JP2003162079A - Electrophotographic photosensitive body and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photosensitive body which does not generate fogging defective picture and does not remarkably deteriorate picture quality and its production method. <P>SOLUTION: This electrophotographic photosensitive body is constituted in such a manner that a film is formed by a vapor deposition method using the metallic complex in which nitrogen atom, oxygen atom and metallic ion have a specified coordination environment and, thereupon, a charge generation layer and a charge transport layer are successively formed. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoconductor for electrophotography used in a copying machine, a laser beam printer, a facsimile (FAX), a color copying machine, a color printer and a color FAX, and a manufacturing method thereof.

[0002]

2. Description of the Related Art Electrophotographic devices such as copiers, printers, and facsimiles have rapidly become popular in recent years because of many advantages such as high speed, low noise, high image quality, and recording on plain paper. . Among them, as a recent tendency, in the fields of printers and facsimiles, the mode of use is shifting from office use to personal use, and there is a demand for smaller size, lower cost, and maintenance-free. At the same time, as the need for documents including images as well as text increases, image processing techniques such as colorization of documents are improved, and higher-resolution and higher-quality image forming techniques are required.

An important element device that supports an electrophotographic apparatus is a photoconductor that converts an image formed by light into an electrostatic image. Since the photoreceptor is inexpensive, easy to design and manufacture, and non-polluting, the development of an organic photoreceptor made of an organic photoconductive material has been actively conducted.
Currently installed in many devices. The structure of the photoconductor can be classified into a function separation type and a single layer type. The molecular design and material selection of the laminated-type photoconductor are easy, whereas the single-layer type photoconductor is manufactured by applying a single coating material, so that the material selection is narrow. Therefore, most of the photoconductors that have been put into practical use at present are laminated type photoconductors in which a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance are sequentially formed on a conductive support. By separating the functions in this way, it becomes possible to satisfy various characteristics such as sensitivity and durability required for the electrophotographic apparatus. With the development of electrophotography, not only the photosensitive characteristics such as charging property, charge retention property and photoconductivity but also long life, pollution-free and low cost are required in the development of photoconductor. Has become.

At present, the materials and shapes generally used as the conductive support of the photoconductor are selected based on the design of electrophotographic apparatuses such as copying machines, printers and facsimiles. Aluminum tubes are generally used because of their advantages such as electrical characteristics and price.

As a charge generating substance, a photoconductor having absorption in a near infrared wavelength region which is an oscillation wavelength region of a semiconductor laser or a light emitting diode has been actively developed.
Phthalocyanine pigments, azo pigments, perylene pigments, anthraquinone pigments, etc. are used. Among them, in recent years,
JP-A-61-217050 and JP-A-61-239
As disclosed in Japanese Unexamined Patent Publication No. 248 and Japanese Unexamined Patent Publication No. 62-134651, oxotitanium phthalocyanine, which has high photosensitivity and sensitizing action and is easy to synthesize and has high quantum efficiency, is particularly attracting attention. .

The method for forming the charge generating layer using the charge generating substance such as oxotitanium phthalocyanine can be roughly divided into two methods, a coating method and a vapor deposition method.
There are many coating methods such as a dip coating method, a spray coating method, a spin coating method, and an electrostatic coating method. in this way,
A conductive support is dipped in a dispersion paint consisting of a specific crystal type oxotitanium phthalocyanine and a dispersion paint consisting of a binder resin and a solvent, coated by pulling it up, and then dried by hot air or the like to give a conductive support. This is a method of forming a charge generation layer on top.

The vapor deposition method is a method of depositing a charge-generating substance such as oxotitanium phthalocyanine vaporized by heating on a conductive support, and exposing the deposited film in an organic solvent or an atmosphere of its vapor. ,
It is to be crystallized to form a predetermined charge generation layer. The vapor deposition method is capable of forming a uniform film at the molecular level, and is suitable for high resolution and high quality electrophotographic devices.

Further, in the laminated type electrophotographic photoreceptor, a layer for preventing charge injection from a conductive support such as aluminum is provided in addition to the charge generation layer and the charge transport layer to prevent deterioration of image quality. Things have also been done. Japanese Patent Application Laid-Open No. 48-4 discloses a structure using a resin film to prevent charge injection.
7344 and JP-A-52-25638 disclose providing a charge injection blocking layer of a nylon resin, and JP-A-49-69332 and JP-A-52-10.
Japanese Unexamined Patent Publication No. 138 discloses that a charge injection blocking layer of a maleic acid resin is provided, and Japanese Patent Laid-Open No. 58-105155 discloses that a charge injection blocking layer of a polyvinyl alcohol resin is provided. In addition, in addition, a structure in which a charge injection blocking layer of an aluminum oxide film is provided by anodizing an aluminum surface which is generally used as a conductive support is disclosed in Japanese Patent Laid-Open No. 4-24926.
It is disclosed in Japanese Patent Application Laid-Open No. 1-1515182 and Japanese Patent Laid-Open No. 11-15182.

[0009]

In the image forming method of reversal development in which exposure is performed by a laser or the like, when charge is injected from the conductive support to the charge generating layer in the unexposed portion, the surface charge is locally generated. However, a fog-like image defect, which is a so-called black spot, occurs on a white background portion where a toner image should not be originally formed, which is a major problem that significantly deteriorates the image quality.

