JP2003177557A - Electrophotographic photoreceptor and its manufacturing method, and method and apparatus for image formation using the photoreceptor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoreceptor which prevents dot defects of a texture part caused in the beginning of photoreceptor use when the photoreceptor using a conductive base with an anodic oxidation film is used for reversal development, to provide a photoreceptor which can output a stable image even when repeatedly used with high resolution, and to provide an image forming method, an image forming unit, and a process cartridge for the image forming unit which obtain stable images with a small number of abnormal images even in repetitive use and have high resolution and high durability. <P>SOLUTION: The manufacturing method for the electrophotographic photoreceptor provided with at least a charge generation layer and a charge transfer layer on a conductive base whose surface is processed by anodic oxidation filming is characterized by that after the surface of the anodic oxidation film is physically rubbed in contact and washed with liquid containing a coating solvent used when a photosensitive film is formed on the anodic oxidation film, the photoreceptor film is formed on the anodic oxidation film. <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 an electrophotographic photosensitive member, a method for manufacturing the same, and an image forming method and apparatus using the photosensitive member. More specifically, the present invention relates to background stains and blacks generated by reversal development. The present invention relates to an electrophotographic photosensitive member having few point defects that cause spots, a manufacturing method thereof, and an image forming method and apparatus using the photosensitive member.

[0002]

2. Description of the Related Art In recent years, the development of information processing system machines using electrophotography has been remarkable. In particular, an optical printer that converts information into a digital signal and records information by light has been remarkably improved in print quality and reliability.

This digital recording technology is applied not only to printers but also to ordinary copying machines, and so-called digital copying machines have been developed. Further, since the conventional analog copying machine equipped with this digital recording technology is provided with various information processing functions, it is expected that the demand thereof will further increase in the future.

In such a digital copying machine or digital printer, the image area ratio of the original is usually 10 or less.
%, The reversal development (negative / positive development) method that writes in the image area considering the deterioration of the light source and the light fatigue of the photoconductor and develops the toner image on the part where the potential of the photoconductor is attenuated is used. Mainstream. This reversal development method requires less light irradiation to the photoconductor, and is a development method advantageous for the photoconductor in consideration of light fatigue during repeated use.
If a minute defect exists on the photoconductor and a phenomenon such as a potential leak occurs, point defects (background stain, black spots, etc.) occur on the background portion (white background) that is not in the document. This defect may be mistaken for a dot in a drawing, a period or a comma in an English manuscript, and can be said to be a fatal defect in an image.

Most of these defects are mainly caused by a local potential leak of the photoconductor, and it is possible to improve the pressure resistance of the photoconductor, the charging uniformity, and the potential holding uniformity. It is a major issue. In view of this point, attempts have been made to provide an undercoat layer between the conductive support and the photosensitive layer. The structure of the undercoat layer is a layer in which a binder resin is a main component and a filler is dispersed if necessary. When the binder resin is used alone, the binder resin is a material having a high electrical insulation property, and therefore the thickness of the undercoat layer needs to be extremely thin, and in most cases, the thickness is 1 μm or less.
In such a case, since the forming method is performed by a wet coating method, it is difficult to avoid pinholes in the coating film, and the expected effect cannot be obtained.

On the other hand, since most of the mainstream photoconductors are hole transport type photoconductors, the undercoat layer is made thicker by adding an electron conductive filler to the undercoat layer.
This pinhole has been avoided. However, in the subbing layer composed of the filler resin dispersion system, the ultrafine-particulate filler of submicron or less is high in cost, and in addition, the workability is poor because of its excessive bulkiness.
Cannot be used in manufacturing. For this reason, submicron (minimum primary particle is about 0.3 μm) fine particles are often used, but reaggregation of the filler occurs in the dispersion or during coating film formation, resulting in a coating film of 1 μm or more. In some cases, defects may occur, and an undercoat layer for designing a photoreceptor having uniform charging property and potential holding property is not formed.

On the other hand, a method of providing an anodic oxide film for directly forming a barrier layer on a conductive support has been studied with an idea different from that of the undercoat layer. In this method, an aluminum substrate, which is a conductive support, is anodized using an electrolyte such as sulfuric acid or oxalic acid to form an aluminum oxide film typified by alumite on the surface of the support. The photoconductor having this oxide film has a high pressure resistance, the chargeability is not significantly deteriorated even when the photoconductor is repeatedly used in the electrophotographic apparatus, and the increase of the point defects in the background portion is not observed so much. However, there are many point defects in the initial stage of using the photoconductor, which causes a problem in practical use. Since the anodic oxide film has a porous structure and is a highly electrically insulating material, physical and chemical changes easily occur between the film formation and the coating. In order to avoid this, the pores of the anodized film are usually filled by a sealing treatment. However, this sealing component adheres not only to the bulk direction of the pores but also to the surface direction, and at the same time, incorporates the organic component as well as the inorganic component. As a result, when the anodic oxide film acts as an electrode (barrier layer), a non-uniform portion of electrical insulation is generated, and as a result, the electric field is concentrated on the portion of low insulation and point defects are thought to occur. To be

As a result of examination by the present inventors, it is found that even if a large number of point defects are generated in the initial stage, the number of the point defects will not be increased if they are forcibly repeatedly used thereafter, and rather they tend to decrease. I understood. The reason for this is not clear, but due to the electric field applied by repeated use of the photoconductor, some kind of barrier is formed on the oxide film surface or at the oxide film / photosensitive layer (charge generation layer) interface, and the barrier property is improved. It is considered that the number of local potential leak points is reduced and the point defects are reduced.

The present invention intends to use the photosensitive member in a stable state by performing a specific cleaning process before mounting the photosensitive member on the electrophotographic apparatus.

As a prior art similar to the present invention, Japanese Patent No. 2
No. 582126 (Japanese Unexamined Patent Publication No. 2-5068), Japanese Patent Publication No. 4-42668 (Japanese Unexamined Patent Publication No. 2-219062), and Japanese Patent No. 2682188 (Japanese Unexamined Patent Publication No. 3-25).
9264) and JP-A-4-81861.

Japanese Patent No. 2582126 describes that an anodized film is formed on an aluminum substrate and then the surface of the coated film is physically contacted and scrubbed. The publication describes that a sufficiently clean anodic oxide film can be obtained by removing the adhered matter on the surface of the coating film generated by the sealing treatment of the anodic oxide film. However, the relationship with the coating film formed on the anodized film, especially the relationship with the coating solvent used for film formation, has not been clarified, and depending on the combination of the cleaning conditions and the coating solvent, the effect may not be obtained. Sometimes it was low and not always satisfactory.

Japanese Examined Patent Publication (Kokoku) No. 4-42668 describes a method for cleaning a base of a photoreceptor in which an anodic oxide film is formed, followed by cleaning with pure water accompanied by rubbing with a soft material, and further with running water cleaning with pure water. ing. In this case, the ionic species attached to the support surface can be easily removed by rubbing and washing,
Furthermore, it is said that a clean anodized film can be obtained by washing away with running water. However, even in this case, the relationship with the coating film formed on the anodized film,
In particular, the relationship with the coating solvent used for film formation has not been clarified, and the effect may be low depending on the coating solvent used, which is not always satisfactory.

Japanese Patent No. 2682188 discloses a method of forming a photosensitive layer containing an organic photoconductive material after cleaning the surface of a substrate having an anodized film while applying stress with a cleaning agent using a weak alkaline cleaning solution. Is listed. In this case, it is possible to remove foreign substances and dirt that cannot be completely removed by ultrasonic cleaning and steam cleaning with an organic solvent.
It is described that a substrate having a clean surface is formed. However, even in this case, the relationship with the coating film formed on the anodized film, particularly the relationship with the coating solvent used for film formation has not been clarified, and depending on the coating solvent used,
The effect was sometimes low and not always satisfactory.

Japanese Unexamined Patent Publication No. 4-81861 describes a method in which the surface of a substrate having an anodized film is washed with a washing liquid containing alcohol or ketone and dried to form a photosensitive layer. In this case, a trace amount of an organic compound is attached to the surface of the substrate in some form such as being taken in by an inorganic compound, and image defects are caused by cleaning with a cleaning liquid containing alcohol or ketone effective for dissolving and removing this. There is a statement that it can be effectively prevented. In this case, it is certainly effective in removing organic substances that dissolve in alcohol or ketone, but when other organic solvent is used as the coating solvent, the effect is not recognized so much and it is not always satisfactory. Was not.

[0015]

In any of the above-mentioned conventional techniques, it is attempted to positively remove the adhered substances and impurities on the surface of the support (anodic oxide film) that are formed through the anodizing treatment and the sealing treatment. To do. This operation itself
It is considered to be effective in preventing the point defects. However, the solvent-soluble components taken in the pores cannot be completely removed only by physical cleaning (rubbing cleaning, etc.), and chemical cleaning (specific solvent).
It is not possible to remove the impurities that are toughly fixed only by itself. Furthermore, the degree of elution of these impurities also changes depending on the solvent used for the coating film formed on the anodized film, and there is a problem in that the relationship with the coating solvent must be taken into consideration.

Therefore, the present invention has been made to solve the above-mentioned problems, and the object of the present invention is to carry out, in addition to physical cleaning, cleaning with a coating solvent formed on a film to obtain a surface. By eluting and removing the fixed components and impurities taken in inside the holes, it is intended to perform more reliable cleaning operation and prevent point defects, especially point defects in the initial state of the photoconductor mounted in the electrophotographic apparatus. However, when a photoreceptor using a conductive support having an anodized film is used for reversal development, it provides a photoreceptor that prevents point defects in the background portion that occur in the initial state of using the photoreceptor, and repeats with high resolution. An object of the present invention is to provide a photoconductor that can output a stable image even in use. An object of the present invention is to provide an image forming method, an image forming apparatus, and an image forming apparatus process cartridge having a high resolution and a high durability, which can obtain a stable image with few abnormal images by repeated use by using this photoreceptor. To do.

[0017]

In order to solve the above-mentioned problems, in the invention according to claim 1, at least a charge generation layer and a charge transport layer are provided on a conductive support whose surface is anodized. In the method for producing an electrophotographic photosensitive member, the surface of the anodized film was physically contacted and scrubbed with a liquid containing a coating solvent used in forming the photosensitive film on the anodized film. After that, the most main feature is to form a photoconductor coating film on the anodized film.

The second aspect of the present invention is characterized in that, in the method for producing an electrophotographic photosensitive member according to the first aspect, the anodic oxide film is sealed.

According to the invention of claim 3, claim 1 or 2
The main feature of the electrophotographic photosensitive member manufacturing method is that cleaning with pure water is performed after the contact scrub cleaning.

According to a fourth aspect of the present invention, the first to third aspects are provided.
The electrophotographic photosensitive member manufactured by the method for manufacturing an electrophotographic photosensitive member according to any one of 1 to 4 is the most main feature.

According to a fifth aspect of the invention, in the electrophotographic photoreceptor of the fourth aspect, the outermost surface layer of the photoreceptor is a charge transport layer, and the charge transport layer contains a polymer having an electron donating group. Is the main feature.

According to the invention of claim 6, claim 4 or 5
The electrophotographic photoreceptor described above is characterized mainly in that a protective layer is provided on the outermost surface of the photoreceptor.

The invention according to claim 7 is characterized in that, in the electrophotographic photosensitive member according to claim 6, the protective layer contains a low molecular charge transporting substance or a polymer having an electron donating property.

In the invention of claim 8, claim 6 or 7
The electrophotographic photoreceptor described above is characterized mainly in that the protective layer contains a filler.

In the invention described in claim 9, claims 4 to 8
In the electrophotographic photosensitive member described in any one of 1 above, the main feature is that the film thickness of the photosensitive layer is 20 μm or less.

According to a tenth aspect of the invention, in the image forming method in which the electrophotographic photosensitive member is repeatedly subjected to at least charging, image exposure, development and transfer, the electrophotographic photosensitive member is defined by any one of the fourth to ninth aspects. The main feature is that it is the described electrophotographic photoreceptor.

According to an eleventh aspect of the invention, there is provided an image forming apparatus comprising at least a charging means, an image exposing means, a developing means, a transferring means and an electrophotographic photosensitive member, the electrophotographic photosensitive member being the fourth aspect. The electrophotographic photosensitive member according to any one of 1 to 9 is a main feature.

According to a twelfth aspect of the present invention, there is provided a process cartridge for an image forming apparatus comprising at least an electrophotographic photosensitive member, the electrophotographic photosensitive member according to any one of the fourth to ninth aspects. The main feature is that it is an electrophotographic photoreceptor.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below with reference to the drawings. FIG. 1 is a cross-sectional view showing the structure of the electrophotographic photosensitive member of the present invention, in which a charge generation layer 35 is formed on a conductive support 31 having an anodized film 33 on its surface.
And a charge transport layer 37.

FIG. 2 is a cross-sectional view showing another constitutional example of the electrophotographic photosensitive member of the present invention. A charge transport layer 37 and a charge are formed on a conductive support 31 having an anodized film 33 on the surface. The generation layer 35 is provided.

FIG. 3 is a sectional view showing still another constitution of the present invention, in which a charge generation layer 35, a charge transport layer 37 and a protective layer are provided on a conductive support 31 having an anodized film 33 on the surface thereof. A layer 39 is provided.

As the conductive support 31, the volume resistance 10
Those exhibiting conductivity of ¹⁰ Ω · cm or less, for example, metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver and platinum, and metal oxides such as tin oxide and indium oxide by vapor deposition or sputtering, Film or cylindrical plastic, paper coated, or aluminum, aluminum alloy, nickel, stainless steel, etc. plates and their materials are formed into pipes by a method such as extrusion or drawing, and then cut, superfinished, polished, etc. It is possible to use a surface-treated tube or the like. In addition, JP-A-5
The endless nickel belt and the endless stainless belt disclosed in JP-A-2-36016 are also conductive supports 3
It can be used as 1. In addition to the above, a support obtained by dispersing conductive powder on a suitable binder resin and coating it on the support can also be used as the conductive support 31 of the present invention. Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc and silver, or metal oxide powder such as conductive tin oxide and ITO. To be Further, the binder resin used at the same time, polystyrene, styrene-acrylonitrile copolymer, styrene-
Butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, Ethyl cellulose resin,
Polyvinyl butyral, polyvinyl formal, polyvinyltoluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, alkyd resin, and other thermoplastic, thermosetting resin or photocurable resin Is mentioned. Such a conductive layer can be provided by dispersing and coating the conductive powder and the binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone or toluene.

Among these, the cylindrical support made of aluminum, which can be easily subjected to the anodic oxide film treatment, can be most preferably used. Aluminum here means
It includes either pure aluminum or aluminum alloy. Specifically, JIS 1000 series, 300
The 0s and 6000s of aluminum or aluminum alloy are most suitable.

