JP2006011037A - Electrophotographic photoreceptor, image forming apparatus, image forming method and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor which ensures little surface deterioration of the electrophotographic photoreceptor in a charging system by an adjacent discharge with an alternating voltage superposed on a direct voltage, has very good mechanical durability, and can perform stable image formation over a prolonged period of time. <P>SOLUTION: The electrophotographic photoreceptor is obtained by forming at least a photosensitive layer 12 and a surface protective layer 13 in this order on a conductive support 1. A film containing hydrogen and nitrogen and having a diamond-like carbon or amorphous carbon structure is disposed as the surface protective layer 13. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is employed in an electrophotographic process having a charger that charges an electrophotographic photosensitive member by using a discharge that is provided in contact with or in close proximity and that is generated by applying a voltage in which an AC component is superimposed on a DC component. The present invention relates to an electrophotographic photosensitive member, an image forming apparatus, a process cartridge for an image forming apparatus, and an image forming method. The present invention particularly relates to the structure of the surface protective layer constituting the electrophotographic photosensitive member.

In recent years, miniaturization and higher image quality have been demanded for electrophotographic apparatuses from the viewpoints of saving office space and expanding business opportunities.
Many attempts have been made to improve the electrophotographic process in order to reduce the size of the electrophotographic apparatus. However, in the charging process, a charging method using proximity discharge tends to be frequently employed. This is a system in which a charging member is brought into contact with the surface of the electrophotographic photosensitive member, or a charging member is disposed in the vicinity without contact to generate a proximity discharge to charge the surface of the electrophotographic photosensitive member. If this method is used, a large-scale charging device is not required, and thus it is very effective for downsizing the device. Further, recent proximity charging systems often employ a system in which an AC voltage is applied in a superimposed manner on a DC voltage in order to achieve uniform charging of the electrophotographic photosensitive member.

  However, the charging method using proximity discharge in which AC voltage is superimposed on DC voltage concentrates the discharge near the surface of the electrophotographic photosensitive member, so that the surface of the electrophotographic photosensitive member is deteriorated and the thickness of the electrophotographic photosensitive member is greatly reduced. all right. Deterioration of the electrophotographic photosensitive member surface due to proximity discharge occurs even when there is no contact member to the image carrier, unlike mechanical rubbing. For this reason, development of an electrophotographic photosensitive member having durability against proximity discharge or a technology for protecting the surface of the electrophotographic photosensitive member is strongly desired.

The deterioration mechanism of the electrophotographic photoreceptor surface due to proximity discharge will be described below.
FIG. 1 shows a state in which only a charging member is placed close to the surface of the electrophotographic photosensitive member in a non-contact state in order to investigate the deterioration state of the surface of the electrophotographic photosensitive member due to the proximity discharge, and a charging experiment is performed for about 150 hours continuously. 3 is a result of measuring a change in film thickness on the surface of the electrophotographic photosensitive member.

  The electrophotographic photosensitive member used in the experiment is an organic photosensitive member using polycarbonate for the charge transport layer, and all the members in contact with the electrophotographic photosensitive member are removed, and an alternating voltage in which an alternating voltage is superimposed on a direct current voltage is applied. Charging was performed using a non-contact charging roller. As a result, it was found that the amount of film scraping on the surface of the electrophotographic photosensitive member gradually increased and the film thickness of the electrophotographic photosensitive member gradually decreased. The mechanism of film thickness reduction has not been clarified at present. However, when an electrophotographic photosensitive member having a reduced film thickness is analyzed, the polycarbonate constituting the electrophotographic photosensitive member is considered to have been decomposed. Acid etc. were detected. Since such a substance has been detected, the following may be considered as a mechanism for reducing the film thickness of the electrophotographic photosensitive member.

  2A and 2B show the state of the surface of the electrophotographic photosensitive member 81 when the surface of the electrophotographic photosensitive member 81 deteriorates due to proximity discharge, and shows the state where the charging roller 82a is opposed to the surface of the electrophotographic photosensitive member with a minute gap. It is explanatory drawing shown taking as an example. Here, FIG. 2A shows the state before deterioration, and FIG. 2B shows the state after deterioration.

  When the proximity discharge is performed, the energy of particles (ozone, electrons, excited molecules, ions, plasma, etc.) generated by the discharge is irradiated to the charge transport layer 81a on the surface of the electrophotographic photosensitive member in the discharge region on the surface of the electrophotographic photosensitive member. . This energy resonates and is absorbed by the binding energy of the molecules constituting the surface of the electrophotographic photosensitive member, and as shown in FIG. 2A, the charge transport layer 81a has a molecular weight drop due to the breakage of the resin molecular chain, Chemical degradation such as a decrease in the degree of entanglement occurs. It is considered that the thickness of the charge transport layer 81a on the surface of the electrophotographic photosensitive member gradually decreases due to such chemical deterioration of the electrophotographic photosensitive member due to the proximity discharge.

