JP4600116B2 - Image forming apparatus, process cartridge, and image forming method - Google Patents

Description

  The present invention relates to an image forming apparatus, a process cartridge, and an image forming method.

  A so-called xerographic image forming apparatus includes an electrophotographic photosensitive member (hereinafter sometimes referred to as “photosensitive member”), 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.

  In recent years, in the field of xerographic image forming apparatuses (electrophotographic apparatuses), there are increasing demands for speeding up of image forming processes, higher image quality, and longer life. In particular, when speeding up, image quality and life are often impaired. More specifically, when the image forming process is speeded up, the electrophotographic photosensitive member used for image writing is subjected to stress due to sliding with a charging member of a contact charging device or a cleaning member of a cleaning device. In many cases, wear causes image quality defects.

  In addition, as a charging device for an electrophotographic apparatus, a contact charging type charging device is widely used from the viewpoint of ecology. However, in the case of the contact charging method, the photoconductor is significantly more than the charging method using a corotron. Wear increases. The occurrence of such rubbing scratches and abrasions not only shortens the life of the photoconductor, but also causes a decrease in image density due to a decrease in sensitivity of the photoconductor and occurrence of fog due to a decrease in charging potential.

  Accordingly, in order to suppress the scratches and wear as described above, a resin having high mechanical strength is used in the electrophotographic photosensitive member, and the life is further extended. For example, a photoreceptor having a cross-linked surface layer has been proposed (see, for example, Patent Documents 1 to 3).

Japanese Patent No. 2575536 JP-A-9-190004 JP 2002-82469 A

  However, the image forming apparatus provided with the photoconductor described in Patent Documents 1 to 3 has the following problems in reliability.

  That is, in the photoconductors described in Patent Documents 1 to 3, scratches and wear on the surface of the photoconductor are suppressed by improving the mechanical strength, but on the other hand, the surface of the photoconductor is hard to be polished because the surface layer is hard. Further, it is difficult to remove discharge products and the like attached to the surface of the photoreceptor. In particular, in the case of the above contact charging method, more discharge products tend to be generated. Further, in high temperature and high humidity environments, the deposits accumulated on the surface of the photoreceptor take in moisture in the air, so And image quality defects such as talc depression occur. Therefore, the reliability with which an excellent image quality can be stably formed over a long period is insufficient.

  Here, in order to improve the scraping effect, a method of providing a cleaning device having a cleaning member having a high hardness is conceivable. However, when it is used repeatedly over a long period of time, a photoreceptor having a cross-linked surface layer is provided. However, the surface layer is worn away unevenly, and foreign matters such as residual toner adhering to the photoreceptor pass through the cleaning device, resulting in streak-like image quality defects.

  Although it is important to use a photoconductor having a cross-linked surface layer in order to improve image quality and extend the life of an image forming apparatus, an effective method that can ensure sufficient reliability has not been obtained. However, further improvement is desired for an image forming apparatus using a photoconductor provided with a cross-linked surface layer.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide an image forming apparatus, a process cartridge, and an image forming method capable of realizing high image quality, long life, and high reliability.

In order to solve the above problems, an image forming apparatus of the present invention includes an electrophotographic photosensitive member having a conductive support and a photosensitive layer formed on the conductive support, a charging unit for charging the electrophotographic photosensitive member, Exposure means for exposing the electrophotographic photosensitive member to form an electrostatic latent image, developing means for developing the electrostatic latent image with toner to form a toner image, transfer means for transferring the toner image to a transfer medium, and electronic In an image forming apparatus having a cleaning device for removing toner remaining on a photographic photosensitive member , the photosensitive layer has an outermost surface layer having a charge transporting ability and a crosslinked structure on the side farthest from the conductive support. The toner includes toner particles and fluorine-containing cerium oxide fine particles.

  According to the image forming apparatus of the present invention, by having the above configuration, an excellent image can be stably formed over a long period of time, and high image quality, long life, and high reliability can be achieved. Is possible. The reason why such an effect is obtained is not clear, but the present inventors speculate as follows.

  In other words, the fluorine-containing cerium oxide fine particles have an appropriate balance of both slipperiness and polishability, so that the outermost surface layer with high wear resistance is uniformly worn while sufficiently suppressing the occurrence of chipping of the cleaning member. It is thought to let you. In addition, the combination of fluorine-containing cerium oxide fine particles and the outermost surface layer having a charge transporting ability and a crosslinked structure reduces the amount of fluorine-containing cerium oxide necessary to maintain cleaning and wear resistance. Therefore, the influence on the original charging property of the developer can be sufficiently reduced, so that good charging characteristics can be maintained. Through these actions, image flow and talc depletion due to accumulation of discharge products, density unevenness due to uneven wear, and cleaning failure due to roughness of the photoreceptor surface can be prevented over a long period of time. It is thought that high image quality, long life and high reliability were achieved.

  In recent years, from the viewpoint of improving image quality, there is a tendency to use a toner having a reduced particle size, a uniform particle size distribution, and a spherical shape. In order to ensure cleaning properties when using such a toner. However, the image forming apparatus of the present invention is suitable for the use of a toner containing such an external additive. The reason is that when the toner as described above is used, the external additive is accumulated on the surface of the photoreceptor by repeated use, and further, filming tends to occur by being pressed by the cleaning member. However, according to the image forming apparatus of the present invention, accumulation of such external additives can be prevented, so that filming can be sufficiently suppressed, and high image quality, long life, and high reliability can be achieved.

  Further, in the direct transfer method that does not use an intermediate transfer member, there is a tendency that a degeneration caused by talc components in the paper surface adhering to the photosensitive member is likely to occur, but according to the image forming apparatus of the present invention, Since deposits on the surface of the photoconductor can be sufficiently removed, such a depression can be prevented over a long period of time, and high image quality, long life and high reliability can be achieved.

  In the image forming apparatus of the present invention, the fluorine content of the fluorine-containing cerium oxide fine particles is preferably 0.1 to 10% by mass. When the fluorine content is less than 0.1% by mass, it tends to be difficult to sufficiently suppress uneven density and poor cleaning. On the other hand, when the fluorine content exceeds 10% by mass, it tends to be difficult to sufficiently suppress filming, image flow, and depression.

  The toner preferably contains 0.3 to 10 parts by mass of fluorine-containing cerium oxide fine particles with respect to 100 parts by mass of the toner particles. When the proportion of the fluorine-containing cerium oxide fine particles is less than 0.3 parts by mass with respect to 100 parts by mass of the toner particles, it tends to be difficult to sufficiently suppress filming, image flow, and depression, If it exceeds 10 parts by mass, it tends to be difficult to sufficiently suppress density unevenness and poor cleaning.

  Further, in the image forming apparatus of the present invention, filming and image flow can be achieved by using a toner containing fluorine-containing cerium oxide fine particles having a fluorine content of 0.1 to 10.0% by mass in the above ratio. In addition, it is possible to prevent depletion, density unevenness, and poor cleaning for a longer period of time, and to significantly reduce the wear of the photosensitive member.

  The fluorine-containing cerium oxide fine particles preferably have a volume average particle size of 0.03 to 6 μm. By using such fluorine-containing cerium oxide fine particles, the effect of suppressing the surface roughness of the photoreceptor and preventing defective cleaning can be obtained more reliably.

  In the image forming apparatus of the present invention, the outermost surface layer has a charge having at least one selected from a phenol derivative having a methylol group and a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, a thiol group, and an amino group. It is preferable to contain a transport material.

式（Ｖ）中、Ｆは正孔輸送性を有するｎ７価の有機基を、Ｔは２価の基を、Ｙは酸素原子又は硫黄原子を、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又は１価の有機基を、Ｒ^７は１価の有機基を、ｍ１は０又は１を、ｎ７は１〜４の整数を、それぞれ示す。但し、Ｒ^６とＲ^７は互いに結合してＹをヘテロ原子とする複素環を形成してもよい。

式（VI）中、Ｆは正孔輸送性を有するｎ８価の有機基を、Ｔは２価の基を、Ｒ^８は１価の有機基を、ｍ２は０又は１を、ｎ８は１〜４の整数を、それぞれ示す。 Moreover, it is preferable that the said outermost surface layer contains the phenol derivative which has a methylol group, and the charge transport material shown by the following general formula (V) or (VI).

In formula (V), F is an n7-valent organic group having hole transportability, T is a divalent group, Y is an oxygen atom or a sulfur atom, and R ⁴ , R ⁵ and R ⁶ are each independently A hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m1 represents 0 or 1, and n7 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 (VI), F is an n8-valent organic group having hole transportability, T is a divalent group, R ⁸ is a monovalent organic group, m2 is 0 or 1, and n8 is 1 to 1 An integer of 4 is shown respectively.

  The charge transport material described above may be incorporated into a crosslinked structure as a structural unit having charge transport ability by reacting with the phenol derivative or with a compound constituting the phenol derivative.

  When the outermost surface layer contains any of the charge transport materials described above and a phenol derivative having a methylol group, it is possible to further improve the abrasion resistance of the photoreceptor, and to clean the outermost surface layer. As a result, the effect of suppressing the deterioration of the photosensitive layer due to the discharge product is improved, the high image quality can be maintained more reliably, and the reliability and life of the image forming apparatus are dramatically improved.

  In the image forming apparatus of the present invention, it is preferable that the abrasion amount per 1000 revolutions of the outermost surface layer of the electrophotographic photosensitive member is 0.1 nm to 20 nm. According to the present invention, image quality defects caused by deposits such as discharge products adhering to the surface of the photoreceptor can be sufficiently suppressed even when a photoreceptor having excellent mechanical strength indicating such wear amount is provided. Therefore, it is possible to realize a long-life image forming apparatus that can maintain high image quality and high reliability over an extremely long period of time.

The process cartridge of the present invention includes an electrophotographic photosensitive member having a conductive support and a photosensitive layer formed on the conductive support, a charging device for charging the electrophotographic photosensitive member, and a charged electrophotographic photosensitive member. an exposure device for forming an electrostatic latent image by exposing the said electrostatic latent image developed by the developing device Ru to form a toner image by toner, and a cleaning device for removing toner remaining on said electrophotographic photosensitive member a least a process cartridge comprising also a current image device, the one of a photosensitive layer, the farthest from the conductive substrate has a top surface layer and having a crosslinked structure having charge transportability , toner, and wherein the toner particles, and a fluorine-containing cerium oxide particles, the early days including the.

  According to the process cartridge of the present invention, as described above, a combination of an electrophotographic photosensitive member provided with an outermost surface layer having a charge transporting ability and a crosslinked structure, and a toner containing fluorine-containing cerium oxide fine particles. It is possible to form an excellent image quality over a long period of time. By applying this process cartridge to an image forming apparatus, an image forming apparatus that achieves high image quality, long life, and high reliability can be effectively realized.

In addition, the image forming method of the present invention includes a conductive support and a photosensitive layer formed on the conductive support, and has a charge transporting function on the side farthest from the conductive support of the photosensitive layer and has a crosslinking function. An electrophotographic photosensitive member preparing step for preparing an electrophotographic photosensitive member provided with an outermost surface layer having a structure, a toner preparing step for preparing a toner containing toner particles and fluorine-containing cerium oxide fine particles, and an electrophotographic photosensitive member A charging step for charging, an exposure step for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, a developing step for developing the electrostatic latent image with the toner to form a toner image, and a toner image The method includes a transfer step of transferring to a transfer medium and a cleaning step of removing toner remaining on the electrophotographic photosensitive member .

  According to the image forming method of the present invention, as described above, a combination of an electrophotographic photosensitive member provided with an outermost surface layer having a charge transporting ability and a crosslinked structure, and a toner containing fluorine-containing cerium oxide fine particles. In addition, excellent image quality can be formed over a long period of time. By applying this method to an image forming apparatus, an image forming apparatus that achieves high image quality, long life, and high reliability can be effectively realized.

  According to the present invention, it is possible to provide an image forming apparatus, a process cartridge, and an image forming method capable of realizing high image quality, long life, and high reliability.

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

  FIG. 1 is a schematic diagram showing a preferred embodiment of the image forming apparatus of the present invention. An image forming apparatus 100 shown in FIG. 1 includes a process cartridge 20 including an electrophotographic photosensitive member 1, an exposure device 30, a transfer device 40, and an intermediate transfer member 50 in an image forming apparatus main body (not shown). . In the image forming apparatus 100, the exposure device 30 is disposed at a position where the electrophotographic photosensitive member 1 can be exposed from the opening of the process cartridge 20, and the transfer device 40 is interposed between the electrophotographic photosensitive member via the intermediate transfer member 50. The intermediate transfer member 50 is disposed such that a part of the intermediate transfer member 50 can come into contact with the electrophotographic photosensitive member 1.

