JP5564805B2 - Electrophotographic photosensitive member, and image forming method, image forming apparatus, and process cartridge using the same - Google Patents

Description

  The present invention relates to an electrophotographic photoreceptor having high durability excellent in ozone resistance and NOx, used in electrophotographic printers, copying machines, and the like, and an image forming method and an image using the electrophotographic photoreceptor The present invention relates to a forming apparatus and a process cartridge.

  An electrophotographic photoreceptor (hereinafter sometimes referred to as “photoreceptor”) has a function of holding surface charges in the dark, a function of receiving light to generate charges, and also receiving light to transport charges. A so-called single-layer type photoreceptor that has both of these functions in one layer, a layer that mainly contributes to charge generation, a surface charge in the dark, and a charge transfer during photoreception. There is a so-called function-separated stacked type photoreceptor in which layers separated into functions are stacked.

  For example, a Carlson method is applied to image formation by electrophotography using these photoreceptors. The image formation by the Carlson method is performed by charging a photoconductor in a dark place by corona discharge, forming an electrostatic latent image such as text or a picture of an original on the surface of the charged photoconductor, The image is developed with toner, and the developed toner image is fixed on a recording medium such as paper. After the toner image is transferred, the photoreceptor is subjected to charge removal, residual toner removal, light charge removal, etc., and then reused. Provided.

  In recent years, electrophotographic photoreceptors using organic substances have been put into practical use due to advantages such as flexibility, thermal stability, and film formability. Recently, a function-separated laminated type photoconductor comprising a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material has become mainstream as a photosensitive layer, and in particular, a vapor deposition layer using an organic pigment as a charge generation material. Alternatively, many negatively charged photoreceptors have been proposed in which a layer dispersed in a resin is used as a charge generation layer, and a low molecular weight organic compound is used as a charge transport material and a layer dispersed in the resin is used as a charge transport layer.

  As described above, the organic material has many advantages that the inorganic material does not have, but at the same time, an organic material that sufficiently satisfies all the characteristics required for the electrophotographic photosensitive member has not been obtained. That is, image quality is deteriorated due to a decrease in charging potential, an increase in residual potential, a change in sensitivity, and the like due to repeated use. Although not all of the causes of this deterioration have been elucidated, as one of the factors, oxidizing gases such as ozone and NOx released from the corona discharge charger, and oxidizing gases such as ozone and NOx in the atmosphere Has been found to cause significant damage to the photosensitive layer. These oxidizing gases cause a chemical change with the material in the photoreceptor, or cause various changes in properties by forming an adsorbate on the surface of the photosensitive layer. For example, a decrease in resolving power due to a decrease in charging potential, an increase in residual potential, or a decrease in surface resistance is observed. As a result, the image quality is significantly lowered and the life of the photoreceptor is shortened.

As a countermeasure against these problems, proposals have been made to prevent deterioration by adding an antioxidant or a stabilizer to the photosensitive layer. For example, as represented by Patent Document 1, many proposals have been made to add a hindered phenol antioxidant and a hindered amine antioxidant. Moreover, Patent Document 2, Patent Document 3, Patent Document 4, and the like have been proposed as addition examples of amine derivatives. According to these proposals, it has an appropriate effect of preventing deterioration.
In recent years, demands for higher durability and higher responsiveness have been increasing for photoconductors due to demands for high speed and downsizing of copiers and printers. In order to cope with high responsiveness, it is necessary to use a charge transport material having a large molecular weight and a charge transport material having a low ionization potential (Ip) value. However, these charge transport materials have low durability against ozone and NOx, and the current situation is that the addition of conventional antioxidants is insufficient.

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention provides an electrophotographic photosensitive member having high ozone resistance and NOx resistance and high durability, and by using the photosensitive member, replacement of the photosensitive member is unnecessary, and high-speed printing or a small diameter of the photosensitive member is possible. It is an object of the present invention to provide an image forming method, an image forming apparatus, and a process cartridge that can realize downsizing of the apparatus in accordance with the process and can stably obtain a high-quality image even in repeated use.

Means for solving the problems are as follows. That is,
<1> An electrophotographic photoreceptor comprising a support and a photosensitive layer on the support, wherein the photosensitive layer contains at least an amine compound represented by the following general formula (1). It is.
However, the In the formula (1), A and B are identical to each other, or different, _-CH 2 X, and _-CH 2 _CH 2 Y (provided that, X and Y are each aromatic Any one of a residue, a cycloalkyl group, and a heterocycloalkyl group, which may be further substituted with a substituent.
<2> In the above <1>, the photosensitive layer has a laminated structure including a charge generation layer and a charge transport layer, and the charge transport layer contains an amine compound represented by the general formula (1) and a charge transport material. The electrophotographic photosensitive member described.
<3> The electrophotographic photosensitive member according to <2>, wherein the charge transport material has a molecular weight of 600 or more.
<4> A charging step for charging the surface of the electrophotographic photosensitive member, an exposure step for exposing the charged electrophotographic photosensitive member surface to form an electrostatic latent image, and developing the electrostatic latent image using toner. An image forming method comprising at least a development step for forming a visible image, a transfer step for transferring the visible image to a recording medium, and a fixing step for fixing the transfer image transferred to the recording medium,
The electrophotographic photosensitive member is an electrophotographic photosensitive member according to any one of <1> to <3>.
<5> The image forming method according to <4>, wherein the exposure step is performed using any one of a laser diode (LD) and a light emitting diode (LED).
<6> An electrophotographic photosensitive member, charging means for charging the surface of the electrophotographic photosensitive member, exposure means for exposing the charged electrophotographic photosensitive member surface to form an electrostatic latent image, and the electrostatic latent image At least development means for developing a visible image by using toner, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transfer image transferred to the recording medium An image forming apparatus,
An electrophotographic photosensitive member according to any one of <1> to <3>, wherein the electrophotographic photosensitive member is an image forming apparatus.
<7> The image forming apparatus according to <6>, wherein the exposure unit is any one of a laser diode (LD) and a light emitting diode (LED).
<8> The image forming apparatus according to any one of <6> to <7>, wherein the image forming apparatus is a tandem type in which a plurality of image forming elements including at least an electrophotographic photosensitive member, a charging unit, a developing unit, and a transfer unit are arranged. It is.
<9> A plurality of intermediate transfer means for primarily transferring the toner image developed on the electrophotographic photosensitive member onto the intermediate transfer member and then secondary transferring the toner image on the intermediate transfer member onto the recording medium. The image formation according to any one of <6> to <7>, wherein the color toner images are sequentially superimposed on the intermediate transfer member to form a color image, and the color image is secondarily transferred onto the recording medium at once. Device.
<10> At least one means selected from charging means, exposure means, developing means, cleaning means, and transfer means, and the electrophotographic photosensitive member according to any one of <1> to <3>. Is a process cartridge.

  According to the present invention, conventional problems can be solved, and the electrophotographic photosensitive member having high ozone resistance and NOx resistance and high durability, and the use of the photosensitive member eliminates the need for replacement of the photosensitive member. In addition, it is possible to provide an image forming method, an image forming apparatus, and a process cartridge that can realize downsizing of the apparatus accompanying high-speed printing or a reduction in the diameter of the photoreceptor, and can stably obtain a high-quality image even in repeated use. .

