JP2007331987A - Surface treatment method of metal oxide particle, electrophotographic photoreceptor and its production method, process cartridge, and electrophotographic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide metal oxide particles excellent in electrostatic property, electric property stability, and pinhole leak resistance and obtaining an image quality stabilized over a long period of time. <P>SOLUTION: The metal oxide particles are produced by a surface treatment method which comprises a process for preparing a microreactor having the first, second, and third minute channels for respectively sending the solutions of three kinds of compositions, an intermediate confluence channel, and a final confluence channel; a process for treating the surface of the metal oxide particles in the intermediate confluence channel by sending the solution of the first composition containing a solvent and the metal oxide particles into the first minute channel and sending the solution of the second composition containing a solvent and a surface treatment agent reactive with the metal oxide particles into the second minute channel; and a process for deactivating excess of the surface treatment agent in the final confluence channel by sending the solution of the third composition containing a solvent and a deactivator for deactivating the surface treatment agent into the third minute channel. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a surface treatment method for metal oxide particles used in an electrophotographic photosensitive member used in an electrophotographic apparatus such as a copying machine or a laser printer, and an electrophotographic photosensitive member using the metal oxide particles surface-treated by the surface treatment method. And a process cartridge having the electrophotographic photosensitive member, and an electrophotographic apparatus.

  An electrophotographic apparatus is used in copying machines, laser printers (laser beam printers) and the like because it can obtain high-quality printing at high speed. In recent years, demands for further enhancement of functionality, image quality, cost reduction, environmental resistance, and the like have been increasing for electrophotographic apparatuses. In recent years, electrophotographic photoreceptors that serve to form latent images and images in electrophotographic processes are also used. Similarly, high performance requirements are being demanded. In order to meet these demands, research and development and commercialization of organic photoreceptors using organic photoconductive materials have become mainstream in recent years. In terms of configuration, the performance has been successfully improved by changing from a single-layer type to a function-separated type photoconductor, which has been put into practical use. In the case of this function-separated type photoreceptor, at present, an undercoat layer is first formed on an aluminum substrate, and then a charge generation layer and a charge transport layer are often formed.

  The undercoat layer plays a major role in preventing image quality defects, and is an important functional layer for suppressing image quality defects caused by substrate defects or stains or coating film defects or unevenness in the photosensitive layer. In addition, repetitive stability and environmental stability in terms of electrical characteristics often depend not only on the charge generation layer and charge transport layer but also on the subbing layer, and an undercoating layer with low charge storage by repeated use is required. Has been. Furthermore, recently, contact charging type charging devices that generate less ozone instead of corotron have been used in electrophotographic devices, and new required characteristics have been added to the undercoat layer. For example, a high electric field applied at the time of contact charging to a defective portion of the photoconductor may locally cause an electrical pinhole leak, which may cause an image quality defect.

  This pinhole leak may occur due to a coating film defect of the above-described photoreceptor itself, but in addition to this, conductive foreign matter generated from within the electrophotographic apparatus contacts or penetrates into the photoreceptor, This occurs because it is easy to form a conductive path between the contact charging device and the photoreceptor substrate. In a noticeable case, foreign matter mixed in from other members in the electrophotographic apparatus or dust mixed in the electrophotographic apparatus may pierce the photoconductor to form a leak point from the contact charging device. Recently, active research has been conducted on measures to increase the resistance to pinhole leaks by increasing the thickness of the undercoat layer to reduce the effects of defects in the photosensitive layer and the effects of foreign substances mixed in the device. Has been.

  In order to satisfy electrical characteristics, image quality stability, etc. while ensuring thick pinhole leak resistance while thickening, the most suitable method is to maintain a suitable resistance and conductivity by dispersing conductive fine powder in the layer. Influential. They are classified into the following two methods according to the layer structure.

  One of them is a method in which a thick conductive powder-dispersed conductive layer is formed on an aluminum substrate and an undercoat layer is further formed thereon (hereinafter referred to as a conductive layer type undercoat layer). In this case, a thick conductive layer conceals substrate defects and at the same time, adjusts resistance, maintains pinhole leakage resistance, and has a blocking (charge injection control) function in the undercoat layer. This method is advantageous in securing quality because the function of the undercoat layer is separated into two layers. In particular, the design of the conductive layer has the merit that it is easy to obtain electrical stability because the resistance can be reduced within a range in which pinhole leakage resistance can be maintained.

  Another method is to simultaneously provide a blocking (charge injection control) function at the interface between the thick film undercoat layer and the charge generation layer, so that one layer also serves as the conductive layer and the undercoat layer. (Hereinafter referred to as a dispersive undercoat layer). The dispersion-type undercoat layer is formed by applying and drying a dispersion in which metal oxide particles are dispersed as a conductive powder in a solution in which a binder resin is dissolved in an organic solvent, using a device using a dispersion medium such as a ball mill or a sand mill. It is formed by doing. It has been found that the dispersion state of the metal oxide particles in the dispersion greatly affects the electrical characteristics and image characteristics when the electrophotographic photoreceptor is used. The dispersion-type undercoat layer has one fewer layers than the conductive layer-type undercoat layer, can simplify the manufacturing facility and process of the photoreceptor, and is a major factor in cost reduction. Then, there is a tendency that the practical application of the dispersion type undercoat layer is actively studied.

  However, the dispersion-type undercoat layer is difficult to control the dispersibility of the metal oxide particles used as the conductive fine powder, so that the film resistance is likely to fluctuate, which is caused by a decrease in injection prevention at the interface with the charge generation layer. It has a problem that image defects such as black spots and fog are likely to occur. In addition, in order to improve these effects, if the resistance in the layer is set high so that an electrical conduction path is difficult to be formed, impurities and defects in the layer become trap sites and negative / It has problems such as generation of ghosts and increase in residual potential.

  Furthermore, in order to solve the above problems, for example, as in Patent Document 1, an undercoat layer in which metal oxide particles surface-treated with a silane compound or the like are dispersed, or surface-treated metal oxide particles are used. In addition, the means for adjusting the blocking function and the resistance adjusting function according to the amount of the surface treatment agent, and further, as in Patent Documents 2 to 4, the undercoat layer contains an additive such as an electron accepting substance or an electron transporting substance. Many methods have been proposed, but even when these methods are used, the improvement in pinhole leakage resistance and electrical characteristics are achieved by increasing the thickness of the undercoat layer, and image quality defects such as fogging, negative and ghosting are prevented. Thus, it is very difficult to obtain an undercoat layer that can satisfy all qualities required for the photoreceptor, and further improvement has been desired.

JP-A-4-222972 JP 7-175249 A JP-A-8-44097 JP-A-9-197701

The object of the present invention is, when used in an undercoat layer of an electrophotographic photoreceptor, is excellent in charging property, electrical property stability, and pinhole leak resistance, and can provide stable image quality over a long period of time. It is to provide a method for surface treatment of metal oxide particles.
Another object of the present invention is to provide a method for producing an electrophotographic photoreceptor including an undercoat layer using metal oxide particles surface-treated by the surface treatment method of the present invention, and an electrophotographic photoreceptor. That is.
Another object of the present invention is to provide a process cartridge and an electrophotographic apparatus equipped with the electrophotographic photosensitive member of the present invention.

The problem to be solved by the present invention has been solved by the following <1>, <10> and <13> to <15>. It is described below together with <2> to <9>, <11>, <12> and <16> which are preferred embodiments.
<1> First, second and third microchannels for feeding three types of compositions, an intermediate merge channel formed by the merge of the first and second microchannels, and the A step of preparing a microreactor having a final merged channel formed by joining a third microchannel to an intermediate merged channel; a first composition containing metal oxide particles and a solvent; A second composition containing a surface treatment agent reactive with the metal oxide particles and a solvent is fed to the second flow path, and the metal oxide is fed into the intermediate merge flow path. A step of performing a surface treatment of the particles, and a third composition containing a deactivator for deactivating the surface treatment agent and a solvent is fed to the third microchannel, and an excess surface is formed in the final merge channel. A method of treating the surface of the metal oxide particles, comprising a step of deactivating the treatment agent,
<2> The surface treatment method for metal oxide particles according to the above <1>, wherein the channel diameters of the microchannel, the intermediate merging microchannel, and the final merging channel are in the range of 10 to 1,000 μm.
<3> The metal oxide particles according to <1> or <2>, wherein the first composition and the second composition are fed so as to satisfy a condition represented by the following formula (1): Surface treatment method,
1 ≦ (V ₂ / V ₁ ) ≦ 100 (1)
(In the formula (1), V ₁ and V ₂ represents the feed rate of the first composition and the second composition, respectively.)
<4> Any one of the above items <1> to <3>, wherein a laminar flow is generated in the intermediate merged flow channel, and the flow channel diameters of the first and second flow channels satisfy the condition represented by the following formula (2): A surface treatment method for metal oxide particles according to one of the above,
1 ≦ (D ₂ / D ₁ ) ≦ 500 (2)
(Equation (2), D ₁ and D ₂ each represent a passage diameter of the first and second micro-channel.)
<5> The surface of the metal oxide particle according to any one of <1> to <4>, wherein the metal oxide contains one or more selected from the group consisting of titanium oxide, zinc oxide, and tin oxide. Processing method,
<6> The surface treatment method for metal oxide particles according to any one of the above <1> to <5>, wherein the surface treatment agent is a silane coupling agent,
<7> When the ratio of the Si intensity in the fluorescent X-ray analysis of the metal oxide particles after the surface treatment with the silane coupling agent is 1, the main metal element intensity of the metal oxide particles is 1.0 × 10 ^-5 to 1.0 × 10 ^-2 in the range of the <6> surface treatment method of metal oxide particles, wherein
<8> The surface treatment method for metal oxide particles according to any one of <1> to <7>, wherein the third composition contains acetic acid or alcohol as a solvent.
<9> The concentration of the metal oxide particles in the first composition is 0.1 to 20% by weight, the concentration of the surface treatment agent in the second composition is 0.001 to 10% by weight, The surface treatment method for metal oxide particles according to any one of the above <1> to <8>, wherein the concentration of the quenching agent in the third composition is in the range of 0.1 to 50% by weight,
<10> First, second and third microchannels for feeding three types of compositions, an intermediate merge channel formed by the merge of the first and second microchannels, and the A step of preparing a microreactor having a final merged channel formed by joining a third microchannel to an intermediate merged channel; a first composition containing metal oxide particles and a solvent; A second composition containing a surface treatment agent reactive with the metal oxide particles and a solvent is fed to the second flow path, and the metal oxide is fed into the intermediate merge flow path. A step of performing a surface treatment of the particles, and a third composition containing a deactivator for deactivating the surface treatment agent and a solvent is fed to the third microchannel, and an excess surface is formed in the final merge channel. A metal oxide particle surface-treated by a surface treatment method having a step of deactivating the treatment agent, a binder, and A process for producing an electrophotographic photoreceptor comprising a step of forming an undercoat layer by coating an undercoat layer coating solution obtained by dispersing an additive on a conductive substrate;
<11> The method for producing an electrophotographic photosensitive member according to <10>, wherein the amount of the additive used is in the range of 0.1 to 10% by weight with respect to the metal oxide particles.
<12> The method for producing an electrophotographic photosensitive member according to <10> or <11>, wherein the additive is an acceptor compound,
<13> First, second and third microchannels for feeding three types of compositions, an intermediate merge channel formed by the merge of the first and second microchannels, and the A step of preparing a microreactor having a final merged channel formed by joining a third microchannel to an intermediate merged channel; a first composition containing metal oxide particles and a solvent; A second composition containing a surface treatment agent reactive with the metal oxide particles and a solvent is fed to the second flow path, and the metal oxide is fed into the intermediate merge flow path. A step of performing a surface treatment of the particles, and a third composition containing a deactivator for deactivating the surface treatment agent and a solvent is fed to the third microchannel, and an excess surface is formed in the final merge channel. A metal oxide particle surface-treated by a surface treatment method having a step of deactivating the treatment agent, a binder, and An electrophotographic photoreceptor produced by a production method comprising a step of forming an undercoat layer by coating an undercoat layer coating solution obtained by dispersing an additive on a conductive substrate. ,
<14> First, second and third microchannels for feeding three kinds of compositions, an intermediate merge channel formed by the merge of the first and second microchannels, and the A step of preparing a microreactor having a final merged channel formed by joining a third microchannel to an intermediate merged channel; a first composition containing metal oxide particles and a solvent; A second composition containing a surface treatment agent reactive with the metal oxide particles and a solvent is fed to the second flow path, and the metal oxide is fed into the intermediate merge flow path. A step of performing a surface treatment of the particles, and a third composition containing a deactivator for deactivating the surface treatment agent and a solvent is fed to the third microchannel, and an excess surface is formed in the final merge channel. A metal oxide particle surface-treated by a surface treatment method having a step of deactivating the treatment agent, a binder, and An electrophotographic photosensitive member produced by a production method comprising a step of forming an undercoat layer by coating an undercoat layer coating solution obtained by dispersing an additive on a conductive substrate, and the electron Charging means for charging the photographic photosensitive member, developing means for developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image, and toner remaining on the surface of the electrophotographic photosensitive member A process cartridge comprising at least one selected from the group consisting of cleaning means for removing
<15> First, second and third microchannels for feeding three kinds of compositions, an intermediate merge channel formed by the merge of the first and second microchannels, and the A step of preparing a microreactor having a final merged channel formed by joining a third microchannel to an intermediate merged channel; a first composition containing metal oxide particles and a solvent; A second composition containing a surface treatment agent reactive with the metal oxide particles and a solvent is fed to the second flow path, and the metal oxide is fed into the intermediate merge flow path. A step of performing a surface treatment of the particles, and a third composition containing a deactivator for deactivating the surface treatment agent and a solvent is fed to the third microchannel, and an excess surface is formed in the final merge channel. A metal oxide particle surface-treated by a surface treatment method having a step of deactivating the treatment agent, a binder, and An electrophotographic photosensitive member produced by a production method comprising a step of forming an undercoat layer by coating an undercoat layer coating solution obtained by dispersing an additive on a conductive substrate, the electrophotographic photosensitive member A charging means for charging the body with an electrostatic charge, an exposure means for exposing the charged electrophotographic photosensitive member, and a developing means for developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image And an electrophotographic apparatus comprising: transfer means for transferring a toner image formed on the surface of the electrophotographic photosensitive member to a transfer target;
<16> An electrophotographic apparatus, wherein the transfer means <15> is an intermediate transfer apparatus for transferring an image formed on the electrophotographic photoreceptor.

