JP2007147769A - Cleaning device and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To remove both discharge products and removal object materials larger than the discharge products existing on an image carrier surface, from the surface, with respect to a cleaning device which is employed in an electrophotographic system of a copying machine, facsimile equipment, a printer, or the like and removes residues such as residual toner, and an image forming apparatus including the cleaning device. <P>SOLUTION: Two rolls 151 and 152 which rotate in a state in which peripheral surfaces 151a and 152a are brought into contact with a surface 11a of an image carrier 11 after transfer of a toner image to a transfer object face 30, wherein one roll 151 out of two rolls 151 and 152 has particles with a particle size of 30 nm to <5 μm dispersed on the peripheral surface, and the other roll 152 has particles with a particle size of 5 nm to <30 nm dispersed on the peripheral surface. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a cleaning device for removing residues such as residual toner, and an image forming apparatus including the cleaning device, which are employed in electrophotographic systems such as copying machines, facsimile machines, and printers.

  In the electrophotographic system, first, a toner image forming cycle is performed. In this toner image forming cycle, the surface of the photoconductor rotating in a predetermined direction is charged by a charger, and the charged photoconductor surface is irradiated with exposure light to obtain an electrostatic latent image on the surface. Is developed with toner using a developing device to form a toner image on the surface of the photoreceptor. The toner image formed by the toner image formation cycle is transferred to a predetermined transfer surface (recording medium or intermediate transfer body) by a transfer unit and finally fixed on the recording medium, thereby fixing the toner image on the recording medium. Is formed.

  A plurality of types of foreign matter such as untransferred toner, external additive particles added to the toner, or discharge products generated during charging remain on the surface of the photoreceptor after the transfer to a predetermined transfer surface. . Further, the outermost surface of the photoreceptor is deteriorated by a discharge phenomenon in charging. If the next toner image forming cycle is performed with the residue remaining on the surface of the photoconductor, or if the next toner image forming cycle is performed using a photoconductor whose outermost surface has deteriorated, an image quality defect occurs in the formed image. . Therefore, it is necessary to remove the residue and the deteriorated film on the outermost surface of the photoconductor by a cleaning unit prior to the next toner image forming cycle.

  Various cleaning methods have been proposed to remove toner residue and deteriorated film. For example, the edge of a plate-like cleaning blade made of a rubber material such as urethane is pressed against the surface of the photoreceptor. In many cases, the surface of the photoreceptor is scraped off by its edge. Hereinafter, the method using this cleaning blade will be described as an example. In the method using the cleaning blade, the surface of the photoconductor is scraped off at the edge thereof, and residues and deteriorated films that are difficult to be removed only by rubbing the surface of the photoconductor are also removed.

  By the way, an electrical and mechanical external force is directly applied to the surface of the photosensitive member by a charger, a developing device, a transfer unit, or the like. For this reason, there is a tendency to use a photoconductor having a protective layer with improved durability against wear and scratches on the surface. However, a photoconductor having a protective layer with improved durability has high surface strength, and it becomes difficult to scrape the photoconductor surface with a cleaning blade.

Therefore, a technique for polishing the surface of the photoreceptor using a polishing roll having abrasive particles or the like carried on the peripheral surface has been proposed (see, for example, Patent Documents 1 to 4). Among these patent documents, the above-mentioned patent document 1 proposes polishing the surface of the photoreceptor using a polishing roll in which abrasive particles having different particle diameters are supported on the peripheral surface.
JP 2004-333790 A JP 2004-157256 A Japanese Patent Laid-Open No. 10-161494 Japanese Patent Laid-Open No. 9-244494

  However, in polishing with a roll having abrasive particles supported on the peripheral surface, polishing with particles having the largest particle size among the particles supported on the peripheral surface tends to be dominant, and the particle size on the peripheral surface of one roll Even if particles having different particle sizes are supported, the effect of particles having a relatively small particle size is not expected. In addition, a plurality of types of residues such as discharge products generated during charging and external additive particles adhering to the surface of the toner base particles during development are firmly attached to the surface of the photoreceptor. Furthermore, the surface of the photoreceptor is deteriorated to a depth of several tens of nanometers to several hundreds of nanometers by a discharge phenomenon during charging. The sizes of the plurality of types of residues are different depending on the types, and the sizes of the residues and the thickness of the deteriorated film are also different. For example, the discharge product is a minute residue smaller than the size of the external additive particles and the thickness of the deteriorated film. This minute discharge product often enters a slight recess on the surface of the photoconductor and adheres to the recess. In polishing using particles having a large particle diameter that cannot enter the recess, the discharge product is It cannot be peeled off from the surface of the photoconductor, resulting in image quality defects in the formed image.

  In view of the above circumstances, the present invention provides a cleaning device capable of removing both a discharge product existing on the surface of an image carrier and an object to be removed larger than the discharge product, and a cleaning device thereof. An object of the present invention is to provide an image forming apparatus provided.

The cleaning device of the present invention that solves the above-described object conveys the toner image to the transfer area where the toner image is transferred to the transfer surface by carrying the toner image on the surface and circulatingly moving around the central axis. In the cleaning device for removing the residue remaining on the surface of the image carrier after the toner image has been transferred to the transfer surface,
Cleaning means for removing residues remaining on the surface of the image carrier after the toner image is transferred to the transfer surface;
Arranged side by side in the moving direction of the image carrier, each having a rotation axis parallel to the central axis of the image carrier, and transferring the toner image onto the transfer surface of the image carrier Two rolls that rotate with their peripheral surfaces in contact with the surface after being made,
One of the two rolls is one in which particles having a particle size of 30 nm or more and less than 5 μm are dispersed and arranged on the peripheral surface,
The other of the two rolls is characterized in that particles having a particle size of 5 nm or more and less than 30 nm are dispersedly arranged on the peripheral surface.

  The image carrier here may be a photoconductor that is uniformly charged and then exposed to light to form an electrostatic latent image, or the toner image is primarily transferred from the photoconductor to perform primary transfer. An intermediate transfer member that secondarily transfers the toner image to the recording medium may be used. That is, the cleaning device of the present invention can be applied as a cleaning device for the surface of the photosensitive member or a cleaning device for the surface of the intermediate transfer member. The cleaning means may be a cleaning blade whose tip is pressed against the surface of the image carrier, or may be a cleaning brush that rotates while contacting the tip of the hair with the surface of the image carrier. However, it is not limited to these blades and brushes.

  According to the cleaning apparatus of the present invention, of the two rolls described above, a roll in which particles having a particle size of 5 nm or more and less than 30 nm are dispersed and arranged on the peripheral surface (hereinafter, may be referred to as a small particle size roll). The discharge product is peeled off from the surface of the image carrier and is removed from the surface of the image carrier in situ or removed from the surface of the image carrier by the cleaning means. The discharge product often enters a fine recess of less than 30 nm on the surface of the image carrier and adheres to the recess, and the particles disposed on the peripheral surface of the small particle size roll are the fine recess. The discharge product is peeled off. Here, if the particles are too small, a sufficient polishing effect cannot be exhibited. Therefore, particles having a size of 5 nm or more are dispersedly arranged on the peripheral surface of the small particle size roll, although the size is less than 30 nm. ing. In addition, the fine irregularities (scratches) on the surface of the image carrier are flattened by the small particle diameter roll.

  On the other hand, among the above two rolls, a roll in which particles having a particle size of 30 nm or more and less than 5 μm are dispersed on the peripheral surface (hereinafter sometimes referred to as a large particle size roll) is larger than the discharge product. The object to be removed is peeled off from the surface of the image carrier and is removed from the surface of the image carrier on the spot or removed from the surface of the image carrier by the cleaning means. Further, large irregularities (scratches) on the surface of the image carrier are smoothed by the large particle diameter roll.

  The number of rolls having different particle diameters is not limited to two and may be three or more.

Further, in the cleaning device of the present invention, the two rolls may be arranged downstream of the cleaning unit in the moving direction of the image carrier.
Of the above two rolls, a roll in which particles having a particle size of 30 nm or more and less than 5 μm are dispersed and arranged on the circumferential surface (large particle size roll), and a particle having a particle size of 5 nm or more and less than 30 nm is dispersed on the circumferential surface. It is preferable that the image carrier is disposed on the upstream side in the moving direction of the roll (small particle diameter roll).

  Since the two rolls are arranged downstream of the cleaning unit in the moving direction of the image carrier, a two-stage finish is provided on the surface of the image carrier from which the residue has been removed by the cleaning unit. Polished.

  In addition, the large particle diameter roll in which particles having relatively large particle diameters are dispersed and positioned is located upstream of the small particle diameter roll in which particles having relatively small particle diameters are dispersed, First, relatively rough polishing is performed to make large irregularities (scratches) on the surface of the image carrier, and then fine polishing is performed to increase the smoothness of the image carrier surface.

