JP2002131936A - Electrophotographic photoreceptor, image forming apparatus using the same and process cartridge for image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having excellent wear resistance and high durability which does not produce abnormal images such as decrease in the image density, contamination on the base or the like even when it is repeatedly used for a long time in any environment. SOLUTION: The electrophotographic photoreceptor has a base coating layer and a photosensitive layer successively laminated on a conductive supporting body. The wear rate (wear amount of the outermost surface layer traveling distance of the photoreceptor) of the outermost surface layer of the photoreceptor is <=1.50×10-11. The base coating layer contains at least an inorganic pigment and a binder resin essentially comprising crosslinked methoxymethylated nylon.

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, an image forming apparatus using the same, and a process cartridge for the image forming apparatus, which are applied to a copying machine, a facsimile, a laser printer, a direct digital plate making machine and the like. .

[0002]

2. Description of the Related Art Conventionally, as a photoreceptor used in an electrophotographic system, an electroconductive support having a photosensitive layer mainly composed of selenium or a selenium alloy, inorganic light such as zinc oxide, cadmium sulfide or the like is used. A photosensitive layer in which a conductive material is dispersed in a binder; a photosensitive layer formed using an organic photoconductive material such as poly-N-vinylcarbazole and trinitrofluorenone or an azo pigment; and amorphous silicon Organic electrophotographic photoreceptors are widely used in recent years because of their low cost, high degree of freedom in photoreceptor design, low pollution, etc. It is being used.

[0003] Generally, the "electrophotographic method"
The photoconductive photoreceptor is first charged in a dark place by, for example, corona discharge, and then image-exposed to selectively dissipate the charge of only the exposed portions to obtain an electrostatic latent image. This is one of image forming methods in which an image is formed by developing and visualizing an image by using fine particles (toner) for detection composed of a coloring agent and a binder such as a polymer substance.

The basic characteristics required of a photoreceptor in such an electrophotographic method include (1) charging to an appropriate potential in a dark place, (2) little electric charge dissipation in a dark place, and ( 3) The charge can be quickly dissipated by light irradiation.

[0005] Organic electrophotographic photoreceptors include photoconductive resins typified by polyvinyl carbazole (PVK), PV
A charge transfer complex type represented by K-TNF (2,4,7-trinitrofluorenone), a pigment dispersion type represented by a phthalocyanine-binder, and a function separation type using a combination of a charge generating substance and a charge transporting substance. Photoconductors and the like are known, and in particular, a function-separated type photoconductor is receiving attention.

The mechanism of the formation of an electrostatic latent image in a function-separated type photoreceptor is that, when the photoreceptor is charged and irradiated with light, the light passes through a transparent charge transport layer and is charged by the charge generating substance in the charge generation layer. The absorbed charge-generating substance, which has absorbed light, generates charge carriers, which are injected into the charge-transporting layer, move in the charge-transporting layer in accordance with the electric field generated by the charging, and charge the photoreceptor surface. The latent image is formed by neutralization. In a function-separated type photoreceptor, it is known to use a charge transport material having absorption mainly in the ultraviolet region and a charge generation material having absorption mainly in the visible region, and the above-mentioned basic characteristics are sufficiently used. We have something to meet.

[0007] The electrophotographic photoreceptor has a basic structure in which a photosensitive layer is formed on a conductive support. However, the adhesion of the photosensitive layer, the coating property, the chargeability, and the improvement of the chargeability of the photosensitive layer are improved. For preventing unnecessary charge injection, covering defects on the support, etc.
It has been practiced to provide an undercoat layer.

The resin used for the undercoat layer is, for example, a water-soluble resin such as polyvinyl alcohol, casein, sodium polyacrylate, an alcohol-soluble resin such as copolymerized nylon and methoxymethylated nylon, a polyurethane, a melamine resin, and phenol. Curable resins that form a three-dimensional network structure, such as resins, alkyd-melamine resins, and epoxy resins, are exemplified. Particularly, methoxymethylated nylon is known as a material having a good balance of various properties (Japanese Patent No. 2785282).

However, methoxymethylated nylon has a very high water absorption and contains a methoxyl group in its structure. Therefore, when the photoreceptor provided with the intermediate layer using methoxymethylated nylon is repeatedly used at a high temperature and a high humidity or at a low temperature and a low humidity, the characteristics of the photoreceptor fluctuate greatly, and an abnormal image such as black spots or a decrease in density is caused.

In order to enhance the effect of concealing defects on the support and to enhance the scattering effect on incident light such as coherent light (for example, laser light), the undercoating layer is formed. It is well known to disperse an inorganic pigment such as titanium oxide (Japanese Patent No. 2885609). But,
Even if inorganic pigments are dispersed in methoxymethylated nylon,
Since various physical properties of methoxymethylated nylon greatly depend on temperature and humidity, an electrophotographic photosensitive member having a photosensitive layer provided on such an undercoat layer still has a large temperature-humidity dependence of photosensitive member characteristics. Such temperature-humidity dependency causes an abnormal image such as background contamination of the image or a decrease in density when repeatedly used in a high-temperature high-humidity or low-temperature low-humidity environment.

In addition, in order to use the photoreceptor for a long period of time, it is conceivable to improve the mechanical durability of the surface of the photoreceptor or to reduce the abrasion from the peripheral process side of the photoreceptor. Therefore, suppression of abnormal images due to repeated use is required more than ever.

[0012]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems. Therefore, an object of the present invention is to provide excellent wear resistance and to be used for a long period of time in any environment. An object of the present invention is to provide a highly durable electrophotographic photoreceptor which does not generate an abnormal image such as a decrease in image density and background stain, an image forming apparatus using the same, and a process cartridge for the image forming apparatus.

[0013]

According to the present invention, first, in an electrophotographic photosensitive member in which at least an undercoat layer and a photosensitive layer are sequentially laminated on a conductive support, at the time of forming an image, The wear rate of the surface layer (abrasion amount of the outermost layer / travel distance of the photoreceptor) is 1.50 × 10 ⁻¹¹ or less, and the undercoat layer contains methoxymethylated nylon crosslinked with an inorganic pigment as a main component. An electrophotographic photoreceptor characterized by comprising an adhesive resin is provided.

Second, at least an electrophotographic photosensitive member, a charging unit, an image exposing unit, a developing unit, a transferring unit, a fixing unit,
An image forming apparatus having a cleaning unit and using the first electrophotographic photosensitive member as the electrophotographic photosensitive member is provided.

Third, the first electrophotographic photosensitive member and at least one means selected from a charging means, a developing means, and a cleaning means are integrally supported, and are detachably attached to the image forming apparatus main body. A process cartridge for an image forming apparatus is provided.

The above-mentioned "wear rate of the outermost surface of the photoreceptor" refers to the amount of wear (reduced film thickness: μ) of the outermost surface of the photoreceptor in practical use.
m) is divided by the traveling distance (m) of the photoconductor, excluding the unit. Here, the travel distance of the photoconductor is obtained from (diameter of photoconductor) × (circumferential ratio) × (rotation speed of photoconductor).

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. As described above, the electrophotographic photoreceptor obtained by sequentially laminating the undercoat layer and the photosensitive layer on the conductive support of the present invention has an abrasion rate of 1.50 × 10
^-11 or less, and the undercoat layer contains an inorganic pigment and a binder resin, and the binder resin is a cross-linked methoxymethylated nylon. .

The inorganic pigment used in the undercoat layer of the photoreceptor of the present invention may be a commonly used pigment, but is preferably a white color having almost no absorption in visible light and near-infrared light or a color close thereto. For example, titanium oxide, zinc white, zinc sulfate,
White pigments such as lead white and lithopone; extenders such as aluminum oxide, silica, calcium carbonate, and barium sulfate;

The ratio P / R of the inorganic pigment (P) to the binder resin (R) in the undercoat layer is suitably in the range of 0.1 / 1 to 5.0 / 1 by volume.