FIG. 1 is a schematic sectional view showing an example of the electrophotographic photosensitive member of the present invention. FIG. 2 is a schematic sectional view showing another example of the electrophotographic photosensitive member of the present invention. FIG. 3 is a schematic view showing an example of the image forming apparatus of the present invention. FIG. 4 is a schematic view showing another example of the image forming apparatus of the present invention. FIG. 5 is a schematic view showing another example of the image forming apparatus of the present invention. FIG. 6 is a schematic view showing another example of the image forming apparatus of the present invention. FIG. 7 is a schematic view showing an example of the process cartridge of the present invention. FIG. 8 is an X-ray diffraction spectrum diagram of the oxytitanium phthalocyanine powder used in the examples.

(Electrophotographic photoreceptor)
The electrophotographic photoreceptor of the present invention comprises a support and a photosensitive layer on the support, and further comprises other layers as necessary.

-Layer structure-
The electrophotographic photoreceptor is not particularly limited with respect to the layer structure, and can be appropriately selected according to the purpose. In the first embodiment, a photosensitive layer (hereinafter, referred to as a single layer structure on the support) It may be referred to as “single-layer type photosensitive layer”) and other layers as necessary. In the second embodiment, a support, a photosensitive layer having a structure in which a charge generation layer and a charge transport layer are stacked on the support (hereinafter also referred to as a “stacked photosensitive layer”), Furthermore, it has another layer as needed. In the second embodiment, the charge generation layer and the charge transport layer may be laminated in reverse. Among these, an electrophotographic photosensitive member having a laminated photosensitive layer is particularly preferable.

Here, the electrophotographic photosensitive member will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the electrophotographic photosensitive member of the present invention. An amine compound represented by the following general formula (1), a charge generation material, and a charge transport material are provided on a support 201. The photosensitive layer 204 is contained.
In FIG. 2, a charge generation layer 202 containing a charge generation material and a charge transport layer 203 containing a charge transport material and an amine compound represented by the following general formula (1) are stacked on a support 201. ing. In this case, a photosensitive layer is formed by the charge generation layer and the charge transport layer. Although not shown in FIGS. 1 and 2, an undercoat layer may be provided between the support and the photosensitive layer or the charge generation layer, and a protective layer is provided on the outermost surface. It doesn't matter.

<Laminated photosensitive layer>
The multilayer photosensitive layer includes a charge generation layer and a charge transport layer, and as described above, the amino compound represented by the general formula (1) is contained in the charge transport layer.

-Charge transport layer-
The charge transport layer contains a charge transport material and an amine compound represented by the following general formula (1), and further contains other components as necessary.
However, the In the formula (1), A and B are identical to each other, or different, represent either a _-CH 2 X, and _{-CH 2} CH 2 Y.
X and Y each represent an aromatic residue, a cycloalkyl group, or a heterocycloalkyl group, which may be further substituted with a substituent.
Examples of the aromatic residue include phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, anthryl group, phenanthryl group, and the like.
Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.
The heterocycloalkyl group is a group in which at least one carbon atom of the cycloalkyl group is substituted with an oxygen atom, a sulfur atom, an N atom, or the like.
Examples of the substituent include an alkyl group, an alkoxyl group, a halogen atom, and a cyano group.

The amine compound represented by the general formula (1) can prevent deterioration of the electrophotographic photosensitive member due to ozone and NOx, and can extend the life.
Specific examples of the amine compound represented by the general formula (1) are shown below, but are not limited thereto.

<No. 1>
<No. 2>
<No. 3>
<No. 4>
<No. 5>
<No. 6>
<No. 7>
<No. 8>
<No. 9>

  The content of the amine compound represented by the general formula (1) in the charge transport layer is preferably 0.01 parts by mass to 0.30 parts by mass with respect to 1 part by mass of the charge transport agent, and 0.02 parts by mass. Part to 0.20 parts by mass is more preferable. When the content is less than 0.01 parts by mass, the charging and the image blur due to the influence of ozone and NOx may become noticeable. When the content exceeds 0.30 parts by mass, the residual potential increases. May occur.

-Charge transport material-
The charge transport material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, trinitrofluorenone, tetracyanoethylene, tetracyanoquinodimethane, quinone, diphenoquinone, naphthoquinone, anthraquinone, or derivatives thereof; Polycyclic aromatic compounds such as anthracene, pyrene, phenanthrene; nitrogen-containing heterocyclic compounds such as indole, carbazole, imidazole; fluorenone, fluorene, oxadiazole, oxazole, pyrazoline, hydrazone, triphenylmethane, triphenylamine, enamine, And stilbene and butadiene compounds. These may be used individually by 1 type and may use 2 or more types together.
The molecular weight of the charge transport material is preferably 600 or more, more preferably 700 to 1,000 from the viewpoint of high-speed response. When the molecular weight is less than 600, sufficient effects due to intramolecular charge transfer cannot be obtained, and the response to high-speed response may be insufficient.

--Binder resin--
Examples of the binder resin include polycarbonate resin, styrene resin, acrylic resin, styrene-acrylic resin, ethylene-vinyl acetate resin, polypropylene resin, vinyl chloride resin, chlorinated polyether, vinyl chloride-vinyl acetate resin, polyester resin, furan. Resin, Nitrile resin, Alkyd resin, Polyacetal resin, Polymethylpentene resin, Polyamide resin, Polyurethane resin, Epoxy resin, Polyarylate resin, Diarylate resin, Polysulfone resin, Polyethersulfone resin, Polyallylsulfone resin, Silicone resin, Ketone resin , Polyvinyl butyral resin, polyether resin, phenol resin, EVA (ethylene / vinyl acetate / copolymer) resin, ACS (acrylonitrile / chlorinated polyethylene / styrene) resin, There are resins such as ABS (acrylonitrile, butadiene, styrene) resin and photo-curing resin such as epoxy arylate. These may be used individually by 1 type and may use 2 or more types together. In addition, it is preferable to use a mixture of resins having different molecular weights because the hardness and wear resistance can be improved. In addition to mechanical, chemical and electrical stability, adhesion, etc., compatibility with the charge transport material is important.

  The method for forming the charge transport layer is not particularly limited, and various methods can be used.In general, a coating liquid in which a charge transport material and an additive are dispersed or dissolved in a solvent together with a binder resin, A method of coating on the charge generation layer and drying is preferable.

  The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohols such as methanol, ethanol, n-propanol, i-propanol, and butanol; pentane, hexane, heptane, octane, cyclohexane, Saturated aliphatic hydrocarbons such as cycloheptane; aromatic hydrocarbons such as toluene and xylene; chlorinated hydrocarbons such as dichloromethane, dichloroethane, chloroform and chlorobenzene; dimethyl ether, diethyl ether, tetrahydrofuran (THF), methoxyethanol, dimethoxyethane, Ethers such as dioxane, dioxolane, anisole; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl formate, propyl formate, methyl acetate, ethyl acetate, Acid propyl, butyl acetate, esters of methyl propionate; N, N-dimethylformamide, and dimethyl sulfoxide. These may be used individually by 1 type and may use 2 or more types together. Among these, ketone solvents, ester solvents, ether solvents, and halogenated hydrocarbon solvents are particularly preferable.

