JP2000056490A - Electrophotographic photoreceptor, process cartridge and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrophotographic photoreceptor which has high sensitivity, little fluctuation of the potential in a bright part and dark part when images are continuously formed, and extremely small transfer memory even in reverse developing system, and with which an image of high quality can be obtd., by incorporating each specified diamine compd. and hydrazone compd. into the photosensitive layer. SOLUTION: This electrophotographic photoreceptor contains a diamine compd. expressed by formula I and a hydrazone compd. expressed by formula II in the photosensitive layer. In formula I, R1 to R4 are hydrogen atoms, alkyl groups, alkoxy groups, aralkyl groups, halogen atoms or the like, R5, R6 are hydrogen atoms or alkyl groups, aralkyl groups or aryl groups which may have substituents, n is independently an integer 0 to 2. In formula II, R7, R8 are alkyl groups, aralkyl groups or aryl groups which may have substituents, m is 1 or 2, A is an aromatic hydrocarbon group or the like which may have substituents.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic photosensitive member, a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus. And a process cartridge having the same.

[0002]

2. Description of the Related Art Conventionally, selenium,
Inorganic photoreceptors having a photosensitive layer mainly composed of zinc oxide, cadmium or the like have been widely used. Although this has some basic characteristics, it has problems such as difficulty in film formation, poor plasticity, and high manufacturing cost. Furthermore, inorganic photoconductive materials are generally highly toxic, and have great restrictions on production and handling.

On the other hand, an organic photoreceptor containing an organic photoconductive compound as a main component has attracted attention in recent years because it has many advantages to compensate for the above-mentioned disadvantages of the inorganic photoreceptor, and many proposals have been made so far. Some have been put into practical use. Such organic photoreceptors include a charge transfer complex formed from a photoconductive polymer represented by poly-N-vinylcarbazole and a Lewis acid such as 2,4,8-trinitro-9-fluorenone. Electrophotographic photoreceptors having a main component have been proposed. These organic photoconductive polymers are superior to inorganic photoconductive polymers in terms of lightness, film-forming properties, and the like, but are more sensitive to inorganic photoconductive materials in terms of sensitivity, durability, and stability due to environmental changes. And it is not always satisfactory.

In addition, a function-separated electrophotographic photosensitive member in which a charge generation function and a charge transport function are shared by different materials, respectively, has remarkably improved sensitivity and durability, which have been disadvantages of conventional organic photosensitive members. Brought. Such a function-separated type photoreceptor has the advantage that the material selection range of the charge generation material and the charge transport material is wide, and that an electrophotographic photoreceptor having arbitrary characteristics can be relatively easily prepared.

As the charge generating material, various azo pigments,
Known are polycyclic quinone pigments, cyanine dyes, squaric acid dyes, and pyrylium salt dyes. Among them, many structures of azo pigments have been proposed from the viewpoints of high light resistance, high charge generation ability, easy material synthesis, and the like. Examples of the charge transport material include pyrazoline compounds described in JP-B-52-4188, JP-A-54-150128, JP-A-55-52063, and JP-A-59-15.
No. 251 and JP-A-1-102469, JP-A-53-27033, JP-A-61-132855, JP-A-2-190862 and JP-A-55-52063. Triphenylamine compounds, stilbene compounds disclosed in JP-A-54-151955 and JP-A-58-198043, JP-A-62-30255 and JP-A-62-2872
No. 57, butadiene compounds are known.

[0006] These charge transporting materials are required to (1) be stable against light and heat, and (2) be stable against ozone, NOx, nitric acid and the like generated by corona discharge ( 3) having high charge transport ability; (4) having high compatibility with organic solvents and binder resins; and (5) being easy and inexpensive to produce.

[0007] Further, with the recent increase in durability, charge transport is provided by providing a protective layer on the photosensitive layer to improve durability, or by storing the photosensitive member for a long time by using a copying machine or a laser beam printer. Cracks may be generated in the layer, or phenomena such as crystallization and phase separation of the charge transport material may occur, resulting in image defects. In addition, in the reversal development system corresponding to recent digitization, since primary charging and transfer charging have opposite polarities, a so-called transfer memory having different chargeability depending on the presence or absence of transfer occurs, and it becomes very easy to appear as density unevenness on an image. I have.

However, in an electrophotographic photosensitive member using a conventional organic compound as a charge transporting material, some of the problems and requirements described above are partially satisfied, but none of them satisfy a high level.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide not only a high sensitivity, but also a small variation in a bright portion potential and a dark portion potential during continuous image formation by repeated charging and exposure, and excellent durability. An object of the present invention is to provide an electrophotographic photoreceptor, a process cartridge having the electrophotographic photoreceptor, and an electrophotographic apparatus capable of obtaining a high-quality image even in a reversal developing system with a very small transfer memory.

[0010]

According to the present invention, in an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the photosensitive layer comprises a diamine compound represented by the following general formula (1) and a diamine compound represented by the following general formula (2) And an electrophotographic photosensitive member containing a hydrazone compound represented by the formula:

[0011]

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Wherein R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom,
Alkyl group, alkoxy group, hydroxy group, nitro group,
An allyl group, an aryl group which may have a substituent, an aralkyl group or a halogen atom, and R ₅ and R ₆ represent a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group or an aryl group; And n independently represents an integer of 0 to 2.

