JP2003021921A - Electrophotographic photoreceptor, electrophotographic apparatus and process cartridge - Google Patents

Abstract

(57) [Problem] To provide a high durability while maintaining the advantages that the charging voltage is only for a desired photoreceptor surface potential, no ozone or charging noise is generated, and a low power and simple device configuration is maintained. An electrophotographic photosensitive member, an electrophotographic apparatus, and a process cartridge are provided. SOLUTION: The electrophotographic photosensitive member has on a conductive support at least a photosensitive layer containing a charge transport material of the following formula (1), (2), (3) or (4) and a surface containing conductive particles. An electrophotographic photosensitive member having a protective layer, an electrophotographic device having the electrophotographic photosensitive member, and a process cartridge. Embedded image (Wherein, Ar _{1 to} Ar ₄ and Ar ₆ are an aryl group, Ar ₅ and A
r _{7 to} Ar ₁₀ are an arylene group, R _{1 to} R ₉ are an alkyl group, etc.)

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an electrophotographic photoreceptor,
More specifically, the present invention relates to an electrophotographic apparatus and a process cartridge, and an electrophotographic photosensitive member having a photosensitive layer containing a specific charge transport material and a surface protective layer containing conductive particles, and having the electrophotographic photosensitive member to perform specific charging. The present invention relates to an electrophotographic device and a process cartridge.

[0002]

2. Description of the Related Art Conventionally, in an electrophotographic apparatus such as a copying machine or a printer, an image bearing member (charged member) such as an electrophotographic photosensitive member.
A corona charger (corona discharger) has been widely used as a charging device for uniformly charging (including static elimination) to a required polarity and potential.

A corona charger is a non-contact type charging device, which is provided with a discharge electrode such as a wire electrode and a shield electrode surrounding the discharge electrode, and has a discharge opening portion opposed to an image carrier, which is a member to be charged. The surface of the image carrier is charged in a predetermined manner by exposing the surface of the image carrier to a discharge current (corona shower) generated by applying a high voltage to the discharge electrode and the shield electrode.

In recent years, medium- and low-speed electrophotographic apparatuses have advantages such as low ozone and low power as a charging device for a charged member such as an image bearing member, as compared with a corona charger, because they have advantages. Many charging devices have been proposed and put into practical use.

The contact charging device is a conductive charging member (contact charging member / contact charger) of a roller type (charging roller), a fur brush type, a magnetic brush type, a blade type, etc. ) Is contacted and a predetermined charging bias is applied to the contact charging member to charge the surface of the body to be charged to a predetermined polarity and potential.

Charging mechanism of contact charging (charging mechanism,
The charging principle) includes a discharge charging mechanism and a direct injection charging mechanism.
There are mixed types of charging mechanisms, and each characteristic appears depending on which one is dominant.

The discharge charging system is a system in which the surface of an object to be charged is charged by a discharge phenomenon occurring in a minute gap between a contact charging member and an object to be charged.

Since the discharge charging system has a constant discharge threshold between the contact charging member and the member to be charged, it is necessary to apply a voltage higher than the charging potential to the contact charging member. Further, although the amount of generation is much smaller than that of the corona charger, the generation of discharge products is inevitable in principle, so that the harmful effect of active ions such as ozone is unavoidable.

The injection charging system is a system in which charges are directly injected from the contact charging member to the body to be charged to charge the surface of the body to be charged.

It is called injection charging or direct charging. More specifically, a medium-resistance contact charging member comes into contact with the surface of the member to be charged and directly injects the charge into the surface of the member to be charged without a discharge phenomenon, that is, basically without using discharge. Therefore, even if the applied voltage to the contact charging member is equal to or lower than the discharge threshold value, the charged body can be charged to a potential corresponding to the applied voltage.

Since this charging system is not accompanied by generation of active ions such as ozone, no harm is caused by discharge products. However, the contact property of the contact charging member to the member to be charged greatly affects the charging property. Therefore, it is necessary to make the contact charging member more dense, have a large speed difference from the charged body, and contact the charged body more frequently.

The following methods have been proposed as typical contact charging processes.

(A) Roller charging In the contact charging device, a roller charging method using a conductive roller (charging roller) as a contact charging member is preferable from the viewpoint of charging stability and is widely used. The charging mechanism of the roller charging is dominated by the discharge charging system. The charging roller is made of a conductive or medium-resistance rubber material or foam. Further, these are laminated to obtain desired characteristics.

The roller charging method includes a "DC charging method" in which voltage is applied only by DC and an "AC" method in which AC is superimposed.
There is a charging method. The DC charging method is a voltage Vd that is a threshold voltage at which charging is started, that is, a charging start voltage Vth, plus a surface potential Vd of a desired object to be charged (hereinafter referred to as a photoconductor).
In this method, + Vth is applied to perform charging. But D
In the C charging method, the resistance value of the contact charging member fluctuates due to environmental changes and the Vth fluctuates when the film thickness changes due to abrasion of the photoconductor, so that the potential of the photoconductor is set to a desired value. It was difficult and the charging could not be made uniform. Therefore, in order to make the charging uniform and improve the charging property, as disclosed in Japanese Patent Laid-Open No. 63-149669, an AC component having a peak-to-peak voltage twice or more Vth is superposed on a DC voltage corresponding to a desired Vd. The "AC charging method" of applying a voltage to the contact charging member was used. It converges to Vd, which is the center of the peak, and is not affected by disturbances such as the environment.

However, in this roller charging method, the essential charging mechanism uses the discharge phenomenon from the contact charging member to the photosensitive member, and even in the "DC charging method", the voltage applied is a value higher than the surface potential of the photosensitive member. Is required and a minute amount of ozone is generated. Further, when the "AC charging method" is used for uniform charging, a larger amount of ozone is generated.
The generation of vibration noise (charging sound) between the contact charging member and the photoconductor due to the electric field of voltage, and the deterioration of the photoconductor surface due to discharge have become remarkable, which has become a new problem.

(B) Fur brush charging For fur brush charging, a member (fur brush charger) having a conductive fiber brush portion is used as a contact charging member.
The conductive fiber brush portion is brought into contact with a photoconductor as a member to be charged, and a predetermined charging bias is applied to charge the surface of the photoconductor to a predetermined polarity and potential. The charging mechanism of this fur brush charging is dominated by the discharge charging system.

As the fur brush charger, a fixed type and a roll type have been put into practical use. A fixed type is made by folding a medium resistance fiber into a base cloth and forming it on a pile and adhering it to an electrode. The roll type is formed by winding the pile around a core metal. As for the fiber density, the contact property is still insufficient for uniform charging, and in order to perform sufficiently uniform charging by injection charging, it is necessary to give the photosensitive member a speed difference such that the mechanical constitution is difficult. Yes, not realistic.

Also in the case of this fur brush charging, in both the fixed type and the roll type, a high charging bias is applied and charging is performed using discharge charging.

(C) Magnetic brush charging For magnetic brush charging, a member (magnetic brush charger) having a magnetic brush portion formed on the brush by magnetically restraining conductive magnetic particles with a magnet roll or the like is used as a contact charging member. The magnetic brush portion is brought into contact with a photoconductor as a member to be charged and a predetermined charging bias is applied to charge the surface of the photoconductor to a predetermined polarity and potential. The charging mechanism in the case of this magnetic brush charging is dominated by the injection charging system.

By using conductive magnetic particles having a particle diameter of 5 to 50 μm as the magnetic brush portion and providing a sufficient speed difference from the photosensitive member, uniform injection charging can be performed. However, there are other adverse effects such as a complicated device configuration, conductive particles forming the magnetic brush portion falling off and adhering to the photoconductor.