  The thickness of the charge transport layer is preferably 3 μm to 50 μm and more preferably 10 μm to 40 μm in order to maintain a practically effective surface potential.

-Charge generation layer-
The charge generation layer includes at least a charge generation material, and includes a binder resin and, if necessary, other components.

-Charge generation material-
The charge generation material is not particularly limited, and a known charge generation material can be used. For example, a monoazo pigment, a disazo pigment, an asymmetrical disazo pigment, a trisazo pigment, an azo pigment having a carbazole skeleton (Japanese Patent Laid-Open No. 53-95033), azo pigments having a distyrylbenzene skeleton (Japanese Patent Laid-Open No. 53-133445), azo pigments having a triphenylamine skeleton (Japanese Patent Laid-Open No. 53-132347), azo having a diphenylamine skeleton Pigments, azo pigments having a dibenzothiophene skeleton (Japanese Patent Laid-Open No. 54-21728), azo pigments having a fluorenone skeleton (Japanese Patent Laid-Open No. 54-22834), azo pigments having an oxadiazol skeleton (Japanese Patent Laid-Open No. 54) -12742), azo pigments having a bisstilbene skeleton (Japanese Patent Laid-Open No. 54-177) 3), azo pigments having a distyryl oxadiazol skeleton (Japanese Patent Laid-Open No. 54-2129), azo pigments having a distyryl carbazole skeleton (Japanese Patent Laid-Open No. 54-14967), etc. Azo pigments; azulenium salt pigments, square methine pigments, perylene pigments, anthraquinone or polycyclic quinone pigments, quinoneimine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments , An indigoid pigment, a bisbenzimidazole pigment, or a phthalocyanine pigment such as metal phthalocyanine or metal-free phthalocyanine. These may be used individually by 1 type and may use 2 or more types together. Among these, oxytitanium phthalocyanine is particularly preferable because it has high sensitivity characteristics.

--Binder resin--
The binder resin used as necessary for the charge generation layer is not particularly limited and can be appropriately selected according to the purpose. For example, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, Polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-vinyl carbazole, polyacrylamide, polyvinyl benzal, polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyphenylene oxide, polyvinyl pyridine, Cellulose resin, casein, polyvinyl alcohol, polyvinyl pyrrolidone, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  The charge generation layer may be obtained by dispersing a charge generation material in a solvent using a known dispersion method such as a ball mill, an attritor, a sand mill, or an ultrasonic wave together with a binder resin as necessary. it can. The binder resin may be added before or after the charge generating material is dispersed. The coating solution for the charge generation layer is mainly composed of a charge generation material, a solvent, and a binder resin, and it contains additives such as a sensitizer, a dispersant, a surfactant, and silicone oil. May be. In some cases, it is also possible to add a charge transport material described later to the charge generation layer. The addition amount of the binder resin is preferably 500 parts by mass or less, more preferably 10 parts by mass to 300 parts by mass with respect to 100 parts by mass of the charge generation material.

  Examples of the solvent include generally used organic materials such as isopropanol, acetone, methyl ethyl ketone, dioxolane, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane, toluene, xylene, and ligroin. Among them, it is preferable to use a ketone solvent, an ester solvent, or an ether solvent. These may be used individually by 1 type and may use 2 or more types together.

The charge generation layer is formed by coating on a support or an undercoat layer using the coating liquid and drying. As the coating method, known methods such as dip coating, spray coating, bead coating, nozzle coating, spinner coating, ring coating, and the like can be used. Further, drying after coating is performed by heating using an oven or the like. The drying temperature of the charge generation layer is preferably 50 ° C to 160 ° C, more preferably 80 ° C to 140 ° C.
The thickness of the charge generation layer is preferably 5 μm or less, and more preferably 0.1 μm to 1 μm.

<Single layer type photosensitive layer>
The single-layer type photosensitive layer is obtained by dissolving or dispersing a charge generating substance, a charge transporting substance, the amine compound represented by the general formula (1), a binder resin, and the like in an appropriate solvent, Or it forms by apply | coating on an undercoat layer and drying.

For details of the amine compound represented by the general formula (1), the charge generation material, and the charge transport material, the amine compound represented by the general formula (1), the charge generation layer, and the charge transport layer may be used. It is possible to use the materials mentioned. Further, as the binder resin, in addition to the resins mentioned in the charge transport layer, the resins mentioned in the charge generation layer may be mixed and used. Examples of other components include plasticizers, fine particles, and various additives. Note that the above-described polymer charge transporting material can also be used favorably as the binder resin.
0.5 mass part-15 mass parts are preferable with respect to 100 mass parts of said binder resins, and, as for content of the amine compound represented by the said General formula (1), 1 mass part-10 mass parts are more preferable. The content of the charge generation material is preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the binder resin. Moreover, 190 mass parts or less are preferable with respect to 100 mass parts of said binder resins, and, as for content of the said charge transport material, 50 mass parts-150 mass parts are more preferable.

The single-layer type photosensitive layer is dissolved or dispersed in a solvent such as tetrahydrofuran, dioxane, dichloroethane, cyclohexanone, toluene, methyl ethyl ketone, and acetone together with the charge generation material, the binder resin, and the charge transport material, and this is dip-coated. It can be formed by coating with a spray coat, bead coat, ring coat or the like. If necessary, various additives such as a plasticizer, a leveling agent, an antioxidant and a lubricant can be added.
The thickness of the single-layer type photosensitive layer is preferably 3 μm to 50 μm and more preferably 10 μm to 40 μm in order to maintain a practically effective surface potential.

<Support>
The support is not particularly limited as long as it has a volume resistance of 10 ¹⁰ Ω · cm or less, and can be appropriately selected according to the purpose. For example, aluminum, nickel, chromium, nichrome, copper Metals such as gold, silver and platinum; metal oxides such as tin oxide and indium oxide deposited or sputtered on a film or cylindrical plastic, paper or aluminum, aluminum alloy, nickel, stainless steel, etc. Or a tube subjected to surface treatment such as cutting, super-finishing, polishing or the like after being made into a raw tube by a method such as extruding and drawing them. Further, an endless nickel belt and an endless stainless steel belt disclosed in JP-A-52-36016 can also be used as a support. Further, it may be a nickel foil having a thickness of 50 μm to 150 μm, or a surface of a polyethylene terephthalate film having a thickness of 50 μm to 150 μm subjected to conductive processing such as aluminum vapor deposition.
In the case of a cylindrical support, the diameter is preferably 60 mm or less, and more preferably 30 mm or less.

  Among these, aluminum alloys such as JIS 3000 series, JIS 5000 series, and JIS 6000 series are used, and EI (Extension Ironing) method, ED (Extension Drawing) method, DI (Drawing Ironing) method, II (Impact Ironing) method, etc. A conductive support formed by a method is preferable, and the surface of the conductive support is further subjected to surface treatment such as diamond cutting or polishing, surface treatment such as anodizing treatment, or these treatments and treatments. Anything such as a non-cutting tube which is not performed may be used.