Further, by forming the undercoat layer in which titanium oxide and aluminum oxide are mixed, fluctuations in the characteristics of the photoreceptor due to repeated use at high temperature and high humidity or low temperature and low humidity are further reduced. This is considered to be due to the fact that by using titanium oxide and aluminum oxide in combination, the dispersed state is improved, and the resistance value becomes optimal for the undercoat layer.

Titanium oxide has a higher refractive index than other white pigments, is chemically and physically stable, has a large hiding power, and has a high whiteness. Titanium oxide includes rutile type and anatase type, and any of them can be used. The aluminum oxide may be a commonly used aluminum oxide. The mixing method of titanium oxide and aluminum oxide may be such that both powders are mixed and dispersed, and the mixing method is not particularly specified.

On the other hand, the methoxymethylated nylon used as the binder resin in the undercoat layer has a good methoxymethylation ratio of 15 mol% or more, so that the dispersion with the inorganic pigment is good and the uniform or uniform undercoating is achieved. A layer is obtained, and a photoreceptor capable of obtaining a good image even when repeatedly used is obtained. It is desirable that the binder resin of the undercoat layer is all crosslinked methoxymethylated nylon, but other resins can be used in combination.

The thickness of the undercoat layer is 0.5 μm or more.
0 μm or less, preferably 2.0 μm to 10 μm or less.

As a method for forming the undercoat layer, first, methoxymethylated nylon is dissolved in a lower aliphatic alcohol such as methanol, ethanol or propanol. At this time, in order to enhance the stability of the solution, a chlorinated hydrocarbon such as trichloroethane, trichloroethylene, dichloroethane, dichloromethane and chloroform may be mixed. As a method for dispersing the inorganic pigment, a conventional method such as a ball mill, a roll mill, a sand mill, and an attritor can be applied.

The methoxymethylated nylon can be crosslinked by heating the coating solution for the undercoat layer after making it acidic.
Here, in order to make the coating solution for the undercoat layer acidic, an organic acid such as maleic acid, citric acid, tartaric acid, succinic acid, or boric acid,
An inorganic acid such as hypophosphorous acid may be added. The addition amount may be from 0.1% by weight to 10% by weight based on the methoxymethylated nylon.

This coating solution is applied by blade coating, knife coating,
An undercoat layer is formed by applying and drying on a conductive support using a coating method such as spray coating or dip coating. The drying temperature is 100 ° C. or higher. When drying is performed at 100 ° C. or higher, crosslinking proceeds, and a photoreceptor having less environmental dependency is obtained. However, when the drying is performed at a temperature lower than 100 ° C., the crosslinking does not proceed completely, the residual methoxyl group increases, and the photoreceptor has great environmental dependency.

Further, by including a polymer charge transport material in at least one layer from the surface farthest from the conductive support, an electrophotographic photosensitive member having excellent abrasion resistance can be provided. Many of the charge transport materials of conventional electrophotographic photoreceptors
It is being developed as a low molecular compound. Since this low molecular compound alone does not have a film-forming property, it is usually used by being dispersed and mixed with an inert polymer. However, the charge transport layer composed of a low molecular charge transport material and an inert polymer is generally soft,
One of the disadvantages is the low abrasion resistance that the film is easily scraped by a mechanical load. Further, as a means for increasing the charge mobility of the photosensitive layer, increasing the content of a low-molecular charge transport substance can be cited, but at the same time, it is known that film forming properties and abrasion resistance deteriorate. . For this,
In the present invention, by using a polymer charge transporting substance having a charge transporting ability in the structure of an inert polymer, it is possible to perform stable image formation with excellent wear characteristics over a long period of time.

Further, in the electrophotographic photoreceptor containing the polymer charge transporting material, by using the polymer charge transporting material having a specific structure, it is possible to provide more abrasion resistance and long-term stable image quality. It became clear.

On the other hand, it is desired that the electrophotographic photoreceptor has less in-machine potential fluctuation in a high-temperature, high-humidity or low-temperature, low-humidity environment than before, because of improved abrasion resistance in long-term repeated use. When the electrophotographic photoreceptor provided with the undercoat layer has been used for a long period of time under a high-temperature, high-humidity, or low-temperature, low-humidity environment with a wear rate of 1.50 × 10 ⁻¹¹ or less, the conventional electrophotography provided with the undercoat layer Compared with the case where the photoreceptor was used, it was found that the increase in the potential of the exposed portion was suppressed. Although it is not clear why such an effect is brought about, the life of the photoreceptor is prolonged due to the improvement of the abrasion resistance. In the photoreceptor having, under the influence of temperature and humidity for a long period of time, a defective image due to accumulation of residual potential and poor charging rise appears remarkably, whereas the inorganic pigment of the present invention is contained and crosslinked. It is conceivable that the use of the undercoat layer made of methoxymethylated nylon as a binder resin suppresses these defective images due to temperature and humidity dependence.

The electrophotographic photoreceptor of the present invention comprises, as shown in FIG. 1, an undercoat layer and a photosensitive layer containing a charge generating substance, a charge transporting substance and a binder resin on a conductive support. The photosensitive layer may be formed by laminating a charge generation layer and a charge transport layer, as shown in FIGS.

The conductive support has a volume resistance of 10 ¹⁰ Ω.
・ Chemical properties such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, etc., tin oxide, indium oxide, etc. Or a sheet of aluminum, aluminum alloy, nickel, stainless steel, etc., coated with cylindrical plastic or paper, and extruded, drawn, etc., made into a tube, then cut, super-finished, polished, etc. A treated tube or the like can be used. Further, an endless nickel belt and an endless stainless belt disclosed in JP-A-52-36016 can also be used as the conductive support.

In addition, a conductive layer formed by dispersing a conductive powder in an appropriate binder resin on the above-mentioned support and coating the same can also be used as the conductive support of the present invention.
Examples of the conductive powder include carbon black, acetylene black, metal powders such as aluminum, nickel, iron, nichrome, copper, zinc, and silver, and metal oxides such as conductive titanium oxide, conductive tin oxide, and ITO. And the like. The binder resins used simultaneously include polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, and vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal,
Polyvinyl toluene, poly-N-vinyl carbazole,
Thermoplastic, thermosetting or photo-curable resins such as acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, and alkyd resin. Such a conductive layer can be provided by dispersing the conductive powder and the binder resin in an appropriate solvent, for example, tetrahydrofuran, dichloromethane, 2-butanone, toluene, or the like, and applying the dispersion.

Further, heat shrinkage of a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, Teflon (registered trademark) or the like containing the above conductive powder on a suitable cylindrical substrate. Also those that have a conductive layer provided by a tube,
It can be favorably used as the conductive support of the present invention.

The photosensitive layer in the present invention may be a single layer type or a laminated type, but here, for convenience of explanation, the laminated type will be described first.

First, the charge generation layer will be described.
The charge generation layer is a layer containing a charge generation substance as a main component, and a binder resin may be used as needed. As the charge generation substance, an inorganic material and an organic material can be used.

Examples of the inorganic material include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compound, and amorphous silicon. As amorphous silicon, a material obtained by terminating a dangling bond with a hydrogen atom or a halogen atom, or a material doped with a boron atom, a phosphorus atom, or the like is preferably used.

On the other hand, as the organic material, a known material can be used. For example, metal phthalocyanine, phthalocyanine pigments such as metal-free phthalocyanine, azulhenium salt pigment, methine squaric acid pigment, azo pigment having a carbazole skeleton, azo pigment having a triphenylamine skeleton, azo pigment having a diphenylamine skeleton, dibenzothiophene skeleton Azo pigment having a fluorenone skeleton, azo pigment having an oxadiazole skeleton, azo pigment having a bisstillene skeleton, azo pigment having a distyryl oxadiazole skeleton, azo pigment having a distyryl carbazole skeleton, perylene Pigments, anthraquinone or polycyclic quinone pigments, quinone imine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, i Jigoido based pigments, and bisbenzimidazole pigments. These charge generating substances can be used alone or as a mixture of two or more kinds. A phthalocyanine pigment having a phthalocyanine skeleton is preferable from the viewpoint of deterioration due to erosion of various discharge products (such as ozone and NOx products) generated in an actual machine and photosensitivity characteristics. Of the metal phthalocyanines, oxotitanium phthalocyanine is preferable, and phthalocyanine having a crystal structure called a Y-type crystal structure is more preferable.

