JP2003149847A - Image forming device and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming device and a process cartridge in which both of the printing durability of an electrophotographic photoreceptor and cleaning characteristics are made high enough and by which excellent image quality is stably obtained over a long term. SOLUTION: This image forming device is equipped with the electrophotographic photoreceptor 1, an electrification means 2, an exposure means 3, a development means 4, a transfer means 5 and a cleaning means 7. In the device, an electrophotographic photoreceptor equipped with a photoreceptive layer provided with a surface layer including a silicone resin having charge transportability and having crosslinked structure on a far side from the substrate is used as the photoreceptor 1. Further, a cleaning means equipped with a cleaning blade consisting of an elastic sheet made of metal is used as the cleaning means 7, wherein the linear pressure of the cleaning blade to the photoreceptor 1 is set to 5 to 25 N/m.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming apparatus and a process cartridge.

[0002]

2. Description of the Related Art In an electrophotographic image forming process, a copy is obtained by sequentially performing the steps of charging, exposing, developing and transferring an electrophotographic photosensitive member. After the transfer step, the residual toner is removed by the cleaning step, and then the photoreceptor is repeatedly used in the next image forming process.

As a photoreceptor used in such an image forming process, from the viewpoint of sensitivity and stability, a layer in which a charge generating material is dispersed in a binder resin (charge generating layer) and a charge transporting material are bound. Layer dispersed or dissolved in resin (charge transport layer)
A function-separated electrophotographic photosensitive member in which and are separately provided on a conductive substrate has been devised and put into practical use.

In the case of the function-separated type photoreceptor, a hole transport material is often used as the charge transport material, and a binder resin thereof is a thermoplastic resin such as polycarbonate resin, polyester resin, acrylic resin, polystyrene resin, or polyurethane. Thermosetting resins such as resins and epoxy resins have been studied. The charge transport layer containing these materials is generally arranged on the surface side of the photoreceptor (the side far from the substrate). However, when such a photoreceptor is repeatedly used in the image forming process, the photoreceptor characteristics are deteriorated due to, for example, the following phenomena (i) to (iii). (I) Deterioration of resin due to ozone generated during the charging process by corona charging and roller charging (ii) Abrasion due to electric shock due to discharge on the surface of the photoconductor, sensitivity deterioration, deterioration of charging ability (iii) After charging Toner development, transfer to transfer medium,
Mechanical destruction due to friction during cleaning.

Therefore, various studies have been conducted in order to avoid such deterioration of the photoreceptor characteristics. As one of them, it has been attempted to blend a polysiloxane resin with a copolymerization component or another resin to improve the performance, life and cleaning property of the photoconductor. Photoreceptors using a resin for the charge transport layer (JP-A-61-238062, etc.) and photoreceptors having a protective layer containing a polysiloxane resin (JP-A-62-18061).
No. 108260), silica gel, urethane resin, and fluororesin dispersed in a thermosetting polysiloxane resin as a protective layer (JP-A-4-346356), and thermosetting polysiloxane resin dispersed in a thermoplastic resin. There is proposed a photoconductor (JP-A-4-273252) in which the resin thus formed is used as a protective layer or a binder resin for a charge transport material.

On the other hand, although polysiloxane is excellent in thermal and mechanical strength, it is extremely incompatible with an organic compound (charge generating material, etc.) that exhibits a function as an electronic device, so that polysiloxane should be put into practical use. Studies have been made to improve this drawback. For example, a resin in which a charge transfer agent having an unsaturated bond is directly bonded to polysiloxane such as poly (hydrogenmethylsiloxane) by hydrosilylation is used as a protective layer or a charge transfer material binder resin (JP-A-8-319353). ), Using a sol-gel method as a protective layer ("Proceedings o
f IS &T's Eleventh International Congress on Advanc
es in Non-Impact Printing Technologies, p.57-5
9 "), one using an organosilicon-modified hole-transporting compound in which silicon having a hydrolyzable group is directly introduced into a charge-transporting agent for an electrophotographic photoreceptor (JP-A-9-190004) and the like have been proposed. , Of these, "Proceedings of
IS &T's Eleventh International Congress on Advances
in Non-Impact Printing Technologies, p.57 ~ 59 ",
Japanese Patent No. 2575536, JP-A-9-190004
The one disclosed in Japanese Patent Laid-Open Publication No. 1994-53242 is particularly noted because a strong film is formed by forming a three-dimensional network of siloxane, and as a result, mechanical strength is dramatically improved.
Among them, the electrophotographic photosensitive member having a surface layer having a charge transporting property and made of a siloxane-based resin having a crosslinked structure has excellent mechanical strength and electrical stability.

[0007]

However, in the image forming apparatus using the above-mentioned conventional electrophotographic photosensitive member, the residual toner is continuously striped in the gap between the surface layer of the photosensitive member and the cleaning member during repeated use. The phenomenon of slipping through easily occurs, and the phenomenon of generation of streaks on the obtained image easily occurs. This cleaning failure is noticeable when the environment is high temperature and high humidity, and when the charging means is of the contact charging type and the charging voltage has an AC component.

The present invention has been made in view of the above-mentioned problems of the prior art. The electrophotographic photosensitive member has sufficiently high printing durability and cleaning characteristics, and a good image quality is stable for a long period of time. An object of the present invention is to provide an image forming apparatus and a process cartridge that can be obtained.

[0009]

As a result of intensive studies aimed at achieving the above object, the present inventors have used a photoreceptor having a surface layer containing a siloxane resin in a conventional image forming apparatus. Cleaning failure that occurs when
It has been found that the surface of the photoconductor has a high strength, so that the contact portion of the cleaning member is chipped. The reason why such cleaning failure is likely to occur in a high-temperature and high-humidity environment is considered to be that the surface of the photoconductor and the cleaning member tend to come into close contact with each other and the cleaning member is likely to be chipped. Also, when an AC voltage is applied by the contact charging method, the discharge product (nitrogen oxide, etc.) due to the contact charging reacts with water and adheres to the surface of the photoconductor, so that the surface of the photoconductor and the cleaning member adhere to each other. The present inventors presume that this is because the cleaning member is more likely to be chipped.

As a result of further diligent research on the basis of the above findings, the inventors of the present invention carried out a cleaning equipped with an electrophotographic photosensitive member having a surface layer containing a specific silicon resin and a cleaning blade made of an elastic thin plate made of metal. The inventors have found that the above problems can be solved by an image forming apparatus in which the linear pressure of the cleaning blade with respect to the electrophotographic photosensitive member is 5 to 25 N / m.

That is, the image forming apparatus of the present invention comprises an electrophotographic photosensitive member having a conductive substrate and a photosensitive layer disposed on the substrate, a charging means for charging the surface of the electrophotographic photosensitive member, and an electrophotographic photosensitive member. An exposure unit that exposes the surface to form an electrostatic latent image, a developing unit that develops the electrostatic latent image with toner to form a toner image, a transfer unit that transfers the toner image to a transfer medium, and an electronic unit. An image forming apparatus comprising: a cleaning unit that removes toner remaining on the surface of a photographic photoreceptor, wherein the photosensitive layer has a silicon resin having a charge transporting property and a crosslinked structure on the side far from the substrate. The cleaning means includes a layer, the cleaning means includes a cleaning blade made of an elastic thin plate made of metal, and the linear pressure of the cleaning blade with respect to the electrophotographic photosensitive member is 5 to 25 N. It is characterized in that it is m.

Further, the process cartridge of the present invention is
What is claimed is: 1. A process cartridge comprising: an electrophotographic photosensitive member including a conductive substrate and a photosensitive layer disposed on the substrate; and a cleaning unit for removing toner remaining on the surface of the electrophotographic photosensitive member, wherein the photosensitive layer is formed from the substrate. The distant side is provided with a surface layer containing a silicon resin having a charge transporting property and a crosslinked structure, the cleaning means is provided with a cleaning blade made of an elastic thin plate made of metal, and the electrophotographic photosensitive material is also provided. The linear pressure of the cleaning blade with respect to the body is 5 to 25 N / m.

In the present invention, an electrophotographic photosensitive member having a surface layer containing the above-mentioned specific silicon resin and a cleaning means having a cleaning blade made of an elastic thin plate made of metal are used. By setting the linear pressure to 5 to 25 N / m, sufficiently high cleaning characteristics can be achieved without damaging either the electrophotographic photosensitive member or the cleaning blade, so that good image quality can be stably obtained for a long period of time. It becomes possible.

Further, in the present invention, it is preferable that the shape factor of the toner is 100 to 140. By using the toner having such a shape factor, both the cleaning characteristic and the transfer characteristic can be further improved, so that the obtained image quality can be further improved. The shape factor in the present invention means the following formula (a): SF = 100πL _max ² / 4A (a) (In the formula, SF represents the shape factor, and L _max is the absolute maximum length of toner particles (average value). ), And A represents the projected area of the toner particles).

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawing,
The same or corresponding parts will be denoted by the same reference symbols and redundant description will be omitted.