In addition, those in which conductive powder is dispersed in an appropriate binder resin and coated on the support can also be used as the support.
Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc, and silver, or metal oxide powder such as conductive tin oxide and ITO. Etc. The binder resin used at the same time includes polystyrene resin, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate. Copolymer, polyvinyl acetate resin, polyvinylidene chloride resin, polyarylate resin, phenoxy resin, polycarbonate resin, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral resin, polyvinyl formal resin, polyvinyl toluene resin, poly-N-vinyl carbazole, An acrylic resin, a silicone resin, an epoxy resin, a melamine resin, a urethane resin, a phenol resin, an alkyd resin, etc. are mentioned.
The conductive layer can be provided by dispersing and applying these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, toluene and the like.

  Furthermore, it is electrically conductive by a heat shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, Teflon (registered trademark) on a suitable cylindrical substrate. Those provided with a conductive layer can also be used favorably as a conductive support.

-Surface protective layer-
On the photosensitive layer, an organic thin film such as polyvinyl formal resin, polycarbonate resin, fluororesin, polyurethane resin, or silicone resin, or a thin film composed of a siloxane structure formed from a hydrolyzate of a silane coupling agent is formed. A surface protective layer may be provided, and in that case, the durability of the photoreceptor is improved, which is preferable. This surface protective layer may be provided in order to improve functions other than the durability improvement.

-Undercoat layer-
An undercoat layer may be provided between the support and the photosensitive layer as necessary. The undercoat layer is provided for the purpose of improving adhesiveness, preventing moire, improving the coatability of the upper layer, and reducing residual potential.

The undercoat layer contains at least a resin and fine powder, and further contains other components as necessary.
Examples of the resin include water-soluble resins such as polyvinyl alcohol resin, casein, and sodium polyacrylate; alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon; polyurethane resins, melamine resins, alkyd-melamine resins, and epoxy resins. And a curable resin that forms a three-dimensional network structure.
Examples of the fine powder include metal oxides such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, and indium oxide, metal sulfides, and metal nitrides.
Moreover, what contains a silane coupling agent, a titanium coupling agent, a chromium coupling agent etc. as an undercoat layer can also be used. Further, as an undercoat layer, an anodized layer of Al ₂ O ₃ , an organic material such as polyparaxylylene (parylene), or an inorganic material such as SiO ₂ , SnO ₂ , TiO ₂ , ITO, or CeO ₂ is vacuum thin film. Those provided by the manufacturing method can also be used.
There is no restriction | limiting in particular about the thickness of the said undercoat layer, According to the objective, it can select suitably, 0.1 micrometer-50 micrometers are preferable, and 0.5 micrometer-20 micrometers are more preferable.

In the electrophotographic photoreceptor of the present invention, an antioxidant, a plasticizer, a lubricant, an ultraviolet ray is added to each layer such as a single-layer type photosensitive layer, a charge generation layer, a charge transport layer, an undercoat layer, and a surface protective layer as necessary. Absorbers, low molecular charge transport materials, leveling agents and the like can be added.
Examples of the antioxidant include hindered phenol-based antioxidants, amine-based antioxidants, and sulfur-based antioxidants.

  Examples of the phenol-based antioxidant include 2.6-di-tert-butylphenol, 2.6-di-tert-4-methoxyphenol, 2-tert-butyl-4-methoxyphenol, and 2.4-dimethyl-6. -Tert-butylphenol, 2.6-di-tert-butyl-4-methylphenol, butylated hydroxyanisole, stearyl propionate-β- (3.5-di-tert-butyl-4-hydroxyphenyl), α- Monophenols such as tocopherol, β-tocopherol, n-octadecyl-3- (3′-5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 2.2′-methylenebis (6-tert-butyl) -4-methylphenol), 4.4'-butylidene-bis- (3-methyl-6-ter) -Butylphenol), 4.4'-thiobis (6-tert-butyl-3-methylphenol), 1.1.3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane; 3.5-trimethyl-2.4.6-tris (3.5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3 (3.5-di-tert-butyl-4-hydroxy) Phenyl) propionate] and polyphenols such as methane. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amine antioxidant include N-phenyl-1-naphthylamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, and N-phenyl-N′-. Ethyl-2-methyl-p-phenylenediamine, N-ethyl-N-hydroxyethyl-p-phenylenediamine, alkylated diphenylamine, N, N'-diphenyl-p-phenylenediamine, N, N'-diallyl-p- Phenylenediamine, N-phenyl-1,3-dimethylbutyl-p-phenylenediamine, 4,4'-dioctyl-diphenylamine, 4,4'-dioctyl-diphenylamine, 6-ethoxy-2,2,4-trimethyl-1 , 2-Dihydroquinoline, 2,2,4-trimethyl-1,2-dihydroquinoline N- phenyl -β- naphthylamine, N, N'and di-2-naphthyl -p- phenylenediamine. These may be used individually by 1 type and may use 2 or more types together.

Examples of the sulfur-based antioxidant include dilauryl-3.3-thiodipropionate, ditridecyl-3.3-thiodipropionate, dimyristyl-3.3-thiodipropionate, and distearyl-3.3. thiodipropionate, lauryl stearyl 3,3-thiopropionate, bis [2-methyl -4- (3-n- alkyl _C 12 _{-C 14)} thiopropionate) -5-t-butylphenyl] Examples thereof include sulfide, pentaerythritol tetra (β-lauryl-thiopropionate) ester, 2-mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- [2-hydroxy-3.5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole. 2- (3.5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- ( 3.5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3.5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy Benzotriazoles such as -5'-tert-octylphenyl) benzotriazole; phenyl salicylate, salicylate Examples include salicylic acid-based compounds such as thiolic acid-p-tert-butylphenyl and salicylic acid-p-octylphenyl. These may be used individually by 1 type and may use 2 or more types together. Among these, benzotriazole ultraviolet absorbers are particularly preferable.

  The addition amount of the antioxidant and the ultraviolet absorber added to any layer of the electrophotographic photoreceptor of the present invention is preferably 1 part by weight to 20 parts by weight with respect to 100 parts by weight of the charge transport material.

Furthermore, an electron accepting material is included in the photosensitive layer of the above-mentioned multilayer type and single layer type photoreceptors as necessary for the purpose of improving sensitivity, reducing residual potential, or reducing characteristic fluctuations during repeated use. It is preferable.
Examples of the electron acceptor include succinic anhydride, maleic anhydride, dibromosuccinic anhydride, phthalic anhydride, 3-nitrophthalic anhydride, 4-nitrophthalic anhydride, pyromellitic anhydride, pyromellitic acid, trimellit Examples include acid, trimellitic anhydride, phthalimide, 4-nitrophthalimide, tetracyanoethylene, tetracyanosinodimethane, chloranil, bromanyl, o-nitrobenzoic acid, and the like. These may be used individually by 1 type and may use 2 or more types together.