  The process cartridge 20 is obtained by integrating a charging device 21, a developing device 25, and a cleaning device 27 together with an electrophotographic photosensitive member 1 by a mounting rail in a case. The case is provided with an opening for exposure.

  First, the developing device 25 provided in the image forming apparatus 100 of the present embodiment will be described.

  As the developing device 25, for example, a general developing device that performs development by bringing a magnetic or non-magnetic one-component developer or two-component developer into contact or non-contact can be used. Such a developing device is not particularly limited as long as it has the functions described above, and can be appropriately selected according to the purpose. For example, a known developing device having a function of attaching the one-component developer or the two-component developer to the photosensitive member 1 using a brush, a roller, or the like can be used.

  Hereinafter, the toner used for the developing device 25 will be described.

  The toner used in the image forming apparatus of this embodiment is configured to include toner particles and fluorine-containing cerium oxide fine particles.

  The toner particles may be, for example, a kneading and pulverizing method in which a binder resin, a colorant and a release agent, and a charge control agent as necessary are added, kneaded, pulverized, and classified; A method of changing the shape by impact force or thermal energy; emulsion polymerization of a polymerizable monomer of a binder resin, formation of a dispersion, a colorant and a release agent, and a charge control agent as required Emulsion polymerization agglomeration method to obtain toner particles by mixing and agglomerating and heat-fusing the dispersion; polymerizable monomer to obtain binder resin, colorant and release agent, charge control as required Suspension polymerization method in which a solution such as an agent is suspended in an aqueous solvent for polymerization; a binder resin, a colorant and a release agent, and a solution such as a charge control agent as necessary are suspended in an aqueous solvent. A toner produced by a granulating solution suspension method or the like is used.

  Further, 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. The toner production method is preferably a suspension polymerization method, an emulsion polymerization aggregation method, or a dissolution suspension method in which an aqueous solvent is used from the viewpoint of shape control and particle size distribution control, and an emulsion polymerization aggregation method is particularly preferable.

  The toner base particles are composed of a binder resin, a colorant, and a release agent, and include silica and a charge control agent as necessary.

  Binder resins used for toner base particles include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, etc. Α-methylene aliphatics such as vinyl esters, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Homopolymers and copolymers of monocarboxylic acid esters, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone Polyester resins by copolymerization of dicarboxylic acids and diols.

  Particularly representative binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer. A polymer, polyethylene, polypropylene, a polyester resin, etc. can be mentioned. In addition, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like can also be mentioned.

  In addition, as colorants, 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, malachite green oxalate, 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 polyethylene, low molecular polypropylene, Fischer tropical wax, montan wax, carnauba wax, rice wax, and candelilla wax.

  As the charge control agent, known ones can be used, and azo metal complex compounds, metal complex compounds of salicylic acid, and resin type charge control agents containing polar groups 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.

Further, the toner particles preferably have an average shape factor (ML ² / A) of less than 150, more preferably 110 to 140, from the viewpoint of obtaining high developability and transferability and high image quality. Further, the toner particles preferably have a volume average particle diameter of 2 to 12 μm, and more preferably 3 to 9 μm. By using a toner satisfying such an average shape factor and volume average particle diameter, developability and transferability are improved, and a high-quality image called so-called photographic image quality can be obtained.

  The fluorine-containing cerium oxide fine particles can be obtained from, for example, a raw material ore (bastonesite) containing fluorine. In this case, fluorine is contained in cerium oxide in the form of R—O—F (R: rare earth, O: oxygen atom, F: fluorine atom). Moreover, the method of processing the cerium oxide which does not contain R-O-F obtained from the raw material ore (monazite) which does not contain a fluorine with a fluorine-containing surface treating agent can also be used. Fluorine-containing surface treatment agents used in this case include trifluoropropyltrimethoxysilane, trifluoropropyltrichlorosilane, tridecafluorodecyltrichlorosilane, tridecafluorooctyltrimethoxysilane, heptadecafluorodecyltrichlorosilane, heptadeca Examples include fluoroalkylsilanes such as fluorodecyltrimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, heptadecafluorodecylmethyldichlorosilane, and fluorine-modified silicone oil.

  The fluorine content in the fluorine-containing cerium oxide fine particles is preferably in the range of 0.1 to 10.0% by mass. When the fluorine content is less than 0.1% by mass, it tends to be difficult to sufficiently suppress uneven density and poor cleaning. On the other hand, when the fluorine content exceeds 10% by mass, it tends to be difficult to sufficiently suppress filming, image flow, and depression.

  The volume average particle diameter of the fluorine-containing cerium oxide fine particles is preferably 0.03 to 6 μm. By using such fluorine-containing cerium oxide fine particles, the effect of suppressing the surface roughness of the photoreceptor and preventing defective cleaning can be obtained more reliably.

  The toner used in the image forming apparatus of this embodiment can be produced by mixing the toner particles and the fluorine-containing cerium oxide fine particles with a Henschel mixer or the like.

  The toner preferably contains the fluorine-containing cerium oxide fine particles in a range of 0.3 to 10 parts by mass with respect to 100 parts by mass of the toner particles. When the proportion of the fluorine-containing cerium oxide fine particles is less than 0.3 parts by mass with respect to 100 parts by mass of the toner particles, it tends to be difficult to sufficiently suppress filming, image flow, and depression, If it exceeds 10 parts by mass, it tends to be difficult to sufficiently suppress density unevenness and poor cleaning. Further, in the present embodiment, filming, image flow, and depression are achieved by using a toner containing fluorine-containing cerium oxide fine particles having a fluorine content of 0.1 to 10.0% by mass in the above ratio. Further, uneven density and poor cleaning can be prevented over a long period of time, and wear of the photosensitive member can be extremely reduced.

  Further, lubricating particles may be added to the toner as necessary. Examples of the lubricating particles 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, silicones having a softening point by heating, olein Aliphatic amides such as acid amides, erucic acid amides, ricinoleic acid amides, stearic acid amides, plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, beeswax, etc. And other mineral waxes such as natural waxes, montan waxes, ozokerites, ceresins, paraffin waxes, microcrystalline waxes, Fischer-Tropsch waxes, and the like, and modified products thereof. These can be used alone or in combination of two or more.

  In addition, the slippery particles preferably have an average particle size of 0.1 to 10 μm, and the above-mentioned slippery particles may be pulverized to make the particle sizes uniform. Further, the amount of the lubricating particles added to the toner is preferably 0.05 to 2.0% by mass, and more preferably 0.1 to 1.5% by mass.

  Furthermore, inorganic fine particles, organic fine particles, composite fine particles obtained by adhering inorganic fine particles to organic fine particles, and the like can be added to the toner for the purpose of removing deposits and deteriorated matters on the surface of the electrophotographic photoreceptor.

  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.

  In addition, the inorganic fine particles are mixed with a titanium coupling agent such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, bis (dioctylpyrophosphate) oxyacetate titanate, γ- (2- Aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxy Silane 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. In addition, those hydrophobized with higher fatty acid metal salts such as silicone oil, aluminum stearate, zinc stearate and calcium stearate are also preferably used.

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

  The particle diameter is preferably a number average particle diameter of 5 nm to 1000 nm, more preferably 5 nm to 800 nm, and still more preferably 5 nm to 700 nm. If the average particle size is less than the lower limit, the polishing ability tends to be lacking. On the other hand, if the average particle size exceeds the upper limit, the surface of the electrophotographic photoreceptor tends to be damaged. Moreover, it is preferable that the sum of the addition amount of the particle | grains mentioned above and lubricity particle | grains is 0.6 mass% or more.

  Other inorganic oxides added to the toner are small-diameter inorganic oxides with a primary particle size of 50 nm or less for powder flowability, 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 for precise charge control. Further, the surface treatment of the small-diameter inorganic fine particles increases the dispersibility and increases the powder flowability. Furthermore, it is also preferable to add carbonates such as calcium carbonate and magnesium carbonate and inorganic minerals such as hydrotalcite in order to remove the discharge purified product.

  In addition, 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.

  Next, the electrophotographic photoreceptor 1 provided in the image forming apparatus 100 of the present embodiment will be described.

  FIG. 2 is a schematic cross-sectional view showing a preferred embodiment of the electrophotographic photosensitive member 1 according to the present invention. As shown in FIG. 2, the electrophotographic photosensitive member 1 includes a conductive support 2 and a photosensitive layer 3. The photosensitive layer 3 has a structure in which an undercoat layer 4, a charge generation layer 5, and a charge transport layer 6 are laminated in this order on a conductive support 2. In the electrophotographic photoreceptor 1 shown in FIG. 2, the charge transport layer 6 is the outermost surface layer.

  3 to 6 are schematic sectional views showing other preferred embodiments of the electrophotographic photosensitive member provided in the image forming apparatus according to the present invention. The electrophotographic photosensitive member shown in FIGS. 3 and 4 includes the photosensitive layer 3 in which the functions are separated into the charge generating layer 5 and the charge transporting layer 6 as in the electrophotographic photosensitive member shown in FIG. 5 and 6 contain the charge generation material and the charge transport material in the same layer (single-layer type photosensitive layer 8).

  The electrophotographic photoreceptor 1 shown in FIG. 3 has a structure in which an undercoat layer 4, a charge generation layer 5, a charge transport layer 6 and a protective layer 7 are sequentially laminated on a conductive support 2. The electrophotographic photoreceptor 1 shown in FIG. 4 has a structure in which an undercoat layer 4, a charge transport layer 6, a charge generation layer 5, and a protective layer 7 are sequentially laminated on a conductive support 2. In the electrophotographic photoreceptor 1 shown in FIGS. 3 and 4, the protective layer 7 is the outermost surface layer. The electrophotographic photoreceptor 1 shown in FIG. 5 has a structure in which an undercoat layer 4 and a single-layer type photosensitive layer 8 are sequentially laminated on a conductive support 2. It is the outermost surface layer. The electrophotographic photoreceptor 1 shown in FIG. 6 has a structure in which an undercoat layer 4, a single-layer type photosensitive layer 8, and a protective layer 7 are sequentially laminated on a conductive support 2. Is the outermost surface layer. In the electrophotographic photoreceptor 1, the undercoat layer 4 is not necessarily provided.

  Hereinafter, each element will be described based on the electrophotographic photosensitive member 1 shown in FIG.

  Examples of the conductive support 2 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 2 include a paper, a plastic film, a belt, and the like on which a conductive polymer, a conductive compound such as indium oxide, or a metal or alloy such as aluminum, palladium, or gold is applied, evaporated, or laminated.

  When the photosensitive member 1 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 2 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 for the light source, it is not particularly necessary to roughen the interference fringes, and it is possible to prevent the occurrence of defects due to the irregularities on the surface of the conductive support 2, which is suitable for longer life.

  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 2 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 2 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 2 that has been 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 5 includes a charge generation material or includes 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 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. Insulating resins such as polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin can be mentioned, but are not limited thereto. These binder resins can be used individually by 1 type or in mixture of 2 or more types.

  The charge generation layer 5 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. At this time, a condition that the crystal type does not change due to dispersion is required. Incidentally, it has been confirmed that the crystal form is not changed before dispersion in any of the above dispersion methods.

  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 5 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, or a curtain coating method is used. Can be used.

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

  The charge transport layer 6 includes a charge transport material and a binder resin, or 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. m3 and m4 each independently represent 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 6 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 5 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 6 is preferably 5 to 50 μm, more preferably 10 to 30 μm.

  In the photosensitive layer 3, additives such as an antioxidant, a light stabilizer, and a heat stabilizer are added for the purpose of preventing deterioration of the photoreceptor due to ozone, an oxidizing gas, or light or heat generated in the image forming apparatus. Can be added. Examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, and organic phosphorus compounds.

  Examples of the light stabilizer include derivatives such as benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine. In addition, at least one kind of electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use.

Examples of the electron acceptor include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, Examples include chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, and phthalic acid. Of these, benzene derivatives having an electron-withdrawing substituent such as fluorenone, quinone, Cl, CN, and NO ₂ are particularly preferable.

  The protective layer 7 needs to have a charge transport capability and a crosslinked structure. Such a protective layer includes, for example, a resin capable of forming a crosslinked structure and a charge transport material. In this case, the charge transport material may be incorporated into the crosslinked structure as a structural unit having charge transport ability by reacting with the resin or reacting with the compound constituting the resin.