FIG. 1 is a schematic configuration diagram showing a preferred embodiment of the image forming apparatus of the present invention. In the apparatus shown in FIG. 1, the electrophotographic photosensitive member 1 is supported by a support 9 and is rotatable about the support 9 in the direction of the arrow at a predetermined rotation speed. Then, the electrophotographic photoreceptor 1
The contact charging member 2, the exposure device 3, the developing device 4, the transfer device 5, and the cleaning blade 7 are arranged in this order along the rotation direction of. The apparatus also includes an image fixing device 6, and the transfer medium P is conveyed to the image fixing device 6 via the transfer device 5. (Electrophotographic Photoreceptor) FIG. 2 is a sectional view schematically showing the structure of the electrophotographic photoreceptor 1. The electrophotographic photosensitive member 1 shown in FIG. 2 has an undercoat layer 12 and a charge generation layer 1 on a conductive substrate 11.
3, the charge transport layer 14 and the protective layer 15 are sequentially laminated to have a photosensitive layer 16, and the protective layer 15 includes an organic group having a charge transporting property and an organic group having the same or different carbon atoms in the organic group. A crosslinked body having a skeleton composed of bonded silicon atoms and oxygen atoms bonded to the silicon atoms is included.

The conductive substrate 11 is formed by molding aluminum into a cylindrical shape (drum shape). As the substrate 11, an aluminum tube may be used as it is, but it is preferable to use a substrate whose outer peripheral surface has been subjected to surface treatment such as anodizing treatment, treatment with an acidic treatment liquid, and boehmite treatment.

The anodizing treatment is to form an oxide film on the surface of aluminum by anodizing aluminum in an electrolyte solution using aluminum as an anode. Examples of the electrolyte solution include sulfuric acid solution and oxalic acid solution. Since the anodic oxide film thus obtained is porous and chemically active, is easily contaminated, and has a large resistance variation due to the environment, the fine pores of the anodic oxide film should be treated with pressurized steam or boiling water (metal salt such as nickel). May be added) to block the volume expansion due to the hydration reaction and perform a sealing treatment to change to a more stable hydrated oxide. The thickness of the anodic oxide film is 0.
3 to 15 μm is preferable. When the film thickness is less than 0.3 μm, the barrier property against charge injection is low and sufficient effect tends not to be obtained. When the film thickness exceeds 15 μm,
The residual potential tends to increase during repeated use in the image forming process.

In the treatment with the acidic treatment liquid, phosphoric acid, chromic acid, hydrofluoric acid or the like is used as the acidic treatment liquid. The mixing ratio of the acid component in these treatment liquids is 10 to 11% by weight for phosphoric acid, 3 to 5% by weight for chromic acid, and 0.5 to 2% by weight for hydrofluoric acid. When the acid component is included, the sum of the acid compounding ratios is 3.5 to 1.
8% by weight is preferred. The treatment temperature is preferably 42 to 48 ° C., whereby a sufficiently thick coating can be efficiently formed. The film thickness of the coating is preferably 0.3 to 15 μm. When the film thickness is less than 0.3 μm, the barrier property against charge injection is low and sufficient effect tends not to be obtained. When the film thickness exceeds 15 μm, the residual potential tends to increase during repeated use in the image forming process.

The boehmite treatment can be carried out by immersing in pure water at 90 to 100 ° C. for 5 to 60 minutes or by contacting with heated steam at 90 to 120 ° C. for 5 to 60 minutes. The film thickness of the coating is preferably 0.1 to 5 μm. This is further added to adipic acid, boric acid, borate, phosphate,
The anodization treatment may be performed using an electrolyte solution having a low film solubility such as phthalate, maleate, benzoate, tartrate, and citrate.

When a laser light source is used as the exposure device 3, the outer peripheral surface of the substrate 11 has a center line average roughness Ra of 0.04 μm in order to prevent interference fringes generated when the laser light is irradiated. It is preferable to roughen the surface to 0.5 μm. As a roughening method, it is preferable to use wet honing performed by suspending an abrasive in water and spraying it on the substrate 11, or centerless grinding in which a support is pressed against a rotating grindstone to continuously perform grinding. . When Ra is less than 0.04 μm, it tends to be close to the mirror surface and the interference preventing effect cannot be obtained. On the other hand, Ra is 0.5 or less.
If it exceeds μm, the image quality tends to be rough even if a film is formed. When a light source that emits non-interfering light is used as the exposure device 3, it is not particularly necessary to roughen the surface to prevent interference fringes and it is possible to prevent the occurrence of defects due to the unevenness of the surface of the base material.
Suitable for longer life.

As the material of the base 11, in addition to aluminum, metal materials such as stainless steel and nickel; polymeric materials such as polyethylene terephthalate, polybutylene terephthalate, polypropylene, nylon, polystyrene, phenol resin, or insulation such as hard paper A material obtained by dispersing a conductive material in a material and subjected to a conductive treatment; a material obtained by laminating a metal foil on the above insulating material; a material on which a metal vapor deposition film is formed on the above insulating material can be used. Further, the shape of the substrate may be a sheet shape, a plate shape, or the like.

As the material of the undercoat layer 12, a zirconium chelate compound, a zirconium alkoxide compound,
Organic zirconium compounds such as zirconium coupling agents, titanium chelate compounds, titanium alkoxide compounds, organic titanium compounds such as titanate coupling agents, aluminum chelate compounds, organoaluminum compounds such as aluminum coupling agents, antimony alkoxide compounds, germanium Alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxide compounds, aluminum titanium alkoxide compounds, and organometallic compounds such as aluminum zirconium alkoxide compounds. , Of these, organic zirconium compounds, organic titanyl compounds, Machine aluminum compound residual potential are preferably used exhibits excellent electrophotographic characteristics lower.

Further, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3,4 -A silane coupling agent such as epoxycyclohexyltrimethoxysilane can be contained and used.

Further, polyvinyl alcohol, polyvinyl methyl ether, poly-N-vinyl imidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, polyethylene, polyester, phenol resin, Binder resins such as vinyl chloride-vinyl acetate copolymer, epoxy resin, polyvinylpyrrolidone, polyvinylpyridine, polyurethane, polyglutamic acid, and polyacrylic acid can also be used. The mixing ratio of these can be appropriately set as necessary.

An electron transporting substance may be mixed and dispersed in the undercoat layer 12 for use. Examples of the electron transporting substance include organic pigments such as perylene pigments, bisbenzimidazole perylene pigments, polycyclic quinone pigments, indigo pigments and quinacridone pigments described in JP-A-47-30330, and cyano groups, nitro groups, and nitroso. Examples thereof include organic pigments such as bisazo pigments or phthalocyanine pigments having electron-withdrawing substituents such as groups and halogen atoms, and inorganic pigments such as zinc oxide and titanium oxide. Among these pigments, perylene pigments, bisbenzimidazole perylene pigments and polycyclic quinone pigments are preferably used because of their high electron mobility. When the amount of the electron-transporting pigment is too large, the strength of the undercoat layer is lowered and a coating film defect is caused. Therefore, the content thereof is preferably 95% by weight or less, more preferably 90% by weight or less. The method of mixing / dispersing the charge-transporting substance is a ball mill,
A conventional method using a roll mill, a sand mill, an attritor, ultrasonic waves or the like is applied. Mixing / dispersion is carried out in an organic solvent, but as the organic solvent, if a metal compound or a resin having a fixed period is dissolved, and if gelation or aggregation does not occur when the electron transporting pigment is mixed / dispersed. Anything can be used. For example, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, acetic acid n.
Ordinary organic solvents such as -butyl, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene can be used alone or in combination of two or more.

The thickness of the undercoat layer 12 is preferably 0.1.
˜20 μm, more preferably 0.2 to 10 μm.
Further, as the coating method used when providing the undercoat layer, a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method,
Bead coating method, air knife coating method,
A usual method such as a curtain coating method can be used. The applied material is dried to obtain an undercoat layer,
Usually, the drying is performed at a temperature at which a solvent can be evaporated and a film can be formed. In particular, it is preferable to form an undercoat layer on a substrate that has been subjected to an acidic solution treatment or a boehmite treatment, since the defect hiding power of the substrate tends to be insufficient.

The charge generation layer 13 is composed of a charge generation material and a binder resin. As such a charge generation material, all known materials such as azo pigments such as bisazo compounds and trisazo compounds, condensed ring aromatic pigments such as dibromoanthanthrone, perylene pigments, pyrrolopyrrole pigments, and flatocyanine pigments can be used. ,
Metallic and metal-free phthalocyanine pigments are preferable, and hydroxygallium phthalocyanine, chlorogallium phthalocyanine, dichlorotin phthalocyanine, and titanyl phthalocyanine having specific crystals are particularly preferable. The chlorogallium phthalocyanine used in the present invention is
For example, a chlorogallium phthalocyanine crystal produced by the method described in JP-A-5-98181 is mechanically dry-ground with an automatic mortar, planetary mill, vibration mill, CF mill, roller mill, sand mill, kneader, or the like. After dry pulverization, it can be produced by performing wet pulverization treatment with a solvent using a ball mill, a mortar, a sand mill, a kneader or the like. Solvents used in the above treatment include aromatics (toluene, chlorobenzene, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol,
Butanol, etc.), aliphatic polyhydric alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.),
Aromatic alcohols (benzyl alcohol, phenethyl alcohol, etc.), esters (acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide, ethers (diethyl ether, tetrahydrofuran, etc.) or these It is a mixture of two or more kinds, or a mixed system of water and these organic solvents. The solvent used is preferably 1 to 200 parts by weight with respect to 1 part by weight of chlorogallium phthalocyanine,
It is more preferably used in the range of 10 to 100 parts by weight. The treatment temperature is 0 ° C to the boiling point of the solvent, preferably 10 to 60 ° C.
Is preferred. Further, at the time of crushing, it is possible to use a grinding aid such as sodium chloride and sodium sulfate. The amount of grinding aid used is
It is preferably 0.5 to 20 times, more preferably 1 to 10 times the pigment. Dichlorotin phthalocyanine is
JP-A-5-140472 and JP-A-5-14047
The dichlorotin phthalocyanine crystal produced by the method described in Japanese Patent No. 3 or the like can be obtained by pulverizing and treating with a solvent in the same manner as chlorogallium phthalocyanine.

