JP4506582B2 - Electrophotographic photosensitive member, image forming apparatus, and process cartridge - Google Patents

Description

  The present invention relates to an electrophotographic photoreceptor, an image forming apparatus, and a process cartridge used for electrophotographic image formation.

  A so-called xerographic image forming apparatus includes an electrophotographic photoreceptor (hereinafter, simply referred to as “photoreceptor”), a charging device, an exposure device, a developing device, and a transfer device, and forms an image by an electrophotographic process using them. I do.

  2. Description of the Related Art In recent years, xerographic image forming apparatuses have been further improved in speed and life due to technological progress of each member and system. Accordingly, demands for high-speed compatibility and high reliability of each subsystem are higher than ever. In particular, there is a strong demand for high-speed compatibility and high reliability for a photoconductor used for image writing and a cleaning member for cleaning the photoconductor. Further, the photosensitive member and the cleaning member are subjected to much stress compared to other members due to their mutual sliding. Therefore, the photoconductor is scratched or worn, which causes image defects.

  In order to suppress such scratches and wear, the electrophotographic photosensitive member uses a resin having high mechanical strength, and further extends its life. For example, in Patent Documents 1 and 2, the protective layer is configured using a charge transport material having a phenol resin and a hydroxyl group.

Patent Document 3 discloses an electrophotographic photosensitive member in which the oxygen permeability of the photosensitive layer is set to a predetermined value or less for the purpose of suppressing the oxidative deterioration of the photosensitive layer.
JP 2002-82469 A JP 2003-186234 A JP-A-7-152162

  However, the conventional electrophotographic photosensitive member has room for improvement in the following points.

  For example, in the case of the electrophotographic photosensitive member described in Patent Documents 1 and 2, the mechanical strength of the photosensitive member is improved by using a crosslinkable resin, but the electron is generated by ozone or NOx generated in the charging step of the electrophotographic process. The surface of the photographic photosensitive member tends to deteriorate. In addition, the surface of the electrophotographic photosensitive member is in a state in which oxidation degradation products easily adhere due to the influence of water absorbed by the photosensitive layer, and the generated oxidation degradation products are removed even if a minute amount is involved by entraining water. It becomes difficult. When an image is formed using an electrophotographic photosensitive member having these oxidized degradation products attached to the surface, the resulting image is adversely affected. In the case of the conventional electrophotographic photosensitive member, the adhering matter was removed by moderately wearing the surface. However, in the case of the electrophotographic photosensitive member provided with a phenol resin cured film on the surface, it is difficult to wear. Problems due to the deposits will occur.

  Further, even when the oxygen permeability of the photosensitive layer is controlled as in the electrophotographic photosensitive member described in Patent Document 3, it is very difficult to suppress the above-described oxidation deterioration and the attachment of deteriorated substances due to adsorbed water. Have difficulty.

  In addition, in the above conventional electrophotographic photosensitive member, subtle dimensional changes caused by absorption of moisture (environmental water) in the use atmosphere are also obstacles to achieving high image quality and long life. It has become.

  The present invention has been made in view of such circumstances, and its purpose is excellent in mechanical strength, and it is difficult for oxidation degradation products to adhere even during long-term use. It is another object of the present invention to provide an electrophotographic photosensitive member that is easy to handle and has excellent dimensional stability even under high temperature and high humidity. Another object of the present invention is to provide an image forming apparatus and a process cartridge that include the above-described electrophotographic photosensitive member and can stably obtain a good image quality over a long period of time.

In order to solve the above-described problems, the present invention provides an electrophotographic photosensitive member comprising a conductive support and a photosensitive layer provided on the conductive support, wherein the photosensitive layer is farthest from the conductive support. on the side, and the phenol resin, ethylene - vinyl acetate copolymer, ethylene - vinyl acetate copolymer and vinyl acetate chloride - ethylene - at least one and, functional group reactive with the phenolic resin selected ester copolymer or al There is provided an electrophotographic photosensitive member having an outermost surface layer obtained by thermosetting a thermosetting resin composition containing a charge transporting compound containing

  According to the electrophotographic photosensitive member of the present invention, the outermost surface layer provided on the side farthest from the conductive support of the photosensitive layer is composed of the thermoset of the specific thermosetting resin composition described above. Adhesion of oxidized degradation products to the surface layer can be sufficiently prevented, and even if adhesion occurs, it can be easily removed. In addition, the outermost surface layer has sufficient mechanical strength and is excellent in dimensional stability even under high temperature and high humidity. Therefore, by performing electrophotographic image formation using the electrophotographic photosensitive member of the present invention, it is possible to achieve high image quality and long life.

In the electrophotographic photoreceptor of the present invention, the water vapor transmission coefficient at 25 ° C. of the outermost surface layer is preferably 1.0 × 10 ⁻¹ μg · μm / cm ² · s or less. As a result, it is possible to more reliably prevent adhesion of oxidative degradation products and dimensional changes due to the influence of water.

Further, the thermosetting resin composition used as the material of the outermost surface layer further contains a charge transporting compound having a functional group reactive with a phenolic resin. Phenolic resin is an insulating resin, and it easily adheres to dust on the surface, and may decompose when subjected to electrical stress. However, it contains the specific charge transporting compound in the thermosetting resin composition. Since the antistatic property of the outermost surface layer obtained is sufficiently enhanced by the caulking, adhesion of dust and the like can be prevented, and resistance to electrical stress can be improved. Further, since the charge transporting compound has a functional group capable of reacting with at least one of the phenol resin or the modified phenol resin, and is capable of forming a chemical bond when the thermosetting resin composition is cured, By using it, the flexibility and film-forming property of the outermost surface layer can be improved.

  In addition, as another method for imparting charge transportability to the outermost surface layer, dispersion of the conductive particles to the outermost surface layer is conceivable, but in this case, a lateral flow of electric charge is likely to occur. On the other hand, when the specific charge transporting compound is contained in the thermosetting resin composition, it is possible to sufficiently prevent the lateral flow of charges in the outermost surface layer to be obtained.

As the charge transporting compound, a compound having a structure represented by any one of the following general formulas (I) to (V) is preferable because it is excellent in film formability, mechanical strength, and stability.
_{^{F [- (X 1) m}} -R 1 -Z 1 H] n ... (I)
[In Formula (I), F represents an n-valent organic group derived from a compound having a hole transporting ability, X ¹ represents an oxygen atom or a sulfur atom, R ¹ represents an alkylene group, Z ¹ represents an oxygen atom, Sulfur atom, NH or COO, m represents 0 or 1, and n represents an integer of 1 to 4. ]
_{^{F [- (X 2) m1}} - (R 2) m2 - (Z 2) m3 G] n1 ... (II)
[In Formula (II), F represents an n1-valent organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, Z ² represents an oxygen atom, S is a sulfur atom, NH or COO, G is an epoxy group, m1, m2 and m3 are each independently 0 or 1, and n1 is an integer of 1 to 4. ]
F [-D-Si (R ³ ) _(3-m4) Q _m4 ] _n2 (III)
[In Formula (III), F is an n2 valent organic group derived from a compound having a hole transporting ability, D is a divalent group having flexibility, and R ³ is a hydrogen atom, substituted or unsubstituted. Q represents a hydrolyzable group, m4 represents an integer of 1 to 3, and n2 represents an integer of 1 to 4. ]

[In Formula (IV), F represents an n3-valent organic group having hole transportability, T ¹ represents a divalent group, Y represents an oxygen atom or a sulfur atom, and R ⁴ , R ⁵ and R ⁶ represent Independently, a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m5 represents 0 or 1, and n3 represents an integer of 1 to 4. However, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]

[In Formula (V), at the n4 monovalent organic group F is having a hole transporting property, the T2 is a divalent radical, the ^{R 8} is a monovalent organic group, a is m6 0 or 1, n4 is 1 Integers of ~ 4 are shown respectively. ]

  The present invention also provides the electrophotographic photosensitive member of the present invention, a charging means for charging the electrophotographic photosensitive member, an exposure means for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, An image forming apparatus comprising: a developing unit that develops a latent image with toner to form a toner image; and a transfer device that transfers the toner image to a transfer medium.

  The present invention also provides the electrophotographic photosensitive member of the present invention, a charging means for charging the electrophotographic photosensitive member, and the electrostatic latent image formed on the electrophotographic photosensitive member is developed with toner to form a toner image. And at least one selected from the group consisting of a developing means for cleaning and a cleaning means for removing the toner remaining on the surface of the electrophotographic photosensitive member.

  According to the image forming apparatus and the process cartridge of the present invention, it is possible to stably obtain a good image quality over a long period of time by including the electrophotographic photosensitive member of the present invention having excellent characteristics as described above. .

  According to the present invention, it is excellent in mechanical strength, hardly adheres to oxidative degradation during long-term use, and even if it adheres, it can be easily removed, and it is dimensionally stable even under high temperature and high humidity. An electrophotographic photoreceptor excellent in the above is provided. In addition, according to the present invention, there is provided an image forming apparatus and a process cartridge that include the above-described electrophotographic photosensitive member and can stably obtain a good image quality over a long period of time.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted.

(Electrophotographic photoreceptor)
FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the electrophotographic photosensitive member according to the present invention. An electrophotographic photoreceptor 100 shown in FIG. 1 is a function-separated type photoreceptor in which a charge generation layer 1 and a charge transport layer 2 are separately provided. The photosensitive layer 6 is subtracted in order from the side close to the conductive support 3. The layer 4, the charge generation layer 1, the charge transport layer 2 and the protective layer 5 are laminated. The outermost surface layer in the electrophotographic photoreceptor 100 shown in FIG. 1 is a protective layer 5, which is a phenol resin, an ethylene-vinyl acetate copolymer, an ethylene-vinyl chloride copolymer, and a vinyl acetate-ethylene- at least one selected ester copolymer or al, is composed of a heat-cured product of a charge transporting compound and a thermosetting resin composition containing a having a functional group reactive with the phenolic resin.

  Hereinafter, each element of the electrophotographic photoreceptor 100 shown in FIG. 1 will be described.

  Examples of the conductive support 3 include a metal plate, a metal drum, and a metal belt formed using a metal or an alloy such as aluminum, copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, or platinum. Etc. Examples of the conductive support 3 include paper, plastic film, belt, and the like coated, vapor-deposited, or laminated with a conductive polymer, a conductive compound such as indium oxide, or a metal or alloy such as aluminum, palladium, or gold.

  When the photosensitive member 100 is used in a laser printer, the laser oscillation wavelength is preferably 350 nm to 850 nm, and the shorter wavelength is preferable because the resolution is excellent. The surface of the conductive support 3 is preferably roughened to a center line average roughness Ra of 0.04 μm to 0.5 μm in order to prevent interference fringes generated when laser light is irradiated. If Ra is less than 0.04 μm, it tends to be close to a mirror surface, so that the effect of preventing interference tends not to be obtained. On the other hand, if Ra exceeds 0.5 μm, the image quality tends to be rough even if a film is formed. . Further, when non-interfering light is used as a light source, it is not particularly necessary to roughen the interference fringes, and defects due to irregularities on the surface of the conductive support 3 can be prevented.

  As a roughening method, a wet honing process in which an abrasive is suspended in water and sprayed on a support, a centerless grinding process in which a support is pressed against a rotating grindstone, and grinding is continuously performed, an anode Examples thereof include an oxidation treatment or a method of forming a layer containing organic or inorganic semiconductive fine particles.

  Anodizing treatment is to form an oxide film on an aluminum surface by anodizing in an electrolyte solution using aluminum as an anode. Examples of the electrolyte solution include a sulfuric acid solution and an oxalic acid solution. However, the porous anodic oxide film as it is after the treatment is chemically active, easily contaminated, and has a large resistance fluctuation due to the environment. Therefore, the anodic oxide film is treated with pressurized steam or boiling water (a metal salt such as nickel may be added), blocked by volume expansion due to micropore hydration reaction, and converted into a more stable hydrated oxide. It is preferable to perform a hole treatment.

  The thickness of the anodized film is preferably 0.3 to 15 μm. When the film thickness is less than 0.3 μm, the barrier property against implantation is poor and the effect tends to be insufficient. On the other hand, if it exceeds 15 μm, the residual potential tends to increase due to repeated use.

  Further, the conductive support 3 may be subjected to treatment with an acidic treatment liquid or boehmite treatment. The treatment with the acidic treatment liquid is carried out as follows using an acidic treatment liquid comprising phosphoric acid, chromic acid and hydrofluoric acid. The mixing ratio of phosphoric acid, chromic acid and hydrofluoric acid in the acidic treatment liquid is such that phosphoric acid is in the range of 10 to 11% by mass, chromic acid is in the range of 3 to 5% by mass, and hydrofluoric acid is in the range of 0.5 to 2% by mass. The concentration of these acids is preferably in the range of 13.5 to 18% by mass. The processing temperature is 42 to 48 ° C., but by keeping the processing temperature high, a thicker film can be formed faster. The film thickness is preferably 0.3 to 15 μm. When the film thickness is less than 0.3 μm, the barrier property against implantation is poor and the effect tends to be insufficient. On the other hand, if it exceeds 15 μm, the residual potential tends to increase due to repeated use.

  The boehmite treatment can be performed by immersing the conductive support 3 in pure water at 90 to 100 ° C. for 5 to 60 minutes, or by contacting it with heated steam at 90 to 120 ° C. for 5 to 60 minutes. The film thickness is preferably 0.1 to 5 μm. This can be further anodized using an electrolyte solution with low film solubility such as adipic acid, boric acid, borate, phosphate, phthalate, maleate, benzoate, tartrate, citrate, etc. Good.

  In the case of forming a layer containing organic or inorganic semiconductive fine particles, organic or inorganic semiconductive fine particles include perylene pigments, bisbenzimidazole perylene pigments, polycyclic rings described in JP-A-47-30330. Organic pigments such as quinone pigments, indigo pigments, quinacridone pigments, organic pigments such as bisazo pigments and phthalocyanine pigments having electron-withdrawing substituents such as cyano group, nitro group, nitroso group, halogen atom, zinc oxide, oxidation Examples include inorganic pigments such as titanium and aluminum oxide. Among these pigments, zinc oxide and titanium oxide are preferable because they have high charge transport ability and are effective for thickening.