  As the resin capable of forming a crosslinked structure, various materials can be used, and a phenol resin, a urethane resin, a melamine resin, a curable acrylic resin, a siloxane resin, and the like are preferable.

  As the charge transport material, for example, those listed as the constituent material of the charge transport layer can be used.

  In the present embodiment, from the viewpoint of obtaining an image having no image quality defect over a longer period of time, the protective layer 7 includes a phenol derivative having a methylol group, a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, a thiol group, and an amino group. It is preferable to contain a charge transport material having at least one selected from the group. In addition, these charge transport materials may be incorporated into a crosslinked structure as a structural unit having charge transport ability by reacting with a resin or reacting with a compound constituting the resin.

  Examples of the phenol derivative having a methylol group include monomers of monomethylolphenols, dimethylolphenols or trimethylolphenols, mixtures thereof, oligomers thereof, or mixtures of these monomers and oligomers. Such phenol derivatives having a methylol group include resorcin, bisphenol, etc., substituted phenols containing one hydroxyl group such as phenol, cresol, xylenol, paraalkylphenol, paraphenylphenol, and two hydroxyl groups such as catechol, resorcinol, hydroquinone, etc. It is obtained by reacting a compound having a phenol structure, such as bisphenols such as substituted phenols, bisphenol A and bisphenol Z, biphenols, etc., with formaldehyde, paraformaldehyde, etc. in the presence of an acid catalyst or an alkali catalyst. Generally what is marketed as a phenol resin can also be used. In the present specification, a relatively large molecule having about 2 to 20 repeating molecular structural units is referred to as an oligomer, and a molecule smaller than that is referred to as a monomer.

As the acid catalyst, sulfuric acid, paratoluenesulfonic acid, phosphoric acid and the like are used. Further, as the alkali catalyst, hydroxides or amine catalysts of alkali metals and alkaline earth metals such as NaOH, KOH, Ca (OH) ₂ and Ba (OH) ₂ 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, the carrier is remarkably trapped by the remaining catalyst, and the electrophotographic characteristics tend to be deteriorated. Therefore, it is preferable to inactivate or remove by neutralizing with an acid or contacting with an adsorbent such as silica gel or an ion exchange resin.

  Moreover, as a phenol derivative which has a methylol group, a phenol resin is preferable and a resol type phenol resin is more preferable.

  As the charge transport material having at least one selected from a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, a thiol group and an amino group, the following general formula (I), (II), (III) or (IV) It is preferable that it is a compound shown by these. As the charge transport material having an epoxy group, those having a plurality of epoxy groups are preferable. The charge transport material having a plurality of epoxy groups is preferably a compound represented by the following general formula (IV).

F-[(X ¹ ) _m ^1- (R ¹ ) _{m 2} -Y] _{m 3} (I)
In the above formula (I), F represents an 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 (1 to 15 carbon atoms are preferred, 1 10 is more preferable), Y represents a hydroxyl group, a carboxyl group (—COOH), a thiol group (—SH) or an amino group (—NH ₂ ), m1 and m2 each independently represents 0 or 1, and m3 represents An integer of 1 to 4 is shown.

^{_{F - [(X 2) n1}} - (R 2) n2 - (Z) n3 G] n4 (II)
In the above formula (II), F represents an 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 (1 to 15 carbon atoms are preferred, 1 10 is more preferable), Z represents an oxygen atom, sulfur atom, NH or COO, G represents an epoxy group, n1, n2 and n3 each independently represents 0 or 1, and n4 represents an integer of 1 to 4. .

F- [D-Si (R ³ ) _(3-a) Q _a ] _b (III)
In formula (III), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group having flexibility, R ³ represents a hydrogen atom, a substituted or unsubstituted alkyl group ( The number of carbon atoms is preferably 1-15, more preferably 1-10, or a substituted or unsubstituted aryl group (carbon number is preferably 6-20, more preferably 6-15), and Q is a hydrolyzable group. A represents an integer of 1 to 3, and b represents an integer of 1 to 4.

In addition, as the divalent group D having flexibility, specifically, a site of F for imparting photoelectric characteristics, a substituted silicon group contributing to the construction of a three-dimensional inorganic glassy network, It is a divalent group that plays a role in linking. In addition, D represents an organic group structure that imparts moderate flexibility to the portion of the inorganic glassy network that is hard but brittle, and plays a role of improving mechanical toughness as a film. Specific examples _{D, -C α H 2α -,} - C β H 2β-2 -, - C γ H 2γ-4 - 2 divalent hydrocarbon group (here represented by, alpha is 1 to 15 Represents an integer, β represents an integer of 2 to 15, and γ represents an integer of 3 to 15), —COO—, —S—, —O—, —CH ₂ —C ₆ H ₄ —, —N═. CH—, — (C ₆ H ₄ ) — (C ₆ H ₄ ) —, and a characteristic group having a structure in which these characteristic groups are arbitrarily combined, and further, the constituent atoms of these characteristic groups are substituted with other substituents. And the like. The hydrolyzable group Q is preferably an alkoxy group, more preferably an alkoxy group having 1 to 15 carbon atoms.

^{_{F - [(X 2) n1}} - (R 2) n2 - (Z) n3 G] n4 (IV)
In the above formula (IV), F represents an 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 (1 to 15 carbon atoms are preferred, 1 10 is more preferable), Z represents an oxygen atom, sulfur atom, NH or COO, G represents an epoxy group, n1, n2 and n3 each independently represents 0 or 1, and n4 represents an integer of 2 to 4. .

  Furthermore, in the present embodiment, from the viewpoint of suppressing filming, image flow, density unevenness, poor cleaning, and depletion over a longer period, the protective layer 7 includes a phenol derivative having a methylol group and the following formula (V Or a charge transport material represented by (VI). In addition, these charge transport materials may be incorporated into a crosslinked structure as a structural unit having charge transport ability by reacting with a resin or reacting with a compound constituting the resin.

ここで、式（Ｖ）中、Ｆは正孔輸送性を有するｎ７価の有機基を、Ｔは２価の基を、Ｙは酸素原子又は硫黄原子を、Ｒ^４、Ｒ^５及びＲ^６はそれぞれ独立に水素原子又は１価の有機基を、Ｒ^７は１価の有機基を、ｍ１は０又は１を、ｎ７は１〜４の整数を、それぞれ示す。但し、Ｒ^６とＲ^７は互いに結合してＹをヘテロ原子とする複素環を形成してもよい。

Here, in formula (V), F is an n7-valent organic group having a hole transporting property, T is a divalent group, Y is an oxygen atom or a sulfur atom, and R ⁴ , R ⁵ and R ⁶ are Each independently represents a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m 1 represents 0 or 1, and n ⁷ 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.

ここで、式（VI）中、Ｆは正孔輸送性を有するｎ８価の有機基を、Ｔは２価の基を、Ｒ^８は１価の有機基を、ｍ２は０又は１を、ｎ８は１〜４の整数を、それぞれ示す。

Here, in formula (VI), F is an n8 valent organic group having hole transporting property, T is a divalent group, R ⁸ is a monovalent organic group, m2 is 0 or 1, n8 Represents an integer of 1 to 4, respectively.

  As the organic group F derived from the compound having a hole transporting ability in the compound represented by the general formula (I), (II), (III), (IV), (V) or (VI), A compound represented by the formula (VII) is preferred.

Here, in formula (VI), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group, Ar ⁵ is a substituted or unsubstituted aryl group or arylene group, and k is 0 or 1 is shown respectively. However, ^{1 to 4 of} Ar ¹ , Ar ² , Ar ³ , Ar ^4, and Ar ⁵ have the above general formula (I), (II), (III), (IV), (V), or (VI) in the compounds _{^{represented, - [(X 1) m1}} - (R 1) m2 -Y], - [(X 2) n1 - (R 2) n2 - (Z) n3 G], - [D-Si ( R ³ ) _(3-a) Q _a ], _a bond for binding to a moiety represented by the structural unit represented by the following formula (V-1) or the structural unit represented by the following formula (VI-1) Have

Specific examples of the substituted or unsubstituted aryl group represented by Ar ^{1 to} Ar ⁴ in the compound represented by the general formula (VII) include aryl represented by the following formulas (VII-1) to (VII-7). Groups are preferred.

  As Ar in the aryl group represented by the above formula (VII-7), an aryl group represented by the following formula (VII-8) or (VII-9) is preferable.

  Moreover, as Z in the aryl group represented by the above formula (VII-7), a divalent group represented by the following formula (VII-10) or (VII-17) is preferable.

Here, in the above formulas (VII-1) to (VII-17), R ¹⁶ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. A substituted or unsubstituted phenyl group, or an aralkyl group having 7 to 10 carbon atoms, R ^{17 to} R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom. An alkoxy group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group substituted or unsubstituted with them, an aralkyl group having 7 to 10 carbon atoms, or a halogen atom, m and s are each independently 0; Or 1, q and r each independently represent an integer of 1 to 10, and t each independently represents an integer of 1 to 3.

In the above formulas (VII-1) to (VII-7), X represents-[(X ¹ ) _m1- (R ¹ ) _m2 -Y] in the compounds represented by the above formulas (I) to (VI). _{^{, - [(X 2) n1}} - (R 2) n2 - (Z) n3 G], - [D-Si (R 3) (3-a) Q a], represented by the formula (V-1) It has a bond for bonding to a structural unit or a site represented by the structural unit represented by the formula (VI-1).

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

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

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 (VII) 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 (I), (II), (IV), (V) or (VI) include the following compounds (I-1) to (I-38) and the following compounds (II). -1) to (II-2), the following compounds (IV-1) to (IV-45), the following compounds (V-1) to (V-40), or the following compounds (VI-1) to (VI- 13). In the following table, Me or a bond is described but a substituent is not described, a methyl group, Et represents an ethyl group.

In addition, a compound represented by the following general formula (VIII-1) can also be added to the protective layer 7 in order to control various physical properties such as strength and film resistance of the protective layer 7.
Si (R ⁵⁰ ) _(4-c) Q _c (VIII-1)

In the above formula (VIII-1), 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 (VIII-1) 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.

  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 7, it is also preferable to use a compound having two or more silicon atoms as shown in the general formula (VIII-2).
B- (Si (R ⁵¹ ) _(3-d) Q _d ) ₂ (VIII-2)

In the above formula (VIII-2), 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 a represents 1 to 3 Indicates an integer. More specific examples of the compound represented by the general formula (VIII-2) include the following compounds (VIII-2-1) to (VIII-2-16).

  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 in terms of 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. Particularly in the case of a siloxane resin, it is preferable to 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, phenol resin and the like. In particular, polyvinyl acetal resin is preferable in terms of electrical characteristics.

  The molecular weight of the resin is preferably 2000-100000, more preferably 5000-50000. If the molecular weight is less than 2000, the desired effect tends not to be obtained. If the molecular weight is more than 100000, the solubility tends to be low and the addition amount is limited, or the film formation tends to be poor during coating. The addition amount is preferably 1 to 40%, more preferably 1 to 30%, and most preferably 5 to 20%. If the amount is less than 1%, it is difficult to obtain a desired effect. If the amount is more than 40%, image blurring under high temperature and high humidity tends to occur. These resins may be used alone or in combination.

  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 (VIII-3) or a derivative thereof.

In the above formula (VIII-3), A ¹ and A ² each independently represent a monovalent organic group.

  Commercially available cyclic siloxane can be mentioned as a cyclic compound which has a repeating structural unit shown by general formula (VIII-3). 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 control the antifouling substance adhesion, lubricity, hardness and the like on the surface of the electrophotographic photosensitive member. They can be used alone or in combination of two or more.

  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 an 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. What was chosen from what was disperse | distributed and generally marketed can be used. The solid content of colloidal silica in the protective layer 7 is not particularly limited, but preferably 0.1 to 0.1 based on the total solid content of the protective layer 7 in terms of film formability, electrical characteristics, and strength. It is used in the range of 50% by mass, more preferably in the range of 0.1-30% by mass.

  The silicone fine particles used as the silicon atom-containing fine particles are spherical and preferably have an average particle size 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, it is possible to improve the lubricity and water repellency of the surface of the electrophotographic photosensitive member while being uniformly incorporated into a strong cross-linked structure, and to maintain good wear resistance and adherence to contaminants over a long period of time. it can. The content of the silicone fine particles in the protective layer 7 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 7. .

  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.

  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.