According to the present invention, when used in the undercoat layer of an electrophotographic photosensitive member, it is excellent in chargeability, electrical property stability, and pinhole leak resistance, and can provide stable image quality over a long period of time. A method for surface treatment of metal oxide particles can be provided.
In addition, according to the present invention, an electrophotographic photoreceptor including an undercoat layer using the surface-treated metal oxide particles is provided, and a process cartridge and an electrophotographic apparatus equipped with the electrophotographic photoreceptor are provided. can do.

The metal oxide particle surface treatment method of the present invention is formed by joining the first, second, and third microchannels, and the first and second microchannels, which feed three types of compositions, respectively. And a step of preparing a microreactor having a final merged channel formed by joining a third microchannel to the intermediate merged channel, and a metal oxide particle and a solvent. A first composition is sent to the first microchannel, and a second composition containing a surface treatment agent reactive with the metal oxide particles and a solvent is sent to the second microchannel. And a step of performing a surface treatment of the metal oxide particles in the intermediate merging channel, and a third step including a deactivator for deactivating the surface treatment agent (hereinafter also simply referred to as “deactivator”) and a solvent. Feeding the composition of the above to the third microchannel and deactivating the excess surface treatment agent in the final merge channel. Characterized in that it.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted.

I. Microreactor The microreactor used in the present invention is an intermediate formed by joining the first, second and third microchannels, and the first and second microchannels for feeding three kinds of compositions, respectively. It is a microreactor having a merged flow channel and a final merged flow channel formed by joining a third micro flow channel to the intermediate merged flow channel. As shown in FIG. 1, the microreactor used in the present invention includes first, second and third microchannels, an intermediate merging channel and a final merging channel, and does not include a micromixer. As shown in FIG. 4, the first and second micro flow channels are merged by the first micro mixer and mixed to flow out as the intermediate merge flow channel, and then the intermediate merge flow channel and the third micro flow channel are mixed. It is good also as a structure which joins a flow path with a 2nd micro mixer, mixes, and makes it flow out as a final merge flow path.
Moreover, the microreactor may be provided with a liquid feed pump and a microsyringe for feeding the composition as necessary, a detection device, a temperature control means, and the like.

Since the microreactor channel (microchannel) is microscale, both the size and flow rate are small, and the Reynolds number is 200 or less. Therefore, a reactor having a microscale channel is an ordinary reactor. It is a device with laminar flow control, not turbulent flow control.
In a laminar-dominated device, mixing two liquid streams can only be mixed by diffusion through the interface. And since the specific interface area is large in a microscale space, it is advantageous for diffusive mixing at the interface where the laminar flow contacts.
In the microchannel, the time required for mixing the two liquids depends on the cross-sectional area of the interface where the two liquids contact and the thickness of the liquid layer. Therefore, according to the diffusion theory, the mixing time (t) is t = W ² / D (W: channel width, D: diffusion coefficient), the smaller the channel width, the faster the diffusion time. That is, if the channel width becomes 1/10, the mixing time becomes 1/100. Further, since the surface area per unit volume is large, the efficiency of heat exchange is extremely high, and temperature control can be easily performed. For this reason, the reaction under laminar flow in a microreactor can be expected to perform a uniform reaction compared to the reaction under turbulent flow when using a conventional macro reactor. In the case of a solution, uniform mixing can be expected as compared with mixing under turbulent flow when a macro mixing device is used.

As described above, by diffusing and mixing the metal oxide particles and the reactive surface treatment agent in the microchannel, the surface treatment agent can be uniformly reacted with the primary particle surface of the metal oxide particles. . Furthermore, the unreacted surface treatment agent remaining in the mixed solution of the surface-treated metal oxide particles is promptly combined with a composition containing a mixture of a deactivator and a solvent that is diffusely mixed as the third composition. By carrying out the hydrolysis reaction, it becomes possible to suppress the side reaction during the subsequent heat drying treatment, stabilize the surface treatment state of the metal oxide particles, improve the dispersibility of the metal oxide particles and increase the electric resistance. It is possible to stabilize the value control.
Further, it goes without saying that the reaction between the metal oxide particles and the surface treatment agent may occur not only in the intermediate merge flow channel but also in the flow channel downstream from the intermediate merge flow channel. Needless to say, the reaction may occur not only in the final merging channel but also in the channel downstream of the final merging channel.

FIG. 1 is a schematic configuration diagram showing an example of a microreactor that is suitably used as a surface treatment method for metal oxide particles according to the present invention.
The microreactor 36 shown in FIG. 1 is connected to the first flow path L1 for feeding the composition 1A, the flow path L2 for feeding the composition 2A, and the end portions of the flow paths L1 and L2. The composition 1 and the composition 2 are merged and the intermediate merge flow path L4 for diffusing and mixing, the flow path L3 for feeding the composition 3, the composition passing through the flow path L4 and the composition 3 are merged. And a final merging flow path L5 for feeding the diffusion-mixed composition 5. The microsyringe 31 in which the composition 1A (first composition) is accommodated at the upstream end of the flow path L1, and the composition 2A (second composition) is stored at the upstream end of the flow path L2. The stored microsyringe 32 is connected to the upstream end portion of the flow path L3 with a microsyringe 33 storing the composition 3A (third composition) through a filter. Composition 1A (first composition) is a mixture of metal oxide particles and a solvent, composition 2A (second composition) is a mixture of a surface treatment agent and a solvent, and composition 3A (third composition). ) Is a mixture of a quencher and a solvent.

  Further, as shown in FIG. 1, the composition 1 in the microsyringe 31, the composition 2 in the microsyringe 32, and the composition 3 in the microsyringe 33 are flow paths L1 by liquid feed pumps P1, P2, and P3, respectively. , L2, and L3, and sent to the microreactor 36 through the filters F1, F2, and F3. The composition 1 and the composition 2 are merged in the intermediate merging flow path L4 to become the composition 4. 4 is passed through the intermediate merging flow path L4 and further passed through the flow path L3 and merged in the final merging flow path L5 to be diffused and mixed to become the composition 5. Here, the filters F1, F2 and F3 may not be provided.

In the present invention, the first composition and the second composition have a liquid feed speed V ₁ and a second composition liquid feed speed V ₂ satisfy the condition represented by the following formula (1). Each of the two compositions is preferably sent to a microreactor.
1 ≦ (V ₂ / V ₁ ) ≦ 100 (1)
Within the above range, the surface treatment of the metal oxide particles becomes uniform and the productivity is improved, so that the amount of the surface treatment agent and the solvent used can be suppressed, and the material cost can be reduced.

FIG. 2 is an enlarged schematic view in the vicinity of an intermediate merge channel where two channels merge in an example of a microreactor that is suitably used as a surface treatment method for metal oxide particles of the present invention.
As shown in FIG. 2, among the channels of the microreactor 36, the channel diameter D2 of the _second channel L2 through which the second composition 2A passes is the first flow through the first composition 1A. it is preferably larger than the passage diameter D ₁ of the road L1. When the channel diameter D ₂ is larger than the channel diameter D _1, clogging of the metal oxide particles in the channel can be prevented, and diffusion mixing of the metal oxide particles and the surface treatment agent can proceed efficiently, and the metal oxide particles Since the surface treatment agent can be uniformly attached to the surface of the surface, the surface treatment can be more uniformly and efficiently controlled. It is more preferable that the ratio D ₂ / D ₁ between the channel diameter D ₂ and the channel diameter D ₁ satisfies the condition expressed by the following formula (2).
1 ≦ (D ₂ / D ₁ ) ≦ 500 (2)
When D ₂ / D ₁ is 1 or more, the surface treatment becomes uniform, which is preferable, and when it is 500 or less, productivity is excellent and cost can be suppressed.

  The width (channel diameter) of the flow path (channel) of the microreactor that can be used in the present invention is preferably in the range of 10 to 1,000 μm, more preferably in the range of 15 to 900 μm, and still more preferably 30. It is in the range of ˜800 μm. Within the above range, a laminar flow is formed satisfactorily, and therefore sufficient molecular diffusion can be achieved. Therefore, in the microreactor that can be used in the present invention, the flow rate and flow rate of the composition are both small, and the Reynolds number (expressed by the formula ρUL / μ, indicating the ratio of inertial force to viscous force of the liquid, It is a laminar flow dominant region, ρ is the density of the liquid, U is the average flow velocity, and μ is the viscosity coefficient of the liquid.

  Conventionally, as a device used for the surface treatment of metal oxide particles, a sand mill type dispersion device using a dispersion medium, a rotor-stator type emulsification device, or the like is used. However, these devices take a lot of time for the dispersion treatment. Therefore, the metal oxide particles have problems such that the electrophotographic characteristics such as sensitivity and dark decay are deteriorated due to the dispersion stress, and the quality of the metal oxide particles is not stable because the particle size is likely to vary. However, in the present invention, the use of the microreactor makes it possible to obtain uniform and stable surface-coated metal oxide particles.

  The microreactor makes it possible to use a laminar flow as a reaction field instead of using a turbulent flow as a reaction field as in a conventional dispersion processing apparatus. When a laminar flow is used as a reaction field, for example, when two liquids are mixed, they can be mixed by diffusion through an interface between the two liquids. Moreover, since the specific interface area is large in a microscale space, it is advantageous when performing diffusive mixing at such an interface.

  In the present invention, productivity can be increased by increasing the amount of processing by increasing the number of flow paths to be used in parallel as required, or by increasing the number of microreactors in parallel (numbering up).

  A microchannel in the microreactor is produced on a solid substrate by a microfabrication technique. Examples of the material used for the substrate include metals such as copper, iron, aluminum, nickel, titanium, niobium, zirconium, molybdenum, tungsten, and alloys thereof in addition to glass, ceramics, silicon, and plastic.

  As a microfabrication method for forming a microchannel, for example, a method using LIGA technology using X-rays, a method using a resist portion as a structure by a photolithography method, a method of etching a resist opening, There are a micro electric discharge machining method, a laser machining method, and a mechanical micro cutting method using a micro tool made of a hard material such as diamond. These techniques may be used alone or in combination.

  Further, when assembling the microreactor, a joining technique is used. Bonding techniques can be broadly divided into solid phase bonding and liquid phase bonding. Solid phase bonding includes anodic bonding, direct bonding, diffusion bonding, and the like. Liquid phase bonding includes fusion welding and adhesive.

  The microreactor can be provided with a heater device or a cooling device. At that time, it is preferable to adjust the temperature using a temperature control device. The heater device or the cooling device can also be built in the microreactor. In the present invention, the entire apparatus may be placed in a temperature-controlled container for temperature control, and an analysis apparatus or the like is installed in the microreactor to observe and control the mixing state of the dispersion. It can also be built inside.

FIG. 3 is a view showing (a) appearance and (b) slit portion (enlarged view) of a micromixer suitably used for the surface treatment of the present invention.
FIG. 4 is a schematic configuration diagram showing another example of a microreactor preferably used for the surface treatment of the present invention.
As a means for promoting diffusion mixing, a micromixer can be installed or a micromixer can be built in the microreactor.
The microreactor 37 shown in FIG. 4 is connected to the first flow path L1m for feeding the composition 1A, the flow path L2m for feeding the composition 2A, and the terminal portions of the flow paths L1m and L2m. , The micromixer 40 for combining and mixing the composition 1 and the composition 2, the flow path L4m for feeding the composition mixed by the micromixer 40, the flow path L3 for feeding the composition 3, A micromixer 41 for joining and mixing the composition passing through the flow path L4m and the composition 3 and a flow path L5m for feeding the composition mixed in the micromixer 41 are provided. The microsyringe 31 in which the composition 1A (first composition) is accommodated at the upstream end of the flow path L1, and the composition 2A (second composition) is stored at the upstream end of the flow path L2. The stored microsyringe 32 is connected to the upstream end portion of the flow path L3 with a microsyringe 33 storing the composition 3A (third composition) through a filter. Composition 1A (first composition) is a mixture of metal oxide particles and a solvent, composition 2A (second composition) is a mixture of a surface treatment agent and a solvent, and composition 3A (third composition). ) Is a mixture of a quencher and a solvent.

  Similar to the microreactor, the micromixer used in the present invention preferably has a plurality of microchannels having an equivalent diameter of 1,000 μm or less, more preferably 10 μm to 700 μm, when the cross section is converted into a circle. A mixing space connected to these microchannels is provided, and a solution is diffusely mixed by introducing a plurality of compositions into the mixing space through a plurality of microchannels.

  Examples of the micromixer include those disclosed in JP-T-9-512742 and International Publication No. 00/76648. Specific examples of the micromixer used in the present invention include known ones such as the German Institute for Microtechnology (IMM) shown in FIG. 3 and the Karlsruhe Research Center (Forssungszentrum Karlsruhe). Although it is mentioned, it is not limited to them at all. Each of these micromixers passes the solution to be mixed through a fine liquid supply path called a plurality of microchannels and the like and supplies it into the mixing space as an extremely thin laminar flow. The solutions led from different flow paths are diffusely mixed together.

  The diffusion mixing of the pigment / solvent mixture in the above micromixer generally causes diffusion when the pigment particles meet at the interface of the mixture. Therefore, when diffusion mixing is performed in a minute space, the area of the interface becomes relatively large. The reaction efficiency is significantly increased. The diffusion time of the molecule itself is proportional to the square of the distance. This means that even if the reaction solution is not actively mixed as the scale is reduced, mixing proceeds by molecular diffusion and the reaction is likely to occur. Further, in the micro space, since the scale is small, the flow is dominated by the laminar flow, and the solutions are diffused and mixed with each other in a laminar flow state.

