JP2003255574A - Electrophotographic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic apparatus capable of extremely lowering the probability of abnormal image generation even in the case of adopting a photoreceptor capable of keeping surface energy low even after repeated use and having high durability. <P>SOLUTION: In the electrophotographic apparatus with at least an electrifying means, an exposure means, a developing means and a transfer means around an electrophotographic photoreceptor, the electrophotographic photoreceptor contains an acrylic modified polyorganosiloxane compound in the top surface layer and the electrifying means is disposed in the vicinity of the electrophotographic photoreceptor. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic apparatus which has high durability and has improved image quality stability for a long period of time.

[0002]

2. Description of the Related Art Conventionally, a copying machine using an electrophotographic method,
Electrophotographic devices such as facsimiles, laser printers, and direct digital plate making machines have become widespread. In the electrophotographic method, at least charging, image exposure, and
Development is performed, and then the toner image is transferred and fixed on the image carrier (transfer paper). Then, one process is completed by cleaning the surface of the electrophotographic photosensitive member.

As a photoconductor (electrophotographic photoconductor) used in an electrophotographic apparatus, (1) a photoconductor in which a photoconductive layer mainly containing selenium or a selenium alloy is provided on a conductive support,
(2) A photoconductor in which an inorganic photoconductive material such as zinc oxide and cadmium sulfide is dispersed in a binder, a photoconductor using an amorphous silicon-based material, and (3) an organic photoconductor are known. . Among them, organic type photoconductors are widely used because they are excellent in cost and productivity, have a high degree of freedom in designing photoconductors, and are non-polluting.

Organic photoconductors are (1) photoconductors using a photoconductive resin represented by polyvinylcarbazole (PVK), and (2) PVK-TNF (2,4,7-trinitro). Fluorenone) and a charge transfer complex type photoreceptor, (3) a pigment dispersion type photoreceptor represented by a phthalocyanine-binder resin, and (4) a function separation type using a charge generating substance and a charge transporting substance in combination. Photoconductors and the like are known. Among them, a function-separated type photoreceptor is generally used.

An example of the electrostatic latent image mechanism in the function-separated type photoconductor is shown below. First, the photoconductor is charged, and then the photoconductor is irradiated with light. The irradiated light passes through the transparent charge transport layer and is absorbed by the charge generating substance in the charge generating layer. The charge generating substance that absorbs light generates charge carriers. The charge carriers are injected into the charge transport layer and further move in the charge transport layer according to the electric field to neutralize the charge on the surface of the photoreceptor.

The function-separated photoreceptor forms an electrostatic latent image by the mechanism as described above. It is known that in order to realize this mechanism, a charge transport substance whose absorption region is mainly in the ultraviolet region and a charge generation substance which is mainly in the visible region are used in combination. Such a photoreceptor is useful because it has excellent image forming properties and the like.

Since many of the charge transport materials have been developed as low molecular weight compounds, they are usually used by being dispersed / mixed in an inert polymer. This is because the low molecular weight compound generally has no film forming property / is poor in film forming property. But,
The charge transport layer composed of a low molecular weight charge transport material and an inert polymer is generally soft and has low abrasion resistance. For example, when repeatedly used, film abrasion is likely to occur due to mechanical load on the surface of the photoconductor by a developing system or a cleaning system. The charge transport layer having the above structure tends to have improved wear resistance by increasing the proportion of the inactive polymer, but it causes a problem that the charge mobility is lowered, and therefore, the charge transport layer is not easily combined with the low molecular weight charge transport material. The content ratio with the active polymer is limited, and the wear resistance has not been dramatically improved.

On the other hand, the photosensitive member is required to have a smaller diameter in order to downsize the electrophotographic apparatus. In order to reduce the diameter of the photoconductor, it is necessary to make the photoconductor highly durable. Further, in recent years, there has been an increasing tendency toward higher printing speeds, full-color printing, maintenance-free, and the like, and the higher durability of the photoreceptor has become an even more important issue.

Various conventional techniques have been proposed to meet the above demands. For example, there is a photoconductor in which the binder resin of the organic photoconductor is improved in order to improve the abrasion resistance of the organic photoconductor (Japanese Patent Laid-Open No. 5-216250, etc.).
However, such a photoconductor has a problem of the composition ratio of the low-molecular-weight charge transport material as described above, and therefore, the abrasion resistance cannot be remarkably improved.

Further, a photoreceptor using a polymer charge transport material is also known. Such photoreceptors are disclosed, for example, in JP-A-51-73888, JP-A-54-8527, JP-A-54-11737, and JP-A-56-15.
No. 0749, No. 57-78402, No. 63-285552, No. 64-1728, No. 64-13061, No. 64-1
No. 9049, No. 3-50555, No. 4-175337, No. 4-225014, No. 4-230767, No. 5-232.
No. 727, Japanese Patent Laid-Open No. 5-310904, and the like. As described above, since the charge transport layer component of the photoconductor using the polymer charge transport material is a polymer, the problem of film abrasion is improved as compared with the photoconductor using the conventional low molecular charge transport material. . However, it is not enough to treat the photoconductor as a stationary part that does not replace until the machine life. In other words, it does not realize maintenance-free.

Further, a technique of adding an inorganic filler having a relatively high hardness to the outermost surface (layer) of the photoconductor is disclosed (Japanese Patent Laid-Open No. 4-281461, etc.). This technology
It is known that a photoreceptor having high abrasion resistance can be provided, although the influence of the increase in residual potential increases depending on the type of filler added.

A technique for cross-linking and hardening the outermost surface layer of the photoreceptor is also known (Japanese Patent Laid-Open No. 56-48637). This technique has side effects such as an increase in residual potential due to residual polymerization initiator and unreacted groups, but it is known that a photoreceptor having high abrasion resistance can be obtained depending on crosslinking conditions and the like. With the above technical development,
Organic photoreceptors have been improved in wear resistance and have achieved high durability.

[0013]

However, it has been found that when the abrasion resistance of the photoconductor is increased, the occurrence of abnormal images such as image blurring becomes remarkable. For example, image blurring occurs when the surface resistance of the photoconductor is reduced, lateral movement of charges occurs, and the electrostatic latent image is blurred. The decrease in the surface resistance of the photoconductor is caused by ozone or NOx gas generated when the photoconductor is charged, and ionic species (hereinafter referred to as a charged product) generated by these gases and moisture in the atmosphere. It is thought that the main reason is that it adheres and deposits on top.

Since the conventional photoreceptor has low abrasion resistance, even if the charged product is deposited on the surface of the photoreceptor, it is removed by abrasion. Therefore, the image blur was not noticeable. On the other hand, it is considered that the image blur becomes remarkable on the photoreceptor having high abrasion resistance because it is difficult to remove the charged products.

Therefore, in order to improve wear resistance / durability, it is necessary to suppress the occurrence of abnormal images. Even if the wear resistance is high, it is difficult to say that high durability has been realized because a photoconductor that is prone to image deterioration such as image blurring and resolution reduction cannot be practically used. is there.

As described above, as a method for suppressing the influence of ozone and NOx generated by charging and the image blur caused by adhesion and accumulation of charged products, the surface energy and friction coefficient of the surface of the photoconductor are reduced, There is known a method of adding an antioxidant to the outermost surface layer or providing a dehumidifying device for heating the photoconductor. Specifically, the following conventional techniques are disclosed.

A technique for containing a fluorine-modified silicone oil in the surface layer (Japanese Patent Laid-Open No. 07-295248, Japanese Patent Laid-Open No. 07-301936, Japanese Patent Laid-Open No. 08-0829).
No. 40, etc.) In this conventional technique, by reducing the surface energy of the photoconductor, effects such as improvement of cleaning property and prevention of foreign matter adhesion can be obtained. However, the above effects were lost early, and there was a big problem in sustaining the effects. In the case of fluorine-modified silicone oil, the effect is poor in sustainability because it migrates to the vicinity of the surface in the process of forming the surface layer of the photoconductor, and due to the influence of minute wear and charging of the surface layer due to repeated use, the surface layer Is thought to be one of the reasons for its early loss. Therefore, this conventional technique cannot be said to sufficiently realize the high durability of the photoconductor.

Technology relating to a system in which various kinds of fine particles are added to the outermost surface layer of the photoconductor As such a conventional technology, for example, the following is disclosed. Technology for adding silicone resin fine particles and fluorine-containing resin fine particles (JP-A-63-65449, etc.) Technology for adding melamine resin particles (JP-A-60-17)
No. 7349, etc.) A technique of incorporating polyethylene powder into the surface layer (Japanese Patent Laid-Open No.
No. 2-143257, etc.) A technique for containing a fluorine-containing resin powder in the surface layer (Japanese Patent Application Laid-Open No.
No. 2-144550, etc.) A technique of incorporating silicone fine particles into the surface layer (Japanese Patent Laid-Open No. HEI 0)
No. 7-128872, JP-A-10-254160, etc.) A technique for incorporating crosslinked organic fine particles in a surface layer (JP-A-20
No. 00-010322, USP 5,998,072, etc.) Technology for containing fine particles of methylsiloxane resin in the surface layer (JP-A-08-190213, etc.)

These conventional techniques are effective in reducing the friction coefficient of the surface of the photoconductor or maintaining the effect of reducing the surface energy, and are effective methods for increasing the durability of the photoconductor. However, such an effect is sustained by a certain amount of abrasion of the surface of the photoreceptor,
The effect is not exerted on the photoreceptor having enhanced abrasion resistance.
Further, since the effect is not exhibited at all when the fine particles are covered with the binder resin, it is necessary to wear the surface of the photoconductor in advance. As described above, it is difficult to apply the above-mentioned conventional technique to a photoreceptor having improved abrasion resistance, and even when it is applied, it is not possible to achieve both high durability and high image quality.

Technology for adding an antioxidant to the outermost surface layer of the photoconductor (Japanese Patent Laid-Open No. 8-292585) This conventional technique suppresses deterioration of the electrostatic characteristics of the photoconductor due to exposure to ozone or NOx gas. This is an effective method. However, there is a drawback in that the photosensitive member has a strong tendency to increase the residual potential. Further, since it is necessary to add a relatively large amount of antioxidant in order to suppress image blur, the residual potential of the photoconductor becomes extremely high due to repeated use. Further, no effect can be obtained for image blur caused by charged products adhering to the surface of the photoconductor, and this method alone is not satisfactory for suppressing image blur. Therefore, it is difficult to increase the durability of the photoconductor only by this conventional technique.

Further, as a technique for suppressing the image blur caused by the charged products attached to the surface of the photoconductor, a method of heating and dehumidifying the photoconductor is disclosed. This method is an effective method for suppressing image blur, because the decrease in resistance on the surface of the photosensitive member is suppressed by dehumidifying the photosensitive member. But,
This technique has many drawbacks such as high power consumption because it requires constant heating of the photoconductor, and much time is required to start up the apparatus. Further, since it is necessary to include a dehumidifying device for heating the photoconductor in the electrophotographic device, it is difficult to downsize the device.

There are also attempts to solve the above problems depending on the type of charging means employed. This attempt will be detailed below. In the electrophotographic apparatus, the charging unit is a corona charging unit such as a corotron or a scorotron that applies a charge to the photoconductor in a non-contact state, and a contact charging such as a charging roller or a charging brush that applies a charge to the photoconductor. It is roughly classified into means.

The corona charging means can be constituted by a simple device, but since the amount of ozone and NOx generated is very large,
It has a great influence (adverse effect) on the environment, the electrostatic characteristics of the photoconductor, and the image characteristics. In particular, if the tandem system is adopted, a plurality of ozone and NOx are generated because a plurality of them are required. Therefore, the corona charging means has a very narrow application range in the electrophotographic system.

In order to suppress the generation of abnormal images due to the charging means, it is first necessary to reduce the amount of ozone or NOx gas generated. Ozone or NOx gas may deteriorate or decompose the constituent materials on the surface of the photoconductor, which may reduce the chargeability and wear resistance of the photoconductor, and may cause abnormal images such as image blur. It was a cause of promotion. Further, when a filler or the like is added to the photoconductor in order to improve abrasion resistance, ozone or NOx gas is adsorbed by the filler, which may further increase the influence of image blur. Therefore, it is necessary to reduce the amount of ozone and NOx gas generated by charging as much as possible.

On the other hand, in the contact charging means, since the charging member such as the charging roller and the charging brush is in contact with the photoconductor, the photoconductor can be charged with a lower applied voltage than the corona charging means.
Therefore, the amounts of ozone and NOx generated can be greatly reduced. Further, since the charging uniformity is superior to that of the corona charging means, it can be said that the charging means is advantageous for improving the durability and image quality of the photoconductor.

However, in the contact charging means, since the charging member is in contact with the photoconductor, the charging member is contaminated by the adhesion of toner or foreign matter. This may cause the following problems, for example. -Deterioration of the charging property of the photoconductor due to contamination of the charging member. -Promotion of contamination on the surface of the photoconductor due to reattachment of the contaminants attached to the charging member to the photoconductor. -Promotion of wear and uneven wear of the photoconductor due to contamination of the charging member. -The efficiency of removing foreign matter on the surface of the photoconductor is reduced due to the surface of the photoconductor being pressed by the charging member. In the contact charging method, the charged products, foreign matters and the like attached to the surface of the photoconductor are pressed by the charging member. Therefore, the amount of foreign matter deposited on the surface of the photoconductor becomes larger than that in the corona charging method, and the probability of occurrence of image blurring or abnormal images increases.・ Remaining charging roller marks on the photoconductor.・ Abnormal images are generated due to deformation of the charging roller.

That is, the contact charging method can lower the amount of ozone and NOx gas generated than the corona charging method, but cannot reduce the probability of occurrence of an abnormal image because the amount of accumulated charged products is not reduced. In other words, the occurrence of abnormal images cannot be suppressed unless the wear rate of the surface of the photoconductor is higher than the deposition rate of the charged product on the photoconductor. That is,
An electrophotographic apparatus employing a photoconductor having high abrasion resistance has a high probability of generating an abnormal image.

In view of such a problem, there is a technique of disposing the charging member in the vicinity of the photoconductor. In this conventional technique, since the charging member and the photoconductor do not come into direct contact with each other in the image forming area, the generation amount of ozone and NOx gas is reduced, and at the same time, the above problems are alleviated, and the photoconductor has high durability and high image quality. This is an effective method. Furthermore, the above-mentioned conventional charging member is not only easily polluted, but also easy to remove even if a contaminant is attached. Therefore, the cleaning can be easily performed, and the durability of the photoconductor can be increased.

However, in the charging means adopting the above-mentioned conventional technique, the gap between the charging member and the photosensitive member must be maintained with extremely high precision, and if the gap between the two cannot be maintained, the charging stability will be deteriorated. . To improve the charging stability, it is sufficient to superimpose an AC component on a DC component. However, this causes an increase in the amount of charged products generated, which easily causes image blurring. In addition, since the charging member is disposed close to the photoconductor, discharge breakdown on the photoconductor surface is more likely to occur than other charging means. As a result, an abnormal image is likely to occur. As described above, even if the charging members are arranged close to each other, it has been difficult to realize high durability of the photoconductor.

That is, the charging means, in which the charging member is disposed close to the photosensitive member in the image area (image forming area), has a small amount of contamination of the charging member and easily removes the attached contaminants and charged products. Therefore, the probability of occurrence of an abnormal image is lower than that of the charging unit as described above. However, the charging stability is low because the photoconductor and the charging member are not in contact with each other. Further, in order to improve the charging stability, an AC component must be superposed, and the amount of charged products generated increases, resulting in a higher probability of abnormal image generation. In addition, there is also a problem that it is difficult to obtain a high-quality image because the photoreceptor is easily destroyed by discharge.