  The surface of these pigments may be surface treated with an organic titanium compound such as a titanate coupling agent, an aluminum chelate compound, an aluminum coupling agent or the like for the purpose of improving dispersibility or adjusting the energy level. In particular, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, β-3,4-epoxy It is preferable to treat with a silane coupling agent such as cyclohexyltrimethoxysilane.

  When there are too many organic or inorganic semiconductive fine particles, the strength of the layer is lowered and a coating film defect is caused. Therefore, it is preferably used at 95% by mass or less, more preferably 90% by mass or less.

  As a method for mixing / dispersing the organic or inorganic semiconductive fine particles, a method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like is applied. Mixing / dispersing is carried out in an organic solvent, but as an organic solvent, a fixed metal compound or resin is dissolved, and no gelation or aggregation occurs when organic / inorganic semiconductive fine particles are mixed / dispersed. Anything is acceptable.

  Examples of the organic solvent include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, and methylene chloride. Ordinary organic solvents such as chloroform, chlorobenzene and toluene can be used alone or in admixture of two or more.

  The undercoat layer 4 is configured to contain an organometallic compound and a binder resin. As organometallic compounds, zirconium chelate compounds, zirconium alkoxide compounds, organozirconium compounds such as zirconium coupling agents, titanium chelate compounds, titanium alkoxide compounds, organotitanium compounds such as titanate coupling agents, aluminum chelate compounds, aluminum coupling agents In addition to organoaluminum compounds such as 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 aluminum zirconium alkoxide compounds. . As the organometallic compound, an organic zirconium compound, an organic titanyl compound, and an organoaluminum compound are particularly preferably used since they have low residual potential and good electrophotographic characteristics.

  As binder resin, 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 , Vinyl chloride-vinyl acetate copolymer, epoxy resin, polyvinyl pyrrolidone, polyvinyl pyridine, polyurethane, polyglutamic acid, polyacrylic acid, and other known binder resins can be used. These mixing ratios can be appropriately set as necessary.

  The undercoat layer 4 includes vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris-2-methoxyethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxy. Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-2-aminoethylaminopropyltrimethoxysilane, γ-mercapropropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, Silane coupling agents such as β-3,4-epoxycyclohexyltrimethoxysilane can also be included.

  In the undercoat layer 4, an electron transporting pigment can also be mixed / dispersed. Examples of the electron transport pigment include organic pigments such as perylene pigment, bisbenzimidazole perylene pigment, polycyclic quinone pigment, indigo pigment, and quinacridone pigment described in JP-A-47-30330, cyano group, nitro group, Examples thereof include organic pigments such as bisazo pigments and phthalocyanine pigments having electron-withdrawing substituents such as nitroso 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, zinc oxide, and titanium oxide are preferably used because of their high electron mobility.

  Further, the surface of these pigments may be surface-treated with the above coupling agent, binder resin or the like for the purpose of controlling dispersibility and charge transport property. If 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 amount is preferably 95% by mass or less, more preferably 90% by mass or less.

  The undercoat layer 4 is configured using a coating solution for forming an undercoat layer containing the above constituent materials.

  As a method for mixing / dispersing the coating solution for forming the undercoat layer, a conventional method using a ball mill, a roll mill, a sand mill, an attritor, an ultrasonic wave, or the like is applied. Mixing / dispersing is carried out in an organic solvent. The organic solvent dissolves a periodical metal compound and a binder resin, and does not cause gelation or aggregation when an electron transporting pigment is mixed / dispersed. I just need it.

  Examples of the organic solvent include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, and methylene chloride. Ordinary organic solvents such as chloroform, chlorobenzene and toluene. These can be used individually by 1 type or in mixture of 2 or more types.

  The coating method used when providing the undercoat layer 4 is a normal 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, or a curtain coating method. Can be used.

  After coating, the coating film is dried to obtain an undercoat layer. Usually, the drying is carried out at a temperature at which the solvent can be evaporated to form a film. In particular, the conductive support 3 subjected to the acidic solution treatment and the boehmite treatment is preferably formed with the undercoat layer 4 because its defect concealing power tends to be insufficient.

  The thickness of the undercoat layer 4 is preferably 0.1 to 30 μm, more preferably 0.2 to 25 μm.

  The charge generation layer 1 includes a charge generation material or a charge generation material and a binder resin.

  Charge generation materials include azo pigments such as bisazo and trisazo, condensed aromatic pigments such as dibromoanthanthrone, organic pigments such as perylene pigments, pyrrolopyrrole pigments, and phthalocyanine pigments, and inorganic pigments such as trigonal selenium and zinc oxide. All known ones can be used. As the charge generation material, an inorganic pigment is preferable when a light source with an exposure wavelength of 380 nm to 500 nm is used, and a metal and a metal-free phthalocyanine pigment are preferable when a light source with an exposure wavelength of 700 nm to 800 nm is used. Among them, hydroxygallium phthalocyanine disclosed in JP-A-5-263007 and JP-A-5-279591, chlorogallium phthalocyanine disclosed in JP-A-5-98181, JP-A-5-140472 and special Dichlorotin phthalocyanine disclosed in Kaihei 5-140473 or titanyl phthalocyanine disclosed in JP-A-4-189873 and JP-A-5-43813 is particularly preferable.

  As the charge generation material, Bragg angles (2θ ± 0.2 °) with respect to CuKα characteristic X-rays of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25 Hydroxygallium phthalocyanine having diffraction peaks at .1 ° and 28.3 °, titanyl phthalocyanine having a strong diffraction peak at 27.2 ° with a Bragg angle (2θ ± 0.2 °) with respect to CuKα characteristic X-ray, CuKα characteristic X Also preferred are chlorogallium phthalocyanines with strong diffraction peaks at 7.4 °, 16.6 °, 25.5 ° and 28.3 ° of the Bragg angle to the line (2θ ± 0.2 °).

  The binder resin can be selected from a wide range of insulating resins. It can also be selected from organic photoconductive polymers such as poly-N-vinyl carbazole, polyvinyl anthracene, polyvinyl pyrene and polysilane. Preferred binder resins include polyvinyl butyral resins, polyarylate resins (for example, polycondensates of bisphenols and aromatic divalent carboxylic acids such as polycondensates of bisphenol A and phthalic acid), polycarbonate resins, polyester resins, Insulating resins such as phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin It can be mentioned, but is not limited to these. These binder resins can be used individually by 1 type or in mixture of 2 or more types.

  The charge generation layer 1 is formed by vapor deposition using the charge generation material or using a charge generation layer forming coating solution containing the charge generation material and a binder resin.

  In the charge generation layer forming coating solution, the mixing ratio (mass ratio) of the charge generation material and the binder resin is preferably 10: 1 to 1:10. Further, as a method for dispersing them, 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. According to these dispersion methods, it is possible to prevent a change in the crystal form of the charge generation material due to the dispersion.

  Further, in this dispersion, it is effective that the particles have a particle size of preferably 0.5 μm or less, more preferably 0.3 μm or less, and still more preferably 0.15 μm or less.

  Moreover, as a solvent used for these dispersions, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, Examples include ordinary organic solvents such as tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene. These can be used individually by 1 type or in mixture of 2 or more types.

  In addition, as a coating method used when the charge generation layer 1 is provided, a normal method such as a blade coating method, a Meyer 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. Can be used.

  The film thickness of the charge generation layer 1 is preferably 0.1 to 5 μm, more preferably 0.2 to 2.0 μm.

  The charge transport layer 2 includes a charge transport material and a binder resin, or includes a polymer charge transport material.

  Examples of charge transport materials include quinone compounds such as p-benzoquinone, chloranil, bromanyl, anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds , Electron transport compounds such as cyanovinyl compounds and ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, etc. Examples thereof include pore transporting compounds. These charge transport materials can be used singly or in combination of two or more, but are not limited thereto.

  Moreover, as a charge transport material, the compound shown by the following general formula (a-1), (a-2) or (a-3) from a mobility viewpoint is preferable.

In the above formula (a-1), R ³⁴ represents a hydrogen atom or a methyl group, and k10 represents 1 or 2. Ar ⁶ and Ar ⁷ represent a substituted or unsubstituted aryl group, and 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 an alkyl group having 1 to 3 carbon atoms. A substituted amino group substituted with an alkyl group can be mentioned.

Here, in said formula (a-2), R ^<35> and R ^<35 '> respectively independently represent a hydrogen atom, a halogen atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group, R ^<36> , R ³⁶ ′, R ³⁷ and R ³⁷ ′ are each independently a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group substituted with an alkyl group having 1 to 2 carbon atoms, A substituted or unsubstituted aryl group, —C (R ³⁸ ) ═C (R ³⁹ ) (R ⁴⁰ ), or —CH═CH—CH═C (Ar) ₂ , R ³⁸ , R ³⁹ and R ⁴⁰ are Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Ar represents a substituted or unsubstituted aryl group. m7 and m8 each independently represents an integer of 0-2.

Here, in the formula (a-3), R ⁴¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group, or —CH═CH. -CH = C (Ar) ₂ is shown. Ar represents a substituted or unsubstituted aryl group. R ⁴² , R ⁴² ′, R ⁴³ , and R ⁴³ ′ are each independently 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 having 1 to 2 carbon atoms. An amino group substituted with a group, or a substituted or unsubstituted aryl group is shown.

  As the binder resin, 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, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole, polysilane, Polymer charge transport materials such as polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 can also be used. These binder resins can be used individually by 1 type or in mixture of 2 or more types. The blending ratio (mass ratio) between the charge transport material and the binder resin is preferably 10: 1 to 1: 5.

  A polymer charge transport material can also be used alone. As the polymer charge transport material, known materials having charge transport properties such as poly-N-vinylcarbazole and polysilane can be used. In particular, polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 have a high charge transporting property and are particularly preferable. The polymer charge transport material alone can be used as the charge transport layer, but it may be formed by mixing with the binder resin.

  The charge transport layer 2 is configured using a charge transport layer forming coating solution containing the above-described constituent materials. Solvents used in the coating solution for forming the charge transport layer include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halogenation such as methylene chloride, chloroform and ethylene chloride. Examples include ordinary organic solvents such as aliphatic hydrocarbons, cyclic ethers such as tetrahydrofuran and ethyl ether, and linear ethers. These can be used individually by 1 type or in mixture of 2 or more types. Moreover, a well-known method can be used as a dispersion | distribution method of said each constituent material.

  Coating methods for applying the charge transport layer forming coating solution onto the charge generation layer 1 include blade coating method, Mayer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain A usual method such as a coating method can be used.

  The film thickness of the charge transport layer 2 is preferably 5 to 50 μm, more preferably 10 to 30 μm.

Protective layer 5, and the phenol resin, ethylene - vinyl acetate copolymer, ethylene - vinyl chloride copolymers and vinyl acetate - ethylene - at least one selected ester copolymer or, et al., Capable of reacting with the phenolic resin It is comprised with the thermosetting material of the thermosetting resin composition containing the charge transportable compound which has a functional group .

  Examples of the phenol resin contained in the thermosetting resin composition include resorcin, bisphenol, substituted phenols containing one hydroxyl group such as phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, catechol, resorcinol, hydroquinone, etc. Monomethylolphenol is obtained by reacting a compound having a phenol structure, such as substituted phenols containing two hydroxyl groups, bisphenols such as bisphenol A and bisphenol Z, and biphenols, with formaldehyde, paraformaldehyde, etc. in the presence of an acid or alkali catalyst. , Dimethylolphenols, trimethylolphenol monomers, and mixtures thereof, or oligomerized thereof, and monomer and oligomer mixtures. Among these, a relatively large molecule having about 2 to 20 repeating molecular structural units is an oligomer, and a smaller molecule is a monomer.

As the acid catalyst used at this time, sulfuric acid, paratoluenesulfonic acid, phenolsulfonic acid, phosphoric acid and the like are used. Further, as the alkali catalyst, hydroxides or oxides of alkali metals and alkaline earth metals such as NaOH, KOH, Ca (OH) ₂ , Mg (OH) ₂ , Ba (OH) ₂ , CaO, MgO, or the like, or Amine-based catalysts and acetates such as zinc acetate and sodium acetate are used.

  Examples of the amine catalyst include, but are not limited to, ammonia, hexamethylenetetramine, trimethylamine, triethylamine, and triethanolamine.

  When a basic catalyst is used, carriers may be significantly trapped by the remaining catalyst, which may deteriorate electrophotographic characteristics. In such a case, it is preferable to inactivate or remove by distilling off under reduced pressure, neutralizing with an acid, or contacting with an adsorbent such as silica gel or an ion exchange resin. A curing catalyst can also be used for curing. The catalyst used at that time is not particularly limited as long as it does not adversely affect the electrical characteristics and the like.

  The content of the phenol resin is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass, based on all components of the outermost surface layer. If the content of the phenol resin is less than the lower limit, the mechanical strength of the outermost surface layer tends to be insufficient, and if the content exceeds the upper limit, the flexibility becomes insufficient and cracks are likely to occur. There is a tendency.

Further, the thermosetting resin composition, in addition to phenolic resins, ethylene - vinyl acetate copolymer, ethylene - vinyl acetate copolymer and vinyl acetate chloride - ethylene - one selected ester copolymer or al or 2 It contains at least a seed and a charge transporting compound having a functional group capable of reacting with the phenol resin .

  Among the above polymers used in combination with a phenol resin, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer and vinyl acetate-ethylene-ester copolymer are preferable from the viewpoint of water vapor barrier function, and ethylene-acetic acid A vinyl copolymer is particularly preferred.

  The average molecular weight of the polymer used in combination with the phenol resin is not particularly limited, but the weight average molecular weight is preferably 500 to 20,000, more preferably 1,000 to 10,000. It is more preferable that it is 8,000-8,000. If the weight average molecular weight is less than 500, the mechanical strength tends to be insufficient, and if it exceeds 20,000, the solubility in the solvent used in the coating solution and the compatibility with the phenol resin are insufficient. Tend to be.

