness of 0.3 μm. Then, a solution prepared by dissolving 1 part of Exemplified Compound [3] -1; 2 parts of polycarbonate resin "Iupilon Z-200" (manufactured by Mitsubishi Gas Chemical Co., Inc.) in 15 parts of 1,2-dichloroethane was placed on a charge generation layer with a doctor blade. It was applied to form a charge transport layer having a film thickness of 15 μm, and Example photoreceptor [3] -1 was produced.

[Examples [3] -2 to 10] Except that the exemplified compounds shown in Table 5 were used in place of the exemplified compound [3] -1, the same procedure as in Example [3] -1 was carried out. [3]-
2 to 10 were produced.

[Comparative Examples [3] -1, 2] Instead of the exemplified compound [3] -1, the following chemical formulas (K-2) and (K-
A comparative photoreceptor was prepared in the same manner as in Example [3] -1, except that the comparative compound of 3) was used.

[0106]

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Evaluation 1 With respect to the electrophotographic photoreceptor samples obtained in Examples [3] -1 to 10 and Comparative Examples [3] -1 and 2, electrostatic copying tester EPA-8100 (manufactured by Kawaguchi Electric Co., Ltd.) was used. Use +
The amount of exposure E1 / 2 (lux) required to reduce the surface potential to half by exposing it to 10 V white light by charging it to 800 V
-Sec) was obtained and used as the sensitivity. Table 5 shows the results.

[0108]

[Table 5]

[Example [3] -11] A 0.5 μm thick intermediate layer made of polyamide resin “CM8000” (manufactured by Toray Industries, Inc.) was provided on a cylindrical aluminum substrate. On top of that, Cu
Bragg angle 2θ of Kα characteristic X-ray of 9.5 °, 2
1 part of titanyl phthalocyanine having peaks at 4.1 ° and 27.2 °, 0.5 part of silicone-butyral resin,
A liquid in which 50 parts of methyl isopropyl ketone was dispersed using a sand mill was dip-coated to form a charge generation layer having a thickness of 0.3 μm. Then, a solution prepared by dissolving 1 part of Exemplified Compound [3] -1; 2 parts of polycarbonate resin "Iupilon Z-200" (manufactured by Mitsubishi Gas Chemical Co., Inc.) in 15 parts of 1,2-dichloroethane is applied onto the charge generation layer by dip coating. And film thickness 2
A charge transporting layer having a thickness of 5 μm is formed, and the photoconductor of Example [3] -1 is prepared.
1 was produced.

[Examples [3] -12 to 14] [3]-[3] -1 was used as the exemplified compound [3] -1 in Example [3] -11.
Example photoconductors [3] -12 to 14 were prepared in the same manner as in Example [3] -11, except that 3, 42 and 55 were used.

Evaluation 2 The electrophotographic photosensitive drums obtained in Examples [3] -11 to 14 were applied to a digital copying machine "Konica-9028" modified by Konica Corp. (charge polarity: positive, reverse development). When the image was mounted and copied, a high-contrast and clear copy image that was faithful to the original image was obtained. Also 5
Even when it was repeated 10,000 times, a clear copy image with high contrast was obtained.

Example [4] [Example [4] -1] 1 part of titanyl phthalocyanine having peaks at 9.5 °, 24.1 ° and 27.2 ° of Bragg angle 2θ to CuKα characteristic X-ray, silicone -Butyral resin 0.5 parts, methyl isopropyl ketone 50
The liquid in which the parts were dispersed using a sand mill was applied onto a PET film on which aluminum was vapor deposited using a wire bar to form a charge generation layer having a thickness of 0.3 μm. Then, 1 part of Exemplified Compound [4] -1 and 2 parts of a polycarbonate resin "Upilon Z-200" (manufactured by Mitsubishi Gas Chemical Co., Inc.)
A solution prepared by dissolving 15 parts of 2-dichloroethane was applied onto the charge generation layer using a doctor blade to form a charge transport layer having a thickness of 30 μm, and Example photoconductor [4] -1 was produced.

[Examples [4] -2 to 10] Except that the exemplified compounds shown in Table 6 were used instead of the exemplified compound [4] -1, the same procedure as in Example [4] -1 was carried out. [4]-
2 to 10 were produced.

[Comparative Example [4] -1] Exemplified Compound [4]-
A comparative photoreceptor was prepared in the same manner as in Example [4] -1, except that the comparative compound represented by the chemical formula (K-1) was used in place of 1.