  In addition, additives such as plasticizers, surface modifiers, antioxidants, and photodegradation inhibitors can also be used. 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. An antioxidant having a hindered phenol, hindered amine, thioether, or phosphite partial structure can be added to the protective layer 7, which is effective in improving the potential stability and image quality when the environment changes.

  Examples of the antioxidant include the following compounds. For example, as the hindered phenol type, “Sumizer BHT-R”, “Sumizer MDP-S”, “Sumizer BBM-S”, “Sumizer WX-R”, “Sumizer NW”, “Sumizer BP-76”, “ Sumilizer BP-101 "," Sumilizer GA-80 "," Sumilizer GM "," Sumilizer GS "or more manufactured by Sumitomo Chemical Co., Ltd.," IRGANOX1010 "," IRGANOX1035 "," IRGANOX1076 "," IRGANOX1098 "," IRGANOX1098 "," IRGANOX1098 " ”,“ IRGANOX1222 ”,“ IRGANOX1330 ”,“ IRGANOX1425WL ”,“ IRGANOX1 20L "," IRGANOX 245 "," IRGANOX 259 "," IRGANOX 3114 "," IRGANOX 3790 "," IRGANOX 5057 "," IRGANOX 565 "or more, manufactured by Ciba Specialty Chemicals," ADK STAB AO-20 "," ADK STAB AO-30 "," ADEKA 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. Examples of hindered amines include “Sanol LS2626”, “Sanol LS765”, “Sanol LS770”, “Sanol LS744”, “Tinuvin 144”, “Tinuvin 622LD”, “Mark LA57”, “Mark LA67”, “Mark LA62”. ”,“ Mark LA68 ”,“ Mark LA63 ”,“ Smilizer TPS ”,“ Smilizer TP-D ”for thioethers,“ Mark 2112 ”,“ Mark PEP 8 ”,“ Mark PEP ”for phosphites -24G "," Mark PEP.36 "," Mark 329K "," Mark HP.10 ", and hindered phenols and hindered amine antioxidants are particularly preferable. 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 7 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, polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, or polyvinyl pyrrolidone resin may be contained. In this case, the insulating resin can be added at a desired ratio, and thereby, adhesion to the charge transport layer 6, coating film defects due to heat shrinkage and repellency, and the like can be suppressed.

  The protective layer 7 is formed using a coating liquid for forming a protective layer containing the above-described constituent materials.

  It is preferable to add or use a catalyst when forming the protective layer forming coating solution or the protective layer forming coating solution. Such catalysts include inorganic acids such as hydrochloric acid, acetic acid, phosphoric acid, sulfuric acid, organic acids such as formic acid, propionic acid, oxalic acid, paratoluenesulfonic acid, benzoic acid, phthalic acid, maleic acid, potassium hydroxide, hydroxide Examples include alkali catalysts such as sodium, calcium hydroxide, ammonia, triethylamine.

Furthermore, a solid catalyst insoluble in the system as shown below can also be used. Amberlite 15, Amberlite 200C, Amberlist 15E (above, manufactured by Rohm and Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical Co.); Levacit SPC-108, Levacit SPC-118 (above, Bayer); Diaion RCP-150H (Mitsubishi Kasei); Sumikaion KC-470, Duolite C26-C, Duolite C-433, Duolite-464 (Above, manufactured by Sumitomo Chemical Co., Ltd.); cation exchange resins such as Nafion-H (manufactured by DuPont); shades such as Amberlite IRA-400, Amberlite IRA-45 (above, manufactured by Rohm and Haas) ion exchange _{resins; Zr (O 3 PCH 2 CH} 2 SO 3 H) 2, Th (O 3 Cobalt tungstate; polyorganosiloxanes containing protonic acid group of the polyorganosiloxane having a sulfonic acid group; CH ₂ CH ₂ COOH) groups containing protonic acid group of ₂ such as inorganic solids are bonded to the surface Heteropolyacids such as phosphomolybdic acid; isopolyacids such as niobic acid, tantalum acid, and molybdic acid; monovalent metal oxides such as silica gel, alumina, chromia, zirconia, CaO, and MgO; silica-alumina, silica-magnesia, silica- Complex metal oxides such as zirconia and zeolites; clay minerals such as acid clay, activated clay, montmorillonite and kaolinite; metal sulfates such as LiSO ₄ and MgSO ₄ ; metal phosphates such as zirconia phosphate and lanthanum phosphate _{; LiNO 3, Mn (NO 3} ) 2 and the like of a metal nitrate; silica An inorganic solid in which a group containing an amino group such as a solid obtained by reacting aminopropyltriethoxysilane on the surface is bonded to the surface; a polyorganosiloxane containing an amino group such as an amino-modified silicone resin; Can be mentioned.

  Further, when preparing a coating solution for forming a protective layer, it is preferable to use a solid catalyst that is insoluble in a photofunctional compound, a reaction product, water, a solvent, etc., because the stability of the coating solution tends to be improved. . The solid catalyst insoluble in the system is not particularly limited as long as the catalyst component is insoluble in a material for forming a resin having a crosslinked structure, other additives, water, a solvent and the like. Although the usage-amount of these solid catalysts is not restrict | limited in particular, 0.1-100 mass parts is preferable with respect to a total of 100 mass parts of the compound which has a hydrolysable 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. The reaction temperature and reaction time are appropriately selected according to the type and amount of the raw material compound or solid catalyst, but the reaction temperature is usually 0 to 100 ° C, preferably 10 to 70 ° C, more preferably 15 to 50. The reaction time is preferably 10 minutes to 100 hours. If the reaction time exceeds the upper limit, gelation tends to occur.

  In the case of preparing a protective layer-forming coating solution, when a catalyst insoluble in the system is used, it is preferable to use a catalyst that is further dissolved in the system for the purpose of improving the strength, storage stability of the solution, 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.

  In addition to organoaluminum compounds, organotin 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 in particular of these catalysts is not restrict | limited, 0.1-20 mass parts is preferable with respect to a total of 100 mass parts of the compound which has a hydrolysable group, and 0.3-10 mass parts is especially preferable.

In the present invention, when an organometallic compound is used as a catalyst, it is preferable to add a multidentate ligand from the viewpoint of pot life and curing efficiency. Examples of such multidentate ligands include those shown below and those derived therefrom, but the present invention is not limited to these. 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 polydentate ligand, a bidentate ligand is particularly preferable, and a bidentate ligand represented by the following general formula (VIII-4) is more preferable, and R in the following general formula (VIII-4) is more preferable. Particularly preferably, ¹⁰ and R ¹¹ are the same. By making R ¹⁰ and R ^{11 the} same, the coordination power of the ligand near room temperature becomes strong, and the coating solution for forming the protective layer can be further stabilized.

ここで、式（ＶＩＩＩ−４）中、Ｒ^１０及びＲ^１１は各々独立に、炭素数１〜１０のアルキル基、フッ化アルキル基、又は炭素数１〜１０のアルコキシ基を示す。

Here, in Formula (VIII-4), R ¹⁰ and R ¹¹ 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.

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

  The protective layer 7 can be formed in the absence of a solvent if the coating solution is liquid, but if necessary, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone In addition to tetrahydrofuran; ethers such as diethyl ether and dioxane; and the like, various solvents may be used. As such a solvent, those having a boiling point of 100 ° C. or less are preferable, and they can be arbitrarily mixed and used. When the organosilicon compound is contained in the coating solution, the organosilicon compound is likely to be precipitated if the solvent is too small. Therefore, the content is preferably 0.5 to 30 parts by mass with respect to 1 part by mass of the organosilicon compound. More preferably, it is part by mass.

  Furthermore, when crosslinking, a curing catalyst may be used in the protective layer forming coating solution. Curing catalysts include bissulfonyldiazomethanes such as bis (isopropylsulfonyl) diazomethane, bissulfonylmethanes such as methylsulfonyl p-toluenesulfonylmethane, sulfonylcarbonyldiazomethanes such as cyclohexylsulfonylcyclohexylcarbonyldiazomethane, 2-methyl Sulfonylcarbonyl alkanes such as 2- (4-methylphenylsulfonyl) propiophenone, nitrobenzyl sulfonates such as 2-nitrobenzyl p-toluenesulfonate, alkyl and aryl sulfonates such as pyrogallol trismethanesulfonate ( g) Benzoin sulfonates such as benzoin tosylate, N- such as N- (trifluoromethylsulfonyloxy) phthalimide. Sulfonyloxyimides, pyridones such as (4-fluorobenzenesulfonyloxy) -3,4,6-trimethyl-2-pyridone, 2,2,2-trifluoro-1-trifluoromethyl-1- ( Photoacid generators such as sulfonic acid esters such as 3-vinylphenyl) -ethyl-4-chlorobenzenesulfonate, onium salts such as triphenylsulfonium methanesulfonate, diphenyliodonium trifluoromethanesulfonate, protonic acids or Lewis acids. Preferred examples include compounds neutralized with Lewis bases, mixtures of Lewis acids and trialkyl phosphates, sulfonic acid esters, phosphate esters, onium compounds, and carboxylic anhydride compounds.

Compounds obtained by neutralizing a protonic acid or Lewis acid with a Lewis base include halogenocarboxylic acids, sulfonic acids, sulfuric acid monoesters, phosphoric acid mono- and diesters, polyphosphoric acid esters, boric acid mono- and diesters, and the like. Various amines such as monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, or trialkylphosphine, triarylphosphine, trialkylphosphite, triaryl Examples thereof include compounds neutralized with phosphite. Examples of the compound obtained by neutralizing a Lewis acid with a Lewis base include compounds obtained by neutralizing a Lewis acid such as BF ₃ , FeCl ₃ , SnCl ₄ , AlCl ₃ , ZnCl ₂ with the above Lewis base.

  Examples of the onium compound include triphenylsulfonium methanesulfonate, diphenyliodonium trifluoromethanesulfonate, and the like.

  Examples of the carboxylic anhydride compound include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, lauric anhydride, oleic anhydride, stearic anhydride, n-caproic anhydride, n-caprylic anhydride, and n-capric anhydride. , Palmitic anhydride, myristic anhydride, trichloroacetic anhydride, dichloroacetic anhydride, monochloroacetic anhydride, trifluoroacetic anhydride, heptafluorobutyric anhydride, and the like.

  Specific examples of Lewis acids include, for example, boron trifluoride, aluminum trichloride, ferrous chloride, ferric chloride, ferrous chloride, ferric chloride, zinc chloride, zinc bromide, stannous chloride. , Metal halides such as stannic chloride, stannous bromide, stannic bromide, organometallic compounds such as trialkylboron, trialkylaluminum, dialkylaluminum halide, monoalkylaluminum halide, tetraalkyltin , Diisopropoxyethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, tris (acetylacetonato) aluminum, diisopropoxy bis (ethyl acetoacetate) titanium, diisopropoxy bis (acetylacetonato) titanium, tetrakis (N-propylacetoacetate Zirconium, tetrakis (acetylacetonato) zirconium, tetrakis (ethylacetoacetate) zirconium, dibutyl bis (acetylacetonato) tin, tris (acetylacetonato) iron, tris (acetylacetonato) rhodium, bis (acetyl) Acetonato) zinc, tris (acetylacetonato) cobalt and other metal chelate compounds, dibutyltin dilaurate, dioctyltin ester malate, magnesium naphthenate, calcium naphthenate, manganese naphthenate, iron naphthenate, cobalt naphthenate, copper naphthenate , Zinc naphthenate, zirconium naphthenate, lead naphthenate, calcium octylate, manganese octylate, iron octylate, cobalt octylate, zinc octylate, zirconium octylate, Tin chill acid, lead octylate, zinc laurate, magnesium stearate, aluminum stearate, calcium stearate, cobalt stearate, zinc stearate, and metal soaps such as stearate lead. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Although the usage-amount of these catalysts is not restrict | limited, 0.1-20 mass parts is preferable with respect to the total 100 mass parts of solid content contained in the coating liquid for protective layer formation, and 0.3-10 mass parts is preferable. Particularly preferred.

  When the coating liquid for forming the protective layer is applied onto the charge transport layer 6, the coating methods are blade coating method, Mayer 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 7 forms by drying a coating film.

  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 reaction temperature and reaction time for curing the curable component in the coating liquid for forming the protective layer are not particularly limited, but the reaction temperature is preferably 60 ° C. from the viewpoint of mechanical strength and chemical stability of the obtained resin. As mentioned above, More preferably, it is 80-200 degreeC, and reaction time becomes like this. Preferably it is 10 minutes-5 hours. In addition, maintaining the organic layer obtained by curing the coating liquid in a high humidity state is effective in stabilizing the characteristics of the organic layer. Furthermore, the protective layer 7 obtained can be hydrophobized by subjecting it to surface treatment using hexamethyldisilazane, trimethylchlorosilane, or the like according to the application.