As the binder resin used as needed in the charge generation layer, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N- Vinyl carbazole, polyacrylamide and the like are used. These binder resins can be used alone or
It can be used as a mixture of more than one species.

As the binder resin for the charge generation layer, in addition to the binder resin described above, polymer charge transport materials represented by the following general formulas 1 to 6 are preferably used. Things.

(A) Polymer having a carbazole ring in the main chain and / or side chain. For example, poly-N-vinyl carbazole,
Compounds described in JP-A-82056, JP-A-54-9632, JP-A-54-11737, and JP-A-4-183719 are exemplified.

(B) Polymer having a hydrazone structure in the main chain and / or side chain. For example, JP-A-57-78402, JP-A-3-5-5
Compounds described in JP-A-0555 / 2005 are exemplified.

(C) Polysilylene polymer For example, JP-A-63-285552,
Compounds described in JP-A-194497 and JP-A-5-70595 are exemplified.

(D) Polymer having a tertiary amine structure in the main chain and / or side chain, for example, N, N-bis (4-methylphenyl) -4-aminopolystyrene, JP-A-1-13061, JP-A-1-19049, JP-A-1-1728,
JP-A-1-105260, JP-A-2-16733
No. 5, JP-A-5-66598, JP-A-5-4
Compounds described in JP-A-03350 are exemplified.

(E) Other polymers For example, a formaldehyde condensation polymer of nitropyrene, JP-A-51-73888, JP-A-56-15074
Compounds described in JP-A No. 9 are exemplified.

The polymer having an electron donating group used in the present invention includes not only the above-mentioned polymer but also a copolymer of a known monomer, a block polymer, a graft polymer, a star polymer, For example, it is also possible to use a crosslinked polymer having an electron donating group as disclosed in JP-A-3-109406.

Further, a low molecular charge transport material may be added to the charge generation layer as needed. The low-molecular charge transport material that can be used in combination with the charge generation layer includes a hole transport material and an electron transport material.

Examples of the electron transporting substance include chloranil, bromanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone,
2,4,8-trinitrothioxanthone, 2,6,8-
Examples thereof include electron accepting substances such as trinitro-4H-indeno [1,2-b] thiophen-4one and 1,3,7-trinitrodibenzothiophene-5,5-dioxide. These electron transport materials can be used alone or as a mixture of two or more.

As the hole transporting material, the following electron-donating materials can be used, and are preferably used. For example, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, 9-
(P-diethylaminostyrylanthracene), 1,1
-Bis- (4-dibenzylaminophenyl) propane,
Styryl anthracene, styryl pyrazoline, phenylhydrazone, α-phenylstilbene derivative, thiazole derivative, triazole derivative, phenazine derivative,
Examples include acridine derivatives, benzofuran derivatives, benzimidazole derivatives, and thiophene derivatives. These hole transport materials can be used alone or as a mixture of two or more.

As a method for forming the charge generation layer, a vacuum thin film preparation method and a casting method from a solution dispersion system are mainly mentioned.

The former method for producing a vacuum thin film includes a vacuum evaporation method,
A glow discharge polymerization method, an ion plating method, a sputtering method, a reactive sputtering method, a CVD method, or the like is used, and the above-mentioned inorganic material and organic material can be favorably formed.

In order to form a charge generation layer by the casting method described below, the above-mentioned inorganic or organic charge generation material is used together with a binder resin, if necessary, using a solvent such as tetrahydrofuran, cyclohexanone, dioxane, dichloroethane or butanone. It can be formed by dispersing with a ball mill, an attritor, a sand mill, or the like, diluting the dispersion liquid appropriately, and applying. The coating can be performed by a dip coating method, a spray coating method, a bead coating method, or the like.

The thickness of the charge generation layer provided as described above is suitably about 0.01 to 5 μm, preferably 0.05 to 2 μm.

The charge transporting layer is a layer for retaining the charged electric charges and moving the electric charges generated and separated in the electric charge generating layer by exposure to combine with the retained electric charges. High electrical resistance is required to achieve the purpose of retaining the charged charge, and in order to achieve the purpose of obtaining a high surface potential with the retained charged charge, the dielectric constant is small and the charge mobility is good. Is required. In addition, good wear characteristics are required for mechanical loads such as contact members, toner development, contact with paper or the like, and cleaning using a brush or blade in an actual machine.

The charge transport layer for satisfying these requirements is composed of a charge transport material and a binder resin used as required. More preferably, it is composed of a polymer charge transport material. The charge transport material and the binder resin can be formed by dissolving or dispersing in a suitable solvent, and then applying and drying the solution. If necessary, a plasticizer, an antioxidant, a leveling agent and the like can be added in an appropriate amount in addition to the charge transport material and the binder resin.

As the charge transport material, there are a hole transport material and an electron transport material.

Examples of the electron transporting substance include chloranil, bromanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone,
2,4,8-trinitrothioxanthone, 2,6,8-
Examples thereof include electron accepting substances such as trinitro-4H-indeno [1,2-b] thiophen-4one and 1,3,7-trinitrodibenzothiophene-5,5-dioxide. These electron transport materials can be used alone or as a mixture of two or more.

As the hole transporting material, the following electron donating materials can be used, and are preferably used. For example, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, 9-
(P-diethylaminostyrylanthracene), 1,1
-Bis- (4-dibenzylaminophenyl) propane,
Styryl anthracene, styryl pyrazoline, phenylhydrazone, α-phenylstilbene derivative, thiazole derivative, triazole derivative, phenazine derivative,
Examples include acridine derivatives, benzofuran derivatives, benzimidazole derivatives, and thiophene derivatives. These hole transport materials can be used alone or as a mixture of two or more.

The polymer charge transporting material having very good abrasion characteristics has the following structure.

(A) Polymer having a carbazole ring For example, poly-N-vinylcarbazole,
No. 82056, JP-A-54-9632, JP-A-54-11737, JP-A-4-175337, JP-A-4-183719, JP-A-6-23
Compounds described in JP-A-4841 are exemplified.

(B) Polymer having a hydrazone structure For example, JP-A-57-78402, JP-A-61-78402
JP-A-20953, JP-A-61-296358,
JP-A-1-134456, JP-A-1-17916
No. 4, JP-A-3-180851, JP-A-3-180851
180852, JP-A-3-50555, JP-A-5-310904, JP-A-6-234840
And the like.

(C) Polysilylene polymer For example, JP-A-63-285552,
88461, JP-A-4-264130, JP-A-4-26
4131, JP-A-4-264132, JP-A-4-264
133 and the compounds described in JP-A-4-289867.

(D) Polymer having a triarylamine structure For example, N, N-bis (4-methylphenyl) -4-aminopolystyrene, JP-A-1-134457, JP-A-2-282264, Kaihei 2-304456
JP, JP-A-4-133065, JP-A-4-13-1
Compounds described in JP-A-33066, JP-A-5-40350, and JP-A-5-202135 are exemplified.

(E) Other polymers For example, a formaldehyde condensation polymer of nitropyrene, JP-A-51-73888, JP-A-56-15074
9, JP-A-6-234836 and JP-A-6-34836.
Compounds described in JP-A-234837 are exemplified.

The polymer having an electron donating group used in the present invention includes not only the above-mentioned polymer but also a copolymer of a known monomer, a block polymer, a graft polymer, a star polymer, For example, it is also possible to use a crosslinked polymer having an electron donating group as disclosed in JP-A-3-109406.

The following compounds are exemplified as polycarbonates, polyurethanes, polyesters, and polyethers having a triarylamine structure, which are more useful as the polymer charge transporting substance used in the present invention. For example, JP-A-64-1728 and JP-A-64-13
No. 061, JP-A-64-19049, JP-A-4-11627, JP-A-4-225014, JP-A-4-230767, JP-A-4-320
No. 420, JP-A-5-232727, JP-A-7-56374, JP-A-9-127713, JP-A-9-222740, JP-A-9-265
197, JP-A-9-212877, JP-A-9-304956, and the like.