(Image forming apparatus and image forming method)
The image forming apparatus according to the present invention includes at least an electrophotographic photosensitive member, a charging unit, an exposure unit, a developing unit, a transfer unit, and a fixing unit. Means, for example, cleaning means, static elimination means, recycling means, control means, and the like.
The electrophotographic photoreceptor is the electrophotographic photoreceptor of the present invention.
The image forming method of the present invention includes at least a charging step, an exposure step, a development step, a transfer step, and a fixing step, and further other steps appropriately selected as necessary, for example, a cleaning step and a charge eliminating step. A recycling process, a control process, and the like.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the charging step can be performed by the charging unit, the exposure step can be performed by the exposing unit, The developing step can be performed by the developing unit, the transferring step can be performed by the transferring unit, the fixing step can be performed by the fixing unit, and the cleaning step can be performed by the cleaning unit. The other steps can be performed by the other means.

-Charging step and charging means-
The charging step is a step of charging the surface of the electrophotographic photosensitive member, and is performed by the charging unit.
The charging means is not particularly limited as long as it can uniformly apply a voltage to the surface of the electrophotographic photosensitive member, and can be appropriately selected depending on the purpose. A non-contact charging means for charging the photoconductor in a non-contact manner is used.
Examples of the non-contact charging means include a non-contact charger and a needle electrode device using a corona discharge, a solid discharge element; a conductive or semiconductive material disposed with a minute gap with respect to the electrophotographic photosensitive member. And a charging roller. Among these, corona discharge is particularly preferable.

The corona discharge is a non-contact charging method that gives positive or negative ions generated by corona discharge in the air to the surface of the electrophotographic photosensitive member, and has a characteristic of giving a certain amount of charge to the electrophotographic photosensitive member. There are a charger and a scorotron charger having a characteristic of giving a constant potential.
The coroton charger is composed of a casing electrode that occupies a half space around the discharge wire, and a discharge wire placed almost at the center thereof.
The scorotron charger is obtained by adding a grid electrode to the corotron charger, and the grid electrode is provided at a position 1.0 mm to 2.0 mm away from the surface of the electrophotographic photosensitive member.

-Exposure process and exposure means-
The exposure can be performed, for example, by exposing the surface of the electrophotographic photosensitive member imagewise using the exposure unit.
The optical system in the exposure is roughly classified into an analog optical system and a digital optical system. The analog optical system is an optical system that directly projects an original onto an electrophotographic photosensitive member by an optical system, and the digital optical system receives image information as an electrical signal, converts this into an optical signal, and converts it into an electrophotographic image. It is an optical system that exposes a photoreceptor to form an image.
The exposure unit is not particularly limited as long as the surface of the electrophotographic photosensitive member charged by the charging unit can be exposed like an image to be formed, and can be appropriately selected according to the purpose. However, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, a liquid crystal shutter optical system, and an LED optical system can be used.
In the present invention, an optical backside system that performs imagewise exposure from the backside of the electrophotographic photosensitive member may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using a toner or a developer to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer, and can be appropriately selected from known ones. For example, the toner or developer is accommodated. Preferred examples include those having at least a developing unit capable of bringing the toner or developer into contact or non-contact with the electrostatic latent image.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrophotographic photosensitive member (photosensitive member), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is caused by an electric attractive force. It moves to the surface of the electrophotographic photoreceptor. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrophotographic photosensitive member.

  The developer accommodated in the developing device is a developer containing the toner, but the developer may be a one-component developer or a two-component developer.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the electrophotographic photosensitive member with the transfer charger using the visible image, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer unit (the primary transfer unit and the secondary transfer unit) includes at least a transfer unit that peels and charges the visible image formed on the electrophotographic photosensitive member toward the recording medium. preferable. There may be one transfer means or two or more transfer means. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

-Fixing Step and Fixing Unit The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium. Alternatively, the toners of the respective colors may be simultaneously formed in a state where they are laminated.

The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose. A fixing unit and a heat source for heating the fixing member are used.
Examples of the fixing member include a combination of an endless belt and a roller, a combination of a roller and a roller, etc., but the warm-up time can be shortened, and in terms of realizing energy saving, A combination of an endless belt and a roller having a small heat capacity is preferable in terms of expansion of the fixable width.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrophotographic photosensitive member, and can be suitably performed by a neutralization unit.
The neutralizing means is not particularly limited and may be appropriately selected from known neutralizers as long as it can apply a neutralizing bias to the electrophotographic photosensitive member. For example, a neutralizing lamp is preferably used. Can be mentioned.

The cleaning step is a step of removing the toner remaining on the electrophotographic photosensitive member, and can be suitably performed by a cleaning unit. In addition, it is also possible to employ a method in which the charge of the residual toner is made uniform by the rubbing member and collected by the developing roller without using the cleaning means.
The cleaning means is not particularly limited, and may be selected from known cleaners as long as the electrophotographic toner remaining on the electrophotographic photosensitive member can be removed. For example, a magnetic brush cleaner Suitable examples include electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

  The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit. There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

Here, FIG. 3 is a schematic view showing an example of the image forming apparatus of the present invention. The electrophotographic photoreceptor 1 of FIG. 3 is the electrophotographic photoreceptor of the present invention. In FIG. 3, the photosensitive member 1 has a drum shape, but may have a sheet shape or an endless belt shape.
The charging charger 3, the pre-transfer charger 7, the transfer charger 10, the separation charger 11, and the pre-cleaning charger 13 are non-contact corona discharge type charging means such as corotron, scorotron, solid state charger (solid state charger), etc. Is used.

As the transfer means, the above charger can be generally used. However, as shown in FIG. 3, a combination of the transfer charger 10 and the separation charger 11 is effective.
The light source such as the exposure unit 5 and the charge removal lamp 2 emits light from a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), an electroluminescence (EL), or the like. All things can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
In addition to the steps shown in FIG. 3, the light source and the like are provided with a transfer step, a static elimination step, a cleaning step, a pre-exposure step and the like using light irradiation, so that the photosensitive member is irradiated with light.

  Next, the toner image developed on the photosensitive member 1 by the developing unit 6 is transferred to the recording medium 9, but not all is transferred, and toner remaining on the photosensitive member 1 is also generated. Such residual toner is removed from the photoreceptor by a cleaning unit 16 including a fur brush 14 and a blade 15. Cleaning may be performed only with a cleaning brush, and a known brush such as a fur brush or a mag fur brush is used as the cleaning brush.

  When a positive (negative) charge is applied to the electrophotographic photosensitive member and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. When this is developed with negative (positive) polarity toner (electrodetection fine particles), a positive image can be obtained, and when developed with positive (negative) polarity toner, a negative image can be obtained. As the developing means, known means are used.

  The wavelength of the static elimination lamp 2 as the static elimination means may be in the wavelength region where the photosensitive member has photosensitivity, and is preferably on the long wavelength side in the practical photosensitive wavelength region of the photosensitive member.

Various conditions of the cleaning blade include a blade contact angle of 10 to 30 degrees, a contact pressure of 0.3 to 4 g / mm, a rubber hardness of 60 to 70 degrees, a rebound resilience, 30 to 70%, and a Young's modulus. A range of 30 to 60 kgf / cm ² , a thickness of 1.5 to 3.0 mm, a free length of 7 to 12 mm, and a blade edge biting amount of 0.2 to 2 mm is preferable, and urethane is a material that satisfies such physical properties. A rubber blade is particularly suitable.