[0013]

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In the formula, R ₇ and R ₈ represent an alkyl group, an aralkyl group or an aryl group which may have a substituent,
m represents 1 or 2, and A represents an aromatic hydrocarbon group, an aliphatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent.

According to the present invention, in an electrophotographic photosensitive member having a photosensitive layer on a conductive support, the photosensitive layer is a diamine compound represented by the following general formula (1) and a butadiene represented by the following general formula (6) An electrophotographic photoreceptor containing the compound is provided.

[0016]

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Wherein R ₁ , R ₂ , R ₃ and R ₄ are a hydrogen atom,
Alkyl group, alkoxy group, hydroxy group, nitro group,
An allyl group, an aryl group which may have a substituent, an aralkyl group or a halogen atom; R ₅ and R ₆ each represent an alkyl group, an aralkyl group or an aryl group which may have a substituent, and n Represents an integer of 0 to 2 independently.

[0018]

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In the formula, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ represent a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, a hydroxy group, a nitro group, an allyl group, and an aryl which may have a substituent. A group, an aralkyl group or a halogen atom,
m independently represents an integer of 0 to 2.

In the above expression, the alkyl group is a group such as methyl, ethyl and propyl, the alkoxy group is a group such as methoxy and ethoxy, the aryl group is a group such as phenyl, naphthyl and anthryl, and the aralkyl group is benzyl and phenethyl. And the like.

The aromatic hydrocarbon group of the above expression is benzene,
Groups obtained by removing one or two hydrogen atoms from naphthalene, anthracene, pyrene, etc .; aliphatic hydrocarbon groups are groups obtained by removing one or two hydrogen atoms from methane, ethane, propane, butane, etc .; aromatics Examples of the heterocyclic group include groups obtained by removing one or two hydrogen atoms from pyridine, quinoline, thiophene, furan, and the like.

The substituents which these groups may have include alkyl groups such as methyl, ethyl, propyl and butyl, alkoxy groups such as methoxy and ethoxy, benzyl and the like.
Aralkyl groups such as phenethyl, halogen atoms such as fluorine, chlorine, and bromine; aryl groups such as phenyl and naphthyl; aromatic ring groups such as pyridyl, quinolyl, thienyl and furyl; acyl groups such as acetyl and benzoyl; and alkyl groups such as dimethylamino. Examples include an amino group, an arylamino group such as diphenylamino and ditolylamino, a haloalkyl group such as trifluoromethyl, a cyano group, a nitro group, a phenylcarbamoyl group, and a carboxyl group.

According to the present invention, there is further provided an electrophotographic photoreceptor,
Charging means for charging the electrophotographic photoreceptor, image exposure means for performing image exposure on the charged photoreceptor to form an electrostatic latent image,
And an electrophotographic apparatus provided with a developing means for developing the photoreceptor on which an electrostatic latent image is formed with toner, wherein the surface layer of the electrophotographic photoreceptor has a diamine compound represented by the general formula (1) and a general formula: An electrophotographic apparatus and a process cartridge provided with an electrophotographic photosensitive member containing a hydrazone compound represented by (2) or a diamine compound represented by general formula (1) and a butadiene compound represented by general formula (6) are provided. You.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION In order for a photosensitive layer to contain a diamine compound represented by the general formula (1) and a hydrazone compound represented by the general formula (2), a diamine compound represented by the general formula (1) is used. The hydrazone compound represented by the formula (2) is mixed or contained as a separately laminated layer. In the following, the same description means the above contents.

In the present invention, the hydrazone compound represented by the general formula (2) is represented by the following general formula (3):
The hydrazone compounds represented by (4) and (5) are particularly preferred.

[0026]

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In the formula, R ₉ and R ₁₀ represent an alkyl group, an aralkyl group or an aryl group which may have a substituent, and R ₁₁ represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a nitro group, It represents an allyl group, an aryl group which may have a substituent, an aralkyl group or a halogen atom.

[0028]

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[0029] In the formula, R ₁₂ is an optionally substituted alkyl group, an aralkyl group or an aryl group, R _13,
R ₁₄ and R ₁₅ are a hydrogen atom, an alkyl group, an alkoxy group,
A hydroxy group, a nitro group, an allyl group, an aryl group which may have a substituent, an aralkyl group or a halogen atom, j and k each represent 1 or 2, and l represents 0 or 1.

[0030]

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[0031] In the formula, R ₁₆ MAY substituted alkyl group, an aralkyl group or an aryl group, R _17,
R ₁₈ , R ₁₉ and R _{20 each} represent a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a nitro group, an allyl group, an aryl group which may have a substituent, an aralkyl group or a halogen atom; Or 1 is shown.