An image forming apparatus of the present invention that solves the above-described object includes a photoconductor that rotates around a central axis in a predetermined direction, charges the surface of the photoconductor, and irradiates the charged photoconductor surface with exposure light. An electrostatic latent image is formed on the surface of the photoconductor, the electrostatic latent image is developed with toner to obtain a toner image on the surface of the photoconductor, and the toner image is transferred to a predetermined transfer surface to be recorded on a recording medium. In an image forming apparatus for forming an image composed of a fixed toner image on the recording medium by fixing to
Cleaning means for removing residues remaining on the surface of the photoreceptor after the toner image is transferred to the transfer surface;
The photoconductors are arranged side by side in the rotation direction, each having a rotation axis parallel to the central axis of the photoconductor, and after the toner image is transferred to the transfer surface of the photoconductor Two rolls rotating in a state in which the peripheral surface is in contact with the surface of
One of the two rolls is one in which particles having a particle size of 30 nm or more and less than 5 μm are dispersed and arranged on the peripheral surface,
The other of the two rolls is characterized in that particles having a particle size of 5 nm or more and less than 30 nm are dispersedly arranged on the peripheral surface.

  The surface to be transferred here may be a surface of the intermediate transfer member in contact with the surface of the image carrier or a recording surface of a recording medium.

  According to the image forming apparatus of the present invention, since the cleaning apparatus of the present invention is provided, both the discharge product existing on the surface of the photoreceptor and the removal object larger than the discharge product are removed from the surface. Removed.

Further, in the image forming apparatus of the present invention, one of the two rolls is a particle in which particles having a particle size of 30 nm or more and less than 0.5 μm are dispersed and arranged on the peripheral surface.
The photoreceptor may be one in which a protective layer containing a resin having a crosslinked structure is formed on the outermost surface, and further, the protective layer has a structural unit having a charge transporting ability. It is preferable.

  The protective layer is, for example, at least one of a phenolic resin obtained by crosslinking a phenol derivative having a methylol group and a siloxane resin obtained by crosslinking a siloxane derivative, and includes a hydroxyl group, a carboxyl group, an alkoxysilyl group, and an epoxy group. And those containing a resin having a charge transporting structural unit containing at least one selected from a thiol group and an amino group.

  The protective layer improves the mechanical strength on the surface of the photoreceptor. However, even if such a protective layer is provided, it is inevitable that the surface of the photoreceptor is deteriorated due to a discharge phenomenon in charging, and a deteriorated film having a thickness of several tens to several hundreds nm is formed on the surface of the protective layer. Arise. It is difficult to remove the deteriorated film formed on the surface of the protective layer by the above cleaning means because the mechanical strength of the protective layer is high, but the deteriorated film has a particle diameter of 30 nm to 0.5 μm from the surface of the photoreceptor. Less than particles are removed by a roll distributed on the peripheral surface. Here, if the particle diameter is less than 30 nm, the particles are too small and the polishing ability is insufficient, and the deteriorated film cannot be sufficiently removed. The particle size of the particles here is 30 nm or more, because it may be too large to remove the deteriorated film without fail, or in some cases the protective layer may be removed deeper than necessary. It is suppressed to a range of less than 0.5 μm.

In the image forming apparatus of the present invention, the image forming apparatus further includes a developing unit that develops the electrostatic latent image formed on the surface of the photoreceptor with toner to which external additive particles having a particle size of 5 nm or more and less than 50 nm are added.
One of the two rolls may be an embodiment in which particles having a particle size of 0.5 μm or more and less than 5 μm are dispersed and arranged on the peripheral surface.

  According to this aspect, the external additive particles of 5 nm or more and less than 50 nm may enter the concave portion larger than the concave portion where the discharge product adheres on the surface of the photoreceptor, and may adhere to the concave portion. The particles having a particle size of 0.5 μm or more and less than 5 μm enter the larger concave portion, and the external additive particles are peeled off. Here, when the particle size of the particles is less than 0.5 μm, the external additive particles cannot be sufficiently removed, and conversely, when the particle size is 5 μm or more, the particles are formed in the recesses to which the external additive particles are attached. Cannot enter and the external additive particles cannot be peeled off, so the particle size of the particles here is limited to a range of 0.5 μm or more and less than 5 μm.

  Examples of the external additive particles mentioned here include inorganic oxide particles such as silica having a particle size of 20 nm or more and 30 nm or less, which controls toner chargeability or enhances toner fluidity. .

  According to the present invention, there is provided a cleaning device capable of removing both a discharge product existing on the surface of the image carrier and an object to be removed larger than the discharge product from the surface, and the cleaning device. An image forming apparatus can be provided.

  Embodiments of the present invention will be described below with reference to the drawings.

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

  The image forming apparatus 1 of the present embodiment is an image forming apparatus that employs a full-color tandem method, and uses four toner image forming units corresponding to four color toners of yellow, magenta, cyan, and black, respectively. Each toner image forming unit forms a toner image of each color in synchronization with the feeding of the intermediate transfer belt, and superimposes these toner images on an intermediate transfer belt as an intermediate medium (primary transfer), on the intermediate transfer belt The toner image superimposed on the toner image is transferred (secondary transfer) to a recording medium, and fixed.

  The image forming apparatus 1 shown in FIG. 1 is a semiconductive intermediate transfer supported by four toner image forming units 10, four primary transfer rolls 20, and three support rolls 31 so as to circulate in a counterclockwise direction. The belt 30 includes a batch transfer device 40 that performs secondary transfer, and a fixing device 50 that fixes an unfixed toner image on a sheet.

  The four toner image forming units 10 are arranged side by side in the circulation direction of the intermediate transfer belt 30, and each toner image forming unit 10 is provided with a drum-shaped photoreceptor 11 that rotates clockwise. Each photoconductor 11 is formed by laminating an undercoat layer, a charge generation layer, and a charge transport layer on a drum-shaped conductive support. The charge transport layer is a layer that becomes the outermost layer of the photoconductor 11, and the charge transport layer (the surface of the photoconductor 11) circulates around the rotation axis when the photoconductor 11 rotates around the rotation axis. Moving. The surface of the photoreceptor 11 is in contact with the intermediate transfer belt 30. In a region where the intermediate transfer belt 30 is in contact with the surface of the photoconductor 11, a primary transfer roll 20 is provided so as to sandwich the intermediate transfer belt 30 with the photoconductor 11, and this region is a primary transfer region.

  Here, FIG. 2 will be used together with FIG. 1 to further explain the image forming apparatus of this embodiment.

  FIG. 2 is a diagram showing one of the four toner image forming units shown in FIG. 1 in more detail than FIG.

  The toner image forming unit 10 shown in FIG. 2 includes a charger 12, an exposure device 13, a developing device 14, a cleaning device 15, and a static eliminator 16 in addition to the photoreceptor 11.

  The charger 12 is a non-contact charging type corotron charger. A charging bias is applied to the charger 12. As the charger, a charger that employs a contact charging method including a charging roll that rotates in contact with the photoreceptor surface 11a or a blade-like charging member may be used. The exposure device 13 irradiates exposure light based on image information toward the photoreceptor surface 11a. The developing device 14 is disposed on the upstream side of the primary transfer region around the photoreceptor 11. The developing device 14 includes a developer container 141 that contains toner, and a developing roll 142 that carries the toner contained in the developer container 141 and rotates while facing the surface 11a of the photoreceptor. The toner stored in the developer container 141 is obtained by adding external additive particles smaller than the toner base particles to the surface of the toner base particles, and has a charging characteristic of charging the negative electrode. An example of the external additive particles is inorganic oxide particles having a particle size of 5 nm or more and less than 50 nm. The static eliminator 16 is disposed on the downstream side of the primary transfer region around the photoconductor 11, and neutralizes residual charges on the surface 11 a that has passed through the primary transfer region of the photoconductor 11.

  When image formation is performed in the image forming apparatus 1 shown in FIG. 1, the surface 11 a of the photoconductor 11 is uniformly charged by a discharge phenomenon by the charger 12 and then exposed based on image information by the exposure device 13. Light is irradiated to form an electrostatic latent image on the photoreceptor surface 11a. Subsequently, toner is supplied from the developing roll 142 to the photoreceptor surface 11a on which the electrostatic latent image is formed, and the electrostatic latent image is developed with toner, so that a toner image is formed on the photoreceptor surface 11a. The toner image formed on the photoreceptor surface 11a moves from the photoreceptor surface 11a to the surface of the intermediate transfer belt 30 in the primary transfer region. The toner images formed by the toner image forming units 10 become toner images that are overlapped on the intermediate transfer belt 30.

  The batch transfer device 40 includes a secondary transfer roll 41 disposed in pressure contact with the toner image carrying surface side of the intermediate transfer belt 30 and a backup roll 42 disposed on the back side of the intermediate transfer belt 30. The intermediate transfer belt 30 is sandwiched between two rolls 41 and 42. A space between these two rolls 41 and 42 becomes a secondary transfer region.

  Further, the image forming apparatus 1 shown in FIG. 1 is provided with a paper tray 60, and the paper P accommodated in the paper tray 60 is sent out from the paper tray 60 by the feed roll 61, and is secondary at a predetermined timing. It is sent to the transfer area. In the secondary transfer area, the toner images overlapped on the intermediate transfer belt 30 are transferred onto the fed paper P. The fixing device 50 includes a fixing roll 51 having a heating mechanism 511 and a pressure roll 52 provided so as to face the fixing roll 51. Between the fixing roll 51 and the pressure roll 52 facing each other, the paper P that has passed through the secondary transfer region is conveyed. The toner constituting the toner image on the paper P is melted by the heating mechanism 511 of the fixing roll 51 and fixed on the paper P.