(D) Charged Particle-Mediated Charging In the charged particle-mediated charging, a photosensitive member, which is a contact charging member in which charged particles are constrained by an elastic foam roller or the like, forming an nip portion with the photosensitive member is a photosensitive member. Touch the body,
A predetermined charging bias is applied to charge the surface of the photoconductor to a predetermined polarity and potential. The charging mechanism is dominated by the injection charging system.

Compared with the above-mentioned magnetic brush charging, there are advantages such as a simpler device configuration.

On the other hand, an approach has been taken so that contact injection charging can be performed from the electrophotographic photosensitive member as well. For example, Japanese Patent Laid-Open No. 6-3921 discloses a trap level or a charge injection layer on the photosensitive member surface. A method has been proposed in which charges are injected into a charge holding member such as conductive particles to perform contact injection charging. Since this does not use the discharge phenomenon, the voltage required for charging is only the desired surface potential of the photoconductor, and ozone is not generated. Furthermore, since no AC voltage is applied, no charging noise is generated, and compared to the roller charging method, it is an ozone-less and low-power excellent charging method.

In addition, as a matter of course, the electrophotographic photosensitive member
It is required to have the required sensitivity, electrical properties and optical properties according to the applied electrophotographic process. Particularly, in the case of a photoconductor that is repeatedly used, the surface of the photoconductor is directly subjected to electrical or mechanical external force such as charging, image exposure, toner development, transfer to paper, and cleaning. Durability is required. In particular,
It is required to have durability against abrasion and scratches on the surface of the photoconductor caused by rubbing on the surface of the photoconductor during transfer or cleaning, and deterioration of the photoconductor and potential characteristics due to ozone and charging products generated during charging. Further, there is also a problem that toner adheres to the surface of the photoconductor due to repeated toner development and cleaning, and good cleaning properties are also required.

In order to satisfy the characteristics required for the photoreceptor as described above, attempts have been made to provide a surface protective layer containing a resin as a main component on the photosensitive layer. For example, JP-A-56-
It is proposed in JP-A-42863 and JP-A-53-103741 to improve hardness and wear resistance by providing a surface protective layer containing a curable resin as a main component.

Further, in order to obtain a better image, the surface protective layer of the photoconductor should have not only the characteristics such as high hardness and excellent abrasion resistance but also the resistance of the surface protective layer itself. Required. If the resistance is too low, the electrostatic latent image flows in the surface protective layer in the surface direction, and problems such as image bleeding and blurring occur. However, when the resistance of the surface protective layer is too high, by repeating the electrophotographic process such as charging-exposure, electric charges are accumulated in the surface protective layer, so-called residual potential increases, and the potential is increased during repeated use of the photoconductor. Is not stable, the image quality becomes unstable. To solve this problem, for example, JP-A-57-30843 proposes to control the resistance of the layer by adding a metal oxide as conductive fine particles to the surface protective layer.

Further, the surface of the metal oxide has high water absorption, and the resistance of the surface protective layer changes depending on the degree of water absorption. Therefore, the resistance depends on the environment, and the metal oxide is added only as conductive fine particles. Then, it was difficult to suppress the resistance to a proper value in all environments. In order to solve this problem, for example, Japanese Patent Laid-Open No. 62-295066 discloses a surface protection in which a fine metal powder or a fine metal oxide powder having a water repellent treatment and improved dispersibility and moisture resistance is dispersed in a binder resin. It has been proposed to control the resistance of the layer by providing it.

In recent years, environmental problems have been greatly highlighted, and many systems have been proposed that do not produce waste toner than electrophotographic apparatuses. This is usually called a toner recycling process (cleanerless system). For example, in a transfer type electrophotographic apparatus, transfer residual toner remaining on the photoconductor after transfer is removed from the photoconductor surface by a cleaner (cleaning device). It becomes waste toner, but there is no cleaner there, and the transfer residual toner on the photoconductor after transfer is removed from the photoconductor by the developing device and collected and reused in the developing device. Have been proposed.

The development / cleaning means that the toner remaining on the photoconductor after transfer is defoamed by the fog removal bias (potential difference between the DC voltage applied to the developing device and the surface potential of the photoconductor) at the time of development in the subsequent steps. Potential difference Vback)
It is a method of collecting by. According to this method, the transfer residual toner is collected by the developing device and reused in the subsequent steps, so that it is possible to eliminate the waste toner and reduce the troublesome maintenance. In addition, the so-called cleanerless structure, which does not have an independent cleaning means, has a large space advantage, and the electrophotographic apparatus can be significantly downsized, which is a great advantage in addition to environmental problems.

In the discharge charging system, (1) the applied voltage needs to be higher than the surface potential of the photoconductor, (2) ozone is generated in a small amount, and (3) the "AC charging method" is used for uniform charging. More ozone is generated,
(4) Vibration noise (charging sound) of the contact charging member and the photoconductor due to the electric field of the AC voltage is generated, and (5) Deterioration of the photoconductor surface due to discharge becomes significant.

On the other hand, when the injection charging system is predominant, these problems are greatly improved, and in particular, charged particle-mediated charging has an advantage that the device structure is simple.

On the other hand, an approach has been proposed in which contact injection charging can be performed from the electrophotographic photosensitive member, that is, a method of injecting charges into a charge holding member such as conductive particles in the charge injection layer to perform contact injection charging. There is. Since this does not use the discharge phenomenon, the voltage required for charging is only the desired surface potential of the photoconductor, and ozone is not generated. Furthermore, AC
Since no voltage is applied, no charging noise is generated, and compared to the roller charging method, it is an ozone-less and low-power excellent charging method.

Further, in order to improve the charging property, the contact property between the charging device (charged particles) and the photoconductor as the member to be charged, specifically, the charge injection layer (surface protection layer), that is, the contact area and the contact probability are increased. Is effective. As a specific method, the particle diameter of the charged particles is reduced, the distance between the charged particles is increased, that is, the density is increased, the carrier of the charged particles is rotated in the opposite direction to the photoconductor (counter rotation), Alternatively, there is a method of making a difference in peripheral speed between the carrier and the photoconductor.

By combining these, it is possible to eliminate the problems as described above and to improve the charging property with a simple device configuration. However, under these conditions for improving the charging property, peeling occurred between the photosensitive layer of the photoconductor and the charge injection layer (surface protective layer), and it became impossible to repeatedly use the layer. That is, if the particle size of the charged particles is small, the charging property is improved, but the surface area of the charged particles is increased, the contact area between the charged particles and the photoconductor surface is increased, and the local pressure in the direction perpendicular to the photoconductor surface and And / or shear stress is repeatedly applied for a long period of time, and peeling occurs between the photosensitive layer of the photoconductor and the charge injection layer (surface protective layer), and the difference in chargeability between the peeled portion and the non-peeled portion, that is, the potential difference. Appears as uneven density on the image,
There was a problem that it could not be used repeatedly. In addition, even when a charged particle carrier having an elastic surface and carrying charged particles is used, the charging property is improved as compared with the case where there is no elasticity, but the contact between the carrier or charged particles and the surface of the photoconductor The area becomes large, and it is still subject to local pressure and / or shear stress in the direction perpendicular to the photoreceptor surface for a long time, and it becomes easier to peel off with repeated use,
The same problem of uneven density occurred.

[0035]

SUMMARY OF THE INVENTION It is an object of the present invention to provide the above-mentioned advantages, that is, the voltage required for charging is only the desired surface potential of the photoconductor, without the generation of ozone or the generation of charging noise. An object is to provide a highly durable electrophotographic photosensitive member that can withstand repeated use, an electrophotographic apparatus having the electrophotographic photosensitive member, and a process cartridge while maintaining advantages such as low power consumption and a simple device configuration.