The alkyl group in the above expression is a group such as methyl, ethyl, propyl and the like, the aryl group is phenyl,
Groups such as naphthyl and anthryl, alkoxy groups include groups such as methoxy and ethoxy, and aralkyl groups include groups such as benzyl and phenethyl. Further, as a substituent which these groups may have, alkyl groups such as methyl, ethyl, propyl and butyl, methoxy, alkoxy groups such as ethoxy, benzyl, aralkyl groups such as phenethyl,
Fluorine, chlorine, halogen atoms such as bromine, phenyl, aryl groups such as naphthyl, pyridyl, quinolyl, thienyl,
Examples include an aromatic ring group such as furyl, an acyl group such as acetyl and benzoyl, an alkylamino group such as dimethylamino, a haloalkyl group such as trifluoromethyl, a cyano group, a nitro group, a phenylcarbamoyl group, and a carboxyl group.

The general formulas (1), (2) and (6)
Representative examples of the compound represented by are given below. However,
It is not limited to these compounds.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

[Table 3]

[0037]

[Table 4]

[0038]

[Table 5]

[0039]

[Table 6]

[0040]

[Table 7]

[0041]

[Table 8]

[0042]

[Table 9]

[0043]

[Table 10]

[0044]

[Table 11]

[0045]

[Table 12]

[0046]

[Table 13]

The photoreceptor of the present invention comprises a diamine compound represented by the general formula (1) and a hydrazone compound represented by the general formula (2) or a diamine compound represented by the general formula (1) It is constituted by combining a charge transporting material comprising a butadiene compound represented by (6) and a suitable charge generating material. Examples of the configuration of the photosensitive layer include the following forms.

(A) Layer containing charge generation material / layer containing charge transport material (B) Layer containing charge transport material / layer containing charge generation material (C) Charge generation material and charge transport material Layer containing (D) layer containing charge generation material / layer containing charge generation material and charge transport material

The diamine compound represented by the general formula (1) and the hydrazone compound represented by the general formula (2) of the present invention,
Alternatively, since the diamine compound represented by the general formula (1) and the butadiene compound represented by the general formula (6) both have a high hole-transporting ability, they can be used as the charge transporting material in the photosensitive layer of the above embodiment. it can. In the case of (A), the photosensitive layer is preferably negatively charged, in the case of (B), positively charged, and in the case of (C) or (D), both positively and negatively charged can be used.

Further, in the electrophotographic photoreceptor of the present invention, a protective layer or an insulating layer may be provided on the surface of the photosensitive layer in order to improve adhesion and restrict charge injection. The configuration of the photoconductor of the present invention is not limited to the above basic configuration. The configuration (A) is particularly preferable among the above configurations, and will be described in more detail below. Examples of the conductive support in the present invention include the following forms. (1) Aluminum, aluminum alloy, stainless steel,
A plate or drum made of metal such as copper. (2) Aluminum, palladium, etc. on a non-conductive support such as glass, resin, paper or the conductive support of the above (1).
A thin film formed by depositing or laminating metals such as rhodium, gold, and platinum. (3) Depositing or coating a layer of a conductive compound such as a conductive polymer, tin oxide, or indium oxide on a non-conductive support such as glass, resin, or paper or the conductive support described in (1) above. What was formed by

Examples of the effective charge generating material used in the present invention include the following materials. These charge generation materials may be used alone or in combination of two or more. (1) Azo pigments such as monoazo, bisazo and trisazo (2) Indigo pigments such as indigo and thioindigo (3) Phthalocyanine such as metal phthalocyanine and non-metal phthalocyanine (4) Perylene anhydride, perylene imide and the like Perylene pigments (5) Polycyclic quinone pigments such as anthraquinone and pyrenequinone (6) Squarylium dyes (7) Pyrylium salts and thiopyrylium salts (8) Triphenylmethane dyes (9) Inorganic substances such as selenium and amorphous silicon material

The layer containing the charge-generating material, that is, the charge-generating layer, can be formed by dispersing the above-described charge-generating material in a suitable binder resin, and applying this to a conductive support. . Further, it can also be formed by forming a thin film on a conductive support by a dry method such as evaporation, sputtering, or CVD.

The binder resin can be selected from a wide range of binder resins, and examples thereof include polycarbonate resin, polyester resin, polyarylate resin, butyral resin, polystyrene resin, polyvinyl acetal resin, diallyl phthalate resin, acrylic resin, methacrylic resin, and vinyl acetate. Resins, phenolic resins, silicone resins, polysulfone resins, styrene-butadiene copolymer resins, alkyd resins, epoxy resins, urea resins, vinyl chloride-vinyl acetate copolymer resins, and the like, but are not limited thereto. Absent. These may be used alone or in combination of two or more kinds as a copolymer polymer.

The binder resin contained in the charge generation layer is preferably at most 80% by weight, more preferably at most 40% by weight. Further, the thickness of the charge generation layer is preferably 5 μm or less, more preferably 0.01 μm to 2 μm. Further, various sensitizers may be added to the charge generation layer.

The layer containing the charge transporting material, that is, the charge transporting layer, comprises at least a diamine compound represented by the general formula (1) and a hydrazone compound represented by the general formula (2) or a diamine represented by the general formula (1) It can be formed by combining a compound and a butadiene compound represented by the general formula (6) with a suitable binder resin. Here, examples of the binder resin used for the charge transport layer include those used for the charge generation layer, and further include photoconductive polymers such as polyvinyl carbazole and polyvinyl anthracene.

