JP4322612B2 - Photoconductor, image forming apparatus using the same, and process cartridge for image forming apparatus - Google Patents

Description

  The present invention relates to a photoreceptor having high durability and realizing high image quality. In addition, the present invention relates to an image forming apparatus using the photosensitive member and a process cartridge for the image forming apparatus.

  In recent years, there has been a remarkable development in information processing system machines using electrophotography. In particular, laser printers and digital copying machines that convert information into digital signals and record information using light have significantly improved print quality and reliability. Furthermore, they have been applied to laser printers or digital copiers capable of full-color printing by fusing with high-speed technology. From such a background, it is particularly important to achieve both high image quality and high durability as a required photoreceptor function.

  As photoconductors used in these electrophotographic laser printers, digital copiers, etc., those using organic photosensitive materials are generally widely applied for reasons such as cost, productivity and non-pollution. Yes. Organic electrophotographic photoreceptors include photoconductive resins represented by polyvinylcarbazole (PVK), charge transfer complex types represented by PVK-TNF (2,4,7-trinitrofluorenone), phthalocyanine-binders In addition, there are known a pigment dispersion type represented by (2) and a function separation type photoreceptor using a combination of a charge generation material and a charge transport material.

  However, organic photoreceptors are generally soft because the photosensitive layer is mainly composed of a low molecular charge transport material and an inert polymer, and when used repeatedly in an electrophotographic process, they are mechanically driven by a development system or a cleaning system. There is a drawback that wear is likely to occur due to the load. As film removal of the photosensitive layer progresses, there is a strong tendency to promote a decrease in charging potential of the photosensitive member, deterioration of photosensitivity, background contamination due to scratches on the surface of the photosensitive member, reduction in image density, or deterioration in image quality. Abrasion resistance was cited as a major issue. Further, in recent years, with the increase in the speed of an electrophotographic apparatus or the reduction in the diameter of the photoreceptor accompanying the downsizing of the apparatus, it has become a more important issue to improve the durability of the photoreceptor.

  As a method for realizing high durability of the photoconductor, a method of providing a protective layer on the outermost surface of the photoconductor and imparting lubricity to the protective layer, curing, or adding a filler is widely known. . In particular, the method of containing a filler in the protective layer is one of the effective methods for enhancing the durability of the photoreceptor. However, when a filler having high electrical insulation is contained, the resistance becomes high and the residual potential is remarkably increased. These increases in residual potential are greatly affected by an increase in resistance and an increase in charge trap sites caused by the inclusion of the filler. On the other hand, when the conductive filler is used, the resistance decreases and the effect of the increase in the residual potential is relatively small, but the so-called image blurring that blurs the outline of the image occurs, and the effect on the image quality appears strongly. .

  Therefore, in the prior art, a highly insulating filler is difficult to use, and a low insulating filler that is relatively less affected by residual potential is used, and a drum heater that heats the photoreceptor against image blur caused by the filler. A means for mounting is used. Although the occurrence of image blur can be suppressed by heating the photoconductor, there are many problems remaining in mounting a drum heater, such as a significant increase in power consumption and an increase in start-up time.

  On the other hand, the increase in the residual potential often seen when using a highly insulating filler leads to a high bright portion potential in the electrophotographic apparatus, leading to a decrease in image density and gradation. In order to compensate for this, it is necessary to increase the dark part potential. However, if the dark part potential is increased, the electric field strength increases, which not only causes image defects such as background stains, but also reduces the life of the photoreceptor. Connected.

  As a method for suppressing the increase in residual potential in the prior art, a method using a protective layer as a photoconductive layer is disclosed (Japanese Patent Publication No. 44-834, Japanese Patent Publication No. 43-16198, Japanese Patent Publication No. 49-10258). Publication). However, since the amount of light reaching the photosensitive layer is reduced by the absorption of light by the protective layer, there arises a problem that the sensitivity of the photosensitive member is lowered, and the effect is slight.

  On the other hand, a method has been disclosed in which the protective layer becomes substantially transparent and the residual potential accumulation is suppressed by setting the average particle size of the metal or metal oxide contained as the filler to 0.3 μm or less ( JP-A-57-30846). Although this method has an effect of suppressing an increase in the residual potential, the effect is insufficient, and the actual situation is that the problem has not been solved. This is because the increase in the residual potential caused when the filler is contained is more likely to be caused by charge traps and filler dispersibility due to the presence of the filler than the charge generation efficiency. Even if the average particle size of the filler is 0.3 μm or more, it is possible to obtain transparency by increasing the dispersibility, and even if the average particle size is 0.3 μm or less, the filler is considerably aggregated. If this is the case, the transparency of the film will be reduced.

  In addition, a method of suppressing an increase in residual potential while providing mechanical strength by a method in which a charge transport material is contained in a protective layer together with a filler is disclosed (JP-A-4-281461, JP-A-2002-207308). Gazette, Unexamined-Japanese-Patent No. 2002-268257 ... patent documents 1-3). The addition of the charge transport material to the protective layer is effective in improving the charge mobility and is an effective method for reducing the residual potential. However, if the increase in residual potential caused by the inclusion of filler is attributed to an increase in resistance due to the presence of filler or an increase in charge trapping sites, it increases the charge mobility and increases the residual potential. There is a limit to the suppression. Accordingly, the thickness of the protective layer and the filler content must be reduced, and the actual situation is that the required durability has not been satisfied.

  Furthermore, a method for suppressing the increase in residual potential by applying a surface treatment to the filler contained in the protective layer is disclosed (Japanese Patent Laid-Open No. 2000-292958, Japanese Patent Laid-Open No. 6-258857, ... Patent) References 4, 5). These methods are thought to suppress the increase in residual potential by uniformly treating the filler and improving the dispersibility of the filler and the environmental stability of the resistance. However, even if these surface treatment methods are used, the effects of the increase in resistance and the increase in charge trap sites due to the presence of the filler cannot be suppressed, and the substantial increase in residual potential has not been solved. .

  As another means for suppressing the increase in the residual potential, a method of adding a Lewis acid or the like in the protective layer (Japanese Patent Laid-Open No. 53-133444), a method of adding an organic protonic acid to the protective layer (Japanese Patent Laid-Open No. 55-55). No. 157748), a method of containing an electron-accepting substance (JP-A-2-4275), and a method of containing a polycarboxylic acid derivative having an acid value of 10 to 400 (mgKOH / g) as a dispersant (JP-A No. No. 2002-268257). These methods improve the charge injectability at the protective layer / charge transport layer interface, and because the low resistance portion is formed in the protective layer, the charge easily reaches the surface. It is believed that Although this method has an effect of reducing the residual potential, it tends to cause image blur, and has a side effect in which the influence on the image is noticeable. Moreover, since it becomes easy to cause the dispersibility fall of a filler when adding an organic acid, the effect is not enough and it is the actual condition that it has not resulted in the solution of a subject.

  In addition to the conductivity of the filler, there is a tendency to promote the occurrence of image blur by increasing the wear resistance of the photoreceptor. This is thought to be due to the fact that the charge transport material contained on the surface of the photoreceptor is decomposed or altered by being repeatedly charged, and this causes a reduction in resistance, thereby increasing image blur. When no filler is added, degradation products that deteriorate due to an increase in the wear amount of the photosensitive member are easily removed, and the influence of image blurring is small.However, the removal of the photosensitive member is improved by improving the abrasion resistance of the photosensitive member. This is considered to be caused by the fact that it is difficult to remain on the surface of the photoreceptor.

  Methods for reducing the effect of charge transport material deterioration by adding an antioxidant have been proposed (Japanese Patent Laid-Open Nos. 2001-51439, 2002-82469, and 2002-207308). Issue gazette). However, many antioxidants cause a significant increase in residual potential upon addition. Increasing the amount added to suppress image blur causes a significant increase in residual potential, and minimizing the effect of increasing the residual potential results in insufficient image blur suppression effects and high image quality has not been realized. It was.

  In the electrophotographic photosensitive member containing a filler for high durability, in order to achieve high image quality, the dispersibility of the filler is improved, and the electric charge is not hindered by the filler in the protective layer, It is important that the charge reaches the surface of the photoreceptor linearly. Further, it is necessary to simultaneously suppress the increase in residual potential and image blur caused by the filler. Furthermore, if the image blur caused by the deterioration of the charge transport material caused by the improvement of the wear resistance is not solved at the same time, both the wear resistance and the high image quality cannot be achieved.

  However, effective means that can solve them simultaneously have not been found, and when filler is included in the outermost surface layer of the photoreceptor for high durability, the effect of image blur and residual potential rise appears strongly, The reality is that there are still issues with high image quality. Furthermore, in order to reduce those influences, it is necessary to mount a drum heater, which is a real obstacle to downsizing the apparatus and reducing power consumption.