In order to prevent such local injection of charges from the conductive support, a charge injection blocking layer of an appropriate insulating material is provided between the conductive support and the charge generation layer as described above. There are several methods. However, for example, polyamide, which is a nylon-based resin, is susceptible to the humidity environment and has problems such as poor adhesion to the aluminum support. Further, when the resin is used as the charge injection blocking layer, a method of dissolving it in an organic solvent, coating and drying is used, and therefore many steps must be taken, so that productivity is increased. It will worsen significantly, leading to higher costs. In addition, a solvent having high volatility is generally used as the solvent in order to smoothly perform the drying process. With the recent increase in awareness of environmental protection, it is necessary to reduce organic solvents, especially solvents containing halogen, and solvents that are difficult to recover due to their high volatility. Even when the charge injection blocking layer of the aluminum oxide film is provided by the anodizing treatment, a uniform oxide film is not produced only by the anodizing and it is necessary to perform the sealing treatment after the anodizing. Since this treatment involves steps of dipping in a sealing solution, washing, and drying, productivity is greatly deteriorated and cost is increased as in the case of the charge injection blocking layer made of resin. Further, a solution of a metal salt such as nickel acetate, which is generally used as a sealing agent, has a large load on the environment and requires a processing device, which results in high cost and is preferably not used.

In view of the above problems, it is an object of the present invention to provide an electrophotographic photoreceptor and a method for producing the same, which do not cause fog-like image defects and do not significantly deteriorate the image quality.

Another object of the present invention is to provide an electrophotographic photosensitive member and a manufacturing method thereof, which can use a simple process with little environmental load for environmental protection.

[0013]

In view of the above problems, the electrophotographic photoreceptor according to claim 1 of the present invention has at least a charge injection blocking layer, a charge generation layer and a charge transport layer on a conductive support. An electrophotographic photoreceptor comprising layers sequentially stacked, wherein the charge injection blocking layer is a metal complex of a ligand having a nitrogen atom and an oxygen atom and a metal ion.
It is a metal complex having a coordination environment represented by 3).

[0014]

[Chemical formula 23]

The electrophotographic photoreceptor according to claim 2 of the present invention is an electrophotographic photoreceptor comprising a conductive support and at least a charge injection blocking layer, a charge generation layer and a charge transport layer which are laminated in this order. In addition, the charge injection blocking layer is a metal complex of a ligand having a nitrogen atom and an oxygen atom and a metal ion, and has a coordination environment represented by the following (Chemical Formula 24). .

[0016]

[Chemical formula 24]

The electrophotographic photoreceptor according to claim 3 of the present invention is an electrophotographic photoreceptor comprising at least a charge injection blocking layer, a charge generation layer and a charge transport layer which are sequentially laminated on a conductive support. And wherein the charge injection blocking layer is a metal complex of a ligand having a nitrogen atom, a ligand having an oxygen atom and a metal ion, and having a coordination environment represented by the following (Chemical Formula 25): It was done.

[0018]

[Chemical 25]

In the electrophotographic photoreceptor according to claim 4 of the present invention, a metal complex having a ligand represented by the following (Chemical Formula 26) is used as the charge injection blocking layer of the electrophotographic photoreceptor according to claim 1. It is a thing.

[0020]

[Chemical formula 26]

The electrophotographic photoreceptor according to claim 5 of the present invention uses a metal complex having a ligand of the following (Chemical Formula 27) as the charge injection blocking layer of the electrophotographic photoreceptor according to claim 2. It is a thing.

[0022]

[Chemical 27]

The electrophotographic photoreceptor according to claim 6 of the present invention uses a metal complex having a ligand represented by the following (Chem. 28) as the charge injection blocking layer of the electrophotographic photoreceptor according to claim 2. It is a thing.

[0024]

[Chemical 28]

In the electrophotographic photoreceptor according to claim 7 of the present invention, a metal complex having a ligand of the following (Chemical Formula 29) is used as the charge injection blocking layer of the electrophotographic photoreceptor according to claim 2. It is a thing.

[0026]

[Chemical 29]

In the electrophotographic photoreceptor according to claim 8 of the present invention, a metal complex having a ligand represented by the following (Chemical Formula 30) is used as the charge injection blocking layer of the electrophotographic photoreceptor according to claim 2. It is a thing.

[0028]

[Chemical 30]

In the electrophotographic photoreceptor according to claim 9 of the present invention, a metal complex having a ligand represented by the following (Chemical Formula 31) is used as the charge injection blocking layer of the electrophotographic photoreceptor according to claim 1. It is a thing.

[0030]

[Chemical 31]

In the electrophotographic photoreceptor according to claim 10 of the present invention, both the ligands of the following (Chemical Formula 32) and (Chemical Formula 33) are used as the charge injection blocking layer of the electrophotographic photoreceptor of the third aspect. It uses a metal complex that it has.

[0032]

[Chemical 32]

[0033]

[Chemical 33]

According to the twelfth aspect of the present invention, in the method for producing an electrophotographic photosensitive member, the electrophotographic photosensitive member is formed by sequentially stacking at least a charge injection blocking layer, a charge generating layer and a charge transport layer on a conductive support. A method of manufacturing a body, wherein the charge injection blocking layer is formed by a vacuum deposition method to form a metal complex composed of a ligand having a nitrogen atom and an oxygen atom represented by the following (Chemical Formula 34) and a metal ion. Is.