Next, the anodic oxide film 33 will be described. The anodic oxide film is various metals, various alloys are anodized in an electrolyte solution, among them aluminum or aluminum alloy anodized film in the electrolyte solution called alumite coating on the photoreceptor of the present invention Is the most suitable. The anodizing treatment is carried out in an acidic bath of chromic acid, sulfuric acid, oxalic acid, phosphoric acid, boric acid, sulfamic acid or the like. Of these, treatment with a sulfuric acid bath is most suitable. For example, sulfuric acid concentration: 10
-20%, bath temperature: 5-25 ° C, current density: 1-4 A / d
The treatment is performed in the range of m ² , electrolysis voltage: 5 to 30 V, and treatment time: 5 to 60 minutes, but is not limited thereto. The anodic oxide film thus produced is porous and has a high insulating property, so that the surface thereof is very unstable. Therefore, there is a change with time after production, and the physical properties of the anodized film are likely to change. To avoid this,
It is desirable to further seal the anodized film. The sealing treatment includes a method of immersing the anodic oxide film in an aqueous solution containing nickel fluoride or nickel acetate, a method of immersing the anodic oxide film in boiling water, a method of treating with pressurized steam, and the like. Of these, the method of immersing in an aqueous solution containing nickel acetate is most preferable.

Subsequent to the sealing treatment, a cleaning treatment of the anodized film is performed. The main purpose of this is to remove excess substances such as metal salts adhered by the sealing treatment, impurities dissolved in the solvent coated on the film, and the like. If this excessively remains on the surface of the support (anodic oxide film), not only will it adversely affect the quality of the coating film formed on it, but in general a low resistance component will remain, so conversely the occurrence of scumming will occur. It also becomes a cause.

The cleaning is a liquid containing at least a coating solvent used for forming a coating film on the coating film, and includes a cleaning step by physical contact scrub cleaning. At this time, as the cleaning solvent to be used, a coating solvent for forming a coating film on the film may be used alone (in the case of coating with a mixed solvent, a mixed solvent), and if necessary, other solvent may be used. You may use a solvent together. From the effect of washing, it is desirable to use a solvent having the same composition as the coating solvent as much as possible.

A rubbing material is used for the physical contact scrub cleaning, but any material that is insoluble in the organic solvent used can be used. At this time, a brush-like, foam-like, sponge-like, or cloth-like form is effective as the form. Materials include sponge, cotton, rayon, cellulose, natural fibers such as wool, synthetic fibers such as polyester, nylon, acrylic and acetate, thermoplastics such as polystyrene, polyethylene and polypropylene,
Examples thereof include thermoplastics such as polyurethane and polyurea.

It is an effective means to carry out the rinse with running solvent such as a shower after the scrubbing. Further, washing with pure water is also an effective means after washing with the organic solvent. At this time, it is preferable that the final cleaning liquid is as clean (deionized) as possible.

The film thickness of the anodized film formed as described above is preferably about 5 to 15 μm. If it is thinner than this, the effect of the barrier property as an anodized film is not sufficient, and if it is thicker than this, the time constant as an electrode becomes too large and the generation of residual potential and the response of the photoreceptor deteriorate. There is a case.

Next, the photosensitive layer will be described. The photosensitive layer is composed of a charge generation layer 35 and a charge transport layer 37. The charge generation layer 35 is a layer containing a charge generation material as a main component. The charge generation layer 35 comprises a charge generation material and a binder resin, if necessary, dispersed in a suitable solvent using a ball mill, an attritor, a sand mill, ultrasonic waves, or the like, and this is coated on a conductive support. It is formed by drying. As the binder resin used for the charge generation layer 35, polyamide,
Polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone,
Polystyrene, polysulfone, poly-N-vinylcarbazole, polyacrylamide, polyvinylbenzal,
Examples thereof include polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyphenylene oxide, polyamide, polyvinyl pyridine, cellulosic resin, casein, polyvinyl alcohol, polyvinyl pyrrolidone, and the like. Among them, polyvinyl acetal typified by polyvinyl butyral is favorably used,
In particular, polyvinyl acetal (butyral) having an acetylation degree of 4 mol% or more is favorably used. The amount of the binder resin is appropriately 0 to 500 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the charge generating substance.

Known charge generating materials can be used for the charge generating layer 35, and representative examples thereof include monoazo pigments, disazo pigments, trisazo pigments, perylene pigments, perinone pigments, quinacridone pigments and quinones. Examples include condensed polycyclic compounds, squaric acid dyes, phthalocyanine pigments, naphthalocyanine pigments, and azurenium salt dyes. Among them, azo pigments and / or phthalocyanine pigments are effectively used. Particularly, as an azo pigment represented by the following structural formula (I), and at least 27.2 as a diffraction peak (± 0.2 °) of a Bragg angle 2θ with respect to titanyl phthalocyanine (particularly CuKα characteristic X-ray (wavelength 1.541Å)). The titanyl phthalocyanine which has a maximum diffraction peak at 0 can be effectively used.

[Chemical 1] (In the formula, Cp ₁ and Cp ₂ represent a coupler residue and may be the same or different. R ₂₀₁ and R ₂₀₂ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a cyano group. They may be the same or different.
Further, Cp ₁ and Cp ₂ are represented by the following formula (II). )

[Chemical 2] (In the formula, R ₂₀₃ represents a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or an aryl group such as a phenyl group.
₂₀₄ , R ₂₀₅ , R ₂₀₆ , R ₂₀₇ and R ₂₀₈ are each a hydrogen atom, a nitro group, a cyano group, a halogen atom such as fluorine, chlorine, bromine or iodine, an alkyl such as a trifluoromethyl group, a methyl group or an ethyl group. Group, an alkoxy group such as a methoxy group and an ethoxy group, a dialkylamino group, a hydroxyl group, and Z is an atomic group necessary for constituting a substituted or unsubstituted aromatic carbocycle or a substituted or unsubstituted aromatic heterocycle. Represents )

[0042] In particular, said Cp ₁ and asymmetric azo pigment Cp ₂ are different structures, Cp ₁ and Cp ₂ than the target azo pigments have the same structure, if the photosensitivity is good many of the photoconductor It can be used effectively because it can support smaller diameters and faster use processes. Further, among the titanyl phthalocyanines having a maximum diffraction peak at 27.2 ° as a Bragg angle 2θ diffraction peak (± 0.2 °), a titanyl phthalocyanine having a minimum angle at 7.3 ° (JP 2001-19871A). Can be used particularly effectively. These charge generating substances may be used alone or in combination of two or more.

Solvents used for forming the charge generation layer include isopropanol, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane, toluene, xylene, Examples include ligroin. When the charge generation layer is directly formed on the anodic oxide film, the solvent used for coating the charge generation layer is used for contact rub cleaning of the anodic oxide film. As the coating method of the coating liquid, a dip coating method, spray coating, beat coating, nozzle coating, spinner coating, ring coating, or the like can be used.

The thickness of the charge generation layer 35 is 0.01 to 5 μm.
m is suitable, and preferably 0.1 to 2 μm.

The charge transport layer 37 can be formed by dissolving or dispersing the charge transport substance and the binder resin in a suitable solvent, coating the resultant on the charge generating layer, and drying. If necessary, a plasticizer, a leveling agent, an antioxidant, etc. may be added.

The charge transport material includes a hole transport material and an electron transport material. Examples of the charge transport substance include chloranil, bromanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone and 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-4-one, 1,3,7-trinitrodibenzothiophene-5,5-dioxide, and benzoquinone derivative. As the hole transport material, poly-N-vinylcarbazole and its derivatives, poly-γ
-Carbazolyl ethyl glutamate and its derivatives, pyrene-formaldehyde condensate and its derivatives, polyvinylpyrene, polyvinylphenanthrene, polysilane,
Oxazole derivative, oxadiazole derivative, imidazole derivative, monoarylamine derivative, diarylamine derivative, triarylamine derivative, stilbene derivative, α-phenylstilbene derivative, benzidine derivative, diarylmethane derivative, triarylmethane derivative, 9-styrylanthracene Examples thereof include derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives and other known materials. These charge transport materials may be used alone or
Used as a mixture of two or more species.