JP-A-4-281461 JP 2002-207308 A JP 2002-268257 A JP 2000-292958 A JP-A-6-258857

The object of the present invention is to improve the wear resistance, which is mechanical durability, and to suppress the image deterioration due to the increase in residual potential or the occurrence of image blurring, and high image quality even for long-term repeated use. It is an object of the present invention to provide a photoconductor capable of stably obtaining an image.
Another object of the present invention is to eliminate the need for replacement of the photosensitive member by using the above-described photosensitive member, and to realize downsizing of the apparatus associated with high-speed printing or a reduction in the diameter of the photosensitive member. An object of the present invention is to provide an image forming apparatus capable of stably obtaining a quality image and a process cartridge for the image forming apparatus.

  As a result of intensive studies, the present inventors have found that the above-mentioned problems can be achieved by including a plurality of charge transport materials including a specific filler and a specific amine compound in the outermost surface layer of the photoreceptor. As a result, the present invention has been completed.

That is, according to the present invention, the following (1) to ( 9 ) are provided.
(1) A surface layer of a photoreceptor having a photosensitive layer formed on a conductive support contains at least a surface-treated filler, a binder resin, and a plurality of charge transport materials, and the surface treatment is performed. The filler is a filler subjected to a surface treatment by applying an impact force by a jet airflow in a pulverizer and agitating while flowing the filler and the silane coupling agent, and at least one of the charge transport materials is A photoconductor characterized by being an amino compound having any one of a dialkylamino group, a dibenzylamino group, a benzylalkylamino group, and an alkylarylamino group.
(2) The photoconductor as described in (1) above, wherein a mixing ratio of the silane coupling agent to the filler is 0.01 to 10% by weight.
(3) The photoreceptor according to (1) or (2) , wherein the filler is α-alumina.
(4) Any one of (1) to (3) above, wherein a maximum difference in oxidation potential (Eox) among the plurality of charge transport materials is within a range of 0.2 (V vs. SCE) or less. The photoreceptor described in 1.
(5) The photoconductor according to any one of (1) to (4) , wherein at least one of the charge transport materials is a polymer charge transport material.
(6) An image forming apparatus comprising at least a charging unit, an image exposure unit, a developing unit, a transfer unit, and a photoconductor, wherein the photoconductor is the photoconductor according to any one of (1) to (5). An image forming apparatus characterized by being a body.
(7) The image formation as described in (6) above, wherein an electrostatic latent image is written on a photosensitive member by using an LD or LED as the image exposure means. apparatus.
(8) A process cartridge for an image forming apparatus, comprising at least one unit selected from a charging unit, an exposure unit, a developing unit, and a cleaning unit and a photoconductor, and is detachable from the main body of the image forming apparatus, A process cartridge for an image forming apparatus, wherein the photoconductor is the photoconductor according to any one of (1) to (5) .
(9) A method for producing a photoreceptor, wherein a surface layer of a photoreceptor having a photosensitive layer formed on a conductive support contains at least a surface-treated filler, a binder resin, and a plurality of charge transport materials. The filler that has been subjected to the surface treatment is a filler that has been subjected to a surface treatment by stirring the filler and the silane coupling agent in a pulverizer while applying an impact force by a jet air flow and causing the filler and the silane coupling agent to flow. A method for producing a photoreceptor, wherein at least one of the charge transport materials is an amino compound having any one of a dialkylamino group, a dibenzylamino group, a benzylalkylamino group, and an alkylarylamino group.

  In order to improve the abrasion resistance of a photoreceptor such as an electrophotographic photoreceptor, it is known that it is effective to form a protective layer containing a filler in the outermost surface layer of the photoreceptor, It has side effects that cause image quality degradation such as an increase in residual potential and occurrence of image blur. As a result of intensive studies, the present inventors have suppressed the increase in the residual potential at the same time as improving the wear resistance by including a filler subjected to surface treatment in the protective layer. One of the factors that made it possible to reduce the residual potential was that the polar surface, which is considered to be a charge trap site, was replaced with an organic functional group due to the modification of the filler surface. This is because the dispersibility of the filler is improved. In addition, the improved dispersibility of the filler is not limited to the effect of suppressing the increase in the residual potential, and further improvement in image quality is achieved by preventing the decrease in the writing light transmittance of the protective layer and the occurrence of uneven image density. In addition, it has various effects such as improved wear resistance and prevention of coating film defects.

  In addition, when fillers that have not been surface-treated are included, oxidizing gases such as ozone and NOx that are generated by electrification are likely to be adsorbed by the fillers, thereby reducing resistance and causing problems such as image flow. was there. However, in the present invention, the surface treatment is performed on the filler, thereby reducing the adsorption of the oxidizing gas and thereby suppressing the occurrence of image blur caused by the filler.

  However, ozone and NOx are known to cause degradation such as decomposition and alteration of the charge transporting material and binder resin constituting the photoreceptor. In particular, a photoconductor having improved wear resistance by containing a filler has a problem in that it is difficult to remove such deteriorated products, and it is rather easy to generate image blur due to the deteriorated products. In the present invention, at least one of the charge transport materials contains an amino compound having any one of a dialkylamino group, a benzylamino group, a benzylalkylamino group, and an alkylarylamino group, thereby suppressing deterioration of the charge transport material. It has become possible to suppress the effects of any image blur when filler is contained without affecting the increase in residual potential, and it has been found that both wear resistance and high image quality can be realized. It was.

  The reason for this is not clarified at the present time, but it is presumed that the substituted amino group contained in the structure effectively suppresses the generation of radical substances with respect to the oxidizing gas. Further, since these compounds also have a charge transport function, they themselves do not work as charge carrier traps, and electrical property deterioration such as increase in residual potential accompanying addition is hardly observed.

  The present invention, by satisfying the above-described configuration requirements, can achieve both high durability and high image quality, and can provide a photoreceptor that can stably obtain a high-quality image even for repeated use. Further, by using the photoconductor, it is possible to provide an image forming apparatus and a process cartridge for the image forming apparatus that can stably obtain a high-quality image even in repeated use.

  More specifically, according to the present invention, the wear resistance of the photoreceptor is improved by adding a filler to the surface layer of the photoreceptor. On the other hand, suppression of a significant increase in residual potential caused by the addition of the filler is achieved by subjecting the filler to a surface treatment such as a silane coupling treatment to reduce charge trap sites and improve dispersibility. Further, adsorption of ozone and NOx gas can be suppressed by surface treatment on the filler, and image blur due to ozone and NOx gas can also be suppressed. Furthermore, the effect of sedimentation is obtained by the surface treatment of the filler, whereby the transparency of the film is improved and an image having a high resolution with no image density unevenness can be obtained. In addition, by improving the coating properties, it is possible to improve the effect of suppressing the occurrence of coating film defects and the stability of the coating solution.

  However, this alone cannot suppress image blurring under high temperature and high humidity caused by deterioration of the charge transport material or binder resin due to charging. This influence is a side effect caused especially by increasing the wear resistance of the photoreceptor, and is caused because it is difficult to remove the deteriorated material. In the present invention, at least one of the plurality of charge transport materials contains an amino compound having any one of a dialkylamino group, a benzylamino group, a benzylalkylamino group, and an alkylarylamino group, so that the charge transport material and the binder resin are contained. It is possible to suppress the deterioration of the image and also to reduce the influence of ozone and NOx, thereby simultaneously suppressing the image blur under high temperature and high humidity. Since these amino compounds have a charge transport function, they have very little influence on the residual potential and are relatively easy to add in a large amount, so that they are very effective in suppressing image blur.

  That is, according to the present invention, it is possible to achieve both high durability and high image quality of a photoconductor, and to stably obtain a high-quality image over a long period of time, an image forming apparatus using the photoconductor, and image formation An apparatus process cartridge is provided.

  In the present invention, it is important to add a filler material subjected to surface treatment for the purpose of improving the wear resistance to the surface layer of the photoreceptor. Examples of the organic filler material include fluororesin powder such as polytetrafluoroethylene, silicone resin powder, a-carbon powder, etc., and inorganic filler material includes metal powder such as copper, tin, aluminum, indium, Titanium oxide, zinc oxide, zirconium oxide, iron oxide, chromium oxide, silica, tin oxide, alumina, zirconium oxide, indium oxide, antimony oxide, bismuth oxide, calcium oxide, tin oxide doped with antimony, tin-doped indium oxide And metal oxides such as tin fluoride, calcium fluoride, and aluminum fluoride, and inorganic materials such as potassium titanate and boron nitride. Among these fillers, the use of metal oxides from the viewpoint of processing efficiency and hardness is advantageous for improving wear resistance.