The following polycarbonates having a triarylamine structure in the branched chain, which are more useful as the polymer charge transporting material used in the present invention, include the following. Polycarbonate having a triarylamine structure in a branched chain as used herein refers to a polymer structure in which one aryl group of the triarylamine structure is branched from the main chain of the polycarbonate via a bonding group or not. Point.

As the polymer charge transporting material used in the present invention, polycarbonates having a triarylamine structure represented by the following general formulas 1 to 6 in the branched chain are effectively used, and specific examples thereof will be described.

[0068]

Embedded image[Wherein, R₁, R_Two, R_ThreeAre each independently substituted or
Is an unsubstituted alkyl group or a halogen atom, R_FourIs hydrogen field
Or a substituted or unsubstituted alkyl group, R_Five, R ₆Is
Substituted or unsubstituted aryl groups, o, p and q are each
Independently, integers of 0 to 4, k and j represent compositions (molar fractions).
Where 0.1 ≦ k ≦ 1, 0 ≦ j ≦ 0.9, and n are
It represents the order and is an integer of 5 to 5000. X is aliphatic 2
Represented by a valent group, a cycloaliphatic divalent group, or the following general formula:
Represents a divalent group.

Embedded image (In the formula, R ₁₀₁ and R ₁₀₂ each independently represent a substituted or unsubstituted alkyl group, aryl group or halogen atom. L and m are integers of 0 to 4, Y is a single bond, and has 1 carbon atom.
~ 12 linear, branched or cyclic alkylene groups,
-O -, - S -, - SO -, - SO 2 -, - CO -, -
CO—O—Z—O—CO— (where Z is an aliphatic divalent group)
Represents Here, R ₁₀₁ and R ₁₀₂ may be the same or different. ) Or

Embedded image (In the formula, a is an integer of 1 to 20, b is an integer of 1 to 2000, R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or an aryl group. Here, R ₁₀₃ and R ₁₀₄ each represent They may be the same or different.)]

(Specific Examples of General Formula 1) R ₁ , R ₂ , and R ₃ each independently represent a substituted or unsubstituted alkyl group or a halogen atom, and specific examples thereof include the following. Yes, they can be the same or different.

The alkyl group is preferably C ₁ -C ₁₂
In particular, it is a C ₁ -C ₈ , more preferably a C ₁ -C ₄ linear or branched alkyl group, and these alkyl groups are furthermore a fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C ₄ alkoxy group, It may contain a phenyl group or a phenyl group substituted with a halogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-
Butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl group,
2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4
-Methylbenzyl group, 4-methoxybenzyl group, 4-phenylbenzyl group and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

R ₄ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and specific examples of the alkyl group include the same as those described above for R ₁ , R ₂ and R ₃ .

R ₅ and R _{6 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] cycloheptenylidenephenyl group, and non-fused polycyclic group such as biphenylyl group and terphenylyl group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The above aryl group may have the following groups as substituents.

(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.

(2) As the alkyl group, R ₁ ,
The same as R ₂ and R ₃ can be mentioned.

(3) As the alkoxy group (—OR ₁₀₅ ), R ₁₀₅ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group.

(4) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. Can be

(5) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group and a p-methylphenylthio group.

(6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, an N, N-dibenzylamino group, and the like. (7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

X is mainly used when a diol compound having a triarylamino group represented by the following general formula (A) is polymerized by a phosgene method, a transesterification method, or the like, by using a diol compound represented by the following general formula (B) in combination. Introduced into the chain.
In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group of the following general formula (A) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0084]

Embedded image

Embedded image

The following are specific examples of the diol compound of the general formula (B).

1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-
Decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2
Aliphatic diols such as -ethyl-1,3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol, and polytetramethylene ether glycol; 1,4-cyclohexanediol;
-Cyclohexanediol, cyclohexane-1,4-
And cyclic aliphatic diols such as dimethanol.

The diol having an aromatic ring includes
4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2 -Bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-
Bis (4-hydroxyphenyl) cyclopentane, 2,
2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylsulfone,
4,4′-dihydroxydiphenylsulfoxide, 4,
4'-dihydroxydiphenyl sulfide, 3,3'-
Dimethyl-4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl oxide, 2,
2-bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) xanthene, ethylene glycol-bis (4-hydroxybenzoate), Examples thereof include diethylene glycol-bis (4-hydroxybenzoate), triethylene glycol-bis (4-hydroxybenzoate) 1,3-bis (4-hydroxyphenyl) -tetramethyldisiloxane, and phenol-modified silicone oil.

[0088]

Embedded image (Wherein R ₇ and R ₈ are a substituted or unsubstituted aryl group,
Ar ₁ , Ar ₂ and Ar ₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1. )

(Specific Examples of General Formula 2) R ₇ and R _{8 each} represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different. Good.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] a cycloheptenylidenephenyl group, a biphenylyl group, a terphenylyl group, or

Embedded image [Where W is -O-, -S-, -SO-, -SO
_{It represents 2-} , -CO- and the following divalent groups.

Embedded image (C is an integer of 1 to 12)

Embedded image (D is an integer of 1 to 3)

Embedded image (E is an integer of 1 to 3)

Embedded image (F is an integer of 1 to 3)]

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene groups represented by Ar ₁ , Ar ₂ and Ar ₃ include the divalent groups of the aryl groups represented by R ₇ and R ₈ , which may be the same or different.
The above-mentioned aryl group and arylene group may have the following groups as substituents. Further, these substituents are represented as specific examples of R ₁₀₆ , R ₁₀₇ and R _{108 in} the above general formula.

(1) Halogen atom, trifluoromethyl group, cyano group and nitro group.

(2) The alkyl group is preferably
C ₁ -C ₁₂ especially C ₁ -C _18, more preferably C ₁ ~
C ₄ straight-chain or branched-chain alkyl groups. These alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group,
₁ -C ₄ alkoxy group, a phenyl group, or a halogen atom, may contain a phenyl group substituted with an alkyl group or a C ₁ -C ₄ alkoxy group C ₁ -C _4. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl,
i-butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4- Examples include a methoxybenzyl group and a 4-phenylbenzyl group.

(3) As the alkoxy group (—OR ₁₀₉ ), R ₁₀₉ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group.

(4) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. Can be

(5) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group and a p-methylphenylthio group.

(6)

Embedded image (Wherein, represents an alkyl group or an aryl group as defined R ₁₁₀ and R ₁₁₁ are each independently (2), the aryl group such as phenyl group, biphenyl group or a naphthyl group, and these are C ₁ ~ C ₄ alkoxy group, C _1-
It may contain a C ₄ alkyl group or a halogen atom as a substituent. Further, a ring may be formed together with a carbon atom on the aryl group. Specifically, a diethylamino group, N
-Methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (p-tolyl) amino group, dibenzylamino group, piperidino group, morpholino group, euroridyl group and the like. )

(7) An alkylenedioxy group or an alkylenedithio group such as a methylenedioxy group or a methylenedithio group.

X is the main chain when a diol compound having a triarylamino group represented by the following general formula (C) is polymerized by a phosgene method, a transesterification method, or the like, by using a diol compound represented by the following general formula (B) in combination. Introduced inside. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group represented by the following general formula (C) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0101]

Embedded image

Embedded image As the diol compound of the general formula (B), the same compounds as those of the general formula 1 can be mentioned.

[0102]

Embedded image (In the formula, R ₉ and R ₁₀ represent a substituted or unsubstituted aryl group, and Ar ₄ , Ar ₅ , and Ar ₆ represent the same or different arylene groups. X, k, j, and n are the same as those in the general formula 1. It is the same.)