Hydroxygallium phthalocyanine is disclosed in JP-A-5-263007 and JP-A-5-279591.
Using a chlorogallium phthalocyanine crystal produced by the method described in Japanese Patent Publication No. JP-A No. 2003-242242, etc., a hydroxygallium phthalocyanine crystal is synthesized by performing hydrolysis or acid pasting in an acid or alkaline solution, and directly performing solvent treatment. Alternatively, the hydroxygallium phthalocyanine crystal obtained by the synthesis is subjected to a wet pulverization treatment using a ball mill, a mortar, a sand mill, a kneader, etc. together with a solvent, or a solvent-treated after a dry pulverization treatment without using a solvent. It can be manufactured. The solvent used in the above treatment is aromatics (toluene, chlorobenzene, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.),
Aliphatic polyhydric alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.), aromatic alcohols (benzyl alcohol, phenethyl alcohol, etc.),
Esters (acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide, ethers (diethyl ether, tetrahydrofuran, etc.) or mixtures of two or more of these, water and these organic solvents A system etc. are mentioned. The amount of such a solvent used is preferably 1 to 200 parts by weight, preferably 10 to 100 parts by weight, relative to 1 part by weight of hydroxygallium phthalocyanine.
It is 100 parts by weight. The processing temperature is preferably 0.
˜150 ° C., preferably room temperature to 100 ° C. Also,
At the time of crushing, a grinding aid such as salt or sodium sulfate may be used. The amount of grinding aid used is preferably 0.
It is 5 to 20 times, more preferably 1 to 10 times.

Oxytitanyl phthalocyanine is obtained by acid pasting oxytitanyl phthalocyanine crystals produced by the method described in JP-A-4-189873, JP-A-5-43813 or the like, or by ball milling, mortar or sand milling. Salt milling with an inorganic salt using a kneader, a kneader or the like to obtain an oxytitanyl phthalocyanine crystal having a relatively low crystallinity having a peak at 27.2 ° in an X-ray diffraction spectrum, and then directly performing a solvent treatment, or Rui, ball mill with solvent,
It can be manufactured by performing a wet pulverization process using a mortar, a sand mill, a kneader or the like. Sulfuric acid (concentration is preferably 70 to 100%, more preferably 95 to 100%) is preferably used as the acid used for acid pasting, and dissolution in such sulfuric acid is preferably -20 to 100 ° C. It is preferably carried out in the range of 0 to 60 ° C. The amount of sulfuric acid is set in the range of preferably 1 to 100 times, more preferably 3 to 50 times the weight of the oxytitanyl phthalocyanine crystal. As a solvent for precipitating oxytitanyl phthalocyanine crystals after such dissolution, water or a mixed solvent of water and an organic solvent is used in any amount, but water and an alcohol solvent such as methanol or ethanol, or water and benzene. A mixed solvent with an aromatic solvent such as toluene or toluene is particularly preferable. The temperature for precipitating the oxytitanyl phthalocyanine crystal is not particularly limited, but it is preferable to cool with ice or the like to prevent heat generation. The ratio of the oxytitanyl phthalocyanine crystal to the inorganic salt is 1 / 0.1 to 1 by weight.
/ 20 is preferable, and 1 / 0.5 to 1/5 is more preferable. Further, the solvent used in the solvent treatment,
Aromatics (toluene, chlorobenzene, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.),
Examples thereof include halogenated hydrocarbons (dichloromethane, chloroform, trichloroethane, etc.) or a mixture of two or more kinds thereof, or a mixed system of water and these organic solvents. The amount of solvent used is oxytitanyl phthalocyanine 1
It is preferably 1 to 100 parts by weight, and more preferably 5 to 50 parts by weight with respect to parts by weight. The solvent treatment temperature is preferably room temperature to 100 ° C, more preferably 50 to 100 ° C. The amount of grinding aid used is preferably 0.
It is 5 to 20 times, more preferably 1 to 10 times.

The binder resin used in the charge generation layer 13 can be selected from a wide range of insulating resins, and organic photoconductive materials such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane can be used. It can also be selected from a water-soluble polymer. Preferred binder resins include polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.),
Polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin, polyacrylamide resin, polyvinylpyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinylpyrrolidone resin Examples of the insulating resin include, but are not limited to: These binder resins may be used alone or in combination of two or more.

The compounding ratio of the charge generating material and the binder resin is preferably in the range of 10/1 to 1/10 by weight. Further, as a method for dispersing these, a usual method such as a ball mill dispersion method, an attritor dispersion method, a sand mill dispersion method or the like can be used, but in this case, a condition that the crystal form of the dispersion does not change is required. It Further, during such dispersion, the average particle size is 0.5 μm or less, more preferably 0.3 μm or less, and further preferably 0.15 μm.
It is effective to use particles of μm or less. As the solvent used for dispersing these, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran. ,
Methylene chloride, chloroform, chlorobenzene,
Ordinary organic solvents such as toluene may be used alone or in combination of two or more.

The thickness of the charge generation layer 13 is preferably 0.
1 to 5 μm, more preferably 0.2 to 2.0 μm is suitable. Examples of the coating method for providing the charge generation layer 13 include a blade coating method, a Mayer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method. further,
For the purpose of increasing the dispersion stability and photosensitivity of the pigment, or stabilizing the electrical characteristics, a charge-generating material treated with a compound represented by the formula (1) described below may be used. The compound may be added to a dispersed solution of the charge generating material.

The charge transport layer 14 comprises a charge transport material. When the charge transport material is a low molecular weight compound, the charge transport material is usually dispersed in the binder resin and held in the layer, but when the polymer charge transport material is used, the binder resin is used. You don't have to.

As the charge transporting material, quinone compounds such as p-benzoquinone, chloranil, bromanil, anthraquinone, tetracyanoquinodimethane compounds, 2,
Fluorenone compounds such as 4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds, cyanovinyl compounds, electron transporting compounds such as ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryls Examples thereof include hole-transporting compounds such as substituted ethylene-based compounds, stilbene-based compounds, anthracene-based compounds, and hydrazone-based compounds, and these can be used alone or in combination of two or more. Among these charge transport materials, the triphenylamine compounds represented by the following general formula (2) and the benzidine compounds represented by the following general formula (3) have high charge (hole) transporting ability and excellent stability. Since it has properties, it can be used particularly preferably. Preferable combinations of R ¹⁴ , Ar ⁶ and Ar ^{7 in} the formula (1) are shown in Tables 1 and 2, R ¹⁵ and R ^{15 ′} , R ¹⁶ , R ^{16 ′} , R ¹⁷ and R ^{17 in the} formula (2). Table 3 shows a preferred combination of

[0036]

[Chemical 1] (In the formula, R ¹⁴ represents a hydrogen atom or a methyl group, n represents 1 or 2, Ar ⁶ and Ar ⁷ may be the same or different and each represents a substituted or unsubstituted aryl group, and aryl. When the group has a substituent, the substituent is a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a substituted amino group substituted with an alkyl group having 1 to 3 carbon atoms. Either of them.)

[0037]

[Chemical 2] (In the formula, R ¹⁵ and R ^{15 ′} may be the same or different,
Each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, R ¹⁶ ,
R ^{16 ′} , R ¹⁷ and R ^{17 ′} may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 2 carbon atoms. Represents an amino group substituted with a group, and m and n each represent an integer of 0 to 2. )

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

The binder resin in which the above charge transporting material is dispersed is not particularly limited, but specifically, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin. , Polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, Examples thereof include phenol-formaldehyde resin and styrene-alkyd resin.

Further, in the present invention, as described above, a polymer charge transport material can be used as the charge transport material. As such a polymer charge transporting material, known materials having a charge transporting property such as poly-N-vinylcarbazole and polysilane can be used. In particular, JP-A-8-17
The polyester-based polymer charge-transporting materials disclosed in JP-A-6293 and JP-A-8-208820 have a high charge-transporting property and are particularly preferable. The polymer charge transport material can be formed into a film by itself, but may be mixed with a binder resin to form a film.

The compounding ratio (weight ratio) of the charge transport material and the binder resin is preferably 10/1 to 1/5. The thickness of the charge transport layer 14 is preferably 5 to 50 μm, more preferably 5 to 25 μm. As a coating method for providing the charge transport layer 14, a usual method such as a blade coating method, a Mayer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method or the like may be used. You can Further, as the solvent used in the coating step, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halogenated aliphatic carbonization such as methylene chloride, chloroform and ethylene chloride. Ordinary organic solvents such as hydrogen or cyclic or linear ethers such as tetrahydrofuran or ethyl ether may be used alone or in combination of two or more.