  Furthermore, as the filler that hardly causes image blurring, a filler having high electrical insulation is preferable, and titanium oxide, alumina, zinc oxide, zirconium oxide, and the like can be used particularly effectively. In addition, these fillers can be used alone or in combination of two or more. Among these fillers, α-type alumina, which has high insulation properties, high thermal stability, and high wear resistance, is a hexagonal close-packed structure, from the viewpoint of suppressing image blur and improving wear resistance. It is particularly useful.

  The average primary particle size of the filler is preferably 0.01 to 0.9 μm from the viewpoint of light transmittance and wear resistance of the surface layer. When the average primary particle size of the filler is less than 0.01 μm, it causes a decrease in wear resistance, a decrease in dispersibility, etc., and when it is greater than 0.9 μm, the sedimentation of the filler in the dispersion is promoted. In addition, toner filming may occur.

  As content of a filler, it is 0.1 to 50 weight%, Preferably it is 5 to 30 weight%. If it is less than 0.1% by weight, the wear resistance is not sufficient, but if it exceeds 50% by weight, the transparency may be impaired.

  Furthermore, these fillers are used after being surface-treated with at least one kind of surface treatment agent. This is effective for improvement of dispersibility, suppression of residual potential increase due to filler addition, and suppression of image blur due to filler. Lowering the dispersibility of the filler not only affects the increase in residual potential, but also lowers the transparency of the coating, causes defects in the coating, and lowers the wear resistance. There is a possibility that it will develop into a big problem that hinders the transformation.

As the surface treatment agent, conventionally known surface treatment agents such as titanate coupling agents, aluminum coupling agents, zircoaluminate coupling agents, higher fatty acids, aluminum stearate, and the like are conventionally used. Although it can be used, surface treatment using a silane coupling agent capable of stably suppressing an increase in residual potential is preferable. Examples of the silane coupling agent used here include the following.
For example, a silane coupling agent having 3-glycidoxypropyl group, 3-methacryloxypropyl group, p-styryl group, 3-acryloxypropyl group, 2- (3,4-epoxycyclohexyl) group, vinyl group, etc. Specifically, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ -Methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyl Trimethoxy Silane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and silylating agents such as chlorosilane, dimethyldichlorosilane, vinyldimethylchlorosilane, trichlorosilane, vinyltrichlorosilane Ester silanes such as trimethylmethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and silazanes such as hexamethyldisilazane, and siloxanes such as hexamethyldisiloxane, octamethylcyclotetrasiloxane, α, ω-dihydroxypolydimethyl Examples thereof include siloxane and dimethylpolysiloxysilazane.

  As the surface treatment method, a conventionally known method can be used. For example, the powder is dispersed in a solvent such as water or an organic solvent, and the surface treatment agent added in the solvent is adsorbed, or the surface treatment agent is used as a solvent. A method of coating the surface of the powder by adding it to the powder to be treated, a method of pulverizing a mixture of the powder and the surface treating agent using a ball mill, dissolving silicon oil in a solvent, After mixing and drying after adding to the body, the surface is treated by baking it, and the surface of the inorganic powder is a method of crosslinking polymerization of methylhydrogen polysiloxane using a ball mill in the presence of metal hydroxide In addition, a method is known in which a powder is surface-treated simultaneously with pulverization and mixing using a falling pulverizer such as an atomizer. However, these methods have problems in processing uniformity, discoloration or quality change, agglomeration, processing efficiency, contamination with foreign matters, and the like, and particularly when used in an electrophotographic photoreceptor, the residual potential is greatly affected. Therefore, it was very difficult to use.

  The surface treatment filler used in the present invention is preferably obtained by mixing a surface treatment agent and a filler, and applying a surface treatment to the mixture by applying an impact force due to a jet stream to the mixture. The surface of the filler is not contaminated with other substances, and the surface treatment agent can be uniformly adsorbed or bonded. It has been found that the photoreceptor containing the surface-treated filler obtained by this method can realize improvement of image quality and stabilization of quality over time by suppressing occurrence of residual potential and reducing aggregation.

  As a processing amount of a surface treating agent, 0.01 to 10 weight% is preferable with respect to a filler, and 0.1 to 5 weight% is more preferable. Excessive addition of surface treatment agent may cause an increase in residual potential due to an increase in unreacted substances and a decrease in wear resistance due to deterioration of film quality. If the addition amount is less than this, the surface treatment effect cannot be obtained. There is a possibility that the influence of residual potential and image blur increases. Details of these surface treatment methods are described in Japanese Patent Publication No. 6-59397.

  The surface-treated filler can be dispersed together with at least an organic solvent using a conventional method such as a ball mill, an attritor, a sand mill, or an ultrasonic wave. Among these, dispersion by a ball mill with less contamination of impurities from the outside is more preferable from the viewpoint of dispersibility. As the material of the media used, all media such as zirconia, alumina, and agate that have been used in the past can be used. However, alumina is particularly preferable from the viewpoint of filler dispersibility and residual potential reduction effect. More preferred. Zirconia has a large amount of media wear during dispersion, and the residual potential increases remarkably due to the mixing of these media. Furthermore, the dispersibility is greatly lowered by the mixing of the wear powder, and the sedimentation property of the filler is promoted. On the other hand, when alumina is used as a medium, it is worn at the time of dispersion, but the amount of wear is kept low and the influence of mixed wear powder on the residual potential is very small. Further, even if wear powder is mixed, there is little adverse effect on dispersibility. Therefore, it is more preferable to use alumina as a medium used for dispersion.

  These methods made it possible to suppress the increase in residual potential and image blur caused by the filler, but due to the increased wear resistance due to the addition of the filler, the charge deterioration of the charge transport material became apparent. It is not possible to suppress image blur caused by. Therefore, the charge transport material should contain a specific amino compound having a charge transport function, that is, an amino compound having at least one of a dialkylamino group, a dibenzylamino group, a benzylalkylamino group, and an alkylarylamino group in the structure. Thus, it was possible to suppress image blur caused by deterioration of the charge transport material without affecting the residual potential.

In addition, since the difference in oxidation potential (Eox) between these amino compounds and other charge transporting substances contained is 0.2 (V vs. SCE) or less, it has an effect on the residual potential. It was found that there is a remarkable suppression effect. The reason for this is considered to be that when there is a large difference in ionization potential of each charge transport material, the charge transport material itself causes a carrier trap site. The method for measuring the oxidation potential (Eox) of various charge transport materials, that is, the first oxidation half-wave potential is described below.
A substance to be measured is dissolved by adding a predetermined amount of acetonitrile and a supporting electrolyte such as tetrabutylammonium perchlorate or tetraethylammonium perchlorate to obtain a test solution. With respect to this test solution, the oxidation potential of the target substance can be measured by an electrochemical analysis means such as polarograph or cyclic voltammetry. For such electrochemical analysis, see A.A. J. et al. Bard, L .; R. He is familiar with books such as "Electrochemical Methods" by Faulkner published in 1980 by Wiley. Here, a dropping mercury electrode is used as a working electrode, a noble metal such as platinum or gold is used as a counter electrode, a saturated sweet potato electrode (SCE) is used as a reference electrode, and measurement can be performed by a potential scanning method using a potentiostat.

  Tables 1 to 5 show specific examples of these amino compounds and their oxidation potentials (Eox). However, the present invention is not limited to these compounds.

  The addition amount of these amino compounds is preferably 0.01 to 150% by weight with respect to the binder resin. If it is less than this, the resistance to oxidizing gas is insufficient, and if it is too much, the film strength is lowered and the wear resistance is deteriorated.

The photoreceptor of the present invention will be described below with reference to the drawings.
FIG. 1 is a cross-sectional view of a photoconductor of the present invention, and a photosensitive layer 33 mainly composed of a charge generation material and a charge transport material is provided on a conductive support 31. The surface-treated filler is contained in the surface layer of the photosensitive layer.

  FIG. 2 shows a structure in which a charge generation layer 35 mainly composed of a charge generation material and a charge transport layer 37 mainly composed of a charge transport material are laminated on a conductive support 31. The surface-treated filler is contained on the surface of the charge transport layer.

  In FIG. 3, a photosensitive layer 33 mainly composed of a charge generation material and a charge transport material is provided on a conductive support 31, and a protective layer 39 is further provided on the surface of the photosensitive layer. In this case, the protective layer 39 contains a surface-treated filler.

  FIG. 4 shows a structure in which a charge generation layer 35 mainly composed of a charge generation material and a charge transport layer 37 mainly composed of a charge transport material are laminated on a conductive support 31. A protective layer 39 is provided on the transport layer. In this case, the protective layer 39 contains a surface-treated filler.