  Moreover, it is preferable that content of the said polymer used together with a phenol resin (in the case of 2 or more types) is 5-120 mass parts with respect to 100 mass parts of phenol resins, and 10-100 masses. More preferably, it is a part. When the content is less than 5 parts by mass, the water vapor barrier function of the obtained outermost surface layer (here, the protective layer 5) tends to be insufficient. Moreover, when the said content exceeds 120 mass parts, it exists in the tendency for the mechanical strength of the outermost surface layer (here protective layer 5) obtained to become inadequate.

The thermosetting resin composition includes a phenol resin, an ethylene - vinyl acetate copolymer, ethylene - vinyl chloride copolymers and vinyl acetate - ethylene - at least one selected ester copolymer or, et al., And the phenol resin a charge transporting compound having a functional group capable of reacting further contained. Thereby, the antistatic property of the outermost surface layer to be obtained is sufficiently enhanced, adhesion of dust and the like and the lateral flow of electric charge can be prevented, and resistance to electrical stress can be improved. Furthermore, the use of the charge transporting compound can improve the flexibility and film forming property of the outermost surface layer.

As the charge transporting compound, a compound having a structure represented by any one of the following general formulas (I) to (V) is preferable because it is excellent in film formability, mechanical strength, and stability.
_{^{F [- (X 1) m}} -R 1 -Z 1 H] n ... (I)
[In Formula (I), F represents an n-valent organic group derived from a compound having a hole transporting ability, X ¹ represents an oxygen atom or a sulfur atom, R ¹ represents an alkylene group, Z ¹ represents an oxygen atom, Sulfur atom, NH or COO, m represents 0 or 1, and n represents an integer of 1 to 4. ]
_{^{F [- (X 2) m1}} - (R 2) m2 - (Z 2) m3 G] n1 ... (II)
[In Formula (II), F represents an n1-valent organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, Z ² represents an oxygen atom, S is a sulfur atom, NH or COO, G is an epoxy group, m1, m2 and m3 are each independently 0 or 1, and n1 is an integer of 1 to 4. ]
F [-D-Si (R ³ ) _(3-m4) Q _m4 ] _n2 (III)
[In Formula (III), F is an n2 valent organic group derived from a compound having a hole transporting ability, D is a divalent group having flexibility, and R ³ is a hydrogen atom, substituted or unsubstituted. Q represents a hydrolyzable group, m4 represents an integer of 1 to 3, and n2 represents an integer of 1 to 4. ]

[In Formula (IV), F represents an n3-valent organic group having hole transportability, T ¹ represents a divalent group, Y represents an oxygen atom or a sulfur atom, and R ⁴ , R ⁵ and R ⁶ represent Independently, a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m5 represents 0 or 1, and n3 represents an integer of 1 to 4. However, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]

[In Formula (V), at the n4 monovalent organic group F is having a hole transporting property, the T2 is a divalent radical, the ^{R 8} is a monovalent organic group, a is m6 0 or 1, n4 is 1 Integers of ~ 4 are shown respectively. ]
The compound represented by the general formula (I) can form a coating film having a very high density when combined with a phenol resin. This is suitable for applications that require high gas barrier properties.

  The compound represented by the general formula (II) has a hard coat action and a high surface hardness due to the presence of a bond containing oxygen or sulfur element. Further, since the surface energy is low and the releasability is excellent, it is suitable for applications requiring releasability.

  Since the compound represented by the general formula (III) has extremely high reactivity with the phenol resin, it can be cured at low temperature and can achieve energy saving in production.

  The compounds represented by the general formulas (IV) and (V) basically provide a similar coating film when the compound represented by the general formula (III) is used. Can be granted. In addition, the thermosetting reaction can be easily controlled, and the film structure can be freely controlled in accordance with the characteristics required for the coating film.

  Moreover, it is preferable that said F in the compound represented by said general formula (I)-(V) is group represented by the following general formula (VI).

[In the formula (VI), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group, Ar ⁵ represents a substituted or unsubstituted aryl group or arylene group, and Ar 1-4 of ^{1 to} Ar ⁵ are the site represented by the following general formula (VII) in the compound represented by the above general formula (I) and the following general formula (VIII) in the compound represented by the above general formula (II). ), A site represented by the following general formula (IX) in the compound represented by the above general formula (III), a site represented by the following general formula (X) in the compound represented by the above general formula (IV), Or it has the bond for couple | bonding with the site | part represented by the following general formula (XI) in the compound represented by the said general formula (V). ]
_{^{- (X 1) n1 R 1}} -Z 1 H (VII)
_{^{- (X 2) n2 - (}} R 2) n3 - (Z 2) n4 G (VIII)
-D-Si (R ³ ) _(3-a) Q _a (IX)

As the substituted or unsubstituted aryl group represented by Ar ^{1 to} Ar ⁴ in the general formula (VI), specifically, an aryl group represented by the following general formulas (1) to (7) is preferable. .

In the above formulas (1) to (7), R ⁹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, phenyl substituted with them. A group or an unsubstituted phenyl group, or an aralkyl group having 7 to 10 carbon atoms, wherein R ^{10 to} R ¹² are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a carbon number, respectively. 1 to 4 alkoxy groups, phenyl or unsubstituted phenyl groups substituted therewith, aralkyl groups having 7 to 10 carbon atoms or halogen atoms, Ar represents a substituted or unsubstituted arylene group, and D represents the above One of the structures represented by general formulas (VII) to (XI) is shown, c and s each represent 0 or 1, and t represents an integer of 1 to 3.

  Moreover, as Ar in the aryl group represented by the above formula (7), an arylene group represented by the following formula (8) or (9) is preferable.

In the above formulas (8) and (9), R ¹³ and R ¹⁴ are each substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. A phenyl group, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom, and t represents an integer of 1 to 3.

  Moreover, as Z 'in the aryl group represented by the above formula (7), divalent groups represented by the following formulas (10) to (17) are preferable.

In formulas (10) to (17), R ¹⁵ and R ¹⁶ are each substituted with a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. A phenyl group, an unsubstituted phenyl group, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom; W represents a divalent group; q and r each represents an integer of 1 to 10; Each represents an integer of 1 to 3.

  In the above formulas (16) to (17), W represents a divalent group represented by the following formulas (18) to (26). In formula (25), u represents an integer of 0 to 3.

In addition, the specific structure of Ar ⁵ in the general formula (VI) is as follows. When k = 0, the structure of c = 1 in the specific structure of Ar ^{1 to} Ar ⁴ and when Ar = 1, the Ar 5 ^The structure of c = 0 in the specific structure of ^{1 to} Ar ⁴ is given.

  Specific examples of the compound represented by the general formula (I) include the following compounds (I-1) to (I-37). In addition, in the following table | surface, although the bond is described, the thing in which the substituent is not described shows a methyl group.

  Specific examples of the compound represented by the general formula (II) include the following compounds (II-1) to (II-47). In the following table, Me or a bond is described but a substituent is not described, a methyl group, Et represents an ethyl group.

Specific examples of the compound represented by the general formula (III) include the following compounds (III-1) to (III-61). In addition, the following compounds (III-1) to (III-61) combine Ar ^{1 to} Ar ⁵ and k of the compound represented by the general formula (VI) as shown in the following table, and an alkoxysilyl group. (S) is the specific one shown in the table below.

  Specific examples of the compound represented by the general formula (IV) include the following compounds (IV-1) to (IV-40). In the following table, Me or a bond is described but a substituent is not described, a methyl group, Et represents an ethyl group.

  Specific examples of the compound represented by the general formula (V) include the following compounds (V-1) to (V-55). In the following table, Me or a bond is described but a substituent is not described indicates a methyl group.

  Moreover, it is preferable that the number of the functional groups which can react with the phenol resin which the said charge transport compound has is two or more. By using such a polyfunctional compound, the function of the charge transporting compound as a soft segment can be improved, and a higher level of flexibility can be imparted to the resulting cured film.

  The content of the charge transporting compound in the thermosetting resin composition is preferably 10 to 90 mass%, more preferably 30 to 70 mass%, based on the total amount of the thermosetting resin composition. When the content of the charge transporting compound is less than the lower limit, the charge transporting property and antistatic property tend to be lowered, and when the content exceeds the upper limit, the mechanical strength tends to be lowered.

  A catalyst can be used when the thermosetting resin composition is prepared or when the thermosetting resin composition is prepared. Catalysts include inorganic acids such as hydrochloric acid, acetic acid and sulfuric acid, organic acids such as formic acid, propionic acid, oxalic acid, benzoic acid, phthalic acid and maleic acid, potassium hydroxide, sodium hydroxide, calcium hydroxide, ammonia and triethylamine Further, an alkali catalyst such as the following, and a solid catalyst insoluble in the system as shown below can also be used.

Examples of solid catalysts insoluble in the system include Amberlite 15, Amberlite 200C, Amberlyst 15E (above, manufactured by Rohm and Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR- W2 (above, manufactured by Dow Chemical Co.); Lebatit SPC-108, Lebatit SPC-118 (above, manufactured by Bayer); Diaion RCP-150H (manufactured by Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C , Duolite C-433, Duolite-464 (manufactured by Sumitomo Chemical Co., Ltd.); Cation exchange resins such as Nafion-H (manufactured by DuPont); Amberlite IRA-400, Amberlite IRA-45 (above, Anion exchange resin such as Rohm &Haas); Zr (O ₃ PCH ₂₎ An inorganic solid in which a group containing a protonic acid group such as CH ₂ SO ₃ H) ₂ or Th (O ₃ PCH ₂ CH ₂ COOH) ₂ is bonded to the surface; a protonic acid such as a polyorganosiloxane having a sulfonic acid group Group-containing polyorganosiloxanes; heteropolyacids such as cobalt tungstic acid and phosphomolybdic acid; isopolyacids such as niobic acid, tantalum acid and molybdic acid; monometallic oxides such as silica gel, alumina, chromia, zirconia, CaO and MgO Composite metal oxides such as silica-alumina, silica-magnesia, silica-zirconia, zeolites; clay minerals such as acid clay, activated clay, montmorillonite, kaolinite; metal sulfates such as LiSO ₄ and MgSO ₄ ; phosphorus acid zirconia, metal phosphates such as lanthanum phosphate; LiNO _3, Mn NO _{3) 2} and the like of a metal nitrate; inorganic solid by reacting aminopropyltriethoxysilane on silica gel containing amino groups such as the resulting solid which group is attached to the surface; amino and amino-modified silicone resin And polyorganosiloxane containing a group.

  Moreover, it is preferable to use a solid catalyst that is insoluble in the system when preparing the thermosetting resin composition because the stability of the coating agent composition tends to be improved. The solid catalyst insoluble in the system is not particularly limited as long as the catalyst component is insoluble in the charge transporting compound having the reactive functional group, other additives, water, solvent and the like.

  The amount of the solid catalyst insoluble in these systems is not particularly limited, but is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the charge transporting compound having the reactive functional group. Further, as described above, these solid catalysts are insoluble in raw material compounds, reaction products, solvents and the like, and therefore can be easily removed after the reaction according to a conventional method.

  Further, when a catalyst that is insoluble in the system is used at the time of preparing the thermosetting resin composition, it is preferable to use a catalyst that is further dissolved in the system for the purpose of improving strength, liquid storage stability, and the like. Such catalysts include, in addition to those described above, aluminum triethylate, aluminum triisopropylate, aluminum tri (sec-butyrate), mono (sec-butoxy) aluminum diisopropylate, diisopropoxyaluminum (ethyl acetoacetate). ), Aluminum tris (ethyl acetoacetate), aluminum bis (ethyl acetoacetate) monoacetylacetonate, aluminum tris (acetylacetonate), aluminum diisopropoxy (acetylacetonate), aluminum isopropoxy-bis (acetylacetonate) Organic aluminum compounds such as aluminum tris (trifluoroacetylacetonate) and aluminum tris (hexafluoroacetylacetonate) It is possible to use.

  Besides organic aluminum compounds, organic compounds such as dibutyltin dilaurate, dibutyltin dioctiate, and dibutyltin diacetate; titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), titanium bis Organic titanium compounds such as (isopropoxy) bis (acetylacetonate); zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate), zirconium bis (isopropoxy) bis (acetylacetonate), etc. Zirconium compounds; etc. can also be used, but from the viewpoints of safety, low cost, and pot life length, it is preferable to use an organoaluminum compound, particularly an aluminum chelate compound. It is more preferable.

  Although the usage-amount of the catalyst melt | dissolved in these systems is not restrict | limited, 0.1-20 mass parts is preferable with respect to 100 mass parts of charge transport compounds which have the said reactive functional group, 0.3-10 mass% Is particularly preferred.

  Moreover, when adding an organometallic compound as a catalyst to a thermosetting resin composition, it is preferable to add a multidentate ligand from the surface of pot life and hardening efficiency. Examples of such multidentate ligands include, but are not limited to, those shown below and those derived therefrom.

  Specifically, β-diketones such as acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, and dipivaloylmethylacetone; acetoacetates such as methyl acetoacetate and ethyl acetoacetate; bipyridine and derivatives thereof; glycine and its Derivatives; ethylenediamine and derivatives thereof; 8-oxyquinoline and derivatives thereof; salicylaldehyde and derivatives thereof; catechol and derivatives thereof; bidentate ligands such as 2-oxyazo compounds; diethyltriamine and derivatives thereof; nitrilotriacetic acid and derivatives thereof And tridentate ligands such as ethylenediaminetetraacetic acid (EDTA) and derivatives thereof. In addition to the organic ligands as described above, inorganic ligands such as pyrophosphoric acid and triphosphoric acid can be exemplified. As the multidentate ligand, a bidentate ligand is particularly preferable, and specific examples include a bidentate ligand represented by the following general formula (XII) in addition to the above.

[In the formula (XII), R ⁵¹ and R ⁵² each independently represent an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, or an alkoxy group having 1 to 10 carbon atoms. ]

As the multidentate ligand, a bidentate ligand represented by the above general formula (XII) is preferably used, and those in which R ⁵¹ and R ⁵² in the general formula (XII) are the same are particularly preferable. By making R ⁵¹ and R ^{52 the} same, the coordination power of the ligand near room temperature becomes strong, and further stabilization of the curable resin composition can be achieved.