Next, FIG. 4 is a schematic view showing an example of an electrophotographic process according to the present invention. The photoreceptor 21 has at least a photosensitive layer and contains an amine compound represented by the general formula (1). The photosensitive member 21 is driven by driving rollers 22a and 22b, and charging by a charger 23, image exposure by a light source 24, development (not shown), transfer using a transfer charger 25, cleaning by a brush 27, and static elimination by a light source 28 are repeatedly performed. Is called.
In the electrophotographic process shown in FIG. 4, image exposure, pre-cleaning exposure, and static elimination exposure are illustrated in the light irradiation process, but other pre-exposure exposure, pre-exposure of image exposure, and other known light irradiation processes are also performed. It is also possible to irradiate the photoconductor with light.

  FIG. 5 is a diagram showing an example of another embodiment of the present invention. In FIG. 5, the photosensitive drum 56 is driven to rotate counterclockwise in the drawing, and its surface is uniformly charged by a charging charger 53 using a corotron, a scorotron, etc. An electrostatic latent image is carried by receiving scanning of laser light L emitted from the apparatus. Since this scanning is performed based on single-color image information obtained by decomposing a full-color image into yellow, magenta, cyan, and black color information, a static color for yellow, magenta, cyan, or black is displayed on the photosensitive drum 56. An electrostatic latent image is formed. A revolver developing unit 50 is disposed on the left side of the photosensitive drum 56 in the drawing. This has a yellow developing device, a magenta developing device, a cyan developing device, and a black developing device in a rotating drum-shaped housing, and each developing device is moved to a developing position facing the photosensitive drum 56 by rotation. Move sequentially. The yellow developing unit, magenta developing unit, cyan developing unit, and black developing unit develop the electrostatic latent image by attaching yellow toner, magenta toner, cyan toner, and black toner, respectively.

On the photosensitive drum 56, electrostatic latent images for yellow, magenta, cyan, and black are sequentially formed. These are sequentially developed by the developing units of the revolver developing unit 50 to become a yellow toner image, a magenta toner image, a cyan toner image, and a black toner image.
An intermediate transfer unit is disposed on the downstream side of the photosensitive drum 56 from the development position. This is because the intermediate transfer belt 58 stretched by a tension roller 59a, an intermediate transfer bias roller 57 as a transfer means, a secondary transfer backup roller 59b, and a belt drive roller 59c is driven by rotation of the belt drive roller 59c. Move endlessly clockwise. The yellow toner image, magenta toner image, cyan toner image, and black toner image developed on the photosensitive drum 56 enter an intermediate transfer nip where the photosensitive drum 56 and the intermediate transfer belt 58 are in contact with each other. Then, while being influenced by the bias from the intermediate transfer bias roller 57, the toner image is superimposed on the intermediate transfer belt 58 and intermediately transferred to form a four-color superimposed toner image.

The surface of the photosensitive drum 56 that has passed through the intermediate transfer nip with the rotation is cleaned of the transfer residual toner by the drum cleaning unit 55. The cleaning unit 55 cleans the transfer residual toner with a cleaning roller to which a cleaning bias is applied. However, a cleaning brush such as a fur brush or a mag fur brush, a cleaning blade, or the like may be used.
The surface of the photosensitive drum 56 from which the transfer residual toner has been cleaned is discharged by the discharging lamp 54. As the static elimination lamp 54, a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), an electroluminescence (EL), or the like is used. A semiconductor laser is used as a light source of the laser optical device. About these emitted lights, you may make it use only a desired wavelength range by various filters, such as a sharp cut filter, a band pass filter, a near-infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter.
On the other hand, a registration roller pair 61 that sandwiches a recording medium 60 sent from a paper feeding cassette (not shown) between two rollers can superimpose the recording medium 60 on a four-color superimposed toner image on the intermediate transfer belt 58. Feed toward the secondary transfer nip at the timing. The four-color superimposed toner images on the intermediate transfer belt 58 are collectively secondary-transferred onto the recording medium 60 under the influence of the secondary transfer bias from the paper transfer bias roller 63 in the secondary transfer nip. By this secondary transfer, a full color image is formed on the recording medium 60.

The recording medium 60 on which the full color image is formed is sent to the paper transport belt 64 by the transfer belt 62. The conveyance belt 64 sends the recording medium 60 received from the transfer unit into the fixing device 65. The fixing device 65 conveys the fed recording medium 60 while being sandwiched in a fixing nip formed by the contact between the heating roller and the backup roller. The full color image on the recording medium 60 is fixed on the transfer paper 60 under the influence of the heating from the heating roller and the pressure applied in the fixing nip.
Although not shown, a bias for attracting the recording medium 60 is applied to the transfer belt 62 and the conveyance belt 64. In addition, a paper neutralization charger that neutralizes the recording medium 60 and three belt neutralization chargers that neutralize each belt (intermediate transfer belt 58, transfer belt 62, and conveyance belt 64) are provided. The intermediate transfer unit also includes a belt cleaning unit having the same configuration as that of the drum cleaning unit 55, thereby cleaning the transfer residual toner on the intermediate transfer belt 58.

Next, FIG. 6 is a schematic diagram showing another embodiment of the present invention. This image forming apparatus is a so-called tandem printer, and does not share the photosensitive drum 80 for each color as shown in FIG. 5, but cyan (C), magenta (M), yellow (Y), and black ( K) photosensitive drums 80Y, 80M, 80C, and 80Bk for the four colors. The drum cleaning unit 85, the charge removal lamp 83, and the charger 84 are also provided with four colors of cyan (C), magenta (M), yellow (Y), and black (K).
In the tandem type, electrostatic latent image formation and development of each color can be performed in parallel, so that the image forming speed can be made much faster than in the revolver type.

  The image forming means in the image forming apparatus described above may be fixedly incorporated in the copying apparatus, facsimile, or printer, but may be incorporated in the image forming apparatus in the form of a process cartridge described below. .

(Process cartridge)
The process cartridge of the present invention has at least one means selected from a charging means, an exposure means, a developing means, a transfer means, a cleaning means, and a static elimination means, and an electrophotographic photosensitive member, and is attached to and detached from the image forming apparatus main body. It is possible.
The electrophotographic photoreceptor is the electrophotographic photoreceptor of the present invention.

Here, FIG. 7 is a schematic view showing a configuration of an image forming apparatus provided with the process cartridge of the present invention.
The photoreceptor 101 has at least a photosensitive layer on a support, and the photosensitive layer contains an amine compound represented by the general formula (1). Reference numeral 103 denotes a charging unit, 102 denotes a developing unit, 107 denotes a transfer unit, and 105 denotes a cleaning unit.
In the present invention, among the constituent elements such as the photosensitive member 101, the charging unit 303, the developing unit 304, and the cleaning unit 305, at least the photosensitive member 302 and the developing unit 304 are integrally coupled as a process cartridge. The process cartridge can be configured to be detachable from a main body of an image forming apparatus such as a copying machine or a printer.