  FIG. 5 shows a structure in which a charge transport layer 37 containing a charge transport material as a main component and a charge generation layer 35 containing a charge generation material as a main component are laminated on a conductive support 31. A protective layer 39 is provided on the generation layer. In this case, the protective layer 39 contains a surface-treated filler.

<About protective layer>
In the photoreceptor of the present invention, the protective layer 39 may be provided on the outermost surface for the purpose of protecting the photosensitive layer. Resin materials used for the protective layer 39 include ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether, aryl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone. , Polybutylene, polybutylene terephthalate, polycarbonate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylpentene, polypropylene, polyphenylene oxide, polysulfone, polystyrene, polyarylate, AS resin, butadiene-styrene copolymer, polyurethane , Polyvinyl chloride, polyvinylidene chloride, epoxy resin, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, poly Steal, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, phenoxy resin, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, silicone resin, melamine resin, alkyd resin, etc. These are thermoplastic or thermosetting resins. From the viewpoint of filler dispersibility, residual potential, and coating film defects, polycarbonate or polyarylate is particularly effective and useful.

As the resin material, a polymer charge transport material having a function as a charge transport material and a function as a binder resin is also used favorably. These high-molecular charge transport materials have a high molecular weight in the photosensitive layer and are entangled with each other to form a higher order structure. Therefore, the abrasion resistance of the photosensitive layer is excellent.
As the polymer charge transport material, known materials can be used, and in particular, a polycarbonate containing a triarylamine structure in the main chain and / or side chain is preferably used. Among these, polymer charge transport materials represented by the following general formulas (I) to (X) are preferably used. These are illustrated below and specific examples are shown.

式中、Ｒ_１、Ｒ_２、Ｒ_３はそれぞれ独立して置換もしくは無置換のアルキル基又はハロゲン原子、Ｒ_４は水素原子又は置換もしくは無置換のアルキル基、Ｒ_５、Ｒ_６は置換もしくは無置換のアリール基、ｏ、ｐ、ｑはそれぞれ独立して０〜４の整数、ｋ、ｊは組成を表し、０．１≦ｋ≦１、０≦ｊ≦０．９、ｎは繰り返し単位数を表し５〜５０００の整数である。Ｘは脂肪族の２価基、環状脂肪族の２価基、または下記一般式で表される２価基を表す。

In the formula, R ₁ , R ₂ and R ₃ are each independently a substituted or unsubstituted alkyl group or a halogen atom, R ₄ is a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₅ and R ₆ are substituted or unsubstituted. Substituted aryl group, o, p and q are each independently an integer of 0 to 4, k and j are compositions, 0.1 ≦ k ≦ 1, 0 ≦ j ≦ 0.9, and n is the number of repeating units Represents an integer of 5 to 5000. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula.

式中、Ｒ_１０１、Ｒ_１０２は各々独立して置換もしくは無置換のアルキル基、アリール基またはハロゲン原子を表す。ｌ、ｍは０〜４の整数、Ｙは単結合、炭素原子数１〜１２の直鎖状、分岐状もしくは環状のアルキレン基、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−ＣＯ−、−ＣＯ−Ｏ−Ｚ−Ｏ−ＣＯ−（式中Ｚは脂肪族の２価基を表す。）または、

In the formula, R ₁₀₁ and R ₁₀₂ each independently represents a substituted or unsubstituted alkyl group, aryl group or halogen atom. l and m are integers of 0 to 4, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, —O—, —S—, —SO—, —SO ₂ —. , -CO-, -CO-O-Z-O-CO- (wherein Z represents an aliphatic divalent group) or

（式中、ａは１〜２０の整数、ｂは１〜２０００の整数、Ｒ_１０３、Ｒ_１０４は置換または無置換のアルキル基又はアリール基を表す。）を表す。ここで、Ｒ_１０１とＲ_１０２、Ｒ_１０３とＲ_１０４は、それぞれ同一でも異なってもよい。

(Wherein, a represents an integer of 1 to 20, b represents an integer of 1 to 2000, R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or aryl group). Here, R ₁₀₁ and R ₁₀₂ , and R ₁₀₃ and R ₁₀₄ may be the same or different.

式中、Ｒ_７、Ｒ_８は置換もしくは無置換のアリール基、Ａｒ_１、Ａｒ_２、Ａｒ_３は同一あるいは異なるアリレン基を表す。Ｘ、ｋ、ｊおよびｎは、前記一般式（Ｉ）の場合と同じである。

In the formula, R ₇ and R ₈ represent a substituted or unsubstituted aryl group, and Ar ₁ , Ar ₂ , and Ar ₃ represent the same or different arylene groups. X, k, j and n are the same as those in the general formula (I).

式中、Ｒ_９、Ｒ_１０は置換もしくは無置換のアリール基、Ａｒ_４、Ａｒ_５、Ａｒ_６は同一あるいは異なるアリレン基を表す。Ｘ、ｋ、ｊおよびｎは、前記一般式（Ｉ）の場合と同じである。

In the formula, R ₉ and R ₁₀ represent a substituted or unsubstituted aryl group, and Ar ₄ , Ar ₅ , and Ar ₆ represent the same or different arylene groups. X, k, j and n are the same as those in the general formula (I).

式中、Ｒ_１１、Ｒ_１２は置換もしくは無置換のアリール基、Ａｒ_７、Ａｒ_８、Ａｒ_９は同一あるいは異なるアリレン基、ｐは１〜５の整数を表す。Ｘ、ｋ、ｊおよびｎは、前記一般式（Ｉ）式の場合と同じである。

In the formula, R ₁₁ and R ₁₂ are substituted or unsubstituted aryl groups, Ar ₇ , Ar ₈ and Ar ₉ are the same or different arylene groups, and p represents an integer of 1 to 5. X, k, j and n are the same as those in the general formula (I).

式中、Ｒ_１３、Ｒ_１４は置換もしくは無置換のアリール基、Ａｒ_１０、Ａｒ_１１、Ａｒ_１２は同一あるいは異なるアリレン基、Ｘ_１、Ｘ_２は置換もしくは無置換のエチレン基、又は置換もしくは無置換のビニレン基を表す。Ｘ、ｋ、ｊおよびｎは、前記一般式（Ｉ）式の場合と同じである。

In the formula, R ₁₃ and R ₁₄ are substituted or unsubstituted aryl groups, Ar ₁₀ , Ar ₁₁ and Ar ₁₂ are the same or different arylene groups, X ₁ and X ₂ are substituted or unsubstituted ethylene groups, or substituted or unsubstituted Represents a substituted vinylene group. X, k, j and n are the same as those in the general formula (I).

式中、Ｒ_１５、Ｒ_１６、Ｒ_１７、Ｒ_１８は置換もしくは無置換のアリール基、Ａｒ_１３、Ａｒ_１４、Ａｒ_１５、Ａｒ_１６は同一あるいは異なるアリレン基、Ｙ_１、Ｙ_２、Ｙ_３は単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のシクロアルキレン基、置換もしくは無置換のアルキレンエーテル基、酸素原子、硫黄原子、ビニレン基を表し同一であっても異なってもよい。Ｘ、ｋ、ｊおよびｎは、前記一般式（Ｉ）式の場合と同じである。

In the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are substituted or unsubstituted aryl groups, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆ are the same or different arylene groups, Y ₁ , Y ₂ and Y ₃ are A single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group may be the same or different. X, k, j and n are the same as those in the general formula (I).

式中、Ｒ_１９、Ｒ_２０は水素原子、置換もしくは無置換のアリール基を表し、Ｒ_１９とＲ_２０は環を形成していてもよい。Ａｒ_１７、Ａｒ_１８、Ａｒ_１９は同一あるいは異なるアリレン基を表す。Ｘ、ｋ、ｊおよびｎは、前記一般式（Ｉ）の場合と同じである。

In the formula, R ₁₉ and R ₂₀ represent a hydrogen atom or a substituted or unsubstituted aryl group, and R ₁₉ and R ₂₀ may form a ring. Ar ₁₇ , Ar ₁₈ and Ar ₁₉ represent the same or different arylene groups. X, k, j and n are the same as those in the general formula (I).

式中、Ｒ_２１は置換もしくは無置換のアリール基、Ａｒ_２０、Ａｒ_２１、Ａｒ_２２、Ａｒ_２３は同一あるいは異なるアリレン基を表す。Ｘ、ｋ、ｊおよびｎは、前記一般式（Ｉ）の場合と同じである。

In the formula, R ₂₁ represents a substituted or unsubstituted aryl group, and Ar ₂₀ , Ar ₂₁ , Ar ₂₂ , and Ar ₂₃ represent the same or different arylene groups. X, k, j and n are the same as those in the general formula (I).