Therefore, the electrophotographic apparatus is (1) made maintenance-free by reducing the number of times of exchanging the photosensitive member,
(2) The device is downsized without the need for a dehumidifier, and (3)
In order to improve the image quality and (4) save energy, it is necessary to increase the abrasion resistance of the photoconductor and reduce the probability of generating an abnormal image. For that purpose, it is important to suppress the generation amount of ozone and NOx and prevent the charging member and the photoconductor from being contaminated. On the other hand, the charging means in which the charging member is disposed close to the photoconductor may not only increase the probability of occurrence of an abnormal image as described above, but also may deteriorate the image quality due to discharge breakdown of the photoconductor surface. There is also. Therefore, there is a demand for the development of an electrophotographic apparatus capable of stably providing a high-quality image for a long period of time even if a highly durable photoreceptor is used. Further, in such an electrophotographic apparatus, further reduction of power consumption and downsizing of the apparatus are desired.

The present invention has been made in view of the above problems, and employs a charging means in which an acryl-modified polyorganosiloxane is contained in the outermost surface layer of a photoconductor and a charging member is disposed in the vicinity of the photoconductor. Therefore, it is an object of the present invention to provide an electrophotographic apparatus which can keep the surface energy low even after repeated use, and can extremely reduce the probability of occurrence of an abnormal image even when a photoconductor having high durability is adopted.
This electrophotographic device can reduce the amount of accumulated charged products,
Contamination of the charging member can be prevented, and contamination of the photoconductor and the charging member can be significantly suppressed. As a result, the probability of occurrence of abnormal images can be reduced.

[0033]

In order to achieve the above object, the electrophotographic apparatus according to claim 1 is provided with at least a charging means, an exposing means, a developing means and a transferring means around the electrophotographic photosensitive member. In the electrophotographic apparatus, the electrophotographic photosensitive member is characterized in that the outermost surface layer contains an acrylic-modified polyorganosiloxane compound, and the charging means is disposed close to the electrophotographic photosensitive member. By adopting the above configuration, the surface energy of the photoconductor is lowered, and by keeping this state for a long time, it is difficult for charged products, contaminants, foreign substances, etc. to adhere, and the adhered substances are also removed. Easier to do. In addition, the above-mentioned charging means generates much less ozone and NOx than the corona charging method. Further, since the charging member is arranged close to the photoconductor, contamination of the charging member / photoconductor can be reduced. Therefore, for example, the transfer efficiency can be increased, the cleaning property can be increased, and the amount of foreign matter attached to the photoconductor or the charging member can be reduced. As a result, even if the abrasion resistance of the photoconductor is increased, the probability of occurrence of an abnormal image such as image blur can be reduced. That is, both high durability and image quality stability can be achieved.

According to a second aspect of the present invention, in the electrophotographic apparatus according to the first aspect, the acrylic modified polyorganosiloxane compound is a compound in which an acrylic polymer is graft-copolymerized on the main chain of siloxane. .

According to a third aspect of the present invention, in the electrophotographic apparatus according to the first or second aspect, the acrylic-modified polyorganosiloxane compound is a polyorganosiloxane represented by the following general formula (1) and the following general formula (3): ), An acrylic acid ester, a methacrylic acid ester and / or a mixture of an acrylic acid ester or / and a methacrylic acid ester of 70 wt% or more and a copolymerizable monomer of 30 wt% or less}. It is characterized in that it is a compound obtained by emulsion graft copolymerization in a ratio of 5:95 to 95: 5.

[0036]

[Chemical 2]

In the general formula (1), R ¹ , R ² and R ³ may be the same or different and each is a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group; Y is a radical reactive group. , SH groups or radical-reactive groups and SH-containing organic groups; Z ¹ and Z
² are hydrogen atoms, lower alkyl groups or groups represented by the above structural formula (2), which may be the same or different; m is a positive integer of 10,000 or less; n is an integer of 1 or more. .

In the above structural formula (2), R ⁴ and R ⁵ may be the same or different and each is a hydrocarbon group or a halogenated hydrocarbon group having 1 to 20 carbon atoms; R ⁶ is 1 to 20 carbon atoms. It is a hydrocarbon group, a halogenated hydrocarbon group, a radical reactive group, an SH group or a radical reactive group, and a productive group having an SH group.

In the general formula (3), R ⁷ is a hydrogen atom or a methyl group; R ⁸ is an alkyl group,
It is an alkoxy-substituted alkyl group, a cycloalkyl group or an aryl group.

According to a fourth aspect of the present invention, in the electrophotographic apparatus according to the third aspect, the weight of the polyorganosiloxane represented by the general formula (1) is an acrylic ester represented by the following general formula (3), Methacrylic acid ester and /
Alternatively, it is characterized by being more than the weight of a mixture of acrylic acid ester or / and methacrylic acid ester of 70% by weight or more and a copolymerizable monomer of 30% by weight or less.

According to a fifth aspect of the present invention, in the electrophotographic apparatus according to any one of the first to fourth aspects, the acrylic modified polyorganosiloxane compound is in the form of microgel.

According to a sixth aspect of the present invention, in the electrophotographic apparatus according to any one of the first to fifth aspects, the outermost surface layer comprises an acrylic-modified polyorganosiloxane compound in an amount of 1 based on the total solid content of the layer. It is characterized in that the content is 40% by weight to 40% by weight.

The invention described in claim 7 is the electrophotographic apparatus according to any one of claims 1 to 6, characterized in that a charging roller is used as the charging means.

According to an eighth aspect of the present invention, in the electrophotographic apparatus according to the seventh aspect, the charging roller applies a voltage in which an alternating current component is superimposed on a direct current component to charge the electrophotographic photosensitive member. Characterize.

According to a ninth aspect of the invention, in the electrophotographic apparatus according to the seventh or eighth aspect, the charging roller has a gap with the electrophotographic photosensitive member in the image forming area of 200 μm or less.

The invention as defined in claim 10 is defined by claim 1 through claim 9.
In any one of the electrophotographic apparatus, the electrophotographic photosensitive member is characterized in that the outermost surface layer contains a filler.

According to an eleventh aspect of the invention, in the electrophotographic apparatus according to the tenth aspect, the filler is one kind of metal oxide.

According to a twelfth aspect of the present invention, in the electrophotographic apparatus according to the eleventh aspect, the metal oxide is p at the isoelectric point.
It is characterized in that H is 5 or more.

According to a thirteenth aspect of the present invention, in the electrophotographic apparatus according to the eleventh or twelfth aspect, the metal oxide is surface-treated.

The invention according to claim 14 is the invention according to claims 10 to 1.
In the electrophotographic apparatus of any one of 3 above, the filler is
The average primary particle diameter is in the range of 0.01 μm to 0.9 μm.

The invention described in claim 15 is from claim 1 to claim 1.
In the electrophotographic apparatus according to any one of 4 above, the electrophotographic photosensitive member is characterized in that the outermost surface layer contains a carboxylic acid compound.

According to a sixteenth aspect of the present invention, in the electrophotographic apparatus according to the fifteenth aspect, the carboxylic acid compound is a polycarboxylic acid compound.

The invention described in claim 17 is from claim 1 to claim 1.
In the electrophotographic apparatus according to any one of 6 above, the electrophotographic photosensitive member is characterized in that the outermost surface layer contains a polymer charge transport substance.

The invention described in claim 18 is from claim 1 to claim 1.
In the electrophotographic apparatus of any one of 7 above, the electrophotographic photosensitive member is characterized in that an outermost surface layer contains an antioxidant.

According to a nineteenth aspect of the present invention, in the electrophotographic apparatus according to the eighteenth aspect, the antioxidant has a hindered amine structure and a hindered phenol structure.

The invention described in claim 20 is from claim 1 to claim 1.
In the electrophotographic apparatus according to any one of 9 above, at least the charging unit and the electrophotographic photosensitive member in the electrophotographic apparatus,
The process cartridge for an electrophotographic apparatus has a structure that is detachable from the main body of the electrophotographic apparatus.

[0057]

BEST MODE FOR CARRYING OUT THE INVENTION The electrophotographic apparatus according to the present invention will be described in detail below with reference to embodiments.

In the electrophotographic apparatus according to the present invention, the charging means is disposed in the vicinity of the photoconductor and the outermost surface layer of the photoconductor contains the acrylic modified polyorganosiloxane compound. As described above, it is difficult to satisfy both the high durability and high image quality of the device only by using the above charging means. Therefore, in the present invention, by including the above compound in the outermost surface layer of the photoconductor, high durability and high image quality of the device are realized. That is, as a result of adopting such a configuration, it becomes difficult for the charged product to adhere to the photoconductor, and it becomes easy to remove the charged product adhered to the photoconductor. Moreover, such an effect can be stably maintained over a long period of time.

Generally, in order to maintain the effect of reducing the surface energy of the photoreceptor, the slipping component is a layer (outermost surface layer).
It is known that it is better to disperse the high-concentration portions in the form of fine particles inhomogeneously rather than uniformly over the whole.
On the other hand, since the compound has an acrylic structure, it has high compatibility with the binder resin (binder resin) forming the outermost surface layer of the photoconductor, and has extremely high dispersibility and orientation in the layer. Therefore, it is considered that the morphology of a plurality of fine microgels is maintained in the layer, and the microgels are dispersed (diffused) almost uniformly throughout the layer. That is, since the above compound is dispersed in the entire layer in the form of fine particles (microgel), the effect of keeping the surface energy low for a long period of time and preventing the adhesion of foreign matters such as charged products can be obtained even after repeated use. It is believed that Further, the transfer efficiency is improved, the cleaning property is improved, the probability of occurrence of an abnormal image due to filming or adhesion of foreign matter is extremely reduced, and the abrasion resistance of the photoconductor can be improved.

In addition, since the above compound was added to the photoconductor, discharge breakdown was less likely to occur. The organic group in the photoconductor produces a carbon-based residue when decomposed by ozone or NOx generated by charging. Since the carbon-based residue is electrically conductive, discharge breakdown easily occurs. In contrast,
The above compound has a high binding energy and is insulative.
It has an i-O bond. Therefore, the above carbon-based residue is
Since it has a Si—O bond, the probability of occurrence of discharge breakdown can be made extremely low. As a result, the probability of occurrence of abnormal images can be reduced.

Further, since the above compound has a structure in which an acrylic polymer is graft-copolymerized with siloxane which is a main chain, while maintaining compatibility with the binder resin,
The polymerization ratio of siloxane can be increased.

As described above, by using the photoconductor containing the acrylic modified polyorganosiloxane compound on the outermost surface, it is difficult for the electrified products and foreign matters to adhere to the photoconductor.
Even if attached, it became easier to remove. As a result, it has become possible to suppress lowering of the resistance of the surface of the photoconductor. Furthermore, this effect has come to be obtained over a long period of time. As a result, improved image quality stability was realized. In addition, by adopting a charging unit having a configuration in which the charging member is not brought into direct contact with the photoconductor in the image forming area (arranged closely)
It has become possible to suppress contamination of the charging member. Further, since the surface of the photoconductor is not abraded and the charged products and foreign matters on the photoconductor surface are easily removed, the amount of contamination of the charging member and the photoconductor can be made extremely low. Therefore, transfer efficiency and cleaning performance can be extremely enhanced, filming and adhesion of foreign matter can be suppressed, abrasion resistance can be improved, uneven wear can be suppressed, contamination of the charging member can be prevented, and discharge damage of the photoconductor can be prevented. As a result, various effects such as being possible can be obtained, and as a result, it is possible to reduce the probability of occurrence of abnormal images and achieve both high durability and high image quality of the device (photoreceptor). The details will be described below.

<Acrylic-modified polyorganosiloxane compound> The acrylic-modified polyorganosiloxane compound is
A compound obtained by graft-polymerizing an acrylic acid ester and / or a methacrylic acid ester represented by the following general formula (3) with a polyorganosiloxane represented by the following general formula (1) by an emulsion polymerization method is preferably used. . If desired, any monomer other than the acrylic acid ester and the methacrylic acid ester may be copolymerized.

[0064]

[Chemical 3] In the general formula (1), R ¹ , R ² and R ³ are methyl groups,
Alkyl group such as ethyl group, propyl group, butyl group, phenyl group, tolyl group, xylyl group, aryl group such as naphthyl group, or the like, having 1 to 20 carbon atoms, or carbon atoms of these hydrocarbon groups. At least one of the bonded hydrogen atoms is a halogenated hydrocarbon group having 1 to 20 carbon atoms substituted with a halogen atom. R ¹ , R ² and R ³ are
They may be the same or different from each other. Y has a radical group such as a vinyl group, an allyl group, a γ-acryloxypropyl group, a γ-methacryloxypropyl group, and a γ-mercaptopyropyr group, an SH group, or a radical reactive group and an SH group. It is an organic group. Z ¹ and Z ² are a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, or a triorganosilyl group represented by the above general formula (2). Z ¹
And Z ² may be the same or different from each other. m is a positive integer of 10,000 or less, preferably an integer in the range of 500 to 8,000. n is an integer of 1 or more, preferably an integer in the range of 1 to 500.

In the above general formula (2), R ⁴ and R ⁵ are the same or different hydrocarbon groups having 1 to 20 carbon atoms or halogenated hydrocarbon groups. As such a group, for example, the groups described above can be adopted. R ⁶
Is an organic group having a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, a radical reactive group, an SH group, or a radical reactive group and / or an SH group.

The polyorganosiloxane represented by the general formula (1) is a cyclic polyorganosiloxane, a liquid polydimethylsiloxane in which both molecular chain ends are blocked with a hydroxyl group, or a liquid polysiloxane in which both molecular chain ends are blocked with an alkoxy group. Dimethyl siloxane, or polydimethyl siloxane in which both ends of the molecular chain are blocked with trimethylsilyl groups,
It can be obtained by reacting with a silane for introducing a radical reactive group and / or an SH group, a hydrolysis product of silane, or the like. Further, if desired, a trifunctional trialkoxysilane or a hydrolysis product thereof may be added to the reaction system in an amount that does not impair the object of the present invention.

Of course, manufacturing methods other than those described above can also be adopted. For example, a cyclic low molecular weight siloxane such as octamethylcyclotetrasiloxane, a dialkoxysilane compound having a radical reactive group and / or an SH group, or a hydrolyzate thereof is used as a raw material. And both
Polymerization in the presence of a strongly alkaline or strongly acidic catalyst gives a high molecular weight polyorganosiloxane. The polyorganosiloxane thus obtained is emulsified and dispersed in an aqueous medium in the presence of a suitable emulsifier for use in the emulsion graft copolymerization in the next step.

When the polyorganosiloxane represented by the general formula (1) has a small molecular weight, the resulting photoreceptor has slidability, abrasion resistance, and sustainability (stability) of these effects. Inferior to Therefore, the molecular weight is preferably as high as possible. Therefore, it is preferable to use a high molecular weight siloxane as a raw material and to emulsify and disperse this.

The following manufacturing method can also be adopted.
As the raw material, for example, the above-mentioned low molecular weight polyorganosiloxane and dialkoxysilane having a radical reactive group and / or SH group or a hydrolyzate thereof are used. Both are emulsion-polymerized in an aqueous medium in the presence of a sulfonic acid type surfactant or a sulfuric acid ester type surfactant to obtain a polyorganosiloxane. In addition, the same raw material as this,
It can also be obtained by emulsifying and dispersing in an aqueous medium with a cationic surfactant such as alkyltrimethylammonium chloride or alkylbenzylammonium chloride, and adding an appropriate amount of a strong alkaline compound such as potassium hydroxide or sodium hydroxide for polymerization. .

For the above reason, in order to obtain a high molecular weight polyorganosiloxane, the temperature may be lowered during the aging treatment after emulsion polymerization. This increases the molecular weight of the polyorganosiloxane. The aging temperature is 30 ° C. or lower, preferably 15 ° C. or lower.

In the above general formula (3), R ⁷ is a hydrogen atom or a methyl group; R ⁸ is an alkyl group, an alkoxy-substituted alkyl group, a cycloalkyl group or an aryl group.