[0035]

[Chemical 34]

The method for producing an electrophotographic photosensitive member according to claim 13 of the present invention is the electrophotographic photosensitive member comprising a conductive support and at least a charge injection blocking layer, a charge generating layer and a charge transport layer sequentially laminated on the conductive support. A method of manufacturing a body, wherein the charge injection blocking layer is formed by a vacuum deposition method to form a metal complex composed of a ligand having a nitrogen atom and an oxygen atom represented by the following (Chemical Formula 35) and a metal ion. Is.

[0037]

[Chemical 35]

The method for producing an electrophotographic photosensitive member according to claim 14 of the present invention is the electrophotographic photosensitive member comprising a conductive support and at least a charge injection blocking layer, a charge generating layer, and a charge transport layer sequentially laminated on the conductive support. A method of manufacturing a body, wherein the charge injection blocking layer is formed by vacuum deposition of a metal complex composed of a ligand having a nitrogen atom represented by the following (Chemical Formula 36), a ligand having an oxygen atom, and a metal ion. It is a manufacturing method of forming by.

[0039]

[Chemical 36]

According to a fourteenth aspect of the present invention, which is a method for producing an electrophotographic photosensitive member, the charge injection blocking layer according to the twelfth aspect is formed by a vacuum evaporation method to form a metal complex having a ligand represented by the following (Chemical Formula 37). It is a manufacturing method.

[0041]

[Chemical 37]

According to a fifteenth aspect of the present invention, which is a method for producing an electrophotographic photosensitive member, the charge injection blocking layer according to the thirteenth aspect is formed by vacuum vapor deposition of a metal complex having a ligand represented by the following (Chemical Formula 38). It is a manufacturing method.

[0043]

[Chemical 38]

According to a sixteenth aspect of the present invention, which is a method for producing an electrophotographic photosensitive member, the charge injection blocking layer according to the thirteenth aspect is formed by vacuum vapor deposition of a metal complex having a ligand represented by the following (Chemical Formula 39). It is a manufacturing method.

[0045]

[Chemical Formula 39]

According to a seventeenth aspect of the present invention, in the method for producing an electrophotographic photoreceptor, the charge injection blocking layer according to the thirteenth aspect is formed by a vacuum evaporation method to form a metal complex having a ligand represented by the following (Chemical Formula 40). It is a manufacturing method.

[0047]

[Chemical 40]

In the method for producing an electrophotographic photoreceptor according to claim 18 of the present invention, the charge injection blocking layer according to claim 13 is formed by a vacuum deposition method of a metal complex having a ligand represented by the following (Chemical Formula 41). It is a manufacturing method.

[0049]

[Chemical 41]

According to a nineteenth aspect of the present invention, which is a method for producing an electrophotographic photosensitive member, the charge injection blocking layer according to the twelfth aspect is formed by a vacuum evaporation method to form a metal complex having a ligand represented by the following (Chemical Formula 42). It is a manufacturing method.

[0051]

[Chemical 42]

The method for producing an electrophotographic photoreceptor according to claim 20 of the present invention is the metal complex having the charge injection blocking layer according to claim 14 having both of the following chemical formulas (43) and (44). Is a vacuum evaporation method.

[0053]

[Chemical 43]

[0054]

[Chemical 44]

[0055]

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

FIG. 1 is a sectional view schematically showing the structure of a laminated electrophotographic photoreceptor according to an embodiment of the present invention. In FIG. 1, the laminated electrophotographic photoreceptor 10 is a conductive support 1
A charge injection blocking layer 12, a charge generation layer 13, and a charge transport layer 14 are laminated on the first layer 1.

The electrically conductive support 11 may be any conventionally known electrically conductive material such as aluminum, nickel, brass, stainless steel, titanium, gold, silver, copper and chromium. For example, in the case of aluminum, a tube (cylindrical) made of the metal material, a plate, a sheet-like support, a tube made of plastic or paper, a plate, or a sheet-like support is vapor-deposited with a metal material or electrically conductive with a conductive paint. A material to which properties are imparted, a tube formed by molding a conductive plastic, a plate, a sheet-shaped support, or the like is used. In particular, a tube obtained by cutting an aluminum alloy or a sheet obtained by vapor-depositing aluminum on a polyethylene terephthalate film is often used. In particular, when an aluminum tube is used for the conductive support 11, it is necessary to clean the surface of the support by washing with a surfactant or an organic solvent before forming the charge injection blocking layer 12 or the charge generation layer 13. Is. Poor cleaning of the aluminum tube causes image defects and reduced adhesion resulting from electrical failure due to the adhering metal cutting powder.