(Specific Examples of Formula 3) R ₉ and R ₁₀ represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different. Good.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] cycloheptenylidenephenyl group, and non-fused polycyclic group such as biphenylyl group and terphenylyl group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

Also, Ar_Four, Ar_Five, And Ar₆Indicated by
The arylene group represented by R₉And R _TenAlly shown in
And may be the same or different.
No. The above aryl group and arylene group are groups shown below.
It may have as a substituent.

(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.

(2) The alkyl group is preferably
C ₁ -C _12, especially C ₁ -C ₈ , more preferably C ₁ -C
₄ is a linear or branched alkyl group, the alkyl group is a fluorine atom, a hydroxyl group, a cyano group, C ₁
It may contain a C ₄ to alkoxy group, a phenyl group, or a halogen atom, a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkoxy group substituted phenyl group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl,
i-butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4- Examples include a methoxybenzyl group and a 4-phenylbenzyl group.

(3) As the alkoxy group (—OR ₁₁₂ ), R ₁₁₂ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group.

(4) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. Can be

(5) Examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, a p-methylphenylthio group and the like.

(6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, an N, N-dibenzylamino group, and the like.

(7) an acyl group; specifically, an acetyl group;
Examples include a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.

X is a diol compound having a triarylamino group represented by the following general formula (D), which is polymerized by a phosgene method, a transesterification method, or the like. Introduced inside. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group represented by the following general formula (D) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0115]

Embedded image

Embedded image As the diol compound of the general formula (B), the same compounds as those of the general formula 1 can be mentioned.

[0116]

Embedded image (Wherein, R ₁₁ and R ₁₂ are substituted or unsubstituted aryl groups, Ar ₇ , Ar ₈ and Ar ₉ are the same or different arylene groups, and s represents an integer of 1 to 5. X, k, j and n Is
This is the same as in the case of general formula 1. )

(Specific Examples of Formula 4) R ₁₁ and R ₁₂ represent a substituted or unsubstituted aryl group. Specific examples thereof include the following, which may be the same or different. Good.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] cycloheptenylidenephenyl group, and non-fused polycyclic group such as biphenylyl group and terphenylyl group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene groups represented by Ar ₇ , Ar ₈ and Ar ₉ include the divalent groups of the aryl groups represented by R ₁₁ and R ₁₂ , which may be the same or different. The above-mentioned aryl group and arylene group may have the following groups as substituents.

(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.

(2) The alkyl group is preferably
C ₁ -C _12, especially C ₁ -C ₈ , more preferably C ₁ -C
₄ is a linear or branched alkyl group, the alkyl group is a fluorine atom, a hydroxyl group, a cyano group, C ₁
It may contain a C ₄ to alkoxy group, a phenyl group, or a halogen atom, a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkoxy group substituted phenyl group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl,
i-butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4- Examples include a methoxybenzyl group and a 4-phenylbenzyl group.

(3) As the alkoxy group (—OR ₁₁₃ ), R ₁₁₃ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group.

(4) The aryloxy group includes a phenyl group and a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. Can be

(5) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.

(6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, an N, N-dibenzylamino group, and the like.

(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group and a benzoyl group.

X is the main chain of the diol compound having a triarylamino group represented by the following general formula (E) when the diol compound is polymerized by a phosgene method, a transesterification method, or the like. Introduced inside. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group represented by the following general formula (E) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0129]

Embedded image

Embedded image As the diol compound of the general formula (B), the same compounds as those of the general formula 1 can be mentioned.

[0130]

Embedded image (Wherein R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are substituted or unsubstituted aryl groups, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆ are the same or different arylene groups, Y ₁ , Y ₂ and Y ₃ Represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, and a vinylene group, and may be the same or different. X, k, j and n are
This is the same as in the case of general formula 1. )

(Specific examples of the general formula 5) R ₁₅ , R ₁₆ , R ₁₇ ,
R ₁₈ represents a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.

As the aromatic hydrocarbon group, a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] cycloheptenylidenephenyl group, and non-fused polycyclic group such as biphenylyl group and terphenylyl group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

Further, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar
As the arylene group represented by _16, it includes divalent groups of the aryl group represented by R _15, R _16, R ₁₇ and R _18, may be the same or different. The above-mentioned aryl group and arylene group may have the following groups as substituents.

(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.

(2) The alkyl group is preferably
C ₁ -C _12, especially C ₁ -C ₈ , more preferably C ₁ -C
₄ is a linear or branched alkyl group, the alkyl group is a fluorine atom, a hydroxyl group, a cyano group, C ₁
It may contain a C ₄ to alkoxy group, a phenyl group, or a halogen atom, a C _{1 to} C ₄ alkyl group or a C _{1 to} C ₄ alkoxy group substituted phenyl group. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl,
i-butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4- Examples include a methoxybenzyl group and a 4-phenylbenzyl group.

(3) As the alkoxy group (—OR ₁₁₅ ), R ₁₁₅ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group.

(4) The aryloxy group includes a phenyl group and a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. Can be

Y ₁ , Y ₂ and Y ₃ represent a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom or a vinylene group. It may be the same or different.

The alkylene group represents a divalent group derived from the alkyl group shown in the above (2). Specifically, a methylene group, an ethylene group, a 1,3-propylene group,
1,4-butylene group, 2-methyl-1,3-propylene group, difluoromethylene group, hydroxyethylene group, cyanoethylene group, methoxyethylene group, phenylmethylene group, 4-methylphenylmethylene group, 2,2-propylene Group, 2,2-butylene group, diphenylmethylene group and the like.

Examples of the cycloalkylene group include a 1,1-cyclopentylene group, a 1,1-cyclohexylene group,
Examples thereof include a 1-cyclooctylene group.

Examples of the alkylene ether group include a dimethylene ether group, a diethylene ether group, an ethylene methylene ether group, a bis (triethylene) ether group, and a polytetramethylene ether group.

X is the main chain when a diol compound having a triarylamino group of the following general formula (G) is polymerized by a phosgene method, a transesterification method, or the like, by using a diol compound of the following general formula (B) in combination. Introduced inside. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group represented by the following general formula (G) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0144]

Embedded image

Embedded image As the diol compound of the general formula (B), the same compounds as those of the general formula 1 can be mentioned.

[0145]

Embedded image (Wherein, R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are a substituted or unsubstituted aryl group, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ , Ar
₂₈ represents the same or different arylene group. X, k, j and n are the same as in the case of the general formula 1. )

(Specific Examples of General Formula 6) R ₂₂ , R ₂₃ , R ₂₄ ,
R ₂₅ represents a substituted or unsubstituted aryl group, and specific examples thereof include the following, which may be the same or different.

Examples of the aromatic hydrocarbon group include a phenyl group,
As a condensed polycyclic group, naphthyl group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a , D] cycloheptenylidenephenyl group, and non-fused polycyclic group such as biphenylyl group and terphenylyl group.

Examples of the heterocyclic group include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group.

The arylene groups represented by Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ and Ar ₂₈ include R ₂₂ ,
The divalent groups of the above-mentioned aryl groups represented by R ₂₃ , R ₂₄ and R ₂₅ are mentioned, and may be the same or different. The above-mentioned aryl group and arylene group may have the following groups as substituents.

(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.

(2) The alkyl group is preferably
C ₁ -C ₁₂ especially C ₁ -C _8, more preferably C ₁ ~
C ₄ straight-chain or branched-chain alkyl groups. These alkyl groups further include a fluorine atom, a hydroxyl group, a cyano group,
₁ -C ₄ alkoxy group, a phenyl group, or a halogen atom, may contain a phenyl group substituted with an alkyl group or a C ₁ -C ₄ alkoxy group C ₁ -C _4. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n-butyl,
i-butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4- Examples include a methoxybenzyl group and a 4-phenylbenzyl group.

(3) As the alkoxy group (-OR ₁₁₈ ), R ₁₁₈ represents the alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group.

(4) Examples of the aryloxy group include a phenyl group and a naphthyl group as the aryl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2-naphthyloxy group, and the like. Can be

(5) Specific examples of the substituted mercapto group or arylmercapto group include a methylthio group, an ethylthio group, a phenylthio group and a p-methylphenylthio group.