  The thickness of the protective layer 7 is preferably 0.5 to 15 μm, more preferably 1 to 10 μm, and further preferably 1 to 5 μm.

  Further, since the protective layer 7 formed from the above-mentioned coating solution for forming a protective layer has excellent mechanical strength and sufficient photoelectric properties, it can be used as it is as a charge transport layer of a multilayer photoreceptor. it can.

  Further, as the protective layer 7, the charge transport material having at least one selected from a phenol derivative having a methylol group and a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, a thiol group and an amino group, the formula (V ) Or a charge transport material represented by the above formula (VI), the phenol derivative-containing layer is preferably formed by the following method. .

The phenol derivative-containing layer is formed by applying a coating solution for forming a protective layer containing a constituent material on the charge transport layer 6 and curing it, as in the method for forming the protective layer 7 described above. Here, it is preferable that the infrared absorption spectrum of the phenol derivative-containing layer satisfies the condition represented by the following formula (C). Thereby, it is possible to further improve the electrical characteristics and the image quality.
(P ₂ / P ₁ ) ≦ 0.2 (C)
Here, in the formula (C), _{P 1} is the absorbance of the maximum absorption peaks at ^{1560cm -1 ~1640cm} -1, _{P 2} represents the absorbance of the maximum absorption peaks at ^{1645cm -1 ~1700cm} -1.

  It is preferable to add a catalyst to the coating liquid for forming the protective layer, or to use the catalyst when preparing the coating liquid for forming the protective layer. Catalysts used include inorganic acids such as hydrochloric acid, acetic acid, phosphoric acid and sulfuric acid, organic acids such as formic acid, propionic acid, oxalic acid, paratoluenesulfonic acid, benzoic acid, phthalic acid and maleic acid, potassium hydroxide, water An alkali catalyst such as sodium oxide, calcium hydroxide, ammonia, triethylamine, or a solid catalyst insoluble in the system can also be used.

  In addition, in order to remove the catalyst at the time of synthesis from a phenol derivative having a methylol group, the phenol derivative is dissolved in an appropriate solvent such as methanol, ethanol, toluene, ethyl acetate, washed with water, reprecipitation using a poor solvent, etc. It is preferable to perform the above treatment or to perform treatment using an ion exchange resin or an inorganic solid. As the ion exchange resin and the inorganic solid, the same ones as described above can be used.

  For the coating liquid for forming the protective layer, alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran; ethers such as diethyl ether and dioxane; Can be used. In order to apply a dip coating method generally used for production of an electrophotographic photosensitive member, an alcohol solvent, a ketone solvent, or a mixed solvent thereof is preferable. In addition, the boiling point of the solvent used is preferably 50 to 150 ° C., and these can be arbitrarily mixed and used.

  In addition, since an alcohol solvent, a ketone solvent, or a mixed solvent thereof is preferable as the solvent, the charge transport material used for forming the protective layer 7 to be used is soluble in these solvents. Is preferred.

  The amount of the solvent can be set arbitrarily, but if the amount is too small, the constituent materials are likely to be precipitated. Parts, more preferably 1 to 20 parts by mass.

  As a coating method when forming the protective layer 7 using the coating liquid for forming the protective layer, the same method as described above can be used.

After applying the coating liquid for forming the protective layer on the charge transport layer 6, a curing process is performed. Usually, during the curing treatment, the curing temperature is higher and the curing time is preferably longer in order to promote the crosslinking reaction of the phenol derivative and increase the mechanical strength of the protective layer 7. However, in such a case, the absorbance ratio (P ₂ / P ₁ ) tends to exceed 0.2, and in this case, the electric characteristics tend to be lowered. Therefore, it is preferable to control the curing temperature, the curing time, the crosslinking atmosphere, or the curing catalyst so that the IR spectrum of the protective layer 7 satisfies the above conditions.

  That is, in order for the IR spectrum of the protective layer 7 to satisfy the condition represented by the above formula (C), the curing temperature during the curing treatment is preferably 100 to 170 ° C, more preferably 100 to 150 ° C, ˜140 ° C. is more preferable. The curing time is preferably 30 minutes to 2 hours, more preferably 30 minutes to 1 hour.

Further, as the atmosphere for performing the curing treatment (crosslinking reaction), the absorbance ratio (P ₂ / P ₁ ) is under a so-called oxidation inert gas atmosphere (inert gas atmosphere) such as nitrogen, helium or argon. It is effective to make it small. When the crosslinking reaction is performed in an inert gas atmosphere, the curing temperature can be set higher than in an air atmosphere (oxygen-containing atmosphere), and the curing temperature is 100 to 160 ° C. (preferably 110 to 150 ° C.). Is possible. The curing time can be 30 minutes to 2 hours (preferably 30 minutes to 1 hour). In addition, in the compound represented by the general formula (I), when the site represented by (— (X ¹ ) _m1- (R ¹ ) _m2 -Y) is —CH ₂ —OH, the influence of the electrical characteristics due to the curing temperature is the greatest. Is apt to be large and is sensitive to oxidation. Therefore, it is preferable to carry out the curing treatment in the above preferred temperature range.

Moreover, when forming the protective layer 7 containing the phenol derivative which has a methylol group, and the charge transport material which has several epoxy groups like the compound shown by said Formula (IV), a crosslinking reaction is fully advanced. From the viewpoint, the curing temperature during the curing treatment is preferably 100 to 170 ° C, and more preferably 100 to 160 ° C. The curing time is preferably 30 minutes to 2 hours, more preferably 30 minutes to 1 hour. When forming the protective layer 7 described above, when the absorbance ratio (P 2 _{/ P 1)} and 0.2 or less is preferably performed under the conditions described above.

  In forming the protective layer 7 containing a phenol derivative having a methylol group and a charge transport material having a plurality of epoxy groups, an air atmosphere (oxygen-containing) is used when a crosslinking reaction is performed in an inert gas atmosphere. The curing temperature can be set higher than that under (atmosphere), and the curing temperature can be 100 to 180 ° C. (preferably 110 to 160 ° C.). The curing time can be 30 minutes to 2 hours (preferably 30 minutes to 1 hour).

  In addition, when forming the protective layer 7 containing a phenol derivative having a methylol group and a charge transport material having a plurality of epoxy groups, it is necessary to adjust film properties such as hardness, adhesiveness, and flexibility. Furthermore, polyglycidyl methacrylate, glycidyl bisphenols, epoxy-containing compounds such as phenol epoxy resin, terephthalic acid, maleic acid, pyromellitic acid, biphenyltetracarboxylic acid, etc., or their anhydrides are added to the coating solution for protection formation May be. As addition amount, 0.05-1 mass part is preferable with respect to 1 mass part of charge transport materials, and 0.1-0.7 mass part is more preferable.

  Furthermore, it is preferable to use a curing catalyst during the curing treatment. As the curing catalyst, the above-described curing catalyst can be used.

  Although the usage-amount of a curing catalyst is not restrict | limited in particular, 0.1-20 mass parts is preferable with respect to a total of 100 mass parts of solid content contained in the coating liquid for protective layer formation, and 0.3-10 mass parts is especially preferable. .

  Further, even when an organic metal compound is used as a catalyst when forming the protective layer 7 containing a phenol derivative having a methylol group and a charge transport material having a plurality of epoxy groups, the surface of pot life and curing efficiency Therefore, it is preferable to add the above multidentate ligand. 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, and still more preferably with respect to 1 mol of the organometallic compound used. 1 mole or more.

In this embodiment, an oxygen permeability at 25 ° C. of the protective layer 7 is more it is not more than ^{4 × 10 12 fm / s ·} Pa ^{preferably, 3.5 × 10 12 fm / s} · Pa or less Preferably, it is 3 × 10 ¹² fm / s · Pa or less.

  Here, the oxygen permeation coefficient is a scale representing the ease of oxygen gas permeation of the layer, but it can also be regarded as a substitute characteristic of the physical gap ratio of the layer if the view is changed. In addition, although the absolute value of the transmittance changes if the type of gas changes, there is almost no reversal of the magnitude relationship between the layers serving as specimens. Therefore, the oxygen permeation coefficient may be interpreted as a measure expressing the general ease of gas permeation.

  That is, when the oxygen permeation coefficient at 25 ° C. of the protective layer 7 satisfies the above conditions, the gas hardly penetrates into the protective layer 7. Therefore, the permeation of the discharge product generated by the image forming process is suppressed, the deterioration of the compound contained in the protective layer 7 is suppressed, the electrical characteristics can be maintained at a high level, and the image quality is improved and the life is extended. It is valid.

In addition, when the protective layer 7 is formed so that the absorbance ratio (P ₂ / P ₁ ) of the infrared absorption spectrum satisfies the above conditions, it is necessary to set the curing temperature relatively low in an air atmosphere. It is. Therefore, it is difficult to lower the oxygen transmission coefficient at 25 ° C. of the protective layer 7, but the absorbance ratio (P ₂ / P ₁ ) satisfies the above conditions, and the oxygen transmission coefficient of the protective layer 7 at 25 ° C. By satisfying the above conditions, it is possible to obtain a photoreceptor that can further improve electrical characteristics and achieve higher image quality.

  In the present embodiment, the outermost surface layer having a charge transporting ability and having a crosslinked structure is the protective layer 7. The outermost surface layer is, for example, the charge transporting layer 6 in the electrophotographic photoreceptor shown in FIG. You can also

  In the case of constituting a single layer type photosensitive layer, the single layer type photosensitive layer is formed containing a charge generating material and a binder resin. The charge generation material is the same as that used for the charge generation layer in the function separation type photosensitive layer, and the binder resin is a binder resin used for the charge generation layer and the charge transport layer in the function separation type photosensitive layer. Similar ones can be used. The content of the charge generating material in the single-layer type photosensitive layer is preferably 10 to 85% by mass, more preferably 20 to 50% by mass, based on the total solid content in the single-layer type photosensitive layer. A charge transport material or a polymer charge transport material may be added to the single-layer type photosensitive layer 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 single-layer type photosensitive layer. Moreover, the solvent and coating method used for coating can be the same as those for the above layers. The thickness of the single-layer type photosensitive layer is preferably about 5 to 50 μm, more preferably 10 to 40 μm.

  Next, each component of the image forming apparatus 100 other than the electrophotographic photoreceptor 1 and the developing device 25 will be described.

  As the charging device 21, for example, a contact charger using a conductive or semiconductive charging roller, a charging brush, a charging film, a charging rubber blade, a charging tube or the like can be used. Further, a non-contact type roller charger using a charging roller in the vicinity of the photoconductor 10, a known charger such as a scorotron charger using a corona discharge, a corotron charger, or the like can also be used.

  Examples of the exposure apparatus 30 include optical system devices that can expose the surface of the photoreceptor 1 with light such as semiconductor laser light, LED light, and liquid crystal shutter light in a desired image-like manner. The wavelength of the light source is in the spectral sensitivity region of the photoreceptor. As the wavelength of the semiconductor laser, near infrared having an oscillation wavelength near 780 nm is the mainstream. However, the present invention is not limited to this wavelength, and an oscillation wavelength laser in the 600 nm range or a laser having an oscillation wavelength in the vicinity of 400 to 450 nm as a blue laser can be used. For color image formation, a surface-emitting laser light source capable of multi-beam output is also effective.

  As the transfer device 40, for example, a contact transfer charger using a belt, a roller, a film, a rubber blade, etc., or a known transfer charger such as a scorotron transfer charger using a corona discharge or a corotron transfer charger. Can be mentioned.

  As the intermediate transfer member 50, a belt-like member (intermediate transfer belt) such as polyimide, polyamideimide, polycarbonate, polyarylate, polyester, rubber or the like having semiconductivity is used. Further, as the form of the intermediate transfer member 50, a drum-like member can be used in addition to the belt-like member.

  In addition to the above-described devices, the image forming apparatus 100 may include, for example, an optical static elimination device that performs optical static elimination on the photoreceptor 1.

  FIG. 7 is a schematic view showing another embodiment of the image forming apparatus of the present invention. In the image forming apparatus 110 shown in FIG. 7, the electrophotographic photosensitive member 1 is fixed to the main body of the image forming apparatus, and the charging device 22, the developing device 25, and the cleaning device 27 are each formed into a cartridge. It is provided independently as a cleaning cartridge. Note that the charging device 22 includes a charging device for charging by a corona discharge method.