The vapor deposition device for depositing the charge injection blocking layer 12 may be any one capable of forming a uniform film over the entire conductive support 11, and if the conductive support 11 is an aluminum tube, the vapor deposition apparatus shown in FIG. A device as shown in is used. Figure 2
FIG. 2 is a schematic view showing the inside of a chamber 21 of a vapor deposition device, in which an attached aluminum tube 22 revolves around the chamber,
A film is formed on the evaporation source 23. A heater, a boat, a crucible, etc. are used as the vapor deposition source. When using a crucible, it is necessary to consider the material and shape suitable for the charge injecting substance because the charge injecting substance and the crucible react with each other to generate a compound, or the crucible material evaporates and deteriorates the film quality. is there. Especially when purity is required, it is preferable to use an electron beam evaporation source or the like. An oil diffusion pump or the like is attached to the exhaust port 24 to achieve a pressure of 6 × 10 ⁻³ Pa or less. The vapor deposition source 23-1 may be a metal having a melting point not lower than the sublimation point of the charge injection blocking substance, and a refractory metal such as tungsten, molybdenum, tantalum, niobium, or an alloy thereof is often used. Furthermore, the vapor deposition source 23-1 is overheated by applying an electric current from the direct current power source, and the vapor deposition source 2
The charge injection blocking substance 20 filled in 3-1 is sublimated and deposited on the aluminum tube 22 which is a conductive support to obtain a predetermined film thickness.

The charge injection blocking layer 12 formed on the conductive support 11 is formed of a charge injection blocking substance under a pressure of 6 × 10 ⁻³ Pa or less by a vapor deposition method by resistance heating in a range of 0.001 to 1 mm.
To form a thin film in the range of. When vapor deposition is performed at a pressure higher than 6 × 10 ⁻³ Pa, when the vapor deposition source is thermally stable, a large amount of heat must be given to heat and vaporize the vapor deposition source, so the vapor deposition source is thermally decomposed. If the film thickness is smaller than 0.001 mm, the effect of preventing charge injection is not observed, and if it is larger than 1 mm, desired charges cannot be obtained, the residual potential becomes high, and dark decay becomes large.

Next, the charge generation layer 13 formed on the charge injection blocking layer 12 is deposited by resistance heating using oxotitanium phthalocyanine as a charge generation material under a pressure of 6 × 10 ⁻³ Pa or less. At 0.03 to 0.5 mm
It is obtained by forming a thin film in the range of and then treating with solvent vapor. If the film thickness is too thin, the durability is not sufficient and black spots and the like due to the injection of charges are observed. If the film thickness is too thick, the residual potential increases and the sensitivity decreases. When oxotitanium phthalocyanine is used as the charge generating substance, the crude pigment obtained by a known synthesis method is washed under reflux in quinoline to give a highly crystalline pigment,
It is preferable to use one obtained by sublimation purification. Those which are not subjected to the sublimation purification treatment have a decreased sensitivity and an increased residual potential due to impurities generated by thermal deterioration during generation or vapor deposition.

The vapor deposition device for vapor depositing the charge generation layer 13 may be any vapor deposition device capable of forming a uniform film over the charge injection blocking layer 12. Similar to the vapor deposition of the charge injection blocking layer, FIG.
The device shown in is used. FIG. 2 shows the charge injection blocking layer 12
After the film formation, the oxotitanium phthalocyanine film is formed under the same conditions and method as those for the charge injection blocking layer 12. Specifically, the vapor deposition source 23-2 is overheated by applying an electric current from a DC power source to sublimate the charge generating substance 20 filled in the vapor deposition source 23-2, and onto the aluminum tube 22 on which the charge injection blocking layer is deposited. Further, it is deposited to obtain a predetermined film thickness. Since oxotitanium phthalocyanine is a sublimable substance, it is preferable to use a boat with a lid.

The vapor-deposited film of oxotitanium phthalocyanine thus formed is in an amorphous state, and is crystallized by exposing it to the vapor of an organic solvent or contacting it with an organic solvent such as dipping in an organic solvent. be able to. In practice, on the charge-generated layer thus crystal-converted, a charge-transporting material coating material comprising a charge-transporting substance, a binder resin, and an organic solvent is used, and the charge is applied by a known coating means such as dip coating. The transport layer 14 is formed.

As shown in FIG. 2, the apparatus for producing the charge injection blocking layer and the charge generation layer by the vapor deposition method can be carried out continuously by installing respective vapor deposition sources in the same vapor deposition kiln.
In that case, the vapor of the charge injection blocking substance may contaminate the charge generating substance in the vapor deposition boat, and the desired charging characteristics may not be obtained. Therefore, it is possible to continuously perform film formation using a vapor deposition kiln in which the chamber for depositing the charge injection blocking substance and the chamber for depositing the charge generating substance are separate chambers in the same vapor deposition kiln. In that case, the device becomes large and the maintainability deteriorates. In addition, there is also a method in which after the charge injection blocking layer is formed, the charge generation layer is leaked once, the vapor deposition source is replaced with a charge generation material, and the vacuum generation is performed again to form the charge generation layer. In this case, the charge injection inhibiting substance does not contaminate the charge generating substance, but once leaks, the productivity is reduced. As a method of forming these charge injection blocking layer and charge generation layer, it is necessary to select a more appropriate method in accordance with the combination of materials and the productivity.

As the charge transport layer material, hydrazone compounds, butadiene compounds, arylamine compounds, stilbene compounds, quinone compounds, anthraquinone compounds, fluorenone compounds, fluorene compounds, pyrarizone compounds, Imidazole-based compounds, oxadiazole-based compounds, oxazole-based compounds, carbazole-based compounds, povinylcarbazole-based compounds, polyacetylene-based compounds and the like are used. These may be used alone or in combination of two or more, and it is preferable to select a material according to characteristics such as mobility according to the process.