[0036]

According to the present invention, charged particles having conductive particles having a particle size of 10 μm to 10 nm as a main component and a surface having conductivity and elasticity and carrying the charged particles are provided. In an electrophotographic photoreceptor for use in an electrophotographic apparatus, which comprises a particle carrier, the charged particles come into contact with the electrophotographic photoreceptor and directly inject charges into the surface of the photoreceptor to charge the electrophotographic photoreceptor. Having at least a photosensitive layer containing a charge-transporting material represented by the following formula (1), (2), (3) or (4) and a surface protective layer containing conductive particles on a conductive support. A photographic photoreceptor is provided.

Further, according to the present invention, there are provided an electrophotographic apparatus and a process cartridge provided with the above electrophotographic photosensitive member.

[0038]

[Chemical 2]

In the formula, Ar _{1 to} Ar ₄ and Ar ₆ represent an aryl group which may have a substituent, and Ar ₅ and Ar _{7 to} Ar _6
10 represents an arylene group which may have a substituent. R ₁ ~
R ₉ represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, a vinyl group which may have a substituent or an aryl group which may have a substituent. X is an alkylene group which may have a substituent, an arylene group which may have a substituent, CR ₁₀ = CR ₁₁ (R ₁₀ and R ₁₁ are an alkyl group which may have a substituent and a substituent An aryl group or a hydrogen atom which may be present), C = O, S = O, S
_{O 2, -NR 12 - (R} 1 2 represents an optionally substituted alkyl group, an aryl group which may have a substituent), combined in one or optionally more oxygen atom or a sulfur atom The organic residues are shown. However, at least two of R _{2 to} R ₅ and at least two of R _{6 to} R ₉ are aryl groups which may have a substituent.

Ar ₁ and Ar ₂ , R ₁ and Ar ₄ , R ₂ and R ₃ , R ₄ and R ₅ , R ₆ and R ₇ or R ₈ and R ₉ are directly or —C.
_{H 2 -, - CH 2 CH} 2 -, - CH = CH -, - O -, -
A ring may be formed via another organic residue such as S-, A
r ₅ and Ar ₆ or Ar ₇ and Ar ₈ may form a ring via a divalent organic residue, and in particular, —O—, —S—, —SO _{2
-, - NR 13 -, -} CR 14 = CR 15 -, - CR 16 R 17 -
Is preferred (R _{13 to} R ₁₇ represent an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent or a hydrogen atom) .

In the present invention, the aryl group includes aromatic hydrocarbon groups such as phenyl group, naphthyl group, anthracenyl group and pyrenyl group; pyridyl group, quinolyl group, thienyl group, furyl group, carbazolyl group, benzimidazolyl group and benzothiazolyl group. And a heterocyclic group such as a group; examples of the alkylene group include a methylene group, an ethylene group,
Examples of the arylene group include groups having 1 to 10 carbon atoms such as a propylene group and a butylene group; an aromatic hydrocarbon such as a benzene group, a naphthalene group, an anthracene group, and a pyrene group; or a pyridine group, a quinoline group, and a thiophene group. And a divalent aromatic hydrocarbon group or a heterocyclic group obtained by removing two hydrogen atoms from a heterocycle such as a furan group; examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and A hexyl group and the like; an aralkyl group includes
Examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group and a furfuryl group.

Examples of the substituent that these groups may have include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group; a methoxy group,
Examples thereof include alkoxy groups such as ethoxy group and butoxy group; examples of halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; examples of aromatic hydrocarbon groups such as phenyl group and naphthyl group; pyridyl group. Heterocyclic groups such as quinolyl group, thienyl group and furyl group; acyl groups such as acetyl group and benzyl group; alkylamino groups such as dimethylamino group, haloalkyl groups such as trifluoromethyl group, cyano Group, nitro group, phenylcarbamoyl group, carboxyl group, hydroxyl group and the like.

It is particularly preferable that all of R _{1 to} R _{9 in} the above formulas (2) to (4) are aryl groups.

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

First, the electrophotographic photosensitive member according to the present invention will be described in detail. The electrophotographic photosensitive member of the present invention has a structure having at least a photosensitive layer containing a charge transport material having a specific structure and a conductive surface protective layer on a conductive support.

The support used in the present invention may be any support as long as it has conductivity, and examples thereof include metals and alloys such as aluminum, chromium, nickel, stainless, copper and zinc, and metals such as aluminum and copper. Laminated foil with plastic film, aluminum,
Examples thereof include those obtained by vapor-depositing indium oxide, tin oxide, and the like on a plastic film, or metals, plastic films, and paper on which a conductive layer is formed by coating a conductive substance alone or with an appropriate binder resin.

As the conductive substance used in this conductive layer, metal powder such as aluminum, copper, nickel and silver,
Metal foils and metal fibers, conductive metal oxides such as antimony oxide, indium oxide and tin oxide, polymer conductive materials such as polypyrrole, polyaniline and polymer electrolytes, carbon black, graphite powder and organic or inorganic electrolytes or these Conductive powder whose surface is coated with a conductive substance of

Examples of the shape of the support include a drum shape, a sheet shape and a belt shape, but it is preferable that the shape is any shape most suitable for the electrophotographic apparatus to which the support is applied.

An undercoat layer may be provided between the support and the photosensitive layer. The undercoat layer functions as a barrier layer or an adhesive layer for controlling charge injection at the interface with the photosensitive layer. The undercoat layer is mainly composed of a binder resin, but may contain the above-mentioned metals or alloys, or their oxides, salts and surfactants.

The binder resin forming the undercoat layer is polyester, polyurethane, polyacrylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, phenol resin, acrylic resin, silicone resin, epoxy resin, urea resin. , Aryl resins, alkyd resins, polyamideimides, polysulfones, polyallyl ethers, polyacetals and butyral resins. The thickness of the undercoat layer is preferably 0.05 to 7 μm, more preferably 0.1 to 2 μm.

The photosensitive layer has at least the above formula (1),
It is basically constituted by combining a charge transporting material composed of the specific amine compound represented by (2), (3) or (4) with an appropriate charge generating material.

Typical examples of the compounds represented by the formulas (1) to (4) are shown in Table 1 below. However, it is not limited to these compounds.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

[Table 4]

[0057]

[Table 5]

[0058]

[Table 6]

[0059]

[Table 7]

[0060]

[Table 8]

[0061]

[Table 9]

[0062]

[Table 10]

[0063]

[Table 11]

[0064]

[Table 12]

[0065]

[Table 13]

[0066]

[Table 14]

[0067]

[Table 15]

[0068]

[Table 16]

[0069]

[Table 17]

[0070]

[Table 18]

[0071]

[Table 19]

[0072]

[Table 20]

[0073]

[Table 21]

[0074]

[Table 22]

[0075]

[Table 23]

[0076]

[Table 24]

[0077]

[Table 25]

[0078]

[Table 26]

[0079]

[Table 27]

[0080]

[Table 28]

[0081]

[Table 29]

[0082]

[Table 30]

[0083]

[Table 31]

[0084]

[Table 32]

[0085]

[Table 33]

[0086]

[Table 34]

[0087]

[Table 35]

[0088]

[Table 36]

[0089]

[Table 37]

[0090]

[Table 38]

[0091]

[Table 39]

The photosensitive layer of the electrophotographic photosensitive member of the present invention is composed of a single layer type containing a charge generating material and a charge transporting material in the same layer, or a charge transporting layer containing a charge transporting material and a charge generating material. The charge-generating layer may be a laminated type having a functionally separated layer, but the laminated type is preferable in terms of electrophotographic characteristics. Further, a laminated type photosensitive layer in which a charge transport layer is laminated on the charge generation layer is preferable. This form will be described below.