  Using a micromixer with the above characteristics, for example, it is possible to control the reaction time and temperature between solutions compared to the conventional batch method using a large volume tank as a mixing and reaction field. Become. In the case of the batch method, the reaction proceeds at the reaction contact surface at the initial stage of mixing, particularly between solutions with a high reaction rate, and the primary product generated by the reaction between the solutions continues to be reacted in the vessel. Therefore, there is a possibility that the product is not uniform and aggregation or precipitation occurs in the mixing container. On the other hand, according to the micromixer, the solution continuously flows with almost no stagnation in the mixing container, so that the primary product generated by the reaction between the solutions continues while staying in the mixing container. It is possible to suppress the reaction, and it becomes possible to take out a pure primary product that has been difficult to take out in the past, and it is difficult to cause aggregation and precipitation in the mixing vessel.

  In addition, when a small amount of chemical substances produced by an experimental production facility is manufactured (scaled up) in a large amount by a large-scale production facility, a large-scale batch method is conventionally used. It took a lot of labor and time to obtain reproducibility in the production facility, but by parallelizing the production line using the micromixer according to the required production amount (numbering up), There is a possibility that the labor and time for obtaining such reproducibility can be greatly reduced.

  Like the microreactor, the flow is in a laminar flow because the Reynolds number is as small as about 10 to several hundreds in a microchannel having an equivalent diameter of 1,000 μm or less. Therefore, in the micromixer as described above, the solution supplied from the two supply ports becomes a two-layer flow in the microchannel, and the stirring and mixing of the two layers is governed by diffusion. A certain amount of time is required.

  Furthermore, it is good also as a structure which connected the some micro mixer processing apparatus. In this case, the micromixer processing apparatus may be the same or different. As a microfabrication technique for forming the flow path of the micromixer, as in the microreactor, a LIGA technique using X-rays, a method of using a resist part as a structure by a photolithography method, and a resist opening part There are a method of etching, a micro electric discharge machining method, a laser machining method, a mechanical micro cutting method using a micro tool made of a hard material such as diamond, and the like. These techniques may be used alone or in combination.

  Joining techniques are used to assemble the micromixer, but the joining techniques can be broadly divided into solid-phase joining and liquid-phase joining. Solid phase bonding includes anodic bonding, direct bonding, and diffusion bonding. Liquid phase bonding includes fusion welding and adhesives. In the present invention, any of the joining techniques described above may be used.

In the present invention, a flow rate control function is required to send liquid into the flow path of the micromixer. In general, there are a method of sending a liquid by pressure generated by a pump or the like prepared outside the micromixer and a method of using electroosmotic flow. The method used as the flow rate control method is appropriately selected according to the purpose, but is preferably a continuous flow type pressure driving method.
In addition, the temperature control of the micromixer may be controlled by placing the entire apparatus in a temperature-controlled container, or a heater structure such as a metal resistor or polysilicon, or a temperature control unit capable of controlling the temperature with a refrigerant is provided in the apparatus. May be provided.

II. Surface Treatment Method (1) Metal Oxide Particle In the present invention, a conductive powder having an average particle diameter of 0.5 μm or less is preferably used as the metal oxide particle. The particle size here means an average primary particle size. The undercoat layer needs to have an appropriate resistance for obtaining leak resistance, and therefore, the metal oxide particles preferably have a powder resistance of about 10 ² to 10 ¹¹ Ωcm. Among them, it is preferable to use metal oxide particles such as titanium oxide, zinc oxide and tin oxide having the above resistance values. Within the above range, excellent leakage resistance can be obtained, and an increase in residual potential can be suppressed. Moreover, 2 or more types of metal oxide particles can be mixed and used.

  Further, the solvent constituting the first composition used together with the metal oxide particles is arbitrarily selected from aromatics, halogenated hydrocarbons, ketones, ketone alcohols, ethers, esters, etc. can do. For example, ordinary organic solvents such as xylene, toluene, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene are used. be able to. Moreover, the solvent used here can be used individually or in mixture of 2 or more types.

  The solid content concentration of the mixed solution of the metal oxide particles and the solvent, which is the first composition introduced into the microchannel of the microreactor, is preferably in the range of 0.1 to 20% by weight, and more preferably. Is in the range of 0.5 to 18% by weight, more preferably in the range of 0.8 to 15% by weight. Within the above range, productivity and cost are excellent, and metal oxide particles are not clogged in the microchannel.

  In the present invention, a mixed liquid in which the metal oxide particles and the solvent are preliminarily dispersed and mixed can be prepared. As a method for performing the preliminary dispersion treatment in this case, various dispersing devices such as a sand mill, a colloid mill, an attritor, a ball mill, a dyno mill, a high-pressure homogenizer, an ultrasonic disperser, a coball mill, and a roll mill can be used.

(2) Surface treatment agent The surface treatment of the metal oxide particles with the surface treatment agent improves the wettability and compatibility of the metal oxide particles with the resin, thereby improving the dispersibility in the resin. The “surface treatment of metal oxide particles” in the present invention is to coat the surface of the metal oxide particles with a surface treatment agent to coat at least a part of the surface of the metal oxide particles.
Examples of the compound used as the surface treating agent in the present invention include an organic zirconium compound such as a zirconium chelate compound, a zirconium alkoxide compound and a zirconium coupling agent, an organic titanium compound such as a titanium chelate compound, a titanium alkoxide compound and a titanate coupling agent, In addition to organoaluminum compounds such as aluminum chelate compounds and aluminum coupling agents, antimony alkoxide compounds, germanium alkoxide compounds, indium alkoxide compounds, indium chelate compounds, manganese alkoxide compounds, manganese chelate compounds, tin alkoxide compounds, tin chelate compounds, aluminum silicon Alkoxide compounds, aluminum titanium alkoxide compounds, aluminum And zirconium alkoxide organometallic compound reactive compounds and silane coupling agent, and the like, but not particularly limited thereto. Among these organometallic compounds, organozirconium compounds, organotitanyl compounds, organoaluminum compounds, especially zirconium alkoxide compounds, zirconium chelate compounds, titanium alkoxide compounds, titanium chelate compounds, and silane coupling agents are good electrons with low residual potential. Among them, a silane coupling agent is particularly preferable in view of improving electrical characteristics, improving environmental stability, and improving image quality.

  Any silane coupling agent can be used as long as it can obtain desired photoreceptor characteristics. Specific examples of silane coupling agents include vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycid. Xylpropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (amino Examples include silane coupling agents such as ethyl) -γ-aminopropylmethylmethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, and γ-chloropropyltrimethoxysilane. It is not limited to. Moreover, these silane coupling agents can also be used in mixture of 2 or more types.

  As the solvent constituting the second composition used together with the surface treating agent, a common organic solvent can be used in the same manner as the solvent used in the first composition. The concentration of the mixture of the surface treatment agent and the solvent is preferably in the range of 0.001 to 10% by weight, more preferably in the range of 0.01 to 8% by weight, and still more preferably 0.05 to 7%. It is in the range of wt%. Within the above range, excellent effects can be obtained in improving electrical characteristics, environmental stability and image quality, and it is also appropriate in terms of material cost.

(3) Deactivator The deactivator used in the third composition is not particularly limited as long as it is a compound that reacts with the used surface treatment agent and deactivates, but water, alcohols, acids, etc. It is preferable to use purified water such as ion-exchanged water, pure water, or distilled water. In particular, when a silane coupling agent is used as the surface treatment agent, it is preferable to use water as the deactivator. The solvent concentration in the mixture of the deactivator and the solvent is preferably in the range of 0.1 to 50% by weight, more preferably in the range of 0.5 to 40% by weight, and further preferably 1 to 30% by weight. % Range.
Further, as the solvent used together with the quenching agent as the third composition in the present invention, acetic acid or alcohols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, and benzyl alcohol are used. It is preferable.

(4) Si Strength In the present invention, it is essential that the amount of the surface treatment agent with respect to the metal oxide particles is an amount capable of obtaining desired electrophotographic characteristics. The electrophotographic characteristics are affected by the amount attached to the metal oxide particles after the surface treatment. When the silane coupling agent is used, the attached amount is the Si intensity in the fluorescent X-ray analysis and the main amount of the metal oxide. It is obtained from the strength of the metal element. A preferable Si intensity in the fluorescent X-ray analysis is in the range of 1.0 × 10 ^{−5 to} 1.0 × 10 ⁻² of the main metal element strength of the metal oxide. Within the above range, charge injection from the undercoat layer to the photosensitive layer (charge generation layer) and residual potential are suppressed, so that excellent image quality can be obtained. In the present invention, by adopting a surface treatment method using a microreactor, it becomes possible to uniformly attach a surface treatment agent to the surface of the metal oxide particles. In comparison, the amount of the surface treatment agent attached to the metal oxide particles tends to increase slightly.

(5) Drying or baking treatment The metal oxide particles surface-treated by the microreactor can be dried after the solvent is distilled off from the liquid by a method such as distillation, filtration, and centrifugation.

  The metal oxide particles surface-treated by the microreactor may be baked. As a result, the dehydration condensation reaction of the surface treatment agent can sufficiently proceed. The baking treatment can be performed under any temperature condition as long as the desired electrophotographic characteristics can be obtained. However, when the surface treatment agent described above is used, the baking treatment is preferably performed at a temperature of 100 ° C. or higher. More preferably, it is carried out at a temperature of 250 ° C. Within the above range, the dehydration condensation reaction can proceed sufficiently without causing the surface treatment agent to decompose by heat. Next, the metal oxide particles after the surface treatment are crushed as necessary. Thereby, since the aggregate of metal oxide particles can be crushed, the dispersibility of the metal oxide particles in the undercoat layer can be improved.

III. Electrophotographic photoreceptor The method for producing an electrophotographic photoreceptor of the present invention is a coating for an undercoat layer obtained by dispersing metal oxide particles, a binder, and additives surface-treated by the surface treatment method of the present invention. It includes a step of forming an undercoat layer by coating a liquid on a conductive substrate.
That is, in the method for producing an electrophotographic photosensitive member of the present invention, the first, second and third microchannels and the first and second microchannels for feeding three kinds of compositions are joined. A step of preparing a microreactor having an intermediate merging channel to be formed and a final merging channel formed by merging a third microchannel with the intermediate merging channel, a metal oxide particle and a solvent; The first composition containing liquid is sent to the first microchannel, and the second composition containing the surface treatment agent reactive with the metal oxide particles and the solvent is sent to the second microchannel. A step of performing a surface treatment of the metal oxide particles in the intermediate merging channel, and a third composition containing a deactivator and a solvent for deactivating the surface treating agent to the third microchannel. A surface treatment method having a step of liquefying and deactivating excess surface treatment agent in the final merged flow path Including a step of forming an undercoat layer by coating an undercoat layer coating solution obtained by dispersing the treated metal oxide particles, binder, and additive on a conductive substrate. And
The electrophotographic photosensitive member of the present invention is an electrophotographic photosensitive member manufactured by the above manufacturing method. That is, the electrophotographic photosensitive member of the present invention is formed by joining the first, second and third microchannels and the first and second microchannels for feeding three kinds of compositions, respectively. A step of preparing a microreactor having an intermediate confluence channel and a final confluence channel formed by merging a third microchannel with the intermediate confluence channel, a first including metal oxide particles and a solvent And a second composition containing a surface treatment agent reactive with the metal oxide particles and a solvent is sent to the second microchannel. A step of performing a surface treatment of the metal oxide particles in the intermediate merging channel, and a third composition containing a deactivator and a solvent for deactivating the surface treating agent are fed to the third microchannel. Surface treatment by a surface treatment method having a step of deactivating excess surface treatment agent in the final merge channel Manufactured by a production method including a step of forming an undercoat layer by coating an undercoat layer coating solution obtained by dispersing a metal oxide particle, a binder, and an additive on a conductive substrate. It is characterized by that.
The electrophotographic photoreceptor of the present invention and the method for producing the same are a laminated electrophotographic photoreceptor having at least one undercoat layer and at least one photosensitive layer on a conductive substrate, and a method for producing the same. Is preferred.
Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted.

(1) First Embodiment FIG. 5 is a cross-sectional view showing a first embodiment of the electrophotographic photosensitive member of the present invention. As shown in FIG. 5, the electrophotographic photosensitive member 100 includes a conductive substrate 3, an undercoat layer 4, a photosensitive layer 6, a charge generation layer 1 that constitutes the photosensitive layer 6, and a charge transport layer 2. Yes. The undercoat layer 4 uses an undercoat layer coating solution obtained by dispersing together with the metal oxide particles surface-treated by the surface treatment method of the present invention described above, a binder and an additive. It is to be painted.

(2) Second Embodiment FIG. 6 is a cross-sectional view showing a second embodiment of the electrophotographic photosensitive member of the present invention. The electrophotographic photoreceptor 110 shown in FIG. 6 has the same configuration as the electrophotographic photoreceptor 100 shown in FIG. 5 except that the photosensitive layer 6 has a single layer structure. The photosensitive layer 6 shown in FIG. 6 is a layer that contains both the charge generating material and the charge transporting material contained in the charge generating layer 1 and the charge transporting layer 2 shown in FIG.

(3) Third Embodiment FIG. 7 is a cross-sectional view showing a third embodiment of the electrophotographic photosensitive member of the present invention. The electrophotographic photoreceptor 120 shown in FIG. 7 has the same configuration as the electrophotographic photoreceptor 100 shown in FIG. 5 except that the protective layer 5 is provided on the photosensitive layer 6. The protective layer 5 is used to prevent chemical change of the charge transport layer 2 when the electrophotographic photosensitive member 120 is charged or to further improve the mechanical strength of the photosensitive layer 6. The protective layer 5 can be formed by coating on the photosensitive layer 6 using a coating solution containing a conductive material in an appropriate binder.

(4) Fourth Embodiment FIG. 8 is a cross-sectional view showing a fourth embodiment of the electrophotographic photosensitive member of the present invention. An electrophotographic photoreceptor 130 shown in FIG. 8 has the same configuration as the electrophotographic photoreceptor 110 shown in FIG. 6 except that the photosensitive layer 6 has a single-layer structure and the protective layer 5 is provided on the photosensitive layer 6.