  A belt cleaner 70 is provided on the downstream side of the batch transfer device 40. Residues such as residual toner that could not be transferred to the paper P exist on the surface of the intermediate transfer belt 30 that has passed through the secondary transfer region. This residue is transferred by the belt cleaner 70 to the intermediate transfer belt 20. Removed from.

  Further, on the surface 11a of the photoconductor 11 shown in FIG. 2 that has passed through the primary transfer region, residual toner and toner base particles that could not be transferred to the surface of the intermediate transfer belt 30 in the primary transfer region. There are adhering external additive particles. There are also discharge products generated by the discharge phenomenon by the charger 12. The cleaning device 15 shown in FIG. 2 is a device for removing a plurality of types of residues such as residual toner, external additive particles, and discharge products from the photoreceptor surface 11a, and the photoreceptor rotation direction rather than the primary transfer region. It is arranged at a position downstream of the charger 12 and upstream of the charger rotation direction. The cleaning device 15 corresponds to an embodiment of the cleaning device of the present invention, and includes a large particle size roll 151, a small particle size roll 152, a cleaning blade 153, and a transport auger 154.

  The cleaning blade 153 is a plate-like member made of a rubber material. As a kind of rubber material used for the cleaning blade 153, a known material can be used. For example, urethane rubber, silicone rubber, fluorine rubber, chloroprene rubber, butadiene rubber, or the like can be used. Among them, it is preferable to use a polyurethane elastic body because of its excellent wear resistance. The cleaning blade 153 shown in FIG. 2 has a rectangular shape that is long in the direction perpendicular to the paper surface of FIG. 2 (the direction in which the rotating shaft 110 of the photoconductor 11 extends). May be referred to as the tip. The cleaning blade 153 is provided by a doctor system that is inclined to the downstream side in the rotation direction of the photoconductor with respect to a vertical line that rises perpendicularly from the surface 11a of the photoconductor 11 after the toner image is transferred to the intermediate transfer belt 30. Yes, the edge of the tip (tip edge portion) 1531 is in pressure contact with the surface 11a. The surface 11 a of the rotating photoconductor 11 is scraped off by the leading edge portion 1531 of the cleaning blade 153. Here, a deteriorated film having a thickness of several tens to several hundreds of nanometers is generated on the outermost surface of the photoconductor 11 due to a discharge phenomenon by the charger 12, but the deteriorated film formed on the surface of the photoconductor shown in FIG. Is scraped off by the cleaning blade 153. Further, residual toner particles and the like present on the surface 11a of the photoconductor 11 are scraped off by the leading edge portion 1531 and removed from the photoconductor surface 11a. Note that the cleaning blade 153 may be provided by a wiper method that is inclined to the upstream side in the photosensitive member rotation direction with respect to a vertical line that rises vertically from the photosensitive member surface 11a. Further, instead of the cleaning blade 153, other types of cleaning means may be provided.

  The transport auger 154 transports the foreign matter removed from the photoreceptor surface 11 a toward the outside of the cleaning device 15.

  The large particle diameter roll 151 and the small particle diameter roll 152 are arranged downstream of the cleaning blade 153 in the rotation direction of the photosensitive member and aligned in the rotation direction, and both are arranged on the rotation shaft 110 of the photosensitive member 10. Parallel rotation axes 1511 and 1521 are provided. The large particle diameter roll 151 is arranged upstream of the small particle diameter roll 152 in the photoconductor rotation direction, and has a roll body 1512 on the outer periphery of the rotation shaft 1511. The small particle size roll 152 also has a roll body 1522 on the outer periphery of the rotating shaft 1521. Any of these rolls 1512 and 1522 are SBR (styrene rubber), CR (chloroprene rubber), NBR (nitrile rubber), U (urethane rubber), EPDM (ethylene / propylene rubber), SI (silicone rubber), natural rubber. It is a foam made of an elastic rubber material such as (NR) or a solid (solid) body made of these rubber materials. The roll bodies 1512 and 1522 may be sponge bodies such as 6,6-nylon and 6-nylon and fiber aggregates such as steel wool. The roll body 151 included in the upstream large particle size roll 151 is formed by molding or extruding a material in which an elastic rubber material and particles having a particle size of 0.5 μm or more and less than 5 μm are blended, and the peripheral surface of the molded product Is subjected to polishing. On the other hand, the roll body 152 included in the small particle size roll 152 on the downstream side is obtained by molding or extruding a mixture of an elastic rubber material and particles having a particle size of 5 nm or more and less than 30 nm. The peripheral surface is polished. That is, in any of the rolls, particles are dispersedly arranged on the peripheral surfaces 151a and 152a, and the upstream large particle size roll 151 is distributed on the peripheral surface 152a of the downstream small particle size roll 152. Particles having a particle size larger than the particles are dispersedly arranged on the peripheral surface 151a.

  Examples of particles dispersed and arranged on the large particle diameter roll peripheral surface 151a and the small particle diameter roll peripheral surface 152a include inorganic particles such as silica, alumina, cesium oxide, titanium oxide, silicon carbide, and strontium iron titanate. Two or more kinds of particles may be dispersedly arranged on each roll surface 151a, 152a.

  Both the large particle size roll 151 and the small particle size roll 152 rotate in a state in which the respective peripheral surfaces 151a and 152a in which the particles are dispersed are in contact with the surface 11a that has passed through the primary transfer region of the photoconductor 11. Thus, the surface 11a is polished. As a result, unlike the roughness of the photoreceptor surface 11a after being polished by the large particle diameter roll 151 and the roughness of the photoreceptor surface 11a after being polished by the small particle diameter roll 152, the upstream large particle diameter roll is different. Reference numeral 151 denotes a relatively rough cut, and the downstream small particle diameter roll 152 performs a relatively fine cut. Note that these two rolls 151 and 152 are driven to rotate with respect to the photoconductor 11, and the rotation speed of the photoconductor 11 is the same as the rotation direction of the photoconductor 11 in a region in contact with the photoconductor surface 11 a. (Peripheral speed) and the same speed (see the arrow in FIG. 2), but may be rotated in the opposite direction, or rotated at a speed difference from the rotational speed (peripheral speed) of the photoconductor 11. It may be.

  Even on the photoreceptor surface 11a scraped off by the cleaning blade 153, there are still various unevennesses (scratches). This is unavoidable for minute scratches where the depth of the recesses and the width in the extending direction of the photosensitive member rotation axis is less than 30 nm, and deep scratches where the recesses reach a depth of 0.5 μm or more are as follows: This is because the cleaning blade 153 cannot be scraped off. The discharge product that is very small enters the fine recess of less than 30 nm and adheres to the recess, and the inorganic oxide particles of 5 nm or more and less than 50 nm, one of the external additive particles, It enters into the concave portion (a concave portion larger than the concave portion to which the discharge product adheres) and adheres to the concave portion. Particles having a particle size of 0.5 μm or more and less than 5 μm dispersed and arranged in the upstream large particle size roll 151 enter the larger concave portion, and the inorganic oxide particles adhering to the larger concave portion are removed. While peeling off from the surface of the photoreceptor, the deep scratches present on the photoreceptor surface 11a are smoothed. Here, when the particle size of the particles is less than 0.5 μm, the inorganic oxide particles cannot be sufficiently removed. On the contrary, when the particle size is 5 μm or more, the particles are formed in the recesses to which the inorganic oxide particles are attached. The particle diameter of the particles dispersed and arranged on the peripheral surface 151a of the large particle diameter roll 151 is in the range of 0.5 μm or more and less than 5 μm. It is suppressed.

  In addition, the discharge product that has entered the fine concave portion and adhered to the concave portion is peeled off by the downstream small particle size roll 152 in which particles having a particle size of 5 nm or more and less than 30 nm are dispersed and arranged. (Scratches) are smoothed and the smoothness of the photoreceptor surface 11a is increased. The particle size of the particles dispersed and arranged on the peripheral surface 152a of the small particle size roll 152 can enter a fine recess to which the discharge product adheres, and if the particles are too small, a sufficient polishing effect cannot be exhibited. In consideration of the above, it is suppressed to a range of 5 nm or more and less than 30 nm.

  The deposits peeled off by these rolls 151 and 152 fall downward and are transported out of the cleaning device 15 by the transport auger 154. Therefore, according to the cleaning device 15 shown in FIG. 2, both the discharge product existing on the photoreceptor surface 11a and the inorganic oxide particles which are external additive particles larger than the discharge product are separated from the photoreceptor. It is removed from the surface 11a.