  By adopting the configuration of the present invention as described above, the electrophotographic photosensitive member of the present invention can suppress image deterioration and residual potential increase due to image blurring and can stably form a high-quality image even for repeated use over a long period of time. It is possible to provide a body, an image forming apparatus, and a process cartridge.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
The following undercoat layer coating solution was applied onto a cylindrical drum made of uncut aluminum having a diameter of 24 mm and dried to form an undercoat layer having a thickness of 1.5 μm.
-Preparation of coating solution for undercoat layer-
Alkyd resin (Beckolite M-6401-50, manufactured by Dainippon Ink & Chemicals, Inc.) and amino resin (Super Becamine G-821-60, manufactured by Dainippon Ink & Chemicals, Inc.) 65:35 (mass ratio) ), And the mixed resin and titanium oxide (CR-EL, manufactured by Ishihara Sangyo Co., Ltd.) at a ratio of 1: 3 (mass ratio) and dissolved in methyl ethyl ketone. Prepared.

Next, 15 g of oxytitanium phthalocyanine powder having a maximum peak at an X-ray diffraction angle Cuka (2θ ± 0.2 degrees) of 27.3 degrees shown in FIG. 8 was added to glass beads and 500 ml of 1,3-dioxolane (polyvinyl butyral resin ( BX-1 (manufactured by Sekisui Chemical Co., Ltd.) is added to a solution of 10 g, dispersed for 20 hours with a sand mill disperser, the resulting dispersion is filtered to remove the glass beads, and the charge generation layer coating solution Was made.
Next, the support on which the undercoat layer was formed was dip-coated with the charge generation layer coating solution and dried to form a charge generation layer having a thickness of 0.2 μm.

Next, polycarbonate resin (PCZ-500, manufactured by Mitsubishi Gas Chemical Co., Inc.) as the binder resin, a compound (molecular weight: 671) represented by the following formula (A) as the charge transport material, and No represented by the following formula . 1 and the compound represented by the following formula (B) as the ultraviolet absorber (binder resin: charge transport material: amine compound of No. 1: UV absorber) is 1: 1: 0. It dissolved in tetrahydrofuran so that it might be set to 1: 0.1, and the coating liquid for charge transport layers was prepared.
Next, the support on which the undercoat layer and the charge generation layer were formed was dip-coated with the charge transport layer coating solution and dried at 130 ° C. for 60 minutes to form a charge transport layer having a thickness of 25.0 μm. Thus, the electrophotographic photosensitive member of Example 1 was produced.
<Formula (A)>
<Formula (B)>
<No. 1>

(Example 2)
In Example 1, except that the mass ratio (binder resin: charge transport material: amine compound of No. 1: UV absorber) in the coating solution for charge transport layer was 1: 1: 0.01: 0.1. In the same manner as in Example 1, an electrophotographic photosensitive member was produced.

(Example 3)
In Example 1, except that the mass ratio (binder resin: charge transport material: amine compound of No. 1: UV absorber) in the coating solution for charge transport layer was 1: 1: 0.3: 0.1. In the same manner as in Example 1, an electrophotographic photosensitive member was produced.

(Example 4)
In Example 1, No. 1 in the coating solution for charge transport layer was used. No. 1 represented by the following formula: An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the amine compound was changed to 2.
<No. 2>

(Example 5)
In Example 1, No. 1 in the coating solution for charge transport layer was used. No. 1 represented by the following formula: An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the amine compound was changed to 3.
<No. 3>

(Example 6)
In Example 1, No. 1 in the charge transport layer coating solution was used. No. 1 represented by the following formula: An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the amine compound 6 was used.
<No. 6>

(Example 7)
In Example 1, No. 1 in the charge transport layer coating solution was used. No. 1 represented by the following formula: An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the amine compound 9 was changed.
<No. 9>

(Example 8)
In the charge transport layer coating liquid of Example 1, a compound represented by the following formula (C) was added as an antioxidant, and the mass ratio (binder resin: charge transport material: No. 1 amine compound: UV absorber) : Antioxidant) was changed to 1: 1: 0.1: 0.1: 0.1, and an electrophotographic photosensitive member was produced in the same manner as in Example 1.
<Formula (C)>

Example 9
In Example 8, an electrophotographic photosensitive member was obtained in the same manner as in Example 8, except that the compound represented by the above formula (C) as an antioxidant was changed to a compound represented by the following formula (D). Was made.
<Formula (D)>

(Example 10)
In Example 1, except that the compound represented by the above formula (A) as the charge transport material in the charge transport layer coating solution was changed to a compound represented by the following formula (E) (molecular weight: 720). In the same manner as in Example 1, an electrophotographic photosensitive member was produced.
<Formula (E)>

(Example 11)
In Example 1, except that the compound represented by the above formula (A) as the charge transport material in the coating liquid for charge transport layer was changed to a compound represented by the following formula (F) (molecular weight: 863). In the same manner as in Example 1, an electrophotographic photosensitive member was produced.
<Formula (F)>

(Example 12)
In Example 1, except that the charge transport material represented by the above formula (A) in the charge transport layer coating solution was changed to a charge transport material represented by the following formula (K) (molecular weight: 451), In the same manner as in Example 1, an electrophotographic photosensitive member was produced.
<Formula (K)>

(Example 13)
In Example 1, except that the charge transport material represented by the above formula (A) in the coating liquid for charge transport layer was changed to a charge transport material represented by the following formula (L) (molecular weight: 500), In the same manner as in Example 1, an electrophotographic photosensitive member was produced.
<Formula (L)>

(Comparative Example 1)
In Example 1, No. 1 in the charge transport layer coating solution was used. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 1 amine compound was not added.

(Comparative Example 2)
In Example 1, No. 1 in the coating solution for charge transport layer was used. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the amine compound 1 was changed to the compound represented by the above formula (C).

(Comparative Example 3)
In Example 1, No. 1 in the charge transport layer coating solution was used. An electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the amine compound of 1 and the compound represented by the above formula (B) were not used, and the compound represented by the following formula (G) was used. .
<Formula (G)>

(Comparative Example 4)
In Example 1, No. 1 in the charge transport layer coating solution was used. An electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the amine compound of 1 and the compound represented by the above formula (B) were not used, but the compound represented by the following formula (H) was used. .
<Formula (H)>

(Comparative Example 5)
In Example 1, No. 1 in the coating solution for charge transport layer was used. An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the amine compound of 1 and the compound represented by the above formula (B) were not used but the compound represented by the following formula (I) was used. .
<Formula (I)>

(Comparative Example 6)
In Example 1, No. 1 in the charge transport layer coating solution was used. An electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the amine compound of 1 and the compound represented by the above formula (B) were not used, but the compound represented by the following formula (J) was used. .
<Formula (J)>

<Evaluation of electrical characteristics with a simple measuring instrument>
For each electrophotographic photosensitive member produced in Examples 1 to 13 and Comparative Examples 1 to 6, a photosensitive drum evaluation device (dynamic mode measurement) was used, and the electrophotographic characteristics were evaluated under the following conditions.

Using the electrophotographic photoreceptor evaluation apparatus, the surface potential of the photoreceptor is about −700 V by the scorotron method in the environment of the temperature of 23 ° C. and the humidity of 50% RH in the electrophotographic photoreceptor produced in the examples and comparative examples. Thus, when the discharge current is adjusted and the charging potential at that time is set to (V0), the electrophotographic photosensitive member is charged and irradiated with a semiconductor laser having a wavelength of 650 nm, the exposure energy amount of 0.13 to 0.15 μJ is applied. The surface potential adjusted so that the surface potential was about ½ (about −300 V) was defined as (VH). The surface potential when exposed with an exposure energy amount of 0.6 μJ / cm ² was defined as a photoreceptor residual potential (VL).