(5) Fifth Embodiment FIG. 9 is a cross-sectional view showing a fifth embodiment of the electrophotographic photosensitive member of the present invention. An electrophotographic photoreceptor 140 shown in FIG. 9 has the same configuration as the electrophotographic photoreceptor 100 shown in FIG. 5 except that an intermediate layer 42 is provided between the photosensitive layer 6 and the undercoat layer 4. The intermediate layer 42 is provided to improve the electrical characteristics of the photoreceptor 140, improve the image quality, and improve the adhesion of the photosensitive layer 6. The constituent material of the intermediate layer 42 is not particularly limited, and can be arbitrarily selected from synthetic resin, organic substance or inorganic substance powder, electron transporting substance, and the like.

(6) Sixth Embodiment FIG. 10 is a cross-sectional view showing a sixth embodiment of the electrophotographic photosensitive member of the present invention. An electrophotographic photoreceptor 150 shown in FIG. 10 has the same structure as that of the electrophotographic photoreceptor 100 shown in FIG. 5 except that the photosensitive layer 6 has a single layer structure and an intermediate layer 42 is provided between the photosensitive layer 6 and the undercoat layer 4. It has the same configuration.

(7) Seventh Embodiment FIG. 11 is a cross-sectional view showing a seventh embodiment of the electrophotographic photosensitive member of the present invention. The electrophotographic photosensitive member 160 shown in FIG. 11 is provided with the protective layer 5 on the photosensitive layer 6 and an intermediate layer 42 between the photosensitive layer 6 and the undercoat layer 4. 100 has the same configuration.

(8) Eighth Embodiment FIG. 12 is a cross-sectional view showing a seventh embodiment of the electrophotographic photosensitive member of the present invention. An electrophotographic photoreceptor 170 shown in FIG. 8 is provided with the exception that the protective layer 5 is provided on the photosensitive layer 6, the photosensitive layer 6 has a single layer structure, and the intermediate layer 42 is provided between the photosensitive layer 6 and the undercoat layer 4. The configuration is the same as that of the electrophotographic photoreceptor 100 shown in FIG.

Further, when the photosensitive layer obtained according to the present invention has two photosensitive layers (a charge generation layer and a charge transport layer), the layer disposed above the charge generation layer for obtaining high resolution is 50 μm. Or less, and more preferably 40 μm or less. In the case where the charge transport layer is a thin film having a thickness of 20 μm or less, a photoreceptor having a structure in which a high-strength protective layer similar to the undercoat layer is disposed on the charge transport layer is particularly effectively used.
Hereinafter, the configuration of the electrophotographic photosensitive member will be described in detail.

IV. Conductive substrate The conductive substrate 3 shown in FIGS. 5 to 12 is not particularly limited as long as it has conductivity. For example, a metal drum such as aluminum, copper, iron, zinc, or nickel is used. be able to. Also, conductive treatment was performed by depositing a metal such as aluminum, copper, gold, silver, platinum, palladium, titanium, nickel-chromium, stainless steel, copper-indium on a polymer sheet, paper, plastic, or glass. A drum, sheet, or plate can be used. Furthermore, a drum-like, sheet-like, or plate-like material obtained by conducting a conductive treatment by depositing a conductive metal compound such as indium oxide on a polymer sheet, paper, plastic, or glass, or laminating a metal foil. Can also be used. In addition, Kern black, indium oxide, tin oxide-antimony oxide powder, metal powder, copper iodide, etc. are dispersed in a binder and coated on a polymer sheet, paper, plastic, or glass. Therefore, a drum-like, sheet-like, plate-like or the like subjected to conductive treatment can also be used.

  Here, when a metal pipe substrate is used as the conductive substrate 3, even if the surface remains as a raw tube, mirror cutting, etching, anodizing, rough cutting, centerless grinding, sand blasting, wet honing, and coloring treatment are performed in advance. It is preferable to perform such processing. By performing the surface treatment and roughening the surface of the substrate, it is possible to prevent grain-like density spots due to interference light in the photosensitive member that may occur when a coherent light source such as a laser beam is used.

V. Undercoat layer The undercoat layer plays a major role in preventing image quality defects, and is an important functional layer for suppressing image quality defects caused by substrate defects or stains or coating film defects or unevenness in the photosensitive layer. is there. The undercoat layer is formed by coating the conductive substrate with an undercoat layer coating solution obtained by dispersing the surface-coated metal oxide particles, the binder, and the additives described above. The

(1) Binder As a binder (binder resin, binder resin) for the coating solution for forming the undercoat layer, an acetal resin such as polyvinyl butyral, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, Polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol resin, phenol-formaldehyde resin, melamine resin, urethane resin A known polymer resin compound such as a charge transporting resin having a charge transporting group or a conductive resin such as polyaniline can be used. Among them, resins insoluble in the upper layer coating solvent are preferably used, and phenol resins, phenol-formaldehyde resins, melamine resins, urethane resins, epoxy resins, and the like are particularly preferably used. The ratio between the metal oxide particles and the binder in the coating solution for forming the undercoat layer can be arbitrarily set within a range where desired electrophotographic photoreceptor characteristics can be obtained.

(2) Additives Various additives can be used in the coating solution for forming the undercoat layer in order to improve electrical characteristics, environmental stability, and image quality. As additives, quinone compounds such as chloranil, bromoanil, anthraquinone, tetracyanoquinodimethane compounds, fluorenone compounds such as 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2,5-bis (4-naphthyl) -1,3,4-oxadiazole, Oxadiazole compounds such as 2,5-bis (4-diethylaminophenyl) -1,3,4-oxadiazole, xanthone compounds, thiophene compounds, 3,3 ′, 5,5′-tetra-t-butyldi Electron transport compounds such as diphenoquinone compounds such as phenoquinone, polycyclic condensation compounds, electron transport pigments such as azo compounds, zirconium chelate compounds Titanium chelate compounds, aluminum chelate compounds, titanium alkoxide compounds, organic titanium compounds, there can be used a known material such as a silane coupling agent. Among these, acceptor compounds such as electron transport compounds and electron transport pigments are preferable.

  Examples of zirconium chelate compounds include zirconium butoxide, zirconium zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl acetoacetate butoxide, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octoate, naphthene. Zirconate, zirconium laurate, zirconium stearate, zirconium isostearate, methacrylate zirconium butoxide, stearate zirconium butoxide, isostearate zirconium butoxide and the like.

  Examples of titanium chelate compounds include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate ammonium salt, Examples include titanium lactate, titanium lactate ethyl ester, titanium triethanolamate, and polyhydroxytitanium stearate.

  Examples of the aluminum chelate compound include aluminum isopropylate, monobutoxy aluminum diisopropylate, aluminum butyrate, diethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate) and the like.

  The silane coupling agent is used for the surface treatment of the metal oxide particles, but it can also be used as an additive added to the coating solution. Specific examples of the silane coupling agent used here include vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- Examples include (aminoethyl) -γ-aminopropylmethylmethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, and γ-chloropropyltrimethoxysilane.

These additives may be used alone or in combination of two or more, or may be used as a mixture or polycondensate of a plurality of compounds.
The amount of the additive used in the undercoat layer is preferably 0.1 to 10% by weight based on the amount of metal oxide particles used. Within the above range, dispersibility and application suitability are improved, and effects such as improved sensitivity, reduced residual potential, and reduced fatigue during repeated use are preferred.

(3) Solvent As the solvent for adjusting the coating solution for forming the undercoat layer, a known organic solvent can be used. For example, it can be arbitrarily selected from alcohol, aromatic, halogenated hydrocarbon, ketone, ketone alcohol, ether, ester and the like. For example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, Organic solvents such as methylene chloride, chloroform, chlorobenzene, and toluene can be used. Moreover, the solvent used for these dispersion | distribution can be used individually or in mixture of 2 or more types. When mixing, any solvent can be used as long as it can dissolve the binder as the mixed solvent.

(4) Dispersion method As a method of dispersing the metal oxide particles in the binder, methods such as a roll mill, a ball mill, a vibration ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker can be used.

(5) Coating method Furthermore, the coating method used to provide this undercoat layer includes blade coating method, wire bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain coating. Ordinary methods such as a method can be used. Using the coating solution for forming the undercoat layer thus obtained, an undercoat layer is formed on the conductive substrate. The undercoat layer is preferably removed from the film after coating by drying in a dryer or natural drying. About drying temperature and time, it can set arbitrarily as needed.

(6) Hardness, thickness and surface roughness of the surface of the undercoat layer Further, the undercoat layer preferably has a Vickers hardness of 35 or more. Furthermore, the thickness of the undercoat layer is preferably 15 μm or more, more preferably 20 μm or more and 50 μm or less. Further, the surface roughness of the undercoat layer is adjusted to ¼ n (where n is the refractive index of the upper layer) to λ of the exposure laser wavelength λ used to prevent moire images. Resin particles can be added to the undercoat layer for adjusting the surface roughness. As the resin particles, silicone resin particles, cross-linked polymethyl methacrylate (PMMA) resin particles, and the like can be used. The undercoat layer can also be polished to adjust the surface roughness. As a polishing method, buffing, sand blasting, wet honing, grinding, or the like can be used.

VI. Photosensitive layer (charge generation layer)
The charge generation layer 1 constituting the photosensitive layer 6 shown in FIGS. 5, 7, 9 and 11 is formed by forming a charge generation material by vacuum vapor deposition or dispersing and coating it together with an organic solvent and a binder resin (hereinafter referred to as “dispersion coating”). "). When the charge generation layer is formed by dispersion coating, the charge generation layer is formed by dispersing the charge generation material together with an organic solvent, a binder resin, an additive, and the like, and applying the obtained dispersion.

(1) Charge generation material Charge generation materials used in the present invention include azo pigments such as chlorodian blue, quinone pigments such as brominated anthanthrone and pyrenequinone, quinocyanine pigments, perylene pigments, indigo pigments, and bisbenzimidazole pigments. Pyrrolopyrrole pigments, phthalocyanine pigments, azulenium salts, squalium, quinacridone, and the like. Among the above charge generating materials, phthalocyanine pigments are most effective as charge generating materials used for photoconductors for digital recording such as laser printers, and hydroxygallium phthalocyanine pigments are particularly preferred. The invention is not limited to these.

  The present invention will be described taking the hydroxygallium phthalocyanine pigment as an example. As the hydroxygallium phthalocyanine pigment having excellent sensitivity and environmental stability, which is preferably used in the present invention, Bragg angle (2θ ± 0.2 °) with respect to CuKα characteristic X-ray is 7.5 °, 9.9 °, Hydroxygallium phthalocyanine pigments with strong diffraction peaks at 12.5 °, 16.3 °, 18.6 °, 22.1 °, 24.1 °, 25.1 ° and 28.3 ° are selected. The crystalline hydroxygallium phthalocyanine pigment is obtained by dissolving chlorogallium phthalocyanine obtained by heat condensation of 1,3-diisoiminoindoline and gallium trichloride in a solvent with an acid such as sulfuric acid or trifluoroacetic acid, Reprecipitation in an alkaline aqueous solution such as aqueous ammonia or sodium hydroxide or cold water and acid pasting (production of type I hydroxygallium phthalocyanine), followed by amides (N, N-dimethylformamide, N, N-dimethyl) Acetamide, N-methylpyrrolidone, etc.), esters (ethyl acetate, n-butyl acetate, i-amyl acetate, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), solvent treatment with organic solvents such as dimethyl sulfoxide It is produced by crystal conversion.

  In the present invention, among the above-mentioned hydroxygallium phthalocyanine pigments, hydroxygallium phthalocyanine characterized in that the maximum peak particularly in the range of 600 to 900 nm of the spectral absorption spectrum has absorption at 810 to 839 nm does not contain coarse particles. It can be most preferably used due to the effects such as the fineness of the pigment particles. Such a hydroxygallium phthalocyanine pigment is obtained by wet-grinding the I-type hydroxygallium phthalocyanine obtained by the acid pasting treatment together with a solvent to convert the crystal. In the method for producing the hydroxygallium phthalocyanine pigment, For the wet pulverization treatment, a pulverizer using a spherical medium having an outer diameter of 0.1 to 3.0 mm is preferable, and a spherical medium having an outer diameter of 0.2 to 2.5 mm is particularly preferable. When the outer shape of the media is larger than 3.0 mm, the pulverization efficiency is lowered, so that the particle diameter is not reduced and aggregates are easily generated. Moreover, when smaller than 0.1 mm, it becomes difficult to isolate | separate a medium and a hydroxygallium phthalocyanine pigment. In addition, when the media is not spherical, but in other shapes such as a columnar shape or an indefinite shape, the grinding efficiency decreases, the media is easily worn by grinding, and the abrasion powder becomes impurities, which degrades the characteristics of the hydroxygallium phthalocyanine pigment. It becomes easy.

  Any material can be used as the medium, but those that do not easily cause image quality defects even when mixed in the pigment are preferable, and glass, zirconia, alumina, menor, and the like can be preferably used.

  Any container material can be used, but those which do not easily cause image quality defects even when mixed in pigments are preferred. Glass, zirconia, alumina, menor, polypropylene, Teflon (registered trademark) (DuPont), polyphenylene sulfide Etc. can be preferably used. Further, glass, polypropylene, Teflon (registered trademark), polyphenylene sulfide, or the like may be lined on the inner surface of a metal container such as iron or stainless steel.

  The amount of media used varies depending on the apparatus used, but is 50 parts by weight or more, preferably 55 to 100 parts by weight, based on 1 part by weight of type I hydroxygallium phthalocyanine. Also, as the media outer diameter decreases, the media density in the device increases even with the same weight, and the viscosity of the mixed solution increases and the grinding efficiency changes. It is desirable to perform wet processing at an optimal mixing ratio by controlling the amount used.

  The temperature of the wet pulverization treatment is preferably in the range of 0 to 100 ° C, more preferably 5 to 80 ° C, and still more preferably 10 to 50 ° C. Within the above range, an appropriate crystal transition speed can be maintained, and an appropriate particle size can be easily obtained.

  As the solvent used for the wet pulverization treatment, the organic solvent can be used. The amount of these solvents used is usually 1 to 200 parts by weight, preferably 1 to 100 parts by weight, based on 1 part by weight of the hydroxygallium phthalocyanine pigment.

  As an apparatus used for the wet pulverization treatment, an apparatus using a media such as a vibration mill, an automatic mortar, a sand mill, a dyno mill, a coball mill, an attritor, a planetary ball mill, or a ball mill as a dispersion medium can be used.

  The progress speed of crystal conversion is greatly influenced by the scale of the wet pulverization process, stirring speed, media material, etc., but the maximum peak in the range of 600 to 900 nm of the spectral absorption spectrum of hydroxygallium phthalocyanine pigment is in the range of 810 to 839 nm. It continues until it is converted into a predetermined hydroxygallium phthalocyanine while monitoring the crystal conversion state by measuring the absorption wavelength of the wet pulverization treatment liquid so as to have absorption inside. Generally, the treatment time for the wet pulverization treatment is in the range of 5 to 500 hours, preferably in the range of 7 to 300 hours. When the processing time is less than 5 hours, the crystal conversion is not completed, and the problem of deterioration of electrophotographic characteristics, particularly insufficient sensitivity is likely to occur. In addition, when the processing time is increased from 500 hours, the sensitivity is lowered due to the influence of the pulverization stress, and problems such as a decrease in productivity and mixing of abrasive powder of the media occur. By determining the wet pulverization processing time in this way, it becomes possible to complete the wet pulverization process in a state where the hydroxygallium phthalocyanine particles are uniformly formed, and when a plurality of lots of wet pulverization processes are repeatedly performed, It becomes possible to suppress the quality variation between.

(2) Binder The binder (binder resin, binder resin) used in the method for producing the dispersion for charge generation layer is polycarbonate, polystyrene, polysulfone, polyester, polyimide, polyester carbonate, polyvinyl butyral, methacrylic acid ester. Examples thereof include polymers, vinyl acetate homopolymers or copolymers, cellulose esters, cellulose ethers, polybutadienes, polyurethanes, phenoxy resins, epoxy resins, silicone resins, fluororesins, and partially crosslinked cured products thereof. One of the resin resins can be used alone or in combination of two or more.

(3) Solvent As the solvent used in the method for producing the dispersion for the charge generation layer, specifically, methanol, ethanol, n-butanol, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate , Dioxane, tetrahydrofuran, methylene chloride, chloroform, toluene, xylene, chlorobenzene, dimethylformamide, dimethylacetamide, water and the like. One of these may be used alone, or a mixture of two or more may be used. Good.

(4) Blending amount The solid content concentration of the binder solution is preferably in the range of 0.1 to 10% by weight, and more preferably in the range of 1.0 to 7.0% by weight. When the amount is in the above range, the amount of the charge generating substance in the dispersion is appropriate, so that good sensitivity can be obtained. In addition, since the viscosity of the dispersion is appropriate, the productivity at the time of applying the photoreceptor is good.

  Further, the solid content concentration of the mixed solution of the charge generating substance and the solvent is preferably 0.1 to 20% by weight, more preferably 1 to 15% by weight. When it is within the above numerical range, the coating film adhesion and adhesion are good, and a charge generation layer excellent in sensitivity and cycle stability can be obtained. The charge generation material and the solvent are preferably subjected to a dispersion treatment in advance. In this case, the dispersion treatment may be performed by a sand mill, a colloid mill, an attritor, a ball mill, a dyno mill, a high-pressure homogenizer, an ultrasonic disperser, a coball mill. And a roll mill.

(5) Coating method Coating methods used when the charge generation layer 1 is provided include blade coating method, wire bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain coating method, etc. The usual method can be used. After the charge generation layer is applied, the solvent in the film is removed by drying or natural drying in a dryer. About drying temperature and time, it can set arbitrarily.

(6) Additive In addition, for the purpose of preventing deterioration of the photoreceptor due to ozone, oxidizing gas, or light / heat generated in the electrophotographic apparatus, the photosensitive layer of the electrophotographic photoreceptor of the present invention has an antioxidant. You may add additives, such as an agent, a light stabilizer, and a heat stabilizer.

For example, examples of the antioxidant include hindered phenol, hindered amine, paraphenylenediamine, arylalkane, hydroquinone, spirochroman, spiroidanone and their derivatives, organic sulfur compounds, and organic phosphorus compounds.
Specifically, for example, methylphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, 2,2′-methylene-bis ( 4-methyl-6-t-butylphenol), 2-t-butyl-6- (3′-t-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 4,4′- Butylidene-bis (3-methyl-6-tert-butylphenol), 4,4′-thio-bis (3-methyl-6-tert-butylphenol), 1,3,5-tris (4-tert-butyl-3) -Hydroxy-2,6-dimethylbenzyl) isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxy-phenyl) propionate] methane, 3,9-bis { -[3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, etc. Is mentioned.

  Examples of hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- {2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl} -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy]- 2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4.5] undecane-2,4-dione 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate Polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diimyl} {(2,2,6,6-tetra Methyl-4-piperidyl) imino} hexamethylene {(2,3,6,6-tetramethyl-4-piperidyl) imino}], 2- (3,5-di-t-butyl-4-hydroxybenzyl)- 2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl- N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate and the like.

  Examples of organic sulfur antioxidants include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis. -(Β-lauryl-thiopropionate), ditridecyl-3,3′-thiodipropionate, 2-mercaptobenzimidazole and the like.

  Examples of the organophosphorus antioxidant include trisnonylphenyl phosfte, triphenyl phosfeto, tris (2,4-di-t-butylphenyl) phosfeto and the like.

Organic sulfur-based and organic phosphorus-based antioxidants are referred to as secondary antioxidants, and a synergistic effect can be obtained by using them together with primary antioxidants such as phenols or amines.
Examples of the light stabilizer include benzophenone-based, benzotriazole-based, dithiocarbamate-based, and tetramethylpiperidine-based derivatives.

  For example, examples of the benzophenone light stabilizer include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, and the like.

  Examples of the benzotriazole-based light stabilizer include 2- (2′-hydroxy-5′methylphenyl) -benzotriazole, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ − Tetrahydrophthalimidomethyl) -5′-methylphenyl] -benzotriazole, 2- (2′-hydroxy-3′-t-butyl5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-) 3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy- 5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like. .

  Other compounds include 2,4-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate, nickel dibutyl-dithiocarbamate, and the like.

The photosensitive layer can contain at least one electron accepting substance for the purpose of improving sensitivity, reducing residual potential, and reducing fatigue during repeated use.
Examples of the electron-accepting substance that can be used in the present invention include succinic anhydride, maleic anhydride, dibromomaleic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, and 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 an electron-withdrawing substituent such as fluorenone, quinone, and —Cl, —CN, and —NO ₂ are particularly preferably used. Furthermore, a small amount of silicone oil can be added to the coating solution for forming a photosensitive layer of the present invention as a leveling agent for improving the smoothness of the coating film.

VII. Photosensitive layer (charge transport layer)
(1) Charge Transport Material Next, the charge transport layer will be described. The charge transport material contained in the charge transport layer is not particularly limited, and a known material can be used. For example, oxadiazole derivatives such as 2,5-bis (p-diethylaminophenyl) -1,3,4-oxadiazole, 1,3,5-triphenyl-pyrazoline, 1- [pyridyl- (2)] Pyrazoline derivatives such as -3- (p-diethylaminostyryl) -5- (p-diethylaminostyryl) pyrazoline, triphenylamine, tri (p-methyl) phenylamine, N, N′-bis (3,4-dimethylphenyl) ) Aromatic tertiary amino compounds such as biphenyl-4-amine, dibenzylaniline, 9,9-dimethyl-N, N′-di (p-nitrile) fluorenon-2-amine, N, N′-diphenyl- Aromatic tertiary diamino compounds such as N, N′-bis (3-methylphenyl)-(1,1-biphenyl) -4,4′-diamine, 3- (4′-dimethylamino) 1,5,6-di (4′-methoxyphenyl) -1,2,4-triazine, 1,2,4-triazine derivatives, 4-diethylaminobenzaldehyde-1,1-diphenylhydrazone, 4-diphenylamino Hydrazone derivatives such as benzaldehyde-1,1-diphenylhydrazone, [p- (diethylamino) phenyl] (1-naphthyl) phenylhydrazone, quinazoline derivatives such as 2-phenyl-4-styryl-quinazoline, 6-hydroxy-2,3 Benzofuran derivatives such as di- (p-methoxyphenyl) -benzofuran, α-stilbene derivatives such as p- (2,2-diphenylvinyl) -N, N′-diphenylaniline, enamine derivatives, carbazole such as N-ethylcarbazole Derivatives, poly-N-vinylcarbazole and derivatives thereof Hole transport materials, quinone compounds such as chloranil, bromoanil, anthraquinone, tetracyanoquinodimethane compounds, 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitro-9-fluorenone, etc. Fluorenone compound, 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, 2,5-bis (4-naphthyl) -1,3,4-oxa Oxadiazole compounds such as diazole and 2,5-bis (4-diethylaminophenyl) -1,3,4-oxadiazole, xanthone compounds, thiophene compounds, 3,3 ′, 5,5′-tetra And electron transport materials such as diphenoquinone compounds such as -t-butyldiphenoquinone. Furthermore, examples of the charge transport material include a polymer having the basic structure of the compound exemplified above in the main chain or side chain. These charge transport materials can be used alone or in combination of two or more.

(2) Binder The binder contained in the charge transport layer is not particularly limited, and a known one can be used. However, a resin capable of forming an electrical insulating film is used. preferable. For example, 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-acetic acid Vinyl copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-carbazole, polyvinyl butyral, polyvinyl formal, polysulfone , Casein, gelatin, polyvinyl alcohol, ethyl cellulose, phenol resin, polyamide, carboxy-methyl cellulose, vinylidene chloride polymer wax, polyurea Emissions, and the like. And these binders can be used individually or in mixture of 2 or more types. In particular, a polycarbonate resin, a polyester resin, a methacrylic resin, and an acrylic resin are preferably used because they are excellent in compatibility with a charge transport material, solubility in a solvent, and strength.

(3) Blending ratio The blending ratio (weight ratio) between the binder and the charge transporting material can be arbitrarily set in consideration of a decrease in electrical characteristics and a decrease in film strength. The layer thickness of the charge transport layer is preferably 5 to 50 μm, and more preferably 10 to 40 μm.

(4) Manufacturing Method The charge transport layer can be formed by preparing a coating solution by mixing a charge transport material, an organic solvent, a binder, etc., coating the solution on the charge generation layer, and further drying. .
In order to prepare a coating solution for forming the charge transport layer, it is mixed with a charge transport material, an organic solvent, a binder and the like. As a method for highly dispersing the charge transport material in the liquid, a dispersion method such as a roll mill, a ball mill, a vibrating ball mill, an attritor, a sand mill, a colloid mill, or a paint shaker can be used.
Furthermore, from the viewpoint of film formability, the particle diameter of the dispersed particles such as pigments contained in the coating liquid for forming the charge transport layer is preferably 0.5 μm or less, and preferably 0.3 μm or less. More preferably, it is still more preferably 0.15 μm or less. When the particle diameter of the dispersed particles exceeds 0.5 μm, the film formability of the charge transport layer is deteriorated and image quality defects are likely to occur.
Furthermore, as a solvent used for the coating liquid for forming the charge transport layer, a common organic solvent such as dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, toluene and the like can be used alone or in combination.
As a method for applying the charge transport layer, usual methods such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method can be used.

VIII. Photosensitive layer (single layer type)
The photosensitive layer 6 shown in FIGS. 6, 8, 10 and 12 includes the charge generation material and the charge transport material contained in the charge generation layer 1 and the charge transport layer 2 shown in FIGS. It is a layer that contains both substances. When the photosensitive layer 6 is thus a single layer type, the pigment content is preferably 0.1 to 50% by weight, more preferably 1 to 20% by weight, based on the total weight of the photosensitive layer 6. More preferably. When the amount is within the above range, moderate sensitivity can be obtained, and adverse effects such as a decrease in chargeability do not occur.

  In addition, when the photosensitive layer is a single layer type, a polycarbonate resin and a methacrylic resin are particularly preferably used as the binder from the viewpoint of compatibility with the hole transporting material. Further, these resins may be selected from organic photoconductive materials such as poly-N-vinyl carbazole, polyvinyl anthracene, polyvinyl pyrene and polysilane. In addition, you may use said binder individually or in mixture of 2 or more types. This photosensitive layer is also prepared by mixing the above-described charge generating substance, the above-described charge transporting substance, the above-described organic solvent, the binder, and the like, and applying it on the conductive substrate by the same method as described above. It can be formed by drying.

IX. Intermediate Layer As shown in FIGS. 9 to 12, an intermediate layer 42 is provided between the undercoat layer 4 and the photosensitive layer 6 in order to improve electrical characteristics, improve image quality, improve image quality maintenance, improve adhesion of the photosensitive layer, and the like. May be. The constituent material of the intermediate layer 42 is not particularly limited, and can be arbitrarily selected from synthetic resin, organic substance or inorganic substance powder, and electron transporting substance.

(1) Intermediate layer-containing compound The intermediate layer is an acetal resin such as polyvinyl butyral, polyvinyl alcohol resin, casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl acetate. In addition to polymer resin compounds such as resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, melamine resin, zirconium, titanium, aluminum, manganese, silicon atoms, etc. Contains organometallic compounds. These compounds can be used alone or as a mixture or polycondensate of a plurality of compounds. Among them, an organometallic compound containing zirconium or silicon is excellent in performance such as a low residual potential, a small potential change due to the environment, and a small potential change due to repeated use.

  Examples of silicon compounds are vinyltrimethoxysilane, γ-methacryloxypropyl-tris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane. , Vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ- Aminopropylmethylmethoxysilane, N, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, and the like. Among these, silicon compounds particularly preferably used are vinyltriethoxysilane, vinyltris (2-methoxyethoxysilane), 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4). -Epoxycyclohexyl) ethyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N Silane coupling agents such as -phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-chloropropyltrimethoxysilane are raised.

  Examples of organic zirconium compounds include zirconium butoxide, zirconium zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl acetoacetate butoxide, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octoate, naphthene. Zirconate, zirconium laurate, zirconium stearate, zirconium isostearate, methacrylate zirconium butoxide, stearate zirconium butoxide, isostearate zirconium butoxide and the like.

  Examples of organic titanium compounds include tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate ammonium salt, Examples include titanium lactate, titanium lactate ethyl ester, titanium triethanolamate, and polyhydroxytitanium stearate.

  Examples of the organoaluminum compound include aluminum isopropylate, monobutoxyaluminum diisopropylate, aluminum butyrate, diethyl acetoacetate aluminum diisopropylate, and aluminum tris (ethyl acetoacetate).

(2) Additive In the intermediate layer, various organic compound fine powders or inorganic compound fine powders can be added for the purpose of improving electrical characteristics and light scattering properties. In particular, white pigments such as titanium oxide, zinc oxide, zinc white, zinc sulfide, lead white and lithopone, inorganic pigments as extender pigments such as alumina, calcium carbonate and barium sulfate, and polytetrafluoroethylene resin particles (for example, DuPont) : Particles made of resin such as “Teflon (registered trademark)”, benzoguanamine resin particles, styrene resin particles, and the like are effective.

  The added fine powder has a particle size of 0.01 to 2 μm. The fine powder is added as necessary, but the addition amount is preferably 10 to 90% by weight, and 30 to 80% by weight with respect to the total weight of the solid content of the intermediate layer. Is more preferable.

  In addition, it is also effective from the viewpoint of low residual potential and environmental stability to include the above-described electron transporting substance, electron transporting pigment, and the like in the intermediate layer 42. The intermediate layer 42 plays the role of an electrical blocking layer in addition to improving the coating properties of layers (photosensitive layer, etc.) laminated above this, but if the film thickness is too large, the electrical barrier is strong. Too much cause desensitization and potential increase due to repetition. Therefore, when the intermediate layer 42 is formed, the thickness is preferably 0.1 to 3 μm.

  In addition, when preparing a coating liquid for forming the intermediate layer 42, when a fine powdery substance is added, it is added to a solution in which a resin component is dissolved and subjected to a dispersion treatment. As the dispersion treatment method, methods such as a roll mill, a ball mill, a vibrating ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker can be used. Further, the intermediate layer 42 can be formed by applying a coating solution for forming the intermediate layer 42 on the conductive substrate 3 and drying it. As a coating method at this time, usual methods such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, and the like can be used.

  In addition to improving the coatability of the layer formed on the intermediate layer, the intermediate layer also serves as an electrical blocking layer, but if the film thickness is too large, the electrical barrier becomes too strong and desensitization And increase in potential due to repetition. Therefore, when the intermediate layer is formed, the film thickness is set to 0.1 to 3 μm. After the application, the intermediate layer is dried in a dryer or naturally dried to remove the solvent in the film. About drying temperature and time, it can set arbitrarily.

X. Protective layer As shown in FIGS. 7, 8, 11, and 12, the protective layer 5 prevents chemical change of the charge transport layer 2 when the electrophotographic photosensitive member 120 is charged, and increases the mechanical strength of the photosensitive layer 6. Used to further improve. The protective layer 5 can be formed by applying a coating solution containing a conductive material in a suitable binder onto the photosensitive layer 6.

  This protective layer has, for example, a configuration in which a curable resin, a cured siloxane resin film containing a charge transport material, and a conductive material are contained in a suitable binder resin. Any curable resin can be used as long as it is a public resin. Examples thereof include phenol resin, polyurethane resin, melamine resin, diallyl phthalate resin, and siloxane resin. In the case of a cured siloxane resin film containing a charge transport material, any material known as a charge transport material can be used. Examples thereof include compounds disclosed in JP-A-10-95787, JP-A-10-251277, JP-A-11-32716, JP-A-11-38656, JP-A-11-236391, and the like. However, it is not limited to this.

  When the protective layer is a film having a configuration in which a conductive material is contained in a suitable binder resin, the conductive material is not particularly limited. For example, a metallocene such as N, N′-dimethylferrocene is used. Compounds, aromatic amine compounds such as N, N′-diphenyl-N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine, molybdenum oxide, tungsten oxide, Antimony oxide, tin oxide, titanium oxide, indium oxide, tin oxide and antimony, solid solution carrier of barium sulfate and antimony oxide, mixture of the above metal oxides, single particles of titanium oxide, tin oxide, zinc oxide or barium sulfate A mixture of the above metal oxides or a single particle of titanium oxide, tin oxide, zinc oxide or barium sulfate coated with the above metal oxides And the like of it.

  As a binder used for this protective layer, polyamide resin, polyvinyl acetal resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polyvinyl ketone resin, polystyrene resin, polyacrylamide resin, polyimide resin, polyamideimide resin, etc. These known resins are used. These can also be used by cross-linking each other as necessary.

  The protective layer can contain an antioxidant. Specific examples of antioxidants include phenolic antioxidants such as 2,6-di-t-butyl-4-methylphenol, styrenated phenol, n-octadecyl-3- (3 ′, 5′-di -T-butyl-4'-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5) '-Methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidene-bis (3-methyl-6-tert-butyl-phenol), 4,4'-thio-bis (3- Methyl-6-tert-butylphenol), 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetrakis [methylene-3- (3 ′, '-Di-t-butyl-4'-hydroxyphenyl) propionate] methane, 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1 , 1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane and the like.

  In the above hindered amine compounds, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- {2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl} -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy]- 2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4.5] undecane-2,4-dione 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine succinate Polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diimyl} {(2,2,6,6-tetra Methyl-4-piperidyl) imino} hexamethylene {(2,3,6,6-tetramethyl-4-piperidyl) imino}], 2- (3,5-di-t-butyl-4-hydroxybenzyl)- 2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl- N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate and the like.

  Dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis as the organic sulfur-based antioxidant -(Β-lauryl-thiopropionate), ditridecyl-3,3′-thiodipropionate, 2-mercaptobenzimidazole and the like.

  In addition to known antioxidants such as trisnonylphenyl phosfetes, triphenyl phosfetes, tris (2,4-di-t-butylphenyl) phosphites as organic phosphorus antioxidants, hydroxyl groups capable of binding to siloxane resins , Antioxidants having functional groups such as amino groups and alkoxysilyl groups.

  The thickness of the protective layer is preferably 1 to 20 μm, and more preferably 1 to 10 μm. As a coating method of the coating liquid for forming this protective layer, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, etc. Can be used.

  In addition, as a solvent used in the coating solution for forming the protective layer, ordinary organic solvents such as dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene can be used alone or in admixture of two or more. It is preferable to use a solvent that hardly dissolves the photosensitive layer to which the coating solution is applied as much as possible.

XI. Process cartridge and electrophotographic apparatus Next, a process cartridge and an electrophotographic apparatus on which the electrophotographic photosensitive member of the present invention is mounted will be described.
The process cartridge of the present invention comprises an electrophotographic photosensitive member of the present invention, a charging means for charging the electrophotographic photosensitive member, and an electrostatic latent image formed on the electrophotographic photosensitive member is developed with toner to form a toner image. And at least one selected from the group consisting of a cleaning means for removing toner remaining on the surface of the electrophotographic photosensitive member.
In other words, the process cartridge of the present invention is formed by combining the first, second, and third microchannels, and the first and second microchannels for feeding three types of compositions, respectively. A step of preparing a microreactor having a flow path and a final merge flow path formed by joining a third micro flow path to the intermediate merge flow path, a first composition comprising metal oxide particles and a solvent The product is fed to the first microchannel, and the second composition containing the surface treatment agent reactive with the metal oxide particles and the solvent is fed to the second microchannel and the intermediate confluence A step of performing a surface treatment of the metal oxide particles in the flow channel, and a third composition containing a deactivator and a solvent for deactivating the surface treatment agent are fed to the third micro flow channel and finally joined. Surface treatment by a surface treatment method having a step of deactivating excess surface treatment agent in the flow path Manufactured by a manufacturing method including a step of forming an undercoat layer by coating a coating liquid for an undercoat layer obtained by dispersing the obtained metal oxide particles, binder, and additive on a conductive substrate. An electrophotographic photosensitive member, a charging unit that charges the electrophotographic photosensitive member, a developing unit that develops an electrostatic latent image formed on the electrophotographic photosensitive member with toner, and a toner image; and And at least one selected from the group consisting of cleaning means for removing toner remaining on the surface of the electrophotographic photosensitive member.
The electrophotographic apparatus of the present invention includes the electrophotographic photosensitive member of the present invention, a charging unit that charges the electrophotographic photosensitive member with an electrostatic charge, an exposure unit that exposes the charged electrophotographic photosensitive member, and the electrophotographic photosensitive member. Developing means for developing the electrostatic latent image formed thereon with toner to form a toner image; and transfer means for transferring the toner image formed on the surface of the electrophotographic photosensitive member to a transfer target. It is characterized by that.
That is, the electrophotographic apparatus of the present invention is an intermediate formed by joining the first, second and third microchannels and the first and second microchannels for feeding three kinds of compositions, respectively. A step of preparing a microreactor having a merged flow channel and a final merged flow channel formed by merging a third micro flow channel with the intermediate merged flow channel, a first including metal oxide particles and a solvent; The composition is sent to the first microchannel, and the second composition containing the surface treatment agent reactive with the metal oxide particles and the solvent is sent to the second microchannel and the intermediate The step of performing the surface treatment of the metal oxide particles in the confluence channel, and the third composition containing a deactivator and a solvent for deactivating the surface treatment agent are sent to the third microchannel and finally A surface-treated gold having a step of deactivating an excess of the surface treatment agent in the confluence channel Electrons manufactured by a manufacturing method including a step of forming an undercoat layer by coating an undercoat layer coating solution obtained by dispersing oxide particles, a binder, and an additive on a conductive substrate. A photographic photosensitive member, a charging means for charging the electrophotographic photosensitive member with an electrostatic charge, an exposing means for exposing the charged electrophotographic photosensitive member, and an electrostatic latent image formed on the electrophotographic photosensitive member are developed with toner. Developing means for forming a toner image, and transfer means for transferring the toner image formed on the surface of the electrophotographic photosensitive member to a transfer target.

The electrophotographic photosensitive member of the present invention is used in an electrophotographic apparatus such as a laser printer, a digital copying machine, an LED printer, and a laser facsimile that emits near-infrared light or visible light, and a process cartridge provided in such an electrophotographic apparatus. Can be installed. The laser beam is preferably a laser that oscillates light of 350 to 800 nm in order to obtain a high-definition image. Further, the spot diameter of the laser beam is preferably 1 × 10 ⁴ μm ² or less, and more preferably 3 × 10 ³ μm ² or less in order to obtain a high-definition image.

  The electrophotographic photoreceptor of the present invention can be used in combination with a one-component or two-component regular developer or reversal developer. Furthermore, the particle diameter of the toner for obtaining a high-definition image is preferably 10 μm or less, more preferably 8 μm or less. These toners can be obtained by known production methods, and spherical toners obtained by a dissolution suspension method or a polymerization method are particularly preferably used. Further, a surface lubricant (metal fatty acid salt) or particles having an abrasive effect can be added to the toner.

  Further, even when the electrophotographic photosensitive member of the present invention is mounted on a contact charging type electrophotographic apparatus using a charging roller or a charging brush, good characteristics with little occurrence of current leakage can be obtained.

  FIG. 13 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of the electrophotographic apparatus of the present invention. An electrophotographic apparatus 200 shown in FIG. 13 includes an electrophotographic photosensitive member 7, a charging means 8 such as corotron or scorotron for charging the electrophotographic photosensitive member 7 by a corona discharge method, a power source 9 connected to the charging means 8, An exposure unit 10 that exposes the electrophotographic photosensitive member 7 charged by the charging unit 8 to form an electrostatic latent image, and a toner image is formed by developing the electrostatic latent image formed by the exposure unit 10 with toner. The image forming apparatus includes a developing unit 11, a transfer unit 12 that transfers a toner image formed by the developing unit 11 to a transfer medium, a cleaning device 13, a static eliminator 14, and a fixing device 15.

  FIG. 14 is a sectional view schematically showing a basic configuration of another embodiment of the electrophotographic apparatus of the present invention shown in FIG. An electrophotographic apparatus 210 shown in FIG. 14 has the same configuration as that of the electrophotographic apparatus 200 shown in FIG. 13 except that it includes a charging unit 8 that charges the electrophotographic photoreceptor 7 by a contact method. In particular, an electrophotographic apparatus that employs contact-type charging means in which an AC voltage is superimposed on a DC voltage can be preferably used because it has excellent wear resistance. In this case, the static eliminator 14 may not be provided.

  The charging means (charging member) 8 is disposed so as to be in contact with the surface of the photoconductor 7 and applies a voltage uniformly to the photoconductor to charge the surface of the photoconductor to a predetermined potential. The charging means 8 includes metals such as aluminum, iron and copper, conductive polymer materials such as polyacetylene, polypyrrole and polythiophene, polyurethane rubber, silicone rubber, epichlorohydrin rubber, ethylene propylene rubber, acrylic rubber, fluorine rubber, styrene-butadiene. A material obtained by dispersing carbon black, copper iodide, silver iodide, zinc sulfide, silicon carbide, metal oxide or the like in an elastomer material such as rubber or butadiene rubber can be used.

Examples of the metal oxide include ZnO, SnO ₂ , TiO ₂ , In ₂ O ₃ , MoO _{3 and the} like, or a composite oxide thereof. Further, the charging means 8 may be made by adding perchlorate in an elastomer material and imparting conductivity.

  Further, the charging means 8 may be provided with a coating layer on the surface thereof. As a material for forming the coating layer, N-alkoxymethylated nylon, cellulose resin, vinyl pyridine resin, phenol resin, polyurethane, polyvinyl butyral, melamine and the like are used alone or in combination. Also, emulsion resin-based materials such as acrylic resin emulsion, polyester resin emulsion, polyurethane, especially emulsion resin synthesized by soap-free emulsion polymerization can be used.