Next, an additive is added to the charge transport material coating material of the present invention to prevent deterioration of the charge transport layer due to light. As these additives, antioxidants such as phenol compounds, phosphonic compounds, amine compounds, sulfur compounds and hydroquinone compounds, and ultraviolet absorbers such as benzotriazole compounds are used. You may use these 1 type or in combination of 2 or more types.

Therefore, by adding an antioxidant and an ultraviolet absorber as optimum additives for the charge transport material, it is possible to effectively realize the stabilization of the characteristics and the prevention of the increase of the peroxide in tetrahydrofuran in a small amount. You can Specifically, the amount added is 0.01% or more and 5% or less, preferably 0.1% or more and 3% or less, and more preferably 0.5% or more and 2% or less with respect to the charge transport material. Further, the ultraviolet absorber does not have a large effect on the increase of peroxide in tetrahydrofuran, but the addition of the ultraviolet absorber stabilizes the repeating characteristics of the photoreceptor. Therefore, mixing with an antioxidant is effective and preferable.

As the binder resin, polyester resin, polycarbonate resin, polysulfone resin, polyester resin, polyarylate resin, acrylic resin,
Polymethacrylate resin, styrene resin, ethylene-vinyl acetate resin, polypropylene resin, vinyl chloride resin,
Resins such as polyurethane resin, epoxy resin, and phenol resin can be used, but they are almost inert to the electrical characteristics of the photoconductor, have high compatibility with charge transporting substances, have strong film strength, and are suitable for coating. Polycarbonate resin is preferable from the viewpoint of high solubility and high stability as a paint. The composition ratio of the binder resin and the charge transport material is preferably 0.25 to 3 and more preferably 0.5 to 2 relative to the binder resin 1 by weight. When it is less than 0.25, the sensitivity is deteriorated, and the coating film is gelled. When it is more than 3, durability is deteriorated.

These charge-transporting substances, additives and binder resins are used as a charge-transporting coating material containing an organic solvent as a main solvent. As the organic solvent, tetrahydrofuran, methanol, ethanol, propanol, butanol, hexane, cyclohexane, toluene, xylene, dichloromethane, dichloroethane, chloroform, diethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate , Dimethylformamide, dimethylacetylamide, dimethylsulfamide and the like are used as a single solvent or a mixed solvent. The charge-transporting coating material is prepared by mixing a solvent with a charge-transporting substance, an additive, and a binder resin, and adjusting the concentration of non-volatile components in the range of 10% to 40%. If the concentration of the non-volatile components is less than 10%, the viscosity of the coating material is low, so that a sufficient film thickness cannot be obtained, and if it is more than 40%, the viscosity is high and the film thickness becomes uneven. When tetrahydrofuran, dimethylformamide, or dimethylacetylamide is used as the solvent, it is preferable to carry out distillation or column chromatography purification with alumina or the like in order to remove peroxides and decomposition products caused by photodegradation.

In general, the charge transport layer coating material thus prepared is used, and a dip coating apparatus 3 as shown in FIG. 3 is used.
At 1, the charge transport layer 14 is formed. Specifically, the aluminum tube 3 which is a conductive support on which a charge generation layer is formed
The charge transport layer is formed by mounting 3 on a movable part 34 provided with a gripping device, immersing it in a pot 32 containing the charge transport layer coating material 30, and then pulling it up at a predetermined speed. A circulation pump 35 and a filter unit 36 are connected to the pot 32. After the dip coating, the organic solvent component is volatilized by a hot air dryer or the like, and after drying, a charge transport layer having a desired film thickness is formed. The thickness of the charge transport layer is 5 to 4
0 mm is preferred. If the film thickness is less than 5 mm, the film will not be sufficiently scraped due to mechanical stress, and if it exceeds 40 mm, the movement of charges will be affected and the characteristics of the photoconductor will be deteriorated.

Further, an overcoat layer may be provided on the charge transport layer 14. This overcoat layer not only serves as a layer for preventing charge injection from the surface of the photoconductor, but also prevents moisture and ozone in the air from directly contacting and adsorbing to the surface of the photoconductor. In addition, the overcoat layer
The abrasion resistance and scratch resistance are improved, and the strength against mechanical stress is improved, leading to a longer life of the photoconductor.

Next, the invention of this embodiment will be described in detail with reference to Examples.

Example 1 An aluminum tube having a diameter of 30 mm and a length of 346 mm was used as a conductive support. As a vapor deposition source, a tungsten boat into which about 0.1 g of tris (8-quinolinolato) aluminum (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged was used. In order to form a charge injection blocking layer on this aluminum tube, tris (8-quinolinolato) aluminum having a film thickness of about 0.1 mm is deposited by a vacuum deposition method under a pressure of 3 × 10 ⁻³ Pa. A film was produced.

The oxotitanium phthalocyanine, which is a charge generating substance, was produced by a known method. Next, this oxotitanium phthalocyanine was treated with a known method under a pressure of about 1 Pa to about 450
Sublimation purification was performed by applying heat of ℃.

The oxotitanyl phthalocyanine obtained as described above was vapor-deposited under a vacuum of 10 ^-2 to 10 ^-4 Pa to a thickness of 0.1 mm on an aluminum tube provided with a charge injection blocking layer. The vapor-deposited film was subjected to a vapor treatment with ethyl acetate at room temperature, so that the vapor-deposited film of oxotitanium phthalocyanine was converted from an amorphous state to a crystalline state.