The charge generation layer in the present invention is formed as a uniform layer in which the charge generation material is formed by a method such as vapor deposition or sputtering, or a dispersion liquid in which the charge generation material is dispersed in a binder resin is applied and dried. It is formed by

Examples of the effective charge generating material used in the present invention include the following materials. These charge generating 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 pigments such as metal phthalocyanine and non-metal phthalocyanine (4) Perylene anhydride, perylene acid Perylene pigments such as imides (5) Polycyclic quinone pigments such as anthraquinone and pyrenequinone (6) Squarylium dye (7) Pyrylium salts, Thiopyrylium salts (8) Triphenylmethane dyes (9) Selenium, amorphous silicon Inorganic materials such as

The binder resin can be selected from a wide range of binder resins, for example, polyester resin, butyral resin, polystyrene resin, polyvinyl acetal resin,
Diallyl phthalate resin, acrylic resin, methacrylic resin, vinyl acetate resin, phenol resin, silicone resin, polysulfone resin, styrene-butadiene copolymer resin, alkyd resin, epoxy resin, urea resin and vinyl chloride-vinyl acetate copolymer resin, etc. Can be mentioned,
It is not limited to these. You may use these individually or in mixture of 2 or more types as a homopolymer or a copolymer polymer.

The resin contained in the charge generating layer is preferably 80% by mass or less, and particularly preferably 40% by mass or less.
The thickness of the charge generation layer is preferably 5 μm or less, and particularly preferably a thin film layer having a thickness of 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 has at least the above formula (1), as described above.
It can be formed by combining a charge-transporting material composed of the specific amine compound represented by (2), (3) or (4) with a suitable binder resin. Examples of the binder resin used in the charge transport layer include those used in the charge generation layer, and further include photoconductive polymers such as polyvinylcarbazole and polyvinylanthracene.

As the charge transport material, the above formula (1),
1 of the amine compound represented by (2), (3) or (4)
They may be used alone or in combination of two or more, and also have a charge transport material having another structure [for example, polycyclic aromatic compounds such as pyrene and anthracene, carbazole type, indole type, oxazole type, thiazole type, oxadiene Heterocyclic compounds such as azole-based, pyrazole-based, pyrazoline-based, thiadiazole-based and triazole-based compounds, triarylmethane-based compounds, or polymers having a group composed of these compounds in the main chain or side chain (for example, poly-
N-vinylcarbazole, polyvinylanthracene, etc.)] and the like.

The mixing ratio of the binder resin and the charge transport material is
10-50 parts of charge transport material per 100 parts by mass of binder resin
It is preferably 0 part by mass. The charge transport layer is electrically connected to the above 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 has a limit to transport charge carriers, the film thickness cannot be increased more than necessary, but it is preferably 5 μm to 40 μm, and particularly preferably 10 μm to 30 μm.

Further, additives such as an antioxidant, an ultraviolet absorber and a plasticizer may be added to the charge transport layer as needed.

In forming such a charge transport layer, a suitable organic solvent is used and a coating method such as a dip coating method, a spray coating method, a spinner coating method, a roller coating method, a Mayer bar coating method and a blade coating method. Can be done using.

The photosensitive layer in the single-layer type electrophotographic photosensitive member is formed by coating and drying a liquid in which the charge generating material and the charge transporting material are dissolved and dispersed in the resin. The thickness of the single-layer type photosensitive layer is preferably 5 to 40 μm, particularly preferably 10 to 30 μm.

As the binder resin for the surface protective layer used in the present invention, a curable resin is more preferable because it has a high surface hardness and excellent abrasion resistance. Examples of curable resins include, but are not limited to, acrylic resins, urethane resins, epoxy resins, and silicone resins.

In the present invention, examples of the conductive particles used in the surface protective layer include metals, metal oxides and carbon black, with metals and metal oxides being preferred.
Examples of the metal include aluminum, zinc, copper, chromium, nickel, silver, stainless steel, and the like, or those obtained by vapor-depositing these metals on the surface of plastic particles. As the metal oxide, zinc oxide, titanium oxide, tin oxide,
Examples thereof include antimony oxide, indium oxide, bismuth oxide, indium oxide doped with tin, tin oxide doped with antimony or tantalum, and zirconium oxide doped with antimony. These may be used alone or in combination of two or more. When two or more kinds are used in combination, they may be simply mixed, or may be in the form of solid solution or fusion.

The content of the conductive particles is preferably 5 to 90% by mass based on the total mass of the surface protective layer. If it is less than 5% by mass, the resistance value of the surface protective layer may be too high, and if it is more than 90% by mass, the resistance of the surface layer of the photoconductor tends to be low, which may cause deterioration of charging ability and pinholes. .

In the present invention, it is particularly preferable to use a metal oxide among the above-mentioned conductive particles from the viewpoint of transparency.

Further, from the viewpoint of reducing the water absorption of the conductive particles and suppressing the environmental fluctuation of the resistance of the surface protective layer, it is preferable to subject the surface of the metal or metal oxide to a water repellent treatment. Examples of the treatment agent used for the water repellent treatment include compounds such as titanate coupling agents, fluorine-containing silane coupling agents, fluorine-modified silicone oils, fluorine-based surfactants, and acetoalkoxyaluminum diisopropylate.

When conductive particles are dispersed in the surface protective layer,
In order to prevent scattering of incident light by dispersed particles, it is preferable that the particle system is smaller than the wavelength of incident light, and generally, the number average particle diameter is preferably 0.3 μm or less.

Further, in the cleaning process for removing the residual toner, the most common blade cleaning method always has a problem of blade reversal. This is a problem that occurs because the frictional force between the surface of the photoreceptor and the blade is very high, and blade reversal occurs when a certain threshold is exceeded. Therefore, in the surface protective layer of the present invention, it is preferable to add lubricating particles to the surface protective layer in order to reduce the frictional force on the surface of the photoreceptor.

As the lubricating particles, fluorine atom-containing resin particles, silicon particles, alumina particles and silicone particles are preferable, and among them, fluorine atom-containing resin particles are preferable. Fluorine atom-containing resin particles and silicone particles are
Due to the low surface energy and the cleavage of the particles themselves, slippage occurs, and in the case of silicon particles and alumina particles, the slippage effect by the particles themselves does not occur, but by dispersing these particles in the film, it becomes There is an effect that unevenness is generated, and as a result, the frictional force with the contacting object is reduced.

Examples of the fluorine atom-containing resin include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polydichlorodifluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene. Examples of the resin include one or two or more selected from the group consisting of a copolymer, a tetrafluoroethylene-ethylene copolymer and a tetilafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer. .
It is also possible to use commercially available fluorine atom-containing resin fine particles as they are. The molecular weight is preferably 3,000 to 5,000,000. The particle size is preferably 0.01 to 10 μm, and particularly preferably 0.05 to 2.0 μm.

In the present invention, various coupling agents and antioxidants may be added to the surface protective layer in order to further improve dispersibility, adhesiveness, environment resistance and the like.

The film thickness of the surface protective layer in the present invention is 0.1.
It is preferably from 10 to 10 μm, and particularly preferably from 1 to 7 μm.

The above surface protective layer can be formed by vapor deposition or coating. In particular, the coating method is preferable because it is possible to form films having various compositions over a wide range from thin films to thick films. Examples of the coating method include a dip coating method, a spray coating method, a beam coating method, a bar coating method, a blade coating method and a roller coating method.

The problems of the present invention are solved by making the electrophotographic photosensitive member have the above-mentioned constitution. That is, the particle size is 10 μm
Charged particles having conductive particles of 10 nm as a main component,
It is composed of a charged particle carrier that has a surface having conductivity and elasticity and carries the charged particles, and the charged particles come into contact with the electrophotographic photosensitive member and directly charge the surface of the photosensitive member to be charged. Since the electrophotographic photoreceptor used in the electrophotographic apparatus has a photosensitive layer containing a charge transporting material of an amine compound having at least a specific structure and a surface protective layer containing conductive particles on a conductive support, electrostatic charging is achieved. The required voltage is only the desired surface potential of the photoconductor, no ozone or charging noise is generated, low power consumption and a simple device configuration, etc. , Peeling does not occur between the photosensitive layer of the photoreceptor and the charge injection layer (surface protective layer), and the difference in chargeability between the peeled portion and the non-peeled portion,
That is, the problem of uneven density on the image due to the potential difference is eliminated.