  In the image forming apparatus 110, the electrophotographic photosensitive member 1 and other apparatuses are separated, and the charging device 22, the developing device 25, and the cleaning device 27 are fixed to the image forming apparatus main body by screws, caulking, adhesion, or welding. It is possible to detach it by the operation by pulling out and pushing in without being done. However, when used, the developing device 25 always performs development with the above-described toner.

  In the image forming apparatus of the present invention, the electrophotographic photosensitive member has the outermost surface layer having a crosslinked structure, and the development with the above-described toner is performed, so that the wear on the surface of the photosensitive member is sufficiently suppressed. Thereby, there is a case where it is not necessary to make a cartridge. Therefore, the charging device 22, the developing device 25, or the cleaning device 27 can be detached and attached by an operation by pulling out and pushing in without being fixed to the main body by screws, caulking, adhesion, or welding. The member cost per hit can be reduced. Also, two or more of these devices can be detachable as an integrated cartridge, thereby further reducing the member cost per print.

  The image forming apparatus 110 has the same configuration as that of the image forming apparatus 100 except that the charging device 22, the developing device 25, and the cleaning device 27 are each formed as a cartridge.

  FIG. 8 is a schematic diagram showing another embodiment of the image forming apparatus of the present invention. The image forming apparatus 120 is a tandem full-color image forming apparatus equipped with four process cartridges 20. In the image forming apparatus 120, four process cartridges 20 are arranged in parallel on the intermediate transfer member 50, and one electrophotographic photosensitive member can be used for one color. The image forming apparatus 120 has the same configuration as that of the image forming apparatus 100 except that it is a tandem system.

  In the tandem-type image forming apparatus 120, the amount of wear of each electrophotographic photosensitive member varies depending on the use ratio of each color, and thus the electrical characteristics of each electrophotographic photosensitive member tend to vary. Along with this, the toner development characteristics gradually change from the initial state, and the hue of the print image changes, so that a stable image cannot be obtained. In particular, in order to reduce the size of the image forming apparatus, a small-diameter electrophotographic photosensitive member tends to be used, and this tendency becomes remarkable when one having a diameter of 30 mmΦ or less is used. Here, when the configuration of the above-described electrophotographic photosensitive member is adopted for the electrophotographic photosensitive member and the above-described toner is used, stable image quality can be obtained over a long period even when the diameter is set to 30 mmΦ or less. Wear on the surface is sufficiently suppressed. Therefore, it is particularly effective for the image forming apparatus of the present invention to be a tandem system.

  FIG. 9 is a schematic view showing another embodiment of the image forming apparatus of the present invention. The image forming apparatus 130 shown in FIG. 9 is a so-called four-cycle image forming apparatus that forms toner images of a plurality of colors with one electrophotographic photosensitive member. The image forming apparatus 130 includes a photosensitive drum 1 that is rotated by a driving device (not shown) at a predetermined rotational speed in the direction of arrow A in the figure, and above the photosensitive drum 1 is a photosensitive member. A charging device 22 for charging the outer peripheral surface of the drum 1 is provided.

  Further, an exposure device 30 having a surface emitting laser array as an exposure light source is disposed above the charging device 22. The exposure device 30 modulates a plurality of laser beams emitted from a light source in accordance with an image to be formed and deflects the laser beams in the main scanning direction so that the axis of the photosensitive drum 1 is on the outer peripheral surface of the photosensitive drum 1. Scan in parallel. Thereby, an electrostatic latent image is formed on the outer peripheral surface of the charged photosensitive drum 1.

  A developing device 25 is disposed on the side of the photosensitive drum 1. The developing device 25 includes a roller-shaped container that is rotatably arranged. Four containers are formed inside the container, and developing units 25Y, 25M, 25C, and 25K are provided in each container. The developing devices 25Y, 25M, 25C, and 25K each include a developing roller 26, and store Y, M, C, and K color toners therein. These toners contain the above-mentioned fluorine-containing cerium oxide fine particles.

  The full-color image is formed by the image forming apparatus 130 while the photosensitive drum 1 is rotated four times. That is, during four rotations of the photosensitive drum 1, the charging device 22 charges the outer peripheral surface of the photosensitive drum 1, and the exposure device 20 includes Y, M, C, K image data representing a color image to be formed. Scanning the outer peripheral surface of the photosensitive drum 1 with the laser beam modulated according to any one is repeated while switching the image data used for modulation of the laser beam each time the photosensitive drum 1 rotates. Further, the developing device 25 operates the developing device corresponding to the outer peripheral surface in a state where any of the developing rollers 26 of the developing devices 25Y, 25M, 25C, and 25K corresponds to the outer peripheral surface of the photosensitive drum 1. The photosensitive drum 1 is the one that develops the electrostatic latent image formed on the outer peripheral surface of the photosensitive drum 1 to a specific color and forms a toner image of the specific color on the outer peripheral surface of the photosensitive drum 1. Each time it rotates, the process is repeated while rotating the container so that the developing unit used for developing the electrostatic latent image is switched. Thus, every time the photosensitive drum 1 rotates, Y, M, C, and K toner images are formed on the outer peripheral surface of the photosensitive drum 1.

  An endless intermediate transfer belt 50 is disposed substantially below the photosensitive drum 1. The intermediate transfer belt 50 is wound around rollers 51, 53, and 55, and is disposed so that the outer peripheral surface is in contact with the outer peripheral surface of the photosensitive drum 1. The rollers 51, 53, and 55 are rotated by a driving force of a motor (not shown) and rotate the intermediate transfer belt 50 in the direction of arrow B in FIG.

  A transfer device (transfer device) 40 is disposed on the opposite side of the photosensitive drum 1 across the intermediate transfer belt 50, and the toner image formed on the outer peripheral surface of the photosensitive drum 1 is intermediate transferred by the transfer device 40. The image is transferred onto the image forming surface of the belt 50. The intermediate transfer belt 50 is also rotated in accordance with the rotation of the photosensitive drum 1, and a full-color toner image is formed on the intermediate transfer belt 50 when the photosensitive drum 1 is rotated four times.

  A lubricant supply device 31 and a cleaning device 27 are disposed on the outer peripheral surface of the photosensitive drum 1 on the opposite side of the developing device 25 with the photosensitive drum 1 interposed therebetween. When the toner image formed on the outer peripheral surface of the photosensitive drum 12 is transferred to the intermediate transfer belt 50, the lubricant is supplied to the outer peripheral surface of the photosensitive drum 1 by the lubricant supply device 31, and the The area carrying the transferred toner image is cleaned by the cleaning device 27.

  A tray 60 is disposed below the intermediate transfer belt 50, and a large number of sheets P as recording materials are accommodated in the tray 60 in a stacked state. A take-out roller 61 is disposed obliquely above and to the left of the tray 60, and a roller pair 63 and a roller 65 are arranged in this order on the downstream side in the take-out direction of the paper P by the take-out roller 61. The uppermost recording sheet in the stacked state is taken out from the tray 60 by the take-out roller 61 rotating, and is conveyed by the roller pair 63 and the roller 65.

  A transfer device 42 is disposed on the opposite side of the roller 55 with the intermediate transfer belt 50 interposed therebetween. The paper P conveyed by the roller pair 63 and the roller 65 is sent between the intermediate transfer belt 50 and the transfer device 42, and the toner image formed on the image forming surface of the intermediate transfer belt 50 is transferred by the transfer device 42. . A fixing device 44 having a pair of fixing rollers is arranged on the downstream side of the transfer device 42 in the conveyance direction of the paper P. The paper P on which the toner image is transferred is transferred by the fixing device 44. After being fused and fixed, the sheet is discharged out of the image forming apparatus 130 and placed on a discharge tray (not shown).

  As the fixing device 44, for example, a commonly used device such as a heat roll fixing device or an oven fixing device can be used. The toner image transferred onto the transfer medium can be fixed by the fixing device 44.

(Process cartridge)
Next, the process cartridge of the present invention will be described. FIG. 8 is a schematic diagram showing a basic configuration of a preferred embodiment of the process cartridge of the present invention.

  The process cartridge 300 is combined and integrated in the case 311 together with the electrophotographic photosensitive member 1 using the charging device 21, the exposure device 30, the developing device 25, the cleaning device 27, and the mounting rail 313. The process cartridge 300 is detachable from the main body of the image forming apparatus including the transfer device 40, the fixing device 44, and other components (not shown), and constitutes the image forming apparatus together with the main body of the image forming apparatus. To do.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

[Developer preparation]
The developer was produced by first producing toner base particles and a carrier, and using them. In the following description, the particle size distribution of the toner and composite particles was measured using a multisizer (manufactured by Nikka Kisha Co., Ltd.) with an aperture diameter of 100 μm. Further, the average shape factor ML ² / A of the toner and the composite particles means a value calculated by the following formula. In the case of a true sphere, ML ² / A = 100.
ML ² / A = (maximum length) ² × π × 100 / (area × 4).

  The average shape factor is calculated by taking the toner projection image from an optical microscope into an image analyzer (LUZEX (III), manufactured by Nireco), measuring the equivalent circle diameter, and calculating the maximum length and area of each particle according to the above formula. It can be obtained by fitting.

<Preparation of toner base particles>
In producing the toner, first, a resin fine particle dispersion, a colorant dispersion, and a release agent dispersion were produced, and toner base particles were produced using them. Next, a toner was manufactured using it.

(Resin fine particle dispersion)
370 parts by mass of styrene, 30 parts by mass of n-butyl acrylate, 8 parts by mass of acrylic acid, 24 parts by mass of dodecanethiol, and 4 parts by mass of carbon tetrabromide were mixed and dissolved. 6 parts by mass of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.), 10 parts by mass of an anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and It added to the flask which mixed 550 mass parts of ion-exchange water, it was emulsion-polymerized, and 50 mass parts of ion-exchange water which melt | dissolved 4 mass parts of ammonium persulfate in this was thrown in, mixing slowly. After carrying out nitrogen substitution, it heated with the oil bath until the contents became 70 degreeC, stirring the inside of the said flask, and emulsion polymerization was continued as it was for 5 hours. As a result, a resin fine particle dispersion in which resin particles having an average particle diameter of 150 nm, a Tg of 58 ° C., and a mass average molecular weight (Mw) of 12000 was obtained was obtained. The solid content concentration of this dispersion was 40% by mass.

(Colorant dispersion)
60 parts by mass of carbon black (Mogal L, manufactured by Cabot), 6 parts by mass of a nonionic surfactant (Nonipol 400, manufactured by Sanyo Chemical Co., Ltd.) and 240 parts by mass of ion-exchanged water were mixed and dissolved. The mixture is stirred for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA), and then dispersed with an optimizer to disperse colorant (carbon black) particles having an average particle size of 250 nm. A colorant dispersant was prepared.

(Release agent dispersion)
100 parts by weight of paraffin wax (HNP0190, manufactured by Nippon Seiwa Co., Ltd., melting point 85 ° C.), 5 parts by weight of a cationic surfactant (Sanisol B50, manufactured by Kao Corporation) and 240 parts by weight of ion-exchanged water are mixed. Dispersion treatment was carried out for 10 minutes in a round stainless steel flask using a homogenizer (Ultra Turrax T50, manufactured by IKA). Furthermore, a release agent dispersion liquid was prepared by dispersing the release agent particles having an average particle diameter of 550 nm by dispersing with a pressure discharge type homogenizer.

(Toner mother particles)
234 parts by mass of the resin fine particle dispersion obtained above, 30 parts by mass of the colorant dispersion, 40 parts by mass of the release agent dispersion, 0.5 parts by mass of polyaluminum hydroxide (Paho2S, manufactured by Asada Chemical Co., Ltd.) and ion exchange Mix 600 parts by weight of water, disperse using a homogenizer (Ultra Turrax T50, manufactured by IKA) in a round stainless steel flask, and then heat to 40 ° C while stirring the flask in a heating oil bath. did. After maintaining at 40 ° C. for 30 minutes, it was confirmed that aggregated particles having a D50 of 4.5 μm were produced. Furthermore, when the temperature of the oil bath for heating was raised and held at 56 ° C. for 1 hour, D50 was 5.3 μm. Thereafter, 26 parts by mass of the resin fine particle dispersion was added to the dispersion containing the aggregate particles, and then the temperature of the heating oil bath was maintained at 50 ° C. for 30 minutes. After adding 1N sodium hydroxide to the dispersion containing the aggregate particles and adjusting the pH of the system to 5.0, the stainless steel flask is sealed and heated to 95 ° C. while continuing to stir using a magnetic seal. And held for 4 hours. After cooling, the toner base particles were filtered off, washed four times with ion exchange water, and then freeze-dried to obtain toner base particles. The toner mother particles had a D50 of 5.8 μm and an average shape factor ML ² / A of 109.