  The large particle diameter roll 151 and the small particle diameter roll 152 have been described above. In addition to these two rolls 151 and 152, the particle diameter is different from the particle diameter of the particles dispersedly arranged on the two roll peripheral surfaces 151a and 152a. One or a plurality of rolls in which particles having a diameter are dispersedly arranged on the peripheral surface may be added. Moreover, the large particle diameter roll 151 and the small particle diameter roll 152 are replaced, the small particle diameter roll 152 that performs relatively fine cutting is disposed on the upstream side, and the large particle diameter roll 151 that performs relatively rough cutting on the downstream side. May be arranged. Furthermore, both the large particle diameter roll 151 and the small particle diameter roll 152 may be arranged upstream of the cleaning blade 153 in the photosensitive member rotation direction, and one of these two rolls is the cleaning blade 153. The other side may be disposed on the upstream side of the cleaning blade and the other side may be disposed on the downstream side of the cleaning blade 153.

  Here, the image forming apparatus adopting the full color tandem system in which four toner image forming units are arranged has been described as an example. However, the image forming apparatus of the present invention is a rotary type in one toner image forming unit. The present invention can also be applied to an image forming apparatus that employs a method of forming a four-color toner image using a full-color developing device. Further, it can be applied to an image forming apparatus provided with an intermediate transfer drum in place of the intermediate transfer belt. Further, the sheet is electrostatically adsorbed and conveyed, and the toner image formed on the photosensitive member is conveyed. The present invention can also be applied to an image forming apparatus that employs a direct transfer method in which a sheet is transferred directly to a sheet using a transfer corotron, a transfer roll, or the like.

  Although the cleaning device 15 for removing the residue from the photoreceptor surface 11a has been described in detail here, the cleaning device of the present invention is applied to the belt cleaner 70 shown in FIG. 1 for removing the residue from the intermediate transfer belt 30. You can also On the intermediate transfer belt 30, discharge products adhere to the inorganic oxide particles and the peeling discharge of the paper P generated during the secondary transfer. Therefore, the cleaning device provided with the large particle diameter roll 151 and the small particle diameter roll 152 shown in FIG. 2 is effective.

  Next, a modification of the image forming apparatus shown in FIG. 1 will be described. Similarly to the image forming apparatus described with reference to FIG. 1, the image forming apparatus in this modification adopts a full-color tandem system and includes four toner image forming units. Hereinafter, description overlapping with the description so far will be omitted, and components having the same names as those of the components of the image forming apparatus illustrated in FIG.

  The photoreceptor provided in the toner image forming unit provided in the image forming apparatus of this modification is formed by laminating a protective layer on the charge transport layer. The protective layer is a layer that becomes the outermost layer of the photoreceptor 11. This protective layer is a high-strength surface layer containing a resin having a structural unit having a charge transport function and having a crosslinked structure.

  Further, the developing device 14 of the image forming apparatus 1 according to this modification includes a developer containing body 141 containing the toner to which the inorganic oxide particles are not added.

  Further, the cleaning device 15 in this modified example includes a large particle diameter roll 151 in which particles having a particle diameter of 30 nm or more and less than 0.5 μm are dispersedly arranged on the peripheral surface 151a instead of the large particle diameter roll shown in FIG. Has been deployed.

  On the protective layer provided on the outermost surface of the photoreceptor 11, a deteriorated film having a thickness of several tens to several hundreds of nanometers is generated due to a discharge phenomenon by the charger 12. Since the protective layer is a layer containing a resin having a crosslinked structure, the mechanical strength is improved, and it is difficult to scrape the deteriorated film generated on the protective layer with the cleaning blade 153. It is scraped off by the large particle diameter roll 151 provided in this modified example, and is transported out of the cleaning device 15 by the transport auger 154. Here, if the particle diameter is less than 30 nm, the particles are too small and the polishing ability is insufficient, and the deteriorated film cannot be sufficiently removed. May be too large to remove the deteriorated film without failure, and in some cases, the protective layer may be removed deeper than necessary. For this reason, in this modification, the particle size of the particles dispersed and arranged on the peripheral surface 151a of the large particle size roll 151 is suppressed to a range of 30 nm or more and less than 0.5 μm.

  In addition, the particles dispersed and arranged in the upstream large particle size roll 151 cannot enter the small concave portion of less than 30 nm to which the discharge product is attached, and the discharge product attached to the small concave portion is on the downstream side. The particles having a particle diameter of 5 nm or more and less than 30 nm are peeled off from the photoreceptor surface 11a by the small particle diameter roll 152 in which the particles are dispersedly arranged.

  According to this modification, both the discharge product present on the photoreceptor surface 11a and the deteriorated film thicker than the size of the discharge product are removed from the photoreceptor surface 11a.

  Next, a photoconductor that can be used in the image forming apparatus described so far will be described in detail.

  As the photosensitive member that can be used here, a known photosensitive member such as an organic photosensitive member or an inorganic photosensitive member such as an amorphous silicon photosensitive member or a selenium photosensitive member can be used. An organic photoreceptor having excellent advantages in terms of properties and the like is preferably used. Further, since the photoreceptor is resistant to scratches on the surface of the photoreceptor due to rocking and rubbing, a high-strength surface layer is formed on the charge transport layer as in the photoreceptor in the image forming apparatus of the above-described modification. It is preferable to provide a protective layer, and it is more preferable to contain a resin having a structural unit having a charge transporting ability and a crosslinked structure as a material constituting the protective layer.

  Hereinafter, the protective layer will be described in detail. As this protective layer, a conductive resin dispersed in a binder resin, a normal charge transport layer material in which lubricating particles such as fluororesin and acrylic resin are dispersed, a hard coating agent such as silicon or acrylic However, from the viewpoints of strength, electrical characteristics, image quality maintenance, etc., those having charge transporting properties and having a crosslinked structure are preferable. When the protective layer contains a resin having a crosslinked structure, the hardness of the surface of the photoconductor is increased and the wear resistance is improved, and scratches on the surface of the photoconductor due to rubbing with the cleaning blade can be suppressed.

  Various materials can be used for forming the crosslinked structure, but phenolic resins, siloxane resins, urethane resins, epoxy resins, and the like are preferable in terms of characteristics, and those made of phenolic resins or siloxane-based resins are particularly preferable. In addition to the resin having a crosslinked structure, the protective layer includes a binder resin not having a crosslinked structure, conductive particles, and lubricating particles made of a fluororesin or an acrylic resin, if necessary. In forming the protective layer, a hard coat agent such as silicon or acrylic can be used as necessary. For forming the protective layer, a protective layer forming solution containing at least a precursor constituting a resin having a crosslinked structure is used.

  Furthermore, from the viewpoint of electrical characteristics, image quality maintenance, etc., it is preferable that the resin having a crosslinked structure has a charge transporting property (including a structural unit having a charge transporting ability). Note that the protective layer may function as a part of the charge transport layer.

As a resin having a structural unit having charge transporting ability and having a crosslinked structure, a phenol derivative or siloxane-based resin having a methylol group as a resin having a crosslinked structure, a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, More preferably, it contains a charge transport material having at least one selected from a thiol group and an amino group. Furthermore, it is more preferable that the infrared absorption spectrum of the phenol derivative-containing layer satisfies the conditions represented by the following formula, so that excellent electrical characteristics and high image quality can be achieved.
(P2 / P1) ≦ 0.2
Wherein, P1 represents the absorbance of the maximum absorption peaks at ^{1560cm -1 ~1640cm} -1, P2 represents the absorbance of the maximum absorption peaks at ^{1645cm -1 ~1700cm} -1. ]
The reason why the above-described effect is obtained by the above formula is not necessarily clear, but the present inventors infer as follows. That is, in the process of forming a coating film using a phenol derivative having a methylol group, it is considered that a part of the methylol group of the phenol derivative becomes an oxide such as a formyl group. Such an oxide such as a formyl group is considered to act as a carrier trap that hinders charge transport in the photoconductor, thereby reducing the electrical characteristics of the photoconductor. Here, in the infrared absorption ^spectrum, the maximum absorption peaks at 1560cm ^-1 ~1640cm -1 (P1) corresponds to the aromatic C-C stretching vibration of a phenol derivative. ^The maximum absorption peaks at 1645cm ^-1 ~1700cm -1 (P2) is thought to be derived from the oxide such as a formyl group. That is, it is considered that a photoconductor having a small absorbance ratio (P2 / P1) has few oxides such as formyl groups in the photoconductor and is excellent in carrier transportability. Therefore, by using the specific material and having the absorbance ratio (P2 / P1) of 0.2 or less, it is possible to achieve excellent electrical characteristics and high image quality. The absorbance ratio (P2 / P1) is preferably 0.18 or less, and more preferably 0.17 or less. When the absorbance ratio (P2 / P1) exceeds 0.2, the carrier transportability is lowered, the electrical characteristics of the photoreceptor are insufficient, and the image quality is lowered.