  The compounding amount of the polydentate ligand can be arbitrarily set, but is preferably 0.01 mol or more, more preferably 0.1 mol or more, with respect to 1 mol of the organometallic compound to be used. It is preferably 1 mol or more, particularly preferably.

  In the present invention, the following components can be used to further enhance the function of the protective layer 5.

For example, a compound represented by the following general formula (XIII) can be added to the protective layer 5 in order to control various physical properties such as strength and film resistance of the protective layer 5.
Si (R ⁵⁰ ) _(4-c) Q _c (XIII)
[In the above formula (XIII), R ⁵⁰ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and c represents an integer of 1 to 4. ]

  Specific examples of the compound represented by the general formula (XIII) include the following silane coupling agents. Examples of silane coupling agents include tetrafunctional silanes such as tetramethoxysilane and tetraethoxysilane (c = 4); methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, methyltrimethoxyethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxy Silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl L) Triethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H , 1H, 2H, 2H-perfluorodecyltriethoxysilane, trifunctional alkoxysilanes such as 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (c = 3); dimethyldimethoxysilane, diphenyldimethoxysilane, methyl And bifunctional alkoxysilanes such as phenyldimethoxysilane (c = 2); monofunctional alkoxysilanes such as trimethylmethoxysilane (c = 1), and the like. Trifunctional and tetrafunctional alkoxysilanes are preferable for improving the strength of the film, and monofunctional and bifunctional alkoxysilanes are preferable for improving the flexibility and film formability.

  The silane coupling agent can be used in any amount, but when a fluorine-containing compound is used, the content of the fluorine-containing compound is preferably 0.25 times or less by mass with respect to the compound not containing fluorine. When this content is exceeded, a problem may occur in the film formability of the crosslinked film.

  In addition, a silicon-based hard coat agent produced mainly from these coupling agents can also be used. Commercially available hard coat agents include KP-85, X-40-9740, X-40-2239 (manufactured by Shin-Etsu Silicone), and AY42-440, AY42-441, AY49-208 (manufactured by Toray Dow Corning). Etc.) can be used.

In order to increase the strength of the protective layer 5, it is also preferable to use a compound having two or more silicon atoms as shown in the following general formula (XIV).
B- (Si (R ⁵¹ ) _(3-d) Q _d ) ₂ (XIV)
[In the above formula (XIV), B represents a divalent organic group, R ⁵¹ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and d represents an integer of 1 to 3. Indicates. ]

  More specific examples of the compound represented by the general formula (XIV) include the following compounds (XIV-1) to (XIV-16).

  Further, a resin soluble in an alcohol solvent or a ketone solvent may be added for controlling the film characteristics and extending the liquid life. Examples of such resins include polyvinyl butyral resins, polyvinyl formal resins, and polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins in which a part of butyral is modified with formal, acetoacetal, or the like (for example, ESREC B, K manufactured by Sekisui Chemical Co., Ltd.). Etc.), polyamide resin, cellulose resin, phenol resin and the like. In particular, polyvinyl acetal resin is preferable from the viewpoint of improving electrical characteristics.

  Various resins can be added for the purposes of discharge gas resistance, mechanical strength, scratch resistance, particle dispersibility, viscosity control, torque reduction, wear amount control, pot life extension, and the like. In the present embodiment, it is preferable to further add a resin that dissolves in alcohol. Examples of resins soluble in alcohol solvents include polyvinyl butyral resins, polyvinyl formal resins, and polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins in which a part of butyral is modified with formal or acetoacetal (for example, manufactured by Sekisui Chemical Co., Ltd.). ESREC B, K, etc.), polyamide resin, cellulose resin and the like. In particular, polyvinyl acetal resin is preferable from the viewpoint of improving electrical characteristics.

  The average molecular weight of the resin is preferably 2,000 to 10,000, and more preferably 5,000 to 50,000. If the average molecular weight is less than 2,000, the desired effect tends not to be obtained. If the average molecular weight is more than 100,000, the solubility is low and the addition amount is limited, or the film formation may be poor at the time of coating. Tend. The addition amount is preferably 1 to 40% by mass, more preferably 1 to 30% by mass, and most preferably 5 to 20% by mass. When the addition amount is less than 1% by mass, it is difficult to obtain a desired effect. When the addition amount is more than 40% by mass, there is a risk of image blurring at high temperature and high humidity. Moreover, although said resin may be used independently, you may mix and use them.

  In order to prolong pot life and control film properties, it is preferable to contain a cyclic compound having a repeating structural unit represented by the following general formula (XV) or a derivative from the compound.

[In the formula (XV), A ¹ and A ² each independently represent a monovalent organic group. ]

  Examples of the cyclic compound having the repeating structural unit represented by the general formula (XV) include commercially available cyclic siloxanes. Specifically, cyclic dimethylcyclosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, 1,3,5-trimethyl-1,3,5- Triphenylcyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7 , 9-pentaphenylcyclopentasiloxane and other cyclic methylphenylcyclosiloxanes, hexaphenylcyclotrisiloxane and other cyclic phenylcyclosiloxanes, and 3- (3,3,3-trifluoropropyl) methylcyclotrisiloxane and other fluorine Atom-containing cyclosiloxanes, methylhydrosiloxa Mixture, pentamethylcyclopentasiloxane, mention may be made of phenyl hydrosilyl group-containing cyclosiloxanes of hydrocyclosiloxane like, cyclic siloxanes and vinyl group-containing cyclosiloxanes such as penta vinyl pentamethylcyclopentasiloxane like. These cyclic siloxane compounds may be used alone or in combination of two or more.

  Furthermore, various fine particles can be added to the protective layer 5 in order to control the contamination resistance adhesion, lubricity, hardness and the like of the surface of the electrophotographic photosensitive member.

  Examples of the fine particles include silicon atom-containing fine particles or fluorine atom-containing resin particles. The silicon atom-containing fine particles are fine particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone fine particles. The colloidal silica used as the silicon atom-containing fine particles preferably has a volume average particle diameter of 1 to 100 nm, more preferably 10 to 30 nm, in an acidic or alkaline aqueous dispersion, or an organic solvent such as alcohol, ketone or ester. It is selected from those dispersed in, and commercially available products can be used. The solid content of colloidal silica in the protective layer 5 is not particularly limited, but preferably 0.1 to 0.1 based on the total solid content of the protective layer 5 in terms of film formability, electrical properties, and strength. It is used in the range of 50% by mass, more preferably in the range of 0.1-30% by mass.

  Silicone fine particles used as silicon atom-containing fine particles are spherical and preferably have a volume average particle diameter of 1 to 500 nm, more preferably 10 to 100 nm, and are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles. A commercially available product can be used.

  Silicone fine particles are small particles that are chemically inert and excellent in dispersibility in resin, and since the content required to obtain sufficient characteristics is low, the electron does not hinder the crosslinking reaction, The surface properties of the photographic photoreceptor can be improved. In other words, in a state in which it is uniformly incorporated into a strong cross-linked structure, it improves the lubricity and water repellency of the surface of the electrophotographic photosensitive member, and maintains good wear resistance and contamination resistance adhesion over a long period of time. Can do. The content of the silicone fine particles in the protective layer 5 is preferably in the range of 0.1 to 30% by mass, more preferably in the range of 0.5 to 10% by mass, based on the total solid content of the protective layer 5. .

  Fluorine atom-containing resin particles include fluorine-based fine particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, and the 8th Polymer Materials Forum Lecture Proceedings p89. And fine particles made of a resin obtained by copolymerizing a fluororesin and a monomer having a hydroxyl group.

Other fine particles include ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO ₂ , ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—. Examples thereof include semiconductive metal oxides such as TiO ₂ , TiO ₂ , SnO ₂ , In ₂ O ₃ , ZnO, and MgO. The volume average particle diameter of these fine particles can be controlled by the material composition, production method, etc., but if they are too small, the dispersion state tends to be unstable, and if they are too large, the smoothness of the surface of the photoreceptor is lowered. Therefore, those having a thickness of 1 to 1,500 nm, more preferably 5 to 1,000 nm are used.

  For the same purpose, an oil such as silicone oil can be added. Examples of the silicone oil include silicone oils such as dimethylpolysiloxane, diphenylpolysiloxane, and phenylmethylsiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, carboxyl-modified polysiloxane, carbinol-modified polysiloxane, methacryl-modified polysiloxane, and mercapto. Examples include reactive silicone oils such as modified polysiloxanes and phenol-modified polysiloxanes. These may be added in advance to the protective layer-forming coating solution, or may be impregnated under reduced pressure or increased pressure after producing the photoreceptor.

  Moreover, the protective layer 5 can also contain additives, such as a plasticizer, a surface modifier, antioxidant, and a photodegradation inhibitor. Examples of the plasticizer include biphenyl, biphenyl chloride, terphenyl, dibutyl phthalate, diethylene glycol phthalate, dioctyl phthalate, triphenyl phosphate, methyl naphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, and various fluorohydrocarbons.

  It is particularly preferable to add an antioxidant to the protective layer 5 for the purpose of preventing deterioration due to an oxidizing gas such as ozone generated in the charging device. When the mechanical strength of the surface of the photoconductor is increased and the photoconductor has a long life, the photoconductor is in contact with the oxidizing gas for a long time, and therefore, stronger oxidation resistance is required than before. Antioxidants are preferably hindered phenols or hindered amines, organic sulfur antioxidants, phosphite antioxidants, dithiocarbamate antioxidants, thiourea antioxidants, benzimidazole antioxidants. , Etc., may be used. The addition amount of the antioxidant in the protective layer 5 is preferably 20% by mass or less, and more preferably 10% by mass or less.

  Examples of the hindered phenol antioxidant include 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-tert-butylphenol), 2,5-di-tert-amylhydroquinone, 2-tert-butyl-6- (3-butyl) -2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 4,4'-butylidenebis (3-methyl-6-t-butylphenol), and the like.

  Further, commercially available hindered phenol-based antioxidants include, for example, “Sumilizer BHT-R”, “Sumilizer MDP-S”, “Sumilizer BBM-S”, “Sumizer WX-R”. , "Sumizer NW", "Sumizer BP-76", "Sumizer BP-101", "Sumizer GA-80", "Sumizer GM", "Sumizer GS", Sumitomo Chemical Co., Ltd., "IRGANOX1010", "IRGANOX" “IRGANOX1076”, “IRGANOX1098”, “IRGANOX1135”, “IRGANOX1141”, “IRGANOX1222”, “IRGANOX1330”, “IR “ANOX1425WL”, “IRGANOX1520L”, “IRGANOX245”, “IRGANOX259”, “IRGANOX3114”, “IRGANOX3790”, “IRGANOX5057”, “IRGANOX565” or more, manufactured by Ciba Specialty Chemicals, “Adekastab AO-20” "ADK STAB AO-40", "ADK STAB AO-50", "ADK STAB AO-60", "ADK STAB AO-70", "ADK STAB AO-80", "ADK STAB AO-330" or more, manufactured by Asahi Denka. As the hindered amine system, “Sanol LS2626”, “Sanol LS765”, “Sanol LS770”, “Sanol LS744” or more manufactured by Sankyo Lifetech Co., Ltd. “Mark LA57”, “Mark LA67”, “Mark LA62”, “Mark LA68”, “Mark LA63” or more manufactured by Asahi Denka Co., Ltd. “Sumilyzer TPS” or more manufactured by Sumitomo Chemical Co., Ltd. As described above, the phosphite system manufactured by Sumitomo Chemical Co., Ltd. includes “Mark 2112”, “Mark PEP · 8”, “Mark PEP · 24G”, “Mark PEP · 36”, “Mark 329K”, and “Mark HP · 10”. Asahi Denka Co., Ltd. is mentioned above. Furthermore, these may be modified with a substituent such as an alkoxysilyl group capable of undergoing a crosslinking reaction with the material forming the crosslinked film.

  The protective layer 5 includes 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 An insulating resin such as a resin, a polyacrylamide resin, a polyvinyl pyridine resin, a cellulose resin, a urethane resin, an epoxy resin, casein, or a polyvinyl pyrrolidone resin may be contained. In this case, the insulating resin can be added at a desired ratio, thereby suppressing adhesion with the charge transport layer 2, coating film defects due to thermal shrinkage, and repelling.

Protective layer 5, and the phenol resin, ethylene - vinyl acetate copolymer, ethylene - vinyl chloride copolymers and vinyl acetate - ethylene - at least one selected ester copolymer or, et al., Capable of reacting with the phenolic resin It is formed using a coating liquid for forming a protective layer in which the above components are added to a thermosetting resin composition containing a charge transporting compound having a functional group , if necessary.

  When preparing the coating solution for forming the protective layer, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; and solvents such as ethers such as tetrahydrofuran, diethyl ether and dioxane, as necessary Can be used. Such solvents can be used singly or in combination of two or more, but preferably have a boiling point of 100 ° C. or lower. The amount of the solvent used can be arbitrarily set, but if the amount of the solvent is too small, the charge transporting material having the reactive functional group is likely to be precipitated. The solvent is preferably used at 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass.

  When the coating solution for forming the protective layer is applied onto the charge transport layer 2, the coating methods are blade coating method, Meyer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain coating. Ordinary methods such as a method can be used. And after application | coating, the protective layer 5 forms by drying a coating film. The thickness of the protective layer 5 is preferably 0.5 to 15 μm, more preferably 1 to 10 μm, and further preferably 1 to 5 μm.

  In addition, in the case of application | coating, when a required film thickness cannot be obtained by one application | coating, a required film thickness can be obtained by apply | coating several times. When performing multiple times of repeated application, the heat treatment may be performed every time of application, or after multiple times of repeated application.

  The electrophotographic photosensitive member of the present invention is not limited to the above embodiment. For example, in the electrophotographic photosensitive member of the present invention, the undercoat layer 4 is not necessarily provided.