More specifically, the smaller the particle size of the charged particles is, the better the charging property is. However, since the surface area of the charged particles is large, the contact area between the charged particles and the surface of the photoconductor is large and the surface of the photoconductor is large. And local pressure and / or shear stress in the vertical direction will be repeatedly applied for a long period of time, and the photosensitive layer of the photoconductor and the charge injection layer (surface protection layer)
Peeling occurs between the two, the difference in the charging property of the peeled portion and the non-peeled portion, that is, the potential difference appears as density unevenness on the image,
It can solve the problem that it cannot withstand repeated use.
Further, even in the case of using a charged particle carrying member having an elastic surface and carrying charged particles, the problem of uneven density due to similar peeling can be solved. This is because the adhesion between the photosensitive layer and the charge injection layer (surface protective layer) was improved, and peeling did not occur, and it is considered that this is due to the structure of the charge transport material contained in the photosensitive layer. To be That is, the amine compound represented by the formula (1), (2), (3) or (4) is bonded to an aryl group which may have a substituent under the conditions according to the above formulas. It is considered that the use of such amino group provides adhesiveness, maintains injection chargeability even after repeated use, does not cause image density unevenness, and achieves high durability and long life.

A specific example of an electrophotographic apparatus using the electrophotographic photosensitive member of the present invention is shown in FIG. In this apparatus, a primary charging member 2, an exposing unit 5, a developing unit 6, and a transferring unit 7 are arranged on the peripheral surface of an electrophotographic photosensitive member 1.

In the image forming method, first, a voltage is applied to the primary charging member 2 to charge the surface of the photoreceptor 1 and then the exposing means 5 is used.
To expose the image corresponding to the original on the surface of the photoconductor 1,
Form an electrostatic latent image. Next, the toner in the developing device 6 is attached to the photoconductor 1 to develop (visible) the electrostatic latent image on the photoconductor 1. Furthermore, the toner image formed on the photoconductor 1 is transferred onto the transfer material P such as paper supplied by the transfer means 7, and the residual toner remaining on the photoconductor 1 without being transferred to the transfer material is cleaned by a cleaner or the like. To collect. In recent years, cleanerless systems have also been studied, and residual toner can be directly collected by a developing device. Further, after the static elimination processing is performed by the pre-exposure from the pre-exposure means, it is repeatedly used for image formation. The pre-exposure means is not always necessary.

In the electrophotographic apparatus shown in FIG. 1, the light source of the exposing means 5 is halogen light, fluorescent lamp, laser light or LE.
D or the like can be used. Also, other auxiliary processes may be added if necessary.

In the present invention, among the components such as the photoconductor 1, the primary charging unit 2, the developing unit 6 and the cleaning unit described above, a plurality of components are integrally combined as a process cartridge, and this process cartridge is constructed. It may be detachably attached to the main body of an electrophotographic apparatus such as a copying machine or a printer. For example, at least one of the primary charging unit 2, the developing unit 6, and the cleaning unit is integrally supported together with the photosensitive member 1 to form a cartridge, and the process cartridge is detachably attached to the apparatus body by using the guide means such as the rail 10 of the apparatus body. It can be 9. Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light L uses reflected light or transmitted light from the original. Alternatively, it is light emitted from a signalized document by scanning a laser beam, driving an LED array, driving a liquid crystal shutter array, or the like performed according to the signal.

The charging device of the present invention shown in FIG. 2 comprises a conductive elastic roller 2 (hereinafter referred to as a charging roller) and conductive particles 3 (hereinafter referred to as a charged particle) mainly for promoting charging. It is composed of a regulating member 4 which is a charged particle supplying means. The photoconductor 1 is charged with the charged particles 3 applied to the contact nip between the charging roller and the electrophotographic photoconductor 1. As a result, the charging roller 2 can come into contact with the electrophotographic photosensitive member 1 with a speed difference, and at the same time, the charge can be directly injected into the photosensitive member 1 densely via the charged particles 3. Therefore, in the present invention, a high charging efficiency, which has not been obtained by the conventional roller charging, can be obtained, and a potential substantially equal to the potential applied to the charging member can be applied to the photoconductor. Therefore, the bias required for charging is sufficient to be a voltage corresponding to the potential required for the photoconductor, and a safe charging system that does not use the discharge phenomenon is realized.

Next, the main constituent members of the charger used in the present invention will be described.

<Charging Roller> The charging roller 2 is manufactured by forming the medium resistance layer 2b of rubber or foam on the cored bar 2a. The medium resistance layer 2b includes a resin (for example, urethane), conductive particles (for example, carbon black),
Formulated with a sulfiding agent, a foaming agent, etc., it was formed into a roller shape on the cored bar 2a. After that, the surface was polished as needed to prepare an elastic conductive roller 2 having a diameter of 12 mm and a longitudinal length of 250 mm. When the roller resistance of this example was measured, it was 100 kΩ. Total pressure 1 on the core of roller 2
100 V was applied to the core metal 2a and the aluminum drum in a state of being pressure-bonded to an aluminum drum having a diameter of 30 mm so as to apply a load of kg, and measurement was performed. Here, the elastic roller 2
Is important to function as an electrode. That is, it is necessary to have elasticity to obtain a sufficient contact state, and at the same time, to have a sufficiently low resistance to charge the moving photoconductor. On the other hand, it is necessary to prevent voltage leakage when a defective portion such as a pinhole exists on the photoconductor. When an organic photoconductor is used as the electrophotographic photoconductor, a resistance of 10 ⁴ to 10 ⁷ Ω is preferable in order to obtain sufficient chargeability and leak resistance.

If the hardness of the charging roller is too low, the shape of the charging roller is not stable, so that the contact property is poor. If the hardness is too high, not only the charging nip cannot be secured, but also the micro contact property to the surface of the photoconductor is deteriorated. The Asker C hardness is preferably in the range of 25 degrees to 50 degrees.

The material of the charging roller is not limited to the elastic foam, but the material of the elastic body may be EPD.
Examples thereof include M, urethane, NBR, silicone rubber, a rubber agent in which a conductive substance such as carbon black or a metal oxide is dispersed in IR or the like for resistance adjustment, or a material obtained by foaming these. In addition, especially without dispersing a conductive substance,
It is also possible to adjust the resistance by using an ion conductive material.

The charging member is not limited to the charging roller, and an elastic body such as a fur brush in which each pile has elasticity can be used. Here, the fur brush roller has a resistance-adjusted fiber (Rec made by Unitika) planted at a density of 155 fibers / mm ² and a fiber length of 3 mm to form a pile, after which the pile is wound and fixed on a core metal of φ6 mm, It is formed into a roller shape.

<Charged particles> In this embodiment, the specific resistance is 10
Conductive zinc oxide particles 3 having an average particle diameter of ⁶ μm · 3 μm were used. As the material for the particles, various conductive particles such as conductive inorganic particles such as other metal oxides and a mixture with an organic substance can be used. Here, the particle resistance is preferably 10 ¹⁰ Ω · cm or less in order to transfer charges through the particles. Here, the resistance was measured by the tablet method and normalized. A powder sample of about 0.5 g was placed in a cylinder with a bottom area of 2.26 cm ² , 15 kg of pressure was applied to the upper and lower electrodes, a voltage of 100 V was applied at the same time, and the resistance value was measured. Was calculated. The particle size is preferably 50 μm or less in order to obtain good charging uniformity. The lower limit of the particle size is 10 assuming that the particles can be stably obtained.
nm is the limit. In the present invention, the particle size when the particles are formed as an aggregate is defined as the average particle size of the aggregate. To measure the particle size, 100 or more are extracted from observation with an optical or electron microscope, and the volume particle size distribution is calculated with the maximum chord length in the horizontal direction, and 50% of that is calculated.
It was determined by the average particle size.