  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 substituted phenols, bisphenol A, bisphenol Z, and the like having a phenol structure 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, triethanolamine and the like. 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.
F-[(X1) m1- (R1) m2-Y] m3 (I)
In the general formula (I), F represents an organic group derived from a compound having a hole transporting ability, X1 represents an oxygen atom or a sulfur atom, R1 represents an alkylene group (the number of carbon atoms is preferably 1 to 15, 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 represent 0 or 1, and m3 represents 1 Represents an integer of ~ 4.
F-[(X2) n1- (R2) n2- (Z) n3G] n4 (II)
In the general formula (II), F represents an organic group derived from a compound having a hole transporting ability, X2 represents an oxygen atom or a sulfur atom, R2 represents an alkylene group (the number of carbon atoms is preferably 1 to 15, 10 is more preferable), Z is an alkylene group, oxygen atom, sulfur atom, NH or COO, G is an epoxy group, n1, n2 and n3 are each independently 0 or 1, n4 is an integer of 1 to 4 Indicates.
F- [D-Si (R3) (3-a) Qa] b (III)
In the general formula (III), F is an organic group derived from a compound having a hole transporting ability, D is a divalent group having flexibility, and R3 is a hydrogen atom, a substituted or unsubstituted alkyl group. (The carbon number is preferably 1-15, more preferably 1-10) or a substituted or unsubstituted aryl group (the carbon number is preferably 6-20, more preferably 6-15), Q is a hydrolyzable group. A represents an integer of 1 to 3, and b represents an integer of 1 to 4.

In addition, the divalent group D having flexibility described above specifically links the F portion for imparting photoelectric characteristics with a substituted silicon group that contributes to the construction of a three-dimensional inorganic glassy network. It is a divalent group that plays a role. 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. Specifically, D is a divalent hydrocarbon group represented by -CαH2α-, -CβH2β-2-, -CγH2γ-4- (where α represents an integer of 1 to 15, β represents 2 to 15 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 those obtained by substituting constituent atoms of these characteristic groups with other substituents. The hydrolyzable group Q is preferably an alkoxy group, more preferably an alkoxy group having 1 to 15 carbon atoms.

  As the organic group F derived from the compound having a hole transporting ability in the compounds represented by the general formulas (I) to (III), a compound represented by the following general formula (IV) is preferable.

In the general formula (IV), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group, Ar ⁵ represents a substituted or unsubstituted aryl group or an arylene group, and 1-4 of Ar ^{1 to} Ar ⁵ are-[(X1) m1- (R1) m2-Y],-[(X2) n1- in the compounds represented by the general formulas (I) to (III). (R2) n2- (Z) n3G], or a site represented by-[D-Si (R3) (3-a) Qa] and a bond, and k is 0 or 1.

  In addition, conductive particles may be added to the protective layer in order to lower the residual potential. Examples of the conductive particles include metals, metal oxides, and carbon black. Among these, metals or metal oxides are more preferable. Examples of the metal include aluminum, zinc, copper, chromium, nickel, silver, and stainless steel, or those obtained by depositing these metals on the surface of plastic particles. Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony and tantalum-doped tin oxide, and antimony-doped zirconium oxide. It is done. These can be used alone or in combination of two or more. When two or more types are used in combination, they may be simply mixed, or may be in the form of a solid solution or fusion. From the viewpoint of transparency of the protective layer, the average particle size of the conductive particles is preferably 0.3 μm or less, and particularly preferably 0.1 μm or less.

In addition, a compound represented by the following general formula (V-1) can also be added to the protective layer in order to control various physical properties such as strength and film resistance of the protective layer.
Si (R ₃₀ ) (4-c) Q _c (V-1)
In the general formula (V-1), R ₃₀ 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 (V-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, it is also preferable to use a compound having two or more silicon atoms as shown in the following general formula (V-2).
B- (Si (R ₃₁ ) _(3-d) Q _d ) ₂ (V-2)
In the above formula (V-2), B represents a divalent organic group, R ₃₁ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q represents a hydrolyzable group, and d represents 1 to 3. Indicates an integer.

  The protective layer has a cyclic compound having a repeating structural unit represented by the following general formula (V-3) for extending pot life, controlling film characteristics, reducing torque, and improving the uniformity of the coating film surface, or Derivatives from the compounds can also be included.

In General Formula (V-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 (V-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.

  Further, various particles can be added in order to control the contamination resistance adhesion, lubricity, hardness, etc. of the photoreceptor surface. They can be used alone or in combination of two or more.

  An example of the particles may include silicon atom-containing particles. The silicon atom-containing particles are particles containing silicon as a constituent element, and specifically include colloidal silica. The colloidal silica used as the silicon atom-containing particles has an average particle diameter of preferably 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 is not particularly limited, but preferably 0.1 to 50 mass based on the total solid content of the protective layer in terms of film formability, electrical properties, and strength. %, More preferably 0.1 to 30% by mass.

  The silicon dioxide particles used as the silicon atom-containing particles are spherical and have an average particle diameter of preferably 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 particles are small particles that are chemically inert and have excellent dispersibility in the resin, and because the content required to obtain sufficient properties is low, photosensitivity can be achieved without hindering the crosslinking reaction. The surface properties of the body can be improved. In other words, it is possible to improve the lubricity and water repellency of the surface of the photoreceptor 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. . The content of the silicone particles in the protective layer 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.

Other particles include fluorine-based particles such as ethylene tetrafluoride, ethylene trifluoride, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, and the 8th Polymer Materials Forum Lecture Proceedings p89. Particles made of a resin obtained by copolymerizing a fluororesin and a monomer having a hydroxyl group, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ —SnO ₂ , ZnO—TiO ₂ , ZnO Examples thereof include semiconductive metal oxides such as —TiO ₂ , MgO—Al ₂ O ₃ , FeO—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, 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, hindered phenols include “Sumilizer BHT-R”, “Sumilizer MDP-S”, “Sumilizer 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 "," 114 " ”,“ 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.

  For the protective layer, 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 resin such as polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin may be contained. In this case, the insulating resin can be added at a desired ratio, thereby suppressing adhesion with the charge transport layer, coating film defects due to heat shrinkage and repellency, and the like.

  The protective layer is formed by applying a coating solution for forming a protective layer containing a compound having the charge transporting structural unit and a constituent material such as a phenol derivative or a siloxane derivative having the methylol group onto the charge transport layer and curing it. Is formed.

  Since the protective layer is formed using the above-described charge transport material, it is preferable to add a catalyst to the protective layer forming coating solution or to use the catalyst when preparing the protective layer forming coating solution. 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.

  Further, in order to remove the catalyst at the time of synthesis from a phenol derivative or siloxane derivative having a methylol group, the phenol derivative was dissolved in an appropriate solvent such as methanol, ethanol, toluene, ethyl acetate, washed with water, and a poor solvent was used. It is preferable to perform treatment such as reprecipitation, or to perform treatment using an ion exchange resin or an inorganic solid.

  For example, as an ion exchange resin, Amberlite 15, Amberlite 200C, Amberlyst 15E (above, manufactured by Rohm and Haas); Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above 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 (DuPont); Amberlite IRA-400, Amberlite IRA-45 (above, Rohm and Anion exchange resins such as (made by Haas) are listed.

Further, as the inorganic solid, an inorganic solid in which a group containing a protonic acid group such as Zr (O ₃ PCH ₂ CH ₂ SO ₃ H) ₂ or Th (O ₃ PCH ₂ CH ₂ COOH) ₂ is bonded to the surface. A polyorganosiloxane containing a protonic acid group such as a polyorganosiloxane having a sulfonic acid group; a heteropolyacid such as cobalt tungstic acid or phosphomolybdic acid; an isopolyacid such as niobic acid, tantalic acid or molybdic acid; silica gel, alumina, Single metal oxides such as chromia, zirconia, CaO, MgO; complex metal oxides such as silica-alumina, silica-magnesia, silica-zirconia, zeolites; clay minerals such as acid clay, activated clay, montmorillonite, and kaolinite ; LiSO _4, metal sulfates MgSO ₄ and the like; phosphoric acid zirconium, phosphorus Metal phosphates such as lanthanum; coupled to on silica gel by reacting aminopropyltriethoxysilane containing an amino group such as the resulting solid which groups _{surface; LiNO 3, Mn (NO 3} ) 2 and the like of a metal nitrate Inorganic solids such as polyorganosiloxanes containing amino groups such as amino-modified silicone resins.

  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 the dip coating method generally used for the production of the photoreceptor, 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.

  Since the solvent is preferably an alcohol solvent, a ketone solvent, or a mixed solvent thereof, the compound having a charge transporting structural unit used for forming the protective layer to be used may be used as the solvent. It is preferable that it is dissolved.

  The amount of the solvent can be set arbitrarily, but if the amount is too small, the constituent materials are likely to be precipitated. Therefore, the amount of the solvent is preferably 0.5 to 30 mass with respect to the total 1 mass part of the solid content contained in the coating liquid for forming the protective layer. Parts, more preferably 1 to 20 parts by mass.

  Coating methods for forming a protective layer using a coating solution for forming a protective layer include blade coating, wire bar coating, spray coating, dip coating, bead coating, air knife coating, and curtain coating. A usual method such as can be used. However, when a required film thickness cannot be obtained by a single application, the necessary film thickness can be obtained by applying a plurality of times. In addition, when performing the multiple application | coating several times, a heat processing may be performed every time of application | coating, and may be after carrying out multiple application | coating several times.