  The electrophotographic photosensitive member shown in FIG. 1 includes a protective layer 5 made of a thermoset of the thermosetting resin composition, but the thermosetting resin composition contains a charge transporting compound. If it is, the resulting thermoset has excellent mechanical strength and sufficient photoelectric properties, so that it can be used as it is as a charge transport layer of a multilayer photoreceptor. An example of such an electrophotographic photoreceptor is shown in FIG. An electrophotographic photoreceptor 100 shown in FIG. 2 has a structure in which an undercoat layer 4, a charge generation layer 1, and a charge transport layer 2 are sequentially laminated on a conductive support 3, and the charge transport layer 2 is thermally cured. It is the outermost surface layer formed by thermosetting the functional resin composition. The conductive support 3, the undercoat layer 4, and the charge generation layer 1 are the same as those of the electrophotographic photosensitive member shown in FIG. 1 (hereinafter the same).

  Further, the order of stacking the charge generation layer 1 and the charge transport layer 2 may be reversed from that in the above embodiment. An example of such an electrophotographic photoreceptor is shown in FIG. The electrophotographic photoreceptor shown in FIG. 3 has a structure in which an undercoat layer 4, a charge transport layer 2, a charge generation layer 1 and a protective layer 5 are sequentially laminated on a conductive support 3. Is the outermost surface layer obtained by thermosetting the thermosetting resin composition.

  In addition, the electrophotographic photoreceptor of the present invention may be a single-layer photoreceptor having a layer (charge generation / charge transport layer) containing both a charge generation material and a charge transport material. Examples of single-layer type photoreceptors are shown in FIGS.

  An electrophotographic photoreceptor 100 shown in FIG. 4 has a structure in which an undercoat layer 4 and a charge generation / charge transport layer 7 are sequentially laminated on a conductive support 3. It is an outermost surface layer formed by thermosetting a thermosetting resin composition. The charge generation / charge transport layer 7 is formed by adding a charge generation material to the thermosetting resin composition, and a binder resin other than a phenol resin or an ethylene-vinyl acetate copolymer, if necessary, a charge transport material, and It can form using the coating liquid which mix | blended other additives. The charge generation material is the same as that used for the charge generation layer in the function-separated type photosensitive layer, and the binder resin other than the phenol resin or ethylene-vinyl acetate copolymer is polyvinyl butyral resin, polyvinyl formal resin, Polyvinyl acetal resins such as partially acetalized polyvinyl acetal resins in which a part of butyral is modified with formal, acetoacetal, or the like (for example, ESREC B, K, etc. manufactured by Sekisui Chemical Co., Ltd.), polyamide resins, cellulose resins, and the like can be used. The content of the charge generation material in the charge generation / charge transport layer 7 is preferably 10 to 85% by mass, more preferably 20 to 50% by mass, based on the total solid content in the charge generation / charge transport layer 7. A charge transport material or a polymer charge transport material may be added to the charge generation / charge transport layer 7 for the purpose of improving photoelectric characteristics. The addition amount is preferably 5 to 50% by mass based on the total solid content in the charge generation / charge transport layer 7. Moreover, the solvent and coating method used for coating can be the same as those for the above layers. The film thickness of the charge generation / charge transport layer 7 is preferably about 5 to 50 μm, and more preferably 10 to 40 μm.

  The electrophotographic photoreceptor 100 shown in FIG. 5 has a structure in which an undercoat layer 4, a charge generation / charge transport layer 7 and a protective layer 5 are sequentially laminated on a conductive support 3. Is the outermost surface layer obtained by thermosetting the thermosetting resin composition.

(Image forming apparatus and process cartridge)
Next, an image forming apparatus and a process cartridge equipped with the electrophotographic photosensitive member of the present invention will be described.
FIG. 6 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of the image forming apparatus of the present invention. An image forming apparatus 200 shown in FIG. 6 includes an electrophotographic photosensitive member 100, a non-contact charging type charging unit 8 that charges the electrophotographic photosensitive member 100, a power source 9 connected to the charging unit 8, and a charging unit 8. An exposure unit 10 that exposes the charged electrophotographic photosensitive member 100 to form an electrostatic latent image; a developing unit 11 that develops the formed electrostatic latent image with toner to form a toner image; and The image forming apparatus includes a transfer unit 12, a cleaning unit 13, a static eliminator 14, and a fixing unit 15 that transfer from the photoconductor 100 to a transfer medium.

  FIG. 7 is a cross-sectional view schematically showing a basic configuration of another embodiment of the image forming apparatus of the present invention. The image forming apparatus 210 shown in FIG. 7 has the same configuration as the image forming apparatus 200 shown in FIG. 6 except that the image forming apparatus 210 includes a charging unit 8 that charges the electrophotographic photosensitive member 100 by a contact charging method. At this time, as the charging means 8, a contact-type charging means in which an AC voltage is superimposed on a DC voltage can be preferably used because it has excellent wear resistance. In this case, the static eliminator 14 may not be provided.

  Examples of the non-contact charging type charging means 8 used in the present invention include a corotron and a scorotron using corona discharge. Moreover, as the charging means 8 of the contact charging system, a charger using a contact charging member such as a charging roller or a charging brush can be cited.

Contact charging members include metals such as aluminum, iron and copper, conductive polymer materials such as polyacetylene, polypyrrole and polythiophene, polyurethane rubber, silicone rubber, epichlorohydrin rubber, ethylene propylene rubber, acrylic rubber, fluorine rubber, styrene A material obtained by dispersing metal oxide particles such as carbon black, copper iodide, silver iodide, zinc sulfide, silicon carbide, and metal oxide in an elastomer material such as butadiene rubber or butadiene rubber can be used. Examples of this metal oxide include ZnO, SnO ₂ , TiO ₂ , In ₂ O ₃ , MoO _{3 and the} like, or a composite oxide thereof. Further, as the contact charging member, a material obtained by adding perchlorate to an elastomer material and imparting conductivity may be used.

  Further, a coating layer may be provided on the surface of the contact charging member. As a material for forming the coating layer, N-alkoxymethylated nylon, cellulose resin, vinyl pyridine resin, phenol resin, polyurethane, polyvinyl butyral, melamine and the like are used alone or in combination. Also, emulsion resin-based materials such as acrylic resin emulsion, polyester resin emulsion, polyurethane, particularly emulsion resin synthesized by soap-free emulsion polymerization can be used. In these resins, in order to further adjust the resistivity, conductive agent particles may be dispersed, or an antioxidant may be contained in order to prevent deterioration. In addition, in order to improve the film formability when forming the coating layer, the emulsion resin may contain a leveling agent or a surfactant. Examples of the shape of the contact charging member include a roller type, a blade type, a belt type, and a brush type.

Electrical resistance of the contact charging member is preferably ^{1 × 10 2 ~1 × 10 14} Ωcm, more preferably ^{1 × 10 2 ~1 × 10 12} Ωcm. Further, as the voltage applied to the contact charging member, either direct current or alternating current can be used. It can also be applied in the form of DC + AC (a DC voltage and an AC voltage superimposed).

  As the exposure unit 10, an optical system device that can expose a light source such as a semiconductor laser, an LED (light emitting diode), and a liquid crystal shutter on the surface of the electrophotographic photoreceptor 100 in a desired image-like manner can be used. Among these, when an exposure apparatus capable of exposing non-interference light is used, interference fringes between the conductive support of the electrophotographic photoreceptor 100 and the photosensitive layer can be prevented.

  When laser light is used as the exposure light source, the oscillation wavelength is preferably 350 to 850 nm, and the shorter wavelength is preferable because the resolution is excellent.

  As the developing means 11, a conventionally known developing device or the like can be used. Further, the type of developer used and the method for producing the same are not particularly limited. For example, a kneading and pulverizing method for kneading, pulverizing, and classifying a binder resin and a colorant, a release agent, and a charge control agent as necessary, A method of changing the shape of the particles obtained by the kneading and pulverization method by mechanical impact force or thermal energy, an emulsion polymerization of a polymerizable monomer of a binder resin, a formed dispersion, a colorant, a release agent Emulsion polymerization aggregation method to obtain a toner particle by mixing a mold agent and, if necessary, a dispersion of a charge control agent, and agglomerating and heat-fusing, a polymerizable monomer and a colorant for obtaining a binder resin A suspension polymerization method in which a solution of a release agent, if necessary, a charge control agent or the like is suspended in an aqueous solvent and polymerized, a binder resin and a colorant, a release agent, and a charge control agent if necessary A solution suspension method in which a solution is suspended in an aqueous solvent and granulated can be used. In addition, a known method such as a production method in which the toner obtained by the above method is used as a core and agglomerated particles are further adhered and heat-fused to have a core-shell structure can be used. From the viewpoint, a suspension polymerization method, an emulsion polymerization aggregation method, and a dissolution suspension method produced with an aqueous solvent are preferable, and an emulsion polymerization aggregation method is particularly preferable.

The toner is composed of a binder resin, a colorant, and a release agent. If necessary, silica or a charge control agent may be used. The volume average particle diameter of the toner is preferably 3 to 9 μm. Further, the average shape index (ML ² / A) of the toner is preferably 100 to 140, more preferably 115 to 140, since a high development, transferability, and high quality image can be obtained. .

  Binder resins used in the toner include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate. , Α-methylene aliphatic monocarboxylic such as methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Examples of homopolymers and copolymers of acid esters, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl butyl ether, and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropenyl ketone Particularly typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene. -Maleic anhydride copolymer, polyethylene, polypropylene and the like. Further examples include polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like.

  In addition, toner colorants include magnetic powders such as magnetite and ferrite, carbon black, aniline blue, caryl blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, and malachite green oxa. Rate, lamp black, rose bengal, C.I. I. Pigment red 48: 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 blue 15: 1, C.I. I. Pigment Blue 15: 3 can be exemplified as a representative one.

  Typical examples of the release agent include low molecular weight polyethylene, low molecular weight polypropylene, Fischer tropic wax, montan wax, carnauba wax, rice wax, and candelilla wax.

  Further, a charge control agent may be added to the toner as necessary. As the charge control agent, known ones can be used. For example, an azo metal complex compound, a metal complex compound of salicylic acid, a resin type charge control agent containing a polar group, or the like can be used.

  When the toner is manufactured by a wet manufacturing method, it is preferable to use a material that is difficult to dissolve in water in terms of controlling ionic strength and reducing wastewater contamination. The toner may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.

  When an external additive is added, it can be produced by mixing the toner and the external additive with a Henschel mixer or a V blender. Further, when the toner is manufactured by a wet method, it can be externally added by a wet method.

  Lubricating particles added to the toner used in the present invention include solid lubricants such as graphite, molybdenum disulfide, talc, fatty acids, fatty acid metal salts, low molecular weight polyolefins such as polypropylene, polyethylene, and polybutene, and heating. Aliphatic amides such as silicones with softening point, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, carnauba wax, rice wax, candelilla wax, wood wax, jojoba oil, etc. Plant waxes, animal waxes such as beeswax, montan waxes, ozokerites, ceresins, paraffin waxes, microcrystalline waxes, Fischer-Tropsch waxes, etc. Has one kind It can be used or in combination of two or more Germany. The volume average particle size of the lubricious particles is preferably 0.1 to 10 μm, and may be pulverized to make the particle sizes uniform as necessary. The amount added to the toner is preferably 0.05 to 2.0 parts by mass, and more preferably 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the toner.

  To the toner used in the present invention, inorganic fine particles, organic fine particles, composite fine particles obtained by adhering inorganic fine particles to the organic fine particles, and the like may be added for the purpose of removing deposits and deteriorated matters on the surface of the electrophotographic photoreceptor 100. Although it is possible, inorganic fine particles having excellent polishing properties are particularly preferable. Inorganic fine particles include silica, alumina, titania, zirconia, barium titanate, aluminum titanate, strontium titanate, magnesium titanate, zinc oxide, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, Various inorganic oxides such as manganese oxide, boron oxide, silicon carbide, boron carbide, titanium carbide, silicon nitride, titanium nitride, and boron nitride, nitrides, borides, and the like are preferably used. Moreover, titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzene sulfonyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, γ- (2-amino) Ethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxysilane Hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxy The treatment may be performed with a silane coupling agent such as silane, decyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, and p-methylphenyltrimethoxysilane. Moreover, it is also preferable to hydrophobize with higher fatty acid metal salts such as silicone oil, aluminum stearate, zinc stearate, calcium stearate.

  Examples of the organic fine particles include styrene resin particles, styrene acrylic resin particles, polyester resin particles, and urethane resin particles.

  If the particle size of the inorganic or organic fine particles is too small, the polishing ability is insufficient, and if it is too large, the surface of the electrophotographic photosensitive member 100 is liable to be damaged, so that the volume average particle size is 5 to 1,000 nm. It is preferably 5 to 800 nm, more preferably 5 to 700 nm. The addition amount of inorganic and organic fine particles to the toner is preferably 0.6 parts by mass or more as the sum of the addition amount of the slippery particles with respect to 100 parts by mass of the toner.

  As other inorganic oxides added to the toner, small-diameter inorganic oxides having an average primary particle size of 40 nm or less are used for powder fluidity, charge control, etc. It is preferable to add a larger-diameter inorganic oxide. These inorganic oxide fine particles may be known ones, but it is preferable to use silica and titanium oxide in combination in order to perform precise charge control. Further, the surface treatment of the small-diameter inorganic fine particles increases the dispersibility and increases the powder flowability.

  The color toner for electrophotography is used by mixing with a carrier. As the carrier, iron powder, glass beads, ferrite powder, nickel powder or those having a resin coating on the surface thereof are used. The mixing ratio with the carrier can be set as appropriate.

  Examples of the transfer unit 12 include a roller-type contact charging member, a contact-type transfer charger using a belt, a film, a rubber blade, or the like, or a scorotron transfer charger or a corotron transfer charger using corona discharge. .

  Although untransferred toner may remain on the surface of the electrophotographic photosensitive member 100 after the transfer, the remaining toner can be removed by the cleaning means 13. As the cleaning means 13, those provided with a cleaning member such as a blade, a magnetic brush, or a conductive fiber brush are preferably used. Hereinafter, a cleaning apparatus including a blade member as an example of the cleaning unit 13 will be described in detail.

  The material of the blade is not particularly limited. For example, a urethane prepolymer composed of a polyol such as a polyester polyol such as polyethylene adipate or polycaprolactone and an isocyanate such as diphenylmethane diisocyanate, 1,4-butanediol, trimethylolpropane, ethylene glycol, Those using a cross-linking agent such as a mixture thereof as a raw material are preferable because the obtained blade member is excellent in wear resistance and has high mechanical strength. Moreover, as a urethane prepolymer which is a constituent material of a blade member, for example, an NCO group content of about 4 to 10% by mass and a viscosity at 70 ° C. of about 1,000 to 3,000 cP are preferably used.