(6) As the alkyl-substituted amino group, the alkyl group represents the alkyl group defined in (2). Specific examples include a dimethylamino group, a diethylamino group, an N-methyl-N-propylamino group, an N, N-dibenzylamino group, and the like.

(7) Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a malonyl group and a benzoyl group.

X is the main chain when a diol compound having a triarylamino group represented by the following general formula (F) is polymerized by a phosgene method, a transesterification method or the like, by using a diol compound represented by the following general formula (B) in combination. Introduced inside. In this case, the produced polycarbonate resin becomes a random copolymer or a block copolymer. X is also introduced into the repeating unit by a polymerization reaction between a diol compound having a triarylamino group represented by the following general formula (F) and a bischloroformate derived from the following general formula (B). In this case, the polycarbonate produced is an alternating copolymer.

[0158]

Embedded image

Embedded image As the diol compound of the general formula (B), the same compounds as those of the general formula 1 can be mentioned.

Other polycarbonates having a triarylamine structure in the branched chain include those described in JP-A-6-234.
JP-A-838, JP-A-6-234839, JP-A-6-295077, JP-A-7-325409, JP-A-9-297419, JP-A-9-807
No. 83, JP-A-9-80784, JP-A-9-80784
Compounds described in 80772, JP-A-9-265201 and the like are exemplified.

The binder resin that can be used in combination with the charge transport layer includes polycarbonate (bisphenol A type, bisphenol Z type), polyester, methacrylic resin, acrylic resin, polyethylene, vinyl chloride, vinyl acetate, polystyrene, phenolic resin, and epoxy resin. Polyurethane, polyvinylidene chloride, alkyd resin, silicone resin, polyvinyl carbazole, polyvinyl butyral, polyvinyl formal, polyacrylate, polyacrylamide, phenoxy resin and the like are used. These binders can be used alone or as a mixture of two or more.

The film thickness of the charge transport layer is suitably about 5 to 100 μm, and preferably about 10 to 22 μm.

In the charge transport layer of the present invention, rubber,
Other antioxidants used for plastics, fats and the like may be added.

In the present invention, a plasticizer can be added to the charge transport layer for the purpose of improving environmental resistance, particularly, for the purpose of preventing reduction in sensitivity and chargeability.
The plasticizer may be added to any layer containing an organic substance, but good results can be obtained by adding it to the charge transport layer.

Furthermore, a leveling agent may be added to the charge transport layer. Examples of the leveling agent include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in a side chain.
The amount used is based on 100 parts by weight of the binder resin.
0 to 1 part by weight is suitable.

Next, a case where the photosensitive layer has a single-layer structure will be described.

When a single-layer photosensitive layer is provided by a casting method, a charge generating substance and a low-molecular-weight or high-molecular-weight charge-transporting substance are often dissolved or dispersed in an appropriate solvent, and the resulting mixture is applied.
It can be formed by drying. The aforementioned materials can be used for the charge generating substance and the charge transporting substance.

Further, a plasticizer can be added to the single-layer photosensitive layer if necessary. Further, as the binder resin that can be used as necessary, the binder resin described above for the charge transport layer may be used as it is, or the binder resin described for the charge generation layer 31 may be mixed and used.

The thickness of the single-layer photosensitive layer is suitably about 5 to 100 μm, and preferably about 10 to 22 μm.

In the photoreceptor of the present invention, a protective layer (not shown) may be provided for the purpose of improving the durability of the photoreceptor. Materials used for this are ABS resin, ACS
Resin, olefin-vinyl monomer copolymer, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallyl sulfone, polybutylene, polybutylene terephthalate, polycarbonate, polyether sulfone, polyethylene, polyethylene Examples include terephthalate, polyimide, acrylic resin, polymethylpentene, polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS resin, butadiene-styrene copolymer, polyurethane, polyvinyl chloride, polyvinylidene chloride, and epoxy resin.

As the method for forming the protective layer, a usual coating method can be used. The thickness of the protective layer is 0.1 to 1
0 μm is appropriate. In addition to the above, known materials such as aC and a-SiC formed by a vacuum thin film forming method can be used as the protective layer.

In the photosensitive member of the present invention, another intermediate layer (not shown) can be provided between the photosensitive layer and the protective layer. The other intermediate layer generally uses a resin as a main component. Examples of these resins include polyamide, alcohol-soluble nylon resin, water-soluble butyral resin, polyvinyl butyral, and polyvinyl alcohol. As a method for forming the another intermediate layer, a normal coating method can be used as described above. The thickness is 0.05 to 2
μm is appropriate.

The electrophotographic photoreceptor of the present invention is used for image formation so that the abrasion rate is 0.00-1.50 × 10 ^-11 . At present, as a charging method in an electrophotographic process, a method using corona discharge and a method using a contact charging device such as a charging roller are used. In both charging methods, a discharge product is generated by discharging at the time of charging. The discharge products adhere to the surface of the photoreceptor, the surface of the photoreceptor has low resistance, and image deletion occurs. However, in normal use, the surface of the photoreceptor will be scraped little by little,
Image deletion is unlikely to occur. In the present invention, the wear rate of the photoconductor is preferably 0.15 to 1.50 × 10 ^−11.
It is preferable that However, when no discharge product is generated at the time of charging due to the charging method, it may not be worn at all.

FIG. 4 is a schematic diagram for explaining the image forming apparatus of the present invention, and the following modified examples also belong to the category of the present invention.

In FIG. 4, the photosensitive member 1 is provided with the electrophotographic photosensitive member manufactured according to the present invention. The photoconductor 1 has a drum shape, but may have a sheet shape or an endless belt shape. The charging charger 3, the pre-transfer charger 7, the transfer charger 10, the separation charger 11, and the pre-cleaning charger 13 include a corotron, a scorotron, and a solid state charger (solid state charger).
A known means such as a charger and a charging roller is used.

As the transfer means, generally, the above-mentioned charger can be used. However, as shown in the figure, a combination of a transfer charger and a separation charger is effective.

The light sources such as the image exposure unit 5 and the neutralizing lamp 2 include a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, and a light emitting diode (LE).
D), semiconductor lasers (LD), electroluminescence (EL), and other general light-emitting materials can be used.
To irradiate only light in a desired wavelength range, various filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used.

The light source and the like can be provided with a transfer step, a charge removal step, a cleaning step, and a pre-exposure step using light irradiation in addition to the steps shown in FIG.
Light is applied to the photoconductor.

The toner developed on the photoreceptor 1 by the developing unit 6 is transferred to the transfer paper 9, but not all is transferred, and some toner remains on the photoreceptor 1. Such toner is removed from the photoconductor by the fur brush 14 and the blade 15. Cleaning may be performed only with a cleaning brush, and a known brush such as a fur brush or a mag fur brush is used as the cleaning brush.

When a positive (negative) charge is applied to the electrophotographic photosensitive member and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. If this is developed with toner of negative (positive) polarity (electrostatic detection fine particles), a positive image can be obtained, and if it is developed with toner of positive (negative) polarity, a negative image can be obtained. A known method is applied to such a developing unit.
In addition, a known method is used for the charge removing means.

FIG. 5 shows an example of another process of the image forming apparatus according to the present invention. The photoconductor 16 is an electrophotographic photoconductor manufactured according to the present invention, and includes driving rollers 17a and 17b.
The charging by the charger 18, the image exposure by the light source 19, the development (not shown), the transfer by the charger 20, the pre-cleaning exposure by the light source 21, the cleaning by the brush 22, and the static elimination by the light source 23 are repeatedly performed. . In FIG. 5, light irradiation for pre-cleaning exposure is performed on the photoconductor 16 (of course, in this case, the support is translucent) from the support side.

The image forming apparatus shown in these figures is an example of the embodiment of the present invention, and other embodiments are of course possible. For example, in FIG. 5, the pre-cleaning exposure is performed from the support side. However, the exposure may be performed from the photosensitive layer side, or the image exposure and the irradiation of the static elimination light may be performed from the support side.