The acrylic acid ester / methacrylic acid ester represented by the above general formula (3) is, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate,
Butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, Alkyl acrylates and alkyl methacrylates such as stearyl acrylate and stearyl methacrylate; alkoxyalkyl acrylates and alkoxyalkyl methacrylates such as methoxyethyl acrylate, methoxyethyl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, cyclohexyl acrylate, cyclo Cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate and benzyl methacrylate are. You may use only 1 type of these compounds,
You may use it in combination of 2 or more type.

Examples of the above-mentioned optional monomers include polyfunctional monomers and ethylenically unsaturated monomers. Examples of the polyfunctional monomer include acrylamide, methacrylamide, diacetone acrylamide, diacetone methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide,
Ethylenically unsaturated amides such as N-methoxymethyl acrylamide and N-methoxymethyl methacrylamide,
Alkyrol of ethylenically unsaturated amide; alkoxyalkylated product; oxirane group-containing unsaturated monomer such as glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-
Hydroxy group-containing unsaturated monomers such as hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, carboxyl group-containing ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, maleic anhydride, crotonic acid and itaconic acid; Amino group-containing unsaturated monomers such as N-dimethylaminoethyl acrylate, N-dimethylaminoethyl methacrylate, N-diethylaminoethyl acrylate and N-diethylaminoethyl methacrylate; addition of ethylene oxide or propylene oxide of acrylic acid or methacrylic acid Unsaturated monomer containing polyalkylene oxide group such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate Relate, trimethylolpropane triacrylate, complete esters of polyhydric alcohols with acrylic acid or methacrylic acid such as trimethylolpropane trimethacrylate; allyl acrylate, allyl methacrylate, and divinylbenzene. These monomers may be used alone or in combination of two or more. Since these monomers participate in the cross-linking between polymers in the acrylic modified polyorganosiloxane, they impart elasticity, durability, heat resistance and the like to the molded body.

Examples of the ethylenically unsaturated monomer include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate,
Examples thereof include vinyl propionate and vinyl versatate. These monomers may be used alone or in combination of two or more. In addition, one or more ethylenically unsaturated monomers and one or more polyfunctional monomers may be used in combination.

These monomers are used in an amount of 30% by weight or less based on the total weight of the compound represented by the general formula (3). When used in a proportion of 30% by weight or more, the resulting acrylic modified polyorganosiloxane has low miscibility with the binder resin.

The compound represented by the above general formula (3) (a mixture with the above-mentioned optional monomer in the case of copolymerizing the above-mentioned optional monomer) has excellent slidability in the obtained photoreceptor, In order to provide abrasion resistance, it is preferable that the glass transition temperature is 20 ° C. or higher, preferably 30 ° C. or higher.

The acrylic modified polyorganosiloxane is
The compound represented by the general formula (1) and the general formula (3)
It was found that it can be obtained by graft-copolymerizing with the monomer represented by the formula (5) at a weight ratio of 5:95 to 95: 5 by an emulsion polymerization method. When the proportion of the polyorganosiloxane represented by the general formula (1) is less than the above range, the above-mentioned effects cannot be sufficiently obtained, and the tackiness, which is a drawback of the acrylic polymer, becomes conspicuous.
On the other hand, when the amount is more than the above range, the acrylic modified polyorganosiloxane becomes less miscible with the binder resin such as polyvinyl chloride resin and easily bleeds on the surface of the photoreceptor. As a result, the resulting photoreceptor has slidability, abrasion resistance and the like deteriorated over time.

For the graft copolymerization by the emulsion polymerization method, a known method can be adopted. For example, an aqueous emulsion of the polyorganosiloxane represented by the above general formula (1)
It may be carried out by a known emulsion polymerization method by adding a monomer represented by the above general formula (3) and using a radical initiator generally used. Moreover, the manufacturing method described in Japanese Patent Publication No. 7-5808 can also be suitably adopted.

The emulsifying agent, coagulant, etc. used for the polymerization are
Since it may impair the electrical characteristics of the photoreceptor (image forming member), it is purified / removed as necessary. Examples of the purification method include a method of stirring and washing with an acid, an alkaline aqueous solution, water and / or alcohol, and a solid-liquid extraction method such as Soxhlet extraction.

As the acrylic modified polyorganosiloxane compound, for example, Charine R-170S, R-170 or R-210 manufactured by Nisshin Chemical Industry Co., Ltd. can be preferably used. Among them, R-170S and R-170 are
The silicone content is as high as about 70%, and the surface energy of the obtained photoreceptor is extremely low, and therefore it is preferably used. Furthermore, the shape is spherical and the average particle size is small R
-170S is particularly preferably used. This is because the probability of occurrence of an abnormal image is extremely low, and such effects can be stably maintained for a long period of time.

<Example of Layer Structure> The above-mentioned acrylic modified polyorganosiloxane compound may be contained in the outermost surface layer of the photoreceptor. The surface of the photoreceptor is the surface on which the latent image is formed, that is, the surface facing the charging unit. That is, the acrylic modified polyorganosiloxane compound is contained within a certain distance range from the surface of the photoreceptor. In addition,
The outermost surface layer may contain a substance other than the acrylic-modified polyorganosiloxane compound and may have an arbitrary function. For example, a filler, an antioxidant or the like may be added. In addition, the depth (layer thickness) of the layer located on the outermost surface and the thickness of the outermost surface layer among the layers (protective layer, charge transport layer, charge generation layer, etc.) classified by the function of the photoreceptor are , May be the same or different. 1 to 5 show the relationship between the layer configuration example of the photoconductor and the range (outermost surface layer) in which the acrylic modified polyorganosiloxane compound is contained.

In the photoreceptor shown in FIG. 1, a photosensitive layer 33 is formed on a conductive support 31. The photosensitive layer 33 contains a charge generating substance and a binder resin as main components. In FIG. 1, the surface is the surface of the photosensitive layer 33 that is not in contact with the conductive support 31. The acrylic modified polyorganosiloxane compound is included in a range from the surface (photosensitive layer 33 side) to an arbitrary position. For example, as shown in FIG. 1B, the photosensitive layer 3
It may be contained in a part of the surface side of No. 3, or may be contained in the entire photosensitive layer 33 (entire range) as shown in FIG. Further, it may be contained in part or all of the conductive support 31 on the side of the photosensitive layer 33.

The photoconductor shown in FIG. 2 has a structure in which a charge generation layer 35 and a charge transport layer 37 are sequentially laminated on a conductive support 31. The charge generation layer 35 contains a charge generation substance as a main component. The charge transport layer 37 contains a charge transport material as a main component. In FIG. 2, the surface is the surface of the charge transport layer 37 that is not in contact with the charge generation layer 35. The acrylic modified polyorganosiloxane compound is included in a range from the surface to an arbitrary position. For example, as shown in FIG. 2B, it may be contained in a part of the charge transport layer 37. Also, FIG.
As shown in (a), the entire charge transport layer 37 (entire range)
May be contained in. In this case, the charge generation layer 35 may also be contained in a part or the whole range (total range) from the charge transport layer 37. Further, it may be contained in a part or the whole range of the conductive support 31.

The photosensitive member shown in FIG. 3 has a structure in which a protective layer 39 is further laminated on the surface side of the photosensitive layer 33 in the photosensitive member shown in FIG. In FIG. 3, the surface is the protective layer 3
9 is a surface which is not in contact with the photosensitive layer 33. The acrylic modified polyorganosiloxane compound is included in a range from the surface to an arbitrary position. For example, as shown in FIG.
It may be contained in the entire area of the protective layer 39.

The photosensitive member shown in FIG. 4 is similar to the photosensitive member shown in FIG. 2 except that a protective layer 39 is further provided on the surface side of the charge transport layer 37.
Are laminated. In FIG. 4, the surface is the surface of the protective layer 39 that is not in contact with the charge transport layer 37. The acrylic modified polyorganosiloxane compound is included in a range from the surface to an arbitrary position. For example, as shown in FIG. 4, it may be contained in the entire area of the protective layer 39.

The photoconductor shown in FIG. 5 has a structure in which a charge transport layer 37, a charge generation layer 35, and a protective layer 39 are sequentially laminated on a conductive support 31. In FIG. 5, the surface is the surface of the protective layer 39 that is not in contact with the charge generation layer 35.
The acrylic modified polyorganosiloxane compound is included in a range from the surface to an arbitrary position. For example, as shown in FIG. 5, it may be contained in the entire area of the protective layer 39. Next, the outermost surface layer will be described.

<Outermost surface layer> The outermost surface layer is a region containing an acrylic modified polyorganosiloxane compound as shown in FIGS. For the outermost surface layer, an acrylic modified polyorganosiloxane compound is dissolved or dispersed in a solvent or a dispersion medium together with a binder resin for forming the outermost surface layer, if necessary, and the obtained coating liquid is applied onto the coating layer. It can be obtained by working. When the outermost surface layer has a role such as the photosensitive layer 33 or the protective layer 39, a material corresponding to this role is also dissolved or dispersed in the above solvent or dispersion medium to obtain a coating liquid. For example, when the entire surface of the photosensitive layer 33 is the outermost layer as shown in FIG. 1A, the material for forming the photosensitive layer 33, which will be described later, is also dissolved or dispersed in the above solvent or dispersion medium to obtain a coating liquid. To get
In other words, a coating liquid in which an acrylic modified polyorganosiloxane compound is dissolved or dispersed may be applied to the coating liquid for forming the outermost layer.

The solvent or dispersion medium for forming the outermost surface layer may be any solvent that can satisfactorily dissolve or disperse the acrylic modified polyorganosiloxane compound. Examples thereof include tetrahydrofuran, dioxane, dioxolane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, cyclopentanone, anisole, xylene, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate and the like. As the dissolution method and the dispersion method, a method using a ball mill, a method using an attritor, a method using a sand mill, a method using a bead mill, a method using ultrasonic waves, and the like can be adopted. Further, the coating liquid may be appropriately diluted with a solution or dispersion containing at least a binder resin.

A method of mechanically mixing the above-mentioned materials using a known apparatus such as a Banbury mixer, a roll mill, a twin-screw extruder and shaping them into pellets to form the outermost surface layer can also be adopted. The extrusion-shaped pellets can be molded in a wide temperature range, and a normal injection molding machine is used for molding. The graft copolymer having the acryl-modified polyorganosiloxane compound shaped into pellets and the resin may be dissolved or dispersed in a solvent or a dispersion medium as described above, and may be coated on the layer to be coated. .

The acrylic modified polyorganosiloxane compound in the outermost surface layer is contained in the range of 1% to 40% by weight, preferably 5% to 20% by weight, based on the total solids in the outermost layer. To be done. When the content is within this range, the state where the surface energy of the surface of the photoconductor is low can be stably maintained for a long period of time as compared with the photoconductor whose content is less than the above range. In addition, the state in which the probability of occurrence of abnormal images is extremely low can be stably maintained for a long period of time. Further, it was found that the probability of occurrence of coating film defects was extremely low and good surface smoothness was obtained as compared with the photoconductor having a content higher than the above range.

Further, as shown in FIGS. 1B and 2B, in order to make a part (surface side) of the photosensitive layer 33 and the charge transport layer 37 the outermost surface layer, a known method is used. In these layers, a concentration gradient may be given so that the concentration of the acrylic modified polyorganosiloxane compound on the surface side becomes high. With this configuration, good resolution can be obtained,
The adhesive performance between the films may be excellent.

The outermost surface layer may contain a filler (material) in order to improve wear resistance. Filler materials include organic fillers and inorganic fillers.

Examples of the organic filler material include fluororesin powder such as polytetrafluoroethylene, silicone resin powder, a-carbon powder and the like. The inorganic filler material is, for example, metal powder such as copper, tin, aluminum, indium, silica, tin oxide, zinc oxide,
Titanium oxide, alumina, zirconia, indium oxide,
Metal oxides such as antimony oxide, bismuth oxide, calcium oxide, tin oxide doped with antimony, indium oxide doped with tin, metal fluorides such as tin fluoride, calcium fluoride and aluminum fluoride, potassium titanate, nitriding An inorganic material such as boron can be used. Among these materials, an inorganic material having a relatively high hardness of filler is preferably used from the viewpoint of abrasion resistance, and further, a metal oxide is particularly preferably used from the viewpoints of light transmittance and coating quality.
Since the deterioration of the light transmittance and the coating film quality greatly affects the image quality, it is important to select a material that does not have a bad influence on the light transmittance and the coating film quality in order to realize the high image quality.

A metal oxide filler having a high electric insulation property is preferably used because the probability of occurrence of an abnormal image can be extremely reduced. This is because if the outermost surface layer contains a conductive filler, the resistance of the surface is lowered and the electric charges are laterally moved, so that an abnormal image such as image blur is easily generated. Therefore, a filler material having a specific resistance of 10 ¹⁰ Ω · cm or more is preferably used. Examples of such filler materials include alumina, zirconia, titanium oxide, silica and the like. On the other hand, a conductive filler having a specific resistance of 10 ¹⁰ Ω · cm or less or a filler having a relatively low specific resistance is
Tin oxide, zinc oxide, acid value indium, acid value antimony,
Examples thereof include antimony-doped tin oxide and tin-doped indium oxide, but this is not preferable because the probability of occurrence of abnormal images increases. However, the fillers may have different specific resistances even if they are made of the same material. Therefore, the filler material to be used is selected according to the specific resistance.

The above filler materials may be used as a mixture of two or more kinds. In this case, it is sufficient that the mixture of the filler materials used has the above-mentioned specific resistance.
That is, a filler material having no specific resistance as described above can also be used.

The filler material preferably has a pH at the isoelectric point of at least 5 in order to reduce the probability of occurrence of abnormal images. Further, the more basic the image, the lower the probability of occurrence of an abnormal image. Since the filler dispersed in the liquid is charged, it may affect the stability of the filler particles and the resolution of the photoconductor. On the other hand, the above-mentioned filler material is preferably used because such problems are extremely small. Examples of such a filler material include titanium oxide, zirconia, and alumina. Alumina is particularly preferably used because the basicity increases in the order of titanium oxide <zirconia <alumina. Furthermore, α-alumina having a hexagonal close-packed structure, which has a high light transmittance, high thermal stability, and can provide a photoreceptor having excellent wear resistance, has a low probability of occurrence of abnormal images and high wear resistance, It can be used very preferably because it can provide a photoreceptor having good coating quality and light transmittance.

The filler material may be surface-treated with at least one surface-treating agent. The abnormal image may occur when ozone or NOx gas is exposed to the filler material on the surface of the photoconductor. Therefore, the specific resistance of the filler and the pH at the isoelectric point are changed by the surface treatment agent, and the probability of occurrence of an abnormal image can be made extremely small as compared with the case where a filler material not subjected to the surface treatment is adopted. In addition, depending on the surface treatment method / surface treatment agent used, the dispersibility of the filler material in the outermost surface layer may be improved, the transparency of the coating film (outermost surface layer) may be improved, and the occurrence of coating film defects may occur. Various effects such as suppression, improvement of abrasion resistance of the photoconductor, and suppression of uneven wear can be obtained.

As the surface-treating agent, all of the conventionally used surface-treating agents can be used, but a surface-treating agent capable of adjusting the specific resistance and pH at the isoelectric point of the filler as described above is preferably used. PH at the isoelectric point of the filler
Can be adjusted by surface treatment. When treated with an acidic treating agent, the isoelectric point moves to the acidic side, and when treated with a basic treating agent, the isoelectric point moves to the basic side. Therefore, the basic treating agent is preferably used. The basic treating agent is, for example, a titanate coupling agent, an aluminum coupling agent,
Zircoaluminate coupling agents and the like are preferably used. Further, Al ₂ O ₃ , TiO ₂ , ZrO ₂ , silicone, aluminum stearate, etc., or a mixture thereof also enhances the dispersibility in the outermost surface layer of the filler, thereby increasing the probability of occurrence of an abnormal image on the obtained photoreceptor. It is preferably used because it can be lowered. The treatment with the silane coupling agent increases the probability of occurrence of an abnormal image, but the effect may be reduced by performing the treatment for mixing the surface treatment agent and the silane coupling agent as described above. Also,
If a basic treating agent is used, p at the isoelectric point of the filler
It may be possible to use a filler having H of 5 or less.