Evaluation 1 With respect to the electrophotographic photosensitive member samples obtained in Examples [4] -1 to 10 and Comparative Example [4] -1, an electrostatic copying tester EPA-8100 (manufactured by Kawaguchi Electric Co., Ltd.) was used. +80
The exposure amount E1 / 2 (lux · s) required to reduce the surface potential to half by exposing to 10 lux of white light after being charged to 0V
ec) was determined and used as the sensitivity. Table 6 shows the results.

[0116]

[Table 6]

[Example [4] -11] A 0.5 μm thick intermediate layer made of polyamide resin “CM8000” (manufactured by Toray Industries, Inc.) was provided on a cylindrical aluminum substrate. On top of that, Cu
Bragg angle 2θ of Kα characteristic X-ray of 9.5 °, 2
1 part of titanyl phthalocyanine having peaks at 4.1 ° and 27.2 °, 0.5 part of silicone-butyral resin,
A liquid in which 50 parts of methyl isopropyl ketone was dispersed using a sand mill was dip-coated to form a charge generation layer having a thickness of 0.3 μm. Next, 1 part of Exemplified Compound [4] -1 and 1.5 parts of a polycarbonate resin "Iupilon Z-200" (manufactured by Mitsubishi Gas Chemical Co., Inc.) were added to 1,2-dichloroethane 1
A liquid dissolved in 5 parts was dip-coated on the charge generation layer to form a charge transport layer having a film thickness of 25 μm.
-11 was produced.

[Examples [4] -12 to 14] The compound [4] -1 in Example [4] -11 was replaced with [4]-
Example photoconductors [4] -12 to 14 were prepared in the same manner as in Example [4] -11, except that 16, 29, and 73 were used.

Evaluation 2 The electrophotographic photosensitive drums obtained in Examples [4] -11 to 14 were mounted on a digital copying machine "Konica-9028" modified by Konica Corp. (charge polarity: positive, reverse development). When the image was mounted and copied, a high-contrast and clear copy image that was faithful to the original image was obtained. Also 5
Even when it was repeated 10,000 times, a clear copy image with high contrast was obtained.

As described above, the electrophotographic photosensitive member using the electron transporting material of the present invention has higher sensitivity than the conventional electrophotographic photosensitive member using the electron transporting material, and the photosensitive member after repeated use. You can see that the characteristics are stable.

[0121]

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

Front Page Continuation (72) Inventor Hirofumi Hayata Konica Stock Company, 1 Sakura-cho, Hino City, Tokyo In-house

Claims (5)

[Claims] 1. An electrophotographic photosensitive member comprising a conductive support and a photosensitive layer containing a compound represented by the following general formula [1] provided on the conductive support. Embedded image (In the formula, X represents O, S, or Se. Q ₁ , Q
₂ is ═O, ═C (CN) ₂ , ═C (CO ₂ R ₅ ) ₂ ,
_{= C (CN) (CO 2} R 5), = N-CN, = N-CO 2
It represents an R _5. R _{1 to} R _{4 each} represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an acyl group or a substituted or unsubstituted alkyl group, alkoxy group, aryl group, sulfonyl group or ester group. R ₅ represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. ) 2. An electrophotographic photoreceptor comprising a conductive layer and a photosensitive layer containing a compound represented by the following general formula [2] provided on the conductive support. Embedded image (In the formula, R _{1 to} R ₄ each represent a hydrogen atom, a substituted or unsubstituted aryl group or a heterocyclic group. R ₅ and R ₆ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or Represents an aryl group.) 3. An electrophotographic photosensitive member comprising a conductive support and a photosensitive layer containing a compound represented by the following general formula [3] provided on the conductive support. Embedded image (In the formula, R represents a hydrogen atom or an OH group, and Ar ₁ to
Ar ₄ each represents a hydrogen atom or a substituted or unsubstituted aryl group. ) 4. An electrophotographic photosensitive member comprising a conductive support and a photosensitive layer containing a compound represented by the following general formula [4] provided on the conductive support. Embedded image (In the formula, Q ₁ and Q ₂ are respectively = O, = C (CN) ₂ , and = C
(CO ₂ R ') ₂ , = C (CN) (CO ₂ R'), = NA
represents r'or = NCN. R'represents a substituted or unsubstituted alkyl group and Ar 'represents a substituted or unsubstituted aryl group. Ar ₁ and Ar ₂ represent a substituted or unsubstituted aryl group, R represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group or an aryl group, and n represents an integer of 1 to 4. ) 5. The photosensitive layer is formed by laminating a charge generation layer and a charge transport layer, and has the general formula [1], [2], [3],
Alternatively, the compound represented by [4] is contained in the charge transport layer, and the electrophotographic photoreceptor according to claim 1, 2, 3, or 4.