The mixing ratio of the binder resin and the charge transporting material is preferably 10 to 500 parts by weight of the charge transporting material per 100 parts by weight of the binder resin. The charge transport layer is electrically connected to the above-described charge generation layer, and has a function of receiving charge carriers injected from the charge generation layer in the presence of an electric field and transporting these charge carriers to the surface. ing. Since the charge transport layer is at a limit capable of transporting charge carriers, it cannot be unnecessarily thick, but preferably has a thickness of 5 μm to 40 μm, more preferably 10 μm to 30 μm.
Further, an antioxidant, an ultraviolet absorber, a plasticizer, or a known charge transport material can be added to the charge transport layer as needed.

When such a charge transport layer is formed, an appropriate organic solvent is used and a coating method such as dip coating, spray coating, spinner coating, roller coating, Meyer bar coating, blade coating, etc. Can be performed.

In the electrophotographic photoreceptor of the present invention, a diamine compound represented by the general formula (1) and a hydrazone compound represented by the general formula (2) or a butadiene compound represented by the formula (6) are mixed in forming the charge transport layer. Or can be separately laminated. In either case of forming by mixing and separately forming by lamination, the weight ratio of diamine compound / hydrazone compound or diamine compound / butadiene compound is 95/5 to 5/5.
A range of 95 is preferred. If the weight ratio is outside this range,
The intended improvement effect is insufficient.

FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge having the electrophotographic photosensitive member of the present invention. In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is driven to rotate around an axis 2 at a predetermined peripheral speed in a direction indicated by an arrow. The photoreceptor 1 receives a uniform charge of a predetermined positive or negative potential on the peripheral surface thereof by the primary charging means 3 during the rotation process, and then receives a charge from an image exposure means (not shown) such as slit exposure or laser beam scanning exposure. It receives image exposure light 4. Thus, an electrostatic latent image is sequentially formed on the peripheral surface of the photoconductor 1.

The formed electrostatic latent image is then transferred to developing means 5
The toner-developed image developed by the toner image is transferred from a paper supply unit (not shown) between the photoconductor 1 and the transfer unit 6 in synchronization with the rotation of the photoconductor 1 and fed to a transfer material 7 fed therefrom. The image is sequentially transferred by the transfer unit 6.

The transfer material 7 which has undergone the image transfer is separated from the photoreceptor surface, introduced into the image fixing means 8 and subjected to image fixing to be printed out as a copy out of the apparatus. The surface of the photoreceptor 1 after the image transfer is cleaned and cleaned by removing the untransferred toner by a cleaning unit 9, and further subjected to a charge removal process by a pre-exposure light 10 from a pre-exposure unit (not shown). Used for image formation. When the primary charging unit 3 is a contact charging unit using a charging roller or the like, the pre-exposure is not necessarily required.

In the present invention, a plurality of components such as the above-described electrophotographic photosensitive member 1, primary charging means 3, developing means 5, and cleaning means 9 are integrally connected as a process cartridge. The process cartridge may be configured to be detachable from a main body of an electrophotographic apparatus such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the photoreceptor 1 to form a cartridge, which can be attached to and detached from the apparatus main body using a guide unit such as a rail 12 of the apparatus main body. Process cartridge 1
It can be 1.

When the electrophotographic apparatus is a copying machine or a printer, the image exposure light 4 is reflected or transmitted from the original, or the original is read by a sensor and converted into a signal. Laser beam scanning,
Light emitted by driving the LED array, driving the liquid crystal shutter array, and the like.

The electrophotographic photosensitive member of the present invention can be used not only for an electrophotographic copying machine but also for a laser beam printer,
It can be widely used in electrophotographic applications such as RT printers, LED printers, liquid crystal printers, and laser plate making.

According to the present invention, not only is the advantage that the residual potential is high, the residual potential is low, and the fluctuations in the bright portion potential and the dark portion potential are small when repeated charging and exposure are performed.
It is possible to provide an electrophotographic photoreceptor in which transfer memory hardly occurs even in a reversal developing system.

[0066]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. “Parts” in the examples indicates parts by weight.

Example 1-1 50 parts of titanium oxide powder coated with tin oxide containing 10% antimony oxide, 20 parts of resole type phenol resin, and methyl cellosolve 20
Parts, 5 parts of methanol and 0.003 parts of silicone oil (polydimethylsiloxane polyoxyalkylene copolymer, average molecular weight 3000) were dispersed for 2 hours by a sand mill using φ1 mm glass beads to prepare a conductive layer paint. Paint the aluminum cylinder (φ30mm ×
(Length: 261 mm) and dried at 145 ° C. for 30 minutes to form a conductive layer having a thickness of 20 μm.

A solution prepared by dissolving 5 parts of methoxymethylated nylon (number average molecular weight 32,000) and 10 parts of alcohol-soluble copolymerized nylon (number average molecular weight 29000) in 95 parts of methanol is dip-coated on the conductive layer, and dried. Thus, an undercoat layer having a thickness of 1 μm was formed.

Next, in the CuKα characteristic X-ray diffraction, the Bragg angles (2θ ± 0.2) of 9.0 °, 14.2 °, 2 °
10 parts of oxytitanium phthalocyanine (TiOPc) having peaks at 3.9 ° and 27.1 ° were dissolved in 400 parts of cyclohexanone in 10 parts of polyvinyl butyral (trade name: Esrec BX-1, manufactured by Sekisui Chemical Co., Ltd.). The mixture was dispersed in a sand mill using φ1 mm glass beads for 3 hours, diluted with 400 parts of ethyl acetate, and collected, and then dip-coated on the undercoat layer at 90 ° C. And dried for 15 minutes.
A μm charge generation layer was formed.

Next, 5 parts of the exemplified diamine compound 1-4,
5 parts of exemplified hydrazone compound 2-1 and bisphenol Z
A solution prepared by dissolving 10 parts of a polycarbonate (number average molecular weight: 45,000) in 80 parts of chlorobenzene, dip-coating the solution on the charge generation layer, drying at 110 ° C. for 1 hour, and forming a charge transport layer having a thickness of 20 μm. Was formed to prepare an electrophotographic photosensitive member.

(Examples 1-2 to 1-6) Except that the compounds shown in Table 1-1 below were used in place of the hydrazone compounds used in Example 1-1, the same as Example 1-1 was used. An electrophotographic photoreceptor was prepared.

Examples 1-7 to 1-8 Same as Example 1-1 except that the compounds shown in Table 1-1 below were used instead of the diamine compounds used in Example 1-1. An electrophotographic photoreceptor was prepared.

Comparative Example 1-1 An electrophotographic photoreceptor was prepared in the same manner as in Example 1-1, except that the hydrazone compound used in Example 1-1 was not used and the diamine compound was changed to 10 parts. .

(Comparative Example 1-2) An electrophotography was performed in the same manner as in Example 1-1, except that the compound represented by the following structural formula (7) was used instead of the hydrazone compound used in Example 1-1. A photoreceptor was made.

[0075]

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(Comparative Example 1-3) Electrophotography was performed in the same manner as in Example 1-1 except that the compound represented by the following structural formula (8) was used instead of the hydrazone compound used in Example 1-1. A photoreceptor was made.

[0077]

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(Comparative Examples 1-4 to 1-6) Examples 1-1 to 1-6
An electrophotographic photosensitive member was prepared in the same manner as in Examples 1-1 to 1-3 except that the diamine compound used in 1-3 was not used and the hydrazone compound was changed to 10 parts.

The thus prepared electrophotographic photosensitive member was mounted on a laser beam printer (trade name: LBP-SX, manufactured by Canon Inc.), the dark portion potential was set to −800 V, and a laser beam of 802 nm was applied thereto. Irradiation was performed to measure the amount of laser light at which the bright portion potential became -150 V, and the sensitivities were compared. Furthermore, the change amount (ΔVD) of the dark portion potential and the change amount (ΔV
L) was measured. A negative sign in the potential fluctuation indicates a decrease in the absolute value of the potential, and a positive sign indicates an increase in the absolute value of the potential.

Further, the electrophotographic photosensitive member prepared as described above was used with a laser beam printer (Canon LBP-S).
X remodeling machine), the primary charging voltage when the transfer current is OFF is Vd1, and the primary charging voltage when the transfer current is ON is Vd.
As No. 2, a so-called transfer memory (Vd1-Vd2) was measured, and an image forming test was performed. The conditions are as follows. Surface potential after primary charging: -800 V, surface potential after image exposure: -150 V (exposure amount: 1.0 μJ / c)
m ² ), transfer potential +800 V, developing polarity: negative polarity, process speed: 48 mm / sec, developing condition (developing bias): -450 V, scan after image exposure: image scan, exposure before primary charging: 8.0 Lux · sec. The red whole surface exposure and image formation were performed by line scanning the laser beam according to the character signal and image signal.
Good prints were obtained for both images. Table 1-1 shows the results of initial sensitivity, potential fluctuation during repeated use, and transfer memory.
Shown in

[0081]

[Table 14]

From these results, it is known that the electrophotographic photoreceptor of the present invention has excellent initial sensitivity and repetition characteristics and is excellent in transfer memory. The electrophotographic photoreceptor of the comparative example in which the diamine compound of the general formula (1) and the hydrazone compound of the general formula (2) are used alone or in combination with another compound as the charge transporting material has excellent initial sensitivity and repetition characteristics. However, the transfer memory does not have the same characteristics as the electrophotographic photoreceptor of the present invention.

(Examples 2-1 to 2-8) Except that diamine compounds and butadiene compounds shown in Table 2-1 below were used instead of the diamine compounds and hydrazone compounds used in Example 1-1, An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1-1. The results are shown in Table 2-1.

Comparative Example 2-1 An electrophotographic photosensitive member was prepared in the same manner as in Example 1-1 except that the butadiene compound used in Example 2-1 was not used and the diamine compound was changed to 10 parts. ,evaluated. The results are shown in Table 2-1.

Comparative Example 2-2 Example 1 was repeated except that the compound represented by the structural formula (7) used in Comparative Example 1-2 was used instead of the butadiene compound used in Example 2-1. -1
An electrophotographic photoreceptor was prepared and evaluated in the same manner as described above. The results are shown in Table 2-1.

Comparative Example 2-3 Example 1 was repeated except that the compound represented by the structural formula (8) used in Comparative Example 1-3 was used instead of the butadiene compound used in Example 2-1. -1
An electrophotographic photoreceptor was prepared and evaluated in the same manner as described above. The results are shown in Table 2-1.

(Comparative Examples 2-4 to 2-6) Examples 2-1 to 2-6
An electrophotographic photoreceptor was prepared in the same manner as in Examples 2-1 to 2-3 except that the butadiene compound was changed to 10 parts without using the diamine compound used in 2-3. The electrophotographic photoreceptor thus produced was evaluated in the same manner as in Example 1-1. The results are shown in Table 2-1.

[0088]

[Table 15]

From these results, it is known that the electrophotographic photoreceptor of the present invention has excellent initial sensitivity and repetition characteristics and is excellent in transfer memory. The electrophotographic photoreceptor of the comparative example in which the diamine compound of the general formula (1) and the butadiene compound of the general formula (6) are used alone or in combination with another compound as the charge transport material is the electrophotographic photoreceptor of the present invention. Are not obtained.

(Example 1-9) A conductive layer, an undercoat layer and a charge generation layer were formed on an aluminum cylinder in the same manner as in Example 1-1. Next, the exemplary diamine compound 1-4
Was dissolved in 80 parts of chlorobenzene, and 10 parts of bisphenol Z-type polycarbonate (number average molecular weight: 45,000) was dissolved in 80 parts of chlorobenzene. This solution was dip-coated on the charge generation layer, and dried at 110 ° C. for 1 hour. Formed a charge transport layer having a thickness of 10 μm.

Further, the exemplified hydrazone compound 2-1 was
, A solution prepared by dissolving 10 parts of bisphenol Z-type polycarbonate (number average molecular weight 45,000) in 80 parts of chlorobenzene, dip-coating this solution on the previously formed charge transport layer, and drying at 100 ° C for 1 hour, 10μ thickness
m, a second charge transport layer was formed, and an electrophotographic photosensitive member was prepared. The initial sensitivity, the potential fluctuation during repeated use, and the transfer memory of the prepared photoreceptor were evaluated in the same manner as in Example 1-1. The results are shown in Table 1-2 below.

(Example 1-10) Except that the order of forming the layer containing the diamine compound and the layer containing the hydrazone compound formed in Example 1-9 was changed, the order of Examples 1-9 was changed. An electrophotographic photoreceptor was prepared in the same manner as described above. The initial sensitivity, the potential fluctuation during repeated use, and the transfer memory of the prepared photoreceptor were evaluated in the same manner as in Example 1-1. The results are shown in Table 1-2 below.

[0093]

[Table 16]

From these results, it is clear that the electrophotographic photoreceptor of the present invention can be prepared by mixing the diamine compound of the general formula (1) and the hydrazone compound of the general formula (2) separately, and mixing the same. It is known that, as in the case of using a layer, it is excellent in initial sensitivity, repetition characteristics and transfer memory.

(Example 2-9) A conductive layer, an undercoat layer and a charge generation layer were formed on an aluminum cylinder in the same manner as in Example 2-1. Next, the exemplified butadiene compound 3-2
0 and 10 parts of bisphenol Z-type polycarbonate (number average molecular weight 35,000) in tetrahydrofuran 8
A solution dissolved in 0 parts was prepared, and this solution was dip-coated on the charge generation layer, dried at 100 ° C. for 20 minutes, and the film thickness was 5 μm.
m of the charge transport layer was formed.

Further, 8 parts of the exemplified diamine compound 1-3,
Bisphenol Z-type polycarbonate (number average molecular weight 3
5000) was prepared by dissolving 10 parts in 80 parts of tetrahydrofuran, dip-coating the solution on the previously formed charge transport layer, and drying at 100 ° C. for 20 minutes to form a film having a thickness of 15 parts.
A second charge transport layer having a thickness of μm was formed, and an electrophotographic photosensitive member was prepared. The initial sensitivity, the potential fluctuation during repeated use, and the transfer memory of the prepared photoreceptor were evaluated in the same manner as in Example 1-1. The results are shown in Table 2-2 below.

Example 2-10 Example 2-9 was repeated except that the order of forming the diamine compound-containing layer and the butadiene compound-containing layer formed in Example 2-9 was reversed. An electrophotographic photoreceptor was prepared in the same manner as described above. The initial sensitivity, the potential fluctuation during repeated use, and the transfer memory of the prepared photoreceptor were evaluated in the same manner as in Example 1-1. The results are shown in Table 2-2 below.

[0098]

[Table 17]

From these results, it is clear that the electrophotographic photoreceptor of the present invention can be prepared by mixing the same diamine compound represented by the general formula (1) and the butadiene compound represented by the general formula (6) separately. It is known that, as in the case of using a layer, it is excellent in initial sensitivity, repetition characteristics and transfer memory.