  The thickness of the blade member is not particularly limited as long as it has sufficient strength to remove the residual toner on the surface of the photoreceptor, and is usually preferably about 1 to 3 mm. For example, when an adhesive that is reactively cured by irradiating ultraviolet rays or the like is used to obtain a cleaning blade by bonding a blade member and a mounting bracket, which will be described later, the blade member is transparent, ultraviolet rays, etc. It is preferable to have a thickness that can pass through. The rubber hardness of the blade member is not particularly limited as long as it has a strength sufficient to remove residual toner on the surface of the electrophotographic photosensitive member 100, but is usually 65 to 80 (JIS K6253 A It is preferable that the measured value is about a value measured with a type hardness meter.

  In manufacturing the blade member, for example, the following method can be employed. First, the raw material of the blade material adjusted so as to have a desired blending amount is stirred and mixed for about 1 to 3 minutes using, for example, a mixing stirrer such as agitator to obtain a mixed solution, which is about 120 to 160 ° C. Rotating at about 100 to 300 rpm, for example, after being injected into a forming drum mold of a centrifugal molding machine, the number of rotations of the forming drum mold is increased to about 600 to 1200 rpm, and the injected mixed liquid is applied to the inner surface of the forming drum mold. The blade material is in a state in which bubbles that are uniformly spread and entrained at the time of injection float on the surface. Here, the amount of the liquid mixture injected into the molding drum mold may be adjusted so that, for example, a blade member having a desired thickness as described above can be obtained. Next, while maintaining the rotational speed of the forming drum mold at about 600 to 1200 rpm and the temperature at about 120 to 160 ° C., before the blade material is cross-linked and cured, for example, the abrasive fine particles are uniformly distributed using a spray gun or the like. After spraying the dispersed suspension onto the blade material, the blade material is cured while rotating the molding drum mold so that abrasive fine particles are present at least on the cleaning surface. The medium for obtaining the suspension in which the abrasive fine particles are uniformly dispersed is not particularly limited as long as it does not exhibit an interaction between the abrasive fine particles and the blade material. For example, when obtaining the blade material When silicone oil such as dimethylpolysiloxane, methylphenylpolysiloxane, trifluoropropylmethylpolysiloxane, etc., which is normally used for foaming, promotes defoaming, is used, blade particles are uniformly distributed This is preferable because it can be transferred to the surface. Although it is sufficient that the abrasive fine particles are uniformly dispersed in the abrasive, the amount of the abrasive fine particles to be present on the cleaning surface can be adjusted by the blending amount of the abrasive fine particles in the suspension. The abrasive fine particles are preferably blended in an amount of about 1 to 20 parts by mass with respect to 100 parts by mass of the medium. Further, the desired amount of abrasive fine particles can be directly mixed and dispersed in the raw material of the blade material, and then molded.

A spray gun or the like is used to spray the suspension onto the blade material. The air pressure and spray amount during spraying may be adjusted according to the amount of abrasive fine particles to be present on the cleaning surface. Usually, the air pressure is about 1 to 10 kg / cm ² and the spray amount is It is preferably about 0.5 to ⁵ mg / cm ² . The time when the suspension material is sprayed onto the blade material may be any time as long as the blade material is spread uniformly in the molding drum mold and before the blade material is cured in a state where air bubbles emerge on the surface of the blade material. For example, since it varies depending on the target depth when impregnating the abrasive fine particles into the blade member, it cannot be determined unconditionally. However, after the blade material is put into the molding drum mold, it is usually 2-10. It is preferable that about a minute pass. In the blade member thus obtained, the abrasive fine particles are firmly adhered at least to the cleaning surface or immersed therein, so that the physical properties such as tensile strength and tear strength and the adhesion to the mounting bracket are reduced. It has excellent durability. Further, since the abrasive fine particles are present at least on the cleaning surface by centrifugal force, the degree of polishing performance can be adjusted by adjusting the spray amount of the suspension of the fine abrasive particles, the timing of spraying, the rotational speed of the molding drum mold, etc. The durability of polishing performance can be controlled.

  The blade member is integrated with the mounting bracket by using, for example, a hot-melt adhesive, double-sided tape, or the like to form a cleaning blade. For example, the blade member is used by being mounted on an image forming apparatus such as for PPC, PPP, or PPF. it can. The mounting bracket is not particularly limited. For example, a mounting bracket made of a rigid metal, an elastic metal, plastic, ceramic, or the like, which is usually used for a cleaning blade, can be used. A mounting bracket made of a treated steel plate, a steel plate that has been subjected to a surface treatment such as zinc phosphate treatment or chromate treatment, or a steel plate that has been subjected to plating treatment is particularly preferred from the viewpoint that it does not cause changes over time such as corrosion. In addition, the blade member may be a single layer or a laminate in which a plurality of materials are bonded together.

  FIG. 8 is a cross-sectional view schematically showing a basic configuration of another embodiment of the image forming apparatus of the present invention. An image forming apparatus 220 shown in FIG. 8 is an image forming apparatus that forms a color image by a tandem method. In the housing 400, four electrophotographic photoreceptors 100a to 100d (for example, the electrophotographic photoreceptor 100a is yellow and the electrophotographic photoreceptor is used. The body 100b can form an image of magenta, the electrophotographic photoreceptor 100c can be cyan, and the electrophotographic photoreceptor 100d can be formed of a black color.) Are arranged in parallel with each other along the intermediate transfer belt 409.

  Here, the electrophotographic photoreceptors 100a to 100d mounted on the image forming apparatus 220 are the electrophotographic photoreceptors of the present invention.

  Each of the electrophotographic photoreceptors 100a to 100d can be rotated in a predetermined direction (counterclockwise on the paper surface), and the charging rolls 402a to 402d, the developing devices 404a to 404d, and the primary transfer roll 410a along the rotation direction. To 410d and cleaning blades 415a to 415d are arranged. Each of the developing devices 404a to 404d can be supplied with toner of four colors of black, yellow, magenta and cyan accommodated in toner cartridges 405a to 405d, and the primary transfer rolls 410a to 410d are respectively intermediate transfer belts. 409 is in contact with the electrophotographic photoreceptors 100a to 100d.

  Further, a laser light source (exposure means) 403 is arranged at a predetermined position in the housing 400, and the surfaces of the electrophotographic photoreceptors 100a to 100d after charging are irradiated with laser light emitted from the laser light source 403. Is possible. Accordingly, charging, exposure, development, primary transfer, and cleaning are sequentially performed in the rotation process of the electrophotographic photoreceptors 100a to 100d, and the toner images of the respective colors are transferred onto the intermediate transfer belt 409 in an overlapping manner.

  The intermediate transfer belt 409 is supported with a predetermined tension by a drive roll 406, a backup roll 408, and a tension roll 407, and can rotate without causing deflection due to the rotation of these rolls. Further, the secondary transfer roll 413 is disposed so as to contact the backup roll 408 via the intermediate transfer belt 409. The intermediate transfer belt 409 passing between the backup roll 408 and the secondary transfer roll 413 is cleaned by, for example, a cleaning blade 416 disposed in the vicinity of the drive roll 406 and then repeatedly used for the next image forming process. Is done.

  A tray (transfer medium tray) 411 is provided at a predetermined position in the housing 400, and the transfer medium 500 such as paper in the tray 411 is transferred to the intermediate transfer belt 409 and the secondary transfer roll by the transfer roll 412. Then, the paper is sequentially transferred between the two fixing rolls 414 that are in contact with each other and the two fixing rolls 414 that are in contact with each other.

  In the above description, the case where the intermediate transfer belt 409 is used as the intermediate transfer member has been described. However, the intermediate transfer member may have a belt shape like the intermediate transfer belt 409 or a drum shape. Also good. In the case of a belt shape, a conventionally known resin can be used as the resin material used as the base material of the intermediate transfer member. For example, polyimide resin, polycarbonate resin (PC), polyvinylidene fluoride (PVDF), polyalkylene terephthalate (PAT), ethylenetetrafluoroethylene copolymer (ETFE) / PC, ETFE / PAT, PC / PAT blend material, polyester Resin materials such as polyether ether ketone and polyamide, and resin materials using these as main raw materials. Furthermore, a resin material and an elastic material can be blended and used.

  As an elastic material, polyurethane, chlorinated polyisoprene, NBR, chloropyrene rubber, EPDM, hydrogenated polybutadiene, butyl rubber, silicone rubber, or the like can be used, or a material obtained by blending two or more kinds can be used. If necessary, a conductive agent imparting electronic conductivity or a conductive agent having ionic conductivity is added to the resin material and elastic material used for these base materials in combination of one kind or two or more kinds. Among these, it is preferable to use a polyimide resin in which a conductive agent is dispersed from the viewpoint of excellent mechanical strength. As the conductive agent, a conductive polymer such as carbon black, metal oxide, or polyaniline can be used. When a belt-shaped configuration such as the intermediate transfer belt 409 is adopted as the intermediate transfer member, generally the thickness of the belt is preferably 50 to 500 μm, more preferably 60 to 150 μm, but the hardness of the material It can be selected as appropriate according to the conditions.

  For example, a belt made of a polyimide resin in which a conductive agent is dispersed is 5 to 20 mass as a conductive agent in a polyamic acid solution which is a polyimide precursor, as described in JP-A-63-311263. % Of carbon black is dispersed, the dispersion is cast on a metal drum and dried, and then the film peeled off from the drum is stretched at a high temperature to form a polyimide film. It can be manufactured by forming a belt.

  The film forming is generally performed by injecting a polyamic acid solution film-forming stock solution in which a conductive agent is dispersed into a cylindrical mold and, for example, heating at 100 to 200 ° C. and rotating at a rotational speed of 500 to 2,000 rpm. While rotating the mold, the film was formed into a film by a centrifugal molding method, and then the obtained film was demolded in a semi-cured state and covered with an iron core, and a polyimide formation reaction ( It can be carried out by subjecting the polyamic acid to a main ring curing (ring-closing reaction). Also, the stock solution is cast on a metal sheet to a uniform thickness and heated to 100-200 ° C. to remove most of the solvent in the same manner as above, and then gradually raised to a high temperature of 300 ° C. or higher. There is also a method of forming a polyimide film. Further, the intermediate transfer member may have a surface layer.

  When a drum-shaped configuration is adopted as the intermediate transfer member, it is preferable to use a cylindrical substrate formed of aluminum, stainless steel (SUS), copper, or the like as the substrate. If necessary, an elastic layer can be coated on the cylindrical substrate, and an outermost surface layer can be formed on the elastic layer.

  The transfer medium according to the present invention is not particularly limited as long as it is a medium that transfers a toner image formed on an electrophotographic photosensitive member. For example, when transferring directly from an electrophotographic photosensitive member to a transfer medium such as paper, paper or the like is the transfer medium. When an intermediate transfer member is used, the intermediate transfer member is a transfer medium.

  FIG. 9 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of the process cartridge of the present invention. The process cartridge 300 is formed by combining the electrophotographic photosensitive member 100 with the charging unit 8, the developing unit 11, the cleaning unit 13, the opening 18 for exposure, and the static eliminator 14 using the mounting rail 16. is there. The process cartridge 300 is detachable from the main body of the image forming apparatus including the transfer unit 12, the fixing unit 15, and other components (not shown). It constitutes. Such a process cartridge 300 can be applied to any of the image forming apparatuses shown in FIGS.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

[Example 1]
The cylindrical aluminum substrate was polished by a centerless polishing apparatus, and the surface roughness was set to Rz = 0.6 μm. In order to clean the aluminum substrate subjected to the centerless polishing treatment, a degreasing treatment, an etching treatment with a 2% by mass sodium hydroxide solution for 1 minute, a neutralization treatment, and a pure water washing were performed in this order. Next, an anodic oxide film (current density 1.0 A / dm ² ) was formed on the surface of the base material with a 10% by mass sulfuric acid solution with respect to the aluminum base material. After washing with water, sealing treatment was performed by dipping in a 1 mass% nickel acetate solution at 80 ° C. for 20 minutes. Further, pure water washing and drying treatment were performed. In this way, a conductive support having a 7 μm anodic oxide film formed on the surface was obtained.

  Next, 1 mass of chlorogallium phthalocyanine having strong diffraction peaks at Bragg angles (2θ ± 0.2 °) of 7.4 °, 16.6 °, 25.5 ° and 28.3 ° in the X-ray diffraction spectrum. Part, 1 part by weight of polyvinyl butyral (ESREC BM-S, Sekisui Chemical) and 100 parts by weight of n-butyl acetate are dispersed with a glass shaker for 1 hour using a glass shaker to form a coating solution for forming a charge generation layer Got. This coating solution was dip-coated on the outer peripheral surface of the conductive support and heat-dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, 2 parts by mass of a benzidine compound represented by the following formula (XVI) and 2.5 parts by mass of a polymer compound (viscosity average molecular weight 39,000) having a structural unit represented by the following formula (XVII) It was made to melt | dissolve in a mass part and the coating liquid for charge transport layer formation was obtained.

  The obtained coating solution was applied onto the charge generation layer by a dip coating method and dried by heating at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

  Next, 30 parts by mass of the compound (57-1) shown in Table 57, 30 parts by mass of the compound (57-2) shown in Table 57, 35 parts by mass of a phenol resin (manufactured by Sumitomo Bakelite Co., Ltd., PR-50404), Dissolve 5 parts by mass of low molecular weight ethylene-vinyl acetate copolymer (Sumitomo Chemical Co., Sumikaflex 500, weight average molecular weight 12,000) and silicone oil (Shin-Etsu Chemical Co., KP-340) in 300 parts by mass of toluene. And it filtered with a 5-micrometer membrane filter, and obtained the coating liquid for protective layer formation. This coating solution was dip-coated on the above charge transport layer and cured at 145 ° C. for 90 minutes to form a protective layer to obtain the desired electrophotographic photosensitive member.