The charge transport layer 14 may be composed of only the charge transport material and the binder resin described above, but may contain various additives as required. Such additives include zirconium chelate compounds, zirconium alkoxide compounds, organic zirconium compounds such as zirconium coupling agents, titanium chelate compounds, titanium alkoxide compounds, organic titanium compounds such as titanate coupling agents, aluminum chelate compounds, aluminum coupling agents. Such as organoaluminum compounds, antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds,
Examples thereof include indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon alkoxide compounds, aluminum titanium alkoxide compounds, and aluminum zirconium alkoxide compounds. Among them, organic zirconium compounds, organic titanyl compounds, and organic aluminum compounds have low residual potential and show good electrophotographic characteristics,
Preferably used.

As additives for the charge transport layer 14, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane. , Γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureido Propyltriethoxysilane, β-
A silane coupling agent such as 3,4-epoxycyclohexyltrimethoxysilane or a curable matrix such as a photocurable resin may be used, and a compound curable with them (for example, represented by the general formula (3) described later). Compound) may be used.

Further, an antioxidant, a light stabilizer, a heat stabilizer or the like is added to the photosensitive layer for the purpose of preventing deterioration of the photoreceptor due to an oxidizing gas such as ozone generated in the image forming process, light or heat. Agents can be added. For example, as the antioxidant, hindered phenol, hindered amine, paraphenylenediamine, aryl alkane,
Hydroquinone, spirochroman, spiroindanone and their derivatives, organic sulfur compounds, organic phosphorus compounds, etc .; Examples of the light stabilizer include benzophenone, benzotriazole, dithiocarbamate, tetramethylpiperidine, and the like. Further, for the purpose of improving sensitivity, reducing residual potential, reducing fatigue during repeated use, etc., at least one electron-accepting substance can be contained, and examples of such electron-accepting substance include succinic anhydride and maleic anhydride. Acid, dibromomaleic anhydride, phthalic anhydride,
Tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-
Examples thereof include dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid and compounds represented by the general formula (1). Among them, fluorenone compounds, quinone compounds, and -Cl, -CN, benzene derivatives having an electron attractive substituent -NO _2, etc. are particularly preferred.

As described above, the protective layer 15 comprises an organic group having a charge transporting property, a silicon atom bonded to the same or different carbon atom in the organic group, and an oxygen atom bonded to the silicon atom. It is configured to include a crosslinked body having a skeleton. As the organic group having a charge transporting property, specifically, triarylamine structure, benzidine structure, arylalkane structure, aryl-substituted ethylene structure, stilbene structure, anthracene structure, hydrazone structure, quinone structure, fluorenone structure, xanthone structure,
Examples thereof include organic groups having a structure such as a benzophenone structure, a cyanovinyl structure and an ethylene structure. By having such an organic group, a charge transporting property is imparted to the crosslinked product.

Examples of such a crosslinked product include the following general formula (3):

[0049]

[Chemical 3] [Wherein Ar¹, Ar², Ar³And Ar^FourAre the same but different
Optionally substituted or unsubstituted aryl
Represents a group, Ar^FiveIs a substituted or unsubstituted divalent aryl
Represents a group or an arylene group, D represents a divalent group, and Q represents
Represents a hydrolyzable group, a represents an integer of 1 to 3, and k represents 0.
Or 1 and m¹, M², M³, M^FourAnd m ^FiveAre the same
They may be different and each represents 0 or 1, m¹~
m^FiveAt least one of is 1, and k is 1.
m^FiveIs 0. ] A polymerizable monomer containing a compound represented by
A crosslinked body obtained by using the body is preferably used.

In the general formula (3), the substituted or unsubstituted aryl group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ is represented by the following formulas (4) to (10):

[0051]

[Chemical 4]

[0052]

[Chemical 5]

[0053]

[Chemical 6]

[0054]

[Chemical 7]

[0055]

[Chemical 8]

[0056]

[Chemical 9]

[0057]

[Chemical 10] (In the formula, R ¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Phenyl group, C7-10 alkylphenyl group, C7-10 alkoxyphenyl group or C7-
Represents an aralkyl group having 10 carbon atoms, and R ² and R ³ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, an alkoxyphenyl group having 7 to 10 carbon atoms, and a carbon number. 7 to 10 represents an aralkyl group or a halogen group, Ar ⁶ represents a substituted or unsubstituted divalent aromatic hydrocarbon group, Z represents a divalent functional group, and s represents 1
Represents an integer of 3 and-is -DS in the general formula (1).
iR ′ _{3-a ′} Q ′ _{a ′} represents a bonding position in the case where the group represented by the bond is present), and a structure having any one of the structures represented by the following is preferable. Further, the substituted or unsubstituted divalent aromatic hydrocarbon group represented by Ar ⁶ in the above formula (10) is represented by the following general formula (11) or (12):

[0058]

[Chemical 11]

[0059]

[Chemical 12] (In the formula, R ⁴ and R ⁵ are each a hydrogen atom and a carbon number of 1 to
4 represents an alkyl group, a C1 to C4 alkoxy group, a phenyl group, a C7 to C10 alkoxyphenyl group, a C7 to C10 aralkyl group or a halogen group, and t represents an integer of 1 to 3. ) Is preferred; as the divalent group represented by Z in the above formula (10), the following formulas (13) to (20):

[0060]

[Chemical 13]

[0061]

[Chemical 14]

[0062]

[Chemical 15]

[0063]

[Chemical 16]

[0064]

[Chemical 17]

[0065]

[Chemical 18]

[0066]

[Chemical 19]

[0067]

[Chemical 20] (In the formula, R ⁶ and R ⁷ are each a hydrogen atom and a carbon number of 1 to
Represents an alkyl group having 4 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, an alkoxyphenyl group having 7 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or a halogen group, and Z ′.
Represents a divalent group, q and r each represent an integer of 1 to 10, and t represents an integer of 1 to 3). Furthermore,
Examples of the divalent group represented by Z ′ in the above formulas (19) and (20) include the following formulas (21) to (29):

[0068]

[Chemical 21]

[0069]

[Chemical formula 22]

[0070]

[Chemical formula 23]

[0071]

[Chemical formula 24]

[0072]

[Chemical 25]

[0073]

[Chemical formula 26]

[0074]

[Chemical 27]

[0075]

[Chemical 28]

[0076]

[Chemical 29] Those having any of the structures represented by (in the formula, p represents an integer of 0 to 3) are preferable.

In the general formula (3), Ar ⁵ has a k of 0.
Is an aryl group exemplified in the description of Ar ^{1 to} Ar ⁴ , and when k is 1, an arylene group obtained by removing a predetermined hydrogen atom from the aryl group.

Further, in the general formula (3), 2 represented by D
The valent group, _{preferably, -C n H 2n -, -} C n H
_{2n-2 -, - C n} H 2n-4 - (n is an integer from 1 to 15,
Preferably an integer of _{2~10), - CH 2 -C 6} H 4
- or _{-C 6 H 4 -C 6 H 4} - a divalent hydrocarbon group represented by oxycarbonyl group (-COO-), a thio group (-S
-), Oxy group (-O-), isocyano group (-N = CH)
-), Or a divalent group formed by combining two or more of these. In addition, these divalent groups may have a substituent such as an alkyl group, a phenyl group, an alkoxy group and an amino group in the side chain. When D is the above-mentioned preferred divalent group, moderate flexibility is imparted to the polyfunctional photofunctional fluorine-containing organic silicate skeleton, and the strength of the layer tends to be improved.

As described above, R in the general formula (3) is a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms) or a substituted or unsubstituted aryl group (preferably 6 to 15 carbon atoms). Or a substituted or unsubstituted aryl group).

In the above formula (3), the hydrolyzable group represented by Q means a siloxane bond (O--Si) by hydrolysis in the curing reaction of the compound represented by the above formula (1).
-O) refers to a functional group capable of forming. Specific preferred examples of the hydrolyzable group according to the present invention include a hydroxyl group, an alkoxy group, a methylethylketoxime group, a diethylamino group, an acetoxy group, a propenoxy group, and a chloro group. "(R"
Is more preferably a group represented by an alkyl group having 1 to 15 carbon atoms or a trimethylsilyl group).

Ar ¹ , Ar ² , Ar ³ in the above formula (3),
Tables 4 to 14 show preferred combinations of the groups represented by Ar ⁴ , Ar ⁵ , D-SiR _3-a Q _a and the integer k. In addition,
In the table, X represents D-SiR _3-a Q _a bonded to Ar ^{1 to} Ar ⁵ , Me represents a methyl group, Et represents an ethyl group,
Pr represents a propyl group.

[0082]

[Table 4]

[0083]

[Table 5]

[0084]

[Table 6]

[0085]

[Table 7]

[0086]

[Table 8]

[0087]

[Table 9]

[0088]

[Table 10]

[0089]

[Table 11]

[0090]

[Table 12]

[0091]

[Table 13]

[0092]

[Table 14]

The crosslinked product contained in the protective layer 15 may be obtained by using only the compound represented by the general formula (3), but is bonded to the compound represented by the general formula (3). Other polymerizable monomers having possible groups may be further used.

Here, the group capable of binding to the compound represented by the general formula (3) means a group capable of binding to the silanol group generated when the compound represented by the general formula (3) is hydrolyzed. and, specifically, the group represented by -SiR _3-a Q a, epoxy group, isocyanate group, carboxyl group, hydroxy group, refers to a halogen. Of these, -Si
A compound having a group represented by R _3-a Q _a , an epoxy group, or an isocyanate group is preferable because it has stronger mechanical strength, and a compound having a group represented by -SiR _3-a Q _a is particularly preferable. Furthermore, when a compound having two or more of these groups in the molecule is used, the crosslinked structure of the cured film becomes three-dimensional, and stronger mechanical strength can be obtained. Table 15 shows preferable examples of such a polymerizable monomer.