  In these resins, in order to further adjust the resistivity, conductive agent particles may be dispersed, or an antioxidant may be contained in order to prevent deterioration. In addition, in order to improve the film formability when forming the coating layer, the emulsion resin may contain a leveling agent or a surfactant. Examples of the shape of the contact charging member include a roller type, a blade type, a belt type, and a brush type.

Furthermore, the electric resistance value of the charging means 8 is preferably 10 ² to 10 ¹⁴ Ωcm, more preferably 10 ² to 10 ¹² Ωcm. Further, as the voltage applied to the contact charging member, either direct current or alternating current can be used. It can also be applied in the form of direct current + alternating current.

FIG. 15 is a sectional view schematically showing a basic configuration of still another embodiment of the electrophotographic apparatus of the present invention shown in FIG. An electrophotographic apparatus 220 shown in FIG. 15 is an intermediate transfer type electrophotographic apparatus. In the housing 400, four electrophotographic photoreceptors 401a to 401d (for example, the electrophotographic photoreceptor 401a is yellow and the electrophotographic photoreceptor 401b is magenta). The electrophotographic photosensitive member 401c can form an image of cyan and the electrophotographic photosensitive member 401d can form a black color) are arranged in parallel along the intermediate transfer belt 409.
Here, the electrophotographic photoreceptors 401a to 401d mounted on the electrophotographic apparatus 220 are respectively the electrophotographic photoreceptors of the present invention. For example, the above-described electrophotographic photoreceptor 100, electrophotographic photoreceptor 110, electrophotographic photoreceptor 120, electrophotographic photoreceptor 130, electrophotographic photoreceptor 140, electrophotographic photoreceptor 150, electrophotographic photoreceptor 160, electrophotographic Any of the photoreceptors 170 may be mounted. Each of the electrophotographic photosensitive members 401a to 401d can be rotated in a predetermined direction (counterclockwise on the paper surface), and the charging rolls 402a to 402d, the developing devices 404a to 404d, and the primary transfer roll 410a along the rotation direction. To 410d and cleaning blades 415a to 415d are arranged. Each of the developing devices 404a to 404d can be supplied with toners of four colors of black, yellow, magenta and cyan accommodated in toner cartridges 405a to 405d, and the primary transfer rolls 410a to 410d are intermediate transfer belts 409 is in contact with the electrophotographic photoreceptors 401a to 401d.
Further, a laser light source (exposure means) 403 is disposed at a predetermined position in the housing 400, and the surface of the electrophotographic photoreceptors 401a to 401d after charging is irradiated with laser light emitted from the laser light source 403. Is possible. Accordingly, charging, exposure, development, primary transfer, and cleaning are sequentially performed in the rotation process of the electrophotographic photosensitive members 401a to 401d, and the toner images of the respective colors are transferred onto the intermediate transfer belt 409 in an overlapping manner.
The intermediate transfer belt 409 is supported with a predetermined tension by a drive roll 406, a backup roll 408, and a tension roll 407, and can rotate without causing deflection due to the rotation of these rolls. Further, the secondary transfer roll 413 is disposed so as to contact the backup roll 408 via the intermediate transfer belt 409. The intermediate transfer belt 409 passing between the backup roll 408 and the secondary transfer roll 413 is cleaned by, for example, a cleaning blade 416 disposed in the vicinity of the drive roll 406 and then repeatedly used for the next image forming process. Is done.
A tray (transfer medium tray) 411 is provided at a predetermined position in the housing 400, and the transfer medium 500 such as paper in the tray 411 is moved by the intermediate transfer belt 409 and the secondary transfer roll by the transfer roll 412. Then, the paper is sequentially transferred between the two fixing rolls 414 that are in contact with each other and the two fixing rolls 414, and then discharged to the outside of the housing 400.

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

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

  When a belt-shaped configuration such as the intermediate transfer belt 409 is employed as the intermediate transfer member, the thickness of the belt is generally preferably 50 to 500 μm and more preferably 60 to 150 μm, but is appropriately selected according to the hardness of the material. be able to.

  For example, a belt made of a polyimide resin in which a conductive agent is dispersed is 5 to 20% by weight as a conductive agent in a polyamic acid solution as a polyimide precursor, as described in JP-A-63-111263. After the carbon black is dispersed and the dispersion is cast on a metal drum and dried, the film peeled from the drum can be stretched at a high temperature to form a polyimide film. 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.

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

  FIG. 16 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of the process cartridge of the present invention. The process cartridge 300 combines the electrophotographic photosensitive member 7 with the charging unit 8, the developing unit 11, the cleaning device (cleaning unit) 13, the opening 18 for exposure, and the static eliminator 14 using the mounting rail 16, and It is an integrated one. The process cartridge 300 is detachable from the main body of the electrophotographic apparatus comprising the transfer means 12, the fixing device 15, and other components not shown, and the electrophotographic apparatus together with the main body of the electrophotographic apparatus. It constitutes. In the process cartridge 300, the transfer system of the transfer unit 12 primarily transfers a toner image to an intermediate transfer member (not shown), and the primary transfer image on the intermediate transfer member is secondarily transferred to a transfer medium. The intermediate transfer method is preferable, and the transfer unit 12 is preferably an intermediate transfer device provided with the above-described intermediate transfer method. Similarly, the transfer means of the electrophotographic apparatus is preferably an intermediate transfer apparatus having the above-described intermediate transfer system.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all. In the following examples, “part” means “part by weight”.

Example 1
<1> Preparation of first composition 1 part of zinc oxide (average particle size: 70 nm, prototype manufactured by Teika) is charged with 20 parts of toluene into a homomixer (ACE homogenizer, manufactured by Nippon Seiki Co., Ltd.) every minute. The mixture was stirred at 15,000 rpm for 2 minutes to prepare a first composition (Composition 1A) as a zinc oxide mixed solution having a solid content concentration of 4.76% by weight.

<2> Preparation of second composition 0.15 part of a silane coupling agent (KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) is used as a surface treatment agent and mixed and stirred together with 20 parts of toluene. 2A) was adjusted.

<3> Preparation of Third Composition A third composition (composition 3A) was prepared by preparing 20 parts of a mixed solution having a water / acetic acid weight ratio of 97: 3 (acetic acid concentration: 3 wt% aqueous solution). .

<4> Surface treatment The composition 1A, the composition 2A, and the composition 3A are respectively applied to the microsyringes 31, 32, and 33 provided with the pumps P1, P2, and P3 of the microreactor processing apparatus as shown in FIG. The liquid was set and fed to the inlet portions of the flow paths L1, L2, and L3 in the microreactor 36, respectively.
The widths of the flow paths L1, L2, L3, L4, and L5 in the microreactor 36 are 300 μm, 500 μm, 500 μm, 500 μm, and 500 μm, respectively, and the depths are 300 μm, 500 μm, 500 μm, 500 μm, and 500 μm, respectively. The lengths of the paths L4 and L5 were 60 cm and 20 cm, respectively.

First, when the flow rate (liquid feeding speed) of L1 and L2 was set to 0.20 ml / hr and 0.25 ml / hr, respectively, the liquid was fed from the compositions 1A and L2 fed from L1 in the flow path L4. The fed composition 2A joined. The composition 1A sent from L1 merged in L4 and the composition 2A sent from L2 each form a two-layer laminar flow and are diffusively mixed while passing through the flow path L4. The adhesion reaction of the silane coupling agent to the surface proceeded. Immediately before the composition merged at L4 advances through the flow path while diffusing and reaches L5, the composition 3A having a liquid feeding speed set to 0.30 ml / hr is fed from L3, whereby L4 at L4 And the composition 3A sent from L3 merged. The two combined compositions are diffused and mixed while passing through the flow path L5, and the adhesion reaction of the silane coupling agent to the surface of the metal oxide particles proceeds and unreacted silane that has not contributed to the adhesion reaction. The hydrolysis reaction of the coupling agent proceeded. The composition diffused and mixed while passing through L5 was continuously discharged from the outlet of the microreactor 36 and collected in the storage vessel 35. At this time, there was no leakage or loss of metal oxide particles. Toluene was distilled off from the recovered composition by distillation under reduced pressure, followed by baking at 150 ° C. for 2 hours. As a result of analyzing the obtained surface-treated zinc oxide by fluorescent X-ray, the ratio of the Si element intensity to the Zn element intensity (Si / Zn) was 1.2 × 10 ⁻⁴ .

<5> Formation of undercoat layer Next, 60 parts of the obtained zinc oxide particles after the surface treatment, a curing agent (blocked isocyanate Sumijoule 3175, manufactured by Sumitomo Bayern Urethane Co., Ltd.): 15 parts, butyral resin (product) Name: “BM-1” (manufactured by Sekisui Chemical Co., Ltd.): 15 parts and methyl ethyl ketone: 85 parts were mixed. The obtained liquid: 38 parts and methyl ethyl ketone: 25 parts were mixed and dispersed for 2 hours with a sand mill using 1 mmφ glass beads to obtain a dispersion.
Dioctyltin dilaurate: 0.005 part and silicone oil SH29PA (manufactured by Toray Dow Corning Silicone): 0.01 part were added as catalysts to the resulting dispersion to obtain an undercoat layer coating solution. This coating solution is applied on an aluminum substrate (conductive substrate) having a diameter of 30 mm, a length of 340 mm, and a thickness of 1 mm by a dip coating method, followed by drying and curing at 160 ° C. for 100 minutes to form an undercoat layer having a thickness of 20 μm. Formed.

<6> Manufacture of Type I Hydroxygallium Phthalocyanine Add 30 parts of 1,3-diiminoisoindoline and 9.1 parts of gallium trichloride to 230 parts of dimethyl sulfoxide and react with stirring at 160 ° C. for 6 hours to produce red purple crystals Got.
The obtained crystal was washed with dimethyl sulfoxide, then washed with ion-exchanged water, and dried to obtain 28 parts of crude crystals of type I chlorogallium phthalocyanine. Next, 10 parts of the obtained crude crystals of type I chlorogallium phthalocyanine sufficiently dissolved in 300 parts of sulfuric acid (concentration 97%) heated to 60 ° C. were dissolved in 600 parts of 25% ammonia water and 200 parts of ion-exchanged water. It was dripped in the mixed solution. The precipitated crystals were collected by filtration, further washed with ion exchange water, and dried to obtain 8 parts of type I hydroxygallium phthalocyanine.
6 parts of the above-mentioned type I hydroxygallium phthalocyanine were wet pulverized at 25 ° C. for 168 hours using a glass ball mill together with 90 parts of N, N-dimethylformamide and 350 parts of spherical glass media having an outer diameter of 0.9 mm. The progress of crystal conversion was monitored by measuring the absorption wavelength of the wet pulverized liquid, and it was confirmed that the maximum peak λ _MAX in the range of 600 to 900 nm of the spectral absorption spectrum of the hydroxygallium phthalocyanine pigment was 820 nm. Next, the obtained crystal is washed with acetone, dried, and the Bragg angle (2θ ± 0.2 °) with respect to CuKα characteristic X-ray is 7.5 °, 9.9 °, 12.5 °, 16. 5.5 parts of a hydroxygallium phthalocyanine pigment having diffraction peaks at 3 °, 18.6 °, 25.1 ° and 28.3 ° were obtained.

  Next, a mixture of 15 parts of the above hydroxygallium phthalocyanine, 10 parts of vinyl chloride / vinyl acetate copolymer resin (VMCH, manufactured by Nihon Unicar) serving as a binder resin, and 300 parts of n-butyl acetate, The beads were dispersed in a sand mill for 4 hours. The obtained dispersion was dip-coated on the undercoat layer as a coating solution for forming a charge generation layer and dried to form a charge generation layer having a layer thickness of 0.2 μm. Furthermore, 4 parts of N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1] biphenyl-4,4′-diamine and bisphenol Z polycarbonate resin (viscosity average molecular weight 40,000) 6 parts were added to 80 parts of chlorobenzene and dissolved. The obtained dispersion is dip-coated on the charge generation layer as a coating solution for forming a charge transport layer and dried at 130 ° C. for 40 minutes to form a charge transport layer having a layer thickness of 25 μm. Completed the production of the body.

(Comparative Example 1)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the same zinc oxide particles as those used in Example 1 were used without surface treatment.

(Example 2)
In Example 1, it replaced with 1 part of zinc oxide as metal oxide particles, except that 1.33 parts of tin oxide (trade name: S1, manufactured by Mitsubishi Materials Corporation, no surface treatment, primary particle size 20 nm) was used. An electrophotographic photoreceptor was obtained in the same manner as in Example 1. Moreover, as a result of analyzing the surface-treated tin oxide obtained at this time by fluorescent X-ray, the ratio of the Si element intensity to the Sn element intensity (Si / Sn) was 1.5 × 10 ⁻³ .

(Comparative Example 2)
An electrophotographic photosensitive member was produced in the same manner as in Example 2 except that the same tin oxide as that used in Example 2 was used without surface treatment.

(Example 3)
In Example 1, instead of 1 part of zinc oxide as metal oxide particles, 1 part of titanium oxide (trade name: TAF-J500 manufactured by Fuji Titanium Industry Co., Ltd., no surface treatment, primary particle size 50 nm) was used. An electrophotographic photoreceptor was obtained in the same manner as in Example 1. Further, the surface-treated titanium oxide obtained at this time was analyzed by fluorescent X-ray, and as a result, the ratio of Si element strength to Ti element strength (Si / Ti) was 1.1 × 10 ⁻³ .

(Comparative Example 3)
An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the same titanium oxide as that used in Example 3 was used without being surface-treated.

(Comparative Example 4)
In Example 1, the surface treatment of zinc oxide particles was performed without using a microreactor. That is, 100 parts of zinc oxide was stirred and mixed with 500 parts of toluene, and 5 parts of a silane coupling agent (trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was added thereto and stirred for 2 hours. Thereafter, toluene was distilled off under reduced pressure, and an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that baking was performed at 150 ° C. for 1 hour. Further, the surface-treated zinc oxide obtained at this time was analyzed by fluorescent X-ray, and as a result, the ratio of the Si element intensity to the Zn element intensity (Si / Zn) was 1.0 × 10 ⁻⁵ .