  Further, the above coating solution for forming a protective layer is cast on a mirror-finished aluminum substrate and cured at 145 ° C. for 90 minutes, and then the single film is peeled off from the aluminum substrate. It measured with the transmittance | permeability measuring apparatus (the Toyo Seiki company make, OTR-C6 type | mold). Further, the single film was cut into 4 × 4 cm and a thickness of 2 mm, and left in an environmental chamber at 80 ° C. and a relative humidity of 95% for 4 hours, and the dimensional change of the side and the dimensional change of the thickness were measured. The results obtained are shown in Table 58.

[Example 2]
Instead of 5 parts by mass of the low molecular weight polyethylene-vinyl acetate copolymer (Sumitomo Chemical Co., Ltd., Sumikaflex 500) in Example 1, a low molecular weight ethylene-vinyl chloride copolymer (Sumitomo Chemical Co., Ltd., Sumikaflex 500, weight) An electrophotographic photosensitive member and a single film were produced in the same manner as in Example 1 except that 5 parts by mass of the average molecular weight 18,000 was used. Furthermore, the same evaluation as Example 1 was implemented about the obtained single film | membrane. The results obtained are shown in Table 58.

[Example 3]
Instead of 5 parts by mass of low molecular weight polyethylene-vinyl acetate copolymer (Sumitomo Chemical Co., Ltd., Sumikaflex 500) in Example 1, low molecular weight vinyl acetate-ethylene-special ester copolymer (Sumikaflex S-951, weight) An electrophotographic photosensitive member and a single film were produced in the same manner as in Example 1 except that 5 parts by mass of the average molecular weight 9,000) was used. Furthermore, the same evaluation as Example 1 was implemented about the obtained single film | membrane. The results obtained are shown in Table 58.

[Example 4]
Instead of 30 parts by mass of the compound (57-1), 30 parts by mass of the compound (57-2) and 35 parts by mass of a phenol resin (manufactured by Sumitomo Bakelite Co., Ltd., PR-50404) in Example 1, the compound (57 -5) An electrophotographic photosensitive member and a single film were produced in the same manner as in Example 1 except that 63 parts by mass and 32 parts by mass of phenol resin (Showa High Polymer Co., Ltd., Shonor BRL-204) were used. Furthermore, the same evaluation as Example 1 was implemented about the obtained single film | membrane. The results obtained are shown in Table 58.

[Example 5]
Instead of 30 parts by mass of the compound (57-1), 30 parts by mass of the compound (57-2) and 35 parts by mass of a phenol resin (manufactured by Sumitomo Bakelite Co., Ltd., PR-50404) in Example 1, the compound (57 -4) An electrophotographic photoreceptor and a single film were produced in the same manner as in Example 1 except that 55 parts by mass and 40 parts by mass of phenol resin (manufactured by Gunei Chemical Co., Ltd., Residtop PL-4852) were used. Furthermore, the same evaluation as Example 1 was implemented about the obtained single film | membrane. The results obtained are shown in Table 58.

[Example 6]
Instead of 30 parts by mass of the compound (57-1), 30 parts by mass of the compound (57-2) and 35 parts by mass of a phenol resin (manufactured by Sumitomo Bakelite Co., Ltd., PR-50404) in Example 1, the compound (57 -3) An electrophotographic photoreceptor and a single film were produced in the same manner as in Example 1 except that 58 parts by mass and 32 parts by mass of a phenol resin (manufactured by Sumitomo Chemical Co., Ltd., PR-50404) were used. Furthermore, the same evaluation as Example 1 was implemented about the obtained single film | membrane. The results obtained are shown in Table 58.

[Example 7]
30 parts by mass of the compound (57-1) in Example 1, 30 parts by mass of the compound (11-2), 34 parts by mass of a phenol resin (manufactured by Sumitomo Bakelite, PR-50404), a low molecular weight polyethylene-vinyl acetate copolymer ( Instead of 5 parts by mass of Sumitomo Chemical Co., Ltd., Sumikaflex 500) and 1 part by mass of silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KP-340), 30 parts by mass of compound (57-1) shown in Table 57, compound (57- 2) 30 parts by mass, 30 parts by mass of a phenol resin (manufactured by Sumitomo Bakelite, PR-50404), low molecular weight polyethylene-vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Sumikaflex 500, weight average molecular weight 12,000) 9 masses Electrophotographic photosensitive member in the same manner as in Example 1 except that 1 part by mass and silicone oil (KP-340, manufactured by Shin-Etsu Chemical Co., Ltd.) were used. Fine-alone film was produced. Furthermore, the same evaluation as Example 1 was implemented about the obtained single film | membrane. The results obtained are shown in Table 58.

[Example 8]
30 parts by mass of the compound (57-1) in Example 1, 30 parts by mass of the compound (57-2), 37 parts by mass of a phenol resin (manufactured by Sumitomo Bakelite, PR-50404), a low molecular weight polyethylene-vinyl acetate copolymer ( Instead of 2 parts by mass of Sumitomo Chemical Co., Ltd., Sumikaflex 500) and 1 part by mass of silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KP-340), 30 parts by mass of compound (57-1) shown in Table 57, compound (57- 2) 30 parts by mass, phenol resin (Sumitomo Bakelite, PR-50404) 30 parts by mass, low molecular weight polyethylene-vinyl acetate copolymer (Sumitomo Chemical Co., Sumikaflex 500, weight average molecular weight 18,000) 9 mass Electrophotographic photosensitive member in the same manner as in Example 1 except that 1 part by mass and 1 part by mass of silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KP-340) are used. Fine-alone film was produced. Furthermore, the same evaluation as Example 1 was implemented about the obtained single film | membrane. The results obtained are shown in Table 58.

[Example 9]
First, in the same manner as in Example 1, a conductive support having an anodized film formed on the surface was prepared.

  Next, 1 part by mass of titanyl phthalocyanine having a strong diffraction peak at a Bragg angle (2θ ± 0.2 °) in an X-ray diffraction spectrum of 27.2 ° is 1 part by mass of polyvinyl butyral (ESREC BM-S, Sekisui Chemical). Then, it was mixed with 100 parts by mass of n-butyl acetate and dispersed with a glass shaker for 1 hour with a paint shaker to obtain a coating solution for forming a charge generation layer. The obtained coating solution was dip-coated on the above conductive support and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, a charge transport layer and a protective layer were formed on the charge generation layer in the same manner as in Example 1 to obtain the target electrophotographic photoreceptor.

[Example 10]
On a cylindrical aluminum substrate subjected to a honing treatment, 100 parts of a zirconium compound (trade name: Orgatics ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 10 parts of a silane compound (trade name: A1100, manufactured by Nippon Unicar Co., Ltd.), isopropanol 400 And an undercoat layer forming coating solution consisting of 200 parts of butanol was applied by dip coating and dried by heating at 150 ° C. for 10 minutes to form a 0.1 μm undercoat layer.

  Next, the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum is 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 °, 1 part by weight of hydroxygallium phthalocyanine having a strong diffraction peak at 28.3 ° is mixed with 1 part by weight of polyvinyl butyral (Esreck BM-S, Sekisui Chemical) and 100 parts of n-butyl acetate, and the mixture is shaken with glass beads for 1 hour. A coating solution for forming a charge generation layer was obtained by dispersion treatment. The obtained coating solution was dip-coated on the undercoat layer and dried by heating at 100 ° C. for 10 minutes, and the charge generation layer having a thickness of about 0.15 μm. Formed.

  Next, 2 parts by mass of a compound represented by the following formula (XVIII) and 3 parts by mass of a polymer compound (viscosity average molecular weight 39,000) having a structural unit represented by the above formula (XVII) are 20 parts by mass of chlorobenzene. Then, a coating solution for forming a charge transport layer was obtained.

  The obtained coating solution was applied onto the charge generation layer by a dip coating method and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

  Next, a protective layer was formed on the charge transport layer in the same manner as in Example 1 to obtain the desired electrophotographic photosensitive member.

[Example 11]
First, in the same manner as in Example 1, a conductive support having an anodized film formed on the surface was prepared.

Next, 100 parts by mass of zinc oxide (SMZ-017N, manufactured by Teica) was mixed with 500 parts by mass of toluene, and 2 parts by mass of a silane coupling agent (A1100: manufactured by Nihon Unicar) was added and stirred for 5 hours. Thereafter, toluene was distilled off under reduced pressure and baked at 120 ° C. for 2 hours. As a result of analyzing the obtained surface-treated zinc oxide by fluorescent X-ray, the ratio of Si element strength to zinc element strength was 1.8 × 10 ⁻⁴ .

  35 parts by mass of the surface-treated zinc oxide, 15 parts by mass of a curing agent (blocked isocyanate Sumijour 3175, manufactured by Sumitomo Bayern Urethane Co., Ltd.), 6 parts by mass of butyral resin (BM-1, manufactured by Sekisui Chemical Co., Ltd.) and methyl ethyl ketone The dispersion was obtained by mixing with 44 parts by mass and carrying out a dispersion treatment for 2 hours in a sand mill using glass beads of 1 mmφ. As a catalyst, 0.005 part by mass of dioctyltin dilaurate and 17 parts by mass of silicone fine particles (Tospearl 130, manufactured by GE Toshiba Silicon Co., Ltd.) were added to the resulting dispersion to obtain an undercoat layer coating solution. This coating solution was applied onto an Al base material by a dip coating method, followed by drying and curing at 160 ° C. for 100 minutes to obtain an undercoat layer having a thickness of 20 μm. The surface roughness of the undercoat layer was measured using a surface roughness profile measuring device Surfcom 570A manufactured by Tokyo Seimitsu Co., Ltd. at a measurement distance of 2.5 mm and a scanning speed of 0.3 mm / sec. The Rz value was 0.24. It was.

  Next, a charge generation layer was formed on the undercoat layer in the same manner as in Example 9.

  Further, a charge transport layer and a protective layer were formed on the charge generation layer in the same manner as in Example 1 to obtain the desired electrophotographic photosensitive member.

[Examples 12 to 24, Comparative Examples 3 and 4]
In Examples 12 to 24 and Comparative Examples 3 and 4, an electrophotographic photosensitive member and a developer were used in combinations shown in Table 59, respectively, to produce an image forming apparatus having the configuration shown in FIG. The elements other than the electrophotographic photosensitive member and the developer were the same as those of Fuji Xerox printer Docu color 400CP.

  Developers 1 to 3 were prepared as follows. Each physical property value was measured by the following method.

Toner, composite particle size distribution:
Using a multisizer (manufactured by Nikka Machine Co., Ltd.), measurement was performed with an aperture diameter of 100 μm.

Average shape factor ML ² / A of toner and composite particles:
The toner or composite particles were observed with an optical microscope, and the image was taken into an image analyzer (LUZEX III, manufactured by Nireco) to measure the equivalent circle diameter. Next, from the maximum length and area of the toner particles or composite particles, the following formula for each of 1000 particles:
(Shape factor) = (maximum length) ² × π × 100 / [4 × (area)]
The average shape factor ML ² / L was determined by determining the value of the shape factor according to the above, and determining the average value (arithmetic average) of 1000 particles.

(Developer-1)
{Manufacture of toner base particles}
<Preparation of resin fine particle dispersion>
370 g of styrene, 30 g of n-butyl acrylate, 8 g of acrylic acid, 24 g of dodecanethiol and 4 g of carbon tetrabromide, and 6 g of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) And 10 g of anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and a solution in 550 g of ion-exchanged water are mixed to start emulsion polymerization in the flask, while slowly mixing for 10 minutes. 50 g of ion exchange water in which 4 g of ammonium persulfate was dissolved was added. After carrying out nitrogen substitution in the flask, the mixed solution was heated with an oil bath until the temperature of the mixed solution reached 70 ° C. while stirring, and emulsion polymerization was continued for 5 hours. As a result, a resin fine particle dispersion in which resin fine particles having a volume average particle size of 150 nm, a glass transition temperature (T _g ) of 58 ° C., and a mass average molecular weight (M _w ) of 11,500 was obtained. The solid content concentration of this dispersion was 40% by mass.

<Preparation of Colorant Dispersion-1>
Carbon black (Mogal L, manufactured by Cabot) 60 g, nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) 6 g and ion-exchanged water 2400 g were mixed, and a homogenizer (Ultra Turrax T50, manufactured by IKA) was used. And stirred for 10 minutes. Then, the dispersion process was carried out with the optimizer, and the colorant dispersion liquid-1 in which the colorant (carbon black) particles having a volume average particle diameter of 250 nm were dispersed was prepared.

<Preparation of Colorant Dispersion-2>
360 g of cyan pigment (B15, manufactured by Dainichi Seika), 5 g of nonionic surfactant (Nonipol 400, manufactured by Sanyo Kasei Co., Ltd.) and 2400 g of ion-exchanged water are mixed together, and a homogenizer (Ultra Turrax T50, manufactured by IKA) is mixed. And stirred for 10 minutes. Thereafter, a colorant dispersion-2 in which colorant (cyan pigment) particles having a volume average particle diameter of 250 nm were dispersed by dispersing with an optimizer was prepared.

<Preparation of Colorant Dispersion-3>
60 g of magenta pigment (R122, manufactured by Dainichi Seika), 5 g of nonionic surfactant (Nonipol 400, manufactured by Sanyo Kasei Co., Ltd.) and 240 g of ion-exchanged water are mixed together, and a homogenizer (Ultra Turrax T50, manufactured by IKA) is mixed. And stirred for 10 minutes. Thereafter, a dispersion treatment with an optimizer was performed to prepare a colorant dispersion-3 in which colorant (magenta pigment) particles having a volume average particle diameter of 250 nm were dispersed.

<Preparation of colored dispersion-4>
90 g of yellow pigment (Y180), 5 g of nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) and 240 g of ion-exchanged water are mixed and stirred for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA). did. Thereafter, a dispersion treatment was performed using an optimizer to prepare a colorant dispersion liquid-4 in which colorant (yellow pigment) particles having a volume average particle diameter of 250 nm were dispersed.