The average primary particle size of the filler is 0.01 to
0.9 μm is preferable, and 0.1 to 0.5 is more preferable.
μm. When the average primary particle size of the filler is within the above range, the light transmittance is kept good, and there is little adverse effect on wear resistance and coating film quality. If the average primary particle size of the filler is smaller than the above range, the filler is likely to aggregate, wear resistance is reduced, and the specific surface area of the filler is increased, so that the probability of occurrence of an abnormal image is increased. If the average primary particle size of the filler exceeds the above range, the sedimentation of the filler is promoted, and the probability of image quality deterioration and abnormal images is increased.

In order to suppress the increase in residual potential caused by the inclusion of the filler material, it is preferable to add one kind of carboxylic acid compound. The carboxylic acid compound may have a nonvolatile content of 100% or may be dissolved in an organic solvent or the like in advance.

As the carboxylic acid compound, for example, known organic fatty acids, high acid value resins, copolymers and the like can be used as long as they are compounds having a carboxyl group in the molecular structure. For example, lauric acid, stearic acid, arachidic acid, behenic acid, adipic acid, oleic acid, maleic acid,
Examples thereof include saturated fatty acids such as maleic anhydride, salicylic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid, unsaturated fatty acids, and aromatic carboxylic acids. Also,
Saturated polyester, unsaturated polyester, terminal carboxylic acid unsaturated polyester, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, styrene-
Acrylic acid copolymer, styrene-acrylic acid-acrylic acid ester copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride Acids and the like can also be preferably used. That is, a saturated or unsaturated hydrocarbon as a basic skeleton, a polymer in which at least one or more carboxyl groups are bonded to this basic skeleton,
The oligomer or copolymer has an effect of suppressing an increase in residual potential and is preferably used in order to improve the dispersibility of the filler.

Among them, the polycarboxylic acid compound having a plurality of carboxylic acid residues has a high acid value and a high adsorptivity to the filler, so that the residual potential can be lowered and the dispersibility of the filler in the outermost surface layer is high. Since it is possible, it is particularly preferably used. Among such polycarboxylic acid compounds,
Polycarboxylic acid type wetting and dispersing agents are highly preferred,
For example, a product name “BYK-P10” manufactured by BYK Chemie.
4 ”is particularly effectively used.

The reason why the residual potential of the outermost surface layer can be lowered (can be kept / reduced) by containing the carboxylic acid compound as described above is that the carboxylic acid compound has an acid value and is adsorbed on the filler. It is thought that this is because of having sex. It is considered that the addition of the filler to the outermost surface layer increases the residual potential because the polar group on the surface of the filler becomes a charge trap site. On the other hand, it is considered that the carboxylic acid compound reduces the residual potential of the outermost surface layer because the carboxyl group is easily adsorbed on the polar group. In addition, the carboxylic acid compound has an affinity for both the filler and the binder resin to improve the wettability, and since it gives steric hindrance and electrical repulsion, it reduces the interaction between the fillers to improve stability. It is believed that this increases the dispersibility of the filler in the outermost surface layer. The carboxylic acid compound also has the effect of improving the dispersibility of the acrylic modified polyorganosiloxane compound in the outermost surface layer. Since the acryl-modified polyorganosiloxane compound has an acryl structure in the molecular structure, it is considered that the acryl-modified polyorganosiloxane compound has high affinity with the carboxylic acid compound and has high dispersibility in the outermost surface layer. As a result, it became possible to improve the quality of the coating film and to stabilize the image quality.

It is preferable to add an antioxidant to the outermost surface layer of the photoreceptor. Antioxidants include, for example, phenolic compounds, hindered phenolic compounds, hindered amine compounds, paraphenylenediamines, hydroquinones, organic sulfur compounds, organic phosphorus compounds, benzophenones, salsylates, benzotriazole. All known antioxidants such as compounds and quenchers (metal complex salts) can be used. Further, an ultraviolet absorber, a light stabilizer and the like can also be used.

Among the antioxidants, those having a high effect of preventing / suppressing the deterioration of the photoreceptor from active gas such as ozone and NOx and enhancing the image quality stability are the compounds having a hindered phenol structure and a hindered amine structure. is there.

The hindered phenol structure has a bulky atomic group at both ortho positions of the phenolic hydroxyl group. The hindered amine structure is a structure in which a bulky atomic group exists near the amino nitrogen atom. As the compound having such a structure, an aromatic amine or an aliphatic amine-based substance is applicable, but a compound containing a 2,2,6,6-tetramethylpiperidine structure is more preferably used.
The details of the mechanism of action of compounds having both of these structures are not clear, but the presence of bulky atomic groups enhances steric hindrance, suppresses thermal vibrations of amino nitrogen atoms and phenolic hydroxyl groups, and increases the radical state. It is thought that stability is enhanced. It is presumed that it was possible to suppress the influence of the active gas from the outside.

Examples of the compound having both the hindered phenol structure and the hindered amine structure include various compounds, and among them, 1- [2- [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpyridine is effective in preventing the resolution reduction of the photoreceptor due to ozone or NOx gas.

[0108]

[Chemical 4]

The photoconductor has a low chargeability and a low wear resistance due to exposure to ozone or NOx gas, but the electrostatic characteristics are stabilized by adding an antioxidant. That is, the image quality is stabilized during long-term repeated use.

When a filler is added to the outermost surface layer, ozone or NOx gas components are easily adsorbed to the filler, so that the effect of image blur is slightly increased as compared with the case where there is no filler. On the other hand, it has been found that when an antioxidant having both a hindered phenol structure and a hindered amine structure is contained together with the filler, the probability of occurrence of abnormal images can be made extremely low. That is, by using the filler and the above-mentioned antioxidant in combination, the probability of occurrence of an abnormal image can be extremely lowered, so that higher image quality can be realized.

Further, when the content of the acrylic modified polyorganosiloxane in the outermost surface layer is increased, there is a case where the charge is lowered particularly by being exposed to ozone or NOx gas. On the other hand, this can be prevented by adding these antioxidants to the outermost surface layer of the photoreceptor. Antioxidants with high effect are 1- [2- [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxy] ethyl] -4- [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpyridine.

Next, each layer of the photoreceptor will be described. As described above, each of the layers described below may be the outermost surface layer in its entirety (the acrylic modified polyorganosiloxane compound may be contained in the entire area), or a part thereof may be the outermost surface layer. It may be. In addition, layers other than those described below may be provided.

<Conductive Support 31> Conductive Support 31
Is a base layer for supporting each layer such as the photosensitive layer 33, and is a layer having a volume resistance of 10 ¹⁰ Ω · cm or less and exhibiting conductivity. As the conductive support 31, for example, the following can be adopted.・ Aluminum, nickel, chrome, nichrome, copper,
A film or cylindrical plastic or paper coated with a metal such as gold, silver or platinum, or a metal oxide such as tin oxide or indium oxide by vapor deposition or sputtering. -Aluminum, aluminum alloy, nickel, stainless steel, etc. plates.・ Aluminum, aluminum alloy, nickel, stainless steel, etc. are extruded / pulled out and subjected to surface treatment such as cutting / superfinishing / polishing. -Endless nickel belt, endless stainless belt, etc. (described in JP-A-52-36016).

Further, the conductive support 31 may be formed by dispersing conductive powder on a suitable binder and dispersing it in a suitable binder resin (binder resin for the conductive support 31). be able to. That is, the conductive powder and the binder resin are dissolved or dispersed in an appropriate solvent or dispersion medium to prepare a coating liquid, and the coating liquid is coated on the support. Conductive powder, for example, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc, silver, conductive tin oxide,
Examples thereof include metal oxide powders such as ITO, carbon black, acetylene black and the like. The binder resin in which the conductive powder is dispersed is, for example, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-acetic acid. Vinyl copolymer, polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene,
Examples thereof include thermoplastic resins such as poly-N-vinylcarbazole, acrylic resins, silicone resins, epoxy resins, melamine resins, urethane resins, phenol resins and alkyd resins, thermosetting resins or photocurable resins. Examples of the solvent or dispersion medium that dissolves or disperses the conductive powder and the binder resin include tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.

Further, heat shrinkage of polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, Teflon (registered trademark), etc. containing the above conductive powder on a suitable cylindrical substrate. A tube-coated one (provided with a conductive layer) can also be favorably used as the conductive support 31.

<Laminate Type Photosensitive Layer 33> The photosensitive layer 33 includes a single layer type as shown in FIG. 1 and a laminated type as shown in FIG. First, the laminated photosensitive layer 33 will be described. The laminated photosensitive layer 33 has a charge generation layer 35 and a charge transport layer 37.

<Charge Generating Layer 35> The charge generating layer 35 contains a charge generating substance as a main component and, if necessary, also contains a binder resin (a binder resin for forming the charge generating layer 35). Also, optional additives are included.

As the charge generating substance, an inorganic material or an organic material may be used. Inorganic materials include, for example, crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds,
Examples thereof include cadmium sulfide, cadmium sulfide-selenium, and amorphous silicon. Amorphous silicon includes dangling bonds terminated with hydrogen atoms or halogen atoms, boron atoms, phosphorus atoms, and the like.
Those that have been used are well used.

As the organic material, known materials can be adopted.
For example, disazo pigments, asymmetric disazo pigments, trisazo pigments, azo pigments having a carbazole skeleton (Japanese Patent Application Laid-Open No. 5-312058).
3-95033), azo pigments having a distyrylbenzene skeleton (JP-A-53-133445), azo pigments having a triphenylamine skeleton (described in JP-A-53-132347), diphenylamine. Azo pigments having a skeleton, azo pigments having a dibenzothiophene skeleton (described in JP-A-54-21728), and azo pigments having a fluorenone skeleton (JP-A-54)
No. 22834), an azo pigment having an oxadiazol skeleton (described in JP-A No. 54-12742), and an azo pigment having a bisstilbene skeleton (JP-A No. 5).
No. 4-17733), an azo pigment having a distyryl oxadiazol skeleton (described in JP-A No. 54-2129), and an azo pigment having a distyryl carbazol skeleton (JP-A No. 54- 14967) and other azo pigments, azurenium salt pigments, squaric acid methine pigments, perylene pigments, anthraquinone pigments, polycyclic quinone pigments, quinone imine pigments, diphenylmethane pigments, triphenylmethane pigments, Benzoquinone pigments, naphthoquinone pigments, cyanine pigments, azomethine pigments, indigoid pigments, bisbenzimidazole pigments, metal phthalocyanines represented by the following general formula (N), phthalocyanine pigments such as metal-free phthalocyanines, etc. Is mentioned. These charge generating substances may be used alone or in combination of two or more.

[0120]

[Chemical 5]

In the general formula (N), M (central metal) is
Represents metal and non-metal (hydrogen) elements. M (central metal)
Is H, Li, Be, Na, Mg, Al, Si, K, C
a, Sc, Ti, V, Cr, Mn, Fe, Co, Ni,
Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, T
c, Ru, Rh, Pd, Ag, Cd, In, Sn, S
b, Ba, Hf, Ta, W, Re, Os, Ir, Pt,
Au, Hg, TI, La, Ce, Pr, Nd, Pm, S
m, Eu, Gd, Tb, Dy, Ho, Er, Tm, Y
Examples include simple substances (elements) such as b, Lu, Th, Pa, U, Np, and Am, and oxides, chlorides, fluorides, hydroxides, and bromides of these elements, but are not limited thereto. Not a thing. The compound represented by the above general formula (N) may have a multimeric structure such as a dimer or trimer, or may have a higher polymer structure. Further, the basic skeleton represented by the general formula (N) may have various substituents.

Incidentally, oxotitanium phthalocyanine having TiO as the central metal, metal-free phthalocyanine, chlorogallium phthalocyanine and the like are preferably used because good photoconductor characteristics (charge generation etc.) can be obtained. Further, phthalocyanine is known to have various crystal systems, for example, α, β, γ, m, Y type etc. in the case of oxotitanium phthalocyanine, and α, β, γ etc. in the case of copper phthalocyanine. It has multiple lines. Phthalocyanines having the same central metal also have various properties depending on the crystal system. It has been reported that the characteristics of the photoconductor using the phthalocyanine pigment having these various crystal systems change accordingly (Journal of the Electrophotographic Society of Japan).
Vol. 29, No. 4 (1990)). As described above, the selection of the phthalocyanine crystal system is very important for the characteristics of the photoconductor. Above all, it is known that a photoreceptor containing Y-type oxotitanium phthalocyanine is effective for increasing the sensitivity.

The binder resin for forming the charge generation layer 35 is, for example, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, Examples thereof include polyvinyl ketone, polystyrene, poly-N-vinyl carbazole, polyacrylamide and the like. These binder resins may be used alone or as a mixture of two or more kinds.

Further, as a binder resin for forming the charge generation layer 35, a polymer charge transporting substance described later (for example, JP-A-64-64) is used.
1728, JP-A-64-13061, JP-A-64-19049, JP-A-4-11627, JP-A-4-225014, and JP-A-4-230.
No. 767, No. 4-320420, No. 5-232727, No. 6-234838, No. 6-234839, No. 6-295.
077, JP 7-56374, JP 7
-325409, JP-A-9-80772,
JP-A-9-80783, JP-A-9-80784, JP-A-9-127713, and JP-A-9-21
1877, JP 9-222740 A, JP 9-265197 A, JP 9-265201 A, JP 9-297419 A, JP 9-30 A.
The substances described in Japanese Patent Publication No. 4956, etc.) can also be used.

The amount of the binder resin for forming the charge generating layer 35 is more than 0 parts by weight and not more than 500 parts by weight, preferably more than 0 parts by weight and not more than 200 parts by weight with respect to 100 parts by weight of the charge generating substance. Contained. Further, if necessary, various additives such as a leveling agent such as dimethyl silicone oil and methylphenyl silicone oil, a sensitizer and a dispersant can be added.

The charge generation layer 35 may be formed by a vacuum thin film forming method or a casting method from a solution dispersion system. The vacuum thin film forming method includes a vacuum vapor deposition method, a glow discharge decomposition method, an ion plating method,
There are a sputtering method, a reactive sputtering method, a CVD method and the like, which are preferably used when an inorganic charge generating substance or an organic charge generating substance is adopted. In the casting method, the charge transport layer 37 is formed as follows, for example. First,
Inorganic charge generating substance or organic charge generating substance, together with a binder resin, if necessary, tetrahydrofuran, dioxane, dioxolane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, cyclopentanone, anisole, xylene, methyl ethyl ketone, acetone , A solvent such as ethyl acetate, butyl acetate or a dispersion medium, ball mill, attritor, sand mill,
A coating solution is obtained by dissolving or dispersing with a bead mill or the like. Then, it can be formed by appropriately diluting this coating liquid and applying it on the coating layer. The coating liquid can be applied by a conventionally known method such as a dip coating method, a spray coating method, a bead coating method, a ring coating method. The film thickness of the charge generation layer 35 is 0.01 to 5 μm, preferably 0.05 to 2 μm.
m.

<Charge Transport Layer 37> The charge transport layer 37 contains a charge transport material as a main component, and a binder resin (a binder resin for forming the charge transport layer 37) or an additive can be appropriately added. As the charge transport material, a hole transport material, an electron transport material, or the like can be adopted.

The electron transport material is, for example, chloranil,
Bromanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone, Two
4,8-Trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophene-4
-One, 1,3,7-trinitrodibenzothiophene-
Examples thereof include electron accepting substances such as 5,5-dioxide and diphenoquinone derivatives. These substances may be used alone or as a mixture of two or more kinds.

The hole-transporting substance is, for example, an oxazole derivative, an oxadiazole derivative, an imidazole derivative,
Monoarylamine derivative, diarylamine derivative,
Triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triarylmethane derivatives, 9-styrylanthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives,
An electron-donating substance such as a butadiene derivative, a pyrene derivative, a bisstilbene derivative, an enamine derivative, etc. is favorably used. In addition, known materials other than these can also be used.
These substances may be used alone or as a mixture of two or more kinds.

The binder resin for forming the charge transport layer 37 is, for example, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride or vinyl chloride. Examples thereof include vinyl acetate copolymer, polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin and the like. These resins may be used alone or in combination of two or more.

The charge transport layer 37 is the charge transport layer 37.
A polymer charge transport material having a function as a binder resin for forming and a function as a charge transport material is also favorably used. The charge transport layer 37 containing the polymer charge transport material has excellent abrasion resistance and can provide a high quality image. The binder resin for forming the charge transport layer 37 and the above-mentioned low molecular charge transport material may be mixed and used. Known materials can be used as the polymer charge transporting material, and in particular, polycarbonate having a triarylamine structure in the main chain and / or side chain is preferably used. In particular, polymer charge transport materials represented by the following structural formulas (I) to (X) are favorably used.

[0132]

[Chemical 6]

In the general formula (I), R _A , R _B and R
_C represents a substituted or unsubstituted alkyl group which may be the same or different, or a halogen atom; R
_D represents a hydrogen atom or a substituted or unsubstituted alkyl group; R _E and R _F each represent a substituted or unsubstituted aryl group, which may be the same or different; o, p, q
Represents an integer of 0 to 4; k and j represent a composition (molar fraction), and 0.1 ≦ k ≦ 1 and 0 ≦ j ≦ 0.9; n
Represents the number of repeating units and is an integer of 5 to 5000; X represents an aliphatic divalent group, a cycloaliphatic divalent group or the divalent group represented by the general formula (4).

In the above general formula (4), R ₁₀₁ and R ₁₀₂ are
Each represents a substituted or unsubstituted alkyl group, aryl group or halogen atom, which may be the same or different;
l and m represent an integer of 0 to 4; Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-,-. SO ₂ -, - CO
-, -CO-O-Z-O-CO- (Z represents an aliphatic divalent group) or a divalent group represented by the general formula (5).

In the above general formula (5), a is an integer of 1 to 20, b is an integer of 1 to 2000, R ₁₀₃ and R ₁₀₄ are substituted or unsubstituted alkyl groups or aryl groups.

[0136]

[Chemical 7]

In the above general formula (II), R _G and R _H are the same or different substituted or unsubstituted aryl groups,
Ar ₁ , Ar ₂ and Ar ₃ represent the same or different arylene groups. X, k, j, and n are the same as in the above general formula (I).

[0138]

[Chemical 8]

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

[0140]

[Chemical 9]

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

[0142]

[Chemical 10]

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

[0144]

[Chemical 11]

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

[0146]

[Chemical 12]

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

[0148]

[Chemical 13]

In the above general formula (VIII), R_{twenty one}Is a substitution or
Unsubstituted aryl group, Ar₂₀, Ar _{twenty one}, Ar_{twenty two}, Ar_{twenty three}
Represents an arylene group which may be the same or different. X,
k, j, and n are the same as those in the above general formula (I).

[0150]

[Chemical 14]

In the general formula (IX), R ₂₂ , R ₂₃ , R ₂₄ ,
R ₂₅ represents a substituted or unsubstituted aryl group which may be the same or different, and Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ and Ar ₂₈ represent an arylene group which may be the same or different. X,
k, j, and n are the same as those in the above general formula (I).

[0152]

[Chemical 15]

In the above general formula (X), R ₂₆ and R ₂₇ may be the same or different and may be a substituted or unsubstituted aryl group, A
r ₂₉ , Ar ₃₀ , and Ar ₃₁ represent the same or different arylene groups. X, k, j and n are represented by the general formula (I) above.
Is the same as.

Some preferred specific examples (forms) of polycarbonate containing a triarylamine structure in its main chain and / or side chain are shown below. If one or more of the compounds shown below are used, extremely excellent photosensitivity (such as high image quality) can be obtained. However, it is not limited to these compounds.

[0155]

[Chemical 16]

[0156]

[Chemical 17]

[0157]

[Chemical 18]

[0158]

[Chemical 19]

[0159]

[Chemical 20]

[0160]

[Chemical 21]

[0161]

[Chemical formula 22]

[0162]

[Chemical formula 23]

[0163]

[Chemical formula 24]

[0164]

[Chemical 25]

The polymer charge transport material is polymerized in the form of a homopolymer, a random copolymer, an alternating copolymer or a block copolymer. In addition, a film forming ability is required to realize the function as a binder resin. In order to have a film forming ability, the molecular weight is 10,000 to 500,000, preferably 50,000 to 4 in terms of polystyrene-converted molecular weight Mw as measured by GPC.
It should be 0,000. Such a polymer charge transport material is
For example, JP-A-8-269183 and JP-A-9-7
1642, JP 9-104746, JP 9-272735, JP 11-29634, JP 9-235367, and JP 9-87.
No. 376, No. 9-110976, No. 9-268226, No. 9-221544, No. 9-227669, No. 9-157.
The substances disclosed in Japanese Unexamined Patent Application Publication No. 378, Japanese Unexamined Patent Application Publication No. 9-302084, Japanese Unexamined Patent Application Publication No. 9-302085, and Japanese Unexamined Patent Application Publication No. 2000-26590 can be preferably used.

For the charge transport layer 37, for example, a coating solution in which at least a charge transport substance and a binder resin are dissolved or dispersed in a suitable solvent or dispersion medium is applied onto a coating layer such as the charge generation layer 35. And dried to form.

The charge transport substance is contained in an amount of 20 to 300 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder resin for forming the charge transport layer 37. However, when the polymer charge transporting substance is used, the charge transporting substance may be used alone or in combination with a binder resin or the like.

As the solvent (dispersion medium) and the dispersion medium which can be used for forming the charge transport layer 37, those which can be used for forming the charge generating layer 35 can be used, but the charge transport substance and the binder resin are preferably used. Those that dissolve or disperse are appropriately selected and used. Also, a plurality of solvents or dispersion media may be mixed and used.

A leveling agent or a plasticizer may be added to the charge transport layer 37, if necessary. The leveling agent is
For example, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain.
Can be used. The leveling agent is preferably added in the range of more than 0 parts by weight and 1 part by weight or less with respect to 100 parts by weight of the binder resin. As the plasticizer, known ones such as dibutyl phthalate and dioctyl phthalate can be used, and it is preferable to add it in the range of more than 0 parts by weight and 30 parts by weight or less with respect to 100 parts by weight of the binder resin.

As the coating method, known coating methods such as a dip coating method, a spray coating method, a bead coating method and a ring coating method can be adopted. The thickness of the charge transport layer 37 is 5 to 50 μm.
m is suitable. Further, 10 to 30 μm is preferable because good resolution can be obtained, good image characteristics such as little background stain can be obtained, and electric characteristics such as charging potential and sensitivity are good.

<Single Layer Type Photosensitive Layer 33> Single Layer Type Photosensitive Layer 3
3 is, for example, the above-mentioned charge generating substance, charge transporting substance,
The binder resin (binder resin for forming the photosensitive layer 33) or the like is dissolved or dispersed in a suitable solvent or dispersion medium to form a coating solution on a conductive support or the like and then dried. As the charge generating substance and the charge transporting substance, the materials mentioned for the laminated photosensitive layer 33 can be used. As the binder resin for forming the photosensitive layer 33, a binder resin for forming the charge transport layer 37 can be used, and further, a binder resin for forming the charge generating layer 35 may be appropriately mixed and used. Further, the above-mentioned polymer charge transport material may be adopted as the binder resin. The amount of the charge generating substance with respect to 100 parts by weight of the binder resin for forming the photosensitive layer 33 is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight. The charge transport material is preferably used in the range of more than 0 parts by weight and 190 parts by weight or less, more preferably 50 to 150 parts by weight, based on the binder resin.

The photosensitive layer 33 can be formed as follows.
(1) A charge generating substance, a binder resin and a charge transporting substance are dissolved or dispersed in a solvent or a dispersion medium such as tetrahydrofuran, dioxane, dichloroethane, cyclohexanone, toluene, methyl ethyl ketone and acetone to prepare a coating liquid. (2) It can be formed by applying this coating liquid on a layer to be coated such as the conductive support 31 using a dip coating method, a spray coating method, a bead coating method, a ring coating method or the like. If necessary, various additives such as a plasticizer, a leveling agent, an antioxidant and a lubricant can be added. Photosensitive layer 33
A film thickness of 5 to 25 μm is suitable.

<Protective Layer 39> The protective layer 39 is the photosensitive layer 33.
And a layer for protecting the charge transport layer 37 and the like, and at least contains a binder resin (a binder resin for forming the protective layer 39). Moreover, preferably, a filler material is contained. As the binder resin for forming the protective layer 39, a binder resin for forming the charge transport layer 37 can be used. As the filler material, one or more of the above can be adopted.

The protective layer 39 may further contain a charge transport material. Protective layer 39 containing charge transport material
Has the advantage that the residual potential can be lowered and sensitivity deterioration can be suppressed. Further, the above-mentioned polymer charge transporting material is preferably adopted as the charge transporting material. The photoconductor having the protective layer 39 containing the polymer charge transport material can have an extremely low probability of generating an abnormal image. This is because the polymer charge transport material is unlikely to be deteriorated or decomposed by ozone or NOx, and is more excellent in scratch resistance than the mixed system of the charge transport material and the binder resin. That is, an organic carbon-based residue that increases the probability of occurrence of an abnormal image is not generated or is unlikely to be generated, and it is difficult for a fine scratch to be formed on the surface of the photoconductor in order to easily remove charged products. can get. As the charge transporting material and the polymer charge transporting material used in the protective layer, one or a plurality of materials arbitrarily selected from the same or similar materials as the materials that can be used in the charge transporting layer 37 can be used.

The protective layer 39 can be formed by applying a binder resin for forming the protective layer 39 onto the layer to be coated in the same manner as the charge transport layer 37. For example, a known coating method such as a dip coating method, spray coating, beat coating, nozzle coating, spinner coating, or ring coating can be used. Among them, the spray coating method is preferably adopted because the film thickness can be easily controlled, the dispersibility of the acrylic-modified polyorganosiloxane and the filler can be favorably maintained, and the coating quality of the obtained photoreceptor (protective layer 39) can be improved. . Also, the protective layer 39 may be formed by a single coating,
When the protective layer 39 is formed by coating the protective layer 39 twice or more, the filler material can be dispersed in the protective layer 39 substantially uniformly. When the filler material is evenly dispersed, the residual potential can be kept low,
The resolution can be increased and the abrasion resistance can be increased. In addition, the quality of the coating film can be improved and the occurrence of coating film defects can be suppressed. The thickness of the protective layer 39 is preferably 0.5 μm to 10 μm, and 2 μm
It is more preferably m to 6 μm.

<Undercoat Layer> The undercoat layer is the conductive support 3
1 and the photosensitive layer 33. The undercoat layer generally contains a resin as a main component, but since the photosensitive layer 33 is applied, it is desirable that the undercoat layer is a resin having high solvent resistance to an organic solvent, particularly a solvent for forming the photosensitive layer 33. Such resins include, for example, polyvinyl alcohol, casein, water-soluble resins such as sodium polyacrylate, copolymer nylon, alcohol-soluble resins such as methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, Examples thereof include curable resins that form a three-dimensional network structure such as epoxy resins. The undercoat layer is made of titanium oxide, silica, alumina, zirconium oxide, for preventing moire, reducing residual potential, etc.
Fine powder pigments of metal oxides such as tin oxide and indium oxide may be added. Further, the undercoat layer may contain a silane coupling agent, a titanium coupling agent, a chromium coupling agent or the like.

The undercoat layer can be formed in the same manner as the photosensitive layer 33. The same solvent may be used as the coating solvent (dispersion medium). In addition, a layer provided with Al ₂ O ₃ on the layer to be coated by an anodization method, an organic substance such as polyparaxylylene (parylene), SiO ₂ , SnO ₂ , TiO ₂ , IT
A layer provided with an inorganic substance such as O or CeO ₂ on the layer to be coated by a vacuum thin film forming method may be used as the undercoat layer. Other than these, known layer forming methods can be adopted. The thickness of the undercoat layer is 0
The range is preferably more than 5 μm and less than 5 μm.

<Intermediate Layer> An intermediate layer may be provided between the undercoat layer and the photosensitive layer 33 or between the photosensitive layer 33 and the protective layer 39. The intermediate layer is generally a binder resin (binder resin).
Is the main component. Examples of the resin that can be used include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As the method for forming the intermediate layer, the known coating method as described above can be used. The suitable thickness of the intermediate layer is 0.05 to 2 μm.

<Items Common to Each Layer> Further, in order to improve environment resistance, in particular, in order to prevent a decrease in sensitivity and an increase in residual potential, an antioxidant or a plasticizer may be added to one or more layers of the photoreceptor. It is preferable to appropriately add agents, lubricants, ultraviolet absorbers, low molecular weight charge transport substances, leveling agents and the like.

<Antioxidant> Examples of the antioxidant include, but are not limited to, the followings. (A) Phenolic compound 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, n-octadecyl-3- (4'- Hydroxy-3 ', 5'-di-t-butylphenol),
2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-
Ethyl-6-t-butylphenol), 4,4'-thiobis- (3-methyl-6-t-butylphenol),
4,4'-butylidene bis- (3-methyl-6-t-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane,
1,3,5-Trimethyl-2,4,6-tris (3,5
-Di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-
t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] crycol ester, tocopherols and the like.

(B) Paraphenylenediamines N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl- p-
Phenylenediamine, N, N'-di-isopropyl-p
-Phenylenediamine, N, N'-Dimethyl-N, N '
-Di-t-butyl-p-phenylenediamine and the like.

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

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

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

<Plasticizer> Examples of the plasticizer include, but are not limited to, the following. (A) Phosphate ester plasticizer triphenyl phosphate, tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, trichloroethyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, Triphenyl phosphate etc.

(B) Phthalate ester type plasticizer dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, di-n-phthalate. Octyl, dinonyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, butylbenzyl phthalate, butyllauryl phthalate, methyloleyl phthalate, octyldecyl phthalate, dibutyl fumarate, Dioctyl fumarate etc.

(C) Aromatic Carboxylate Plasticizers Trioctyl trimellitate, Tri-n-trimellitic acid
-Octyl, octyl oxybenzoate and the like.

(D) Aliphatic dibasic acid ester plasticizers Dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, di-n-adipate
Octyl, adipic acid-n-octyl-n-decyl, diisodecyl adipate, dicapryl adipate, di-2-ethylhexyl azelate, dimethyl sebacate,
Diethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, di-2-ethylhexyl sebacate, di-2-ethoxyethyl sebacate, dioctyl succinate, diisodecyl succinate, dioctyl tetrahydrophthalate, dihydrotetrahydrophthalate -N-octyl and the like.

(E) Fatty acid ester derivative butyl oleate, glycerin monooleate, methyl acetylricinoleate, pentaerythritol ester, dipentaerythritol hexaester,
Triacetin, tributyrin, etc.

(F) Oxyacid ester type plasticizers Methyl acetylricinoleate, butyl acetylricinoleate, butylphthalylbutyl glycolate, tributyl acetylcitrate and the like.

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

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

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

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

(K) Sulfonic acid derivative p-toluene sulfonamide, o-toluene sulfonamide, p-toluene sulfone ethylamide, o-toluene sulfone ethylamide, toluene sulfone-N-ethylamide, p-toluene sulfone-N-cyclohexyl Amide etc.

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

(M) Other terphenyls, partially hydrogenated terphenyls, camphor, 2
-Nitrodiphenyl, dinonylnaphthalene, methyl abietate and the like.

<Lubricant> Examples of the lubricant include, but are not limited to, the followings. (A) Hydrocarbon compound Liquid paraffin, paraffin wax, microwax, low-polymerization polyethylene, etc.

(B) Fatty acid compounds Lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, etc.

(C) Fatty acid amide compounds Stearyl amide, palmityl amide, olein amide, methylene bis stearamide, ethylene bis stearamide and the like.

(D) Ester Compounds Lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, fatty acid polyglycol esters, etc.

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

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

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

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

<Ultraviolet Absorber> Examples of the ultraviolet absorber include, but are not limited to, the followings. (A) Benzophenone-based 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ', 4-trihydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4- Methoxybenzophenone etc.

(B) Salsylates Phenyl salsylates, 2,4 di-t-butylphenyl 3,5-di-t-butyl 4-hydroxybenzoate and the like.

(C) Benzotriazole (2′-hydroxyphenyl) benzotriazole,
(2'-hydroxy5'-methylphenyl) benzotriazole, (2'-hydroxy5'-methylphenyl)
Benzotriazole, (2'-hydroxy 3'-tert-butyl 5'-methylphenyl) 5-chlorobenzotriazole

(D) Cyanoacrylate-based ethyl-2-cyano-3,3-diphenylacrylate, methyl 2-carbomethoxy3 (paramethoxy) acrylate and the like.

(E) Quencher (metal complex salt system) Nickel (2,2 'thiobis (4-t-octyl) phenolate) n-butylamine, nickel dibutyldithiocarbamate, nickel dibutyldithiocarbamate, cobalt dicyclohexyldithiophosphate and the like.

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

<Structure Other than Photoreceptor and Electrophotographic Method> Next, the structure of the electrophotographic apparatus other than the photosensitive member and the electrophotographic method will be described in detail with reference to the drawings. The above electrophotographic apparatus forms at least a toner image on the above-described photoconductor (electrophotographic photoconductor) by performing charging, exposure, and development, and transfers and fixes the toner image onto an image carrier (transfer paper). Let Then, the surface of the photoconductor is cleaned. However, this process is an example of the image forming process in the electrophotographic apparatus according to the present invention, and in some cases, some steps may be omitted in the above process or another step may be provided. Good.

FIG. 6 is a schematic diagram showing one structural example of the electrophotographic apparatus. In FIG. 6, the above-mentioned photoconductor is adopted as the photoconductor 1. Although the photoreceptor 1 has a drum shape, it may have a sheet shape, an endless belt shape, or the like.

As the charging member 3, a charging roller device is mainly used, and the photoconductor 1 and the charging member are arranged close to each other in the image forming area without contact. Thus, in order to dispose the charging member close to the photoconductor 1, a gap may be provided in the non-image forming area of the photoconductor 1. For example, the gap material may be provided on the charging member, on the photoconductor 1, or on the flange portions set at both ends of the photoconductor. However, any configuration may be adopted as long as the photoconductor 1 and the charging member are arranged close to each other.

FIG. 7 shows an example in which a gap member is provided on the charging member. In this example, the gap material has an insulating property,
A material having high wear resistance is preferably used. The gap material may have any shape such as a tape shape, a seal shape, a tube shape and the like. The thickness of the gap is 10 to 200 μ
m is preferable, 20 to 100 μm is more preferable, and 40 to 80 μm is still more preferable. When the thickness of the gap is within this range, the charging member and the photoconductor 1 rarely come into contact with each other, so that the deterioration of the image quality is extremely small.
In addition, the stability of charging does not deteriorate, uneven charging is extremely unlikely to occur, and it is not necessary to increase the applied voltage for maintaining the required charging level. Therefore,
Since the amount of charged products generated can be reduced, the probability of occurrence of abnormal images can be extremely reduced.

Further, the charging member may be charged with the charging of the photosensitive member 1 by superimposing an AC component on a DC component. By superimposing the AC component, uneven charging can be reduced. As a result, it is possible to prevent unevenness in image density and reduction in contrast.

The image exposure section 5 forms an electrostatic latent image on the charged photoreceptor 1. The light source is, for example, a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (L
D), electroluminescence (EL), or other luminescent material may be appropriately selected and used. In addition, various filters such as a sharp cut filter, a bandpass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter may be used to irradiate only light in a desired wavelength range.

The developing unit 6 visualizes the electrostatic latent image formed on the photoconductor 1. The developing method includes a one-component developing method using a dry toner, a two-component developing method, and a wet developing method using a wet toner. When the photoreceptor is positively charged and imagewise exposed, a positive electrostatic latent image is formed on the surface of the photoreceptor. A positive image can be obtained by developing it with a negative polarity toner (electro-detection fine particles), and a negative image can be obtained by developing it with a positive polarity toner. The sign may be reversed.

The transfer charger 10 transfers the toner image visualized on the photoconductor 1 onto the transfer body. The pre-transfer charger 7 may be used for better transfer. As a transfer method, an electrostatic transfer method using a transfer charger or a bias roller, a mechanical transfer method such as an adhesive transfer method, a pressure transfer method, or a magnetic transfer method can be adopted. The electrostatic transfer method may be performed using a charging means.

The separation charger 11 and the separation claw 12 are means for separating the transfer member from the photosensitive member. Besides, as the separating means, electrostatic attraction induction separating means, side end belt separating means,
A tip grip conveying means, a curvature separating means, etc. can also be used. Further, the separation charger may use charging means.

The fur brush 14 and the cleaning blade 15 clean the toner left on the photoconductor after transfer. Further, the pre-cleaning charger 13 may be used to perform the cleaning more efficiently. In addition, a web method, a magnet brush method, or the like may be adopted as the cleaning method. Any one or a plurality of cleaning methods may be adopted as the cleaning method.

The charge eliminating means removes the latent image on the photoconductor 1. As the charge eliminating means, for example, the charge eliminating lamp 2 and the charge eliminating charger may be used, which may be realized by using the exposure light source and the charging means, respectively.

Document reading means, paper feeding means, fixing means,
Known means can be adopted as the paper discharge means and the like. Further, it is of course possible to adopt a configuration / process other than that shown in FIG. For example,
In the configuration example of FIG. 6, the light irradiation step on the photoconductor includes image exposure,
Although it is realized by pre-cleaning exposure and static elimination exposure, the photoconductor may be irradiated with light by a known light irradiation process such as pre-transfer exposure and pre-exposure of image exposure.

The image forming means as described above may be fixedly incorporated in the electrophotographic apparatus, but one or more of them may be provided in a process cartridge which is detachable from the electrophotographic apparatus. The cartridge may be installed in the electrophotographic apparatus so as to be incorporated in the electrophotographic apparatus. FIG. 8 shows one structural example of such a process cartridge for an electrophotographic apparatus. The process cartridge has a photoconductor (photoconductor drum 101), and in addition, a charging unit 102, a developing unit, a transfer unit 106,
The device (component) is provided with at least one of a cleaning unit (such as the cleaning blade 107) and a charge removing unit.

(Examples) The present invention will be described below with reference to Examples. However, the present invention should not be construed as being limited to the following examples. In addition, hereinafter, “part” means part by weight.

(Example 1) A coating liquid for an undercoat layer, a coating liquid for a charge generation layer, a coating liquid for a charge transport layer having the following composition was placed on an aluminum drum (conductive support 31) having a diameter of 30 mm.
An undercoat layer having a thickness of about 3.5 μm and a charge generation layer 3 having a thickness of about 0.2 μm, which are sequentially applied / dried by a dip coating method.
5, a charge transport layer 37 having a thickness of about 25 μm was formed, and a photoconductor was produced.

[0227]     [Coating liquid for undercoat layer]   ・ Alkyd resin 6 parts     (Beckosol 1307-60-EL, manufactured by Dainippon Ink and Chemicals)   ・ Melamine resin 4 parts     (Super Beckamine G-821-60, manufactured by Dainippon Ink and Chemicals)   ・ Titanium oxide 40 parts   ・ Methyl ethyl ketone 50 parts

[0228]     [Coating liquid for charge generation layer]   ・ 2.5 parts of bisazo pigment represented by the following general formula (6)   ・ Polyvinyl butyral (XYHL, made by UCC) 0.5 part   ・ Cyclohexanone 200 parts   ・ Methyl ethyl ketone 80 parts

[0229]     [Coating liquid for charge transport layer]   ・ Acrylic modified polyorganosiloxane 2 parts     (Charline R-170S, manufactured by Nissin Chemical Industry Co., Ltd.)   ・ Bisphenol Z polycarbonate 10 parts     (Panlite TS-2050, manufactured by Teijin Kasei)   7 parts of low molecular weight charge transport material represented by the following general formula (7)   ・ Tetrahydrofuran 100 parts   ・ 1% silicone oil tetrahydrofuran solution 1 part     (Silicone oil: KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0230]

[Chemical formula 26]

Example 2 A photoconductor was prepared in the same manner as in Example 1, except that the charge transport layer coating liquid was changed to the following charge transport layer coating liquid. [Coating liquid for charge transport layer] -Acrylic modified polyorganosiloxane 2 parts (Charline R-170S, manufactured by Nissin Chemical Industry) -Bisphenol Z polycarbonate 10 parts (Panlite TS-2050, manufactured by Teijin Chemicals) -The following general formula Low molecular charge transport material represented by (7) 7 parts Tetrahydrofuran 100 parts 1% Silicone oil tetrahydrofuran solution 1 part (Silicone oil: KF50-100CS, Shin-Etsu Chemical Co., Ltd.) Polycarboxylic acid compound 0.1 parts ( BYK-P104, solid content about 50%, manufactured by BYK Chemie) ・ Antioxidant represented by the following general formula (8) (manufactured by Sumitomo Chemical Co., Ltd.) 0.2 part

[0232]

[Chemical 27]

Example 3 Example 1 was repeated except that the charge transport layer coating solution was changed to the following charge transport layer coating solution and the charge transport layer 37 was formed by the ring coating method. A photoconductor was prepared in the same manner as in. [Coating liquid for charge transport layer] -Acrylic modified polyorganosiloxane 2 parts (Charline R-170S, manufactured by Nissin Chemical Industry) -Bisphenol Z polycarbonate 10 parts (Panlite TS-2050, manufactured by Teijin Chemicals) -The following structural formula (7) Low molecular weight charge transport material 7 parts-Tetrahydrofuran 100 parts-1% Silicone oil tetrahydrofuran solution 1 part (Silicone oil: KF50-100CS, Shin-Etsu Chemical Co., Ltd.)-Α-alumina 1 part (Sumicorundum AA-03, average) Primary particle size: 0.3 μm, pH 8 to 9, manufactured by Sumitomo Chemical Co., Ltd.-0.2 parts of antioxidant represented by the following general formula (8) (manufactured by Sumitomo Chemical Co., Ltd.)

[0234]

[Chemical 28]

Example 4 All of Example 1 except that the charge transport layer coating liquid was changed to the following charge transport layer coating liquid and the charge transport layer was formed by the ring coating method. A photoconductor was prepared in the same manner as in. [Coating liquid for charge transport layer] -Acrylic modified polyorganosiloxane 1 part (Charline R-170S, manufactured by Nissin Chemical Industry) -Bisphenol Z polycarbonate 10 parts (Panlite TS-2050, Teijin Chemicals) -The following general formula Low-molecular charge transport material represented by (7) 7 parts-Tetrahydrofuran 100 parts-1% Silicone oil tetrahydrofuran solution 1 part (Silicone oil: KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)-Alumina 3 parts (Sumicorundum AA- 03, average primary particle size: 0.3 μm, pH 8-9, manufactured by Sumitomo Chemical Co., Ltd.-Polycarboxylic acid compound 0.04 parts (BYK-P104, solid content about 50%, manufactured by BYK Chemie) -The following general formula (9 ) Antioxidant represented by (Sumitomo Chemical Co., Ltd.) 0.15 part

[0236]

[Chemical 29]

Example 5 A photoconductor was prepared in the same manner as in Example 1 except that the coating liquid for charge transport layer was changed to the coating liquid for charge transport layer described below. [Coating liquid for charge transport layer] -Acrylic modified polyorganosiloxane 2 parts (Charline R-170S, manufactured by Nissin Chemical Industry) -Bisphenol Z polycarbonate 10 parts (Panlite TS-2050, manufactured by Teijin Chemicals) -The following structural formula Low molecular charge transport material represented by (7) 7 parts Tetrahydrofuran: 100 parts 1% Silicone oil tetrahydrofuran solution 1 part (Silicone oil: KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.) α-alumina 3 parts (Sumicorundum AA) -03, average primary particle size: 0.3 μm, pH 8 to 9, manufactured by Sumitomo Chemical Co., Ltd.-Polycarboxylic acid compound 0.06 parts (BYK-P104, solid content about 50%, manufactured by BYK Chemie) -The following structural formula ( 10) Antioxidant represented by 10) 0.15 part (Sanol LS-2626, manufactured by Sankyo)

[0238]

[Chemical 30]

Example 6 Example 1 was repeated except that the coating solution for charge transport layer was changed to the following coating solution for charge transport layer and the charge transport layer was formed by the ring coating method.
A photoconductor was prepared in the same manner as in. [Coating liquid for charge transport layer] -Acrylic modified polyorganosiloxane 2 parts (Charline R-210, manufactured by Nissin Chemical Industry) -Bisphenol Z polycarbonate 10 parts (Panlite TS-2050, manufactured by Teijin Chemicals) -The following general formula Low molecular charge transport material represented by (7) 7 parts-Tetrahydrofuran 100 parts-1% Silicone oil tetrahydrofuran solution 1 part (Silicone oil: KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)-Silica 2 parts (KMPX-100, average) (Primary particle size about 0.1 μm, pH 2-3, made by Shin-Etsu Silicone)

[0240]

[Chemical 31]

Example 7 A photoreceptor was prepared in the same manner as in Example 1 except that the coating liquid for charge transport layer was changed to the coating liquid for charge transport layer described below. [Coating liquid for charge transport layer] -Acrylic modified polyorganosiloxane 2 parts (Charline R-170, manufactured by Nissin Chemical Industry) -Bisphenol Z polycarbonate 10 parts (Panlite TS-2050, manufactured by Teijin Kasei) -The following general formula Low molecular weight charge transport material represented by (7) 7 parts Tetrahydrofuran 100 parts 1% Silicone oil tetrahydrofuran solution 1 part (Silicone oil: KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.) Titanate coupling treated titanium oxide 3 parts (CR-EL, average primary particle size of about 0.3 μm, pH 6 to 7, manufactured by Ishihara Sangyo) ・ Polycarboxylic acid compound 0.05 part (BYK-P104, solid content of about 50%, manufactured by BYK Chemie) ・ The following general formula Antioxidant represented by (11) (Sumitomo Chemical Co., Ltd.) 0.1 part

[0242]

[Chemical 32]

Example 8 Example 1 was repeated except that the charge transport layer coating liquid was changed to the following charge transport layer coating liquid and the charge transport layer was formed by the ring coating method.
A photoconductor was prepared in the same manner as in. [Coating liquid for charge transport layer] -Acrylic modified polyorganosiloxane 2 parts (Charline R-170S, manufactured by Nissin Chemical Industry) -Bisphenol Z polycarbonate 10 parts (Panlite TS-2050, manufactured by Teijin Chemicals) -The following general formula Low-molecular charge transport material represented by (7) 7 parts-Tetrahydrofuran 110 parts-1% Silicone oil tetrahydrofuran solution 1 part (Silicone oil: KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)-Alumina 4 parts (Sumicorundum AA- 03, average primary particle size: 0.3 μm, pH 8 to 9, manufactured by Sumitomo Chemical Co., Ltd.)-Polycarboxylic acid compound 0.2 part (acrylic acid / hydroxyethyl methacrylate copolymer) -Represented by the following general formula (11) Antioxidant (Sumitomo Chemical Co., Ltd.) 0.1 part

[0244]

[Chemical 33]

(Example 9) A coating liquid for an undercoat layer, a coating liquid for a charge generation layer, and a coating liquid for a charge transport layer having the following compositions were ring-formed on an aluminum drum (conductive support 31) having a diameter of 30 mm. Approximately 3.5 μm by applying / drying sequentially according to the coating method
Undercoating layer, charge generation layer 3 having a thickness of about 0.2 μm
5, a charge transport layer 37 having a thickness of about 25 μm was formed, and a photoconductor was produced.

[0246]     [Coating liquid for undercoat layer]   ・ Alkyd resin 6 parts     (Beckosol 1307-60-EL, manufactured by Dainippon Ink and Chemicals)   ・ Melamine resin 4 parts     (Super Beckamine G-821-60, manufactured by Dainippon Ink and Chemicals)   ・ Titanium oxide 40 parts   ・ Methyl ethyl ketone 50 parts

[0247]     [Coating liquid for charge generation layer]   8 parts of titanyl phthalocyanine having XD spectrum shown in FIG.   ・ Polyvinyl butyral 0.5 part     (S-REC BM-S, Sekisui Chemical Co., Ltd.)   ・ Methyl ethyl ketone 400 parts

[0248]     [Coating liquid for charge transport layer]   ・ Acrylic modified polyorganosiloxane 2 parts     (Charline R-170S, manufactured by Nissin Chemical Industry Co., Ltd.)   ・ Bisphenol Z polycarbonate 10 parts     (Panlite TS-2050, manufactured by Teijin Kasei)   ・ 7 parts low molecular weight charge transport material represented by the following general formula (12)   ・ Tetrahydrofuran 100 parts   ・ 1% silicone oil tetrahydrofuran solution 1 part     (Silicone oil: KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)   ・ Spherical silicone particles 4 parts     (Average primary particle size of about 0.5 μm, "Tospearl 105" made by Toshiba Silicone)

[0249]

[Chemical 34]

Example 10 An undercoat layer coating liquid, a charge generating layer coating liquid, and a charge transport layer coating liquid having the following compositions were dipped in a φ30 mm aluminum drum (conductive support 31). By applying / drying sequentially according to the coating method, about 3.
An undercoat layer having a film thickness of 5 μm, a charge generation layer 35 having a film thickness of about 0.2 μm, and a charge transport layer 37 having a film thickness of about 20 μm were formed. A protective layer coating solution having the following composition was applied / dried on the charge transport layer 37 by a ring coating method to form a protective layer 39 having a film thickness of about 5 μm, and the photoconductor 10 was manufactured.

[0251]     [Coating liquid for undercoat layer]   ・ Alkyd resin 6 parts     (Beckosol 1307-60-EL, manufactured by Dainippon Ink and Chemicals)   ・ Melamine resin 4 parts     (Super Beckamine G-821-60, manufactured by Dainippon Ink and Chemicals)   ・ Titanium oxide 40 parts   ・ Methyl ethyl ketone 50 parts

[0252]     [Coating liquid for charge generation layer]   ・ 2.5 parts of bisazo pigment represented by the following general formula (6)   ・ Polyvinyl butyral (XYHL, made by UCC) 0.5 part   ・ Cyclohexanone 200 parts   ・ Methyl ethyl ketone 80 parts

[0253]     [Coating liquid for charge transport layer]   ・ Bisphenol Z polycarbonate 10 parts     (Panlite TS-2050, manufactured by Teijin Kasei)   7 parts of low molecular weight charge transport material represented by the following general formula (7)   ・ Tetrahydrofuran 100 parts   ・ 1% silicone oil tetrahydrofuran solution 1 part     (Silicone oil: KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)   -Antioxidant represented by the following general formula (8) (Sumitomo Chemical Co., Ltd.) 0.15 part

[0254]     [Coating liquid for protective layer]   ・ Acrylic modified polyorganosiloxane 2 parts     (Charline R-170S, manufactured by Nissin Chemical Industry Co., Ltd.)   ・ Bisphenol Z polycarbonate 10 parts     (Panlite TS-2050, manufactured by Teijin Kasei)   7 parts of low molecular weight charge transport material represented by the following general formula (7)   ・ Tetrahydrofuran 230 parts

[0255]

[Chemical 35]

Example 11 The procedure of Example 10 was repeated except that the protective layer coating solution was changed to the following protective layer coating solution.
A photoconductor was prepared in the same manner as in Example 10. [Coating liquid for protective layer] -Acrylic modified polyorganosiloxane 3 parts (Charline R-170S, manufactured by Nisshin Chemical Industry Co., Ltd.)-Bisphenol Z polycarbonate 10 parts (Panlite TS-2050, manufactured by Teijin Chemicals) -Following Low molecular weight charge transport material represented by the general formula (7) 7 parts Tetrahydrofuran: 260 parts Polycarboxylic acid compound 0.1 parts (BYK-P104, solid content about 50%, manufactured by BYK Chemie)

[0257]

[Chemical 36]

Example 12 The procedure of Example 10 was repeated except that the protective layer coating solution was changed to the following protective layer coating solution.
A photoconductor 12 was produced in the same manner as in Example 10. [Coating liquid for protective layer] -Acrylic modified polyorganosiloxane 4 parts (Charline R-170S, manufactured by Nisshin Chemical Co., Ltd.)-Bisphenol Z polycarbonate 10 parts (Panlite TS-2050, manufactured by Teijin Chemicals) -Following Low molecular weight charge transport material represented by general formula (7) 7 parts Tetrahydrofuran 270 parts Antioxidant represented by general formula (10) 0.2 parts (Sanol LS-2626, Sankyo)

[0259]

[Chemical 37]

Example 13 Example 10 was repeated except that the protective layer coating solution was changed to the following protective layer coating solution and the protective layer 39 was formed by spray coating.
A photoconductor was prepared in the same manner as in. [Coating liquid for protective layer] -Acrylic modified polyorganosiloxane 2 parts (Charline R-170S, manufactured by Nissin Chemical Industry Co., Ltd.)-Bisphenol Z polycarbonate 10 parts (Panlite TS-2050, manufactured by Teijin Chemicals) -Following Low molecular weight charge transport material represented by general formula (7) 7 parts α-alumina 3 parts (Sumicorundum AA-03, average primary particle size: 0.3 μm, pH 8-9, manufactured by Sumitomo Chemical Co., Ltd.) Polycarboxylic acid Compound 0.08 part (BYK-P104, solid content about 50%, manufactured by BYK Chemie) -tetrahydrofuran 400 parts-cyclohexanone 120 parts

[0261]

[Chemical 38]

Example 14 The procedure of Example 10 was repeated except that the protective layer coating solution was changed to the following protective layer coating solution.
A photoconductor was prepared in the same manner as in Example 10. [Coating Liquid for Protective Layer] 2 parts of acrylic modified polyorganosiloxane (Charline R-170S, manufactured by Nissin Chemical Industry Co., Ltd.) 18 parts of polymer charge transport material represented by the following general formula (13) 260 parts of tetrahydrofuran

[0263]

[Chemical Formula 39]

(Example 15) Example 10 was repeated except that the protective layer coating solution was changed to the following protective layer coating solution and the protective layer 39 was formed by spray coating.
A photoconductor was prepared in the same manner as in. [Coating liquid for protective layer] -Acrylic modified polyorganosiloxane 2 parts (Charline R-170S, manufactured by Nissin Chemical Industry Co., Ltd.)-Polymer charge transporting material represented by the following general formula (13) 18 parts-α-alumina 5 Part (Sumicorundum AA-03, average primary particle size: 0.3 μm, pH 8-9, manufactured by Sumitomo Chemical Co., Ltd.)-Polycarboxylic acid compound 0.10 part (BYK-P104, solid content about 50%, manufactured by BYK Chemie)・ Tetrahydrofuran 400 parts ・ Cyclohexanone 120 parts

[0265]

[Chemical 40]

(Example 16) The procedure of Example 10 was repeated except that the protective layer coating solution was changed to the following protective layer coating solution.
A photoconductor was prepared in the same manner as in Example 10. [Coating Liquid for Protective Layer] 2 parts of acrylic modified polyorganosiloxane (Charline R-170S, manufactured by Nissin Chemical Industry Co., Ltd.) 18 parts of polymer charge transport material represented by the following general formula (14) α-alumina 6 parts (Sumicorundum AA-03, average primary particle size: 0.3 μm, pH 8-9, manufactured by Sumitomo Chemical Co., Ltd.)-Polycarboxylic acid compound 0.15 parts (BYK-P104, solid content about 50%, BYK) Chemistry) -Tetrahydrofuran 230 parts-Cyclohexanone 70 parts-Antioxidant represented by the following general formula (10) 0.2 parts (Sanol LS-2626, manufactured by Sankyo)

[0267]

[Chemical 41]

Example 17 An undercoat layer coating liquid, a charge generating layer coating liquid, and a charge transport layer coating liquid having the following compositions were dipped in an aluminum drum (conductive support 31) having a diameter of 30 mm. Approximately 3.5 μm by applying / drying sequentially according to the coating method
Undercoating layer, charge generation layer 3 having a thickness of about 0.2 μm
5, the charge transport layer 37 having a thickness of about 20 μm was formed. A protective layer coating solution having the following composition is applied / dried on the charge transport layer 37 by a ring coating method to form a protective layer 3 having a thickness of about 5 μm.
9 was formed to prepare a photoconductor.

[0269]     [Coating liquid for undercoat layer]   ・ Alkyd resin 6 parts     (Beckosol 1307-60-EL, manufactured by Dainippon Ink and Chemicals)   ・ Melamine resin 4 parts     (Super Beckamine G-821-60, manufactured by Dainippon Ink and Chemicals)   ・ Titanium oxide 40 parts   ・ Methyl ethyl ketone 50 parts

[0270]     [Coating liquid for charge generation layer]   -Oxotitanium phthalocyanine having XD spectrum shown in FIG.                                                                   8 copies   ・ Polyvinyl butyral 0.5 part     (S-REC BM-S, Sekisui Chemical Co., Ltd.)   ・ Methyl ethyl ketone 400 parts

[0271]     [Coating liquid for charge transport layer]   ・ Bisphenol Z polycarbonate 10 parts     (Panlite TS-2050, manufactured by Teijin Kasei)   ・ 8 parts low molecular weight charge transport material represented by the following general formula (7)   ・ Tetrahydrofuran 100 parts   ・ 1% silicone oil tetrahydrofuran solution 1 part     (Silicone oil: KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0272]     [Coating liquid for protective layer]   ・ Acrylic modified polyorganosiloxane 2 parts     (Charline R-170S, manufactured by Nissin Chemical Industry Co., Ltd.)   ・ Bisphenol Z polycarbonate 10 parts     (Panlite TS-2050, manufactured by Teijin Kasei)   ・ 8 parts low molecular weight charge transport material represented by the following general formula (7)   ・ Α-alumina 3 parts     (Sumicorundum AA-03, average primary particle size: 0.3 μm, pH 8-9,       Sumitomo Chemical Co., Ltd.)   ・ Polycarboxylic acid compound 0.08 part     (BYK-P104, solid content about 50%, made by BYK Chemie)   ・ Tetrahydrofuran 400 parts   ・ Cyclohexanone 120 parts

[0273]

[Chemical 42]

(Example 18) Example 1 was repeated except that the protective layer coating solution was changed to the following protective layer coating solution and the protective layer 39 was formed by a spray coating method.
A photoconductor was prepared in the same manner as in No. 7. [Coating liquid for protective layer] -Acrylic modified polyorganosiloxane 3 parts (Charline R-170S, manufactured by Nisshin Chemical Industry Co., Ltd.)-Bisphenol Z polycarbonate 10 parts (Panlite TS-2050, manufactured by Teijin Chemicals) -Following Low-molecular charge transport material represented by general formula (12) 8 parts α-alumina 5 parts (Sumicorundum AA-03, average primary particle size: 0.3 μm, pH 8-9, manufactured by Sumitomo Chemical Co., Ltd.) ・ Polycarboxylic acid Compound 0.10 parts (BYK-P104, solid content about 50%, manufactured by BYK Chemie) -Tetrahydrofuran 400 parts-Cyclohexanone 120 parts

[0275]

[Chemical 43]

Example 19 Example 1 was repeated except that the protective layer coating solution was changed to the following protective layer coating solution and the protective layer 39 was formed by a spray coating method.
A photoconductor was prepared in the same manner as in No. 7. [Coating Liquid for Protective Layer] Acrylic-modified polyorganosiloxane 3 parts (Charline R-170S, manufactured by Nissin Chemical Industry Co., Ltd.) 18 parts of polymeric charge transport material represented by the following general formula (13) α-alumina 5 parts (Sumicorundum AA-03, average primary particle size: 0.3 μm, pH 8-9, manufactured by Sumitomo Chemical Co., Ltd.)-Polycarboxylic acid compound 0.10 parts (BYK-P104, solid content about 50%, BYK) Chemie) Tetrahydrofuran 400 parts Cyclohexanone 120 parts Antioxidant represented by the following general formula (10) 0.15 parts (Sanol LS-2626, Sankyo)

[0277]

[Chemical 44]

Comparative Example 1 A photoconductor was prepared in the same manner as in Example 1 except that the coating liquid for charge transport layer in Example 1 was changed to the coating liquid for charge transport layer described below. [Coating liquid for charge transport layer] 10 parts of bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals) 7 parts of low molecular charge transport material represented by the following general formula (7) -Tetrahydrofuran 100 parts-1 % Silicone Oil Tetrahydrofuran Solution 1 Part (Silicone Oil: KF50-100CS, Shin-Etsu Chemical Co., Ltd.)

[0279]

[Chemical formula 45]

Comparative Example 2 A photoconductor was prepared in the same manner as in Comparative Example 1 except that the charge transport layer coating liquid in Comparative Example 1 was changed to the following charge transport layer coating liquid. [Coating liquid for charge transport layer] 10 parts of bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals) 7 parts of low molecular charge transport material represented by the following general formula (7) -Tetrahydrofuran 100 parts-1 % Silicone Oil Tetrahydrofuran Solution 1 Part (Silicone Oil: KF50-100CS, Shin-Etsu Chemical Co., Ltd.) α-Alumina 2 Parts (Sumicorundum AA-03, Average Primary Particle Size: 0.3 μm, pH 8-9, Sumitomo Chemical Co., Ltd.) -Polycarboxylic acid compound 0.05 part (BYK-P104, solid content about 50%, BYK Chemie) -Antioxidant represented by the following general formula (11) (Sumitomo Chemical Co., Ltd.) 0.1 part

[0281]

[Chemical formula 46]

(Comparative Example 3) A photoconductor was prepared in the same manner as in Comparative Example 1 except that the coating solution for charge transport layer in Comparative Example 1 was changed to the following coating solution for charge transport layer. [Coating liquid for charge transport layer] 10 parts of bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals) 7 parts of low molecular charge transport material represented by the following general formula (7) -Tetrahydrofuran 100 parts-1 % Silicone Oil Tetrahydrofuran Solution 1 Part (Silicone Oil: KF50-100CS, Shin-Etsu Chemical Co., Ltd.) Titanium Oxide 3.5 Parts (CR-EL, Average Primary Particle Size: 0.3 μm, pH 6 to 7, Ishihara Sangyo Co., Ltd.) Polycarboxylic acid compound 0.10 part (BYK-P104, solid content about 50%, manufactured by BYK Chemie) -Antioxidant represented by the following general formula (10) 0.15 part (Sanol LS-2626, manufactured by Sankyo).