[0095]

[Table 15] In addition to the above-mentioned polymerizable monomer, a silane coupling agent or a hard coating agent may be used. Examples of silane coupling agents include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane. Silane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-
β (aminoethyl) γ-aminopropyltriethoxysilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, etc .; as hard coating agents, KP-85, X-40-9740, X-40-2
239 (above, Shin-Etsu Silicone Co., Ltd.), and AY42
Commercially available hard coat agents such as -440, AY42-441, AY49-208 (all manufactured by Toray Dow Corning) can be used. Further, in order to impart water repellency and the like, (tridecafluoro-1,1,2,2
-Tetrahydrooctyl) triethoxysilane, (3,
3,3-trifluoropropyl) trimethoxysilane,
3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H
-Perfluorodecyltriethoxysilane, 1H, 1
It is also possible to use one or more of fluorine-containing compounds such as H, 2H, 2H-perfluorooctyltriethoxylan.

The crosslinked product according to the present invention can be obtained by hydrolyzing the above polymerizable monomer. The amount of water added in such hydrolysis is not particularly limited,
The amount is preferably 0.3 to 5 times, and more preferably 0.5 to 3 times the theoretical amount necessary to hydrolyze all the hydrolyzable groups of the polymerizable monomer. . If the amount of water added is less than 0.3 times the theoretical amount, the amount of unreacted compounds increases, and a film is formed using a coating liquid containing a crosslinked product in the electrophotographic photoreceptor manufacturing process described later. At that time, phase separation may occur or the strength of the obtained film tends to be insufficient. On the other hand, when the amount of water added exceeds 5 times the theoretical amount, the raw material compounds tend to precipitate and the storage stability of the reaction product (crosslinked product) tends to decrease.

Further, the above-mentioned hydrolysis of the polymerizable monomer may be carried out without using a solvent, or may be carried out using a predetermined solvent (preferably a solvent having a boiling point of 100 ° C. or lower). . In the present invention, as the solvent preferably used in the hydrolysis, alcohols such as methanol, ethanol, propanol and butanol; acetone,
Ketones such as methyl ethyl ketone; ethers such as tetrahydrofuran, diethyl ether, dioxane,
And so on. The amount of these solvents used is determined by the formula (1)
Is preferably 0.5 to 1 part by weight of the compound represented by
The amount is preferably 30 parts by weight, more preferably 1 to 20 parts by weight. If the amount of the solvent used is less than the lower limit, the compound represented by the formula (1) tends to be precipitated, while if the amount exceeds the upper limit, only a thin film tends to be obtained.

In the above hydrolysis, it is preferable to use a solid catalyst which is insoluble in any of the raw material compounds, reaction products, solvents and water. Examples of such solid catalysts include Amberlite 15E and Amberlite 20.
0C, Amberlyst 15 (above, manufactured by Rohm and Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical Co.); Levatit SPC-108, Levatit S
PC-118 (above, Bayer); Diaion R
CP-150H (manufactured by Mitsubishi Kasei); SUMIKAION KC-
470, Duolite C26-C, Duolite C-4
33, Duolite-464 (manufactured by Sumitomo Chemical Co., Ltd.); cation exchange resins such as Nafion-H (manufactured by DuPont); Amberlite IRA-400, Amberlite IRA-45 (or Rohm and Haas) Anion exchange resin such as Zr (O ₃ PCH ₂ CH)
₂ SO ₃ H) ₂ , Th (O ₃ PCH ₂ CH ₂ COOH)
Inorganic solids having a group containing a protonic acid group such as ₂ bonded to the surface; a polyorganosiloxane containing a protonic acid group such as a polyorganosiloxane having a sulfonic acid group; a heteropoly such as cobalt tungstic acid, phosphomolybdic acid Acids; isopoly acids such as niobic acid, tantalic acid and molybdic acid; unitary metal oxides such as silica gel, alumina, chromia, zirconia, CaO, MgO; silica-alumina, silica-magnesia, silica-
Complex metal oxides such as zirconia and zeolites; clay minerals such as acid clay, activated clay, montmorillonite and kaolinite; metal sulfates such as LiSO ₄ and MgSO ₄ ; metal phosphates such as zirconia phosphate and lanthanum phosphate Salts; metal nitrates such as LiNO ₃ and Mn (NO ₃ ) ₂ ; inorganic solids having amino group-containing groups bonded to the surface, such as solids obtained by reacting aminopropyltriethoxysilane on silica gel; Examples thereof include amino group-containing polyorganosiloxanes such as amino-modified silicone resins. The amount of these solid catalysts used is
It is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the raw material compound having a hydrolyzable group. Further, the reaction temperature and reaction time when carrying out the hydrolysis using these solid catalysts are appropriately selected depending on the kinds of the raw material compounds and the solid catalysts, but the reaction temperature is preferably 0 to 100 ° C., more preferably 10 to 10. 70 ° C., more preferably 15-50
C., and the reaction time is preferably 10 minutes to 100 hours. If the reaction time exceeds 100 hours, the reaction product tends to gel.

In addition to the above solid catalysts, protic acids such as hydrochloric acid, acetic acid, phosphoric acid and sulfuric acid; bases such as ammonia and triethylamine; organic compounds such as dibutyltin diacetate, dibutyltin dioctoate and stannous octoate. Tin compounds; Organic titanium compounds such as tetra-n-butyl titanate and tetraisopropyl titanate; Organic aluminum compounds such as aluminum tributoxide and aluminum triacetylacetonate; Iron salts, manganese salts, cobalt salts, zinc salts of organic carboxylic acids, The hydrolysis can be carried out using a curing catalyst such as an organic carboxylic acid salt such as a zirconium salt. Among these curing catalysts, metal compounds are preferable from the viewpoint of storage stability of reaction products, and metal acetylacetonate or acetylacetate is preferable. The amount of these curing catalysts used is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the raw material compound having a hydrolyzable group, from the viewpoint of storage stability and strength of the reaction product, and It is preferably from 0.3 to 10 parts by weight. Further, the reaction temperature and reaction time when carrying out hydrolysis using the above-mentioned curing catalyst are appropriately selected according to the kind of the raw material compound and the curing catalyst to be used, but the reaction time is preferably 60 ° C. or more, more preferably It is 80 to 170 ° C., and the reaction time is preferably 10 minutes to 5 hours. When the reaction temperature is lower than the lower limit, the mechanical strength of the obtained crosslinked product tends to be insufficient.

If necessary, the obtained reaction product may be subjected to a hydrophobizing treatment using hexamethyldisilazane or trimethylchlorosilane.

An antioxidant is preferably added to the protective layer 15 for the purpose of preventing deterioration due to an oxidizing gas such as ozone generated in the charger. If the mechanical strength of the surface of the photoconductor is increased and the photoconductor has a long life, the photoconductor is in contact with an oxidizing gas for a long time, and therefore stronger oxidation resistance than the conventional one is required. As the antioxidant, hindered phenol-based or hindered amine-based is desirable, organic sulfur-based antioxidant, phosphite-based antioxidant,
You may use well-known antioxidants, such as a dithiocarbamate type antioxidant, a thiourea type antioxidant, and a benzimidazole type antioxidant. The addition amount of the antioxidant is preferably 15% by weight or less, more preferably 10% by weight or less.

As the hindered phenolic antioxidant, 2,6-di-t-butyl-4-methylphenol,
2,5-di-t-butylhydroquinone, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxyhydrocinnamide, 3,5-di-t-butyl-4
-Hydroxy-benzylphosphonate-diethyl ester, 2,4-bis [(octylthio) methyl] -o
-Cresol, 2,6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-)
t-butylphenol), 2,2'-methylenebis (4
-Ethyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), -2,5-di-t-amylhydroquinone, 2-t.
-Butyl-6- (3-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate,
4,4'-butylidene bis (3-methyl-6-t-butylphenol) and the like can be mentioned.

(Developing Device and Toner) The developing device 4 develops the electrostatic latent image formed on the photoconductor 1 with toner to form a toner image. Although not shown in detail, it is black. It is possible to supply four color toners of yellow, cyan, and magenta. The shape factor of such a toner (toner particles when an external additive is included) is preferably 100 to 140, more preferably 100 to 135.
And more preferably 100 to 125. If the shape factor of the toner exceeds 140, sufficient transferability cannot be obtained.

The toner is not particularly limited as long as its shape factor satisfies the above conditions, but toner particles containing at least a binder resin and a colorant,
It is preferably composed of an external additive.

The toner particles are composed of at least a binder resin and a colorant, and if necessary, a release agent and other components.

As the binder resin for the toner particles, styrenes such as styrene and chlorostyrene; monoolefins such as ethylene, propylene, butylene and isoprene; vinyl such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate. Esters; α-methylene aliphatic mono-esters such as methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate, etc. Carboxylic acid esters; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl butyl ether, vinyl methyl ketone, vinyl hexyl ketone,
Examples thereof include homopolymers and copolymers of vinyl ketones such as vinyl isopropenyl ketone; and typical binder resins include polystyrene and styrene.
Examples thereof include an alkyl acrylate copolymer, a styrene-alkyl methacrylate copolymer, a styrene-acrylonitrile copolymer, a styrene-butadiene copolymer, a styrene-maleic anhydride copolymer, polyethylene and polypropylene. Further, polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like can be mentioned.