  After applying the coating liquid for forming the protective layer on the charge transport layer, a curing process is performed. Usually, during the curing treatment, the curing temperature is higher and the curing time is longer in order to promote the crosslinking reaction of the phenol derivative or siloxane derivative and increase the mechanical strength of the protective layer. However, in such a case, the absorbance ratio (P2 / P1) tends to exceed 0.2 in the case of a phenol-based resin, and the electrical characteristics are remarkably deteriorated. Therefore, in the case of a phenol-based resin, it is preferable to control with a curing temperature, a curing time, a crosslinking atmosphere or a curing catalyst so that the IR spectrum of the protective layer satisfies the above conditions. That is, in the case of a phenol-based resin, the curing temperature during the curing treatment is preferably 100 to 170 ° C. so that the IR spectrum of the protective layer satisfies the condition represented by (P2 / P1) ≦ 0.2. 100-150 degreeC is further more preferable, and 100-140 degreeC is more preferable. The curing time is preferably 30 minutes to 2 hours, more preferably 30 minutes to 1 hour. In the case of a siloxane-based resin, the curing temperature during the curing treatment is preferably in the range of 100 to 170 ° C, more preferably in the range of 100 to 150 ° C, and even more preferably in the range of 100 to 140 ° C. The curing time is preferably 30 minutes to 2 hours, more preferably 30 minutes to 1 hour.

Further, as an atmosphere for performing the curing treatment (crosslinking reaction), the absorbance ratio (P2 / P1) is reduced under a so-called oxidation inert gas atmosphere (inert gas atmosphere) such as nitrogen, helium, and argon. It is effective. 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). Further, in the compound represented by the general formula (I), when the site represented by (— (X1) m1- (R1) m2-Y) is —CH ₂ —OH, the influence of the electrical characteristics due to the curing temperature is the greatest. Since it tends to be large and is sensitive to oxidation, it is preferable to perform the curing treatment in the above preferred temperature range.

  Furthermore, it is preferable to use a curing catalyst during the curing treatment. Examples of the curing catalyst include bissulfonyldiazomethanes such as bis (isopropylsulfonyl) diazomethane, bissulfonylmethanes such as methylsulfonyl p-toluenesulfonylmethane, and sulfonylcarbonyldiazomethanes such as cyclohexylsulfonylcyclohexylcarbonyldiazomethane, 2 Sulfonylcarbonyl alkanes such as methyl-2- (4-methylphenylsulfonyl) propiophenone, nitrobenzyl sulfonates such as 2-nitrobenzyl p-toluenesulfonate, alkyl and aryl sulfonates such as pyrogallol trismethanesulfonate (G) Benzoinsulfonates such as benzoin tosylate, N- (trifluoromethylsulfonyloxy) phthalimide N-sulfonyloxyimides, pyridones such as (4-fluorobenzenesulfonyloxy) -3,4,6-trimethyl-2-pyridone, 2,2,2-trifluoro-1-trifluoromethyl-1 Photoacid generators such as sulfonate esters such as-(3-vinylphenyl) -ethyl-4-chlorobenzenesulfonate, onium salts such as triphenylsulfonium methanesulfonate and diphenyliodonium trifluoromethanesulfonate, protonic acid or Lewis Examples thereof include compounds obtained by neutralizing acids 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 Compounds neutralized with phosphite, as well as NureCure 2500X, 4167, X-47-110, 3525, 5225 commercially available as acid-base blocking catalysts (trade name, King Ndasutori Co., Ltd.), and the like. 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 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 curing catalysts is not specifically limited, 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. preferable.

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

  Specifically, β-diketones such as acetylacetone, trifluoroacetylacetone, hexafluoroacetylacetone, and dipivaloylmethylacetone; acetoacetates such as methyl acetoacetate and ethyl acetoacetate; bipyridine and derivatives thereof; glycine and its Derivatives; ethylenediamine and derivatives thereof; 8-oxyquinoline and derivatives thereof; salicylaldehyde and derivatives thereof; catechol and derivatives thereof; bidentate ligands such as 2-oxyazo compounds; diethyltriamine and derivatives thereof; nitrilotriacetic acid and derivatives thereof And tridentate ligands such as ethylenediaminetetraacetic acid (EDTA) and derivatives thereof. In addition to the organic ligands as described above, inorganic ligands such as pyrophosphoric acid and triphosphoric acid can be exemplified. As the multidentate ligand, a bidentate ligand is particularly preferable, and specific examples include a bidentate ligand represented by the following general formula (V-4) in addition to the above.

In the formula (V-4), R ³² and R ³³ each independently represent an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group, or an alkoxy group having 1 to 10 carbon atoms.

As the bidentate ligand, those in which R ³² and R ^{33 in the} general formula (V-4) are the same are particularly preferable. By making R ³² and R ^{33 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.

  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.

Oxygen permeability at 25 ° C. of the protective layer is preferably not more than ^{4 × 10 12 fm / s ·} Pa, more preferably not more than ^{3.5 × 10 12 fm / s ·} Pa, 3 × 10 12 More preferably, it is 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 satisfies the above conditions, the gas hardly penetrates into the protective layer. Therefore, the permeation of the discharge product generated by the toner image formation cycle is suppressed, the deterioration of the compound contained in the protective layer is suppressed, the electrical characteristics can be maintained at a high level, and high image quality and long life are achieved. It is valid.

  In the case of a phenol resin, when the protective layer is formed so that the absorbance ratio (P2 / P1) of the infrared absorption spectrum satisfies the above conditions, the curing temperature should be set relatively low in an air atmosphere. is required. Therefore, it is difficult to lower the oxygen transmission coefficient at 25 ° C. of the protective layer, but the absorbance ratio (P2 / P1) satisfies the above condition, and the oxygen transmission coefficient at 25 ° C. of the protective layer satisfies the above condition. By satisfying these conditions, a photoreceptor that can further improve electrical characteristics and achieve higher image quality can be obtained.

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

  By providing the protective layer on the outermost surface of the photoconductor, the photoconductor scratches and abrasion caused by the force acting on the photoconductor from the cleaning blade are remarkably improved, and further, the permeation of discharge products generated during charging is further improved. Is suppressed, the deterioration of the workpiece contained in the protective layer is suppressed, and the electrical characteristics can be maintained at a high level. Therefore, the protective layer is also effective for improving the image quality.

  Next, the developer container 141 of the developing device 14 shown in FIG. 2 will be described in detail. As described above, the developer container 141 contains toner, and this toner has various external additive particles attached to the surface of the toner base particles, and is particularly limited by the manufacturing method. is not. Examples of the toner include particles obtained by a kneading and pulverizing method in which a binder resin, a colorant, a release agent, a transfer auxiliary agent, and the like are kneaded, pulverized, and classified as necessary. Method of changing shape with mechanical impact force or thermal energy, emulsion polymerization of binder resin polymerizable monomer, and formed dispersion, colorant, mold release agent, transfer aid, if necessary Emulsion polymerization aggregation method to obtain toner particles by mixing with a dispersion liquid such as a charge control agent and heat-fusing, polymerizable monomer and colorant, release agent, necessary to obtain a binder resin Depending on the suspension polymerization method in which a solution such as a charge control agent is suspended in an aqueous solvent for polymerization, a binder resin and a colorant, a release agent, a transfer aid, and a solution such as a charge control agent as necessary. What is obtained by the dissolution suspension method etc. which suspend and granulate in an aqueous solvent can be used. In addition, a toner produced by 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 give a core-shell structure can be used. From the viewpoint of particle size distribution control, a suspension polymerization method, an emulsion polymerization aggregation method and a dissolution suspension method which are produced with an aqueous solvent are preferable, and an emulsion polymerization aggregation method is particularly preferable.

  The toner may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.

The toner is composed of a binder resin, a colorant, a release agent, and the like. The volume average particle size of the toner is preferably in the range of 2 to 12 μm, and more preferably in the range of 3 to 9 μm. Further, the average shape factor (ML ² / A) × (100π / 4) of the toner base particles: ML is the absolute maximum length of the toner base particles, and A is the projected area of the toner base particles. By using those in the range, more preferably from 100 to 130, it is possible to obtain images with high development, transferability, and high image quality.

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

  In addition, toner colorants include magnetic powders such as magnetite and ferrite, carbon black, aniline blue, caryl blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, and malachite green oxa. Rate, lamp black, rose bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 can be exemplified as a representative one.

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

  Further, various external additive particles are added to the toner. That is, to the toner, inorganic particles, organic particles, composite particles obtained by adhering inorganic particles to the organic particles, and the like can be added for the purpose of removing deposits and deteriorated substances on the surface 11a of the photoreceptor 11. Inorganic particles having excellent polishing properties are particularly preferred. Inorganic particles include silica, alumina, titania, zirconia, barium titanate, aluminum titanate, strontium titanate, magnesium titanate, zinc oxide, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, Various inorganic oxides such as manganese oxide, boron oxide, silicon carbide, boron carbide, titanium carbide, silicon nitride, titanium nitride, and boron nitride, nitrides, borides, and the like are preferably used. Moreover, titanium coupling agents such as tetrabutyl titanate, tetraoctyl titanate, isopropyl triisostearoyl titanate, isopropyl tridecyl benzene sulfonyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, γ- (2-amino) Ethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) γ-aminopropyltrimethoxysilane Hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane The treatment may be performed with a silane coupling agent such as run, decyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, o-methylphenyltrimethoxysilane, and p-methylphenyltrimethoxysilane. Further, hydrophobic treatment with a higher fatty acid metal salt such as silicone oil, aluminum stearate, zinc stearate, calcium stearate can be preferably performed.