The method for measuring the charge amount of the charged particles in the present invention will be described below with reference to FIG. 23 ° C / 60% relative humidity
% Environment, iron powder carrier DSP-138, 19.6
A mixture of g with charged particles and 0.4 g is put in a polyethylene bottle having a volume of 50 to 100 ml and shaken by hand 50 times. Next, 1.0 to 1.2 g of the mixture is put into a metal measuring container 92 having a 500-mesh screen 93 on the bottom, and a metallic lid 94 is placed on it. At this time, the total mass of the measurement container 92 is weighed and set as W1 (g). Next, the suction device 91
(At least the portion in contact with the measurement container 92 is an insulator), suction is performed from the suction port 97, the air flow rate control valve 96 is adjusted, and the pressure of the vacuum gauge 95 is set to 4900 hPa. In this state, suction is performed for 1 minute to remove the toner by suction. The potential of the electrometer 99 at this time is V (volt). Here, 98 is a capacitor, and the capacitance is C (μF). In addition, the mass of the entire measurement container after suction is weighed and is W2 (g). The triboelectric charge amount (μC / g) of this toner is calculated by the following mathematical formula (1).

[0130]     Triboelectric charge amount (μC / g) = CV / (W1-W2) (1)

The triboelectric charge amount of the electrically conductive particles for charging used in the present invention with respect to the iron powder carrier was +5 μC / g.

If the contact frequency between the charging member and the electrophotographic photosensitive member is high, the charge can be injected more efficiently. That is, the particle size and density of the charged particles, the elasticity of the carrier that carries the charged particles, and the like influence. Alternatively, the charging member can inject charges more efficiently by giving a speed difference to the surface of the body to be charged, that is, the surface of the electrophotographic photosensitive member. The charging member and the electrophotographic photosensitive member are preferably rotated in opposite directions, that is, counter rotated. That is, a good condition for these charging means is that damage to the electrophotographic photosensitive member becomes large, which causes a film shift or peeling between the photosensitive layer and the surface protective layer. If deviation or peeling occurs, the chargeability deteriorates, resulting in image defects such as unevenness on the image.

[0133]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, "part" in an Example shows a mass part.

Example 1 Using a 30 mmφ aluminum cylinder (JIS A3003 aluminum alloy) as a support, a 5% by mass methanol solution of a polyamide resin (trade name: Amilan CM8000, manufactured by Toray) was applied on the support by a dipping method. Then, it was dried to form an undercoat layer having a film thickness of 1 μm.

Next, as a charge generation material, the Bragg angle (2θ ± 2) in CuKα characteristic X-ray diffraction represented by the following formula:
4 parts of oxytitanium phthalocyanine pigment which is a crystalline form having strong peaks at 9.6 ° and 27.2 ° of 0.2 °,

[0136]

[Chemical 3] Polyvinyl butyral resin (Product name: S-REC BX-
2 parts of Sekisui Chemical Co., Ltd. and 110 parts of cyclohexanone were dispersed in a sand mill for 4.5 hours using φ1 mm glass beads, and then 130 parts of ethyl acetate was added to prepare a coating liquid for the charge generation layer. did. This coating solution is applied onto the undercoat layer prepared above by dip coating and dried to give a film thickness of 0.1.
An 8 μm charge generation layer was formed.

Then, the amine type compound Nos. 1
7.5 parts, bisphenol Z type polycarbonate (trade name: Z-200, manufactured by Mitsubishi Gas Chemical Co., Inc.) 10 parts,
It was dissolved in 60 parts of monochlorobenzene / 20 parts of dichloromethane. This solution is applied onto the charge generation layer by dip coating,
It was dried with hot air at 10 ° C. for 1 hour to form a charge transport layer having a film thickness of 20 μm.

Next, as a protective layer, antimony-doped tin oxide fine particles were surface-treated with 7 parts of a fluorine atom-containing compound of the following formula (trade name: LS-1090, manufactured by Shin-Etsu Silicone Co., Ltd.) (treatment amount: 7%). 50 copies,

[0139]

[Chemical 4] 150 parts of a mixed solvent of ethanol (special grade reagent manufactured by Kishida Chemical Co., Ltd. 99.5%) and water as a dispersion solvent (ethanol 1
(49 parts + 1 part of water) is dispersed in a sand mill for 50 hours, 18 parts of polytetrafluoroethylene fine particles (average particle size 0.18 μm) are further added, and the mixture is further dispersed in the sand mill for 12 hours. It was Then, 30 parts of an acrylic resin represented by the following formula as a resin component and 2 parts of 2-methylthioxanthone as a photopolymerization initiator were dissolved to obtain a coating liquid for a protective layer. This coating solution is applied onto the charge transport layer by dip coating to form a film, which is 800 mW / c with a high pressure mercury lamp.
Photocuring for 60 seconds at a light intensity of m ² and then 120
It was dried with hot air at 2 ° C. for 2 hours to form a protective layer having a film thickness of 3 μm to obtain an electrophotographic photoreceptor.

[0140]

[Chemical 5]

The dispersibility of the protective layer coating material was good, and the protective layer produced was a uniform and uniform film. 2 (b) is
It is a layer block diagram of the obtained laminated type photoreceptor. The binder layer 25 may be omitted as shown in FIG. 2A, or the undercoat layer 26 for the purpose of preventing interference fringes may be provided as shown in FIG. 2C.

The produced electrophotographic photosensitive member was set at 23.5 ° C./5.
After being left overnight in an environment of 5% RH, evaluation was performed using a laser printer (trade name: LBP-SX, a modified machine manufactured by Canon Inc.). The laser printer was remodeled as an electrophotographic apparatus using the charged particle interposition charging means shown in FIG. 1, and the process cartridge of FIG. 1 was rebuilt so that it could be incorporated into the laser printer. The specific conditions of each device were as follows.

The charging roller was prepared by forming a medium resistance layer of rubber on a cored bar. The medium resistance layer is formulated with urethane resin, conductive particles (carbon black), a sulfiding agent, a foaming agent, etc., and is molded into a roller shape on a cored bar, and then the surface is polished to a diameter of 12 mm and a longitudinal length of 250.
mm elastic conductive roller was prepared. When the resistance of this roller was measured, it was 100 kΩ. The measurement was performed by applying 100 V to the core metal and the conductive support in a state where the core metal of the roller was pressure-bonded to the electrophotographic photosensitive member so that a total pressure of 1 kg was applied.

In this embodiment, as the electroconductive particles (charged particles) for the electrophotographic photosensitive member and the charging roller to be injected and charged through the electroconductive particles, the specific resistance is 10 ⁶ Ω · cm, and the average particle size is 3 μm. The conductive zinc oxide particles of Here, the resistance was measured by the tablet method and normalized. A 0.5 g powder sample was placed in a cylinder with a bottom area of 2.26 cm ² , 15 kg of pressure was applied to the upper and lower electrodes, a voltage of 100 V was applied at the same time, the resistance value was measured, and then normalized to calculate the specific resistance. did.

Further, in order to uniformly supply the charged particles to the contact nip between the roller and the photosensitive member, a charged particle coating means is provided. As a supply means, a regulation blade is brought into contact with the electrophotographic photosensitive member to hold the charged particles between the photoreceptor and the regulation blade. Then, as the electrophotographic photosensitive member rotates, a fixed amount of charged particles are applied to the charging roller.