As the colorant for the toner particles, magnetic powder such as magnetite and ferrite, carbon black, aniline blue, calcyl blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite. Green oxalate, lamp black, rose bengal, C.I. I. Pigment Red 4
8: 1, C.I. I. Pigment Red 122, C.I. I.
Pigment Red 57: 1, C.I. I. Pigment Yellow 97, C.I. I. Pigment Yellow 17, C.I.
I. Pigment Yellow 74, C.I. I. Pigment
Yellow 180, C.I. I. Pigment Blue 15:
1, C.I. I. Pigment Blue 15: 3 and the like can be illustrated as a typical example.

Typical examples of the releasing agent that can be contained in the toner particles include low molecular weight polyethylene, low molecular weight polypropylene, Fischer-Tropsch wax, montan wax, carnauba wax, rice wax and candelilla wax. be able to.

If necessary, a charge control agent may be added to the toner particles. As the charge control agent, known ones can be used, and an azo metal complex compound, a salicylic acid metal complex compound, and a resin type charge control agent containing a polar group can be used. When toner particles are manufactured by a wet method, it is preferable to use a material that is difficult to dissolve in water from the viewpoint of controlling ionic strength and reducing wastewater pollution.

The toner particles may be either magnetic toner containing a magnetic material or non-magnetic toner containing no magnetic material. Further, the volume average particle diameter of the toner particles is preferably in the range of 2 to 9 μm,
More preferably, it is in the range of 3 to 7 μm.

The method for producing the toner particles is not particularly limited as long as the shape factor can be set within the above range, and a known production method can be applied. For example, a binder resin and a colorant, and if necessary, a release agent,
A kneading and pulverizing method of kneading, pulverizing, and classifying a charge control agent; a method of changing the shape of particles obtained by the kneading and pulverizing method by mechanical impact force or thermal energy; Emulsion polymerization aggregation method in which a dispersion liquid obtained by emulsion polymerization and a dispersion liquid of a colorant, and if necessary, a release agent, a charge control agent and the like are mixed, agglomerated and heat-fused to obtain toner particles.
Suspension polymerization method in which a polymerizable monomer for obtaining a binder resin and a colorant, and if necessary, a solution of a release agent, a charge control agent, etc., is suspended in an aqueous solvent for polymerization; binder resin and coloring And a releasing agent, and if necessary, a solution of a charge control agent or the like is suspended in an aqueous solvent and granulated, and a dissolution suspension method; Further, a production method may be performed in which the toner particles obtained by the above method are used as cores, and agglomerated particles are further attached and heated and fused to have a core-shell structure.

Further, it is desirable that the toner contains particles in the range of 50 to 500 nm as an external additive from the viewpoint of further improving the cleaning property. By depositing the external additive having an average particle diameter of 50 to 500 nm contained in the toner on the minute deformation portion of the cleaning blade tip portion, the spherical toner is effectively suppressed from entering the edge portion deformation portion of the cleaning blade, and the spherical toner Rolling can be suppressed (sealing effect), and cleaning performance can be improved.

In order to easily supply particles having an average particle diameter of 50 to 500 nm to the tip of the cleaning blade, it is most effective to add and attach them to the toner as an external additive, and the cleaning blade can be stably used. In order to supply the toner to the tip of the edge of the toner, it is effective that the toner is carried to the edge of the cleaning blade while being held on the surface of the toner particles. The external additive held on the surface of the toner particles is separated from the surface of the toner particles by the stress of rubbing against the cleaning blade, and is effectively supplied to the deformed portion of the cleaning blade tip.

If the external additive is smaller than 50 nm,
It tends to be difficult to stay in the deformed portion of the cleaning blade tip and it becomes difficult to form an effective seal. On the other hand, if it is larger than 500 nm, it is hard to adhere to the surface of the toner particles, and the toner particles are easily separated from the surface of the toner particles due to the stirring force in the developing device, so that it cannot be effectively supplied to the cleaning blade and is stable for a long time Therefore, it tends to be difficult to exert the sealing effect and the cleaning blade behavior stabilizing effect. The average particle diameter of the external additive contained for improving the cleaning property is more preferably in the range of 80 to 300 nm.

The specific gravity of the external additive is 1.3 to
It is preferably within the range of 1.9. When the specific gravity is more than 1.9, the peeling of the external additive from the toner particles is likely to be accelerated due to the stress in the developing machine, and it may not be possible to effectively supply the external additive to the cleaning blade. On the other hand, when the specific gravity is less than 1.3, the external additive is apt to aggregate and disperse, and the spikes of the external additive become nonuniform.
Since the stress is selectively applied to the convex portion, the peeling of the external additive from the toner particles is accelerated, and it is impossible to effectively supply the external additive to the cleaning blade, so that the sealing effect can be stably exhibited for a long period of time. May not be possible.

The external additive is preferably spherical. Since the external additive has a spherical shape, the external additive can be uniformly dispersed on the surface of the toner particles, and peeling of the external additive can be effectively suppressed. Wadell is the definition of a sphere
The true sphericity can be discussed, and the sphericity Ψ is preferably 0.6 or more, more preferably 0.8 or more.

The content of the external additive contained for improving the cleaning property is preferably 0.5 to 5 parts by weight, and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the toner particles. More preferable. If it is less than 0.5 parts by weight, the cleaning property of the spherical toner is likely to be deteriorated, and cleaning failure may occur. If it is more than 5 parts by weight, filming / comment on the photoconductor is likely to occur. Each is not preferable.

The effect of the spherical external additive is
It is considered that the more the external additive is closer to monodisperse, the higher the effect is exhibited. Here, the definition of monodisperse can be discussed by the standard deviation with respect to the average particle size including the aggregate, and the standard deviation is preferably D ₅₀ × 0.22 or less.

The material of the external additive is not particularly limited, but silica is considered to be particularly preferable. The reason for this is that silica has a refractive index of around 1.5, and even if the particle size is increased, the transparency decreases due to light scattering, and especially the PE value (index of light transmission) during image formation on OHP. It does not affect the.

Typical fumed silica has a specific gravity of 2.2.
The maximum particle size is 50 nm from the viewpoint of manufacturing. Further, the particle size can be increased as an agglomerate, but uniform dispersion is difficult and a stable sealing effect cannot be obtained. On the other hand, other typical inorganic fine particles include titanium oxide (specific gravity 4.2, refractive index 2.6), alumina (specific gravity 4.0, refractive index 1.8), zinc oxide (specific gravity 5.6, refractive index 2.0), all of them have a high specific gravity, and when the particle diameter is larger than 50 nm, the toner particles are peeled off from the toner particles so that the sealing effect at the edge tip deformation portion of the cleaning blade is effectively exhibited. May occur easily. Further, its refractive index is also high, which is disadvantageous for producing a color image.

Silica suitable as a material for an external additive contained for improving the cleaning property, particularly a specific gravity of 1.3 to 1.
The spherical monodisperse silica in 9 can be obtained by a sol-gel method which is a wet method. According to the method, a wet method,
Moreover, since it is a method of manufacturing without firing, its specific gravity can be controlled to be lower than that of the vapor phase oxidation method or the like. Further, it is possible to further adjust the specific gravity by controlling the kind of the hydrophobic treatment agent or the treatment amount in the hydrophobic treatment step. The particle size of silica can be freely controlled by the hydrolysis ratio in the sol-gel method, the weight ratio of alkoxysilane, ammonia, alcohol, and water in the condensation polymerization step, the reaction temperature, the stirring rate, and the feeding rate. The monodisperse, spherical silica can also be achieved by the sol-gel method.

The specific method for producing silica is as follows. First, a silane compound such as tetramethoxysilane is added dropwise and stirred in the presence of water and alcohol while using ammonia water as a catalyst while applying temperature. Next, the silica sol suspension produced by the reaction is centrifuged,
Separate into wet silica gel, alcohol, and aqueous ammonia. A solvent is added to the wet silica gel to bring it into a silica sol state again, and a hydrophobizing agent is added to hydrophobize the silica surface. As the hydrophobizing agent, a general silane compound can be used. Next, the solvent is removed from the hydrophobized silica sol, dried, and sieved to obtain the desired monodisperse silica. The silica thus obtained may be treated with the sol-gel method again as described above.

As the silane compound, a water-soluble one can be used. Such silane compounds, the chemical structural formula R _a SiX _4-a (wherein, a is an integer of 0 to 3, R
Represents a hydrogen atom, an organic group such as an alkyl group and an alkenyl group, and X represents a hydrolyzable group such as a chlorine atom, a methoxy group and an ethoxy group. The compound represented by the formula (1) can be used, and any type of chlorosilane, alkoxysilane, silazane, and special silylating agent can be used. Specifically, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyl Triethoxysilane, dimethyldiethoxysilane,
Phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) acetamide, N, N-bis (trimethylsilyl) urea, tert-butyldimethylchlorosilane , Vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-
Typical examples include glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like.

As the hydrophobic treatment agent, dimethyldimethoxysilane, hexamethyldisilazane, methyltrimethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane and the like are particularly preferable.