  Examples of the organic particles include styrene resin particles, styrene acrylic resin particles, polyester resin particles, and urethane resin particles. If the particle size is too small, the polishing ability is insufficient, and if it is too large, the surface 11a of the photoreceptor is likely to be damaged. Therefore, the average particle size is in the range of 5 to 1000 nm, preferably in the range of 5 to 800 nm. More preferably, the one in the range of 5 to 700 nm is used. Moreover, it is preferable that the sum with the addition amount of the said lubricant is 0.6 mass% or more.

  Other external additive particles added to the toner include external additive particles having a particle size of 5 nm or more and less than 50 nm. As a specific example of the external additive particles, inorganic oxide particles (for example, manufactured by Nippon Aerosil Co., Ltd.) having a particle size of 20 nm or more and 30 nm or less, such as silica, which controls toner chargeability or enhances toner fluidity, are used. RY50).

  Further, a lubricant may be added to the toner in order to form a lubricant film on both the photoreceptor surface 11 and the leading edge 1531 of the cleaning blade 153 to suppress wear of the leading edge 1531. Examples of the lubricant include those containing at least one of a fatty acid metal salt and a higher alcohol.

  Fatty acid metal salts include metal salts of stearic acid cadmium, barium, lead, iron, nickel, cobalt, copper, aluminum, magnesium, etc .; dibasic lead stearate; zinc oleate, magnesium, iron, cobalt, copper, Metal salts such as lead and calcium; metal salts such as palmitic acid and aluminum and calcium; lead caprylate; lead caproate; zinc linoleate; cobalt linoleate; calcium ricinoleate; metal salts such as ricinoleic acid and zinc and cadmium; Among them, zinc stearate is preferable because of its high lubricating effect.

The developer container 141 may contain a so-called two-component developer containing a toner and a carrier, or may contain a one-component developer containing no carrier. As the carrier in the two-component developer, iron powder, glass beads, ferrite powder, nickel powder, or those having a surface coated with resin coating are used. Further, the mixing ratio of the carrier and the toner can be set as appropriate.
(Example)
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these. Unless otherwise specified, all “parts” mean “parts by mass”.
[Preparation of Photoreceptor A]
100 parts of zinc oxide (SMZ-017N: manufactured by Teika) was stirred and mixed with 500 parts of toluene, and 2 parts of a silane coupling agent (A1100: manufactured by Nihon Unicar) was added and stirred for 5 hours. Thereafter, toluene was distilled off under reduced pressure and baked at 120 ° C. for 2 hours. As a result of analyzing the obtained surface-treated zinc oxide by fluorescent X-ray, the Si element strength was 1.8 × 10 ⁻⁴ of the zinc element strength.

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

  Next, the Bragg angle (2θ ± 0.2 °) in the X-ray diffraction spectrum is 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 °, 28 . 1 part of hydroxygallium phthalocyanine having a strong diffraction peak at 3 ° is mixed with 1 part of polyvinyl butyral (ESREC BM-S, Sekisui Chemical) and 100 parts of n-butyl acetate, and dispersed with a glass shaker for 1 hour in a paint shaker. As a result, a coating solution was obtained. The obtained 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, a coating solution prepared by dissolving 2 parts of the charge transporting compound (1) and 3 parts of a polymer compound (viscosity average molecular weight 39,000) in 20 parts of chlorobenzene having the following structure is applied onto the charge generation layer by dip coating. And heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 22 μm. The photoreceptor thus formed up to the charge transport layer is referred to as a photoreceptor A.

[Preparation of Photosensitive Member B]
5 parts of the following compound (1), 7 parts of resol type phenolic resin (PL-4852, manufactured by Gunei Chemical Co., Ltd.), 0.03 part of methylphenylpolysiloxane, and 20 parts of isopropanol are mixed and dissolved. A coating solution for forming a protective layer was obtained. This protective layer-forming coating solution is applied on the charge transport layer of the photoreceptor prepared in the same manner as the photoreceptor A by a dip coating method and dried at 130 ° C. for 40 minutes to crosslink a phenol derivative having a methylol group. A protective layer having a film thickness of 3 μm containing a resin was formed. The photoreceptor thus formed up to the protective layer is referred to as a photoreceptor B.

[Preparation of Photoreceptor C]
To the constituent materials shown below, 5 parts of methyl alcohol and 0.3 part of ion exchange resin (Amberlyst 15E) were added, and the reaction for protecting group exchange was carried out for 24 hours by stirring at room temperature.
Constituent material Compound (2) having the following structure 2 parts Compound (3) having the following structure 1 part Colloidal silica 0.3 part Me (MeO) ₂ -Si- (CH ₂ ) ₄ -Si-Me (OMe) ₂ 2 parts ( Heptadecafluoro-1,1,2,2-tetrahydrodecyl) methyldimethoxysilane 0.1 part hexamethylcyclotrisiloxane 0.3 part ZX-022 (Fuji Kasei Kogyo Co., Ltd.) 0.25 part

Thereafter, 10 parts of n-butanol and 0.25 parts of distilled water were added and hydrolysis was carried out for 5 minutes. 0.1 parts of aluminum trisacetylacetonate (Al (aqaq) 3), 0.1 part of acetylacetone, 3,5-di-t-butyl-to the liquid obtained by filtering and separating the ion exchange resin from the hydrolyzed product 0.4 parts of 4-hydroxytoluene (BHT) was added, and this coating solution was applied on the charge transport layer of the photoconductor produced in the same manner as photoconductor A by a ring-type dip coating method and air-dried at room temperature for 30 minutes. After that, the film was cured by heating at 130 ° C. for 1 hour to form a protective layer having a thickness of 3 μm containing a siloxane-based resin in which a siloxane derivative was crosslinked. The photoreceptor formed up to the protective layer in this way is referred to as a photoreceptor C.
Example 1
As a testing machine, an image forming apparatus having the same basic configuration as that of the image forming apparatus shown in FIG. 1 was used. That is, in the image forming apparatus used here, the above-mentioned photoreceptor A in which the protective layer, which is a high-strength surface layer, is omitted and the outermost surface is composed of a charge transport layer is incorporated. Further, as the developing device, a developing device having a developer containing body containing toner added with RY50 manufactured by Nippon Aerosil Co., Ltd., which is an inorganic oxide particle having a particle size of 20 nm to 30 nm was used.

  Furthermore, here, a roll body having a diameter of 16 mm is prepared by adding 5 wt% of particles having a particle diameter of 0.5 μm to the foamed rubber, and the roll body in which the 0.5 μm particles are dispersedly arranged is upstream. It was used as a roll body of the large particle roll on the side. Further, a roll body having a diameter of 16 mm is prepared by adding 5 wt% of particles having a particle diameter of 5 nm to the foamed rubber, and the roll body in which the 5 nm particles are dispersed and arranged is a roll of a small particle roll on the downstream side. Used as a body.

  Table 1 shows a characteristic configuration of the image forming apparatus used here.

In Table 1, the column of “large particle size roll” represents the particle size of the particles dispersed and arranged in the roll body of the large particle size roll, and the column of “small particle size roll” represents the particle size of the small particle size roll. The particle size of the particles dispersed and arranged in the roll body (hereinafter the same). In addition, “present” in the column of “inorganic oxide particles” indicates that a developing device having a developer container containing toner added with RY50 manufactured by Nippon Aerosil Co., Ltd. was used (hereinafter the same) ).

  In the test, a running test in which 5 sheets of process direction streak charts each having a color area coverage of 10% were repeatedly collected every 20 seconds was performed under an environment of normal temperature and humidity (20 ° C., 55% RH). After ten thousand sheets, 10,000 sheets were performed even in an environment of high temperature and high humidity (28 ° C., 80%), and finally 10,000 sheets were performed in an environment of low temperature and low humidity (10 ° C., 20% RH).

  The evaluation was performed after a total of 30,000 running tests were performed, and then a 20% halftone sample image and a character sample image were collected. It was observed whether or not there was an image quality defect in the spot. The results are also shown in Table 1 above.

As shown in Table 1, there was no image quality defect in the formed image of the 20% halftone sample image and the formed image of the character sample image, and both formed images had good image quality.
(Example 2)
The large roll is replaced with a roll having 5 wt% of particles having a particle size of 4 μm, and the small roll is replaced with a roll having 5 wt% of particles having a diameter of 29 nm added. Except for the above, an image forming apparatus having the same configuration as that of the image forming apparatus used in Example 1 was used, a test similar to Example 1 was performed, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 1 above together with the characteristic configuration of the image forming apparatus used in Example 2.