Example 1-11 A 35% methanol solution of alcohol-soluble nylon (6-66-610-12 quaternary nylon copolymer) was applied on an aluminum cylinder (φ30 mm × length 261 mm) and dried. The undercoat layer having a thickness of 1.5 μm was formed. Next, 8 parts of the exemplified diamine compound 1-9 and 3 parts of the exemplified hydrazone compound 2-2.
Parts of bisphenol A type polycarbonate resin (weight average molecular weight 42,000)
(0 parts by weight) / 80 parts by weight of dichloromethane (20 parts by weight) solution and dip-coated on the undercoat layer prepared above to form a charge transport layer having a thickness of 20 μm after drying.

Further, pigment 2 represented by the following structural formula (9)
0 parts and butyral resin (butyralization degree 65 mol%)
10 parts were added to 350 parts of tetrahydrofuran,
and dispersed in a sand mill using glass beads of m for 20 hours. This dispersion was dip-coated on the charge transport layer prepared above so that the film thickness after drying was 0.7 μm, and dried.

[0102]

Embedded image

The initial sensitivity, potential fluctuation during repeated use, and evaluation of the transfer memory of the electrophotographic photosensitive member prepared as described above were evaluated in the same manner as in Example 1-1 (however, charging and transfer were of opposite polarities). The results are shown below.

Sensitivity E _1/5 = 2.5 (lux · sec) 5000 sheet repetition characteristics ΔVD = −30 (V) ΔV
L: -40 (V) Transfer memory Vd1-Vd2 = 5 (V)

(Example 2-11) The exemplified hydrazone compound used in Example 1-11 was replaced with the exemplified butadiene compound 3-2.
An electrophotographic photoreceptor was prepared in the same manner as in Example 1-11, except that 1 was used. Evaluation of initial sensitivity, potential fluctuation during repeated use, and transfer memory was performed in the same manner as in Example 1-11. Was. The results are shown below.

Sensitivity E _1/5 = 2.7 (lux · sec) 5000 sheet repetition characteristics ΔVD = −35 (V) ΔV
L: -35 (V) Transfer memory Vd1-Vd2 = 5 (V)

From these results, it can be seen that the electrophotographic photoreceptor of the present invention is excellent in transfer memory in initial sensitivity and repetition characteristics even as a positive charging photoreceptor.

Example 2-12 10 parts of a bisazo pigment represented by the following structural formula (10) was used as a butyral resin (butyralization degree: 68 mol%) and 10 parts of cyclohexanone was used.
Disperse for 40 hours in a sand mill together with the solution dissolved in 0 parts,
A coating solution was prepared. The coating liquid was applied on an aluminum sheet with a Meyer bar so that the film thickness after drying was 0.24 μm, to form a charge generation layer.

[0109]

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Next, 4 parts of the exemplified diamine compound 1-7 and 4 parts of the exemplified butadiene compound 3-25 were used as charge transporting materials.
Parts, 10 parts of bisphenol A type polycarbonate (weight average molecular weight: 42,000) was dissolved in 80 parts of monochlorobenzene, and this solution was applied on the above-mentioned charge generation layer with a Meyer bar to form a charge transport layer having a dry film thickness of 22 μm. And a two-layer electrophotographic photosensitive member was prepared.

(Examples 2-13 to 2-16) Example 2
Example 2 was repeated except that the diamine compound and the butadiene compound used in Example 12 were the compounds shown in Table 2-3 below.
An electrophotographic photosensitive member was prepared in the same manner as in No. 12.

Comparative Example 2-7 An electrophotographic photosensitive member was prepared in the same manner as in Example 2-12, except that the butadiene compound used in Example 2-12 was not used and the diamine compound was changed to 8 parts. .

Comparative Example 2-8 An electrophotographic photosensitive member was prepared in the same manner as in Example 2-12, except that the butadiene compound was changed to 8 parts without using the diamine compound used in Example 2-12. .

The electrophotographic photoreceptor produced in this way was used as an electrostatic copying paper tester Model-S manufactured by Kawaguchi Electric Co., Ltd.
Using P-428, corona charging was performed in a static manner at -5 kV, and after holding for 1 second in a dark place, exposure was performed at an illuminance of 20 Lux, and charging characteristics were examined. As the charging characteristics, the surface potential (V0) and the potential (V1) when darkly attenuated for 1 second are reduced by 1 /.
The exposure amount (E _1/5 ) required to attenuate to 5 was measured.

Further, in order to measure the fluctuation of the light portion potential and the dark portion potential when the photoreceptor is repeatedly used, the photosensitive member prepared in this embodiment was replaced with a PPC copier NP-3825 manufactured by Canon Inc.
To the photoreceptor drum cylinder.
00 sheets were copied, and the variation ΔVL of the light portion potential (VL) and the variation ΔVD of the dark portion potential (VD) at the initial stage and after copying 5,000 copies were measured. The initial VD and VL were set to be -700 V and -200 V, respectively. Table 2-3 shows the results of the initial sensitivity of the prepared photoreceptor and the potential fluctuation during repeated use.

[0116]

[Table 18]

From these results, it is known that the electrophotographic photoreceptor of the present invention has excellent initial characteristics and repetition characteristics as a photoreceptor for a copying machine.