<Preparation of release agent dispersion>
100 g of paraffin wax (HNP0190, manufactured by Nippon Seiwa Co., Ltd., melting point: 85 ° C.), 5 g of a cationic surfactant (Sanisol B50: manufactured by Kao Corporation) and 240 g of ion-exchanged water are mixed and made of round stainless steel The mixture was dispersed in the flask for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA). Thereafter, a dispersion treatment was performed using a pressure discharge type homogenizer to prepare a release agent dispersion liquid in which release agent particles having a volume average particle diameter of 550 nm were dispersed.

<Preparation of toner mother particles K1>
234 parts by mass of the resin fine particle dispersion, 30 parts by mass of the colorant dispersion-1, 40 parts by mass of the release agent dispersion, and 0.5 parts by mass of polyaluminum hydroxide (Paho2S, manufactured by Asada Chemical Co., Ltd.) Then, 600 parts by mass of ion-exchanged water was charged into each of the round stainless steel flasks, and mixed and dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA). Thereafter, the mixed solution was heated with stirring in an oil bath for heating and maintained at 40 ° C. for 30 minutes. At this time, it was confirmed that aggregated particles having a volume average particle diameter of 4.5 μm were produced in the mixed solution. Furthermore, when the temperature of the heating oil bath was raised and maintained at 56 ° C. for 1 hour, the volume average particle size was 5.3 μm. After adding 26 parts by mass of the resin fine particle dispersion to the dispersion containing the aggregate particles, the mixture was held at 50 ° C. for 30 minutes using a heating oil bath. After adding 1N sodium hydroxide to the dispersion containing the aggregate particles to adjust the pH of the dispersion to 7.0, the flask is sealed, and heated with continuous stirring using a magnetic seal at 80 ° C. Held for 4 hours. After the dispersion was cooled, the toner base particles produced in the dispersion were filtered off, washed four times with ion exchange water, and then lyophilized to obtain toner base particles K1. Toner base particles K1 had a volume average particle size of 5.9 μm and an average shape factor ML ² / L of 132.

<Preparation of toner base particles C1>
Toner base particle C1 was prepared in the same manner as toner base particle K1, except that colored particle dispersion-2 was used instead of colored particle dispersion-1. The resulting toner base particles C1 had a volume average particle size of 5.8 μm and an average shape factor ML ² / A of 131.

<Preparation of toner mother particles M1>
Toner base particles M1 were prepared in the same manner as toner base particles K1, except that Colored Particle Dispersion-3 was used instead of Colored Particle Dispersion-1. The resulting toner base particles M1 had a volume average particle size of 5.5 μm and an average shape factor ML ² / A of 135.

<Preparation of toner mother particles Y1>
Toner base particles Y1 were prepared in the same manner as toner base particles K1, except that Colored Particle Dispersion-4 was used instead of Colored Particle Dispersion-1. The resulting toner base particles Y1 had a volume average particle size of 5.9 μm and an average shape factor ML ² / A of 130.

<Manufacture of carriers>
14 parts by mass of toluene, 2 parts by mass of a styrene-methacrylate copolymer (component ratio: 90/10) and 0.2 part of carbon black (R330: manufactured by Cabot Corporation) were mixed and dispersed by stirring with a stirrer for 10 minutes. A coating solution was prepared. Next, 100 parts by mass of the coating liquid and ferrite particles (volume average particle size: 50 μm) are put in a vacuum degassing type kneader and stirred at 60 ° C. for 30 minutes, and then degassed by further reducing pressure while heating. A carrier was obtained by drying. This carrier had a volume resistivity value of 10 ¹¹ Ω · cm when an applied electric field of 1,000 V / cm was applied.

<Preparation of Toner-1 and Developer-1>
100 parts by mass of each of the toner base particles K1, C1, M1, and Y1, 1 part by mass of rutile type titanium oxide (particle size: 20 nm, treated with n-decyltrimethoxysilane), silica (particle size: 40 nm, gas 2.0 mass parts prepared by phase oxidation method and treated with silicone oil), 1 mass part cerium oxide (volume average particle size: 0.7 μm), 0.3 mass higher fatty acid alcohol (higher fatty acid alcohol having a molecular weight of 700) 0.3 mass The parts were blended with a 5 L Henschel mixer at a peripheral speed of 30 m / s for 15 minutes. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to obtain toner-1 (four colors of black, cyan, magenta, and yellow). Further, 100 parts by mass of carrier and 5 parts by mass of toner-1 were stirred for 20 minutes at 40 rpm using a V-blender, and sieved with a sieve having an opening of 212 μm, thereby developing-1 (black, cyan, Magenta and yellow).

(Developer-2)
<Preparation of toner mother particles K2>
234 parts by mass of resin fine particle dispersion (prepared at the time of preparing composite fine particles), 30 parts by mass of colorant dispersion-1, 40 parts by mass of release agent dispersion, polyaluminum hydroxide (Paho2S, manufactured by Asada Chemical Co., Ltd.) ) And 600 parts by mass of ion-exchanged water were each placed in a round stainless steel flask, and mixed and dispersed using a homogenizer (Ultra Turrax T50, manufactured by IKA). Thereafter, the mixed solution was heated while being stirred in a heating oil bath and maintained at 40 ° C. for 30 minutes, and then it was confirmed that aggregated particles having a volume average particle size of 4.5 μm were formed. Furthermore, when the temperature of the heating oil bath was raised and maintained at 56 ° C. for 1 hour, the volume average particle size was 5.3 μm. Thereafter, 26 parts by mass of a resin fine particle dispersion was added to the dispersion containing the aggregated particles, and then heated with an oil bath for heating and held at 50 ° C. for 30 minutes. After adding 1N sodium hydroxide to the dispersion containing the aggregated particles to adjust the pH of the system to 5.0, the flask is sealed and heated with continuous stirring using a magnetic seal at 95 ° C. Hold for 5 hours. After the dispersion was cooled, the toner base particles produced in the dispersion were filtered off, washed four times with ion exchange water, and then lyophilized to obtain toner base particles K2. Toner base particles K2 had a volume average particle size of 5.8 μm and an average shape factor ML ² / A of 109.

<Preparation of toner mother particle C2>
Toner base particles C2 were prepared in the same manner as toner base particles K2, except that Colored Particle Dispersion-2 was used instead of Colored Particle Dispersion-1. The resulting toner base particles C2 had a volume average particle size of 5.7 μm and an average shape factor ML ² / L of 110.

<Preparation of toner mother particles M2>
Toner base particles M2 were prepared in the same manner as toner base particles K2, except that Colored Particle Dispersion-3 was used instead of Colored Particle Dispersion-1. The resulting toner base particles M2 had a volume average particle size of 5.6 μm and an average shape factor ML ² / A of 114.

<Preparation of toner mother particle Y2>
Toner base particles Y2 were prepared in the same manner as toner base particles K2, except that Colored Particle Dispersion-4 was used instead of Colored Particle Dispersion-1. The resulting toner base particles Y2 had a volume average particle size of 5.8 μm and an average shape factor ML ² / A of 108.

<Preparation of Toner-2 and Developer-2>
Toner-1 except that toner base particles K2, C2, M2, and Y2 were used, respectively, and aluminum oxide (volume average particle size: 0.1 μm) was used instead of cerium oxide (volume average particle size: 0.7 μm). In addition, toner-2 and developer-2 (four colors of black, cyan, magenta, and yellow, respectively) were prepared in the same manner as developer-1.

(Developer-3)
<Preparation of toner mother particles K3>
100 parts by mass of polyester resin (linear polyester obtained from terephthalic acid-bisphenol A ethylene oxide adduct-cyclohexanedimethanol, T _g : 62 ° C., M _n : 12,000, M _w : 32,000), carbon black 4 parts by mass (Mogal L, manufactured by Cabot) and 5 parts by mass of carnauba wax were kneaded with an extruder and pulverized with a jet mill. The obtained pulverized product was classified with a wind classifier to obtain toner mother particles K3. The resulting toner base particles K3 had a volume average particle size of 5.9 μm and an average shape factor ML ² / A of 145.

<Preparation of toner base particles C3>
Toner base particles C3 were prepared in the same manner as toner base particles K3 except that a cyan colorant (CI Pigment Blue 15: 3) was used instead of carbon black. The resulting toner base particles C3 had a volume average particle size of 5.6 μm and an average shape factor ML ² / A of 141.

<Preparation of toner mother particles M3>
Toner base particles M3 were prepared in the same manner as toner base particles K3 except that magenta colorant (R122) was used instead of carbon black. The resulting toner base particles M3 had a volume average particle size of 5.9 μm and an average shape factor ML ² / A of 149.

<Preparation of toner mother particles Y3>
Toner base particles Y3 were prepared in the same manner as toner base particles K3 except that a yellow colorant (Y180) was used instead of carbon black. The resulting toner base particles Y3 had a volume average particle size of 5.8 μm and an average shape factor ML ² / A of 144.

<Preparation of Toner-3 and Developer-3>
Toner-3 and developer-3 (four colors of black, cyan, magenta, and yellow, respectively) in the same manner as toner-2 and developer-2 except that toner base particles K3, C3, M3, and Y3 were used, respectively. Was prepared.

[Print test]
For each of the image forming apparatuses of Examples 13 to 26 and Comparative Examples 3 and 4, a print test of 10,000 sheets was performed in an environment of high temperature and high humidity (28 ° C., 75% RH), and then low temperature and low humidity (10 ° C., 20 % RH), 10,000 print tests were performed. The presence or absence of deposits on the surface of the electrophotographic photosensitive member after the print test was visually evaluated. The print image quality was visually evaluated for the presence of image defects. Further, the amount of wear on the surface of the electrophotographic photosensitive member after the print test was evaluated with an overcurrent meter. The results obtained are shown in Table 59.

1 is a schematic cross-sectional view showing a preferred embodiment of an electrophotographic photoreceptor of the present invention. It is a schematic cross section which shows other embodiment of the electrophotographic photoreceptor of this invention. It is a schematic cross section which shows other embodiment of the electrophotographic photoreceptor of this invention. It is a schematic cross section which shows other embodiment of the electrophotographic photoreceptor of this invention. It is a schematic cross section which shows other embodiment of the electrophotographic photoreceptor of this invention. 1 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of an image forming apparatus of the present invention. It is sectional drawing which shows schematically the basic composition of other suitable one Embodiment of the image forming apparatus of this invention. It is sectional drawing which shows schematically the basic composition of other suitable one Embodiment of the image forming apparatus of this invention. 1 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of a process cartridge of the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Charge generation layer, 2 ... Charge transport layer, 3 ... Conductive support body, 4 ... Undercoat layer, 5 ... Protective layer, 6 ... Photosensitive layer, 7 ... Charge generation / charge transport layer, 8 ... Charging means, 9 DESCRIPTION OF SYMBOLS ... Power supply, 10 ... Exposure means, 11 ... Developing means, 12 ... Transfer means, 13 ... Cleaning means, 14 ... Static eliminator, 15 ... Fixing means, 16 ... Mounting rail, 18 ... Opening for exposure, 20 ... Covered Transfer body, 100, 100a to 100d, electrophotographic photosensitive member, 200, 210, 220, image forming apparatus, 300, process cartridge, 500, medium to be transferred.

Claims (5)

An electrophotographic photosensitive member comprising a conductive support and a photosensitive layer provided on the conductive support,
The photosensitive layer is the farthest from the conductive support, and the phenol resin, ethylene - vinyl acetate copolymer, ethylene - vinyl acetate copolymer and vinyl acetate chloride - ethylene - at least selected ester copolymer or al An electrophotographic photosensitive member comprising an outermost surface layer obtained by thermosetting a thermosetting resin composition containing one kind and a charge transporting compound having a functional group capable of reacting with the phenol resin . The electrophotographic photosensitive member according to claim 1, wherein the outermost surface layer has a water vapor transmission coefficient at 25 ° C. of 1.0 × 10 ⁻¹ μg · μm / cm ² · s or less. The electrophotographic photosensitive member according to claim 1 , wherein the charge transporting compound has a structure represented by any one of the following general formulas (I) to (V).
_{^{F [- (X 1) m}} -R 1 -Z 1 H] n ... (I)
[In Formula (I), F represents an n-valent organic group derived from a compound having a hole transporting ability, X ¹ represents an oxygen atom or a sulfur atom, R ¹ represents an alkylene group, Z ¹ represents an oxygen atom, Sulfur atom, NH or COO, m represents 0 or 1, and n represents an integer of 1 to 4. ]
_{^{F [- (X 2) m1}} - (R 2) m2 - (Z 2) m3 G] n1 ... (II)
[In Formula (II), F represents an n1-valent organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, Z ² represents an oxygen atom, S is a sulfur atom, NH or COO, G is an epoxy group, m1, m2 and m3 are each independently 0 or 1, and n1 is an integer of 1 to 4. ]
_{^{F [-D-Si (R 3}} ) (3-m4) Q m4] n2 ... (III)
[In Formula (III), F is an n2 valent organic group derived from a compound having a hole transporting ability, D is a divalent group having flexibility, and R ³ is a hydrogen atom, substituted or unsubstituted. Q represents a hydrolyzable group, m4 represents an integer of 1 to 3, and n2 represents an integer of 1 to 4. ]

[In Formula (IV), F represents an n3-valent organic group having hole transportability, T ¹ represents a divalent group, Y represents an oxygen atom or a sulfur atom, and R ⁴ , R ⁵ and R ⁶ represent Independently, a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m5 represents 0 or 1, and n3 represents an integer of 1 to 4. However, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]

[In the formula (V), F represents an n4-valent organic group having a hole transporting property, T ² represents a divalent group, R ⁸ represents a monovalent organic group, m6 represents 0 or 1, and n4 represents An integer of 1 to 4 is shown respectively. ] The electrophotographic photosensitive member according to any one of claims 1 to 3 ,
Charging means for charging the electrophotographic photoreceptor;
Exposure means for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image; and
Developing means for developing the electrostatic latent image with toner to form a toner image;
An image forming apparatus comprising: a transfer device that transfers the toner image to a transfer medium. The electrophotographic photosensitive member according to any one of claims 1 to 3 ,
A charging means for charging the electrophotographic photosensitive member; a developing means for developing a latent electrostatic image formed on the electrophotographic photosensitive member with toner to form a toner image; and At least one selected from the group consisting of cleaning means for removing toner remaining on the surface;
A process cartridge comprising: