JP4972897B2 - Cleaning device, image forming apparatus, and process cartridge - Google Patents

Description

  The present invention relates to a cleaning device that removes residues on the surface of a member to be cleaned, a process cartridge including the cleaning device, and an image forming apparatus.

Conventionally, an image is formed by electrophotography in which the surface of a latent image carrier is charged and exposed to develop an electrostatic latent image formed with colored toner to form a toner image, and the toner image is transferred to a transfer paper or the like. (Or transferred to a transfer sheet or the like via an intermediate transfer member), and this is fixed by a heat roll or the like to form an image.
Untransferred toner, discharge products generated by the charging process, and the like remain on the surface of the latent image carrier after the transfer process, particularly on the surface of the photoreceptor. Therefore, a cleaning process for removing these residues prior to the next image forming process is required.

  As a means for cleaning the photosensitive member, a blade cleaning method using an elastic cleaning blade or a brush cleaning method using a magnetic brush or a fur brush is used. Of these, the method of bringing the elastic blade into contact with the photosensitive member is most widely used because of its simplicity.

However, the cleaning blade method removes the residue by mechanical rubbing between the blade and the photoconductor. Therefore, when using an organic photoconductor, the photoconductor is likely to be scratched and worn, resulting in a significantly long life of the photoconductor. The reality is that it cannot be realized.
Similarly, the cleaning blade tip is easily worn and chipped by mechanical rubbing, and the cleaning blade tip is damaged and the surface of the photoconductor is uneven, resulting in a gap between the cleaning blade and the photoconductor. It has a drawback that reliability cannot be maintained for a long time.

Damage to the blade tip due to mechanical rubbing can be caused by high-temperature and high-humidity conditions in which the frictional force between the photoconductor and the cleaning blade increases, or low-image-density images that can easily deplete external additives at the cleaning blade tip. However, there is a drawback that the life of the photosensitive member and the cleaning performance is affected by the use conditions.
In addition, these phenomena tend to significantly deteriorate the abrasion and chipping of the tip of the cleaning blade, especially when using a high-speed machine used for on-demand printing or a contact charger that increases the friction of the photoreceptor. There is.

  On the other hand, in particular, in this type of image forming apparatus, a demand for higher image quality has progressed, and as a means for this, toner by a polymerization method has been used. The toner produced by the polymerization method can be remarkably reduced in particle size, narrowed in particle size distribution, and spheroidized, and can improve dot reproducibility, developability, and transferability. On the other hand, when the blade cleaning method is used, a toner having a small particle size and a nearly spherical shape requires a higher blade pressing pressure for toner removal than the conventional irregularly pulverized toner, and the durability of the cleaning blade In addition, there is a problem that scratches / wear of the photoconductor deteriorates.

  Also, the image bearing member such as an intermediate transfer member needs to remove the surface residue prior to the next image forming process, and similarly contacts the transfer belt, transfer roll, charging roll or conductive fur brush cleaner from the fur brush. Since the function of the collecting roll for collecting the toner is originally deteriorated due to the accumulation of the surface adhering material, it is necessary to remove the adhering material. When the cleaning blade method is used, the same problems as those in the case of the above photoreceptor are essential. Have.

Various proposals have been made to solve these problems.
For example, there has been proposed a cleaning blade in which a low friction layer mainly composed of rubber and resin is formed on the edge portion of the cleaning blade (see, for example, Patent Documents 1 to 3).
This cleaning blade is a low friction layer forming material in which silicone powder, fluororesin powder, polymethyl methacrylate (PMMA) powder, etc. are mixed in a binder such as urethane rubber, silicone rubber, silicone resin, fluororubber, fluororesin, nylon, etc. Is applied to the image carrier contact portion (edge portion) of the cleaning blade by dipping or the like to form a low friction layer. In this way, friction between the image carrier and the cleaning blade can be reduced, and damage to the cleaning blade can be prevented.

  However, the cleaning blade on which the low friction layer is formed is effective in the initial stage, but it cannot be maintained because the low friction layer is worn by the friction between the photosensitive member and the blade.

  Furthermore, many methods have been proposed in which a powder or liquid lubricant is added to urethane rubber, which is a material constituting the cleaning blade, to improve lubricity (see, for example, Patent Document 4).

  However, for example, a urethane rubber cleaning blade obtained by adding a powder lubricant becomes brittle, and chipping of the edge portion of the cleaning blade may be accelerated. Further, when a urethane rubber cleaning blade obtained by adding the above liquid lubricant is used, there arises a problem that the liquid lubricant exudes to the surface of the cleaning blade and contaminates the image carrier.

Further, conventionally, a proposal has been made to increase the life of the blade by reducing the friction between the photosensitive member and the cleaning blade by increasing the hardness of the cleaning blade (see, for example, Patent Documents 5 to 7).
These high-hardness cleaning blades can reduce the contact area between the blade and the photoconductor and suppress the increase in friction, but it is not possible to prevent scratches on the photoconductor only by increasing the hardness. It has been found that the increase in hardness does not necessarily fully explain the friction suppressing effect.

As described above, it is the actual situation that a technique that fundamentally solves the above-described problems and satisfies a long-term stable cleaning performance has not yet been found.
JP-A-8-27227 Japanese Patent Laid-Open No. 9-258632 Japanese Patent Laid-Open No. 11-24522 JP-A-7-306616 Japanese Patent Laid-Open No. 8-248851 Japanese Patent Laid-Open No. 10-49015 JP-A-11-38655

  The present invention has been made in view of the above circumstances of the prior art. That is, an object of the present invention is to provide a cleaning apparatus and an image forming apparatus that can extend the life of the cleaning performance and the life of the photosensitive member, and can form a uniform image without defects over a long period of time.

  As a result of intensive studies in view of the above circumstances, the present inventors have completed the present invention described below.

<1> A cleaning device including a cleaning member that scrapes off residues on the surface of the member to be cleaned by contacting the surface of the member to be cleaned, wherein a contact portion of the cleaning member with the member to be cleaned is represented by the following formula: The rubber elastic body satisfying (1) is configured, and the non-contact surface is formed of an elastic material having a modulus 100% lower than that of the rubber elastic body satisfying the formula (1) forming the contact surface. Do Ri, 23 ° C. in the formula (1), the contact angle a with water at 55% RH, a 75 to 100 °, 100% modulus B at 23 ° C., at 6.3~19.6Mpa Yes,
The cleaning member, when it is in contact with the photosensitive member, a cleaning device according to claim Rukoto used in pressure-contact force of the contact angles and 1.5~5.0gf / mm in the range of 5 to 30 ° .
A ≧ −2.5 × B + 102 (1)
[In Formula (1), A represents the contact angle (°) with pure water at 23 ° C. and 55% RH, and B represents 100% modulus (MPa) at 23 ° C. ]

<2> In the rubber elastic body, a holding member is provided on a surface side that does not come into contact with the member to be cleaned, the holding member is rotatably attached to the housing, and an urging unit attached to the housing The cleaning apparatus according to <1>, wherein the holding member operates.

<3> The cleaning device according to <1> or <2>, wherein the rubber elastic body is provided with a plate-like spring member on a surface side that does not contact the member to be cleaned.

<4> A photoconductor, a charging device for charging the surface of the photoconductor, an exposure device for exposing the charged photoconductor surface to form an electrostatic latent image, and developing the electrostatic latent image with toner particles. An image forming apparatus comprising: a developing device that forms a toner image on the surface of a photoconductor; a transfer device that transfers the toner image to a transfer target; and a cleaning device that removes residues on the surface of the photoconductor after transfer. Because
The image forming apparatus, wherein the cleaning device includes the cleaning device according to any one of <1> to <3>.

<5> A photoconductor, a charging device for charging the surface of the photoconductor, an exposure device for exposing the charged photoconductor surface to form an electrostatic latent image, and developing the electrostatic latent image with toner particles. A developing device that forms a toner image on the surface of the photosensitive member, a first transfer device that transfers the toner image to the intermediate transfer member, and a first transfer device that transfers the toner image formed on the surface of the intermediate transfer member to the transfer member. An image forming apparatus comprising: a second transfer device; and a cleaning device for removing residues on the surface of the intermediate transfer member after transfer,
The image forming apparatus, wherein the cleaning device includes the cleaning device according to any one of <1> to <3>.

<6> The transfer device according to any one of <1> to <3>, wherein the transfer target is an intermediate transfer member and includes a cleaning device that cleans the intermediate transfer member. The image forming apparatus according to <4>, further comprising:

<7> The image forming apparatus according to any one of <4> to <6>, wherein the layer provided on the outermost surface of the photoreceptor contains a fluorine-based resin.

<8> Any of the above <4> to <7>, wherein the protective layer provided on the outermost surface of the photoreceptor contains a resin having a structural unit having a charge transporting ability and a crosslinked structure The image forming apparatus according to claim 1.

<9> The protective layer includes a phenol derivative having a crosslinked structure and a methylol group or a siloxane-based resin having a crosslinked structure, and further includes a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, a thiol group, and an amino group. The image forming apparatus according to any one of <4> to <8>, further comprising a charge transport material containing at least one selected from the group.

<10> A process cartridge detachable from the image forming apparatus, comprising at least an image carrier and a cleaning device for removing residues on the surface of the image carrier after transfer,
The process cartridge includes the cleaning device according to any one of <1> to <3>.

<11> The process cartridge according to <10>, wherein the image bearing member is a photosensitive member, and a layer provided on the outermost surface of the photosensitive member contains a fluorine-based resin.

<12> The image carrier is a photoreceptor, and a protective layer provided on the outermost layer of the photoreceptor contains a resin having a structural unit having a charge transporting function and having a crosslinked structure. The process cartridge according to <10>, wherein the process cartridge is characterized in that

<13> The protective layer is composed of a phenol derivative having a methylol group or a siloxane-based resin as a resin having a crosslinked structure, and further comprising a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, a thiol group, and an amino group. The process cartridge according to <12>, further comprising a charge transport material containing at least one selected from the above.

<14> The image carrier is an intermediate transfer member, and has a cleaning device for cleaning the intermediate transfer member, and the cleaning device is the cleaning device according to any one of <1> or <3>. The image forming apparatus according to <12> or <13>, further comprising:

  According to the present invention, it is possible to provide a cleaning device and an image forming apparatus capable of extending the life of the cleaning performance and the life of the photosensitive member and forming a uniform image without defects over a long period of time.

  First, the cleaning device of the present invention will be described in detail, and then the image forming apparatus and process cartridge provided with the cleaning device will be described.

<Cleaning device>
(1) Explanation of Formula (1) The cleaning device of the present invention includes a cleaning member that scrapes off the residue on the surface of the member to be cleaned by contacting the surface of the member to be cleaned. Such a cleaning member is formed of a rubber elastic body that satisfies the following formula (1) at least in a contact portion with the member to be cleaned, and the non-contact surface satisfies the formula (1) that constitutes the contact surface. It is made of an elastic material having a modulus 100% lower than that of the rubber elastic body.

A ≧ −2.5 × B + 102 (1)
In formula (1), A represents a contact angle (°) with pure water at 23 ° C. and 55% RH, and B represents 100% modulus (MPa) at 23 ° C.

The contact angle A can be measured using a goniometer or the like.
In the present invention, pure water is dropped on the surface of the charging member in an environment of 23 ° C. and 55% RH, and the contact angle after standing for 10 seconds is determined as a contact angle measuring device CA-X roll type (Kyowa Interface Science Co., Ltd.). ). The average value when the measurement place is changed and the measurement is repeated five times is defined as the contact angle A.

100% modulus B refers to the stress at 100% elongation.
In this invention, the value (MPa) calculated | required in the environment of 23 degreeC by the measurement based on JISK6254: 93 (vulcanized rubber physical test method) is defined as a modulus B.

Although the mechanism by which the effect of the present invention is achieved is not clarified, the present inventors presume as follows.
Conventionally, the tip of the cleaning blade that is in contact with the surface of the photoconductor is used in a state of being deformed by being pulled downstream in the photoconductor rotation direction due to friction with the photoconductor. When the cleaning blade comes into direct contact with the smooth photoreceptor surface, the frictional resistance increases due to the close contact and the deformation of the blade tip increases, but the substantial contact area is reduced by inclusions such as external additive particles, so the frictional resistance is reduced. The blade tip is lowered and the blade tip is in a certain equilibrium state.
However, when an image having a low image density continues, the external additive particles are depleted at the tip of the blade, so that the deformation of the tip of the cleaning blade appears remarkably. Since the pressure contact force increases due to the repulsive stress of this deformation, large wear occurs at the photoreceptor and the blade tip. Further, since the deformation of the tip portion is increased, it is considered that carriers and foreign matters are easily sandwiched between the photosensitive member and the blade tip portion, so that the photoconductor is scratched or the blade tip portion is chipped.

  According to the present invention, the adhesion force between the member to be cleaned and the cleaning blade is reduced by increasing the contact angle of the contact portion with water on the contact surface of the cleaning blade with the member to be cleaned as compared with the prior art. , Can reduce friction. Note that the contact angle of water at the contact portion of the cleaning blade is considered to be a factor related to the adhesion force between the member to be cleaned and the cleaning blade, and in fact, by increasing the contact angle of water, The frictional resistance with the cleaning blade is reduced.

Further, by increasing the 100% modulus, the deformation of the blade tip is suppressed, the variation of the contact area is reduced, and the increase in frictional resistance can be suppressed.
As a result of intensive studies, the inventors of the present invention have found that when the contact angle with water and the 100% modulus are in the relationship of formula (1), the blade tip is deformed even when images with a low image density are continuously formed at high speed. Found that the increase is difficult.

  In the case of the conventional cleaning blade, if the amount of the external additive at the blade tip portion is extremely reduced by use, the adhesion force is high and the material is easily deformed to increase the frictional resistance. When the blade is used, even if the area where the blade is in direct contact with the surface of the member to be cleaned is increased, the friction is small, and the deformation of the tip of the cleaning blade can be maintained stably and suppressed.

  However, since no excessive stress is applied to the blade in any image, the blade is hardly damaged and the edge wear is uniform. Furthermore, even when spherical toner that is difficult to clean is used, the cleaning performance can be improved by suppressing the deformation of the blade tip, and the cleaning blade contact pressure can be set low even when spherical toner is used. Thus, damage to the photoreceptor and the blade can be suitably suppressed, and a long life can be achieved.

Moreover, regarding the effect of reducing the wear resistance of the blade, it is not necessarily explained only by the rubber hardness, and it is presumed as follows that it is indicated by 100% modulus as the actual condition.
The rubber material of the blade generally used in electrophotography shows a complicated “stress-strain” relationship when considering a high deformation region. From the measurement result of the strain state of the blade tip by the strain gauge, nip observation, and the like, it is estimated that the amount of deformation of the blade tip during running ranges from several hundred μm to several mm.
However, since the measurement of hardness shows the behavior in the minute deformation region, it may not match the actual situation.
On the other hand, the 100% modulus is in line with the behavior in the middle to large deformation region, and shows a good correlation with the measured value of the blade tip deformation amount in actual running, and seems to have a relationship with the blade wear in the long term.

Hereinafter, the effect of the present invention will be described with reference to FIG.
FIG. 1 shows the relationship between the maintenance performance of the cleaning performance, the contact angle A of the cleaning blade with water, and the 100% modulus B using Fuji Xerox DocuCenter Color400. In this test, the AC voltage output value to be applied to the contact charger is set higher than the original setting value of the DocuCenter Color 400, and images of low image density are continuously flowed under high temperature and high humidity conditions. This is an experiment in which stress is accelerated.
The maintenance of cleaning is evaluated by observing the tip of the cleaning blade after running with a microscope (Laser Microscope VK8500, manufactured by Keyence Corporation), and the damage state of the blade edge and the poor cleaning condition when the solid image is continuously flowed. It was judged by. In FIG. 1, ◯ indicates that the blade edge is damaged and has good cleaning properties, and X indicates that a defect has occurred.

  From FIG. 1, it is clear that when the blade having a contact angle between the blade 100% modulus and water is in a specific range, damage to the tip of the cleaning blade is suppressed and the cleaning performance is improved.

(2) Cleaning member The cleaning member of the cleaning device of the present invention is characterized in that at least the contact portion with the member to be cleaned is made of a rubber elastic body satisfying the above formula (1).

  As a kind of rubber elastic body used for the cleaning member concerning the present invention, a publicly known thing can be used, for example, urethane rubber, silicone rubber, fluorine rubber, chloroprene rubber, butadiene rubber, etc. can be used. Among them, it is preferable to use a polyurethane elastic body because of its excellent wear resistance.

As the polyurethane elastic body, a polyurethane generally synthesized through an addition reaction between an isocyanate and a polyol and various hydrogen-containing compounds is used. As a polyol component, a polyether-based polyol such as polypropylene glycol or polytetramethylene glycol, Polyester polyols such as adipate polyols, polycaprolactam polyols, polycarbonate polyols are used, and polyisocyanate components include aromatics such as tolylene diisocyanate, 4,4'diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, toluidine diisocyanate, etc. Polyisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexane It is manufactured by preparing a urethane prepolymer using an aliphatic polyisocyanate such as xylmethane diisocyanate, adding a curing agent to the urethane prepolymer, pouring it into a predetermined mold, crosslinking and curing, and then aging at room temperature. ing.
As the curing agent, a dihydric alcohol such as 1,4-butanediol and a trihydric or higher polyhydric alcohol such as trimethylolpropane or pentaerythritol are usually used in combination.

  In order to obtain the polyurethane elastic body satisfying the above formula (1), it can be obtained by adjusting the polyol material, the molecular weight of the polyol, and the material and blending of the isocyanate and the crosslinking agent.

  In general, when the molecular weight of the polyol is lowered, the molecular chain length between cross-linking points is shortened and the micro Brownian motion is lowered to increase the modulus, but the polarity is increased and the contact angle with water is lowered. Further, although the amount of the crosslinking agent can be increased to increase the crosslinking density to increase the modulus, the contact angle with water tends to be lowered.

  This will be described with reference to FIG. In FIG. 1, the cleaning blade used in x has a known rubber elastic body. In general, if the same raw material is used to simply increase the 100% modulus, the contact angle of water decreases because the molecular weight between crosslinking points tends to decrease. As a result, the physical properties of the rubber elastic body of the cleaning blade used in x move in the direction of the arrow P in FIG. 1, and the rubber elastic body having physical property values of the present invention (shown by ◯ in FIG. 1) Will be different.

  Thus, it is difficult to make the modulus and the contact angle in a range satisfying the formula (1) only by changing only the molecular weight of the polyol or adjusting the crosslinking density, but the above-described polyol material while balancing the physical properties, It can be produced by a combination of the molecular weight of the polyol, the material of the isocyanate and the crosslinking agent, and the combination.

  It is important that the rubber elastic body used for the cleaning member according to the present invention satisfies the formula (1), and the relational expression (1) between the contact angle A with pure water and the 100% modulus B is presented. As long as it is done, those skilled in the art relating to rubber production and the like can obtain the rubber elastic body according to the present invention.

Further, the 100% modulus at 23 ° C. of the elastic body preferably satisfies 6.3 to 19.6 Mpa (65 to 200 kgf / cm ² ) after satisfying the formula (1) (in FIG. 1, a broken line). More preferably, it is a case where it is set to 6.3 to 14.7 Mpa (65 to 150 kgf / cm ² ).
If the 100% modulus at 23 ° C. is lower than 6.3 Mpa (65 kgf / cm ² ), it may not be possible to suppress the blade tip deformation under stress conditions such as continuous running of high-speed and low-image density images. Prone to occur. On the other hand, if it exceeds 19.6 Mpa (200 kgf / cm ² ), if scratches are generated on the surface of the photoreceptor, the followability to the unevenness of the rubber becomes insufficient. In particular, when a spherical toner is used, poor cleaning occurs. It may be easier.

  The contact angle with water at 23 ° C. and 55% RH satisfies the formula (1), and is more preferably 75 to 100 ° (indicated by a broken line in FIG. 1), more preferably. , 80 to 95 °. If the angle is less than 75 °, particularly when a contact charger is used, the increase in friction between the blade and the photoconductor may not be suppressed when the surface of the photoconductor becomes extremely high friction due to the adhesion of discharge products. On the other hand, if the angle is higher than 100 °, wear tends to be accelerated due to a decrease in cohesive force between rubber molecules.

(3) Cleaning Device FIG. 2 to FIG. 7 are schematic views showing the configuration of the cleaning device of the present invention.

FIG. 2 shows a cleaning blade having a rubber elastic body 20 configured by laminating an elastic material and supporting the rubber elastic body 20 with a holder 33.
In the rubber elastic body 20, the first layer 30 provided on the contact surface with the member to be cleaned 1 is configured by an elastic body satisfying the formula (1), and the second layer 31 provided on the non-contact surface is formed from the first layer 30. Is also made of an elastic material having a low 100% modulus.
By adopting such a configuration, it is possible to absorb the vibration of the cleaning blade tip, and to suitably adjust the contact pressure of the entire cleaning blade, and to control the deformation of the blade tip more stably.

  The 100% modulus of the second layer 31 at 23 ° C. is preferably 3.0 to 6.2 MPa, and more preferably 3.5 to 6.0 MPa.

Further, it is more preferable that the permanent elongation of the constituent material of the second layer is smaller than that of the first layer, so that the settling of the entire cleaning blade during long-term storage can be suitably suppressed.
The permanent elongation of the first layer 30 is preferably 8% or less at 23 ° C., more preferably 5% or less. The permanent elongation of the second layer 30 is preferably 5% or less at 23 ° C., more preferably 3% or less. Here, the measurement of the permanent elongation is a value after 100% elongation and standing for 20 minutes in accordance with the method defined in JIS K6262: 97.

Furthermore, by making the rebound resilience of the constituent material of the second layer 31 larger than that of the first layer 30, it is possible to improve the dynamic followability of the entire cleaning blade.
The rebound resilience at 23 ° C. of the first layer 30 is preferably 30 to 60%, and more preferably 40 to 60%. The rebound resilience at 23 ° C. of the second layer 30 is preferably 10 to 40%, and more preferably 10 to 30%. Here, the measurement of the impact resilience is in accordance with the method defined in JIS K6255: 96.

In the case of the rubber elastic body 20 in which the first layer and the second layer are laminated in this manner, the thickness of the first layer 30 is preferably 25% or less, more preferably 20% or less of the total thickness. .
Further, the overall thickness of the rubber elastic body 20 is preferably 1.0 to 4.0 mm, more preferably 1.5 to 3.0 mm.

In FIG. 2, the rubber elastic body 20 is shown as a two-layer laminate, but may be provided as a single-layer body including only the first layer 30. However, the 1st layer 30 is comprised with the elastic body which satisfy | fills Formula (1).
However, as described above, when the second layer 31 is provided and the 100% modulus, permanent elongation, and impact resilience of the second layer 31 are adjusted, the blade tip is deformed, loosely stored for a long period of time, and dynamically followed. Therefore, the rubber elastic body 20 is preferably a laminated structure.

  Furthermore, the rubber elastic body 20 may be a laminate of three or more layers.

The cleaning apparatus shown in FIGS. 3 to 5 is a reference example, and is a cleaning blade having a plate spring member.
In the rubber elastic body 20, a plate spring member 32 is provided on the surface side that does not contact the member to be cleaned 1.
It is possible to control the entire contact pressure with the plate spring member, and it is possible to control the contact pressure stably without being affected by the use environment, settling in long-term storage, and the like.

The material of the plate spring member is not particularly limited as long as it is a plate-like plate spring member, but a plate spring member such as a metal thin plate or a plastic thin plate can be suitably used.
As the metal thin plate material, any metal material can be used as long as it is a flexible metal thin plate, but a SUS stainless steel plate, phosphor bronze plate, or the like is preferably used.
Polymer materials used for plastic sheets include reinforcement of thermoplastic resins such as polyethylene terephthalate, polystyrene, polyacrylate, polyethylene, polypropylene, polyarylate, and styrene acrylate copolymers, glass fiber reinforced plastic, and carbon fiber reinforced plastic. A plastic or a thermosetting polymer material having a small rubber elasticity cured by three-dimensional crosslinking is preferably used.

  Further, the plate spring member and the rubber elastic body can be bonded by a known bonding method (hot melt, double-sided tape, instantaneous adhesive, etc.).

In the cleaning device 19, the rubber elastic body 20 may be provided at any position of the plate-like spring member as long as the first layer 30 is provided so as to contact the member to be cleaned 1.
For example, the holder 33 is provided at one end of the plate spring member, and the rubber elastic body 20 is provided at the other end. As shown in FIG. 3, the tip of the rubber elastic body 20 and the tip of the plate spring member may be attached in accordance with the length of the plate spring member, or as shown in FIG. The layer 30 may have a free length such that the tip of the rubber elastic body 20 protrudes from the tip of the plate spring member, and the rubber elastic body may be attached. Or as shown in FIG. 5, you may attach to the middle of the length direction of a plate-shaped spring member. However, in the case shown in FIG. 5, the first layer 30 of the rubber elastic body 20 must be attached so as to contact the member to be cleaned 1 so that the plate-like spring member does not contact the member to be cleaned 1.

  The contact pressure when the rubber elastic body 20 attached to the plate spring member contacts the member to be cleaned 1 is preferably 10 to 80 g / cm, more preferably 15 to 50 g / cm. When the cleaning member is brought into contact with the contact pressure within this range, the cleaning property and durability are good. The contact pressure can be adjusted by adjusting the material, thickness, length, and biting amount of the leaf spring member as appropriate.

  In the case of the cleaning device provided with the plate-like spring member shown in FIGS. 3 to 5, the thickness of the first layer 30 made of a rubber elastic body is preferably 0.3 to 3.0 mm, and 0.5 to More preferably, it is 2.0 mm.

Further, the cleaning device shown in FIGS. 6 and 7 is a cleaning blade having a laminated structure of elastic materials and provided with a plate spring member.
The first layer 30 is made of a rubber elastic body that satisfies the formula (1), and the second layer of the non-contact surface is made of an elastic material having a low 100% modulus, so that vibrations at the tip of the cleaning blade can be absorbed. The contact pressure of the entire cleaning blade can be suitably adjusted, and the deformation of the blade tip can be controlled more stably. Further, it is possible to control the entire contact pressure with the plate spring member, and it is possible to control the contact pressure stably without being affected by the use environment and settling in long-term storage.

  In the cleaning apparatus shown in FIGS. 6 and 7, the rubber elastic body having the laminated structure shown in FIG. 2 and the plate-like spring member shown in FIGS.

In the case of the cleaning device shown in FIGS. 6 and 7, the total thickness of the rubber elastic body composed of the first layer 30 and the second layer 31 is preferably 1.0 to 4.0 mm, and 1.5 More preferably, it is -3.0 mm.
The thickness of the first layer 30 is preferably 25% or less, more preferably 20% or less of the total thickness.

  The cleaning device shown in FIGS. 8 to 10 is a cleaning blade in which a holding member rotatably attached to a housing is provided on the rubber elastic body, and the holding member is operated by an urging means attached to the housing. .

The rubber elastic body satisfying the above formula (1) is less likely to absorb vibration because it tends to have a higher modulus of 100% than the conventional one when the contact angle with water in the formula (1) is considered. Yes. Therefore, as described above, the rubber elastic body 20 according to the present invention is preferably provided with the second layer 31 on the non-contact surface. When the second layer 31 is made of an elastic material lower than the 100% modulus of the first layer 30, the vibration of the tip of the cleaning blade is easily absorbed by the second layer 31.
As a more preferred configuration, the present invention presents the cleaning device of FIGS. In the cleaning apparatus of FIGS. 8 to 10, the urging means can more suitably adjust the contact pressure of the entire cleaning blade.

  In the cleaning device shown in FIG. 8, a holding member 34 is attached to a holder (housing) 33 so as to be rotatable about a rotation shaft 35, and an urging means 38 attached to the housing 33 is interposed via a support member 36. Then, the holding member 34 is operated. A rubber elastic body 20 is attached to the holding member 34. The holding member 34 and the rubber elastic body 20 can be bonded by a known bonding method (hot melt, double-sided tape, instantaneous adhesive, etc.).

  The operation of the holding member 34 by the urging means 38 will be described. The biasing unit 38 couples the support member 36 coupled to the holding member 34 and the holder (housing) 33. When the urging means 38 contracts, the rubber elastic body that rotates around the rotation shaft 35 and is coupled to the holding member 34 so that the angle formed by the holding member 34 and the housing 33 becomes small. 20 operates, and the state shown in FIG. On the other hand, when the urging means is extended, the holding member 34 rotates about the rotation shaft 35 so that the angle formed by the holding member 34 and the housing 33 is increased, and is coupled to the holding member 34 accordingly. The rubber elastic body 20 operates and enters the state shown in FIG.

The expansion and contraction of the urging means 38 is actually caused mainly by contact stress or friction between the rubber elastic body and the member 1 to be cleaned. For example, when an image with a low image density is created even during non-image formation or image formation, a toner component (external toner additive) supplied as a lubricant between the cleaning blade and the member to be cleaned And the like, the friction between the cleaning blade and the member to be cleaned 1 is greatly increased, and as a result, a load is applied to the biasing means 38 in the extending direction. On the other hand, when the lubricant is sufficiently supplied, the friction decreases, so that a load is applied in the direction of relative contraction as shown in FIG.
Since the supply amount of the lubricant actually fluctuates, the cleaning blade adjusts the contact stress while changing its posture with respect to the member to be cleaned 1 each time the urging means 38 expands and contracts. It is thought that there is. However, as long as the lubricant is secured to some extent, even if there is a slight change in posture, it can be stabilized by the force of returning to the original position of the biasing means 38.

However, in this way, the contact pressure adjustment is performed in such a manner that the contact posture or angle of the cleaning blade with respect to the member to be cleaned 1 (hereinafter referred to as “WA” (Working Angle)) is allowed to basically change. On the other hand, there is a problem that the toner cleaning performance of the cleaning blade becomes unstable when trying to cope with it. In this case, the smaller the WA is, the lower the cleaning performance tends to be.
In the contact pressure adjustment shown in FIG. 8, when the lubricant has decreased as described above, the state changes in a direction in which the WA increases beyond an allowable range that can be stabilized. For example, immediately after such a state, When the toner and the toner component serving as the lubricant are supplied, this acts as a trigger, and the cleaning blade changes its posture to return to the original position. However, at that time, the force for returning to the original positions of the urging means 38 and the cleaning blade itself simultaneously acts, resulting in an excessive restoring force, and as a result, the WA becomes too small. Alternatively, the WA once returned to the original position may continue to vibrate as it is.

Therefore, in the present invention, in order to solve these problems, a cleaning device shown in FIGS. 8 to 10 is presented as a cleaning device combined with a cleaning blade that satisfies the above formula (1). The present inventors have noted that the problem that the cleaning performance becomes unstable is caused by the magnitude of blade distortion that occurs when the cleaning blade comes into contact with the member to be cleaned. Then, it was found that the problem can be solved by using a cleaning blade satisfying the above formula (1) in which the distortion is absolutely reduced.
In particular, when WA has become too small, the conventional cleaning blade tends to come into contact with the member to be cleaned in a so-called abdominal contact state, whereas in the cleaning blade satisfying the above formula (1), Since distortion can be reduced absolutely, this is not the case, and it is possible to always keep contact with the surface of the member to be cleaned in a posture like a scraper. As a result, it is possible to keep the cleaning performance stable even under a situation where the WA varies due to the variation in the amount of lubricant.

  The cleaning device of FIG. 9 is provided with a recess 40 cut out in a holder (housing) 33, and connects the holding member 34 via a support shaft 42 that engages with the recess 40. The support shaft 42 slides in the recess by the biasing means 38.

In FIG. 9, the operation of the holding member 34 by the biasing means 38 will be described.
The opening of the recess 40 is cut out in the longitudinal direction of the holding member 34. The shape of the opening may be either a rectangle or an ellipse, but the direction of the long side or the long diameter substantially coincides with the longitudinal direction of the holding member 34. The urging means 38 is coupled to the opening of the recess 40 and the support shaft 42 so that the expansion / contraction direction thereof substantially coincides with the longitudinal direction of the holding member.
As the biasing means 38 expands and contracts, the holding member 34 slides along the notch direction of the recess 40 (longitudinal direction of the holding member 34). At this time, WA does not fluctuate.

For example, when settling occurs in the rubber elastic body due to use, the member to be cleaned 1 is dragged by the rotation of the member 1 to be cleaned, and a load is applied to the urging unit 38 in the extending direction. Works and returns to the original position. In addition, since there is no change in WA, the cleaning performance is stable, and uniform image formation with no defects over a long period of time is possible.
Note that the recess 40 may be a hole through which the holder 33 passes. 9 is combined with the configuration of the cleaning device of FIG. 8, and biasing means are provided at two locations between the recess 40 and the support shaft 42 and between the support member 36 and the housing 33. May be.

  The cleaning device of FIG. 10 has two rotating shafts. A first holding member 44 is attached to a holder (housing) 33 so as to be rotatable about a first rotation shaft 46. The second holding member 48 is attached to be rotatable about the second rotation shaft 50. The second holding member 48 includes the rubber elastic body 20. The first urging means 54 couples the first support member 52 and the first holding member installed in the housing 33. Further, the second urging means 58 connects the second supporting member 56 installed on the second holding member 48.

The operation of the rubber elastic body 20 by the first urging means 54 and the second urging means 58 will be described.
When the first urging means 54 contracts, the first holding member 44 rotates about the first rotation shaft 46 and the rotation shaft 50 rotates in a direction approaching the support member 52. The operation of the second holding member 48 by the second urging means 58 is the same as that of the cleaning device of FIG.
That is, in the cleaning device of FIG. 10, the second urging means operates in a direction similar to the rotation direction of the member 1 to be cleaned, similarly to the cleaning device of FIG. 8, and the first urging means In a similar manner to the cleaning device 9, the second holding member 48 operates in a direction approximate to the longitudinal direction. That is, in FIG. 10, it is possible to enjoy the effect of the cleaning device of FIG. 8 and the effect of the cleaning device of FIG.
Further, since there are two each of the rotating shaft and the urging means, it is easy to relieve the stress and more easily absorb the vibration at the tip of the cleaning blade.

8 to 10, the urging means can be a coil spring, a bellows-like spring, or an elastic material such as rubber or synthetic resin.
8 to 10, the rubber elastic body 20 is shown as being composed of the first layer 30 and the second layer 31, but even if it is composed of only a single layer of the first layer 30. Good.

(4) Member to be cleaned The member to be cleaned in the present invention is a toner such as a photoreceptor, an intermediate transfer member, a transfer belt, a transfer roll, a charging roll, a collecting roll that contacts a conductive fur brush cleaner and collects toner from the fur brush. And the part where discharge products accumulate.
Hereinafter, a member to be cleaned that comes into contact with the cleaning device of the present invention will be described.

(I) Photosensitive member As the photosensitive member used in the image forming apparatus and the process cartridge of the present invention, a known photosensitive member such as an organic photosensitive member, an inorganic photosensitive member such as an amorphous silicon photosensitive member or a selenium photosensitive member is used. However, an organic photoreceptor having excellent advantages in terms of cost, manufacturability, discardability and the like is preferably used.

As the charge transport layer as the outermost layer of the organic photoreceptor, one formed by a known technique can be applied. These charge transport layers are formed containing a charge transport material and a binder resin, or are formed containing a polymer charge transport material.
In the organic photoreceptor, there are a case where the photosensitive layer is a single layer and a case where the photosensitive layer has a function-separated multi-layer laminated structure, and any case may be used in the present invention.

FIG. 11 is a schematic cross-sectional view showing a preferred embodiment of the photoreceptor. A photoreceptor 10 shown in FIG. 11 is a function-separated photoreceptor, and a charge generation layer 14 and a charge transport layer 15 are separately provided on a photosensitive layer 18 included in the photoreceptor 10.
More specifically, in the photoreceptor 10 shown in FIG. 11, the undercoat layer 13, the charge generation layer 14, the charge transport layer 15, and the protective layer 16 are laminated on the conductive substrate 11 in this order. .
In the following, the outermost protective layer 16 with which the cleaning device of the present invention abuts and the charge transport layer 15 which is the outermost layer when no protective layer is provided will be described in detail. A known technique can be applied to the conductive substrate 11, the undercoat layer 13, and the charge generation layer 14.

(Charge transport layer)
As the charge transport layer 15, a layer formed by a known technique can be used. These charge transport layers are formed containing a charge transport material and a binder resin, or are formed containing a polymer charge transport material.
Charge transport materials include quinone compounds such as p-benzoquinone, chloranil, bromanyl, anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, xanthone compounds, benzophenone compounds , Electron transport compounds such as cyanovinyl compounds and ethylene compounds, triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene compounds, hydrazone compounds, etc. Examples thereof include pore-transporting compounds. These charge transport materials may be used alone or in combination of two or more, but are not limited thereto.
These charge transport materials can be used alone or in combination of two or more. From the viewpoint of mobility, compounds represented by the following general formulas (3), (4) and (5) are preferred.

In the general formula (3), R ¹⁴ represents a hydrogen atom or a methyl group. N represents 1 or 2. Ar ⁶ and Ar ^{7 each} represent a substituted or unsubstituted aryl group, —C (R ¹⁸ ) ═C (R ¹⁹ ) (R ²⁰ ), or —CH═CH—CH═C (Ar) ₂ , and R ¹⁸ , R ¹⁹ and R ²⁰ represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and Ar represents a substituted or unsubstituted aryl group.
As the substituent of the aryl group in the general formula (3), a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. A substituted amino group substituted with is preferred.

In the general formula (4), R ¹⁵ and R ^{15 ′} may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
R ¹⁶ , R ^{16 ′} , R ¹⁷ and R ^{17 ′} may be the same or different, and may be a hydrogen atom, a halogen atom,
An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group substituted with an alkyl group having 1 to 2 carbon atoms, a substituted or unsubstituted aryl group, -C (R ¹⁸ ) = C ( R ¹⁹ ) (R ²⁰ ), or —CH═CH—CH═C (Ar) ₂ .
R ^18, R ¹⁹ in the general formula (4), R ²⁰ and Ar are respectively the same as R ^18, R ^19, R ²⁰ and Ar in the general formula (3). m and n are each independently an integer of 0 to 2.

In General Formula (5), R ²¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a substituted or unsubstituted aryl group, or —CH═CH—CH═C ( Ar) ₂ is represented. Ar represents a substituted or unsubstituted aryl group.
R ²² and R ²³ may be the same or different and substituted with a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 2 carbon atoms. An amino group or a substituted or unsubstituted aryl group is represented.

Further, the binder resin used for the charge transport layer is polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride- Acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N- Vinyl carbazole, polysilane, and polymer charge transport materials such as polyester polymer charge transport materials disclosed in JP-A-8-176293 and JP-A-8-208820 can also be used.
These binder resins can be used alone or in admixture of two or more. The blending ratio (weight ratio) between the charge transport material and the binder resin is preferably 10: 1 to 1: 5.

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

  The thickness of the charge transport layer used in the present invention is generally 5 to 50 μm, preferably 10 to 30 μm.

  As a coating method, a normal method such as a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method can be used.

  Furthermore, as a solvent used when providing a charge transport layer, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, ketones such as acetone and 2-butanone, and halogenation such as methylene chloride, chloroform and ethylene chloride Ordinary organic solvents such as aliphatic hydrocarbons, cyclic ethers such as tetrahydrofuran and ethyl ether and linear ethers can be used alone or in admixture of two or more.

Additives such as antioxidants, light stabilizers, and heat stabilizers are added to the photosensitive layer to prevent photoconductor deterioration caused by ozone, oxidizing gas, or light or heat generated in the copying machine. can do.
For example, examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and derivatives thereof, organic sulfur compounds, and organic phosphorus compounds.
Examples of the light stabilizer include derivatives such as benzophenone, benzotriazole, dithiocarbamate, and tetramethylpiperidine.

In addition, at least one kind of electron accepting substance can be contained for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use.
Examples of the electron acceptor usable in the photoreceptor of the present invention include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o -Dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, phthalic acid and the like. Of these, benzene derivatives having electron-withdrawing substituents such as fluorenone, quinone and Cl, CN, NO ₂ are particularly preferred.

The photoreceptor of the present invention preferably contains fluororesin particles particularly when the charge transport layer is provided on the outermost surface. Further, even when the charge transport layer is not provided on the outermost surface (when a protective layer is provided), fluororesin particles may be contained.
By containing fluororesin particles, the frictional force between the cleaning blade and the photoconductor is further reduced, and scratches and abrasion of the photoconductor and abrasion and chipping of the tip of the cleaning blade are suppressed, thereby extending the life of the photoconductor. In addition, the gap between the photosensitive member and the cleaning blade can be suppressed in a long-term use, and the lifetime of the cleaning performance can be further increased.

  The content of the fluororesin in the charge transport layer is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, and particularly preferably 3 to 10% by mass with respect to the total amount of the charge transport layer. If the content is less than 0.1% by mass, the friction reducing effect due to the dispersion of the fluororesin particles is not sufficient in combination with the contact-type charger. On the other hand, if the content exceeds 40% by mass, the light transmission property and the charge transport property are remarkable. And the residual potential increases due to repeated use.

  Examples of the fluorine resin particles used in the present invention include a tetrafluoroethylene resin, a trifluorinated ethylene resin, a hexafluoropropylene resin, a vinyl fluoride resin, a vinylidene fluoride resin, a difluorodiethylene chloride resin, and their It is desirable to appropriately select one or two or more types from among the copolymers, but tetrafluoroethylene resin and vinylidene fluoride resin are particularly preferable. The primary particle size of the fluororesin is preferably 0.05 to 1 μm, more preferably 0.1 to 0.5 μm. When the primary particle size is less than 0.05 μm, aggregation during dispersion tends to proceed. If it exceeds 1 μm, image quality defects are likely to occur.

(Protective layer)
In the photoreceptor according to the present invention, as shown in FIG. 11, it is preferable to provide a high-strength surface layer as the protective layer 16 for enhancing the resistance to scratches on the surface layer. By increasing the resistance to scratches with a high-strength surface layer, the life of the photoconductor can be extended, and the gap between the photoconductor and the cleaning blade can be suppressed during long-term use, resulting in a longer life of cleaning performance. It becomes possible.

  A normal cleaning blade deteriorates faster when it comes into contact with a photoconductor having such a high-strength surface layer. Therefore, the cleaning blade must be replaced in a short period of time. However, when the cleaning blade of the present invention is used, the cleaning performance can be maintained without deteriorating for a long time even for a photoreceptor having a high-strength surface layer.

  As this high-strength surface layer, conductive fine particles dispersed in a binder resin, lubricating fine particles such as fluororesin and acrylic resin dispersed in a normal charge transport layer material, hard materials such as silicone and acrylic A coating agent can be used, but those having a crosslinked structure are preferable from the viewpoint of film strength.

  Various materials can be used to form a crosslinked structure, but in terms of characteristics, phenol resin, siloxane resin, urethane resin, epoxy resin, melamine resin, curable acrylic resin, etc. are preferable, especially those made of phenol resin Is preferred.

  In addition to the resin having a crosslinked structure, the protective layer includes a binder resin not having a crosslinked structure, conductive fine particles, and lubricating fine particles made of a fluororesin or an acrylic resin, if necessary. In forming the outermost surface layer, a hard coat agent such as silicone or acrylic can be used as necessary.

  The details of the method for forming the outermost surface layer will be described later. For the formation of the outermost surface layer, a solution for forming the outermost surface layer 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., the protective layer preferably has a charge transport capability. As a method for imparting charge transporting capability to the protective layer, (1) a resin having a crosslinked structure includes a structural unit having charge transporting capability, or (2) a resin having a crosslinked structure and a charge transporting material are contained. And the like. Further, by combining (1) and (2), the protective layer may contain a charge transporting material after including a structural unit having a charge transporting ability in a resin having a crosslinked structure.

  In the case of using a resin having a cross-linked structure including the structural unit having the charge transporting capability (1) above, in the laminated structure type photoreceptor as shown in FIG. It can also function.

  First, a method for adding a charge transporting ability to the protective layer by including a structural unit having a charge transporting ability in the resin having the crosslinked structure (1) will be described.

  As the structural unit having a charge transporting ability, a case where it is constituted by using a compound represented by the following general formulas (I) to (V) or a derivative thereof is particularly preferable because of excellent strength and stability.

F- [D-Si (R ¹ ) _(3-a) Q _a ] _b General formula (I)
In general formula (I), F represents an organic group derived from a compound having a hole transporting ability, D represents a divalent group having flexibility, and R ¹ represents a hydrogen atom, a substituted or unsubstituted group. Represents an alkyl group (carbon number is preferably 1-15, more preferably 1-10) or a substituted or unsubstituted aryl group (carbon number is preferably 6-20, more preferably 6-15); Represents a decomposable group, a represents an integer of 1 to 3, and b represents an integer of 1 to 4;
When a is 3, it becomes a siloxane resin having a three-dimensional crosslinked structure by hydrolysis, and when a is 2, it becomes a siloxane polymer having a linear structure. That is, the crosslinking ratio can be changed by changing the ratio of a.

  In addition, as the divalent group D having flexibility, specifically, a site of F for imparting photoelectric characteristics, a substituted silicon group contributing to the construction of a three-dimensional inorganic glassy network, It is a divalent group that plays a role in linking. In addition, D represents an organic group structure that imparts moderate flexibility to the portion of the inorganic glassy network that is hard but brittle, and plays a role of improving mechanical toughness as a film.

Specific examples _{D, -CαH 2 α -, -} CβH 2 β -2 -, - CγH 2 γ -4 - 2 divalent hydrocarbon group (here represented by, alpha is an integer from 1 to 15 , Β represents an integer of 2 to 15, and γ represents an integer of 3 to 15), —COO—, —S—, —O—, —CH ₂ —C ₆ H ₄ —, —N═CH—, -(C ₆ H ₄ )-(C ₆ H ₄ )-and a characteristic group having a structure in which these characteristic groups are arbitrarily combined, and further, constituent atoms of these characteristic groups are substituted with other substituents And the like.
The hydrolyzable group Q is preferably an alkoxy group, more preferably an alkoxy group having 1 to 15 carbon atoms.

F-[(X ¹ ) _n1 R ² —ZH] _n2 general formula (II)

Here, in the general formula (II), F represents an organic group derived from a compound having a hole transporting ability, X ¹ represents an oxygen atom or a sulfur atom, R ² represents an alkylene group, Z represents an oxygen atom, Sulfur atom, NH or COO, n1 represents 0 or 1, and n2 represents an integer of 1 to 4. In general formula (II), ZH represents a hydroxyl group, a thiol group, an amino group, or a carboxyl group.

F-[(X ² ) _n ^3- (R ³ ) _{n 4-} (Z) _{n 5} G] _{n 6} general formula (III)
In the general formula (III), F represents an organic group derived from a compound having a hole transporting ability, X ² represents an oxygen atom or a sulfur atom, R ³ represents an alkylene group (the number of carbon atoms is preferably 1 to 15, 1 to 10 is more preferable), Z represents an oxygen atom, sulfur atom, NH or COO, G represents an epoxy group, n3, n4 and n5 each independently represents 0 or 1, and n6 represents an integer of 1 to 4. Show.

Here, in the general formula (IV), F represents an n7-valent organic group having hole transportability, T represents a divalent group, Y represents an oxygen atom or a sulfur atom, R ⁴ , R ⁵ and R ^6. Each independently represents a hydrogen atom or a monovalent organic group, R ⁷ represents a monovalent organic group, m1 represents 0 or 1, and n7 represents an integer of 1 to 4. However, R ⁶ and R ⁷ may combine with each other to form a heterocycle having Y as a heteroatom.

Here, in general formula (V), F is an n8-valent organic group having hole transportability, T is a divalent group, R ⁸ is a monovalent organic group, m2 is 0 or 1, n8 represents an integer of 1 to 4, respectively.

  Next, the method (2) of adding a resin having a crosslinked structure and a charge transporting material to impart charge transporting capability to the protective layer will be described.

  As the resin having a crosslinked structure, various materials can be used as described above, and phenol resin, siloxane resin, urethane resin, epoxy resin, melamine resin, curable acrylic resin, etc. are preferable, and phenol resin or siloxane is used. Based resins are more preferable, and phenol derivatives having a methylol group are particularly preferable.

  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. As the alkali catalyst, hydroxides or amine catalysts of alkali metals and alkaline earth metals such as NaOH, KOH, Ca (OH) ₂ and Ba (OH) ₂ are used.

  Examples of the amine catalyst include, but are not limited to, ammonia, hexamethylenetetramine, trimethylamine, triethylamine, and triethanolamine. When a basic catalyst is used, the carrier is remarkably trapped by the remaining catalyst, and the electrophotographic characteristics tend to be deteriorated. Therefore, it is preferable to inactivate or remove by neutralizing with an acid or contacting with an adsorbent such as silica gel or an ion exchange resin.

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

The charge transport material contained in the protective layer is preferably at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an alkoxysilyl group, an epoxy group, a thiol group, and an amino group.
As such a charge transport material, it is preferable to use a compound represented by the above general formulas (I) to (V) or a derivative thereof.

  As the organic group F derived from the compound having a hole transporting ability in the compound represented by the general formula (I), (II), (III), (IV) or (V), the following general formula (VI) The compound shown by these is preferable.

Here, in general formula (VI), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represents a substituted or unsubstituted aryl group, Ar ⁵ represents a substituted or unsubstituted aryl group or arylene group, k Represents 0 or 1, respectively. However, 1-4 of Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are compounds represented by the above general formula (I), (II), (III), (IV) or (V) in, - [D-Si (R 1) (3-a) Q a], - [(X 1) n1 R 2 -ZH], - [(X 2) n3 - (R 3) n4 - (Z) _n5 G], a structural unit represented by the following general formula (IV-1), or a bond for binding to a site represented by the structural unit represented by the following general formula (V-1). In the following general formula (IV-1), T, Y, R ⁴ , R ⁵ , R ⁶ , R ⁷ and m1 are T, Y, R ⁴ , R ⁵ , R ⁶ , are each with R ⁷ and m1 synonymous, T, R ⁸ and m2 in formula (V-1), respectively synonymous T, and R ⁸ and m2 in formula (V).

Conductive particles may be added to the protective layer 16 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 (VII-1) can also be added to the protective layer 16 in order to control various physical properties such as strength and film resistance of the protective layer.

Si (R ³⁰ ) _(4-c) Q _c General formula (VII-1)
In the general formula (VII), 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 (VII) 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, silicone-based hard coating agents mainly produced 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 Chemical Co., Ltd.), and AY42-440, AY42-441, AY49-208 (manufactured by Toray Dow). Corning) or the like 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 general formula (VII-2).

Formula (VII-2): B- (Si (R ³¹ ) _(3-d) Q _d ) ₂

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

  Furthermore, various fine particles can be added 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.

Examples of the fine particles include silicon atom-containing fine particles.
The silicon atom-containing fine particles are fine particles containing silicon as a constituent element, and specific examples include colloidal silica and silicone fine particles.

The colloidal silica used as the silicon atom-containing fine particles preferably has a volume average particle diameter of 1 to 100 nm, more preferably 10 to 30 nm, in an acidic or alkaline aqueous dispersion, or an organic solvent such as alcohol, ketone or ester. It is selected from those dispersed in, and commercially available products can be used.
The solid content of colloidal silica in the protective layer 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 silicone fine particles used as the silicon atom-containing fine particles are spherical and preferably have an average particle size of 1 to 500 nm, more preferably 10 to 100 nm, and are selected from silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles. A commercially available product can be used.

  Silicone fine particles are small particles that are chemically inert and excellent in dispersibility in resins, and because the content required to obtain sufficient properties is low, photosensitivity can be achieved without inhibiting the crosslinking reaction. The surface properties of the body can be improved. That is, 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 maintain good wear resistance and contamination resistance adhesion over a long period of time.

  The content of the silicone fine 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 fine particles include fluorine-based fine particles such as ethylene tetrafluoride, trifluoride ethylene, propylene hexafluoride, vinyl fluoride, vinylidene fluoride, and the 8th Polymer Materials Forum Lecture Proceedings p89. Fine particles comprising 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”, “Sumizer MDP-S”, “Sumizer BBM-S”, “Sumizer WX-R”, “Sumizer NW”, “Sumizer BP-76”, Sumilizer BP-101 "," Sumilizer GA-80 "," Sumilizer GM "," Sumilizer GS "or more manufactured by Sumitomo Chemical Co., Ltd.," IRGANOX1010 "," IRGANOX1035 "," IRGANOX1076 "," IRGANOX1098 "," IRGANOX1098 "," IRGANOX1098 "," IRGANOX1098 " ”,“ IRGANOX1222 ”,“ IRGANOX1330 ”,“ IRGANOX1425WL ”,“ IRGANOX1520L ” ”,“ 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 ”,“ ADK STAB AO ” -40 "," ADK STAB AO-50 "," ADK STAB AO-60 "," ADK STAB AO-70 "," ADK STAB AO-80 "," ADK STAB AO-330 "or more manufactured by Asahi Denka. 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 15, coating film defects due to heat shrinkage, and repellency.

  The protective layer is formed by applying a coating liquid for forming a protective layer containing the above-described constituent materials on the charge transport layer 15 and curing it.

  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.

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

  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 Metal sulfates such as LiSO ₄ and MgSO ₄ ; gold such as zirconia phosphate and lanthanum phosphate Metal nitrate; LiNO ₃ , Mn (NO ₃ ) _2, etc. Metal nitrate; Group containing amino group such as solid obtained by reacting aminopropyltriethoxysilane on silica gel is bonded to the surface Inorganic solids: 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.

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

  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 after multiple application | coating may be carried out.

  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 and increase the mechanical strength of the protective layer.

The curing temperature during the curing treatment is preferably 100 to 170 ° C, more preferably 110 to 160 ° C, and even more preferably 120 to 150 ° C. The curing time is preferably 30 minutes to 2 hours, more preferably 30 minutes to 1 hour.
In addition, as an atmosphere for performing the curing treatment (crosslinking reaction), the absorbance ratio (P2 / P1) may be performed in a so-called oxidation inert gas atmosphere (inert gas atmosphere) such as nitrogen, helium, and argon. It is effective in reducing the size. Incidentally, 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, present in 1645cm ^-1 ~1700cm ^-1 The maximum absorption peak (P2) is considered to be derived from an oxide such as a formyl group.
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).

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 , and ZnCl ₂ with the above Lewis base.

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

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

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

  Although the usage-amount of these 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 (VII-4) in addition to the above.

In the general formula (VII-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.

Among the above, as the multidentate ligand, a bidentate ligand represented by the general formula (VII-4) is more preferable, and R ³² and R ^{33 in the} general formula (VII-4) are the same. Are particularly preferred. By making R ³² and R ^{33 the} same, the coordination power of the ligand near room temperature becomes strong, and the coating liquid 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 penetration of the discharge product generated by the image forming process 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 it is effective for high image quality and long life. It is.

  When the protective layer is to be formed so that the absorbance ratio (P2 / P1) of the infrared absorption spectrum satisfies the above conditions, it is necessary to set the curing temperature relatively low in an air atmosphere. 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 6 μm.

(Ii) Intermediate transfer member Belt-shaped intermediate transfer member In the case of a belt-shaped intermediate transfer member, a conventionally known resin can be used as the resin material used as the substrate. For example, polyimide resin, polycarbonate resin (PC), polyvinylidene fluoride (PVDF), polyalkylene terephthalate (PAT), ethylenetetrafluoroethylene copolymer (ETFE) / PC, ETFE / PAT, PC / PAT blend material, polyester Resin materials such as polyether ether ketone and polyamide, and resin materials using these as main raw materials. Furthermore, a resin material and an elastic material can be blended and used.

  As an elastic material, polyurethane, chlorinated polyisoprene, NBR, chloropyrene rubber, EPDM, hydrogenated polybutadiene, butyl rubber, silicone rubber, or the like can be used, or a material obtained by blending two or more kinds can be used. If necessary, a conductive agent imparting electron conductivity or a conductive agent having ionic conductivity is added to the resin material and elastic material used for these substrates, or a combination of two or more types. Among these, it is preferable to use a polyimide resin in which a conductive agent is dispersed from the viewpoint of excellent mechanical strength. As the conductive agent, a conductive polymer such as carbon black, metal oxide, or polyaniline can be used.

When a belt-shaped configuration is employed as the intermediate transfer member, generally the thickness of the belt is preferably 50 to 500 μm, more preferably 60 to 150 μm, but it can be appropriately selected according to the hardness of the material.
For example, a belt made of a polyimide resin in which a conductive agent is dispersed is 5 to 20% by mass as a conductive agent in a polyamic acid solution, which is a polyimide precursor, as described in JP-A-63-311263. After the carbon black is dispersed, the dispersion is cast on a metal drum and dried, and then the film peeled off from the drum is stretched at a high temperature to form a polyimide film. Can be produced.

  The film molding is generally performed by injecting a polyamic acid solution film-forming stock solution in which a conductive agent is dispersed into a cylindrical mold and, for example, heating at 100 to 200 ° C. at a rotational speed of 500 to 2000 rpm. The film was formed into a film by a centrifugal molding method while rotating, and then the obtained film was demolded in a semi-cured state and covered with an iron core. It can be carried out by proceeding a ring-closing reaction) and carrying out main curing. In addition, the stock solution is cast on a metal sheet to a uniform thickness and heated to 100 to 200 ° C. to remove most of the solvent in the same manner as described above, and then gradually raised to a high temperature of 300 ° C. or higher. There is also a method of forming a polyimide film. The intermediate transfer member may have a surface layer.

2. Drum-shaped intermediate transfer member In the case of a drum-shaped intermediate transfer member, a cylindrical substrate formed of aluminum, stainless steel (SUS), copper, or the like is preferably used as the substrate. If necessary, an elastic layer can be coated on the cylindrical substrate, and a surface layer can be formed on the elastic layer.

(Iii) Transfer Roll A transfer roller in which an elastic layer, a release layer, etc. are arranged on a core bar made of aluminum, iron, or stainless steel is preferably used.
Silicone rubber or the like is used as the elastic layer, and fluororubber, fluororesin or the like is used as the surface release layer, and fluororesin is often used because of particularly good release properties.

(Iv) Charging roll As the charging roll, one provided with an elastic layer, a resistance layer, a protective layer and the like on the outer peripheral surface of the core material is preferably used.
As the material of the core material, a conductive material such as iron, copper, brass, stainless steel, aluminum, nickel, or the like is used. Also, a resin molded product in which conductive particles or the like are dispersed can be used.
As the material of the elastic layer, a material having conductivity or semiconductivity, for example, a material in which conductive particles or semiconducting particles are dispersed in a rubber material can be used. EPDM, polybutadiene, natural rubber, polyisobutylene, SBR, CR, NBR, silicone rubber, urethane rubber, epichlorohydrin rubber, SBS, thermoplastic elastomer, norbornene rubber, fluorosilicone rubber, ethylene oxide rubber, chloroprene rubber, isoprene Rubber, epoxy rubber or the like is used. Examples of the conductive particles or semiconductive particles include carbon black, zinc, aluminum, copper, iron, nickel, chromium, titanium, and other metals, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ — Metal oxides such as SnO ₂ , ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , Sb ₂ O ₃ , In ₂ O ₃ , ZnO, and MgO can be used. These materials can be used individually by 1 type or in mixture of 2 or more types.

  As the material of the resistance layer and the protective layer, conductive particles or semiconductive particles are dispersed in a binder resin, and the resistance is controlled. As binder resin, acrylic resin, cellulose resin, polyamide resin, methoxymethylated nylon, ethoxymethylated nylon, polyurethane resin, polycarbonate resin, polyester resin, polyethylene resin, polyvinyl resin, polyarylate resin, polythiophene resin, PFA, FEP, A polyolefin resin such as PET, a styrene butadiene resin, or the like is used. As the conductive particles or semiconductive particles, the same carbon black, metal, and metal oxide as the elastic layer are used. If necessary, an antioxidant such as hindered phenol and hindered amine, a filler such as clay and kaolin, and a lubricant such as silicone oil can be added. As a means for forming these layers, blade coating method, Meyer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain coating method, melt molding method, injection molding method, etc. should be used. Can do.

  When the photosensitive member is charged using these conductive members, a voltage is applied to the conductive member. The applied voltage may be a DC voltage or a DC voltage superimposed with an AC voltage.

(V) Collection Roll A collection roller that collects toner from a roll-shaped conductive fur brush has a configuration in which a resistance layer is provided on the outer periphery of a metal shaft. Examples of the binder resin constituting the resistance layer include general-purpose thermoplastic resins such as polyethylene, polypropylene, polystyrene, ABS, EVA, and methacrylic resin; thermosetting resins such as epoxy, phenol, urea / melamine, polyurethane, and silicone; nylon 6 Engineering plastics such as nylon 66, nylon 11, nylon 12, polyacetal, polycarbonate, polyphenylene ether, polyethylene terephthalate, polyphenylene sulfide, polyarylate, polyamideimide, polyimide; liquid crystal polymers such as polyetheretherketone, polyetherimide, polyphenylene sulfide Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polychlorotrifluoro Styrene (PCTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene - can be exemplified a fluorine resin such as ethylene copolymer (ETFE), not particularly limited thereto.

<Residue on the surface of the member to be cleaned>
Untransferred toner, discharge products generated by the charging process, and the like remain on the member to be cleaned. Hereinafter, the toner will be described.

  The toner used in the image forming method of the present invention is not particularly limited by the production method. For example, the particles obtained by kneading and pulverizing method, kneading and pulverizing method of kneading, pulverizing, and classifying binder resin and colorant, release agent, charge control agent, etc., if necessary, to mechanical impact force or thermal energy The method of changing the shape, emulsion polymerization of the polymerizable monomer of the binder resin, and mixing the formed dispersion with a dispersion of a colorant, a release agent, and a charge control agent as necessary. An emulsion polymerization aggregation method for obtaining toner particles by aggregation, heat fusion, a solution of a polymerizable monomer and a colorant, a release agent, and a charge control agent as necessary in order to obtain a binder resin in an aqueous solvent Suspension polymerization method in which the polymer is suspended and polymerized, a solution such as a binder resin and a colorant, a release agent, and a charge control agent, if necessary, suspended in an aqueous solvent and granulated, etc. What is obtained can be used.

  In addition, a known method such as a production method in which the toner obtained by the above method is used as a core, and agglomerated particles are further adhered and heat-fused to give a core-shell structure can be used, but from the viewpoint of shape control and particle size distribution control Suspension polymerization method, emulsion polymerization aggregation method, and dissolution suspension method, which are produced from an aqueous solvent, are preferred, and emulsion polymerization aggregation method is particularly preferred.

  The toner particles include a binder resin, a colorant, a release agent, and the like. If necessary, silica or a charge control agent may be used.

The volume average particle size of the toner particles is preferably in the range of 2 to 12 μm, more preferably in the range of 3 to 9 μm.
Further, the average shape index of toner (100 × π × ML ² / (A × 4): ML is the absolute maximum length of toner particles, A is the projected area of toner particles, and π is the circumferential ratio) is 100 to By using those in the range of 145, it is possible to obtain images with high development, transferability and high image quality. More preferably, it is 125-140. By using a toner having an average shape index of 125 to 140, it is possible to obtain a high-quality transfer image and to suppress the deterioration of the adhesion of the toner or the external additive to the contact charging member due to poor cleaning. .

When such a small particle size and spheroidized toner is used, a high quality image can be obtained, but such toner is difficult to clean. Therefore, in the conventional cleaning blade, the contact pressure is increased and the toner is scraped off from the member to be cleaned.
However, when the cleaning device of the present invention is used, even when the toner having the above shape is applied, the member to be cleaned is hardly damaged and the cleaning blade is not easily damaged. As a result, the member to be cleaned and the cleaning blade can be used continuously for a long time.

Binders used in toners 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. Class: α-methylene aliphatic monocarboxylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Examples of homopolymers and copolymers of acid esters; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone; Particularly typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene. -Maleic anhydride copolymer, polyethylene, polypropylene and the like.
Further examples include polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like.

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

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

In addition, a charge control agent may be added to the toner as necessary.
Known charge control agents can be used, but azo metal complex compounds, metal complex compounds of salicylic acid, and resin type charge control agents containing polar groups can be used. When the toner is manufactured by a wet manufacturing method, it is preferable to use a material that is difficult to dissolve in water in terms of controlling ionic strength and reducing wastewater contamination.

  The toner in the present invention may be either a magnetic toner containing a magnetic material or a non-magnetic toner not containing a magnetic material.

  As the inorganic oxide added to the toner, a small-diameter inorganic oxide having a primary particle size of 40 nm or less is used for powder flowability, charge control, etc., and a larger diameter is used for further reducing adhesion and controlling charge. Inorganic oxides can be mentioned. As these inorganic oxide fine particles, known ones can be used, and the following can be exemplified. 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, manganese oxide, boron oxide Various inorganic oxides such as silicon carbide, boron carbide, titanium carbide, silicon nitride, titanium nitride, boron nitride, calcium carbonate, calcium carbonate, magnesium carbonate and calcium phosphate, nitrides and borides are preferably used. The Further, 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, octyltrimethoxy The treatment may be performed with a silane coupling agent such as silane, 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.

  The toner in the present invention can be produced by mixing the toner particles and the external additive with a Henschel mixer or a V blender. In addition, when the toner particles are produced by a wet method, external addition can be performed by a wet method.

  In addition, when the toner in the present invention is used as a color toner, it is preferably used by mixing with a carrier. Examples of the carrier include iron powder, glass beads, ferrite powder, nickel powder, or the surface thereof. A resin coating is used. Further, the mixing ratio of the carrier and the toner can be set as appropriate.

<Image forming apparatus>
An image forming apparatus of the present invention includes a photosensitive member, a charging device that charges the surface of the photosensitive member, an exposure device that exposes the charged surface of the photosensitive member to form an electrostatic latent image, and the electrostatic latent image as a toner. A developing device for developing with particles and forming a toner image on the surface of the photoconductor; a transfer device for transferring the toner image to a transfer target; and a cleaning device for removing residues on the surface of the photoconductor after transfer. Prepare. The cleaning device including the above-described cleaning member is applied to the cleaning device.
In the image forming apparatus of the present invention, the transfer target may be an intermediate transfer member, and may further include a cleaning device that cleans the intermediate transfer member.

  FIG. 12 is a schematic view showing an image forming apparatus of the present invention. FIG. 12 shows a cleaning device for cleaning the photoconductor.

  An image forming apparatus 100 shown in FIG. 12 exposes a photoconductor 107, a charging device 108 for charging the photoconductor 107, a power source 109 connected to the charging device 108, and the photoconductor 107 charged by the charging device 108. An exposure device 110 for forming an electrostatic latent image, a developing device 111 for developing the electrostatic latent image formed by the exposure device 110 with toner to form a toner image, and a toner image formed by the developing device 111 The transfer device 112 for transferring to the transfer medium 500, the cleaning device 113 for removing the toner remaining on the photoconductor 107 after transfer, the charge eliminator 114, and the toner image transferred onto the transfer medium 500 are fixed. A fixing device 115. In the present invention, an image forming apparatus in which the static eliminator 114 is not provided may be used.

  In FIG. 12, the cleaning device 113 applies the above-described cleaning device. A cleaning blade included in the cleaning device is in contact with the photoconductor 107. The contact angle is preferably 5 to 30 °, and more preferably 10 to 25 °.

Further, it is preferable to apply the above-described one to the photoconductor 107 as well.
The charging device 108 is not limited in the charging method, and may be either a non-contact method or a contact method. However, when the contact method is adopted, it is preferable to include the charging roller.
The transfer device 112 is not limited to the charging method, and may be either a non-contact method or a contact method. However, when the contact method is adopted, it is preferable to include the transfer roller.

As the developing device 111, a known developing device using a regular or reversal developer such as a one-component system or a two-component system can be used.
The toner used in the developing device 111 is preferably the above-described toner.
For development, either a one-component developer composed of toner or a two-component developer composed of a carrier and the toner may be used.

  As the exposure apparatus 110 and the static eliminator 114, known ones that are normally used can be appropriately applied.

FIG. 13 is an explanatory diagram for cleaning the intermediate transfer member.
In FIG. 13, an intermediate transfer belt 150 is provided as an intermediate transfer member. The intermediate transfer belt 150 is supported with a predetermined tension by a tension roll 152, a backup roll 154, and a drive roll (not shown), and can rotate without causing deflection due to the rotation of these rolls.

  After the intermediate transfer belt 150 passes between the backup roll 154 and the transfer roll 156, the intermediate transfer belt 150 is cleaned by, for example, the cleaning device 113 disposed in the vicinity of the drive roll 152, and is repeatedly used for the next image forming process. .

The image forming process using the intermediate transfer belt is as follows.
A toner image formed on a photoreceptor (not shown) is transferred onto an intermediate transfer belt 150 sandwiched between a primary transfer roll (not shown). The transfer roll 156 shown in FIG. 10 is disposed so as to contact the backup roll 154 via the intermediate transfer belt 150, and the toner image on the intermediate transfer belt 150 is placed between the transfer roll 156 and the backup roll 154. The image is transferred to the medium 500 to be transferred.

  Although a photoconductor is not illustrated in FIG. 13, an image forming apparatus that includes four photoconductors corresponding to four color toners of black, yellow, magenta, and cyan and performs color printing may be used. It is also preferable to include a cleaning device for cleaning each photoconductor and a cleaning device for cleaning the intermediate transfer member.

(6) Process Cartridge of the Present Invention The process cartridge is a cartridge in which some of the components of the image forming apparatus are incorporated into the cartridge for the purpose of replacing the consumable parts of the image forming apparatus in a timely manner so that the replacement work can be easily performed. It is. The process cartridge is traded in a state where it is mounted in the image forming apparatus, and is also traded alone as a replacement part or a repair part.

  The process cartridge of the present invention is a process cartridge that includes at least an image carrier and a cleaning device that removes residues on the surface of the image carrier after transfer, and is detachable from the image forming apparatus. Such a cleaning apparatus includes the cleaning member described so far.

  The image carrier provided in the process cartridge may be either a photosensitive member or an intermediate transfer member, and the cleaning device of the present invention cleans the photosensitive member and the intermediate transfer member. In the case where the process cartridge is provided with both the photosensitive member and the intermediate transfer member, it is sufficient that a cleaning device for cleaning at least one of them is provided, and more preferably, the cleaning device for both the photosensitive member and the intermediate transfer member. Is provided.

  Next, examples of the present invention will be described. EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, these description does not limit this invention at all.

<Example 1>
(Preparation of cleaning members 1-9 of the present invention and comparative cleaning members 1-8)
Table 1 shows the photosensitive member contact portion rubber elastic bodies used in the cleaning members 1 to 9 of the present invention and the comparative cleaning members 1 to 8.
The rubber elastic body was a polyurethane rubber, and was prepared by changing the polyol material, the molecular weight of the polyol, the material and the compounding of the isocyanate and the cross-linking agent, and changing the 100% modulus and the contact angle with water.

  The cleaning member was molded with the two-layer structure shown in FIG. 2, and the first layer on the photoreceptor contact surface was made of the material shown in Table 1 and the thickness was 0.3 mm. The material of the second layer was the material of the comparative cleaning member 3, the thickness of the second layer was 1.7 mm, and the total thickness of the rubber elastic body was 2 mm. Only the comparative cleaning member 3 has a single-layer structure.

  The free length of the cleaning blade and the amount of biting into the photosensitive member were adjusted, and the pressure contact force to the photosensitive member was set to 3.5 gf / mm.

(Preparation of photoreceptor 3)
To 170 parts by weight of n-butyl alcohol in which 4 parts by weight of polyvinyl butyral resin (S-REC BM-S, manufactured by Sekisui Chemical Co., Ltd.) is dissolved, 30 parts by weight of an organic zirconium compound (acetylacetone zirconium butyrate) and an organic silane compound (γ-amino) 3 parts by weight of propyltrimethoxysilane) was added, mixed and stirred to obtain a coating solution for forming an undercoat layer. This coating solution is dip-coated on an aluminum support roughened by a honing treatment, air-dried at room temperature for 5 minutes, and then the support is heated to 50 ° C. in 10 minutes, 50 ° C. and 85 ° C. It was put in a constant temperature and humidity chamber of% RH (dew point 47 ° C.) and subjected to a humidification hardening acceleration treatment for 20 minutes. Then, it put into the hot air dryer and dried for 10 minutes at 170 degreeC, and formed the undercoat layer.

As a charge generating material, gallium chloride phthalocyanine is used, and a mixture comprising 15 parts by weight thereof, 10 parts by weight of vinyl chloride-vinyl acetate copolymer resin (VMCH, manufactured by Nippon Union Carbide) and 300 parts by weight of n-butyl alcohol. Dispersed for 4 hours in a sand mill.
The obtained dispersion was dip-coated on the undercoat layer and dried to form a charge generation layer having a thickness of 0.2 μm.

  Next, 40 parts by weight of N, N′-bis (3-methylphenyl) -N, N′-diphenylbenzidine and 60 parts by weight of bisphenol Z polycarbonate resin (molecular weight 40,000) were added to 235 parts by weight of tetrohydrofuran and monochlorobenzene. A coating solution obtained by sufficiently dissolving and mixing in 100 parts by weight is prepared, the coating solution is dip-coated on an aluminum support coated up to the charge generation layer, and dried at 120 ° for 40 minutes to obtain a film thickness. A 22 μm charge transport layer was formed.

Next, 2 parts of the following compound 1 and 2 parts of RESITOP PL4852 (manufactured by Gunei Chemical Co., Ltd.) were dissolved in 10 parts of isopropyl alcohol to obtain a coating solution for forming a protective layer.
This protective layer-forming coating solution is dip-coated on the applied charge transport layer, air-dried at room temperature for 30 minutes, and then dried at 140 ° C. for 60 minutes to form a protective layer having a thickness of 4 μm. Was made.

(Evaluation)
Using Fuji Xerox DocuCentre Color 400, the AC voltage output value applied to the contact charger is set higher than the original setting value of DocuCentre Color 400, and images of low image density are obtained under high temperature and high humidity conditions of 28 ° C. and 80% RH. Accelerated experiments were conducted under the condition that 20,000 sheets were continuously formed and conditions more severe than the environmental conditions in normal driving.

  Evaluation of cleaning maintainability is based on observation of the tip of the cleaning blade after running with a microscope (Laser Microscope VK8500 manufactured by Keyence Corporation), and the damage of the blade edge and poor cleaning when a solid image is formed continuously. A condition is judged based on the following evaluation method, and the result is shown in FIG. In FIG. 1, the cleaning blade evaluated as “x” or “xx” in any one of the blade edge damage condition and the defective cleaning condition is indicated as “x”, and the others are indicated as “◯”.

<Evaluation of blade edge damage>
Blade edge damage was evaluated by sensory evaluation by observing the damage state of the edge tip with a laser microscope (Keyence Co., Ltd. VK8500). Judgment criteria are as follows.

◎: Small edge wear ○: During edge wear ×: Large edge wear XX: Large edge wear, many edge defects

<Evaluation of poor cleaning conditions>
The evaluation was performed by cleaning the presence or absence of a poorly-cleaned image in the printed image while running under low temperature and low humidity, and periodically cleaning an untransferred A3-sized image density 100% image. Judgment criteria are as follows.

◎: There is no cleaning problem in both the printed image and the untransferred image. ○: There is no cleaning problem in the printed image.

The evaluation results are shown in FIG.
As can be seen from FIG. 1, it is clear that the use of a blade having a contact angle between the blade 100% modulus and water within a specific range suppresses damage to the tip of the cleaning blade and improves the cleaning performance.

<Example 2>
In Example 1, the type of the photoconductor was fixed, and the cleaning performance was evaluated only with the configuration of the cleaning blade shown in FIG. 2, but in Example 2, the type of photoconductor and the configuration of the cleaning blade were various. The details were evaluated by changing.

(Preparation of cleaning members 10-12 of the present invention and comparative cleaning member 9)
Table 2 shows the photosensitive member contact portion rubber elastic bodies used in the cleaning members 10 to 12 of the present invention and the comparative cleaning member 9. As in Example 1, the rubber elastic body was a polyurethane rubber, and was prepared by changing the polyol material, the molecular weight of the polyol, and the material and blending of the isocyanate and the crosslinking agent to change the 100% modulus and the contact angle with water.

  In the cleaning members 10 to 12 and the comparative cleaning member 9 of the present invention, as in Example 1, the first layer is made of the material shown in Table 2, the thickness is 0.3 mm, and the second layer is made of the comparative cleaning material. The material of the member 3 was used, the thickness of the second layer was 1.7 mm, and the total thickness of the rubber elastic body was 2 mm.

  In the cleaning members 10 to 12 of the present invention, the rubber elastic body of the cleaning member 1 is attached to the tip of the plate spring member 32 by hot melt in the structure shown in FIGS. The leaf spring member was a SUS material having a thickness of 0.08 mm.

Similarly to the other cleaning members, the cleaning members 10 to 12 of the present invention are set so that the pressure contact force to the photosensitive member is 3.5 gf / mm.
In the cleaning members 10 to 12 of the present invention, a load is applied to the photosensitive member by the plate-like spring member 32. This pressure contact force can be expressed by the following equation (2).

Formula (2); pressure contact force = ((3 × E × I) / L ³ ) × bite amount) / blade longitudinal length

  In the formula (2), E represents the Young's modulus of the plate spring member 32, I represents the sectional moment of inertia of the plate spring member 32, and L represents the length of the plate spring member 32.

  The comparative cleaning member 9 has the structure shown in FIG. 2 and is made of a single layer so that its thickness is 2 mm.

  In addition, the cleaning members 1 to 3 of the present invention and the comparative cleaning members 1 to 3 manufactured in the examples were used as cleaning members.

(Preparation of photoreceptor 1)
To 170 parts by weight of n-butyl alcohol in which 4 parts by weight of polyvinyl butyral resin (S-REC BM-S, manufactured by Sekisui Chemical Co., Ltd.) is dissolved, 30 parts by weight of an organic zirconium compound (acetylacetone zirconium butyrate) and an organic silane compound (γ-amino) 3 parts by weight of propyltrimethoxysilane) was added, mixed and stirred to obtain a coating solution for forming an undercoat layer. This coating solution is dip-coated on an aluminum support roughened by a honing treatment, air-dried at room temperature for 5 minutes, and then the support is heated to 50 ° C. in 10 minutes, 50 ° C. and 85 ° C. It was put in a constant temperature and humidity chamber of% RH (dew point 47 ° C.) and subjected to a humidification hardening acceleration treatment for 20 minutes. Then, it put into the hot air dryer and dried for 10 minutes at 170 degreeC, and formed the undercoat layer.

As a charge generating material, gallium chloride phthalocyanine is used, and a mixture comprising 15 parts by weight thereof, 10 parts by weight of vinyl chloride-vinyl acetate copolymer resin (VMCH, manufactured by Nippon Union Carbide) and 300 parts by weight of n-butyl alcohol. Dispersed for 4 hours in a sand mill.
The obtained dispersion was dip-coated on the undercoat layer and dried to form a charge generation layer having a thickness of 0.2 μm.

  Next, 40 parts by weight of N, N′-bis (3-methylphenyl) -N, N′-diphenylbenzidine and 60 parts by weight of bisphenol Z polycarbonate resin (molecular weight 40,000) were added to 235 parts by weight of tetrohydrofuran and monochlorobenzene. A coating solution obtained by sufficiently dissolving and mixing in 100 parts by weight is dip-coated on an aluminum support coated up to the charge generation layer and dried at 120 ° for 40 minutes to form a charge transport layer having a thickness of 26 μm. The photoreceptor 1 was produced.

(Preparation of photoconductor 2)
Photosensitive member 2 was prepared in the same manner as in the preparation of photosensitive member 1, except that the following charge transport layer was used.
40 parts by weight of N, N′-bis (3-methylphenyl) -N, N′-diphenylbenzidine and 60 parts by weight of bisphenol Z polycarbonate resin (molecular weight 40,000) were added to 280 parts by weight of tetrohydrofuran and 120 parts by weight of toluene. After sufficiently dissolving and mixing, 10 parts by weight of tetrafluoroethylene resin particles were added and further mixed. At this time, the room temperature was set to 25 ° C., and the liquid temperature in the mixing step was kept at 25 ° C.
Then, it disperse | distributed with the sand grinder using a glass bead, and the tetrafluoroethylene resin particle dispersion liquid was created. At this time, water at 24 degrees was passed through the vessel of the sand cylinder and the temperature of the dispersion was maintained at 50 degrees to obtain a charge transport layer coating solution.
The obtained coating solution is dip-coated on the product up to the charge generation layer in the same manner as the photoreceptor 1, and dried at 120 ° for 40 minutes to form a charge transport layer having a thickness of 26 μm. A photoreceptor 2 was prepared.

(Sample preparation)
Using Fuji Xerox Docu-Center Color 500 in which the charger is modified to a contact charging roll (applying an AC voltage superimposed with a DC voltage) as a test machine, the cleaning member and the photoconductor are replaced with those prepared above, and in full color Durability test of 100,000 sheets with low image density images at high temperature and high humidity (28 ° C, 80% RH) and low temperature and low humidity (10 ° C, 20% RH). The amount of wear of the photoreceptor and the scratches on the photoreceptor were measured.

(Evaluation of cleaning properties)
The evaluation was performed by cleaning the presence or absence of a poorly-cleaned image in the printed image while running under low temperature and low humidity, and periodically cleaning an untransferred A3-sized image density 100% image. Judgment criteria are as follows.

◎: There is no cleaning problem in both the printed image and the untransferred image. ○: There is no cleaning problem in the printed image.

(Evaluation of blade edge damage)
Blade edge damage was evaluated by sensory evaluation by observing the damage state of the edge tip with a laser microscope (Keyence Co., Ltd. VK8500). Judgment criteria are as follows.

◎: Small edge wear ○: During edge wear ×: Large edge wear XX: Large edge wear, many edge defects

(Measurement of photoconductor wear)
From the difference between the initial film thickness of the photoconductor and the film thickness of the photoconductor after the durability test, the wear amount of the photoconductor was determined.

(Measurement of photoconductor scratches)
The 10-point average roughness Rz of the photoreceptor after the durability test was measured using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd., Surfcom 1400D). Rz was performed according to JIS B0601: 94. Regarding the Rz measurement, there is a description that the standard length and the evaluation length can be omitted if they are standard values in the JIS standard. Unless otherwise specified, the standard length and evaluation length are standard values. Using.

Table 3 shows combinations of cleaning members and photosensitive members, and results.

  As shown in Table 3, when the cleaning member according to the present invention was used, good results were obtained in cleaning properties, edge damage, photoconductor wear, and photoconductor scratches. In particular, even in the photosensitive member 3 having a high hardness on the surface of the photosensitive member, the cleaning member according to the present invention has little edge damage, excellent durability, and good cleaning properties.

<Example 3>
The same test machine as in Example 2 was used, the cleaning member for the intermediate transfer belt was replaced with a test member, and full color high temperature and high humidity (28 ° C., 80%) and low temperature and low humidity (10 ° C., 20%) RH), a durability test of 100,000 sheets with a low image density image was performed, and the cleaning property of the cleaning member for the intermediate transfer belt and the degree of damage of the cleaning tip were measured.
The cleaning members were set in accordance with Table 1 so that the contact pressure on the intermediate transfer belt was 3.0 gf / mm for all the cleaning members. Table 4 shows the test cleaning members and the results.

(Cleanability)
Evaluation was performed by cleaning the presence or absence of poorly-cleaned images in the printed image while running under low temperature and low humidity, and periodically cleaning an untransferred A3-sized image density 300% image (3-color overlay). Judgment criteria are as follows. The practically usable range is ◎ and ○.

◎: There is no cleaning problem in both the printed image and the untransferred image. ○: There is no cleaning problem in the printed image.

(Blade edge damage)
Blade edge damage was evaluated by sensory evaluation by observing the damage state of the edge tip with a laser microscope (Keyence Co., Ltd. VK8500). Judgment criteria are as follows. The practically usable range is ◎ and ○.

◎: Edge wear is small ○: Edge wear is in progress ×: Edge wear is large XX: Edge wear is large and edge chipping is large.

  As shown in Table 4, when the cleaning member according to the present invention was used, good results were obtained in the cleaning performance and edge damage evaluation even in the cleaning of the intermediate transfer member.

<Example 4>
In Example 2, the cleaning performance was evaluated using a cleaning blade having a leaf spring member, but in Example 4, detailed evaluation was performed using a cleaning blade having the configuration shown in FIG.

(Rubber elastic body)
As shown in Table 5, the rubber elastic bodies used in Example 4 were the rubber elastic bodies used in the cleaning members 1 and 2 of the present invention produced in Example 1 and the comparative cleaning member 3. In Table 5, the rubber elastic body used for the cleaning member 1 of the present invention is Sample 1, the rubber elastic body used for the cleaning member 2 of the present invention is Sample 2, and the rubber elastic body used for the comparative cleaning member 3 is shown. Shown as Sample 3.

(Configuration of cleaning blade)
As shown in FIG. 8, a 2 mm × 40 mm × 390 mm holding member 34 made of steel was attached to the housing 33 so as to be rotatable about a rotation shaft 35. The holding member 34 was bonded to the second layer 31 side of the rubber elastic body 20. The rubber elastic body 20 was attached in a state where the entire surface of the second layer 31 was held by the holding member 34 so that the cleaning blade did not have a free length. Further, as the urging means 38, a brass spring (thickness of brass to be formed φ0.5 mm, spring width 5 mm) was used.
Further, in the same manner as in Example 2, the “cleaning member 10 of the present invention” which is a cleaning blade having the structure of FIG.

(Evaluation)
Fuji Xerox Docu-Center Color 500 was used as a testing machine, except that the rubber elastic body, the configuration of the cleaning blade, and the photosensitive body shown in Table 5 were changed to become a photoconductor, and high temperature and high humidity (28 ° C, 80 ° C). % RH), 100,000 durability running tests with low image density images were performed.
The evaluation items were to measure the deformation amount of the tip of the cleaning blade and the torque fluctuation of the photosensitive member in order to monitor the fluctuation of the pressure contact force of the cleaning blade during running, and after running the same method as in Example 1. In addition, evaluation was made for poor cleaning, damage to the blade edge, wear amount of the photoreceptor, and scratches on the photoreceptor.

As shown in Table 6, the rubber elastic body according to the present invention is used, and the structure of the cleaning blade is configured to operate the holding member by the urging means as shown in FIG. The fluctuations in stress and WA could be reliably suppressed, and better results were obtained in cleaning properties, edge damage, photoconductor wear, and photoconductor scratches.
Therefore, in the case of the cleaning blade having the configuration of FIG. 8, it can be seen that the cleaning performance and the photoreceptor life can be further extended, and uniform image formation without defects can be performed over a long period of time.

It is the figure which showed the relationship between the contact angle A and 100% modulus B about maintainability of cleaning performance. It is the schematic of the structure in an example of the cleaning apparatus of this invention. It is the schematic of the structure in another example of the cleaning apparatus of this invention. It is the schematic of the structure in another example of the cleaning apparatus of this invention. It is the schematic of the structure in another example of the cleaning apparatus of this invention. It is the schematic of the structure in another example of the cleaning apparatus of this invention. It is the schematic of the structure in another example of the cleaning apparatus of this invention. It is the schematic of the structure in another example of the cleaning apparatus of this invention. It is the schematic of the structure in another example of the cleaning apparatus of this invention. It is the schematic of the structure in another example of the cleaning apparatus of this invention. 1 is a schematic cross-sectional view showing a preferred embodiment of a photoreceptor. 1 is a schematic view showing an image forming apparatus of the present invention. FIG. 10 is an explanatory diagram for cleaning an intermediate transfer member.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Member to be cleaned 10 Photoconductor 13 Undercoat layer 14 Charge generation layer 15 Charge transport layer 16 Protective layer 18 Photosensitive layer 19 Cleaning device 20 Rubber elastic body 32 Plate-like spring member 33 Case (holder)
DESCRIPTION OF SYMBOLS 100 Image forming apparatus 107 Photoconductor 108 Charging apparatus 109 Power supply 110 Exposure apparatus 111 Developing apparatus 112 Transfer apparatus 113 Cleaning apparatus 114 Charger 115 Fixing apparatus 150 Intermediate transfer belt 152 Tension roll

Claims (4)

A cleaning device including a cleaning member that scrapes off residues on the surface of the member to be cleaned by contacting the surface of the member to be cleaned, wherein a contact portion of the cleaning member with the member to be cleaned is represented by the following formula (1) it consists of a rubber elastic body which satisfies the non-abutting surface, said Ri Na consists of low elastic material 100% modulus than the formula rubber elastic body which satisfies the (1) which constitutes the abutment surface, The contact angle A with water at 23 ° C. and 55% RH in the formula (1) is 75 to 100 °, and the 100% modulus B at 23 ° C. is 6.3 to 19.6 Mpa,
The cleaning member, when it is in contact with the photosensitive member, a cleaning device according to claim Rukoto used in pressure-contact force of the contact angles and 1.5~5.0gf / mm in the range of 5 to 30 ° .
A ≧ −2.5 × B + 102 (1)
[In Formula (1), A represents the contact angle (°) with pure water at 23 ° C. and 55% RH, and B represents 100% modulus (MPa) at 23 ° C. ]   In the rubber elastic body, a holding member is provided on a surface side that does not come into contact with the member to be cleaned, the holding member is rotatably attached to the housing, and the holding member is provided by an urging means attached to the housing. The cleaning apparatus according to claim 1, wherein the cleaning apparatus operates. A photoconductor, a charging device for charging the surface of the photoconductor, an exposure device for exposing the charged photoconductor surface to form an electrostatic latent image, and developing the electrostatic latent image with toner particles. An image forming apparatus comprising: a developing device that forms a toner image on a surface; a transfer device that transfers the toner image to a transfer target; and a cleaning device that removes residues on the surface of the photoreceptor after transfer. ,
An image forming apparatus comprising the cleaning device according to claim 1 or 2. A process cartridge detachable from an image forming apparatus, comprising at least an image carrier and a cleaning device for removing residues on the surface of the image carrier after transfer;
3. A process cartridge comprising the cleaning device according to claim 1 or 2.

Images