On the other hand, in the light irradiation step, image exposure, pre-cleaning exposure, and charge removal exposure are shown, but in addition, pre-transfer exposure, pre-exposure of image exposure, and other known light irradiation steps are provided. Light irradiation can also be performed on the body.

The image forming apparatus as described above may be fixed and incorporated in a copying machine, a facsimile, or a printer, or may be incorporated in the apparatus in the form of a process cartridge. The process cartridge includes a photoreceptor, and further includes a charging unit, an exposing unit, a developing unit, a transferring unit, a cleaning unit, and a discharging unit.
Devices (parts). Although there are many shapes and the like of the process cartridge, a general example is shown in FIG. The photoreceptor 24 has an electrophotographic photoreceptor manufactured by the present invention on a conductive support. A good image can be provided by using the image forming apparatus according to the present invention described above.

[0184]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto. All parts are by weight.

Example 1 73 parts of methoxymethylated nylon (30 mol% methoxymethylation) was dissolved in 1000 parts of methanol, and rutile-type titanium oxide 2 was added thereto.
81.3 parts were added and the mixture was dispersed in a ball mill for 72 hours. Then, tartaric acid dissolved in methanol (solid content 1
(0%) was added to prepare a coating liquid for an undercoat layer. An aluminum support (outer diameter 30 mmφ), 13
After drying at 0 ° C. for 20 minutes, an undercoat layer having a thickness of 3.5 μm was formed.

Next, 4 parts of a polyvinyl butyral resin (Eslec BL-S, manufactured by Sekisui Chemical Co., Ltd.) was dissolved in 150 parts of cyclohexanone, and the resulting product was dissolved in 150 parts of cyclohexanone.
10 parts of the trisazo pigment of 5) was added, and
After the time dispersion, 210 parts of cyclohexanone was further added to carry out dispersion for 3 hours. This was taken out into a container and diluted with cyclohexanone so that the solid content was 1.5% by weight. The coating liquid for a charge generation layer thus obtained was applied on the undercoat layer and dried to form a charge generation layer having a thickness of 0.2 μm.

Embedded image

Furthermore, 83 parts of dichloromethane, 10 parts of a bisphenol Z-type polycarbonate resin, and silicone oil (KF-50, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.002
Was dissolved, and 8 parts of a charge transporting material having the following structural formula (Formula 36) was added thereto to prepare a charge transport layer coating solution.
The coating solution for a charge transport layer thus obtained was applied on the charge generation layer and dried to form a charge transport layer having a thickness of 20 μm.
As described above, the electrophotographic photosensitive member of Example 1 was manufactured.

Embedded image

(Example 2) In Example 1, 281.3 parts of rutile-type titanium oxide and 2 parts of aluminum oxide were used instead of 281.3 parts of rutile-type titanium oxide at the time of preparing the coating liquid for the undercoat layer. A photosensitive drum of Example 2 was prepared in exactly the same manner as in Example 1 except for using the same.

(Examples 3 and 4) The methoxymethylation rate of methoxymethylated nylon was 13 mol%,
Photoconductor drums of Examples 3 and 4 were prepared in the same manner as Example 1 except that the content was 20 mol%.

Example 5 83 parts of dichloromethane, 10 parts of a polymer charge-transporting substance having the following structural formula (Chemical Formula 37, molecular weight of 100,000 to 200,000), silicon oil (KF-50, manufactured by Shin-Etsu Chemical Co., Ltd.) .002 parts were dissolved to prepare a charge transport layer coating solution. A photoreceptor drum of Example 5 was prepared in the same manner as in Example 1 except that the thus obtained coating solution for a charge transport layer was used.

Embedded image

Example 6 A photosensitive drum of Example 6 was prepared in the same manner as in Example 5, except that a polymer charge transporting substance having the following structural formula (Chemical Formula 38, molecular weight of 100,000 to 200,000) was used. .

Embedded image

Example 7 An example was performed in the same manner as in Example 5 except that a polymer charge transporting material having the following structural formula (Chemical Formula 39, molecular weight of 100,000 to 200,000, k / j ≒ 1/1) was used. 7 were prepared.

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Example 8 The procedure of Example 5 was repeated except that a polymer charge transporting material having the following structural formula (Chemical formula 40, molecular weight 100,000 to 200,000, k / j ≒ 1 / 2.3) was used. Example 8 A photosensitive drum of Example 8 was prepared.

Embedded image

Example 9 Example 9 was repeated in the same manner as in Example 5 except that a polymer charge transporting material having the following structural formula (Formula 41, molecular weight of 100,000 to 200,000, k / j ≒ 1/1) was used. Nine photosensitive drums were prepared.

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Example 10 The procedure of Example 5 was repeated except that a polymer charge transporting material having the following structural formula (Chemical formula 42, molecular weight 100,000 to 200,000, k / j ≒ 1 / 1.73) was used. Example 10 A photosensitive drum of Example 10 was prepared.

Embedded image

Example 11 The procedure of Example 5 was repeated except that a polymer charge transporting material having the following structural formula (Formula 43, molecular weight of 100,000 to 200,000, k / j ≒ 1 / 1.83) was used. A photosensitive drum of Example 11 was produced.

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Example 12 The procedure of Example 5 was repeated except that a polymer charge transporting material having the following structural formula (Formula 44, molecular weight of 100,000 to 200,000, k / j ≒ 1 / 1.67) was used. A photosensitive drum of Example 12 was produced.

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Example 13 The procedure of Example 5 was repeated except that a polymer charge transporting material having the following structural formula (Chemical formula 45, molecular weight 100,000 to 200,000, k / j ≒ 1 / 4.59) was used. Example 13 A photosensitive drum of Example 13 was produced.

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Example 14 The procedure of Example 5 was repeated except that a polymer charge transporting material having the following structural formula (Chemical formula 46, molecular weight 100,000 to 200,000, k / j ≒ 1 / 3.13) was used. Example 14 A photosensitive drum of Example 14 was produced.

Embedded image

(Comparative Example 1) The procedure of Example 5 was repeated, except that tartaric acid was not added, the drying temperature was 95 ° C, and the methoxymethylated nylon was not crosslinked. Created a body drum.

Comparative Example 2 The procedure of Example 5 was repeated, except that tartaric acid was not used, the drying temperature was 95 ° C., and the methoxymethylated nylon was not crosslinked. Created a body drum.

(Evaluation 1) Examples 1 to 14, Comparative Examples 1 and 2
Was mounted on a digital electrophotographic copier Imagio MF2200 modified machine manufactured by Ricoh Co., Ltd. (a zinc stearate supply system was mounted on the surface of the photoconductor to reduce the wear of the photoconductor). Film thickness reduction after initial and 50,000 sheet passing tests (A4) in the environment, dark area potential (VD),
The exposure part potential (VL) and image quality were evaluated. Imagio M
The F2200 remodeling machine has an initial V when each photoconductor is mounted.
The charge voltage and the amount of exposure light were adjusted so that D and the initial VL became -900 V and -200 V, respectively. Tables 1 and 2 show these results.

[0203]

[Table 1]

[0204]

[Table 2]

[0205]

(1) According to the first aspect of the present invention, the electrophotographic photosensitive member has a wear rate of the outermost layer of the photosensitive member of 1.50 × 10 ^-11.
Since the undercoat layer is made of methoxymethylated nylon crosslinked with an inorganic pigment, the image characteristics are good under any environment, the potential fluctuation in the actual machine is small, and a high-quality hard disk is used. Copies are obtained stably over the long term.

(2) According to the second aspect of the invention, by using titanium oxide and aluminum oxide together as the inorganic pigment contained in the undercoat layer, the photoreceptor characteristics due to repeated use at high temperature and high humidity or low temperature and low humidity Becomes smaller, and stable image formation can be performed.