As the binder resin, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, poly Vinyl acetate, polyvinylidene chloride, polyarylate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, Urethane resin,
Examples include thermoplastic or thermosetting resins such as phenolic resins and alkyd resins.

The amount of the charge transport material is 20 to 300 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder resin.
Parts by weight are suitable. The thickness of the charge transport layer is 5 to 5
It is preferably about 0 μm. Especially when high resolution is required, it is preferable that the film thickness of the charge transport layer is 20 μm or less, and thinning of the charge transport layer is most effective for improving the resolution.

As the solvent used for forming the charge transport layer, tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone or the like is used.

Further, the charge transport layer may contain a polymer having an electron donating group. The polymer having an electron-donating group is a polymer charge-transporting substance having a function as a charge-transporting substance and a function of a binder resin, or a monomer or an oligomer having an electron-donating group at the time of forming the charge-transporting layer. In this state, a polymer having a two-dimensional or three-dimensional crosslinked structure is finally included by carrying out a curing reaction or a crosslinking reaction after film formation.

The charge transport layer composed of these polymer charge transport substances or the polymer having a crosslinked structure has excellent abrasion resistance. Usually, in the electrophotographic process, the charging potential (potential of unexposed portion) is constant, and therefore, when the surface layer of the photoconductor is worn by repeated use, the electric field strength applied to the photoconductor is correspondingly increased. As the electric field strength increases, the frequency of occurrence of scumming increases, and thus the high wear resistance of the photoconductor is advantageous for scumming. This tendency is particularly remarkable when the anodized film of the present invention is included.

Known materials can be used as the polymer charge transporting material, but the triarylamine structure is used as the main chain and / or
Alternatively, a polycarbonate containing a side chain is preferably used.

Examples of the polycarbonate containing a triarylamine structure in the main chain and / or side chain include the following.

[Chemical 3] (In the formula, R₁, R₂, R₃Each independently replaced
Is an unsubstituted alkyl group or halogen atom, R_FourIs hydrogen
Child or substituted or unsubstituted alkyl group, R_Five, R ₆Is
A substituted or unsubstituted aryl group, o, p, and q are each
Independently, an integer of 0 to 4, k and j represent compositions, and 0.1 ≦
k ≦ 1, 0 ≦ j ≦ 0.9, n represents the number of repeating units 5
Is an integer of ~ 5000. X is an aliphatic divalent group, a cyclic fat
Represents an aliphatic divalent group or a divalent group represented by the following general formula
You )

[Chemical 4] (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 from 0 to 4, Y is a single bond, and has 1 to 1 carbon atoms.
2, a linear, branched or cyclic alkylene group, -O
-, - S -, - SO -, - SO 2 -, - CO -, - CO
-O-Z-O-CO- (in the formula, Z represents an aliphatic divalent group), or

[Chemical 5] (In the formula, a represents an integer of 1 to 20, b represents an integer of 1 to 2000, and R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or aryl group.). Where R ₁₀₁ and R ₁₀₂ , R
₁₀₃ and R ₁₀₄ may be the same or different.

[Chemical 6] (In the formula, R ₇ and R ₈ are substituted or unsubstituted aryl groups,
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 formula (III). )

[Chemical 7] (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 represented by the formula (III). Is the same as.)

[Chemical 8] (In the formula, 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 p is an integer of 1 to 5. X, k, j and n. Is
This is the same as the case of the formula (III). )

[Chemical 9] (In the formula, R₁₃, R₁₄Is a substituted or unsubstituted aryl
Group, Ar_Ten, Ar₁₁, Ar ₁₂Are the same or different Arylene
Group, X₁, X₂Is a substituted or unsubstituted ethylene group, or
It represents a substituted or unsubstituted vinylene group. X, k, j
And n are the same as in the case of the formula (III). )

[Chemical 10] (In the formula, 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 Are 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
This is the same as the case of the formula (III). )

[Chemical 11] (In the formula, R ₁₉ and R ₂₀ represent a hydrogen atom or a substituted or unsubstituted aryl group, and R ₁₉ and R ₂₀ may form a ring. Ar ₁₇ , Ar ₁₈ and Ar ₁₉ are the same or different. Represents an arylene group, and X, k, j and n are the same as in the case of the formula (III).)

[Chemical 12] (In the formula, R ₂₁ represents a substituted or unsubstituted aryl group, Ar
₂₀ , Ar ₂₁ , Ar ₂₂ , and Ar ₂₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of the formula (III). )

[Chemical 13] (In the formula, R ₂₂ , R ₂₃ , R ₂₄ , and R ₂₅ are substituted or unsubstituted aryl groups, Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ , and Ar.
₂₈ represents the same or different arylene groups. X, k, j and n are the same as in the case of the formula (III). )

[Chemical 14] (In the formula, R₂₆, R₂₇Is a substituted or unsubstituted aryl
Group, Ar₂₉, Ar₃₀, Ar ₃₁Are the same or different Arylene
Represents a group. X, k, j and n are the same as in the case of the formula (III).
It is the same. )

These polymer charge transport substances may be used alone, or may be used as a mixture of two or more kinds with other polymer charge transport substances. It is also possible to use a low molecular charge transport material together.

Other polymers having an electron-donating group include copolymers of known monomers, block polymers, graft polymers, star polymers, and, for example, JP-A-3.
-109406, JP 2000-206723 A
It is also possible to use a cross-linked polymer having an electron donating group as disclosed in JP-A No. 2001-34001 and the like.

In the photoconductor of the present invention, a plasticizer or a leveling agent may be added to the charge transport layer 37. As the plasticizer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount thereof is 0 to 30 relative to the binder resin.
About wt% is appropriate. As the leveling agent, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain are used, and the amount thereof is 0 to the binder resin. 1% by weight is suitable.

In the photoreceptor of the present invention, an undercoat layer can be provided between the anodized film 33 and the photosensitive layer (charge generation layer or charge transport layer). The subbing layer generally contains a resin as a main component, but considering that the photosensitive layer is coated on the resin with a solvent, the resin may be a resin having high solvent resistance to a general organic solvent. desirable. Such resins include polyvinyl alcohol, casein,
Water-soluble resin such as sodium polyacrylate, copolymer nylon, alcohol-soluble resin such as methoxymethylated nylon, polyurethane, melamine resin, phenol resin,
Examples include alkyd-melamine resins, epoxy resins, and other curable resins that form a three-dimensional network structure. Further, in order to prevent moire and reduce the residual potential, a fine powder pigment of a metal oxide such as titanium oxide, silica, alumina, zirconium oxide, tin oxide or indium oxide may be added to the undercoat layer.

These undercoat layers can be formed by using an appropriate solvent and coating method as in the above-mentioned photosensitive layer. When an undercoat layer is used, the solvent used for coating the undercoat layer is used for contact rub cleaning of the anodized film. Further, a silane coupling agent, a titanium coupling agent, a chromium coupling agent or the like can be used as the undercoat layer of the present invention. In addition, the undercoat layer of the present invention is provided with Al ₂ O ₃ by anodic oxidation,
Organic substances such as polyparaxylylene (parylene) and Si
Those provided with an inorganic substance such as O ₂ , SnO ₂ , TiO ₂ , ITO, and CeO ₂ by the vacuum thin film forming method can also be favorably used. Besides these, known ones can be used. The thickness of the undercoat layer is suitably 0 to 5 μm.

In the photoreceptor of the present invention, a protective layer may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer (charge generation layer or charge transport layer). Materials used for the protective layer include 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,
Examples thereof include resins such as polyethylene terephthalate, polyimide, acrylic resin, polymethylpentene, polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS resin, butadiene-styrene copolymer, polyurethane, polyvinyl chloride, polyvinylidene chloride and epoxy resin. As a method for forming the protective layer, a usual coating method is adopted. The thickness of the protective layer is 0.1 to 10 μm.
The degree is appropriate. In addition to the above, known materials such as aC and a-SiC formed by the vacuum thin film forming method can be used as the protective layer.