In this embodiment, the charging roller is rotated with a speed difference with respect to the electrophotographic photosensitive member. The electrophotographic photosensitive member has a drum shape with a diameter of 30 mm and a peripheral speed of about 50.
It rotates at a constant speed of mm / sec. First, charged particles are applied to the surface of the photoconductor by a regulating blade. After that, it reaches the charging roller portion. The charging roller was driven at about 80 rpm so that the roller surface moved in the opposite direction to the photoreceptor at a constant speed, and a DC voltage of -700 V was applied to the roller core metal. This allows
The surface of the photoconductor is charged to a potential equal to the applied voltage. In this embodiment, the charging is performed by injection charging by the charged particles existing in the contact nip between the roller and the body to be charged rubbing the surface of the body to be charged without a gap. Further, as a cleaning means for the residual toner after transfer, a simultaneous cleaning means for development collected by a developing device (toner recycling process)
And

The electrophotographic photosensitive member was evaluated at 23.5 ° C./5.
5% RH, 23.5 ° C / 5% RH and 30 ° C / 78% R
In the H environment, the light potential at the initial stage of durability adjustment was adjusted to -150 V by the exposure amount, and 20,000 A4 size prints were durable in each environment, and evaluated by image evaluation and peeling of the surface protective layer. did. The results are shown in Table 2. In addition, ◯ and Δ in the table indicate the presence or absence of peeling and the image evaluation result. ○
Indicates that there is no peeling and there is no problem in the image evaluation result. Δ indicates that there is no peeling in appearance and slight image unevenness can be confirmed.

(Examples 2 to 22) Amine-based compound example N
o. 1 instead of 1, amine-based compound example N shown in Table 1
o. 8, No. 26, No. 36, No. 39, No.
42, No. 51, No. 69, No. 73, No. 7
6, No. 77, No. 87, No. 106, No. 1
12, No. 131, No. 135, no. 151, N
o. 156, No. 164, No. 176, no. 17
9 and No. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that 194 was used. The results are shown in Table 2.

(Comparative Examples 1 to 4) As the charge transport material, the amine-based compound example No. 1 shown in Table 1 was used. Instead of 1, the comparison CTM1, the comparison CTM2, and the comparison CTM represented by the following formulas
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 3 and Comparative CTM4 were used, and the same evaluation was performed. The results are shown in Table 2. In Comparative Example 1, peeling occurred from the beginning, and the chargeability was poor, and an image could not be formed. In Comparative Examples 2 to 4, peeling and image unevenness occurred during durability.

[0150]

[Chemical 6]

[0151]

[Table 40]

From the results of Table 2, it can be said that the use of the electrophotographic photosensitive member of the present invention makes it possible to realize stable injection charging without image defects due to peeling due to repeated use.

[0153]

As described above, according to the present invention, the charging property is good, and the voltage required for charging is only the desired surface potential of the photoconductor, and neither ozone nor charging noise is generated. Peeling between the photosensitive layer and the charge injection layer (surface protective layer) due to local pressure and / or shear stress in the direction perpendicular to the surface of the photoconductor from the charging member due to low power and a simple device configuration. No longer occurs.

Further, according to the present invention, there is no image defect such as density unevenness due to deterioration of chargeability due to peeling, and a highly durable electrophotographic photoreceptor which can withstand repeated use, and an electrophotographic photoreceptor having the electrophotographic photoreceptor. It has become possible to provide an apparatus and a process cartridge.

[Brief description of drawings]

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

FIG. 2 is a diagram showing in detail charged particle supply means of the electrophotographic apparatus of FIG.

FIG. 3 is a diagram showing a layer structure of an electrophotographic photosensitive member.

FIG. 4 is a diagram showing a schematic configuration of an apparatus for measuring a triboelectric charge amount of toner particles.

[Explanation of symbols]

1 Electrophotographic photoreceptor (image bearing body, charged body) 2 Charging roller (contact charging member) 2a core metal 2b flexible member 3 Charged particles (conductive particles) 4 Regulation blade (charged particle supply means) 5 Exposure means 6 developing means 6a Magnet roller 6b Development sleeve 7 Transfer roller 8 fixing means 9 Process cartridge 10 Guide member a Development area b Transfer nip n Charging nip L exposure light 21 Protective layer 22 Charge transport layer 23 Charge generation layer 24 Conductive support 25 tie layer 26 Undercoat layer

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 9/08 374 G03G 9/08 374 15/02 101 15/02 101 15/08 507 15/08 507B F Term (reference) 2H005 AA08 CB07 DA03 DA09 EA01 2H068 AA03 AA05 AA06 AA31 AA37 BA12 BB31 BB32 BB57 CA05 CA33 CA37 FA27 FC01 FC02 2H077 AA37 AC16 EA03 EA24 2H200 FA07 FA09 FA10 GA16 GA21 B37 H22B25 HA50 GB22 GA50 GA52 GA50 HB46 HB47 LA06 LA12 MA01 MA03 MA08 MA13 MA14 MA20 MB01 MB06 MC01 MC02 MC06 MC15

Claims (52)