(Example 1-12) N on a glass support
-Methoxy dimethylated 6 nylon resin (weight average molecular weight 2
8000) and 8 parts of an alcohol-soluble copolymerized nylon resin (weight average molecular weight 26000) in methanol 3
A solution dissolved in a mixed solution of 0 parts / 80 parts of butanol was applied by dip coating, and an undercoat layer having a thickness of 1 μm after drying was provided.

Next, 5 parts of the exemplified diamine compound 2-1, 5 parts of the exemplified hydrazone compound 2-22, and bisphenol A
Type polycarbonate resin (weight average molecular weight 29000)
10 parts are dissolved in 80 parts of a monochlorobenzene (40 parts by weight) / dichloromethane (60 parts by weight) solution, applied by a Meyer bar onto the undercoat layer prepared above, and dried to a charge transporting thickness of 18 μm. Created layers. Further, 65 parts of an acrylic monomer represented by the following structural formula (11), 35 parts of ultrafine tin oxide particles having an average particle size of 400 ° before dispersion, 2.5 parts of 2-methylthioxanthone as a photoinitiator, and 280 parts of methyl cellosolve were sand-milled. For 80 hours.

[0120]

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Using this dispersion, a film was formed on the above-mentioned photosensitive layer by a beam coating method and dried, and then light-cured with a high-pressure mercury lamp at a light intensity of 8 mW / cm ² for 60 seconds to form a film. Provided a 2.5 μm protective layer. The light-sensitive layer thus obtained was observed with a transmission microscope while irradiating light from the back surface at an angle of 15 °, but no cracks and no crystallization of the charge transporting material occurred.

[0122]

As described above, the electrophotographic photoreceptor of the present invention has high sensitivity, has small fluctuations in the light portion potential and dark portion potential during continuous image formation by repeated charging and exposure, and has excellent durability. In addition, the reversal developing system has a remarkable effect that a transfer memory is extremely small and a high-quality image can be obtained.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus having a process cartridge having an electrophotographic photosensitive member of the present invention.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Tetsuro Kanamaru 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2H068 AA20 BA12 BA13 BA21 BA24 FA01 FA13 FA27 FC01 FC05 FC08 FC11 FC15

Claims (5)

[Claims] 1. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer has the following general formula (1): ## STR1 ## (Wherein R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a nitro group, an allyl group, an aryl group which may have a substituent, an aralkyl group or a halogen R ₅ and R ₆ represent a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group or an aryl group, and n independently represents an integer of 0 to 2)
And a diamine compound represented by the following general formula (2): (Wherein, R ₇ and R ₈ represent an alkyl group, an aralkyl group or an aryl group which may have a substituent, m represents 1 or 2, and A represents an aromatic group which may have a substituent. (Indicating an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or an aromatic heterocyclic group). 2. The electrophotographic photoreceptor according to claim 1, wherein the hydrazone compound (2) is represented by any of the following general formulas (3), (4) and (5). Embedded image (Wherein, R ₉ and R ₁₀ represent an alkyl group, an aralkyl group or an aryl group which may have a substituent, and R ₁₁ represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a nitro group, an allyl group Represents an aryl group, an aralkyl group, or a halogen atom which may have a substituent). (Wherein, R ₁₂ is an alkyl group which may have a substituent,
An aralkyl group or an aryl group, and R ₁₃ , R ₁₄ and R
₁₅ represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a nitro group, an allyl group, an aryl group which may have a substituent, an aralkyl group or a halogen atom, j and k each represent 1 or 2, l represents 0 or 1) (Wherein, R ₁₆ is an alkyl group which may have a substituent,
Represents an aralkyl group or an aryl group, and represents R ₁₇ , R ₁₈ , R ₁₉
And R ₂₀ represent a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a nitro group, an allyl group, an aryl group which may have a substituent, an aralkyl group or a halogen atom, and i represents 0 or 1) 3. An electrophotographic photosensitive member having a photosensitive layer on a conductive support, wherein the photosensitive layer has the following general formula (1). (Wherein R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a nitro group, an allyl group, an aryl group which may have a substituent, an aralkyl group or a halogen R ₅ and R ₆ each represent an alkyl group, an aralkyl group or an aryl group which may have a substituent, and n independently represents an integer of 0 to 2), and a diamine compound represented by the following formula: General formula (6) (Wherein, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ represent a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, a hydroxy group, a nitro group, an allyl group, an aryl group which may have a substituent, An aralkyl group or a halogen atom, and m independently represents an integer of 0 to 2). 4. An electrophotographic photoreceptor according to claim 1, a charging means for charging the electrophotographic photoreceptor, and an image for forming an electrostatic latent image by exposing the charged photoreceptor to an image. An electrophotographic apparatus comprising: an exposing unit; a developing unit that develops the electrostatic latent image formed on the photoconductor with toner; and a transfer unit that transfers a visualized image. 5. An electrophotographic photoreceptor according to claim 1, a charging means for charging the electrophotographic photoreceptor, and an image for forming an electrostatic latent image by exposing the charged photoreceptor to an image. At least one unit selected from the group consisting of an exposure unit, a developing unit for developing the electrostatic latent image formed with the toner with toner, and a cleaning unit is integrally supported and detached from the main body of the electrophotographic apparatus. A process cartridge characterized by being flexible.