In particular, when a protective layer is provided and a high resolution is required, it is preferable that the total thickness of the photosensitive layer and the protective layer is 20 μm or less. Is most effective.

A charge-transporting substance can be used for the protective layer, which is an effective means from the standpoint of suppressing an increase in residual potential due to stacking the protective layers. As the charge-transporting substance, the materials as mentioned above in the description of the charge-transporting layer can be used. Regarding the proper use of the hole transporting material and the electron transporting material, it is preferable to select appropriately depending on the polarity of charging and the layer structure. Further, as the charge-transporting substance, the above-described polymer charge-transporting substance and the polymer having an electron-donating group can also be used.

In addition, a filler may be added to the protective layer for the purpose of improving abrasion resistance. Examples of the organic filler material include fluororesin powder such as polytetrafluoroethylene, silicone resin powder, and a-carbon powder, and examples of the inorganic filler material include metal powder such as copper, tin, aluminum, and indium. Silica, tin oxide, zinc oxide, titanium oxide, indium oxide,
Examples thereof include metal oxides such as antimony oxide, bismuth oxide, antimony-doped tin oxide and tin-doped indium oxide, and inorganic materials such as potassium titanate. In particular, from the viewpoint of the hardness of the filler, it is advantageous to use the inorganic material among them. In particular, silica, titanium oxide,
Alumina can be effectively used.

The average primary particle size of the filler is 0.0
The thickness is preferably 1 to 0.5 μm from the viewpoint of wear resistance of the protective layer. When the average primary particle diameter of the filler is 0.01 μm or less, abrasion resistance and dispersibility are deteriorated, and when it is 0.5 μm or more, sedimentation of the filler in the dispersion is promoted. The toner filming may occur. The higher the filler material content in the protective layer, the better the wear resistance, but
If it is too high, side effects such as increase in residual potential may occur. Therefore, approximately 50% by weight based on the total solid content
Hereafter, it is preferably about 30% by weight or less.

In the photoreceptor of the present invention, it is possible to provide an intermediate layer between the photosensitive layer and the protective layer.
Generally, a binder resin is used as a main component. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As a method of forming the intermediate layer, a usual coating method is adopted as described above. In addition,
The suitable thickness of the intermediate layer is about 0.05 to 2 μm.

Further, in the present invention, for the purpose of improving the environment resistance, in particular, for the purpose of preventing a decrease in sensitivity and an increase in residual potential, each layer is provided with an antioxidant, a plasticizer, a lubricant, an ultraviolet absorber and a low molecular weight compound. Charge transport materials and leveling agents can be added. Representative materials for these compounds are described below.

Examples of the antioxidant that can be added to each layer include, but are not limited to, the followings. (A) Phenol compound 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, n-octadecyl-3- (4 '-Hydroxy-3', 5'-di-t-butylphenol),
2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-
Ethyl-6-t-butylphenol), 4,4'-thiobis- (3-methyl-6-t-butylphenol),
4,4'-butylidene bis- (3-methyl-6-t-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane,
1,3,5-Trimethyl-2,4,6-tris (3,5
-Di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-
t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, tocopherols and the like. (B) Para-phenylenediamines N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-
Phenylenediamine, N, N'-di-isopropyl-p
-Phenylenediamine, N, N'-dimethyl-N, N '
-Di-t-butyl-p-phenylenediamine and the like. (C) Hydroquinones 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t
-Octyl-5-methylhydroquinone, 2- (2-octadecenyl) -5-methylhydroquinone and the like. (D) Organic sulfur compounds Dilauryl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, ditetradecyl-3,3'-thiodipropionate and the like. (E) Organic phosphorus compounds Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine, and the like.

Examples of the plasticizer that can be added to each layer include, but are not limited to, the following. (A) Phosphate ester plasticizer triphenyl phosphate, tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, trichloroethyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, Examples include triphenyl phosphate. (B) Phthalate ester plasticizers dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, phthalate. Acid dinonyl, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, butylbenzyl phthalate, butyllauryl phthalate, methyloleyl phthalate, octyldecyl phthalate, dibutyl fumarate, dioctyl fumarate and so on. (C) Aromatic carboxylic acid ester-based plasticizer trioctyl trimellitate, tri-n trimellitate
-Octyl, octyl oxybenzoate and the like. (D) Aliphatic dibasic acid ester plasticizer dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, di-n-adipate
Octyl, adipic acid-n-octyl-n-decyl, diisodecyl adipate, dicapryl adipate, di-2-ethylhexyl azelate, dimethyl sebacate,
Diethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, di-2-ethylhexyl sebacate, di-2-ethoxyethyl sebacate, dioctyl succinate, diisodecyl succinate, dioctyl tetrahydrophthalate, dihydrotetrahydrophthalate -N-octyl and the like. (E) Fatty acid ester derivative butyl oleate, glycerin monooleate, methyl acetylricinoleate, pentaerythritol ester, dipentaerythritol hexaester,
Examples include triacetin and tributyrin. (F) Oxyester plasticizers such as methyl acetylricinoleate, butyl acetylricinoleate, butylphthalylbutyl glycolate, and tributyl acetylcitrate. (G) Epoxy plasticizer Epoxidized soybean oil, epoxidized linseed oil, epoxy butyl stearate, decyl epoxy stearate, octyl epoxy stearate, benzyl epoxy stearate, dioctyl epoxy hexahydrophthalate, didecyl epoxy hexahydrophthalate, etc. There is. (H) Dihydric alcohol ester plasticizers such as diethylene glycol dibenzoate and triethylene glycol di-2-ethylbutyrate. (I) Chlorine-containing plasticizers such as chlorinated paraffin, chlorinated diphenyl, chlorinated fatty acid methyl, and methoxychlorinated fatty acid methyl. (J) Polyester plasticizers Polypropylene adipate, polypropylene sebacate, polyester, acetylated polyester and the like. (K) Sulfonic acid derivatives p-toluenesulfonamide, o-toluenesulfonamide, p-toluenesulfoneethylamide, o-toluenesulfoneethylamide, toluenesulfone-N-ethylamide, p-toluenesulfone-N-cyclohexylamide and the like. is there. (L) Citric Acid Derivatives Triethyl citrate, triethyl citrate citrate, tributyl citrate, acetyl citrate tributyl, acetyl citrate tri-2-ethylhexyl, acetyl citrate -n-octyldecyl and the like. (M) Other terphenyls, partially hydrogenated terphenyls, camphor, 2
-Nitrodiphenyl, dinonylnaphthalene, methyl abietate and the like.

Examples of the lubricant that can be added to each layer include, but are not limited to, the following. (A) Hydrocarbon-based compound Liquid paraffin, paraffin wax, microwax, low-polymerization polyethylene and the like. (B) Fatty acid compounds Lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and the like. (C) Fatty acid amide compounds Stearyl amide, palmityl amide, olein amide, methylene bis stearamide, ethylene bis stearamide and the like. (D) Ester-based compounds: lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, fatty acid polyglycol esters, etc. (E) Alcohol compounds Cetyl alcohol, stearyl alcohol, ethylene glycol, polyethylene glycol, polyglycerol and the like. (F) Metal soaps Lead stearate, cadmium stearate, barium stearate, calcium stearate, zinc stearate, magnesium stearate and the like. (G) Natural waxes such as carnauba wax, candelilla wax, beeswax, whale wax, ivorot wax, and montan wax. (H) Others include silicone compounds and fluorine compounds.

Next, the image forming method and the image forming apparatus of the present invention will be described in detail with reference to the drawings.