<Preparation of carrier>
First, 14 parts by mass of toluene, 2 parts by mass of a styrene-methacrylate copolymer (component ratio 90/10), and 0.2 parts by mass of carbon black (R330, manufactured by Cabot Corporation) were stirred for 10 minutes with a stirrer and dispersed. A coating solution was prepared. Next, the coating solution and 100 parts by mass of ferrite particles (average particle size 50 μm) are put in a vacuum degassing 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 of 10 ¹¹ Ωcm when an applied electric field of 1000 V / cm.

<Developer 1>
1 part by mass of rutile type titanium oxide (average particle size: 20 nm, surface treatment: n-decyltrimethoxylane treatment), silica (particle size: 40 nm, surface treatment) with respect to 100 parts by mass of the toner base particles obtained above. : Silicone oil treatment, particle production method: gas phase oxidation method) 2.0 parts by mass, hydrophobic silica (trade name: Aerosil, particle size: 45 nm, surface treatment: silicon oil treatment) 1 part by mass, and higher fatty acid 0.3 parts by mass of alcohol (higher fatty acid alcohol having a molecular weight of 700) and zinc stearate, pulverized by a jet mill at a mass ratio of 5: 1, and having an average particle size of 8.0 μm, is further mixed. Was blended with a 5 L Henschel mixer at a peripheral speed of 30 m / s × 15 minutes. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to obtain a toner (composite particle). Next, 100 parts by mass of the carrier obtained above was added to 5 parts by mass of the toner (composite particles), and the mixture was stirred at 40 rpm for 20 minutes using a V-blender. Thereafter, developer 1 was obtained by sieving with a sieve having an opening of 212 μm.

<Developer 2>
1 part by mass of rutile type titanium oxide (average particle size: 20 nm, surface treatment: n-decyltrimethoxylane treatment), silica (particle size: 40 nm, surface treatment) with respect to 100 parts by mass of the toner base particles obtained above. : Silicone oil treatment, particle production method: gas phase oxidation method) 2.0 parts by mass, hydrophobic silica (trade name: Aerosil, particle size: 45 nm, surface treatment: silicon oil treatment) 1 part by mass, fluorine-containing cerium oxide (Fluorine content: 1.0% by mass, average particle size: 0.7 μm) 0.5 parts by mass, and higher fatty acid alcohol (higher fatty acid alcohol having a molecular weight of 700) and zinc stearate in a mass ratio of 5: 1 The mixture was pulverized with a jet mill at a ratio of 0.3 parts by mass with an average particle size of 8.0 μm, and the mixture was further blended with a 5 L Henschel mixer at a peripheral speed of 30 m / s × 15 minutes. Was Tsu. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to obtain a toner (composite particle). Next, 100 parts by mass of the carrier obtained above was added to 5 parts by mass of the toner (composite particles), and the mixture was stirred at 40 rpm for 20 minutes using a V-blender. Thereafter, developer 2 was obtained by sieving with a sieve having an opening of 212 μm.

<Developer 3>
1 part by mass of rutile type titanium oxide (average particle size: 20 nm, surface treatment: n-decyltrimethoxylane treatment), silica (particle size: 40 nm, surface treatment) with respect to 100 parts by mass of the toner base particles obtained above. : Silicone oil treatment, particle production method: gas phase oxidation method) 2.0 parts by mass, hydrophobic silica (trade name: Aerosil, particle size: 45 nm, surface treatment: silicon oil treatment) 1 part by mass, fluorine-containing cerium oxide (Fluorine content: 0.5% by mass, average particle size: 0.7 μm) 0.5 parts by mass, and higher fatty acid alcohol (higher fatty acid alcohol having a molecular weight of 700) and zinc stearate in a mass ratio of 5: 1 The mixture was pulverized with a jet mill at a ratio of 0.3 parts by mass with an average particle size of 8.0 μm, and the mixture was further blended with a 5 L Henschel mixer at a peripheral speed of 30 m / s × 15 minutes. Was Tsu. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to obtain a toner (composite particle). Next, 100 parts by mass of the carrier obtained above was added to 5 parts by mass of the toner (composite particles), and the mixture was stirred at 40 rpm for 20 minutes using a V-blender. Thereafter, developer 3 was obtained by sieving with a sieve having an opening of 212 μm.

<Developer 4>
1 part by mass of rutile type titanium oxide (average particle size: 20 nm, surface treatment: n-decyltrimethoxylane treatment), silica (particle size: 40 nm, surface treatment) with respect to 100 parts by mass of the toner base particles obtained above. : Silicone oil treatment, particle production method: gas phase oxidation method) 2.0 parts by mass, hydrophobic silica (trade name: Aerosil, particle size: 45 nm, surface treatment: silicon oil treatment) 1 part by mass, cerium oxide (average) (Particle size: 0.7 μm) 0.5 parts by mass and higher fatty acid alcohol (higher fatty acid alcohol having a molecular weight of 700) and zinc stearate were pulverized by a jet mill at a mass ratio of 5: 1, and an average particle size of 8 0.3 parts by mass of the mixture having a thickness of 0.0 μm was mixed, and the mixture was further blended with a 5 L Henschel mixer at a peripheral speed of 30 m / s × 15 minutes. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to obtain a toner (composite particle). Next, 100 parts by mass of the carrier obtained above was added to 5 parts by mass of the toner (composite particles), and the mixture was stirred at 40 rpm for 20 minutes using a V-blender. Then, developer 4 was obtained by sieving with a sieve having an opening of 212 μm.

<Developer 5>
1 part by mass of rutile type titanium oxide (average particle size: 20 nm, surface treatment: n-decyltrimethoxylane treatment), silica (particle size: 40 nm, surface treatment) with respect to 100 parts by mass of the toner base particles obtained above. : Silicone oil treatment, particle production method: gas phase oxidation method) 2.0 parts by mass, hydrophobic silica (trade name: Aerosil, particle size: 45 nm, surface treatment: silicon oil treatment) 1 part by mass, fluorine-containing cerium oxide (Fluorine content: 12% by mass, average particle size: 0.7 μm) 0.5 parts by mass, and higher fatty acid alcohol (higher fatty acid alcohol having a molecular weight of 700) and zinc stearate in a ratio of 5: 1 by mass 0.3 parts by mass of pulverized with a jet mill and having an average particle size of 8.0 μm was mixed, and the mixture was further blended with a 5 L Henschel mixer at a peripheral speed of 30 m / s × 15 minutes. It was. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to obtain a toner (composite particle). Next, 100 parts by mass of the carrier obtained above was added to 5 parts by mass of the toner (composite particles), and the mixture was stirred at 40 rpm for 20 minutes using a V-blender. Thereafter, developer 5 was obtained by sieving with a sieve having an opening of 212 μm.

<Developer 6>
1 part by mass of rutile type titanium oxide (average particle size: 20 nm, surface treatment: n-decyltrimethoxylane treatment), silica (particle size: 40 nm, surface treatment) with respect to 100 parts by mass of the toner base particles obtained above. : Silicone oil treatment, particle production method: gas phase oxidation method) 2.0 parts by mass, hydrophobic silica (trade name: Aerosil, particle size: 45 nm, surface treatment: silicon oil treatment) 1 part by mass, fluorine-containing cerium oxide (Fluorine content: 0.5% by mass, average particle size: 0.7 μm) 15 parts by mass, and higher fatty acid alcohol (higher fatty acid alcohol having a molecular weight of 700) and zinc stearate in a ratio of 5: 1 by mass 0.3 parts by mass of pulverized with a jet mill and having an average particle size of 8.0 μm was mixed, and the mixture was further blended with a 5 L Henschel mixer at a peripheral speed of 30 m / s × 15 minutes. It was. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to obtain a toner (composite particle). Next, 100 parts by mass of the carrier obtained above was added to 5 parts by mass of the toner (composite particles), and the mixture was stirred at 40 rpm for 20 minutes using a V-blender. Thereafter, developer 6 was obtained by sieving with a sieve having an opening of 212 μm.

<Production of photoconductor>
(Photoreceptor 1)
First, a 84 mmφ cylindrical aluminum base material subjected to a honing treatment was prepared. Next, 20 parts by mass of a zirconium compound (trade name: Orgatics ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), 2.5 parts by mass of a silane compound (trade name: A1100, manufactured by Nihon Unicar Co., Ltd.), polyvinyl butyral resin (trade name: 2.5 parts by mass of Eslex BM-S (manufactured by Sekisui Chemical Co., Ltd.) and 45 parts by mass of butanol were mixed to obtain a coating solution for forming an undercoat layer. This coating solution was dip-coated on an aluminum substrate and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer of 1.5 μm.

  Next, 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 is 1 1 part by mass and 1 part by mass of polyvinyl butyral (trade name: ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 100 parts by mass of n-butyl acetate are further mixed with glass beads for 1 hour with a paint shaker and dispersed. Thus, a coating solution for forming a charge generation layer was obtained. This coating solution was dip-coated on the undercoat layer 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, 2 parts by mass of the charge transport material represented by the following formula (CT-1) and 2.5 masses of the polymer compound having a structural unit represented by the following formula (B-1) (viscosity average molecular weight: 56000). Part and 20 parts by mass of chlorobenzene were mixed to obtain a coating solution for forming a charge transport layer.

  This coating solution was applied onto the charge generation layer by a dip coating method, and heated at 130 ° C. for 45 minutes to form a charge transport layer having a thickness of 23 μm. In this way, the photoreceptor in which the charge generation layer and the charge transport layer are formed on the aluminum base material is referred to as “photoreceptor 1”.

(Photoreceptor 2)
First, a photoreceptor 1 was prepared in the same manner as described above. Next, 2.5 parts by mass of methyltrimethoxysilane, 0.3 parts by mass of colloidal silica, 0.5 parts by mass of Me (MeO) ₂ —Si— (CH ₂ ) ₄ —Si—Me (OMe) ₂ , (hepta Decafluoro-1,1,2,2-tetrahydrodecyl) methyldimethoxysilane (0.1 part by mass) and hexamethylcyclotrisiloxane (0.3 part by mass) were dissolved in methyl alcohol (5 parts by mass). To this solution, 0.5 part by mass of an ion exchange resin (Amberlyst 15E, manufactured by Rohm and Haas) was added, and the protective group was exchanged for 24 hours by stirring at room temperature.

Thereafter, 10 parts by mass of n-butanol and 0.3 parts by mass of distilled water were added to this solution, followed by hydrolysis for 15 minutes. 0.1 parts by mass of aluminum trisacetylacetonate (Al (aqaq) ₃ ), 0.1 parts by mass of acetylacetone, 3,5-di-t with respect to the solution obtained by decanting the ion exchange resin from the hydrolyzed product 0.4 parts by mass of -butyl-4-hydroxytoluene (BHT) and 2 parts by mass of a compound represented by the following formula (CT-2) were added to obtain a coating solution for forming a protective layer. This coating solution was applied onto the charge transport layer of the photoreceptor 1 by a dip coating method and air-dried at room temperature for 30 minutes. Then, it hardened by heat-processing at 170 degreeC for 1 hour, and formed the protective layer with a film thickness of about 3.5 micrometers. This photoreceptor was designated as photoreceptor 2.

(Photoreceptor 3)
First, a photoreceptor 1 was prepared in the same manner as described above. Next, 2 parts by mass of the compound represented by the following formula (CT-3) and 2 parts by mass of the compound represented by the following formula (C-1) were mixed with 5 parts by mass of isopropyl alcohol, 3 parts by mass of tetrahydrofuran and 0. It was dissolved in 3 parts by mass of a mixed solvent. To this solution, 0.05 part by mass of an ion exchange resin (Amberlyst 15E, manufactured by Rohm and Haas) was added, and the mixture was stirred at room temperature for 24 hours for hydrolysis.

Thereafter, 0.04 parts by mass of aluminum trisacetylacetonate (Al (aqaq) ₃ ) and polyvinyl butyral (trade name: ESREC BX-) with respect to 2 parts by mass of the solution obtained by filtering and separating the ion exchange resin from the hydrolyzed product. 1 part by mass of L, manufactured by Sekisui Chemical Co., Ltd. was added to obtain a coating solution for forming a protective layer. This coating solution was applied onto the charge transport layer of the photoreceptor 1 by a dip coating method and dried with hot air at 170 ° C. for 1 hour to form a protective layer having a thickness of 4.5 μm. This photoreceptor was designated as Photoreceptor 3.