  Each of the produced electrophotographic photoreceptors was exposed at an ozone concentration of 5 ppm for 5 days using an ozone exposure test apparatus (manufactured by Directec). The surface potential (VO), sensitivity potential (VH), and residual potential (VL) of the photoconductor before and after exposure were measured. For neutralization, an LED (20 μW) having a wavelength of 660 nm was used. The drum rotation speed of the electrophotographic photosensitive member was 150 rpm, and the time from when the laser beam was irradiated until the potential was measured (movement time from the exposure position to the measurement position) was 0.06 seconds. The results are shown in Table 1.

Similarly, the electrophotographic photosensitive member was exposed for 4 days at a NO concentration of 40 ppm and a NO ₂ concentration of 10 ppm with a NOx exposure test apparatus (manufactured by Directec). The surface potential (VO), sensitivity potential (VH), and residual potential (VL) of the photoconductor before and after exposure were measured. For neutralization, an LED (20 μW) having a wavelength of 660 nm was used. The drum rotation speed of the electrophotographic photosensitive member was 150 rpm, and the time from when the laser beam was irradiated until the potential was measured (movement time from the exposure position to the measurement position) was 0.06 seconds. The results are shown in Table 1.

<Evaluation of actual image (halftone evaluation)>
For each of the electrophotographic photoreceptors produced in Examples 1 to 13 and Comparative Examples 1 to 6, an initial photoreceptor and a photoreceptor subjected to an ozone exposure test or a NOx exposure test were used as a color printer (manufactured by Ricoh Co., Ltd., CX220), a halftone image (2by2) was output in a room temperature environment at a temperature of 23 ° C. and a humidity of 50% RH, and the image density difference (measured with a Macbeth densitometer) ΔID between the initial stage and the exposure was compared. The results are shown in Table 2.
ΔID = initial ID−post-exposure ID

In Table 1, the surface potentials V0 and VH are superior to the initial set value V0 of about 700V and VH of about 350V, respectively, as the potential change after light irradiation is smaller.
Examples 1 to 13 are electrophotographic photoreceptors excellent in ozone resistance and NOx resistance by adding the amine compound represented by the above general formula (1) to the photosensitive layer. The charging potential, sensitivity potential, The residual potential and image density were good. In Example 2, no. In the case where the amount of compound No. 1 was small, the surface potential and sensitivity potential were slightly inferior to those of Example 1, but the density difference on the image was small and practically acceptable.
In Example 3, no. This is a case where the amount of amine compound 1 added is large, and VL is somewhat high, but the image density is the same level as in Example 1, and there is no practical problem. In Examples 1 to 7, although a charge transport material having a molecular weight of 671 and a relatively large molecular weight was used, the electrical characteristics were also very low and good.
Further, Examples 12 and 13 using a low molecular weight charge transport material have high VH and VL, but are excellent in ozone resistance and NOx resistance.

On the other hand, Comparative Example 1 was a photoconductor produced without adding the compound represented by the general formula (1) to the photosensitive layer, but V0 and VH after ozone exposure and NOx exposure were significantly reduced. In addition, the image density change ΔID also has a remarkably large value.
In Comparative Examples 2 to 6, photoconductors were prepared by adding different compounds to the photosensitive layer. However, the decrease in V0 and VH after exposure to ozone and exposure to NOx was large, and both showed changes in image density. It was a result inferior compared with Examples 1-13 largely.

  Therefore, by containing the amine compound represented by the general formula (1) in the photosensitive layer, the ozone resistance and NOx resistance of the photoreceptor can be improved. In addition, by using these photoconductors, it is not necessary to replace the photoconductors, and it is possible to reduce the size of the apparatus due to high-speed printing or reducing the diameter of the photoconductor, and to stably obtain high-quality images even during repeated use. Image forming method, image forming apparatus, and process cartridge can be provided.

  The electrophotographic photosensitive member of the present invention can cope with the process of reducing the diameter and speed of the photosensitive member accompanying the downsizing and speeding up of the image forming apparatus, and is excellent in light resistance. It can be widely used in digital plate-making machines, full-color copying machines using direct or indirect electrophotographic multicolor image development systems, full-color laser printers, full-color plain paper fax machines, and the like.

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Static elimination lamp 3 Charger charger 5 Exposure part 6 Developing means 7 Charger before transfer 9 Recording medium 10 Transfer charger 11 Separation charger 13 Charger before cleaning 14 Fur brush 15 Blade 16 Cleaning means 101 Photoconductor 102 Exposure means 103 Charging Means 105 Cleaning means 106 Developing means 107 Transfer means 201 Support body 202 Charge generation layer 203 Charge transport layer 204 Photosensitive layer

JP-A-1-230055 JP-A-3-172852 JP 2002-333731 A JP-A-4-56866

Claims (9)

The support has a photosensitive layer on the support, and the photosensitive layer has a charge generation layer and a charge transport layer . 2, an amine compound represented by No. 2 below. 3, an amine compound represented by No. 3, No. 6 and the following No. 6 An electrophotographic photoreceptor comprising any one of the amine compounds represented by 9 and a charge transport material .
The electrophotographic photosensitive member according to claim 1, wherein the charge transport material has a molecular weight of 600 or more. A charging step for charging the surface of the electrophotographic photosensitive member, an exposure step for exposing the charged surface of the electrophotographic photosensitive member to form an electrostatic latent image, and developing the electrostatic latent image with toner to make it visible An image forming method comprising at least a developing step for forming an image, a transfer step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium,
An image forming method, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to claim 1. The image forming method according to claim 3, wherein the exposure step is performed using one of a laser diode (LD) and a light emitting diode (LED). An electrophotographic photosensitive member; a charging unit that charges the surface of the electrophotographic photosensitive member; an exposing unit that exposes the surface of the charged electrophotographic photosensitive member to form an electrostatic latent image; and An image forming apparatus comprising at least a developing unit that develops a visible image using the developing unit, a transfer unit that transfers the visible image to a recording medium, and a fixing unit that fixes the transferred image transferred to the recording medium Because
An image forming apparatus, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to claim 1. The image forming apparatus according to claim 5, wherein the exposure unit is one of a laser diode (LD) and a light emitting diode (LED). 7. The image forming apparatus according to claim 5, wherein the image forming apparatus is of a tandem type in which a plurality of image forming elements including at least an electrophotographic photosensitive member, a charging unit, a developing unit, and a transfer unit are arranged. The toner image developed on the electrophotographic photosensitive member is first transferred onto the intermediate transfer member, and then the toner image on the intermediate transfer member is secondarily transferred onto the recording medium. The image forming apparatus according to claim 5, wherein a color image is formed by sequentially superimposing images on an intermediate transfer member, and the color image is secondarily transferred collectively onto a recording medium. 3. A process cartridge comprising at least one means selected from a charging means, an exposure means, a developing means, a cleaning means, and a transfer means, and the electrophotographic photosensitive member according to claim 1. .