[Claims] 1. A charged particle containing conductive particles having a particle size of 10 μm to 10 nm as a main component and a surface having conductivity and elasticity, and a charged particle carrier for supporting the charged particles, In the electrophotographic apparatus used in the electrophotographic apparatus in which the charged particles are in contact with the electrophotographic photosensitive member and the charge is directly injected to the surface of the photosensitive member, the electrophotographic photosensitive member has at least the following formula ( 1), (2), (3)
Alternatively, an electrophotographic photoreceptor having a photosensitive layer containing the charge transport material of (4) and a surface protective layer containing conductive particles. [Chemical 1] [In the formula, Ar _{1 to} Ar ₄ and Ar ₆ represent an aryl group which may have a substituent, and Ar ₅ and Ar _{7 to} Ar ₁₀ represent an arylene group which may have a substituent. R _{1 to} R ₉ represent an alkyl group which may have a substituent, an aralkyl group which may have a substituent, a vinyl group which may have a substituent or an aryl group which may have a substituent. Show. X is an alkylene group which may have a substituent, an arylene group which may have a substituent, CR ₁₀ = CR ₁₁ (R ₁₀ and R ₁₁ are an alkyl group which may have a substituent and a substituent a represents an aryl group or a hydrogen atom even), C = O, S = O, SO 2, -NR 12
- (R _{1 2} represents an optionally substituted alkyl group, an aryl group which may have a substituent), an organic residues combined in one or optionally more oxygen atom or a sulfur atom . However, at least two of R _{2 to} R ₅ and R ₆ to
At least two of R ₉ are aryl groups which may have a substituent. In addition, Ar ₁ and Ar ₂ , R ₁ and Ar ₄ , R ₂
And R ₃ , R ₄ and R ₅ , R ₆ and R ₇ or R ₈ and R ₉ may form a ring directly or through another organic residue, and Ar ₅ and Ar ₆
Or, Ar ₇ and Ar ₈ may form a ring via another organic residue] 2. Particles carried on the charged particle carrier
Resistance is 10¹²-10 ^-1Ω · cm, and the supported amount of the particles
Is 0.1 mg / cm²~ 50 mg / cm²Is an electronic photograph
The electrophotographic photosensitive member according to claim 1, which is used in an apparatus. 3. The electron according to claim 1 or 2, wherein the ratio of charged particles coating the charged particle support is Rc, and 0.2 ≦ Rc ≦ 1. Photoreceptor. 4. The surface roughness Ra of the charged particle carrier is 1 to 5.
The electrophotographic photosensitive member according to claim 1, which is used in an electrophotographic apparatus having a surface resistance of 00 μm and a surface resistance of 10 ⁴ to 10 ¹⁰ Ω · cm. 5. The electrophotographic photosensitive member according to claim 1, wherein the charged particle carrying member is used in an electrophotographic apparatus which is an elastic member having a porous surface. 6. An electrophotographic apparatus comprising: charged particles having a resistance of 10 ¹² to 10 ⁻¹ Ω · cm, and a charged particle supply means for supplying the particles to the surface of the charged particle carrier. 5. The electrophotographic photosensitive member according to any one of 5 above. 7. The charged particle supplying means stores the charged particles together with a developer in the developing means and transfers the charged particles onto the photoreceptor.
7. The electrophotographic photosensitive member according to claim 6, which is used for an electrophotographic apparatus in which a part of the image is not transferred and remains on the photosensitive member and is supplied to a charging unit when being transferred to a recording medium. 8. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer is a layer in which a charge generation layer and a charge transport layer are laminated in this order. 9. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer is a layer containing a charge generating material and a charge transporting material. 10. The electrophotographic photoreceptor according to claim 1, wherein the binder resin used in the surface protective layer is a curable resin. 11. The electrophotographic photosensitive member according to claim 1, wherein the conductive particles are a metal or a metal oxide. 12. The electrophotographic photosensitive member according to claim 1, wherein the conductive particles are subjected to a water repellent treatment. 13. The electrophotographic photosensitive member according to claim 1, wherein the surface protective layer contains lubricating particles. 14. The electrophotographic photosensitive member according to claim 13, wherein the lubricating particles are at least one of fluorine atom-containing resin particles, silicon particles, alumina particles and silicone particles. 15. A charged particle carrier having a conductive particle having a particle size of 10 μm to 10 nm as a main component and a surface having conductivity and elasticity, the charged particle carrying member carrying the charged particle, In the electrophotographic apparatus in which the charged particles come into contact with the electrophotographic photosensitive member and directly inject charges to the surface of the electrophotographic photosensitive member to charge the electrophotographic photosensitive member, the electrophotographic photosensitive member has at least the above formula (1) on the conductive support, (2), (3) or (4)
An electrophotographic apparatus comprising a photosensitive layer containing the charge transporting material of 1. and a surface protective layer containing conductive particles. 16. When the ratio of the charged particles coating the charged particle carrier is defined as the coverage Rc, 0.2 ≦ Rc ≦ 1.
The electrophotographic apparatus according to claim 15, wherein 17. The surface roughness Ra of the charged particle carrying member is 1 to
The electrophotographic apparatus according to claim 15 or 16, which has a surface resistance of 10 ⁴ to 10 ¹⁰ Ω · cm and a surface resistance of 10 ⁴ to 10 ¹⁰ Ω · cm. 18. The electrophotographic apparatus according to claim 15, wherein the charged particle carrier is an elastic body having a porous body surface. 19. The charged particle supplying means for supplying charged particles having a resistance of 10 ¹² to 10 ⁻¹ Ω · cm and supplying the particles to the surface of the charged particle carrier. The described electrophotographic apparatus. 20. Electrophotographic apparatus The electrophotographic apparatus according to claim 19, wherein the charged particle supplying means directly coats the charging member. 21. The electrophotographic apparatus according to claim 19, wherein the charged particle supplying means directly coats the electrophotographic photosensitive member. 22. When the charged particles are stored in the developing means together with the developer and are transferred onto the photoconductor and transferred to the recording medium, the charged particle supply unit transfers the particles onto the photoconductor without partially transferring them. 20. The electrophotographic apparatus according to claim 19, wherein the electrophotographic apparatus remains on the sheet and is supplied to the charging unit. 23. The electrophotographic apparatus according to claim 15, wherein a cleaning unit is not provided between the transfer process and the primary charging process. 24. The electrophotographic apparatus according to claim 15, wherein the charged particles are positively charged. 25. The electrophotographic apparatus according to claim 15, wherein the charged particles are positively charged with respect to the iron powder carrier. 26. When charged particles are stored in a developing means together with a developer, transferred to the photosensitive member and transferred to a recording medium, a part of the charged particles remains untransferred and charged on the photosensitive member. 23. The electrophotographic apparatus according to claim 22, wherein in the charging means supplied to the apparatus, the charged particles are positively charged in the developing device. 27. The electrophotographic apparatus according to claim 15, wherein the photosensitive layer is a layer in which a charge generation layer and a charge transport layer are laminated in this order. 28. The electrophotographic apparatus according to claim 15, wherein the photosensitive layer is a layer containing a charge generating material and a charge transporting material. 29. The electrophotographic apparatus according to claim 15, wherein the binder resin used for the surface protective layer is a curable resin. 30. The electrophotographic apparatus according to claim 15, wherein the conductive particles are a metal or a metal oxide. 31. The electrophotographic apparatus according to claim 15, wherein the conductive particles are treated to be water repellent. 32. The electrophotographic apparatus according to claim 15, wherein the surface protective layer contains lubricating particles. 33. The electrophotographic apparatus according to claim 32, wherein the lubricating particles are at least one of fluorine atom-containing resin particles, silicon particles, alumina particles and silicone particles. 34. A charged particle carrier having a conductive particle having a particle diameter of 10 μm to 10 nm as a main component, and a surface having conductivity and elasticity, the charged particle carrying member carrying the charged particle, In the process cartridge in which the charged particles come into contact with the electrophotographic photosensitive member and directly inject charges to the surface of the electrophotographic photosensitive member to charge the electrophotographic photosensitive member, the electrophotographic photosensitive member has at least the above formula (1), ( A process cartridge having a photosensitive layer containing the charge transport material of 2), (3) or (4) and a surface protective layer containing conductive particles. 35. When the ratio of the charged particles coating the charged particle carrier is taken as the coverage Rc, 0.2 ≦ Rc ≦ 1.
The process cartridge according to claim 34, wherein the process cartridge is 36. The surface roughness Ra of the charged particle carrier is 1 to
The process cartridge according to any one of claims 34 to 35, which has a surface resistance of 10 ⁴ to 10 ¹⁰ Ω · cm and a surface resistance of 500 μm. 37. The process cartridge according to claim 34, wherein the charged particle carrier is an elastic body having a porous body surface. 38. The method according to claim 34, further comprising: charged particles having a resistance of 10 ¹² to 10 ⁻¹ Ω · cm, and a charged particle supply means for supplying the particles to the surface of the charged particle carrier. Process cartridge described. 39. The process cartridge according to claim 38, wherein the charged particle supplying means directly coats the charging member. 40. The process cartridge according to claim 38, wherein the charged particle supplying means directly coats the electrophotographic photosensitive member. 41. When the charged particle supply means stores charged particles in a developing means together with a developer, transfers the charged particles onto the photosensitive member, and is transferred onto a recording medium, a part thereof is not transferred to the photosensitive member. 39. The process cartridge according to claim 38, wherein the process cartridge remains above and is supplied to the charging means. 42. The process cartridge according to claim 34, wherein a cleaning unit is not provided between the transfer process and the primary charging process. 43. The process cartridge according to claim 34, wherein the charged particles are positively charged. 44. The process cartridge according to claim 34, wherein the charged particles are positively charged with respect to the iron powder carrier. 45. When charged particles are stored in a developing means together with a developer, transferred to the photosensitive member and transferred to a recording medium, a part of the charged particles remains untransferred and charged on the photosensitive member. 42. The process cartridge according to claim 41, wherein in the charging means supplied to the apparatus, the charged particles are positively charged in the developing device. 46. The process cartridge according to claim 34, wherein the photosensitive layer is a layer in which a charge generation layer and a charge transport layer are laminated in this order. 47. The process cartridge according to claim 34, wherein the photosensitive layer is a layer containing a charge generating material and a charge transporting material. 48. The process cartridge according to claim 34, wherein the binder resin used for the surface protective layer is a curable resin. 49. The process cartridge according to claim 34, wherein the conductive particles are metal or metal oxide. 50. The process cartridge according to claim 34, wherein the conductive particles are water-repellent treated. 51. The process cartridge according to claim 34, wherein the surface protective layer contains lubricating particles. 52. The process cartridge according to claim 51, wherein the lubricating particles are at least one of fluorine atom-containing resin particles, silicon particles, alumina particles and silicone particles.