式中、Ｒ_２２、Ｒ_２３、Ｒ_２４、Ｒ_２５は置換もしくは無置換のアリール基、Ａｒ_２４、Ａｒ_２５、Ａｒ_２６、Ａｒ_２７、Ａｒ_２８は同一あるいは又は異なるアリレン基を表す。Ｘ、ｋ、ｊおよびｎは、前記一般式（Ｉ）の場合と同じである。

In the formula, R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ represent substituted or unsubstituted aryl groups, and Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ and Ar ₂₈ represent the same or different arylene groups. X, k, j and n are the same as those in the general formula (I).

式中、Ｒ_２６、Ｒ_２７は置換もしくは無置換のアリール基、Ａｒ_２９、Ａｒ_３０、Ａｒ_３１は同一あるいは異なるアリレン基を表す。Ｘ、ｋ、ｊおよびｎは、前記一般式（Ｉ）の場合と同じである。

In the formula, R ₂₆ and R ₂₇ represent a substituted or unsubstituted aryl group, and Ar ₂₉ , Ar ₃₀ and Ar ₃₁ represent the same or different arylene groups. X, k, j and n are the same as those in the general formula (I).

  As the solvent to be used, tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone and the like can be used. However, a solvent having a high viscosity is preferable at the time of dispersion, but a solvent having high volatility is preferable at the time of coating. When there is no solvent satisfying these conditions, it is possible to use a mixture of two or more solvents having respective physical properties, which may have a great effect on filler dispersibility and residual potential. .

  As a method for forming the protective layer, conventional methods such as dip coating, spray coating, beat coating, nozzle coating, spinner coating, ring coating, etc. can be used. preferable. Furthermore, it is possible to form the protective layer by coating the required film thickness of the protective layer at one time. It is more preferable from the viewpoint of sex. By doing so, a further effect can be obtained with respect to reduction of residual potential, improvement of resolution, and improvement of wear resistance. In addition, about 0.1-10 micrometers is suitable for the thickness of a protective layer, Preferably it is 2-6 micrometers.

<About conductive support>
The conductive support 31 has a volume resistance of 1 × 10 ¹⁰ Ω · cm or less, such as a metal such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, tin oxide, oxidation Metal oxide such as indium by vapor deposition or sputtering, film or cylindrical plastic, paper coated, or aluminum, aluminum alloy, nickel, stainless steel plates, etc. and methods such as extrusion and drawing After forming the tube, it is possible to use a tube subjected to surface treatment such as cutting, superfinishing or polishing. Further, an endless nickel belt or an endless stainless steel belt disclosed in Japanese Patent Application Laid-Open No. 52-36016 can also be used as the conductive support 31.

In addition, a material obtained by dispersing conductive powder in an appropriate binder resin and coating it on the support can also be used as the conductive support 31 of the present invention. Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc and silver, or metal oxide powder such as conductive tin oxide and ITO. It is done. The binder resin used at the same time is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, Examples thereof include thermoplastic, thermosetting resins, and photocurable resins such as melamine resin, urethane resin, phenol resin, and alkyd resin.
Such a conductive layer can be provided by dispersing and coating these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.

  Furthermore, a conductive layer is provided on a suitable cylindrical substrate by a heat-shrinkable tube containing the conductive powder in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, and Teflon. Can be used favorably as the conductive support 31 of the present invention.

<About photosensitive layer>
Next, the photosensitive layer 33 will be described. The photosensitive layer may have a laminated structure or a single layer structure. In the case of a laminated structure, the photosensitive layer is composed of a charge generation layer 35 having a charge generation function and a charge transport layer 37 having a charge transport function. In the case of a single layer structure, the photosensitive layer is a layer having a charge generation function and a charge transport function at the same time.
Hereinafter, each of the photosensitive layer having a laminated structure and the photosensitive layer having a single layer structure will be described.

<Photosensitive layer having a laminated structure>
(I) Charge generation layer The charge generation layer 35 is a layer mainly composed of a charge generation material. A known charge generation material can be used for the charge generation layer 35, and representative examples thereof include monoazo pigments, disazo pigments, trisazo pigments, perylene pigments, perinone pigments, quinacridone pigments, and quinone condensed polycycles. Examples thereof include compounds, squalic acid dyes, other phthalocyanine pigments, naphthalocyanine pigments, and azulenium salt dyes. These charge generation materials may be used alone or in combination of two or more.

  In the charge generation layer 35, a charge generation material is dispersed in a suitable solvent together with a binder resin as necessary using a ball mill, an attritor, a sand mill, an ultrasonic wave, etc., and this is applied onto a conductive support. It is formed by drying.

As the binder resin used for the charge generation layer 35 as necessary, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, polysulfone, poly-N -Vinylcarbazole, polyacrylamide, polyvinyl benzal, polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyphenylene oxide, polyamide, polyvinyl pyridine, cellulosic resin, casein, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Can be mentioned.
The amount of the binder resin is suitably 0 to 500 parts by weight, preferably 10 to 300 parts by weight with respect to 100 parts by weight of the charge generating material. The binder resin may be added before or after dispersion.

  Examples of the solvent used here include isopropanol, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane, toluene, xylene, and ligroin. In particular, ketone solvents, ester solvents, and ether solvents are preferably used. These may be used alone or in combination of two or more.

  The charge generation layer 35 includes a charge generation material, a solvent, and a binder resin as main components, and includes any additive such as a sensitizer, a dispersant, a surfactant, and silicone oil. Also good.

As a coating method of the coating solution, methods such as dip coating, spray coating, beat coating, nozzle coating, spinner coating, ring coating, and the like can be used.
The thickness of the charge generation layer 35 is suitably about 0.01 to 5 μm, preferably 0.1 to 2 μm.

(Ii) Charge Transport Layer The charge transport layer 37 can be formed by dissolving or dispersing a charge transport material and a binder resin in an appropriate solvent, and applying and drying the solution on the charge generation layer. As the binder resin, the binder resin and the polymer charge transporting substance described above for the protective layer 39 can be improved, and other binder resins mentioned in the charge generation layer 35 are mixed and used. Also good. Further, if necessary, two or more kinds of plasticizers, leveling agents, antioxidants and the like can be added.

Charge transport materials include hole transport materials and electron transport materials.
Examples of the electron transporting material include chloroanil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-tri Examples thereof include electron-accepting substances such as nitrodibenzothiophene-5,5-dioxide and benzoquinone derivatives.

  Examples of hole transport materials include poly-N-vinylcarbazole and derivatives thereof, poly-γ-carbazolylethyl glutamate and derivatives thereof, pyrene-formaldehyde condensates and derivatives thereof, polyvinylpyrene, polyvinylphenanthrene, polysilane, oxazole derivatives, Oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triarylmethane derivatives, 9-styrylanthracene derivatives, pyrazolines Derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives, etc. Other known materials may be used. These charge transport materials may be used alone or in combination of two or more.

  As binder resin, ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether, aryl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone, polybutylene, polybutylene terephthalate , Polycarbonate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylpentene, polypropylene, polyphenylene oxide, polysulfone, polystyrene, polyarylate, AS resin, butadiene-styrene copolymer, polyurethane, polyvinyl chloride, poly Vinylidene chloride, epoxy resin, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, polyester, vinyl chloride Heat of vinyl acid copolymer, polyvinyl acetate, phenoxy resin, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, melamine resin, alkyd resin, etc. A plastic or thermosetting resin is mentioned.

  The amount of the charge transport material is appropriately 20 to 300 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder resin. The thickness of the charge transport layer is preferably 25 μm or less from the viewpoint of resolution and responsiveness. Regarding the lower limit, although it differs depending on the system to be used (particularly the charging potential), 5 μm or more is preferable.

  As the solvent used here, tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone and the like are used. These may be used alone or in combination of two or more.

  Further, when the charge transport layer is the outermost surface layer of the photoreceptor, a filler material is added at least to the surface portion of the charge transport layer for the purpose of improving the wear resistance. As the filler material at this time, all the filler materials used for the protective layer 39 can be used, and the entire charge transport layer can contain a filler. It is effective to use a layer configuration in which the filler concentration is sequentially changed.

  As a coating method of the coating liquid obtained as described above, conventional coating methods such as dip coating, spray coating, beat coating, nozzle coating, spinner coating, ring coating, and the like can be used. When the surface of the photosensitive layer contains a filler, the entire photosensitive layer can contain a filler, but the filler concentration gradient is provided so that the outermost surface side of the charge transport layer has the highest filler concentration and the lower the support side. It is preferable that the charge transport layer is formed in a plurality of layers so that the filler concentration increases sequentially from the support side to the surface side.