A charge transport layer was formed by a coating method on the charge generation layer that had been subjected to the crystal conversion treatment. The charge-transporting layer paint is the charge-transporting substance shown below (Chemical formula 45), the binder resin is the polycarbonate resin (P-300 manufactured by Idemitsu Kosan Co., Ltd.) shown below (Chemical formula 46), and alumina for columns (Wako Pure Chemical Industries Ltd.) The product dissolved in tetrahydrofuran from which the peroxide was removed by the company) was used. An aluminum tube in which a charge injection blocking layer and a charge generating layer were sequentially laminated was dipped in this coating, and applied uniformly on the vapor deposition film at a constant speed, and then the solvent was evaporated by a drier to form a charge transport layer of about 20 mm. Formed. According to the above procedure, a photoconductor was prepared in which a charge injection blocking layer, a charge generation layer and a charge transport layer were sequentially laminated on an aluminum tube.

[0076]

[Chemical formula 45]

[0077]

[Chemical formula 46]

A drum tester (CYNTHIA55 manufactured by Gentec Co., Ltd.) was used to evaluate the charging characteristics. The initial charging potential when the photoconductor is negatively charged in the dark by corona discharge of the applied voltage set so that the corona current becomes −30 mA is V
₀ (V), dark decay 2 seconds after the surface potential V ₂ (V), dark decay 2
The charge retention rate for 2 seconds was measured as DDR (%), and then monochromatic light with an energy of 2.1 mJ / cm ² · s having a peak at 800 nm was irradiated for 4 seconds, at which time the surface potential was V ₀ /
2, V _0/5 to become an exposure amount of each _{E 1/2, E 1/5 (mJ /} c
m ² ), and the surface potential after 4 seconds of exposure is the residual potential V _r
It was measured as (V).

A commercially available digital multi-function peripheral (Wakio DP-2000, manufactured by Matsushita Electric Transmission Systems Co., Ltd.) was used for evaluation of the development characteristics. As the evaluation image, a pattern image sample having an image area of 5% was used and evaluated as follows.

◯: Good (black spots are not seen) Δ: Bad (black spots are seen) ×: Very bad The above results are shown in (Table 1). In addition, (Table 1) also shows the results of the following Examples 2 to 11 and Comparative Examples 1 and 2.

Example 2 Tris (5,7-dichloro-8-hydroxyquinolato) aluminum (III) (manufactured by SYNTEC) was used as a charge injection blocking substance, and was manufactured and evaluated in the same manner as in Example 1. did.

Example 3 Tris (5-chloro-8-hydroxyquinolato) aluminum (III) (manufactured by SYNTEC) was used as a charge injection blocking substance, and was manufactured and evaluated in the same manner as in Example 1.

Example 4 Bis as a charge injection blocking substance
[2- (2-benzoxazolyl) phenolate] Zinc (II) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used and manufactured and evaluated in the same manner as in Example 1.

(Example 5) 976 mg of 10-hydroxybenzoquinoline and 565 mg of zinc acetate were mixed in methanol and stirred at room temperature for 1 hour, and then the precipitate was collected by filtration. The precipitate collected by filtration was washed with hexane and then vacuum dried to obtain bis [10-hydroxybenzoquinoline] zinc (II).
Got Using bis [10-hydroxybenzoquinoline] zinc (II) as the charge injection blocking substance, the same method as in Example 1 was used for the production and evaluation.

Example 6 2- (o-Hydroxyphenyl) benzoxazole and zinc acetate were mixed in methanol and stirred at room temperature for 1 hour, and then the precipitate was collected by filtration.
The precipitate collected by filtration was washed with hexane and then vacuum dried to obtain bis [2- (o-hydroxyphenyl) benzoxazole] zinc (II). This bis [2- (o-hydroxyphenyl) benzoxazole] zinc (II) was used as a charge injection blocking substance and manufactured and evaluated in the same manner as in Example 1.

(Example 7) 2- (o-Hydroxyphenyl) benzothiazole and zinc acetate were mixed in methanol and stirred at room temperature for 1 hour, and then the precipitate was collected by filtration. The precipitate collected by filtration was washed with hexane and then vacuum dried to obtain bis [2- (o-hydroxyphenyl) benzothiazole].
Zinc (II) was obtained. The bis [2- (o-hydroxyphenyl) benzothiazole] zinc (II) thus obtained was used as a charge injection blocking substance and manufactured and evaluated in the same manner as in Example 1.

(Example 8) 2- (o-hydroxyphenylazo) phenol and zinc acetate were mixed in methanol,
After stirring at room temperature for 1 hour, the precipitate was collected by filtration. The precipitate collected by filtration was washed with hexane and then dried in vacuum,
(O-Hydroxyphenylazo) phenol] zinc (II)
A complex was obtained. The obtained [2- (o-hydroxyphenylazo) phenol] zinc (II) complex was used as a charge injection blocking substance and manufactured and evaluated in the same manner as in Example 1.

Example 9 Tris (benzoylacetonato) mono (phenanthroline) europium (III) (manufactured by SYNTEC) was used as a charge injection blocking substance and was manufactured and evaluated in the same manner as in Example 1.