FIG. 4 is a schematic diagram for explaining the image forming process and the image forming apparatus of the present invention, and the following modified examples also belong to the scope of the present invention. In FIG. 4, the photoconductor 1 has an oxide film on the conductive support,
At least a charge generation layer and a charge transport layer are provided thereon, and the surface of the anodized film is subjected to a specific cleaning treatment. Although the photoconductor 1 has a drum shape,
It may be in the form of a sheet or an endless belt.
As the charging charger 3, the pre-transfer charger 7, the transfer charger 10, the separation charger 11, and the pre-cleaning charger 13, known means such as a corotron, a scorotron, a solid state charger (solid state charger), and a charging roller are used. To be As the charging member, one that is in contact with or placed close to the photoconductor is preferably used. Further, when the photoconductor is charged by the charging member, charging unevenness can be effectively reduced by charging the photoconductor with an electric field in which a direct current component and an alternating current component are superimposed on the charging member. Generally, the above charger can be used as the transfer means, but it is effective to use a combination of a transfer charger and a separation charger as shown in the figure.

The light sources such as the image exposure unit 5 and the static elimination lamp 2 are fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light emitting diodes (LE).
D), semiconductor lasers (LD), electroluminescence (EL) and the like can be used in general.
Further, various filters such as a sharp cut filter, a bandpass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.

Such a light source or the like is provided with a process such as a transfer process using light irradiation, a charge eliminating process, a cleaning process, or a pre-exposure process in addition to the process shown in FIG.
The photoconductor is irradiated with light.

The toner developed on the photoconductor 1 by the developing unit 6 is transferred to the transfer paper 9, but not all of the toner is transferred, and some toner remains on the photoconductor 1. Such toner is used in the cleaning brush 1.
It is removed from the photoconductor by the blade 4 and the blade 15. Cleaning may be performed only with a cleaning brush, and known cleaning brushes such as a fur brush and a magfur brush are used.

When the electrophotographic photoreceptor is positively (negatively) charged and imagewise exposed, a positive (negative) electrostatic latent image is formed on the surface of the photoreceptor. By developing this with a toner of positive (negative) polarity, a negative image is obtained and reverse development is performed. A known method is applied to the developing means, and a known method is used for the charge removing means.

FIG. 5 shows another example of the image forming process according to the present invention. The photoconductor 21 has an oxide film on a conductive support, on which at least a charge generation layer and a charge transport layer are provided, and the surface of the anodized film is subjected to a specific cleaning treatment. Driven by the drive rollers 22a and 22b, charging by the charger 23, image exposure by the light source 24, reversal development (not shown), transfer using the charger 25,
Pre-cleaning exposure by the light source 26, cleaning by the brush 27, and static elimination by the light source 28 are repeated. In FIG. 5, the photoreceptor 21 (of course, the support is transparent in this case) is irradiated with light for pre-cleaning exposure from the support side.

The image forming process illustrated above is an example of the embodiment of the present invention, and, of course, other embodiments are possible. For example, in FIG. 5, the pre-cleaning exposure is performed from the support side, but this may be performed from the photosensitive layer side, or the image exposure charge removal light may be irradiated from the support side.

On the other hand, in the light irradiation process, image exposure, pre-cleaning exposure, and static elimination exposure are shown, but in addition, pre-transfer exposure, pre-exposure for image exposure, and other known light irradiation processes are provided to perform exposure. It is also possible to irradiate the body with light.

The image forming means as described above may be fixedly incorporated in a copying machine, a facsimile machine or a printer, but may be incorporated in these machines in the form of a process cartridge. The process cartridge is one device (component) that contains a photoconductor and that also includes a charging unit, an exposure unit, a reversal developing unit, a transfer unit, a cleaning unit, and a charge eliminating unit. There are many shapes of process cartridges and the like, and as a general example, the one shown in FIG. 6 is given. The photoreceptor 16 has an electrically conductive support and an oxide film on the electrically conductive support, and at least a charge generation layer and a charge transport layer are provided thereon. The surface of the anodized film is subjected to a specific cleaning treatment. It has been given.

[0079]

EXAMPLES The present invention will be described below with reference to examples.
The invention is not limited by the examples. All parts are parts by weight.

[0080]Example 1 Aluminum cylinder with a length of 334 mm and a diameter of 60 mm
-(JIS1050) as a conductive support,
The anodic oxide film is treated to coat the charge generation layer with the following composition
Solution and charge transport layer coating solution are sequentially formed to give a charge of 0.3 μm
A photoconductor is obtained by forming a generation layer and a charge transport layer of 20 μm.
It wasAnodized film treatment The surface of the support is mirror-polished, degreased and washed with water.
After carrying out the procedure, the temperature of the solution is 20 ℃
Soak and anodize at 30V for 30 minutes
went. After washing with water, add 7% nickel acetate.
The sealing treatment was performed with an aqueous solution (50 ° C.). Then the above
The support is a cellulosic soaked with tetrahydrofuran.
It is a non-woven cloth made of cloth and long while rotating the support.
Scrubbing was performed in the hand direction. After this, tet on the support
Sprinkle lahydrofuran like a shower and rinse thoroughly
After cleaning, it is dried to form a 7μm anodic oxide film.
Got a support.Charge generation layer coating liquid     3 parts titanyl phthalocyanine having XD spectrum shown in FIG.     Polyvinyl butyral 2 parts     Tetrahydrofuran 120 partsCharge transport layer coating liquid     7 parts charge transport material with the following structure

[Chemical 15] Z type polycarbonate 10 parts Methylene chloride 80 parts

[0081]Example 2 Rinsing with tetrahydrofuran in Example 1
Other than washing with pure water after (shower washing)
A photoconductor was prepared in the same manner as in Example 1.

[0082]Example 3 The charge transport layer coating liquid in Example 1 was prepared as follows.
A photoconductor was prepared in the same manner as in Example 1 except that
It wasCharge transport layer coating liquid     Polymer charge transport material with the following structure 10 parts

[Chemical 16] (N = 200) 80 parts of methylene chloride

[0083]Example 4 The thickness of the charge transport layer in Example 1 was set to 18 μm and
On the charge transport layer, apply a protective layer coating solution having the following composition,
A protective layer having a thickness of μm was formed to prepare a photoconductor. (Protective layer coating liquid)     2 parts charge transport material with the following structure

[Chemical 17] Z type polycarbonate 10 parts Methylene chloride 80 parts

[0084]Example 5 The thickness of the charge transport layer in Example 1 was set to 18 μm and
On the charge transport layer, apply a protective layer coating solution having the following composition,
A protective layer having a thickness of μm was formed to prepare a photoconductor. Curing condition: 130 ° C-1 hourProtective layer coating liquid     270 parts of tin oxide     Styrene-methyl methacrylate-2-hydroxy       Ethyl methacrylate (10/40/50 molar ratio) 100 parts     710 parts of acetone     Cellosolve acetate 730 parts     Methyl isobutyl ketone 160 parts     Hardener (Sumijour HT: Sumitomo Bayer) 60 parts

[0085]Example 6 The thickness of the charge transport layer in Example 1 was set to 18 μm and
On the charge transport layer, apply a protective layer coating solution having the following composition,
A protective layer having a thickness of μm was formed to prepare a photoconductor.Protective layer coating liquid     Z type polycarbonate 10 parts     7 parts charge transport material with the following structural formula

[Chemical 18] Alumina fine particles 4 parts (specific resistance: 2.5 × 10 ¹² Ω · cm, average primary particle size: 0.3 μm) Tetrahydrofuran 400 parts Cyclohexanone 200 parts

[0086]Example 7 The thickness of the charge transport layer in Example 1 was set to 25 μm
Except for the above, a photoconductor was prepared in the same manner as in Example 1.