  This problem is not only a problem that occurs in a photoreceptor using polycarbonate, but polyarylate (Patent Document 1), polystyrene (Patent Document 2), acrylic resin (Patent Document 3), and urethane resin (Patent Document 4). ) Etc., the same film thickness reduction occurs, and this problem has not been solved.

  The electrophotographic photoreceptor disclosed in the following Patent Document 1 is formed by laminating a charge generation layer and a charge transport layer in this order on a support, and the charge generation layer contains a phthalocyanine compound. It is characterized by containing polyarylate resin.

JP 2003-195564 A Japanese Patent Laid-Open No. 10-90932 Japanese Patent Laid-Open No. 10-59478 JP 2004-12865 A

  The present invention has been made in view of the above-described problems of the prior art, and the object thereof is a charging method based on proximity discharge in which an AC voltage is superimposed on a DC voltage, and the surface of the electrophotographic photoreceptor is less deteriorated and mechanical durability is improved. It is to provide an electrophotographic photosensitive member that has very good properties and can perform stable image formation over a long period of time (claims 1 to 11 and claim 23).

  Another object of the present invention is to provide an image forming apparatus comprising the electrophotographic photosensitive member (claims 12 to 22). A further object of the present invention is to provide a process cartridge comprising the electrophotographic photosensitive member (claim 24). A further object of the present invention is to provide an image forming method using the image forming apparatus.

As a result of intensive studies, the present inventors have found that the object can be achieved by using an electrophotographic photoreceptor according to the following claims (1) to (11), and have achieved the present invention.
That is, the invention of claims 1 to 11 relates to an electrophotographic photosensitive member having a predetermined configuration provided in each image forming apparatus,
At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In the electrophotographic photosensitive member provided in an image forming apparatus having a container,
Each has the following characteristics.

(1) Claim 1: It has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon containing hydrogen or an amorphous carbon structure. An electrophotographic photoreceptor characterized by the above.
(2) Claim 2: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen. An electrophotographic photosensitive member, characterized in that:
(3) Claim 3: a conductive support having at least a photosensitive layer and a surface protective layer in this order, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. An electrophotographic photosensitive member, characterized in that:
(4) Claim 4: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, the surface protective layer having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen. Further, the electrophotographic photosensitive member is characterized in that it is a film having a nitrogen to carbon content atomic ratio (N / C ratio) of 0.05 or more.
(5) Claim 5: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, the surface protective layer having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. And an electrophotographic photoreceptor, wherein the film has a fluorine-to-carbon content atomic ratio (F / C ratio) of 0.005 or more.
(6) Claim 6: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen. An electrophotographic photoreceptor, wherein the ratio of the atomic ratio of nitrogen to carbon (N / C ratio) is greater in the vicinity of the outermost layer than in the vicinity of the photosensitive layer of the surface protective layer.
(7) Claim 7: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. An electrophotographic photoreceptor, wherein the ratio of the atomic amount of fluorine to carbon (F / C ratio) is greater in the vicinity of the outermost layer than in the vicinity of the photosensitive layer of the surface protective layer.
(8) Claim 8: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen. Further, it is a film having a nitrogen to carbon content atomic ratio (N / C ratio) of 0.005 or less in the vicinity of the surface protective layer in the vicinity of the photosensitive layer and 0.05 or more in the vicinity of the outermost layer. An electrophotographic photosensitive member.
(9) Claim 9: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. In addition, the atomic ratio of fluorine to carbon (F / C ratio) is 0.001 or less in the vicinity of the photosensitive layer in the surface protective layer and 0.005 or more in the vicinity of the outermost layer. An electrophotographic photoreceptor.
(10) Claim 10: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen. A film in which the atomic ratio of nitrogen to carbon (N / C ratio) is larger in the vicinity of the outermost layer than in the vicinity of the photosensitive layer of the surface protective layer, and the N / C ratio is gradually inclined in concentration. An electrophotographic photoreceptor, characterized in that
(11) Claim 11: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. Further, a film in which the ratio of the atomic content of fluorine to carbon (F / C ratio) is larger in the vicinity of the outermost layer than in the vicinity of the photosensitive layer of the surface protective layer, and the F / C ratio is gradually inclined in concentration. An electrophotographic photoreceptor, characterized in that

Further, as a result of intensive studies, the present inventors have found that the object can be achieved by using the image forming apparatus described in the following claims (12) to (22), and have accomplished the present invention.
That is, the invention of claims 12 to 22 relates to an image forming apparatus provided with an electrophotographic photosensitive member having a predetermined configuration, respectively.
At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In an image forming apparatus having a container,
Each of the electrophotographic photosensitive members has the following configuration.