(Photoreceptor 4)
First, a photoreceptor 1 was prepared in the same manner as described above. Next, 5 parts by mass of a compound represented by the following formula (CT-4), 6 parts by mass of a resol type phenol resin (trade name: PL-2211, manufactured by Gunei Chemical Co., Ltd.), and 0.03 parts by mass of methylphenylpolysiloxane Was dissolved in 10 parts by mass of isopropyl alcohol to obtain a coating solution for forming a protective layer. This coating solution was applied on the charge transport layer of the photoreceptor 1 by a ring-type dip coating method and dried at 160 ° C. for 45 minutes to form a protective layer having a thickness of 4.0 μm. This photoreceptor was designated as Photoreceptor 4.

(Photoreceptor 5)
First, a photoreceptor 1 was prepared in the same manner as described above. Next, 5 parts by mass of a compound represented by the following formula (CT-5), 6 parts by mass of a resol type phenol resin (trade name: PL-2211, manufactured by Gunei Chemical Co., Ltd.), and 0.03 parts by mass of methylphenylpolysiloxane Was dissolved in 10 parts by mass of isopropyl alcohol to obtain a coating solution for forming a protective layer. This coating solution was applied on the charge transport layer of the photoreceptor 1 by a ring-type dip coating method and dried at 160 ° C. for 45 minutes to form a protective layer having a thickness of 4.0 μm. This photoreceptor was designated as photoreceptor 5.

(Photoreceptor 6)
First, a photoreceptor 1 was prepared in the same manner as described above. Next, 5 parts by mass of a compound represented by the following formula (CT-6), 6 parts by mass of a resol type phenol resin (trade name: PL-2211, manufactured by Gunei Chemical Co., Ltd.), and 0.03 parts by mass of methylphenylpolysiloxane Was dissolved in 10 parts by mass of isopropyl alcohol to obtain a coating solution for forming a protective layer. This coating solution was applied on the charge transport layer of the photoreceptor 1 by a ring-type dip coating method and dried at 160 ° C. for 45 minutes to form a protective layer having a thickness of 4.0 μm. This photoreceptor was designated as photoreceptor 6.

(Examples 1-20, Comparative Examples 1-10)
The above photoreceptors 1 to 6 and developers 1 to 6 are combined as shown in Tables 54 and 55 below, and have the same configuration as the image forming apparatus shown in FIG. 9 (however, the lubricant supply device 31 in the figure). The transfer devices 40 and 42 were mounted on a full-color laser printer having a roll shape (BTR) (Fuji Xerox Co., Ltd., “Docu Center Color 500”, with an intermediate transfer member). Next, a continuous print test of 500,000 sheets was performed on A4 paper in an environment of high temperature and high humidity (30 ° C., 80% RH). After this test, the surface of the photoreceptor was observed, and then a full-scale halftone output test of 20% density was performed on A3 paper, and filming, image flow, and density unevenness were evaluated. These evaluations were performed according to the following criteria.
<Filming>
A: No adhesion is confirmed on the surface of the photoconductor (the output image quality is very good and no adhesion is observed by observation with a laser microscope).
B: Adhesion on the surface of the photoconductor is not visually confirmed (output image quality is good, but adhesion is observed by observation with a laser microscope)
C: It can be visually confirmed that a semi-transparent object is adhered to the surface of the photosensitive member (the output image quality is a level at which there is no practical problem)
D: brown adhesion on the surface of the photoreceptor can be visually confirmed (a level causing a defect in image quality)
<Image flow>
A: White spots and image flow are not confirmed in the output image (brightness is not confirmed by observation with a high-power CCD camera with fine lines)
B: White spots and image flow are not confirmed in the output image (the thin line is confirmed to be thinned by observation with a high magnification CCD camera)
C: A slight decrease in density (white spots) is confirmed in the output image, but there is no problem in practical use. D: The output image causes a decrease in density and white spots are confirmed <density unevenness>
A: Density unevenness is not confirmed in the output image (very good)
B: Slight density unevenness is confirmed in the output image, but there is no practical problem. Level C: A density difference is confirmed in the output image.

In addition, after 500,000 continuous printing tests on A4 paper performed in the same manner as described above, an image of 100% density on the entire surface of A3 paper is output untransferred for 10 sheets under low temperature and low humidity (10 ° C, 10% RH). Cleaning properties were evaluated. The cleaning property was evaluated according to the following criteria.
<Cleanability>
A: No toner slippage is confirmed even with an output of 20 sheets B: No toner slippage is confirmed C: Toner slipping is partially observed, but there is no practical problem.
D: Toner slippage is seen over the entire surface

Also, instead of the full color laser printer (Fuji Xerox Co., Ltd., “Docu Center Color 500”, with intermediate transfer member), a monochrome laser printer (Fuji Xerox Co., Ltd., “Docu Center 550”, without intermediate transfer member) is used. In a high temperature and high humidity (30 ° C., 80% RH) environment, a continuous print test of 500,000 sheets was performed on A4 paper. After this test, a 20% density full-scale halftone output test was performed on A3 paper to evaluate talc depression. The talc depression was evaluated according to the following criteria.
<Talc Depression>
A: White spots and image flow are not confirmed in the output image (brightness is not confirmed by observation with a high-power CCD camera with fine lines)
B: White spots and image flow are not confirmed in the output image (the thin line is confirmed to be thinned by observation with a high magnification CCD camera)
C: A slight decrease in density (white spots) is confirmed in the output image, but there is no practical problem. Level D: The output image has a density drop, and white spots are confirmed.

  The results obtained are shown in Tables 54 and 55.

  As shown in Tables 54 and 55, in Examples 1 to 20, filming, image flow, density unevenness, poor cleaning, and talc depletion are all sufficiently suppressed even after output of 500,000 sheets. It was confirmed that high image quality can be maintained. Therefore, according to the present invention, it is possible to realize an image forming apparatus that can achieve all of high image quality, long life, and high reliability.

  Furthermore, in order to confirm a more effective combination for higher image quality, longer life, and higher reliability from the present example, the combination of Examples 1 to 20 was evaluated under more severe conditions. It was. In the 500,000 sheet output test of Examples 1 to 20, the above characteristics were evaluated in the same manner except that the number of output sheets was 1 million. Further, in this test, the wear rate of the electrophotographic photosensitive member was also evaluated. The wear rate is determined by measuring the film thickness of each electrophotographic photosensitive member at the beginning and the film thickness of each electrophotographic photosensitive member after 1500 kcycles for each image forming apparatus. "Thickness" (hereinafter referred to as "wear") was calculated. Further, the wear rate [nm / kcycle] of each electrophotographic photosensitive member was calculated based on this wear margin. Here, 1 kcycle means 1000 cycles. The results obtained are shown in Table 56.

As shown in Table 56, a toner in which 0.5 parts by mass of fluorine-containing cerium oxide having a fluorine content of 0.5 or 1.0% by mass with respect to 100 parts by mass of toner base particles is blended with a toner having a crosslinked structure. In Examples 1 to 6 in combination with a photoreceptor having a surface layer, filming, image flow, density unevenness, poor cleaning, and talc depletion are all sufficiently suppressed even after the output test of 1 million sheets. I found out. Furthermore, it was confirmed that the wear rate was extremely small. Also in Examples 13 to 20 in which a photoreceptor having an outermost surface layer containing a resol type phenol resin and a compound represented by the above formula (V) or (VI) and a toner containing fluorine-containing cerium oxide are combined. It was found that filming, image flow, density unevenness, poor cleaning and talc depletion were all sufficiently suppressed even after the output test of 1 million sheets. Further, in Examples 13 to 15 and Examples 17 to 19 using the developer 2, 3 or 5, it was confirmed that the wear rate was extremely small.

1 is a schematic diagram showing a preferred embodiment of an image forming apparatus of the present invention. 1 is a schematic cross-sectional view showing a preferred embodiment of an electrophotographic photosensitive member according to the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member according to the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member according to the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member according to the present invention. FIG. 6 is a schematic cross-sectional view showing another preferred embodiment of the electrophotographic photosensitive member according to the present invention. It is a schematic diagram which shows other suitable embodiment of the image forming apparatus of this invention. It is a schematic diagram which shows other suitable embodiment of the image forming apparatus of this invention. It is a schematic diagram which shows other suitable embodiment of the image forming apparatus of this invention. It is a schematic diagram showing a preferred embodiment of the process cartridge of the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Electrophotographic photosensitive member, 2 ... Conductive support body, 3 ... Photosensitive layer, 4 ... Undercoat layer, 5 ... Charge generation layer, 6 ... Charge transport layer, 7 ... Protective layer, 8 ... Single layer type photosensitive layer, 21 ... 22 charging device, 24 ... developing device, 27 ... cleaning device, 30 ... exposure device, 40 ... transfer device, 50 ... intermediate transfer member, 100, 110, 120, 130 ... image forming device, 300 ... process cartridge.

Claims (8)

An electrophotographic photosensitive member having a conductive support and a photosensitive layer formed on the conductive support, charging means for charging the electrophotographic photosensitive member, and exposing the charged electrophotographic photosensitive member to electrostatic latent exposing means for forming an image, developing means for developing to form a toner image the electrostatic latent image with a toner, the toner remaining the toner image onto a transfer means and the electrophotographic photosensitive member is transferred onto a transfer medium In an image forming apparatus including a cleaning device to be removed ,
The photosensitive layer has, on the farthest side from the conductive support, an outermost surface layer having a charge transporting ability and a crosslinked structure;
The image forming apparatus, wherein the toner includes toner particles and fluorine-containing cerium oxide fine particles.   The image forming apparatus according to claim 1, wherein a fluorine content of the fluorine-containing cerium oxide fine particles is 0.1 to 10% by mass.   The image forming apparatus according to claim 1, wherein the toner contains 0.3 to 10 parts by mass of the fluorine-containing cerium oxide fine particles with respect to 100 parts by mass of the toner particles.   The image forming apparatus according to claim 1, wherein the fluorine-containing cerium oxide fine particles have a volume average particle diameter of 0.03 to 6 μm.   The outermost surface layer contains a phenol derivative having a methylol group and a charge transport material having at least one selected from a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, a thiol group, and an amino group. The image forming apparatus according to claim 1, wherein the image forming apparatus is an image forming apparatus. The said outermost surface layer contains the phenol derivative which has a methylol group, and the charge transport material shown by the following general formula (V) or (VI), The any one of Claims 1-4 characterized by the above-mentioned. The image forming apparatus described in 1.

[In the formula (V), F represents an n7-valent organic group having a hole transporting property, T represents a divalent group, Y represents an oxygen atom or a sulfur atom, and R ⁴ , R ⁵ and R ⁶ are independent of each other. Represents a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m1 represents 0 or 1, and n7 represents an integer of 1 to 4, respectively. However, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom. ]

[In the formula (VI), F represents an n8-valent organic group having a hole transport property, T represents a divalent group, R ⁸ represents a monovalent organic group, m2 represents 0 or 1, and n8 represents 1 Integers of ~ 4 are shown respectively. ] An electrophotographic photosensitive member having a conductive support and a photosensitive layer formed on the conductive support, a charging device for charging the electrophotographic photosensitive member, and exposing the charged electrophotographic photosensitive member to electrostatic an exposure device for forming a latent image, the electrostatic latent image developing to a developing device Ru to form a toner image by toner, and least well out of the cleaning device that removes the toner remaining on the electrophotographic photoconductor a process cartridge comprising, before Symbol developing device,
Before SL photosensitive layer farthest from the conductive support, having a top surface layer and having a crosslinked structure having a charge transporting ability,
The toner, the process cartridge to the toner particles, and a fluorine-containing cerium oxide particles, wherein the early days including the. An outermost surface layer comprising a conductive support and a photosensitive layer formed on the conductive support, the outermost surface layer having a charge transporting function and having a cross-linking structure on the side of the photosensitive layer farthest from the conductive support. An electrophotographic photosensitive member preparing step for preparing the provided electrophotographic photosensitive member;
A toner preparation step of preparing a toner including toner particles and fluorine-containing cerium oxide fine particles;
A charging step for charging the electrophotographic photoreceptor;
Exposing the charged electrophotographic photosensitive member to form an electrostatic latent image; and
A developing step of developing the electrostatic latent image with the toner to form a toner image;
A transfer step of transferring the toner image to a transfer medium;
A cleaning step of removing toner remaining on the electrophotographic photosensitive member;
An image forming method comprising:

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