[0087]Example 8 The thickness of the charge transport layer in Example 1 was set to 15 μm
Except for the above, a photoconductor was prepared in the same manner as in Example 1.

[0088]Example 9 The thickness of the charge transport layer in Example 6 was set to 23 μm
Except for the above, a photoconductor was prepared in the same manner as in Example 6.

[0089]Example 10 The thickness of the charge transport layer in Example 6 was set to 13 μm
Except for the above, a photoconductor was prepared in the same manner as in Example 6.

[0090]Comparative Example 1 Catalytic rubbing with tetrahydrofuran in Example 1
Only cleaning with pure water after the sealing process without cleaning.
Example 1 except that (no physical scrubbing) was performed.
Similarly, a photoconductor was prepared.

[0091]Comparative example 2 Catalytic rubbing with tetrahydrofuran in Example 1
Rubbing with pure water after sealing without cleaning.
Rinsing (rubbing material is the same as in Example 1)
A photoconductor was prepared in the same manner as in Example 1.

[0092]Comparative Example 3 Catalytic rubbing with tetrahydrofuran in Example 1
After the sealing treatment without cleaning, use a weak alkaline cleaning solution.
Contact scrubbing cleaning with (rubbing material is the same as in Example 1)
Example 1 except that the cleaning was performed and further the cleaning was performed with pure water.
Similarly, a photoconductor was prepared.

[0093]Comparative Example 4 Catalytic rubbing with tetrahydrofuran in Example 1
Contact without sealing and without solvent after cleaning and sealing
Scrub cleaning (rubbing material is the same as in Example 1), and
Photosensitization as in Example 1 except that cleaning with pure water was performed.
The body was made.

[0094]Comparative Example 5 Catalytic rubbing with tetrahydrofuran in Example 1
After the sealing treatment without washing, wash with methanol.
Cleans (without physical scrubbing) and then rinses with pure water
A photoconductor was prepared in the same manner as in Example 1 except that cleaning was performed.
It was

[0095]Comparative Example 6 Catalytic rubbing with tetrahydrofuran in Example 1
After the sealing treatment without cleaning, methyl ethyl ketone was used.
Cleaning (without physical scrubbing), and then pure water
Except that the cleaning was performed by
It was made.

[0096]Comparative Example 7 Catalytic rubbing with tetrahydrofuran in Example 1
After the sealing treatment without cleaning, use a 5% nitric acid aqueous solution.
Cleaning (without physical scrubbing) and then using pure water.
A photoconductor was prepared in the same manner as in Example 1 except that cleaning was performed.
did.

The photoconductors of Examples 1 to 10 and Comparative Examples 1 to 7 produced as described above were mounted in a process cartridge as shown in FIG. 6, and a copying machine (manufactured by Ricoh: imagio)
It was mounted on MF4550) and a running test of 20,000 sheets (continuous run) was performed. At this time, initial and 20000
A white solid image after printing was output and the level of background stain was evaluated. In addition, the amount of wear was measured by measuring the film thickness of the photoconductor before and after running 20,000 sheets. Furthermore, the resolution at the initial stage of running was evaluated. The results are shown in Table 1. The background stain rank in the table represents the level of background stain in stages, and the larger the number, the better. Evaluation was made on a scale of 5 with a maximum of 5 and a minimum of 1. Ranks 2 and below are levels that cannot withstand actual use.

[0098]

[Table 1]

From Table 1, it is understood that the photoconductor using the cleaning method of the present invention has a good background stain rank from the initial stage. Further, it is found that when a polymer charge transporting material is used for the charge transporting layer, or when a protective layer is used, the abrasion resistance is good, and in addition, the background stain rank does not easily decrease. Further, it is understood that the thinner the charge transport layer or the total thickness of the charge transport layer and the protective layer, the better the resolution.

[0100]Example 11 Aluminum cylinder with a length of 340 mm and a diameter of 30 mm (J
IS1050) is used as a conductive support, and this is used as the following anode
After applying an oxide film treatment, apply the charge generation layer coating solution
The load transport layer coating liquid is sequentially formed to generate a charge of 0.3 μm.
A 20 μm charge transport layer was formed to obtain a photoreceptor.Anodized film treatment The surface of the support is mirror-polished, degreased and washed with water.
After carrying out the procedure, the temperature of the solution is 20 ℃
Soak and anodize at 30V for 30 minutes
went. After washing with water, add 7% nickel acetate.
The sealing treatment was performed with an aqueous solution (50 ° C.). Then 2-
Non-fibrous material formed from cellulose impregnated with butanone
With a cloth, scrub and wash the support in the longitudinal direction while rotating the support.
Carried out. After that, shake 2-butanone like a shower.
After thoroughly rinsing and washing, dry and
A support on which an anodized film was formed was obtained.Charge generation layer coating liquid     10 parts of bisazo pigment having the following structure

[Chemical 19]     Polyvinyl butyral 2 parts     2-butanone 200 parts     Cyclohexanone 400 partsCharge transport layer coating liquid     7 parts charge transport material with the following structure

[Chemical 20] Z type polycarbonate 10 parts Methylene chloride 80 parts

[0101]Comparative Example 8 Contact scrub cleaning with 2-butanone in Example 11
After performing the sealing treatment without performing
Same as Example 11 except that no physical scrubbing was performed).
Thus, a photoconductor was prepared.

[0102]Comparative Example 9 Contact scrub cleaning with 2-butanone in Example 11
After performing the sealing treatment without performing the above, contact scrubbing with pure water
Except that cleaning (rubbing material is the same as in Example 11) was performed
A photoconductor was prepared in the same manner as in Example 11.

[0103]Comparative Example 10 Contact scrub cleaning with 2-butanone in Example 11
After performing the sealing treatment without performing the
Contact scrubbing (rubbing material is the same as in Example 11)
Example 11, except that cleaning with pure water was further performed
Similarly, a photoconductor was prepared.

[0104]Comparative Example 11 Contact scrub cleaning with 2-butanone in Example 11
After performing the sealing treatment without performing
Rinse (rubbing material is the same as in Example 11)
Photosensitization as in Example 11 except that washing with water was performed.
The body was made.

[0105]Comparative Example 12 Contact scrub cleaning with 2-butanone in Example 11
Cleaning with ethanol after sealing without performing
(Without physical scrubbing) and further cleaning with pure water
A photoconductor was prepared in the same manner as in Example 11 except that
It was

[0106]Comparative Example 13 Contact scrub cleaning with 2-butanone in Example 11
After performing the sealing treatment without performing
(Without physical scrubbing) and then with pure water.
A photoconductor was produced in the same manner as in Example 11 except that the above was used.

[0107]Comparative Example 14 Contact scrub cleaning with 2-butanone in Example 11
After performing the sealing treatment without washing, washing with 5% nitric acid aqueous solution
Cleans (without physical scrubbing) and then rinses with pure water
A photoconductor was prepared in the same manner as in Example 11 except that cleaning was performed.
It was

The photoconductors of Example 11 and Comparative Examples 8 to 14 described above were mounted in a process cartridge as shown in FIG. 6, and the writing light source was mounted in a copying machine (Imagio MF2200 manufactured by Ricoh Co., Ltd.). ,
A running test was performed on 10,000 sheets (continuous run).
At this time, white solid images at the initial stage and after 10,000 sheets were output to evaluate the background stain level. The results are shown in Table 2.
The background stain rank in the table represents the level of background stain in stages, and the larger the number, the better. Evaluation was made on a scale of 5 with a maximum of 5 and a minimum of 1. Ranks 2 and below are levels that cannot withstand actual use.