The external additive is supplied to the cleaning blade while being held on the surface of the toner particles. However, depending on the image pattern on the surface of the electrophotographic photosensitive member, the amount of the external additive supplied may be extremely small. May occur. In order to prevent this, it is desirable to form a toner image that is not transferred to the transfer body on the surface of the electrophotographic photosensitive member at an arbitrary or predetermined timing (interval) in the non-image forming cycle. By forming a non-transferred toner image on the surface of the electrophotographic photosensitive member, the external additive is supplied to the cleaning blade to stabilize the behavior of the cleaning blade tip and maintain the cleaning performance stably regardless of the image pattern. You can

The "non-image forming cycle" means a cycle in which the toner image formed on the electrophotographic photosensitive member can be conveyed as it is to the cleaning means (cleaning step) when the transfer member is not supplied. . The toner image formed here may be a pattern such that the external additive is supplied to the entire cleaning blade in the longitudinal direction, and may be a solid image, a halftone image, a line image, or the like. . The timing at which the toner image that is not transferred is created may be a fixed number of sheets, a cycle, a time, or the like, or may be an arbitrary timing.

Further, in the present invention, the toner may further contain an inorganic compound for controlling the fluidity and the chargeability of the toner as an external additive. In order to control the fluidity and chargeability of the toner, it is necessary to sufficiently coat the surface of the toner particles with an external additive, but external additives such as spherical monodisperse silica contained for improving the cleaning property are included. In that case, a sufficient coating cannot be obtained. Therefore, together with the external additive contained for improving the cleaning property,
It is desirable to use an inorganic compound having a small diameter together.

As the small-diameter inorganic compound that can be contained in the toner, known compounds can be used, and examples thereof include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, and oxides. Zinc, silica sand, clay, mica, wollastonite, diatomaceous earth, cerium chloride, red iron oxide, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, silicon carbide, silicon nitride, calcium carbonate, magnesium carbonate, calcium phosphate Etc. can be mentioned. The surface of these inorganic fine particles may be subjected to a known surface treatment depending on the purpose.

The average particle size of the small-diameter inorganic compound that can be contained in the toner is preferably less than 50 nm, more preferably 5 to 30 nm. Further, the addition amount of toner particles is 100
The amount is preferably 0.3 to 3.0 parts by weight with respect to parts by weight.

The above toner may be used as a one-component type developer which constitutes a developer by itself, or may be used as a two-component type developer which is mixed with a carrier to constitute a developer. .

As such a carrier, as a core material,
Magnetic metals such as iron, nickel and cobalt; magnetic oxides such as ferrite and magnetite; glass beads; and the like are used, but a magnetic material is preferable in order to adjust the volume resistivity using the magnetic brush method. . The average particle size of the core material is usually in the range of 10 to 500 μm, preferably 30 to 100 μm.

Further, these carriers preferably have a resin coating layer coated with a resin or the like in order to impart an electrostatic property, and as the resin, polyethylene, polypropylene, polystyrene, polyacrylonitrile,
Polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid copolymer, straight silicone resin composed of organosiloxane bond or its modification Examples include, but are not limited to, products, fluororesins, polyesters, polyurethanes, polycarbonates, phenol resins, amino resins, melamine resins, benzoguanamine resins, urea resins, amide resins, and epoxy resins.

As the method for forming the resin coating layer on the surface of the core material of the carrier, a dipping method of immersing the core material in a coating layer forming solution, a spray method of spraying the coating layer forming solution on the core material surface, a core Apply the fluidized bed method of spraying the coating layer forming solution in the state of floating the material with fluidized air, the kneader coater method of removing the solvent after mixing the core material and the coating layer forming solution in the kneader coater can do.

In the present invention, the mixing ratio (weight ratio) of the toner and the carrier is preferably toner:
Carrier = 1: 100 to 30: 100 or so, more preferably 3: 100 to 20: 100 or so.

(Cleaning Device) Cleaning Device 7
Is equipped with a cleaning blade made of an elastic thin plate made of metal, and the cleaning blade is arranged such that one end thereof is fixed and the other end is in contact with the surface of the photoconductor 1. The material of the cleaning blade is not particularly limited as long as it has appropriate mechanical strength and elastic modulus, but a stainless plate, a phosphor bronze plate, a carbon steel plate, a galvanized steel plate, a brass plate or the like is preferably used. These Young's moduli are usually 10,000 MPa or more, which is sufficiently larger than that of a cleaning blade made of polyurethane elastomer (Young's modulus: about 1 to 10 MPa).

The linear pressure of the cleaning blade with respect to the photosensitive member 1 is set to be 5 to 25 N / m. If the linear pressure is less than 5 N / m, the toner remaining on the surface of the photoconductor 1 after the transfer process easily slips through the cleaning blade, and sufficient cleaning characteristics cannot be obtained. On the other hand, if the linear pressure exceeds 25 N / m, the surface of the photoconductor 1 is likely to be damaged, and the photoconductor characteristics are deteriorated at an early stage and the image quality is deteriorated.

The linear pressure of the cleaning blade can be set within the above range by adjusting the thickness of the elastic thin plate, the free length, the installation angle, the amount of biting into the photosensitive member 1, and the like. Is 0.01-
It is preferably within the range of 0.5 mm. The thickness is 0.
When it is less than 01, the cleaning blade is likely to be turned over and the cleaning property tends to be deteriorated. On the other hand, when the thickness exceeds 0.5 mm, the cleaning blade tends to be difficult to be inserted into the photoconductor 1 and the surface of the photoconductor 1 tends to be damaged.

The free length of the cleaning blade is 5
It is preferably ˜15 mm, and the installation angle is preferably 5 to 60 ° with respect to the surface of the photoreceptor 1. The free length referred to here is the length from one fixed position to the other end, and the installation angle is based on a plane that passes through the fixed position of the cleaning blade and is perpendicular to the photosensitive member surface (0
°), and the front side in the moving direction of the surface of the photoconductor is positive.

As described above, in this embodiment, the surface of the photoconductor 1 is provided with the protective layer 15 containing the specific silicon resin, and the cleaning blade 7 made of a metal elastic thin plate is used to clean the photoconductor 1. By setting the linear pressure of the blade 7 to 5 to 25 N / m, a sufficiently high cleaning property can be achieved without damaging either the photoreceptor 1 or the cleaning blade 7,
It is possible to stably obtain good image quality over a long period of time. The above-mentioned image forming apparatus having such excellent characteristics is an electrophotographic apparatus such as a copying machine, a laser printer, an LED printer, a liquid crystal shutter type printer, and a display, recording, light printing, plate making using electrophotographic technology. It is very useful in image forming apparatuses such as facsimiles.

The present invention is not limited to the above embodiment. For example, the electrophotographic photosensitive member 1 and the cleaning device may be integrated and used as a process cartridge. At this time, the process cartridge may further include the charging device 3, the developing device 5, the transfer device 5, and the like.

In the electrophotographic photosensitive member 1, the protective layer 15 includes an organic group having a charge transporting property, a silicon atom bonded to the same or different carbon atom in the organic group, and an oxygen atom bonded to the silicon atom. However, the protective layer may be formed by dispersing a charge transporting substance in a predetermined silicon resin.

The electrophotographic photosensitive member 1 is a function-separated type photosensitive member in which a charge generating layer and a charge transporting layer are separately provided.
In the present embodiment, as long as the charge transporting substance and the siloxane-based resin are contained in the surface layer, a single-layer type photoreceptor including the charge generating material and the charge transporting material in the same layer may be used.

The electrophotographic photoreceptor 1 may contain a charge transporting substance and a siloxane-based resin in its surface layer. For example, when the charge transporting layer contains the charge transporting substance and the siloxane-based resin, it is protected. The layer 15 may not be provided.

Further, in the above embodiment, an example of the image forming apparatus using color toner is shown, but the image forming apparatus of the present invention may be one for black and white image formation using only black toner.

In the apparatus shown in FIG. 1, the charging device 2 may be of a contact charging type such as a charging roller, or may be of a non-contact charging type such as a corotron charger. From the viewpoint of preventing ozone generation, the contact charging type is preferable.

Further, in the apparatus shown in FIG. 1, as the exposure apparatus 3, a semiconductor laser, an LED (light emitting diode) is provided on the surface of the electrophotographic photosensitive member 1.
e), an optical system device capable of exposing a light source such as a liquid crystal shutter in a desired image manner can be used. Examples of the transfer device include a contact type transfer charger using a belt, a roller, a film, a rubber blade, etc., a scorotron transfer charger using corona discharge, a corotron transfer charger, and the like.

The apparatus shown in FIG. 1 directly transfers the toner image formed on the surface of the electrophotographic photosensitive member 1 onto the transfer medium P, but the image forming apparatus of the present invention further comprises an intermediate transfer member. It may be provided. As a result, the toner image on the surface of the electrophotographic photosensitive member 1 can be transferred to the intermediate transfer member and then transferred from the intermediate transfer member to the transfer medium P. As such an intermediate transfer member, one having a structure in which an elastic layer containing rubber, an elastomer, a resin and the like and at least one coating layer are laminated on a conductive support can be used.

[0148]

EXAMPLES The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited to the following examples.

[Example 1] (Preparation of electrophotographic photosensitive member) Drawing tube made of JIS A3003 alloy (diameter: 84 mm, length: 340 mm)
The outer peripheral surface of was polished by a centerless polishing apparatus, and the surface roughness was Ra = 0.2 μm. Then, degreasing treatment, 2
Etching treatment with a weight% sodium hydroxide solution for 1 minute, neutralization treatment, and pure water washing were sequentially performed. Next, anodizing treatment with a 10 wt% sulfuric acid solution (current density 1.0 A /
dm ² ) to form an anodized film on the outer peripheral surface of the drawn tube. After washing with water, it was immersed in a 1% by weight nickel acetate solution at 80 ° C. for 20 minutes for sealing treatment. Further, washing with pure water and drying were performed to obtain a conductive substrate having an anodized film of 7 μm formed on the outer peripheral surface.