<Photosensitive layer having a single layer structure>
Next, the case where the photosensitive layer has a single layer structure 33 will be described. A photoreceptor in which the above-described charge generating material is dispersed in a binder resin can be used. The photosensitive layer can be formed by dissolving or dispersing a charge generating substance, a charge transporting substance, and a binder resin in a suitable solvent, and applying and drying them. Moreover, a plasticizer, a leveling agent, antioxidant, etc. can also be added as needed.

  As the charge transport material, any of the charge transport materials and amino compounds mentioned in the charge transport layer 37 can be used. As the binder resin, in addition to the binder resin previously mentioned in the charge transport layer 37, the binder resin mentioned in the charge generation layer 35 may be mixed and used. Of course, the polymer charge transport materials mentioned above can also be used favorably. The amount of the charge generating material with respect to 100 parts by weight of the binder resin is preferably 5 to 40 parts by weight, and the amount of the charge transporting material is preferably 0 to 190 parts by weight, and more preferably 50 to 150 parts by weight. The photosensitive layer is formed by dip coating, spray coating, bead coating, a coating solution in which a charge generating material and a binder resin are dispersed together with a charge transporting material using a solvent such as tetrahydrofuran, dioxane, dichloroethane, and cyclohexane. It can be formed by coating with a ring coat or the like. The film thickness of the photosensitive layer is suitably about 5 to 25 μm.

  The outermost surface layer of the photosensitive layer contains a filler that has been subjected to a surface treatment to improve wear resistance. Even in this case, it is possible to use all the surface treatment fillers described in the protective layer 39. In this case, as in the case of the charge transport layer, the entire photosensitive layer may contain a filler. However, a filler concentration gradient may be provided, or a plurality of photosensitive layers may be configured, and the filler concentration may be sequentially changed. To do is an effective means.

<About the undercoat layer>
In the photoreceptor of the present invention, an undercoat layer can be provided between the conductive support 31 and the photosensitive layer, although not shown. In general, the undercoat layer is mainly composed of a resin. However, considering that the photosensitive layer is coated with a solvent on these resins, the resin may be a resin having high solvent resistance with respect to a general organic solvent. desirable. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. Further, a metal oxide fine powder pigment exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the undercoat layer in order to prevent moire and reduce residual potential.

These undercoat layers can be formed using an appropriate solvent and a coating method like the above-mentioned photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer of the present invention. In addition, in the undercoat layer of the present invention, Al ₂ O ₃ is provided by anodic oxidation, organic matter such as polyparaxylylene (parylene), SiO ₂ , SnO ₂ , TiO ₂ , ITO, CeO ₂ A material provided with an inorganic material such as a vacuum thin film can also be used favorably. In addition, known ones can be used. The thickness of the undercoat layer is suitably from 0 to 5 μm.

<About the intermediate layer>
In the photoreceptor of the present invention, an intermediate layer (not shown) can be provided between the photosensitive layer and the protective layer. In the intermediate layer, a binder resin is generally used as a main component. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As a method for forming the intermediate layer, a generally used coating method as described above is employed. The thickness of the intermediate layer is suitably about 0.05 to 2 μm.

<Additives to each layer>
In the present invention, in order to improve environmental resistance, in order to prevent a decrease in sensitivity and an increase in residual potential, oxidation is performed on each layer such as a charge generation layer, a charge transport layer, an undercoat layer, a protective layer, and an intermediate layer. Inhibitors, plasticizers, lubricants, UV absorbers, low molecular charge transport materials and leveling agents can be added. Representative materials of these compounds are described below.

  Examples of the antioxidant that can be added to each layer include, but are not limited to, the following.

(A) Phenol compounds 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, n-octadecyl-3- (4'- Hydroxy-3 ', 5'-di-t-butylphenol), 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-ethyl- 6-t-butylphenol), 4,4'-thiobis- (3-methyl-6-t-butylphenol), 4,4'-butylidenebis- (3-methyl-6-t-butylphenol), 1,1,3 -Tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxy Benzyl) ben Zen, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis (4'-hydroxy-3'-t -Butylphenyl) butyric acid] glycol ester, tocopherols and the like.

(B) Paraphenylenediamines N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylene Diamine, N, N'-di-isopropyl-p-phenylenediamine, N, N'-dimethyl-N, N'-di-t-butyl-p-phenylenediamine and the like.

(C) Hydroquinones 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, 2 -(2-octadecenyl) -5-methylhydroquinone and the like.

(D) Organic sulfur compounds Dilauryl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, ditetradecyl-3,3'-thiodipropionate, and the like.

(E) Organic phosphorus compounds Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine and the like.

  Examples of the plasticizer that can be added to each layer include, but are not limited to, the following.

(A) Phosphate ester plasticizer Triphenyl phosphate, tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, trichloroethyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, Triphenyl phosphate etc.

(B) Phthalate ester plasticizers Dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, phthalate Dinonyl acid, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, butyl lauryl phthalate, methyl oleyl phthalate, octyl decyl phthalate, dibutyl fumarate, dioctyl fumarate Such.

(C) Aromatic carboxylic acid ester plasticizers Trioctyl trimellitic acid, tri-n-octyl trimellitic acid, octyl oxybenzoate, and the like.

(D) Aliphatic dibasic ester plasticizer dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, di-n-octyl adipate, adipic acid n-octyl-n-decyl , Diisodecyl adipate, dicapryl adipate, di-2-ethylhexyl azelate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, di-2-ethylhexyl sebacate, di-2 sebacate -Ethoxyethyl, dioctyl succinate, diisodecyl succinate, dioctyl tetrahydrophthalate, di-n-octyl tetrahydrophthalate and the like.

(E) Fatty acid ester derivatives butyl oleate, glycerin monooleate, methyl acetylricinoleate, pentaerythritol ester, dipentaerythritol hexaester, triacetin, tributyrin and the like.

(F) Oxyacid ester plasticizers Methyl acetyl ricinoleate, butyl acetyl ricinoleate, butyl phthalyl butyl glycolate, tributyl acetyl citrate and the like.

(G) Epoxy plasticizer Epoxidized soybean oil, epoxidized linseed oil, butyl epoxy stearate, decyl epoxy stearate, octyl epoxy stearate, benzyl epoxy stearate, dioctyl epoxy hexahydrophthalate, didecyl epoxy hexahydrophthalate, etc. .

(H) Dihydric alcohol ester plasticizers such as diethylene glycol dibenzoate and triethylene glycol di-2-ethylbutyrate.

(I) Chlorinated plasticizer Chlorinated paraffin, chlorinated diphenyl, chlorinated fatty acid methyl, methoxychlorinated fatty acid methyl and the like.

(J) Polyester plasticizer Polypropylene adipate, polypropylene sebacate, polyester, acetylated polyester and the like.

(K) Sulfonic acid derivatives p-toluenesulfonamide, o-toluenesulfonamide, p-toluenesulfoneethylamide, o-toluenesulfoneethylamide, toluenesulfone-N-ethylamide, p-toluenesulfone-N-cyclohexylamide and the like.

(L) Citric acid derivatives Triethyl citrate, triethyl acetyl citrate, tributyl citrate, tributyl acetyl citrate, tri-2-ethylhexyl acetyl citrate, n-octyldecyl acetyl citrate and the like.

(M) Others Terphenyl, partially hydrogenated terphenyl, camphor, 2-nitrodiphenyl, dinonylnaphthalene, methyl abietate and the like.

  Examples of the lubricant that can be added to each layer include, but are not limited to, the following.

(A) Hydrocarbon compound Liquid paraffin, paraffin wax, microwax, low-polymerized polyethylene and the like.

(B) Fatty acid compounds Lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and the like.

(C) Fatty acid amide compounds Stearylamide, palmitylamide, oleinamide, methylenebisstearamide, ethylenebisstearamide and the like.

(D) Ester compounds Lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, fatty acid polyglycol esters, and the like.

(E) Alcohol compounds Cetyl alcohol, stearyl alcohol, ethylene glycol, polyethylene glycol, polyglycerol and the like.

(F) Metal soap Lead stearate, cadmium stearate, barium stearate, calcium stearate, zinc stearate, magnesium stearate and the like.

(G) Natural wax Carnauba wax, candelilla wax, beeswax, whale wax, ivotaro, montan wax and the like.

(H) Others Silicone compounds, fluorine compounds, etc.

  Examples of the ultraviolet absorber that can be added to each layer include, but are not limited to, the following.

(A) Benzophenone series 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ', 4-trihydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4 -Methoxybenzophenone and the like.

(B) Salsylate type Phenyl salsylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like.