Example 10 Tris (dibenzoylmethane) mono (phenanthroline) as a charge injection blocking substance
Example 1 using Europium (III) (manufactured by SYNTEC)
It was manufactured and evaluated by the same method.

Example 11 Tris (dibenzoylmethane) mono (phenanthroline) as a charge injection blocking substance
Example 1 using Europium (III) (manufactured by SYNTEC)
It was manufactured and evaluated by the same method.

Comparative Example 1 A photoconductor in which a charge generation blocking layer and a charge transporting layer were sequentially laminated without providing a charge injection blocking layer on an aluminum tube was manufactured and evaluated in the same manner as in Example 1.

Comparative Example 2 A polyamide resin as a charge injection inhibiting substance was dissolved in a mixed solvent of ethyl alcohol and toluene, the coating material was applied onto an aluminum tube, and then a polyamide resin film was formed by drying. .
The subsequent manufacturing and evaluation methods after the generation of the charge generation material were the same as in Example 1.

[0093]

[Table 1]

According to Examples 1 to 10, the image evaluation was comparable with the initial image even when 30,000 images were output.

In the above examples, the vacuum deposition method was applied as the method for producing the photoconductor. It is considered that this vacuum vapor deposition method is superior to the coating method in terms of productivity deterioration, cost increase, and environmental pollution. Generally, when the charge generating layer is formed by a coating method, the shape of the charge generating substance such as oxotitanyl phthalocyanine is small,
The cohesive force between particles became large, and image defects such as unevenness due to particle aggregation tended to occur after the coating of the charge generating substance coating material.

Therefore, along with the development of electrophotographic photoconductors which are pollution-free and inexpensive, it is desired to develop photoconductor materials and construction methods that use a simple process and have a small load on the environment. Although the above method can be applied, the vacuum vapor deposition method of the present embodiment is considered to be suitable.

[0097]

As described above, according to the electrophotographic photosensitive member of the present invention, it is possible to provide an electrophotographic photosensitive member which does not cause fog-like image defects and does not significantly deteriorate the image quality.

According to the method for producing an electrophotographic photosensitive member of the present invention, a film formed by vapor deposition of a metal complex having a specific coordination environment of nitrogen atoms, oxygen atoms and metal ions is formed as a charge injection blocking layer. Then, by sequentially forming the charge generation layer and the charge transport layer thereon, it becomes possible to provide an electrophotographic photoreceptor in which fog-like image defects do not occur and image quality is not significantly deteriorated. In particular, when the vacuum vapor deposition method is used, it is possible to manufacture an electrophotographic photoreceptor having a low environmental load for environmental protection.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing the structure of an electrophotographic photosensitive member used in an example of the present invention.

FIG. 2 is a cross-sectional view showing the configuration of a vacuum vapor deposition device used in an example of the present invention.

FIG. 3 is a sectional view showing the configuration of a coating apparatus used in an example of the present invention.

[Explanation of symbols]

10 Laminated Electrophotographic Photoreceptor 11 Conductive Support 12 Charge Injection Blocking Layer 13 Charge Generation Layer 14 Charge Transport Layer 20-1 Charge Injection Blocking Material 20-2 Charge Generating Material (oxotitanium phthalocyanine) 21 Vapor Deposition Chamber 22 Aluminum Tube (conductive support) 23-1 Deposition source (for charge injection blocking material) 23-2 Deposition source (for charge generation material) 30 Charge transport layer coating material 31 Immersion coating device 32 Pot part 33 Aluminum tube 34 Support material Movable part with gripping device 35 Circulation pump 36 Filter unit

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masayuki Ono             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. F term (reference) 2H068 AA19 AA42 BA16 BA39 BA42                       BA57 EA22

Claims (22)