[0283]

[Chemical 47]

(Comparative Example 4) A photoconductor was prepared in the same manner as in Example 10, except that the protective layer coating liquid was changed to the protective layer coating liquid described below. [Coating liquid for protective layer] 10 parts of bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals) 7 parts of low molecular charge transporting material represented by the following general formula (7) -160 parts of tetrahydrofuran

[0285]

[Chemical 48]

Comparative Example 5 Same as Comparative Example 4 except that the protective layer coating liquid was changed to the following protective layer coating liquid and the protective layer 39 was formed by a spray coating method. A photoconductor was prepared. [Coating Liquid for Protective Layer] 10 parts of bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals) 7 parts of low-molecular charge transport material represented by the following general formula (7) α 3 parts of alumina (Sumiko Random AA-03, average primary particle size: 0.3 μm, pH 8-9, manufactured by Sumitomo Chemical Co., Ltd.-Polycarboxylic acid compound 0.06 parts (BYK-P104, solid content about 50%, manufactured by BYK Chemie) -Tetrahydrofuran 350 Parts-cyclohexanone 100 parts-antioxidant represented by the following general formula (10) 0.15 parts (Sanol LS-2626, manufactured by Sankyo)

[0287]

[Chemical 49]

(Comparative Example 6) Similar to Comparative Example 4 except that the protective layer coating solution was changed to the following protective layer coating solution and the protective layer 39 was formed by a spray coating method. A photoconductor was prepared. [Coating liquid for protective layer] 10 parts of bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals) 7 parts of low-molecular charge transport material represented by the following general formula (7) -α alumina 5 parts (Sumiko Random AA-03, average primary particle size: 0.3 μm, pH 8 to 9, manufactured by Sumitomo Chemical Co., Ltd.-Polycarboxylic acid compound 0.10 parts (BYK-P104, solid content about 50%, manufactured by BYK Chemie) -Tetrahydrofuran 350 Parts-cyclohexanone 100 parts-antioxidant represented by the following general formula (10) 0.15 parts (Sanol LS-2626, manufactured by Sankyo)

[0289]

[Chemical 50]

(Comparative Example 7) A photoconductor was prepared in the same manner as in Comparative Example 4 except that the protective layer coating liquid in Comparative Example 4 was changed to the following protective layer coating liquid. [Coating liquid for protective layer] -Polymer charge transport substance represented by the following general formula (13) 18 parts-α-alumina 3 parts (Sumicorundum AA-03, average primary particle size: 0.3 µm, pH 8-9) , Manufactured by Sumitomo Chemical Co., Ltd.-Polycarboxylic acid compound 0.05 part (BYK-P104, solid content about 50%, manufactured by BYK Chemie) -Tetrahydrofuran 350 parts-Cyclohexanone 100 parts-Oxidation represented by the following general formula (10) Inhibitor 0.15 parts (Sanol LS-2626, manufactured by Sankyo)

[0291]

[Chemical 51]

(Comparative Example 8) A photoconductor was prepared in the same manner as in Comparative Example 4 except that the protective layer coating liquid was changed to the protective layer coating liquid described below. [Coating liquid for protective layer] -Polymer charge transport substance represented by the following general formula (13) 18 parts-α-alumina 5 parts (Sumicorundum AA-03, average primary particle size: 0.3 µm, pH 8 to 9) , Manufactured by Sumitomo Chemical Co., Ltd. ・ Polycarboxylic acid compound 0.10 parts (BYK-P104, solid content about 50%, manufactured by BYK Chemie) ・ Tetrahydrofuran 350 parts ・ Cyclohexanone 100 parts ・ Oxidation represented by the following general formula (10) Inhibitor 0.15 parts (Sanol LS-2626, manufactured by Sankyo)

[0293]

[Chemical 52]

Comparative Example 9 Same as Comparative Example 4 except that the protective layer coating solution was changed to the following protective layer coating solution and the protective layer 39 was formed by a spray coating method. A photoconductor was prepared. [Coating Liquid for Protective Layer] 10 parts of bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals) 7 parts of low-molecular charge transport material represented by the following general formula (7) α 3 parts of alumina (Sumiko Random AA-03, average primary particle size: 0.3 μm, pH 8-9, manufactured by Sumitomo Chemical Co., Ltd.-Polycarboxylic acid compound 0.10 parts (BYK-P104, solid content about 50%, manufactured by BYK Chemie) -Spherical silicone Fine particles 2 parts (average primary particle size of about 0.5 μm, "Tospearl 105" manufactured by Toshiba Silicone) -Tetrahydrofuran 350 parts-Cyclohexanone 100 parts-Antioxidant represented by the following general formula (10) 0.15 parts (Sanol LS -2626, manufactured by Sankyo)

[0295]

[Chemical 53]

The photosensitive member produced as described above was mounted in an electrophotographic process cartridge (without a pre-cleaning exposure unit). In this process cartridge, the charging means is a charging roller and the image exposure light source is 655.
It was set in a remodeled machine of the product name imagioMF2200 manufactured by Ricoh Co., Ltd. which adopted a semiconductor laser of nm.
In addition, both ends (non-image forming area) of the charging roller are 5
A Teflon (registered trademark) tape having a thickness of 0 μm was wound around and fixed, and the charging member was placed close to the photoconductor.

Then, the following evaluation was performed. (1) Image evaluation in an initial state (after one image formation) under an environment of 25 ° C. and 50% RH. (2) Image evaluation in the initial state at 30 ° C. and 90% RH environment. (3) Image evaluation after printing 60,000 sheets under 25 ° C. and 50% RH environment and measurement of photoconductor wear amount. For image formation, AC (1 kHz, 1.
8kV (peak to peak) + DC (-750V) was applied. As for the amount of wear, the difference from the initial state was measured. (4) Image evaluation after printing 60,000 sheets under the environment of 30 ° C. and 90% RH and measurement of the amount of abrasion of the photoconductor as in (3). The image evaluation was visually performed according to the following criteria. ⊚: No deterioration of image quality, good level ○: No deterioration of image quality, but no problem Δ: Level of obvious deterioration of image quality ×: Difficult image discrimination and difficult image discrimination Table 1 Shown in.

[0298]

[Table 1]

As is clear from Table 1, even in the conventional photoconductor, a good image was obtained in the initial state even when a charging roller in which ozone and NOx were generated in a relatively small amount was used. When repeatedly used below, image quality deterioration was confirmed. In addition, it was confirmed that the photosensitive member containing no filler had a large variation in film thickness due to abrasion, and the occurrence of scumming. Image blur occurred on the photoreceptor containing the filler. It was confirmed that the higher the content of the filler, the more likely an abnormal image would occur.

On the other hand, it was confirmed that the wear amount of the photoreceptor containing the acrylic modified polyorganosiloxane compound in the outermost surface layer was reduced as compared with the conventional case when the filler was not included. In addition, the occurrence of background stain was not recognized even after printing 60,000 sheets. It has been found that the photoreceptor containing the filler can form a good image either in the initial state or after printing 60,000 sheets. It was also found that good images can be obtained even if the amount of filler added is increased.

Although the preferred embodiments of the present invention have been described above, the above-described embodiments are merely examples for explaining the present invention, and the scope of the present invention is limited to the embodiments. Absent. A person skilled in the art can implement the present invention in various other modes in which various variations, improvements, modifications, simplifications, etc. are added to the above embodiments without departing from the gist of the present invention.

[0302]

As is apparent from the above description, according to the present invention, the outermost surface layer of the photoconductor contains an acrylic-modified polyorganosiloxane, and the charging member is disposed close to the photoconductor. Therefore, the amount of ozone and NOx gas generated is extremely small, and the surface energy and friction coefficient of the photoconductor are extremely low, and these characteristics can be stably maintained for a long period of time. Thereby, for example, the probability of occurrence of an abnormal image can be made extremely low. That is, it has become possible to both suppress the generation of ozone and the like and prevent the charging product from adhering to the photoconductor, and to maintain this effect.

Further, the probability of occurrence of abnormal images can be made extremely low for a long period even in the case of a photoreceptor having a wear resistance improved by containing a filler in the outermost surface layer. This is due to the fact that the durability of the surface energy reducing effect can be remarkably enhanced and that the charging member is not in contact with the photoconductor. That is, as in the prior art, the problem that the probability of occurrence of an abnormal image was extremely high due to the adherence of the charged product to the photoconductor was solved, especially under high temperature and high humidity. That is, high durability and high image quality of the electrophotographic apparatus have been realized. Further, even if the outermost surface layer does not contain a filler, the abrasion resistance of the photoreceptor can be increased.

Further, the cleaning property of the photoconductor and the transfer efficiency can be improved, the occurrence of an abnormal image due to filming or the adhesion of foreign matter can be suppressed, and the discharge breakdown can be suppressed.
It has become possible to provide an electrophotographic apparatus having high durability and high image quality such that abrasion resistance can be improved and uneven abrasion can be suppressed. Moreover, such an effect can be maintained even after repeated use.

Also, use of a basic metal oxide as the filler, surface treatment of the filler, inclusion of a polymer charge transporting substance in the outermost surface layer of the photoreceptor, addition of an antioxidant or the like. Thus, it becomes possible to further reduce the probability of occurrence of an abnormal image (give a further margin to the influence of the abnormal image / image blur).

If the outermost surface layer contains a carboxylic acid compound, the stability of the electrostatic characteristics of the photoconductor can be improved, and extremely good high durability and high image quality can be realized.

As described above, since the electrophotographic apparatus according to the present invention can suppress the generation of abnormal images without the need for a dehumidifying device such as a drum heater, it is possible to reduce the size and power consumption. became.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of the layer structure of an electrophotographic photoreceptor according to the present invention.

FIG. 2 is a cross-sectional view showing another layer configuration example of the electrophotographic photoreceptor according to the present invention.

FIG. 3 is a cross-sectional view showing another layer configuration example of the electrophotographic photoreceptor according to the present invention.

FIG. 4 is a cross-sectional view showing another layer configuration example of the electrophotographic photoreceptor according to the present invention.

FIG. 5 is a cross-sectional view showing another layer configuration example of the electrophotographic photoreceptor according to the present invention.

FIG. 6 is a schematic diagram for explaining an electrophotographic process cartridge and an electrophotographic apparatus according to the present invention.

FIG. 7 is a diagram for explaining the positional relationship between the charging unit and the electrophotographic photosensitive member according to the present invention.

FIG. 8 is a schematic diagram for explaining one configuration example of an electrophotographic process cartridge according to the present invention.

FIG. 9 shows an XD spectrum of oxytitanium phthalocyanine.

[Explanation of symbols]

1 photoconductor 2 Static elimination lamp 3 charging roller 5 Image exposure unit 6 Development unit 7 Charger before transfer 8 Registration roller 9 Transfer paper 10 Transfer charger 11 Separation Charger 12 separate nails 13 Charger before cleaning 14 fur brush 15 cleaning brush 31 conductive support 33 Photosensitive layer 35 Charge generation layer 37 Charge Transport Layer 39 Protective layer 101 photosensitive drum 102 charging device 103 exposure means 104 developing device 105 transfer body 106 transfer device 107 cleaning blade

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 15/02 101 G03G 15/02 101 102 102 (72) Inventor Lee Hong-gu 1 Nakamagome, Ota-ku, Tokyo Chome No. 3-6 F-term in Ricoh Co., Ltd. (reference) 2H068 AA03 AA04 AA05 AA14 AA16 BA04 BA12 BA57 BA58 BA60 BB07 BB08 BB20 BB33 BB49 BB53 CA06 CA22 CA29 CA33 CA37 CA40 FA03 FA27 2H200 FA02 FA08 FA13 GA61 GA23 GA12 GA12 GA31 GA23 GA12 GA12 GB21 HA12 HA13 HA22 HA28 HB03 HB12 HB48 JA02 LA07 NA06 NA09 NA10

Claims (20)

[Claims] 1. An electrophotographic apparatus comprising at least a charging means, an exposing means, a developing means and a transferring means around an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member has an acryl-modified polyorganosiloxane compound as an outermost surface layer. The electrophotographic apparatus is characterized in that the charging means is disposed close to the electrophotographic photosensitive member. 2. The electrophotographic apparatus according to claim 1, wherein the acrylic-modified polyorganosiloxane compound is a compound in which an acrylic polymer is graft-copolymerized on a main chain of siloxane. 3. The acrylic-modified polyorganosiloxane compound is a polyorganosiloxane represented by the following general formula (1) and an acrylic ester, a methacrylic acid ester and / or an acrylic represented by the following general formula (3). A compound obtained by emulsion-grafting and copolymerizing an acid ester or / and a mixture of 70% by weight or more of a methacrylic acid ester and 30% by weight or less of a copolymerizable monomer at a weight ratio of 5:95 to 95: 5. Claim 1 characterized by the above.
Or the electrophotographic apparatus according to 2. [Chemical 1] The above general formula (1), R ¹ , R ² and R ³ may be the same or different and each is a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms; Y is a radical reactive group or an SH group. Or an organic group having a radical-reactive group and an SH group; Z ¹ and Z
² are hydrogen atoms, lower alkyl groups or groups represented by the above structural formula (2), which may be the same or different; m is a positive integer of 10,000 or less; n is an integer of 1 or more. . In the above structural formula (2), R ⁴ and R ⁵ may be the same or different and each is a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group; R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms. , A halogenated hydrocarbon group, a radical-reactive group, an SH group or a radical-reactive group, and a SH group-containing productive group. In the general formula (3), R ⁷ is a hydrogen atom or a methyl group; R ⁸ is an alkyl group,
It is an alkoxy-substituted alkyl group, a cycloalkyl group or an aryl group. 4. The weight of the polyorganosiloxane represented by the general formula (1) is such that the acrylic acid ester, methacrylic acid ester and / or acrylic acid ester or / and methacrylic acid represented by the following general formula (3) is used. The electrophotographic apparatus according to claim 3, wherein the amount of the acid ester is more than the weight of the mixture of 70% by weight or more and the copolymerizable monomer of 30% by weight or less. 5. The electrophotographic apparatus according to claim 1, wherein the acrylic modified polyorganosiloxane compound is in the form of a microgel. 6. The outermost layer comprises an acrylic modified polyorganosiloxane compound in an amount of 1% by weight to 40% by weight based on the total solid content of the layer. The electrophotographic apparatus according to any one of 1. 7. The electrophotographic apparatus according to claim 1, wherein the charging unit is a charging roller. 8. The electrophotographic apparatus according to claim 7, wherein the charging roller charges the electrophotographic photosensitive member by applying a voltage in which an AC component is superimposed on a DC component. 9. The electrophotographic apparatus according to claim 7, wherein the charging roller has a gap with an electrophotographic photosensitive member in an image forming area of 200 μm or less. 10. The electrophotographic apparatus according to claim 1, wherein a filler is contained in an outermost surface layer of the electrophotographic photosensitive member. 11. The electrophotographic apparatus according to claim 10, wherein the filler is one of metal oxides. 12. The metal oxide is p at the isoelectric point.
The electrophotographic apparatus according to claim 11, wherein H is 5 or more. 13. The electrophotographic apparatus according to claim 11, wherein the metal oxide is surface-treated. 14. The filler has an average primary particle size of 0.
14. The electrophotographic photosensitive member according to claim 10, wherein the electrophotographic photosensitive member is in the range of 01 μm to 0.9 μm. 15. The electrophotographic apparatus according to claim 1, wherein the electrophotographic photosensitive member contains a carboxylic acid compound in the outermost surface layer. 16. The electrophotographic apparatus according to claim 15, wherein the carboxylic acid compound is a polycarboxylic acid compound. 17. The electrophotographic apparatus according to claim 1, wherein the outermost surface layer of the electrophotographic photosensitive member contains a polymer charge transport material. 18. The electrophotographic photosensitive member according to claim 1, wherein the outermost surface layer contains an antioxidant.
7. The electrophotographic apparatus according to any one of items 7. 19. The electrophotographic apparatus according to claim 18, wherein the antioxidant has a hindered amine structure and a hindered phenol structure. 20. In the electrophotographic apparatus, at least a charging unit and an electrophotographic photosensitive member are provided in a process cartridge for an electrophotographic apparatus having a structure detachable from an electrophotographic apparatus main body. Item 1
21. The electrophotographic apparatus according to any one of items 1 to 19.