Example 4
In Example 1, the surface treatment of zinc oxide particles was carried out by incorporating a micro mixer (type: SSIMM) manufactured by IMM Germany as shown in FIG. The flow path in the micromixer 44 is defined by a slit as shown in FIG. 3B, and the slit width is 40 μm and the depth is 300 μm. The composition 1A, the composition 2A, and the composition 3A in Example 1 are set in the microsyringes 31, 32, and 33 having the pumps P1, P2, and P3, respectively, of the micromixer processing apparatus as shown in FIG. The solution was fed to the inlet portions of the flow paths L1m, L2m, and L3m in the micromixers 40 and 41, respectively. In addition, Teflon (registered trademark) tubes having an inner diameter of 1000 μm (DuPont: tubes made of resin such as “Teflon (registered trademark)”) were used as the flow paths of L1 m to L5 m.

  In FIG. 4, the L1m, L2m, and L3m flow rates (liquid feeding speeds) were set to 4 ml / min, 5 ml / min, and 6 ml / min, respectively. The composition 1A and the composition 2B are respectively introduced into the inlet part of the micromixer 40 through L1m and L2m, mixed and diffused while passing between the slits, set to 20 ° C. with a temperature controller, and then from the outlet part It is introduced into the inlet portion of the micromixer 41 through the flow path L4, diffused and mixed by the micromixer 41 together with the composition 3A introduced from the other inlet portion through L3m, and continuously into 35 through the flow path L5m. Recovered.

Toluene was distilled off from the recovered composition by vacuum distillation in the same manner as in Example 1, followed by baking at 150 ° C. for 2 hours. As a result of analyzing the obtained surface-treated zinc oxide by fluorescent X-ray, the ratio of the Si element intensity to the Zn element intensity (Si / Zn) was 1.7 × 10 ⁻³ .
Further, an electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface-treated zinc oxide obtained by the above method was used.

<Electrophotographic characteristic evaluation test of electrophotographic photosensitive member>
(1) Initial characteristics evaluation (initial potential measurement)
The electrophotographic photosensitive members of Examples 1 to 4 and Comparative Examples 1 to 4 are mounted on a laser printer (trade name: XP-15 modified machine, manufactured by Fuji Xerox Co., Ltd.) having the same structure as FIG. The electrophotographic characteristics of each electrophotographic photosensitive member were evaluated as follows.
Measures the surface potential A [V] of each electrophotographic photosensitive member when the electrophotographic photosensitive member is charged with a scorotron charger with a grid applied voltage of −700 V in a normal temperature and normal humidity (20 ° C., 40% RH) environment. did.
Next, using a 780 nm semiconductor laser, each electrophotographic photosensitive member 1 second after being charged is irradiated with light of 10 mJ / m 2 to discharge, and the surface of each electrophotographic photosensitive member at this time is discharged. The potential B [V] was measured.
Subsequently, 3 seconds after the discharge, each electrophotographic photosensitive member is irradiated with 50 mJ / m ² of red LED light to eliminate static electricity, and the surface potential C [V] of each electrophotographic photosensitive member at this time is measured. did.
Here, the higher the value of the potential A, the higher the acceptance potential of the electrophotographic photosensitive member, so that the contrast can be increased. Further, the lower the potential B, the higher the sensitivity of the electrophotographic photosensitive member. Further, the lower the value of the potential C, the smaller the residual potential, and it is evaluated as an electrophotographic photosensitive member with less image memory and so-called fogging. These results are shown in Table 1.

(2) Characteristic evaluation after repeated use The operation described in (1) above was repeated 10,000 times, and the potentials A to C after charging and exposure were measured. These results are shown in Table 1.

(3) Stability evaluation against changes in use environment The above operation is performed under two different environments of low temperature and low humidity (10 ° C., 15% RH) and high temperature and high humidity (28 ° C., 85% RH). The potentials A to C were measured. Then, the fluctuation amounts (ΔA, ΔB, ΔC) of the potentials A to C between these different environments were measured, and the stability of each electrophotographic photosensitive member was evaluated against changes in the usage environment. These results are shown in Table 1.

(4) Image quality evaluation at the initial stage and after printing 10,000 sheets The electrophotographic photosensitive members of Examples 1 to 4 and Comparative Examples 1 to 4 have contact charging devices and intermediate transfer devices having the same structure as in FIG. It was mounted on a full color printer (trade name: Docu Center Color C620, manufactured by Fuji Xerox Co., Ltd.), and an initial print image quality evaluation and a continuous print test on 10,000 sheets of paper were performed.
And the image quality after printing 10,000 sheets,
“No abnormality”; good image quality was obtained,
“Full-scale fogging”; a large number (5000 or more) of fine black spots (diameter 0.15 mm or less) were confirmed on the entire paper surface (100 mm × 200 mm).
“Several sunspots”; a large number (100 or more) of large black spots (diameter of 0.3 mm or more) were confirmed on the entire paper surface (100 mm × 200 mm).
Evaluation was performed based on the evaluation criteria. These results are shown in Table 1.

According to the present invention, when used in the undercoat layer of an electrophotographic photosensitive member, it is excellent in stability of electrical characteristics such as chargeability, dischargeability and charge removal resistance against repeated use and changes in use environment, and is resistant to pinhole leakage. It was possible to provide a surface treatment method for metal oxide particles that is excellent in properties and can obtain stable image quality over a long period of time without causing image quality defects such as fogging, negative and ghost.
In addition, according to the present invention, an electrophotographic photoreceptor including an undercoat layer using the surface-treated metal oxide particles is provided, and a process cartridge and a laser printer equipped with the electrophotographic photoreceptor are provided. I was able to.

It is a schematic block diagram which shows an example of the microreactor processing apparatus used suitably for the surface treatment of this invention. It is a figure which shows the flow path confluence | merging part (enlarged view) of the microreactor used suitably for the surface treatment of this invention. It is a figure which shows (a) external appearance and (b) slit part (enlarged view) of the micromixer used suitably for the surface treatment of this invention. It is a schematic block diagram which shows another example of the microreactor used suitably for the surface treatment of this invention. 1 is a cross-sectional view showing a first embodiment of an electrophotographic photosensitive member of the present invention. It is sectional drawing which shows 2nd embodiment of the electrophotographic photoreceptor of this invention. It is sectional drawing which shows 3rd embodiment of the electrophotographic photoreceptor of this invention. It is sectional drawing which shows 4th embodiment of the electrophotographic photoreceptor of this invention. It is sectional drawing which shows 5th embodiment of the electrophotographic photoreceptor of this invention. It is sectional drawing which shows 6th embodiment of the electrophotographic photoreceptor of this invention. It is sectional drawing which shows 7th embodiment of the electrophotographic photoreceptor of this invention. It is sectional drawing which shows 8th embodiment of the electrophotographic photoreceptor of this invention. 1 is a cross-sectional view schematically illustrating a basic configuration of a preferred embodiment of an electrophotographic apparatus of the present invention. It is sectional drawing which shows schematically the basic composition of another embodiment of the electrophotographic apparatus of this invention shown in FIG. 1 is a cross-sectional view schematically showing a basic configuration of a full-color printer which is one of the electrophotographic apparatuses of the present invention. 1 is a cross-sectional view schematically showing a basic configuration of a preferred embodiment of a process cartridge of the present invention.

Explanation of symbols

1 Photosensitive layer (charge generation layer)
2 ... Photosensitive layer (charge transport layer)
3 ... conductive substrate 4 ... undercoat layer 5 ... protective layer 6 ... photosensitive layer 7 ... electrophotographic photosensitive member 8 ... charging means 9 ... power source 10 ... exposure Means 11... Development means 12... Transfer means 13... Cleaning device 14... Static eliminator 15... Fixing device 16 .. Mounting rail 18. Intermediate layer 100, 110, 120, 130, 140, 150, 160, 170 ... electrophotographic photosensitive member 200 ... electrophotographic apparatus (corona discharge method)
210 ... Electrophotographic apparatus (contact method)
220 ... Electrophotographic apparatus (intermediate transfer system)
300... Process cartridge 400... Housing 401 a to 401 d... Electrophotographic photosensitive member 402 a to 402 d.
404a to 404d, developing devices 405a to 405d, toner cartridge 406, driving roll 407, tension roll 408, backup roll 409, intermediate transfer belt 410a to 410d, primary transfer Roll 411 ... Tray (transfer tray)
412 ... Transfer roll 413 ... Secondary transfer roll 414 ... Fixing rolls 415a to 415d ... Cleaning blade 416 ... Cleaning blade 500 ... Transfer medium A ... First composition B ... Mixed diffusion region C of first composition and second composition C ... Second composition 1A ... First composition 2A ... Second composition 3A ... -3rd composition 6A ... liquid mixture 31, 32, 33 ... micro syringe 35 ... container 36, 37 ... micro reactor 40, 41 ... micro mixer L1, L2, L3, L4 , L5 ... channels F1, F2, F3 ... filters P1, P2, P3 ... syringe pumps L1m, L2m, L3m, L4m, L5m ... channel D1 ... channel diameter D2 of L1 ..L2 channel diameter

Claims (5)

First, second, and third microchannels for feeding three kinds of compositions, an intermediate merging channel formed by merging the first and second microchannels, and the intermediate merging channel Preparing a microreactor having a final merged channel formed by merging a third microchannel in the channel;
A first composition containing metal oxide particles and a solvent is fed to the first microchannel, and a second composition containing a surface treatment agent having reactivity with the metal oxide particles and a solvent is prepared. A step of sending the liquid to the second microchannel and performing a surface treatment of the metal oxide particles in the intermediate merging channel; and
Feeding a third composition containing a deactivator for deactivating the surface treatment agent and a solvent to the third microchannel and deactivating the excess surface treatment agent in the final merge channel. A method for surface treatment of metal oxide particles. First, second, and third microchannels for feeding three kinds of compositions, an intermediate merging channel formed by merging the first and second microchannels, and the intermediate merging channel A step of preparing a microreactor having a final merged channel formed by joining a third microchannel to the channel, and a first composition containing metal oxide particles and a solvent into the first microchannel The second composition containing a surface treatment agent reactive with the metal oxide particles and a solvent is fed to the second microchannel, and the surface of the metal oxide particles in the intermediate merge channel A step of performing a treatment, and a third composition containing a deactivator for deactivating the surface treatment agent and a solvent is fed to the third microchannel, and an excess surface treatment agent is removed in the final merge channel. A metal oxide particle, a binder, and an additive that are surface-treated by a surface treatment method having a deactivation step. Process for producing an electrophotographic photoreceptor which comprises a step of forming an undercoat layer by coated with a coating solution for the lower obtained by dispersion treatment coating layer on a conductive substrate. First, second, and third microchannels for feeding three kinds of compositions, an intermediate merging channel formed by merging the first and second microchannels, and the intermediate merging channel A step of preparing a microreactor having a final merged channel formed by joining a third microchannel to the channel, and a first composition containing metal oxide particles and a solvent into the first microchannel The second composition containing a surface treatment agent reactive with the metal oxide particles and a solvent is fed to the second microchannel, and the surface of the metal oxide particles in the intermediate merge channel A step of performing a treatment, and a third composition containing a deactivator for deactivating the surface treatment agent and a solvent is fed to the third microchannel, and an excess surface treatment agent is removed in the final merge channel. A metal oxide particle, a binder, and an additive that are surface-treated by a surface treatment method having a deactivation step. An electrophotographic photosensitive member, characterized by being manufactured by a manufacturing method comprising a step of forming an undercoat layer by coated with a dispersion treatment by undercoat layer coating solution obtained on a conductive substrate. First, second, and third microchannels for feeding three kinds of compositions, an intermediate merging channel formed by merging the first and second microchannels, and the intermediate merging channel A step of preparing a microreactor having a final merged channel formed by joining a third microchannel to the channel, and a first composition containing metal oxide particles and a solvent into the first microchannel The second composition containing a surface treatment agent reactive with the metal oxide particles and a solvent is fed to the second microchannel, and the surface of the metal oxide particles in the intermediate merge channel A step of performing a treatment, and a third composition containing a deactivator for deactivating the surface treatment agent and a solvent is fed to the third microchannel, and an excess surface treatment agent is removed in the final merge channel. A metal oxide particle, a binder, and an additive that are surface-treated by a surface treatment method having a deactivation step. Electrophotographic photosensitive member manufactured by a manufacturing method comprising a step of forming an undercoat layer by coated with a dispersion treatment by undercoat layer coating solution obtained on a conductive substrate, and,
Charging means for charging the electrophotographic photosensitive member, developing means for developing a latent electrostatic image formed on the electrophotographic photosensitive member with toner to form a toner image, and remaining on the surface of the electrophotographic photosensitive member A process cartridge comprising: at least one selected from the group consisting of cleaning means for removing the toner. First, second, and third microchannels for feeding three kinds of compositions, an intermediate merging channel formed by merging the first and second microchannels, and the intermediate merging channel A step of preparing a microreactor having a final merged channel formed by joining a third microchannel to the channel, and a first composition containing metal oxide particles and a solvent into the first microchannel The second composition containing a surface treatment agent reactive with the metal oxide particles and a solvent is fed to the second microchannel, and the surface of the metal oxide particles in the intermediate merge channel A step of performing a treatment, and a third composition containing a deactivator for deactivating the surface treatment agent and a solvent is fed to the third microchannel, and an excess surface treatment agent is removed in the final merge channel. A metal oxide particle, a binder, and an additive that are surface-treated by a surface treatment method having a deactivation step. Electrophotographic photosensitive member manufactured by a manufacturing method comprising a step of forming an undercoat layer by coated with a dispersion treatment by undercoat layer coating solution obtained on a conductive substrate,
Charging means for charging the electrophotographic photosensitive member with an electrostatic charge,
Exposure means for exposing the charged electrophotographic photosensitive member;
Developing means for developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image; and
An electrophotographic apparatus comprising: transfer means for transferring a toner image formed on the surface of the electrophotographic photosensitive member to a transfer target.

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