[Claims] 1. An electrophotographic photoreceptor comprising a conductive support, and at least a charge injection blocking layer, a charge generation layer, and a charge transport layer sequentially laminated on the conductive support, wherein the charge injection blocking layer is a nitrogen atom and oxygen. An electrophotographic photoreceptor, which is a metal complex of a ligand having an atom and a metal ion, and a metal complex having a coordination environment represented by the following (Chemical Formula 1). [Chemical 1] 2. An electrophotographic photoreceptor comprising a conductive support, and at least a charge injection blocking layer, a charge generation layer and a charge transport layer sequentially laminated on the conductive support, wherein the charge injection blocking layer comprises nitrogen atoms and oxygen. A photoreceptor for electrophotography, which is a metal complex of a ligand having an atom and a metal ion, and a metal complex having a coordination environment represented by the following (Chemical Formula 2). [Chemical 2] 3. An electrophotographic photoreceptor comprising a conductive support, and at least a charge injection blocking layer, a charge generation layer, and a charge transport layer sequentially laminated on the conductive support, wherein the charge injection blocking layer has a nitrogen atom. An electrophotographic photoreceptor, which is a metal complex of a ligand, a ligand having an oxygen atom, and a metal ion, and a metal complex having a coordination environment represented by the following (Chemical Formula 3). [Chemical 3] 4. The electrophotographic photosensitive material according to claim 1, wherein the charge injection blocking layer is a metal complex having a ligand which is an organic compound represented by the following chemical formula (4) or a derivative thereof. body. [Chemical 4] 5. The electrophotographic photosensitive material according to claim 2, wherein the charge injection blocking layer is a metal complex having a ligand which is an organic compound represented by the following (Chemical Formula 5) or a derivative thereof. body. [Chemical 5] 6. The electrophotographic photoreceptor according to claim 2, wherein the charge injection blocking layer is a metal complex having a ligand which is an organic compound represented by Chemical Formula 6 and a derivative thereof. [Chemical 6] 7. The electrophotographic photosensitive material according to claim 2, wherein the charge injection blocking layer is a metal complex having a ligand which is an organic compound represented by the following chemical formula (7) or a derivative thereof. body. [Chemical 7] 8. The electrophotographic photosensitive material according to claim 2, wherein the charge injection blocking layer is a metal complex having a ligand which is an organic compound represented by the following chemical formula (8) or a derivative thereof. body. [Chemical 8] 9. The electrophotographic photosensitive material according to claim 1, wherein the charge injection blocking layer is a metal complex having a ligand which is an organic compound represented by the following chemical formula (9) or a derivative thereof. body. [Chemical 9] 10. The charge injection blocking layer is a metal complex having a ligand which is an organic compound represented by the following (Chemical formula 10) and its derivative and an organic compound represented by the following (Chemical formula 11) and its derivative. The electrophotographic photoconductor according to claim 3, wherein the electrophotographic photoconductor is present. [Chemical 10] [Chemical 11] 11. An electrophotographic photoreceptor comprising a conductive support, and at least a charge injection blocking layer, a charge generation layer, and a charge transport layer sequentially laminated on the conductive support, wherein the charge generation layer is oxotitanium phthalocyanine. The electrophotographic photoreceptor according to claim 1, wherein the photoreceptor is an electrophotographic photoreceptor. 12. A method for producing an electrophotographic photoreceptor comprising a conductive support, and at least a charge injection blocking layer, a charge generation layer, and a charge transport layer sequentially laminated on the conductive support, the charge injection blocking layer comprising: A method for producing an electrophotographic photoreceptor, which comprises forming a metal complex composed of a ligand having a nitrogen atom and an oxygen atom represented by Chemical formula 12 and a metal ion by a vacuum deposition method. [Chemical 12] 13. A method for producing an electrophotographic photosensitive member comprising a conductive support, and at least a charge injection blocking layer, a charge generation layer and a charge transport layer, which are sequentially laminated on the conductive support, wherein the charge injection blocking layer is: A process for producing an electrophotographic photoreceptor, which comprises forming a metal complex composed of a ligand having a nitrogen atom and an oxygen atom represented by Chemical formula 13 and a metal ion by a vacuum deposition method. [Chemical 13] 14. A method for producing an electrophotographic photosensitive member comprising a conductive support, and at least a charge injection blocking layer, a charge generation layer and a charge transport layer sequentially laminated on the conductive support, wherein the charge injection blocking layer is: A metal complex composed of a ligand having a nitrogen atom represented by the chemical formula (14), a ligand having an oxygen atom, and a metal ion is formed by a vacuum deposition method. Law. [Chemical 14] 15. The metal complex having a ligand which is an organic compound represented by the following (Chemical Formula 15) and a derivative thereof is formed in the charge injection blocking layer by a vacuum deposition method. For manufacturing a photoconductor for electrophotography. [Chemical 15] 16. The metal complex having a ligand which is an organic compound represented by the following (Chemical Formula 16) and a derivative thereof is formed in the charge injection blocking layer by a vacuum deposition method. For manufacturing a photoconductor for electrophotography. [Chemical 16] 17. The metal complex having a ligand, which is an organic compound represented by the following (Chemical Formula 17) and a derivative thereof, is formed in the charge injection blocking layer by a vapor deposition method. Manufacturing method of electrophotographic photoreceptor. [Chemical 17] 18. The metal complex having a ligand, which is an organic compound represented by the following (Chemical Formula 18) and a derivative thereof, is formed in the charge injection blocking layer by a vacuum deposition method. For manufacturing a photoconductor for electrophotography. [Chemical 18] 19. The metal complex having a ligand, which is an organic compound represented by the following (Chemical Formula 19) and a derivative thereof, is formed in the charge injection blocking layer by a vacuum deposition method. For manufacturing a photoconductor for electrophotography. [Chemical 19] 20. The charge injection blocking layer is formed by a vacuum deposition method of a metal complex having a ligand which is an organic compound represented by the following (Chemical Formula 20) and a derivative thereof. For manufacturing a photoconductor for electrophotography. [Chemical 20] 21. A charge injection blocking layer comprising a metal complex having a ligand which is an organic compound represented by the following (Chemical formula 21) and its derivative and an organic compound represented by the following (Chemical formula 22) and its derivative. The method for producing an electrophotographic photosensitive member according to claim 13, wherein the electrophotographic photosensitive member is formed by a vacuum vapor deposition method. [Chemical 21] [Chemical formula 22] 22. A method for producing an electrophotographic photosensitive member comprising a conductive support, and at least a charge injection blocking layer, a charge generation layer and a charge transport layer, which are sequentially laminated on the conductive support, wherein the charge generation layer is oxotitanium. The method for producing an electrophotographic photosensitive member according to claim 12, wherein phthalocyanine is formed by a vacuum vapor deposition method.