(3) According to the invention of claim 3, the methoxymethylation rate of the methoxymethylated nylon is 15 mol%.
By doing as described above, the dispersion with the inorganic pigment is further improved, a uniform and uniform undercoat layer can be formed, and a better image can be obtained. (4) According to the invention of claim 4, the abrasion resistance of the photoreceptor is improved by including the polymer charge transport material in at least one layer from the surface farthest from the conductive support. .

(5) According to the invention of the fifth to fourteenth aspects, the use of a specific polymer charge transport material of the above (4) makes the photoreceptor more excellent in abrasion resistance. .

(6) According to the fifteenth aspect of the present invention, there is provided an image forming apparatus capable of stably supplying a high-quality image using the photoreceptor of the present invention.

(7) According to the sixteenth aspect of the present invention, the photoreceptor of the present invention and at least one unit selected from a charging unit, a developing unit, and a cleaning unit are integrally supported to form an image forming apparatus main body. A long-life process cartridge for an image forming apparatus, which is detachable from the printer, is provided.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a layer configuration of an electrophotographic photoreceptor of the present invention.

FIG. 2 is a cross-sectional view illustrating another layer configuration of the electrophotographic photosensitive member of the present invention.

FIG. 3 is a cross-sectional view illustrating another layer configuration of the electrophotographic photosensitive member of the present invention.

FIG. 4 is a schematic view illustrating the image forming apparatus of the present invention.

FIG. 5 is a schematic view illustrating another process of the image forming apparatus of the present invention.

FIG. 6 is a schematic view illustrating a process cartridge incorporated in the image forming apparatus of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 photoconductor 2 static elimination lamp 3 charging charger 4 eraser 5 image exposure unit 6 developing unit 7 pre-transfer charger 8 registration roller 9 transfer paper 10 transfer charger 11 separation charger 12 separation claw 13 pre-cleaning charger 14 fur brush 15 cleaning brush 16 photoconductor 17a Driving roller 17b Driving roller 18 Charging charger 19 Image exposure source 20 Transfer charger 21 Pre-cleaning exposure 22 Cleaning brush 23 Static elimination light source 24 Photoconductor 25 Charging charger 26 Image exposure unit 27 Developing roller 28 Cleaning brush

Continued on the front page (72) Inventor Hirofumi Yamanan 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Takaaki Ikegami 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company F term (reference) 2H068 AA08 AA20 AA28 AA43 AA44 BA12 BA13 BB23 BB26 BB28 BB29 BB33 BB40 BB49 CA29 CA33 FA03 FA07

Claims (16)

[Claims] 1. An undercoat layer on a conductive support,
An electrophotographic photoreceptor in which photosensitive layers are sequentially laminated, and a wear rate of the outermost layer of the photoreceptor (abrasion amount of outermost layer / travel distance of the photoreceptor) is 1.50 × 10 ⁻¹¹ or less during image formation. An electrophotographic photoreceptor, wherein the undercoat layer contains a binder resin containing methoxymethylated nylon crosslinked with an inorganic pigment as a main component. 2. The inorganic pigment contained in the undercoat layer is titanium oxide and aluminum oxide.
2. The electrophotographic photoreceptor of claim 1. 3. The electrophotographic photoreceptor according to claim 1, wherein the methoxymethylated nylon has a methoxymethylation ratio of 15 mol% or more. 4. The electrophotographic photoreceptor according to claim 1, wherein at least one layer from the surface farthest from the conductive support contains a polymer charge transport material. 5. The electrophotographic photoreceptor according to claim 4, wherein the polymer charge transporting material is at least one polymer of polycarbonate, polyurethane, polyester, and polyether. 6. The electrophotographic photoconductor according to claim 4, wherein the polymer charge transporting material is a polymer compound having a triarylamine structure. 7. The electrophotographic photoreceptor according to claim 4, wherein the polymer charge transporting material is a polycarbonate having a triarylamine structure. 8. The electrophotographic photosensitive member according to claim 4, wherein the polymer charge transporting material is a polycarbonate having a triarylamine structure in a branched chain. 9. The polymer charge transport material according to the following general formula:
Having a triarylamine structure represented by 1 in the branched chain
5. The method according to claim 4, wherein the material is polycarbonate.
Electrophotographic photoreceptor. Embedded image[Wherein, R₁, R_Two, R_ThreeAre each independently substituted or
Is an unsubstituted alkyl group or a halogen atom, R_FourIs hydrogen field
Or a substituted or unsubstituted alkyl group, R_Five, R ₆Is
Substituted or unsubstituted aryl groups, o, p and q are each
Independently, integers of 0 to 4, k and j represent compositions (molar fractions).
Where 0.1 ≦ k ≦ 1, 0 ≦ j ≦ 0.9, and n are
It represents the order and is an integer of 5 to 5000. X is aliphatic 2
Represented by a valent group, a cycloaliphatic divalent group, or the following general formula:
Represents a divalent group. Embedded image(Where R₁₀₁, R₁₀₂Are each independently substituted or omitted
Represents a substituted alkyl group, aryl group or halogen atom.
You. l and m are integers of 0 to 4; Y is a single bond;
~ 12 linear, branched or cyclic alkylene groups,
-O-, -S-, -SO-, -SO_Two-, -CO-,-
CO—O—Z—O—CO— (wherein Z is an aliphatic divalent group)
Represents Where R₁₀₁, R₁₀₂Are the same or different
You may. ) Or(Where a is an integer of 1 to 20, b is an integer of 1 to 2,000
Number, R₁₀₃, R₁₀₄Is a substituted or unsubstituted alkyl group or
Represents an aryl group. Where R₁₀₃And R₁₀₄Respectively
They may be the same or different. )] 10. The electrophotographic photosensitive member according to claim 4, wherein the polymer charge transporting material is a polycarbonate having a triarylamine structure represented by the following general formula 2 in a branched chain. Embedded image (Wherein R ₇ and R ₈ are a substituted or unsubstituted aryl group,
Ar ₁ , Ar ₂ and Ar ₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of the general formula 1. ) 11. The electrophotographic photoconductor according to claim 4, wherein the polymer charge transporting material is a polycarbonate having a triarylamine structure represented by the following general formula 3 in a branched chain. Embedded image (In the formula, R ₉ and R ₁₀ represent a substituted or unsubstituted aryl group, and Ar ₄ , Ar ₅ , and Ar ₆ represent the same or different arylene groups. X, k, j, and n are the same as those in the general formula 1. It is the same.) 12. The electrophotographic photosensitive member according to claim 4, wherein the polymer charge transporting material is a polycarbonate having a triarylamine structure represented by the following general formula 4 in a branched chain. Embedded image (Wherein, R ₁₁ and R ₁₂ are substituted or unsubstituted aryl groups, Ar ₇ , Ar ₈ and Ar ₉ are the same or different arylene groups, and s represents an integer of 1 to 5. X, k, j and n Is
This is the same as in the case of general formula 1. ) 13. The electrophotographic photosensitive member according to claim 4, wherein the polymer charge transporting material is a polycarbonate having a triarylamine structure represented by the following general formula 5 in a branched chain. Embedded image (Wherein R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are substituted or unsubstituted aryl groups, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆ are the same or different arylene groups, Y ₁ , Y ₂ and Y ₃ Represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group, and may be the same or different X, k, j and n are the same as in the case of the general formula 1.) 14. The electrophotographic photoconductor according to claim 4, wherein the polymer charge transporting material is a polycarbonate having a triarylamine structure represented by the following general formula 6 in a branched chain. Embedded image (Wherein, R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ are a substituted or unsubstituted aryl group, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ , Ar
₂₈ represents the same or different arylene group. X, k, j and n are the same as in the case of the general formula 1. ) 15. The image forming apparatus according to claim 1, wherein the image forming apparatus includes at least a photoconductor, a charging unit, an image exposing unit, a developing unit, a transfer unit, a fixing unit, and a cleaning unit. An image forming apparatus comprising a photographic photoreceptor. 16. An image forming apparatus comprising the electrophotographic photosensitive member according to claim 1 and at least one unit selected from a charging unit, a developing unit, and a cleaning unit. A process cartridge for an image forming apparatus, which is detachable from a main body.