[0109]

[Table 2]

[0110]

As described above, in the method for producing an electrophotographic photosensitive member according to claim 1, the surface of the electrophotographic photosensitive member is provided with at least a charge generation layer and a charge transport layer on a conductive support whose surface is anodized. A liquid containing a coating solvent used when forming a photoconductor coating on the anodized film is used, and the surface of the anodized film is physically contacted and rubbed to clean the anodized film. According to the method for manufacturing an electrophotographic photosensitive member, which is characterized by forming a film, a more reliable cleaning operation is performed by eluting and removing the adhered components on the surface and the impurities taken in the pores, resulting in point defects. Can be prevented, and in particular, point defects in the initial state of the photoconductor mounted in the image forming apparatus can be prevented.

According to the method for producing an electrophotographic photosensitive member according to claim 2, according to the method for producing an electrophotographic photosensitive member characterized in that the anodic oxide film is subjected to a sealing treatment, an anode usually produced. Since the oxide film is porous and has high insulation, the surface is in an unstable state, there is a change with time after production, and the physical properties of the anodic oxide film tend to change, so to avoid this, By further sealing the anodic oxide film, it becomes possible to obtain a photoconductor in which an image with less background stain than in the initial state can be obtained.

In the method for manufacturing an electrophotographic photosensitive member according to claim 3 or claim 2, after the contact scrub cleaning, cleaning with pure water is performed. For example, it is effective to rinse the solvent used with running water like a shower after scrubbing, and further, after cleaning the organic solvent, the final cleaning solution should be as clean as possible (deionized). Cleaning with pure water enables stable images with less background stains.

Any one of claims 1 to 3 of claim 4
According to the electrophotographic photosensitive member manufactured by the method for manufacturing an electrophotographic photosensitive member according to the item, by performing a reliable cleaning operation by eluting and removing the fixed components on the surface and the impurities taken in the pores, point defects It is possible to prevent the occurrence of point defects in the image in the initial state of the photoconductor mounted on the image forming apparatus.

In the electrophotographic photosensitive member according to claim 5 or 4, the outermost surface layer of the photosensitive member is a charge transport layer, and the charge transport layer contains a polymer having an electron donating group. According to the electrophotographic photoreceptor, the charge transport layer composed of a polymer charge transport material or a polymer having a crosslinked structure has excellent wear resistance, and in particular, it may have the anodic oxide film of the present invention. It is advantageous in reducing dirt.

According to the electrophotographic photosensitive member of claim 6 or claim 4, the protective layer is provided on the outermost surface of the photosensitive member, and the electrophotographic photosensitive member has excellent abrasion resistance. Therefore, it is possible to advantageously prevent the background stain and the point defect of the image obtained by using the photoreceptor having the anodized film of the present invention.

The electrophotographic photosensitive member according to claim 7 or 6, wherein the protective layer contains a low molecular charge transporting substance or a polymer having an electron donating property. By using the charge-transporting substance, it is possible to suppress an increase in residual potential due to the lamination of the protective layer.

The electrophotographic photosensitive member according to claim 8 or 6, wherein the protective layer contains a filler, and the electrophotographic photosensitive member according to claim 6 or 7. It is possible to further enhance the durability of.

Any one of claims 4 to 8 of claim 9
In the electrophotographic photosensitive member according to the item 1, the thickness of the photosensitive layer is 2
According to the electrophotographic photoconductor characterized by being 0 μm or less, it is possible to obtain an image with high resolution.

According to claim 10, at least charging, image exposure,
An image forming method in which development and transfer are repeated, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 4 to 9, By using the body, an image forming method capable of preventing point defects from the initial stage to the lapse of time is provided.

An image forming apparatus comprising at least a charging means, an image exposing means, a developing means, a transferring means and an electrophotographic photosensitive member according to claim 11, wherein the electrophotographic photosensitive member is any one of claims 4 to 9. According to the image forming apparatus, which is the electrophotographic photosensitive member described in (1), there is provided an image forming apparatus capable of preventing point defects from the initial stage to the elapsed time.

A process cartridge for an image forming apparatus, comprising at least the electrophotographic photosensitive member according to claim 12, wherein the electrophotographic photosensitive member is any one of claims 4 to 9.
According to the process cartridge for an image forming apparatus, which is the electrophotographic photosensitive member according to the item 1, there is provided a stable image forming apparatus and a process cartridge for the image forming apparatus with little background stain from the initial stage to the elapsed time. .

[0122]

[Brief description of drawings]

FIG. 1 is a sectional view showing a configuration of an electrophotographic photosensitive member of the present invention.

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

FIG. 3 is a sectional view showing still another configuration of the present invention.

FIG. 4 is a schematic diagram for explaining an image forming process and an image forming apparatus of the present invention.

FIG. 5 illustrates another example of an image forming process according to the present invention.

FIG. 6 shows an example of a process cartridge used in the image forming apparatus of the present invention.

FIG. 7 is a characteristic diagram of titanyl phthalocyanine having an XD spectrum used in the present invention.

[Explanation of symbols]

1 photoconductor 2 Static elimination lamp 3 Charger 5 Image exposure unit 6 Development unit 7 Charger before transfer 8 Registration roller 9 Transfer paper 10 Transfer charger 11 Separation Charger 12 separate nails 13 Charger before cleaning 14 cleaning brush 15 blades 16 photoconductor 17 Charger 18 cleaning brush 19 Image exposure unit 20 developing roller 21 photoconductor 22 Drive roller 23 Charger 24 Image exposure source 25 Transfer Charger 26 Cleaning before exposure 27 cleaning brush 31 conductive support 33 Anodized film 35 Charge generation layer 37 Charge Transport Layer 39 Protective layer

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2H035 CA07 CB01                 2H068 AA02 AA04 AA09 AA35 AA37                       AA59 BA13 BB25 BB49 CA06                       CA29 CA33 EA05 EA14

Claims (12)

[Claims] 1. A method for producing an electrophotographic photosensitive member comprising at least a charge generation layer and a charge transport layer provided on a conductive support, the surface of which is subjected to an anodized film treatment, wherein a photosensitive coating film is formed on the anodized film. A liquid containing a coating solvent used in forming, characterized in that the surface of the anodized film is subjected to physical contact scrub cleaning, and then a photoreceptor coating film is formed on the anodized film. Method for manufacturing electrophotographic photoreceptor. 2. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the anodic oxide film is sealed. 3. The electrophotographic photosensitive member manufacturing method according to claim 1, wherein cleaning with pure water is performed after the contact scrub cleaning. 4. An electrophotographic photosensitive member manufactured by the electrophotographic photosensitive member manufacturing method according to claim 1. 5. The electrophotographic photoreceptor according to claim 4, wherein the outermost surface layer of the photoreceptor is a charge transport layer, and the charge transport layer contains a polymer having an electron donating group. Photoconductor. 6. The electrophotographic photosensitive member according to claim 4, wherein a protective layer is provided on the outermost surface of the photosensitive member. 7. The electrophotographic photosensitive member according to claim 6, wherein the protective layer contains a low molecular weight charge transport material or a polymer having an electron donating property. 8. The electrophotographic photoreceptor according to claim 6 or 7, wherein the protective layer contains a filler. 9. The electrophotographic photosensitive member according to claim 4, wherein the photosensitive layer has a film thickness of 20 μm or less. 10. An electrophotographic photoreceptor, at least charged,
An image forming method in which image exposure, development and transfer are repeated, wherein the electrophotographic photosensitive member is any one of claims 4 to 9.
An image forming method, which is the electrophotographic photosensitive member according to the item 1. 11. At least a charging means, an image exposing means,
An image forming apparatus comprising a developing means, a transfer means, and an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 4 to 9. Image forming apparatus. 12. A process cartridge for an image forming apparatus, comprising at least an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 4 to 9. A process cartridge for an image forming apparatus characterized by the above.