(C) Benzotriazole series (2'-hydroxyphenyl) benzotriazole, (2'-hydroxy-5'-methylphenyl) benzotriazole, (2'-hydroxy-5'-methylphenyl) benzotriazole, (2'- Hydroxy-3'-tertiarybutyl-5'-methylphenyl) -5-chlorobenzotriazole and the like.

(D) Cyanoacrylate-based ethyl-2-cyano-3,3-diphenyl acrylate, methyl-2-carbomethoxy-3- (paramethoxy) acrylate, and the like.

(E) Quencher (metal complex)
Nickel [2,2′-thiobis (4-t-octyl) phenolate] normal butylamine, nickel dibutyldithiocarbamate, nickel dibutyldithiocarbamate, cobalt dicyclohexyldithiophosphate and the like.

(F) HALS (hindered amine)
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6 6-tetramethylpyridine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy- 2,2,6,6-tetramethylpiperidine and the like.

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

FIG. 6 is a schematic diagram for explaining an image forming apparatus and an image forming method using the same according to the present invention, and the following examples also belong to the category of the present invention.
In FIG. 6, a photoreceptor 1 contains a filler, a binder resin and a plurality of charge transport materials in the outermost surface layer of a photosensitive layer formed on a conductive support, and at least one of the charge transport materials is dialkyl. An amino compound having any one of an amino group, a dibenzylamino group, a benzylalkylamino group, and an alkylarylamino group, wherein the filler is subjected to a surface treatment. The photosensitive member 1 has a drum shape, but may be a sheet shape or an endless belt shape. As the charging charger 3, the pre-transfer charger 7, the transfer charger 10, the separation charger 11, and the pre-cleaning charger 13, a corotron, a scorotron, a solid charger (solid state charger), a charging roller, or the like is used, and known means are used. All are usable.

  As the transfer means, the above charger can be generally used. However, as shown in the figure, a combination of a transfer charger and a separation charger is effective.

  In addition, light sources such as the image exposure unit 5 and the charge removal lamp 2 emit light such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electroluminescence (EL). All things can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.

  In addition to the steps shown in FIG. 6, the light source and the like are provided with a transfer step, a static elimination step, a cleaning step, a pre-exposure step, and the like using light irradiation, so that the photosensitive member is irradiated with light.

  The toner developed on the photosensitive member 1 by the developing unit 6 is transferred to the transfer paper 9, but not all is transferred, and some toner remains on the photosensitive member 1. Such toner is removed from the photoreceptor by the fur brush 14 and the blade 15. Cleaning may be performed only with a cleaning brush, and a known brush such as a fur brush or a mag fur brush is used as the cleaning brush.

  When the photosensitive member is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner.

  A known method is applied to the developing unit, and a known method is also used for the charge eliminating unit.

  FIG. 7 shows another example of the image forming apparatus according to the present invention. The photoreceptor 21 contains a filler, a binder resin, and a plurality of charge transport materials at least on the outermost surface layer of the photosensitive layer formed on the conductive support, and at least one of the charge transport materials is a dialkylamino group, An amino compound having any one of a dibenzylamino group, a benzylalkylamino group, and an alkylarylamino group, wherein the filler is subjected to a surface treatment, and is driven by driving rollers 22a and 22b. Charging, image exposure using the light source 24, development (not shown), transfer using the charger 25, exposure before cleaning using the light source 26, cleaning using the brush 27, and charge removal using the light source 28 are repeated. In FIG. 7, the photosensitive member 21 (of course, the support is translucent in this case) is irradiated with pre-cleaning exposure light from the support side.

  The above-described image forming apparatus and the image forming process using the image forming apparatus exemplify the embodiments of the present invention, and other embodiments are of course possible. For example, in FIG. 7, the pre-cleaning exposure is performed from the support side, but this may be performed from the photosensitive layer side, or image exposure and neutralization light irradiation may be performed from the support side.

  On the other hand, the light irradiation process is illustrated as image exposure, pre-cleaning exposure, and static elimination exposure. In addition, a pre-transfer exposure, a pre-exposure of image exposure, and other known light irradiation processes are provided to light the photosensitive member. Irradiation can also be performed.

  The image forming means as described above may be fixedly incorporated in a copying apparatus, a facsimile, or a printer, but may be incorporated in these apparatuses in the form of a process cartridge. A process cartridge is a single device (part) that contains a photosensitive member and includes a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, and a charge eliminating unit. There are many shapes and the like of the process cartridge, but a general example is shown in FIG. The photoreceptor 16 contains a filler, a binder resin, and a plurality of charge transport materials on the outermost surface layer of the photosensitive layer formed on the conductive support, and at least one of the charge transport materials is a dialkylamino group, An amino compound having any one of a dibenzylamino group, a benzylalkylamino group, and an alkylarylamino group, wherein the filler is subjected to a surface treatment.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not restrict | limited by an Example. All parts are parts by weight.

ポリビニルブチラール： ５部
２−ブタノン： ２００部
シクロヘキサノン： ４００部
◎電荷輸送層塗工液
ビスフェノールＺ型ポリカーボネート： １０部
下記構造式で表される電荷輸送物質： １０部

酸化電位：０．７６（Ｖ ｖｓ ＳＣＥ）
テトラヒドロフラン： １００部 Example 1
An undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following composition are sequentially applied onto an aluminum cylinder by dip coating and dried to obtain a 3.5 μm undercoat layer, 0. A 2 μm charge generation layer and a 23 μm charge transport layer were formed.
◎ Undercoat layer coating solution Titanium dioxide powder: 400 parts Melamine resin: 65 parts Alkyd resin: 120 parts 2-butanone: 400 parts ◎ Bisazo pigment represented by the following structural formula: 12 parts

Polyvinyl butyral: 5 parts 2-butanone: 200 parts Cyclohexanone: 400 parts Charge transport layer coating solution Bisphenol Z-type polycarbonate: 10 parts Charge transport material represented by the following structural formula: 10 parts

Oxidation potential: 0.76 (V vs SCE)
Tetrahydrofuran: 100 parts

ビスフェノールＺ型ポリカーボネート： ６部
テトラヒドロフラン： ２２０部
シクロヘキサノン： ８０部 Further, a protective layer having the following composition was formed on the charge transport layer by spray coating to form a protective layer having a thickness of about 4.0 μm, thereby producing an electrophotographic photosensitive member.
Protective layer coating liquid Surface treatment filler: 2 parts (α-alumina (average particle size 0.1 to 0.3 μm, AKP-50, manufactured by Sumitomo Chemical Co., Ltd.) 100 parts and γ-glycidoxypropylmethyldiethoxysilane 9 .5 parts were mixed with a Hensyl mixer and then surface-treated by crushing at a nozzle air pressure of 10 kg / cm ² using a fluidized bed jet mill)
Compound of exemplary compound 10: 0.5 part Charge transport material represented by the following structural formula: 3.5 parts

Bisphenol Z-type polycarbonate: 6 parts Tetrahydrofuran: 220 parts Cyclohexanone: 80 parts

Example 2
In Example 1, an electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the surface treatment filler α-alumina contained in the protective layer coating solution was changed to the following material.
Surface treatment filler: 2 parts (100 parts of titanium oxide (average particle size 0.015 μm, MT-100SA, manufactured by Teika Co., Ltd.) and 9.5 parts of γ-glycidoxypropylmethyldiethoxysilane were mixed with a Hensyl mixer. And then surface-treated by crushing at a nozzle air pressure of 10 kg / cm ² using a fluidized bed jet mill)

Example 3
In Example 1, an electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the surface treatment filler α-alumina contained in the protective layer coating solution was changed to the following material.
Surface treatment filler: 2 parts (α-alumina (average particle size 0.4 to 0.7 μm, AKP-3000, manufactured by Sumitomo Chemical Co., Ltd.) 100 parts and γ-glycidoxypropylmethyldiethoxysilane 9.5 parts After mixing with a Hensyl mixer, surface treatment was performed using a fluidized bed jet mill with a nozzle air pressure of 10 kg / cm ² )

Example 4
In Example 1, an electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the surface treatment filler α-alumina contained in the protective layer coating solution was changed to the following material.
Surface treatment filler: 2 parts (α-alumina (average particle size 1.0 μm, AM-27, manufactured by Sumitomo Chemical Co., Ltd.) 100 parts and γ-glycidoxypropylmethyldiethoxysilane 9.5 parts with a Hensyl mixer After mixing, surface treatment was performed by crushing with a fluidized bed jet mill at a nozzle air pressure of 10 kg / cm ² )

Example 5
In Example 1, an electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the surface treatment filler α-alumina contained in the protective layer coating solution was changed to the following material.
Surface treatment filler: 2 parts (α-alumina (average particle size 0.1 to 0.3 μm, AKP-50, manufactured by Sumitomo Chemical Co., Ltd.) 100 parts and γ-glycidoxypropylmethyldiethoxysilane 9.5 parts Surface treatment by grinding with a ball mill)