Next, the Bragg angles (2θ ± 0.2 °) in the X-ray diffraction spectrum are 7.4 °, 16.6 °,
1 part by weight of chlorogallium phthalocyanine having a strong diffraction peak at 25.5 ° and 28.3 ° was mixed with 1 part by weight of polyvinyl butyral (Eslec BM-S, Sekisui Chemical Co., Ltd.) and 100 parts by weight of n-butyl acetate to prepare glass beads. A charge generation layer coating solution was prepared by performing a dispersion treatment with a paint shaker for 1 hour. This coating solution was applied onto the outer peripheral surface of the substrate by dip coating, and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

Further, 2 parts by weight of a benzidine compound (compound (V-27) in Table 3) and 3 parts by weight of a polymer compound represented by the following formula (30) (viscosity average molecular weight: 39,000) were added to 20 parts of chlorobenzene. A coating solution for a charge transport layer was prepared by dissolving it in parts by weight. This coating solution was applied onto the above charge generation layer by a dip coating method and heated at 110 ° C. for 40 minutes to form a charge transport layer having a film thickness of 20 μm.

[0152]

[Chemical 30] Furthermore, 2 parts by weight of compound (13) in Table 6, 2 parts by weight of methyltrimethoxysilane, and 0.5 parts of tetramethoxysilane.
Parts by weight, 0.3 parts of colloidal silica, 5 parts of isopropyl alcohol, 3 parts of tetrahydrofuran, 0.3 parts of distilled water
Ion-exchange resin (Amberlyst 15
E) 0.5 part was added and hydrolyzed for 24 hours by stirring at room temperature.

2 parts by weight of the liquid obtained by filtering and separating the ion exchange resin from the reaction solution after hydrolysis, 0.04 parts by weight of aluminum trisacetylacetonate and 3,5-di-
t-Butyl-4-hydroxytoluene (BHT) 0.1
By weight, the coating solution is applied onto the above charge transport layer by a ring type dip coating method, air-dried at room temperature for 30 minutes, and then heat-treated at 170 ° C. for 1 hour to be cured to form a film having a thickness of 3 μm. A protective layer was formed to obtain the intended electrophotographic photoreceptor.

(Preparation of image forming apparatus and continuous print test) An image forming apparatus having the structure shown in FIG. 1 was prepared using the obtained electrophotographic photosensitive member. Here, as the cleaning blade, a carbon steel plate (JIS-SK75, thickness:
0.1 mm), the free length thereof was 13 mm, the installation angle with respect to the surface of the photosensitive member was 20 °, and the linear pressure with respect to the surface of the photosensitive member was set to 10 N / m. A contact charging device equipped with a charging roll is used as the charging device, and the charging device is -650V.
DC voltage of 1.6kHz, I _AC = 2.4mA
AC voltage was superimposed. As the developing device, a developing device capable of supplying a two-component color toner having a shape factor of 130 (black, yellow, cyan, magenta) was used.

Using the image forming apparatus thus obtained, a continuous print test of 10,000 sheets was carried out (test environment: 28 ° C., 85% RH) to obtain 100th sheet, 1000th sheet and 10000th sheet. The image quality was evaluated for each of the images. Fuji Xerox PP is used as the printing paper.
C paper (L, A4) was used. The results obtained are shown in Table 16.

[Example 2] An image forming apparatus was produced in the same manner as in Example 1 except that a carbon steel plate (JIS-SK75) having a thickness of 0.1 mm was used as the cleaning blade and the linear pressure was 20 N / m. Then, a continuous print test was performed. Table 16 shows the result of image quality evaluation.

[Example 3] An image forming apparatus was prepared in the same manner as in Example 1 except that a stainless steel plate (SUS-304) having a thickness of 0.1 mm was used as the cleaning blade and the linear pressure was set to 15 N / m. Then, a continuous print test was performed. Table 16 shows the result of image quality evaluation.

[Comparative Example 1] An image forming apparatus was produced in the same manner as in Example 1 except that a stainless steel plate (SUS-304) having a thickness of 0.1 mm was used as the cleaning blade and the linear pressure was 3 N / m. Then, a continuous print test was performed. Table 16 shows the result of image quality evaluation.

[Comparative Example 2] An image forming apparatus was prepared in the same manner as in Example 1 except that a 0.2 mm thick stainless steel plate (SUS-304) was used as the cleaning blade and the linear pressure was 30 N / m. Then, a continuous print test was performed. Table 16 shows the result of image quality evaluation.

[Comparative Example 3] A polyurethane elastomer blade (Hokushin Kogyo 238) was used as a cleaning blade.
778, hardness: 77, Young's modulus: 8.5 MPa), an image forming apparatus was prepared in the same manner as in Example 1 except that the linear pressure was 15 N / m, and a continuous print test was conducted.
Table 16 shows the result of image quality evaluation.

[Comparative Example 4] As a cleaning blade, a polyurethane elastomer blade (manufactured by Hokushin Kogyo 238) was used.
657, hardness: 66, Young: 5.6 MPa),
An image forming apparatus was produced in the same manner as in Example 1 except that the linear pressure was set to 15 N / m, and a continuous print test was conducted.
Table 16 shows the result of image quality evaluation.

[0162]

[Table 16]

As shown in Table 16, in Examples 1 to 3, good image quality was maintained even on the 10000th image, and the electrophotographic photosensitive member surface was sufficiently damaged and the cleaning failure was sufficiently generated. It was confirmed that it was prevented.

On the other hand, in Comparative Examples 1, 3 and 4, streaks were observed due to poor cleaning, and in Comparative Example 2, streaks were observed due to damage on the surface of the photoconductor.
It was not possible to maintain good image quality up to the first sheet.

[0165]

As described above, according to the present invention, the electrophotographic photosensitive member having the surface layer containing the specific silicon resin and the cleaning means having the cleaning blade made of the elastic thin plate made of metal are used. By setting the linear pressure of the cleaning blade to the photographic photosensitive member at 5 to 25 N / m, sufficiently high cleaning characteristics can be achieved without damaging either the electrophotographic photosensitive member or the cleaning blade, so that good cleaning properties can be obtained for a long period of time. It is possible to obtain stable image quality.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram showing a preferred embodiment of an image forming apparatus of the present invention.

FIG. 2 is a schematic cross-sectional view showing an example of an electrophotographic photosensitive member according to the present invention.

[Explanation of symbols]

1 ... Electrophotographic photoreceptor, 2 ... Charging device, 3 ... Exposure device, 4
... developing device, 5 ... transfer device, 6 ... image fixing device, 7 ... cleaning device, 9 ... support, 11 ... conductive substrate, 12 ...
Undercoat layer, 13 ... Charge generation layer, 14 ... Charge transport layer, 15
... Protective layer, 16 ... Photosensitive layer.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takahiro Suzuki             Fuji Zero, 1600 Takematsu, Minamiashigara City, Kanagawa Prefecture             X Co., Ltd. (72) Inventor Kazuhiro Ozeki             Fuji Zero, 1600 Takematsu, Minamiashigara City, Kanagawa Prefecture             X Co., Ltd. (72) Inventor Taku Aoshima             Fuji Zero, 2274 Hongo, Ebina City, Kanagawa Prefecture             X Co., Ltd. (72) Inventor Naotoshi Ishikawa             Fuji Zero, 2274 Hongo, Ebina City, Kanagawa Prefecture             X Co., Ltd. F-term (reference) 2H005 AA15 AA21 FA01                 2H068 AA03 AA37 BA12 BB32 BB58                 2H134 GA01 GB02 HD03 HD05 HD11                       HD19 KD02 KG07 KG08 KH01                       KH15

Claims (3)

[Claims] 1. An electrophotographic photosensitive member comprising a conductive substrate and a photosensitive layer disposed on the substrate, a charging unit for charging the surface of the electrophotographic photosensitive member, and a static exposure by exposing the surface of the electrophotographic photosensitive member. An exposure unit that forms an electrostatic latent image, a developing unit that develops the electrostatic latent image with toner to form a toner image, and a transfer unit that transfers the toner image onto a transfer medium.
An image forming apparatus comprising: a cleaning unit that removes toner remaining on the surface of the electrophotographic photosensitive member, wherein the photosensitive layer has a charge transporting property and a crosslinked structure on the side far from the substrate. And a cleaning blade comprising a metal elastic thin plate, and the linear pressure of the cleaning blade against the electrophotographic photosensitive member is 5 to 25 N / m. An image forming apparatus characterized in that there is. 2. The shape factor of the toner is 100 to 140.
The image forming apparatus according to claim 1, wherein: 3. A process cartridge comprising an electrophotographic photosensitive member including a conductive base and a photosensitive layer disposed on the base, and a cleaning unit for removing toner remaining on the surface of the electrophotographic photosensitive member. The photosensitive layer is provided with a surface layer containing a silicon resin having a charge transporting property and a cross-linking structure on the side far from the substrate, and the cleaning means is a cleaning blade made of a metal elastic thin plate. A process cartridge provided, wherein the cleaning blade has a linear pressure of 5 to 25 N / m with respect to the electrophotographic photosensitive member.