The results here were the same as the results in Example 1, and all the formed images had good image quality.
(Example 3)
The photoconductor is replaced with a photoconductor B provided with a protective layer containing a phenolic resin cross-linked with a phenol derivative, which is a high-strength surface layer on the outermost surface, and the developing device has no RY50 manufactured by Nippon Aerosil Co., Ltd. Instead of a developing device having a developer container containing the added toner. Moreover, the large particle diameter roll was replaced with one having a roll body to which 5 wt% of particles having a particle diameter of 30 nm were added. Except for these changes, an image forming apparatus having the same configuration as that of the image forming apparatus used in Example 1 was used, a test similar to that in Example 1 was performed, and evaluation was performed in the same manner as in Example 1. It was. The results are shown in Table 1 together with the characteristic configuration of the image forming apparatus used here. “None” shown in the column of “Inorganic oxide particles” indicates that RY50 manufactured by Nippon Aerosil Co., Ltd. used a developing device having a developer container containing an additive-free toner (hereinafter the same). ).

Similar to the result in Example 1, the results in Example 3 were all good in image quality.
Example 4
The photoconductor was replaced with photoconductor C provided with a protective layer containing a siloxane-based resin crosslinked with a siloxane derivative, which is a high-strength surface layer on the outermost surface. In addition, the large roll is replaced with a roll having 5 wt% of particles having a particle diameter of 0.4 μm, and a roll having 5 wt% of particles having a diameter of 29 nm is added. It replaced with what it has. Except for these changes, an image forming apparatus having the same configuration as that of the image forming apparatus used in the third embodiment is used, a test similar to the first embodiment is performed, and an evaluation is performed in the same manner as the first embodiment. It was. The results are shown in Table 1 together with the characteristic configuration of the image forming apparatus used in Example 4.

The results here were the same as the results in Example 1, and all the formed images had good image quality.
(Comparative Example 1)
An image forming apparatus having the same configuration as that of the image forming apparatus used in Example 2 was used except that the roll having a large particle diameter was replaced with a roll body to which particles having a particle diameter of 5 μm were added at 5 wt%. The same test as in Example 1 was performed, and the evaluation was performed in the same manner as in Example 1. The results are shown in Table 1 together with the characteristic configuration of the image forming apparatus used here.

As a result in Comparative Example 1, streaky density unevenness was confirmed in the rotation direction of the photosensitive member (process direction) in both the formed image of the 20% halftone sample image and the formed image of the character sample image.
(Comparative Example 2)
An image forming apparatus having the same configuration as that of the image forming apparatus used in Example 3 was used except that the roll having a large particle diameter was replaced with a roll body added with 5 wt% of particles having a particle diameter of 29 nm. The same test as in Example 1 was performed, and the evaluation was performed in the same manner as in Example 1. Table 1 shows the results together with the characteristic configuration of the image forming apparatus used in Comparative Example 2.

As a result, an image flow in which characters flow in the extending direction of the rotation axis of the photosensitive member was confirmed in the character sample image.
(Comparative Example 3)
Implementation was performed using an image forming apparatus having the same configuration as that of the image forming apparatus used in Example 3 except that the small-diameter roll was replaced with a roll having 5 wt% of particles having a particle diameter of 4 nm added thereto. The same test as in Example 1 was performed, and the evaluation was performed in the same manner as in Example 1. The results are shown in Table 1 together with the characteristic configuration of the image forming apparatus used here.

In Comparative Example 3, a so-called white spot was observed in which the image was whitened both in the formed image of the 20% halftone sample image and the formed image of the character sample image.
(Comparative Example 4)
Implementation was performed using an image forming apparatus having the same configuration as that of the image forming apparatus used in Example 4 except that the small-diameter roll was replaced with a roll having 5 wt% of particles having a particle size of 30 nm added. The same test as in Example 1 was performed, and the evaluation was performed in the same manner as in Example 1. Table 1 shows the results together with the characteristic configuration of the image forming apparatus used in Comparative Example 4.

  Similar to the result in Comparative Example 3, the result here was also confirmed to be white in any of the formed images.

  Concentration unevenness in Comparative Example 1 was caused by the fact that RY50 manufactured by Nippon Aerosil Co., Ltd., which is an inorganic oxide particle, was not removed from the surface of the photoconductor but was charged on the surface of the photoconductor. This is considered to be an image quality defect caused by an abnormal charging caused by RY50 manufactured by Co., Ltd. On the other hand, in Example 2 using the large particle diameter roll in which particles having a particle diameter of 4 μm are dispersed, the density unevenness generated in Comparative Example 1 does not occur. In a large-diameter roll in which particles having a particle size of 5 μm are dispersed, the particles do not enter the concave portion to which RY50 manufactured by Nippon Aerosil Co., Ltd. has adhered, and RY50 manufactured by Nippon Aerosil Co., Ltd. may be peeled off from the surface of the photoreceptor. I think I couldn't.

  The image flow in Comparative Example 2 is considered to be an image quality defect caused by the deterioration film on the surface of the photoreceptor not being removed. In Comparative Example 2, since the mechanical strength of the surface of the photoreceptor is enhanced by the protective layer, it is considered difficult to remove the deteriorated film with the cleaning blade, but a photoreceptor having the same protective layer was used. In Example 3, the image flow generated in Comparative Example 1 does not occur. Comparing Comparative Example 2 and Example 3, in Example 3, a large particle size roll in which particles having a particle size of 30 nm were dispersed was used, whereas in Comparative Example 2, particles having a particle size of 29 nm were used. A dispersed large particle roll was used. From this, it can be said that a deteriorated film cannot be sufficiently removed with a large-diameter roll in which particles having a particle diameter of 29 nm are dispersed.

  The white spots in Comparative Example 3 and Comparative Example 4 are considered to be image quality defects caused by the discharge products not being removed from the surface of the photoreceptor and the remaining discharge products absorbing moisture. On the other hand, white spots are not generated in Example 3 using the small particle size roll in which particles having a particle size of 5 nm are dispersedly arranged. From this, it can be said that the discharge product cannot be sufficiently removed by a small particle roll in which particles having a particle diameter of 4 nm are dispersed. Further, white spots were not generated even in Example 4 using a small particle diameter roll in which particles having a particle diameter of 29 nm were dispersed and small particles having a particle diameter of 30 nm used in Comparative Example 4 were dispersed. With the particle size roll, it is considered that the particles could not enter the fine recesses to which the discharge product adhered, and the discharge product could not be peeled off from the surface of the photoreceptor.

  From the above results, a large-diameter roll in which particles having a particle diameter of 30 nm or more and less than 5 μm are dispersed and a small-diameter roll in which particles having a particle diameter of 5 to 30 nm are dispersed are used. It was confirmed that both the discharge product existing on the surface and the removal target larger than the discharge product can be removed from the surface.

1 is a diagram illustrating a schematic configuration of an image forming apparatus according to an embodiment of the present invention. FIG. 2 is a diagram showing one of the four toner image forming units shown in FIG. 1 in more detail than FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Image forming apparatus 10 Toner image forming unit 11 Photoconductor 11a Surface 110 Rotating shaft 12 Charger 13 Exposure device 14 Developing device 15 Cleaning device 151 Large particle diameter roll 151a Peripheral surface 1511 Rotating shaft 152 Small particle diameter roll 152a Peripheral surface 1521 Rotation Shaft 153 Cleaning blade 16 Static eliminator 20 Primary transfer roll 30 Intermediate transfer belt 40 Batch transfer device 50 Fixing device 60 Paper tray 70 Belt cleaner

Claims (2)

A toner image is carried on the transfer surface of an image carrier that conveys the toner image to a transfer area where the toner image is transferred to the transfer surface by carrying the toner image on the surface and circulatingly moving around the central axis. In a cleaning device for removing from the surface the residue remaining on the surface after the transfer
Cleaning means for removing residues remaining on the surface of the image carrier after the toner image is transferred to the transfer surface;
Arranged side by side in the moving direction of the image carrier, each having a rotation axis parallel to the central axis of the image carrier, and transferring the toner image onto the transfer surface of the image carrier Two rolls that rotate in a state in which the peripheral surface is in contact with the surface after being made,
One of the two rolls is one in which particles having a particle size of 30 nm or more and less than 5 μm are dispersed and arranged on the peripheral surface,
The other of the two rolls is a cleaning device in which particles having a particle size of 5 nm or more and less than 30 nm are dispersedly arranged on the peripheral surface. A photosensitive member rotating around a central axis in a predetermined direction, charging the surface of the photosensitive member, and irradiating the charged photosensitive member surface with exposure light to form an electrostatic latent image on the photosensitive member surface; The electrostatic latent image is developed with toner to obtain a toner image on the surface of the photoreceptor, and the toner image is transferred onto a predetermined transfer surface and fixed on the recording medium, thereby fixing the toner image on the recording medium. In an image forming apparatus for forming an image comprising:
Cleaning means for removing residues remaining on the surface of the photoreceptor after the toner image is transferred to the transfer surface;
The photoconductors are arranged side by side in the rotation direction, each having a rotation axis parallel to the central axis of the photoconductor, and after the toner image is transferred to the transfer surface of the photoconductor Two rolls rotating in a state in which the peripheral surface is in contact with the surface of
One of the two rolls is one in which particles having a particle size of 30 nm or more and less than 5 μm are dispersed and arranged on the peripheral surface,
The other of the two rolls is an image forming apparatus in which particles having a particle size of 5 nm or more and less than 30 nm are dispersedly arranged on the peripheral surface.

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