Example 6
In Example 1, an electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the surface treatment method of the surface treatment filler contained in the protective layer coating solution was changed to the following.
Surface treatment filler: 2 parts (α-alumina (average particle size 0.1 to 0.3 μm, AKP-50, manufactured by Sumitomo Chemical Co., Ltd.) 100 parts and γ-glycidoxypropylmethyldiethoxysilane 15 parts After mixing with a mixer, surface treatment was performed by crushing with a fluidized bed jet mill at a nozzle air pressure of 10 kg / cm ² )

Example 7
In Example 1, an electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the surface treatment method of the surface treatment filler contained in the protective layer coating solution was changed to the following.
Surface treatment filler: 2 parts (α-alumina (average particle size 0.1 to 0.3 μm, AKP-50, manufactured by Sumitomo Chemical Co., Ltd.) 100 parts and γ-glycidoxypropylmethyldiethoxysilane 0.01 part After mixing with a Hensyl mixer, surface treatment was performed using a fluidized bed jet mill with a nozzle air pressure of 10 kg / cm ² )

Example 8
In Example 1, an electrophotographic photoreceptor was prepared in the same manner as in Example 1 except that the surface treatment method of the surface treatment filler contained in the protective layer coating solution was changed to the following.
Surface treatment filler: 2 parts (200 parts of α-alumina (average particle size 0.1 to 0.3 μm, AKP-50, manufactured by Sumitomo Chemical Co., Ltd.) and 0.01 part of γ-glycidoxypropylmethyldiethoxysilane After mixing with a Hensyl mixer, surface treatment was performed using a fluidized bed jet mill with a nozzle air pressure of 10 kg / cm ² )

Example 9
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the compound of Exemplified Compound 10 contained in the protective layer was changed to the Exemplified Compound 1 compound.

Example 10
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the compound of Exemplified Compound 10 contained in the protective layer in Example 1 was changed to the Exemplified Compound 18 compound.

酸化電位：０．７８（Ｖ ｖｓ． ＳＣＥ） Example 11
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the charge transport material and binder resin contained in the protective layer were changed to the following materials.
Polymer charge transport material represented by the following structural formula: 20 parts

Oxidation potential: 0.78 (V vs. SCE)

Comparative Example 1
In Example 1, an electrophotographic photoreceptor was produced in the same manner as in Example 1 except that the surface treatment filler contained in the protective layer was changed to the following material.
Untreated α-alumina filler (average particle size 0.1 to 0.3 μm, AKP-50, manufactured by Sumitomo Chemical): 2 parts

Comparative Example 2
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface treatment filler contained in the protective layer was not added in Example 1.

Comparative Example 3
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the binder resin contained in the protective layer was not added.

Comparative Example 4
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that Example Compound 10 contained in the protective layer was not added in Example 1.

Comparative Example 5
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the charge transport material contained in the protective layer was not added.

Comparative Example 6
In Comparative Example 1, an electrophotographic photoreceptor was prepared in the same manner as Comparative Example 1 except that the following wetting and dispersing agent was included in the protective layer coating solution.
Wetting and dispersing agent (low molecular weight unsaturated polycarboxylic acid polymer solution, BYK-P104, manufactured by Big Chemie): 0.02 part

  The electrophotographic photosensitive member produced in the examples and comparative examples as described above is mounted on an electrophotographic process cartridge, the charging method is a DC contact roller method, and the image exposure light source is a 655 nm semiconductor laser. After setting the dark part potential to 700 (-V) with the MF2200 remodeling machine, a total of 50,000 sheets were printed continuously, and the initial image and the image after 50,000 sheets were printed at that time. In addition, symbols used for evaluation of the image quality indicate that 良好 is good, ◯ is low in image density, Δ is low in image density, X is high in image density, and XX is no image. Further, the light portion potential at the initial stage and after printing 50,000 sheets was measured. Furthermore, the amount of wear was evaluated from the difference in film thickness at the initial stage and after printing 50,000 sheets. In addition, evaluation was performed on images output in a high-temperature and high-humidity environment of 27 ° C./81% after printing 50,000 sheets. Here, symbols used for the evaluation of the image quality indicate that ◎ is good, ◯ is low in image resolution, Δ is low in image resolution, x is image blurring, and xx is no image. The results are shown in Table 6. Furthermore, the oxidation potential difference (ΔE) between the amino compound used here and the charge transport material is also shown.

  From the evaluation results of Table 6, it was made possible to significantly reduce the bright part potential by surface-treating the filler surface contained in the outermost surface layer of the photoreceptor with a silane coupling agent. Further, it was confirmed that the bright part potential increase was small even after printing 50,000 sheets, and that a high-quality image was stably obtained on the photoconductor added with the compounds represented by the general formulas (a) to (d). . At the same time, the amount of wear was suppressed and it was confirmed that the wear resistance was improved. In addition, it was confirmed that the photoconductor including the filler not subjected to the surface treatment showed a significant increase in the bright portion potential and a decrease in the wear resistance. Further, the photoconductor of Comparative Example 6 in which a wetting and dispersing agent was added to the protective layer coating solution showed relatively good photoconductor properties.

  Further, the electrophotographic photoreceptors produced in the examples and comparative examples were left in a desiccator adjusted to a nitrogen oxide gas concentration of 30 ppm for 1 day, and image (resolution) evaluation was performed before and after. The results are shown in Table 7.

  From the evaluation results in Table 7, it can be seen that the resistance to the oxidizing gas is greatly improved by incorporating the compounds represented by the general formulas (a) to (d) on the outermost surface of the photoreceptor. Further, it can be seen from the results of Table 7 that the image blur caused by the oxidizing gas is large in the photoconductor of Comparative Example 6 which showed relatively good wear resistance and bright portion potential characteristics.

It is sectional drawing of the photoreceptor of this invention. It is sectional drawing of the photoreceptor of another example of this invention. It is sectional drawing of the photoreceptor of another example of this invention. It is sectional drawing of the photoreceptor of another example of this invention. It is sectional drawing of the photoreceptor of another example of this invention. 1 is a schematic view of an image forming apparatus of the present invention. It is the schematic of the image forming apparatus of another example of this invention. FIG. 2 is a schematic view of an example of a process cartridge for an image forming apparatus according to the present invention.

Explanation of symbols

(Figures 1-5)
31 Conductive Support 33 Photosensitive Layer 35 Charge Generation Layer 37 Charge Transport Layer 39 Protective Layer

Claims (9)

A surface layer of a photoreceptor having a photosensitive layer formed on a conductive support, which contains at least a surface-treated filler, a binder resin, and a plurality of charge transport materials, and the surface-treated filler The filler and the silane coupling agent are subjected to a surface treatment by applying an impact force by a jet stream in a pulverizer and stirring while flowing , wherein at least one of the charge transport materials is a dialkylamino group A photoconductor characterized by being an amino compound having any one of a dibenzylamino group, a benzylalkylamino group, and an alkylarylamino group. The photoreceptor according to claim 1 , wherein a mixing ratio of the silane coupling agent to the filler is 0.01 to 10% by weight. The photoreceptor according to claim 1 , wherein the filler is α-alumina. The photoconductor according to claim 1 , wherein a maximum difference in oxidation potential (Eox) among the plurality of charge transport materials is in a range of 0.2 (V vs. SCE) or less. The photoconductor according to claim 1 , wherein at least one of the charge transport materials is a polymer charge transport material. An image forming apparatus comprising at least a charging unit, an image exposure unit, a developing unit, a transfer unit, and a photoconductor, wherein the photoconductor is the photoconductor according to claim 1. An image forming apparatus. 7. The image forming apparatus according to claim 6 , wherein an electrostatic latent image is written on a photosensitive member by using an LD or an LED as the image exposure unit. A process cartridge for an image forming apparatus, comprising at least one unit selected from a charging unit, an exposing unit, a developing unit, and a cleaning unit and a photoconductor, and is detachable from the main body of the image forming apparatus, 6. A process cartridge for an image forming apparatus, which is the photosensitive member according to claim 1 .   A method for producing a photoreceptor, comprising a surface layer of a photoreceptor having a photosensitive layer formed on a conductive support, containing at least a surface-treated filler, a binder resin, and a plurality of charge transport materials. The filler subjected to the surface treatment is a filler which has been subjected to a surface treatment by applying an impact force to the filler and the silane coupling agent in a pulverizer by a jet stream and stirring while flowing, and the charge transport material. At least one of which is an amino compound having any one of a dialkylamino group, a dibenzylamino group, a benzylalkylamino group, and an alkylarylamino group.

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