(12) Claim 12: It has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having diamond-like carbon containing hydrogen or an amorphous carbon structure. An electrophotographic photoreceptor characterized by the above.
(13) Claim 13: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen. An electrophotographic photosensitive member, characterized in that:
(14) Claim 14: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. An electrophotographic photosensitive member, characterized in that:
(15) Claim 15: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen. Further, the electrophotographic photosensitive member is characterized in that it is a film having a nitrogen to carbon content atomic ratio (N / C ratio) of 0.05 or more.
(16) Claim 16: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. And an electrophotographic photoreceptor, wherein the film has a fluorine-to-carbon content atomic ratio (F / C ratio) of 0.005 or more.
(17) Claim 17: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen. An electrophotographic photoreceptor, wherein the ratio of the atomic ratio of nitrogen to carbon (N / C ratio) is greater in the vicinity of the outermost layer than in the vicinity of the photosensitive layer of the surface protective layer.
(18) Claim 18: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, wherein the surface protective layer has a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. An electrophotographic photoreceptor, wherein the ratio of the atomic amount of fluorine to carbon (F / C ratio) is greater in the vicinity of the outermost layer than in the vicinity of the photosensitive layer of the surface protective layer.
(19) Claim 19: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen. In addition, the atomic ratio of nitrogen to carbon (N / C ratio) is 0.005 or less in the vicinity of the photosensitive layer of the surface protective layer and 0.05 or more in the vicinity of the outermost layer. An electrophotographic photoreceptor.
(20) Claim 20: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, wherein the surface protective layer has a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. In addition, the atomic ratio of fluorine to carbon (F / C ratio) is 0.001 or less in the vicinity of the photosensitive layer in the surface protective layer and 0.005 or more in the vicinity of the outermost layer. An electrophotographic photoreceptor.
(21) Claim 21: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen. A film in which the atomic ratio of nitrogen to carbon (N / C ratio) is larger in the vicinity of the outermost layer than in the vicinity of the photosensitive layer of the surface protective layer, and the N / C ratio is gradually inclined in concentration. An image forming apparatus.
(22) Claim 22: A film having at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. Further, a film in which the ratio of the atomic content of fluorine to carbon (F / C ratio) is larger in the vicinity of the outermost layer than in the vicinity of the photosensitive layer of the surface protective layer, and the F / C ratio is gradually inclined in concentration. An image forming apparatus.

Further, the above objects can be achieved by the following inventions.
(23) Claim 23: The electrophotographic photosensitive member according to any one of claims 1 to 11, wherein the photosensitive layer has a structure in which a charge generation layer, a charge transport layer and a surface protective layer are laminated in this order. An electrophotographic photosensitive member comprising:

(24) Claim 24: An electrophotographic photosensitive member and at least one means selected from a charging means, a developing means, and a cleaning means for cleaning the surface of the electrophotographic photosensitive member are integrally supported, and the image forming apparatus main body is supported. In a process cartridge that is detachable,
A process cartridge, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 1 to 11 or claim 23.

  (25) Claim 25: Charging that is provided in contact with or in proximity to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. 24. An image forming method comprising using a container and the electrophotographic photosensitive member according to any one of claims 1 to 11 or claim 23.

In the invention according to claim 1, in the electrophotographic photosensitive member employed in the image forming apparatus having the predetermined configuration described above, at least the photosensitive layer and the surface protective layer are provided in this order on the conductive support, and the surface protective layer is provided in this order. By making an electrophotographic photosensitive member characterized by being a film having a diamond-like carbon or amorphous carbon structure containing hydrogen, there is little deterioration of the electrophotographic photosensitive member due to charging, and high wear resistance, A highly durable and high performance electrophotographic photosensitive member having good electrical characteristics can be obtained. Thus, the photoconductor provided with the above film on the surface layer has not only mechanical durability but also energy irradiation of particles (ozone, electrons, excited molecules, ions, plasma, etc.) generated by discharge. It has very high durability.
Therefore, by using this electrophotographic photosensitive member, it is possible to provide a high-performance and highly reliable image forming process, an image forming apparatus, and a process cartridge for the image forming apparatus that can provide good images over a long period of time.

  In the inventions of claims 2 and 3, in addition to the effect of the invention of claim 1, there is an effect of improving the transparency and electrical characteristics of the film, that is, the surface protective layer. Therefore, it is possible to increase the film thickness. According to the inventions of claims 4 and 5, these characteristics are further improved.

  According to the sixth and seventh aspects of the invention, the transparency and electrical characteristics of the surface protective layer are improved, and the adhesiveness between the surface protective layer and the photosensitive layer is improved.

  In the invention of claim 8, as the surface protective layer, a film having a diamond-like carbon containing hydrogen and nitrogen or an amorphous carbon structure is formed, and the content ratio of nitrogen to carbon (N / C ratio) is set to a predetermined value. Since it is limited to the range, an effect superior to that of the invention of claim 6 can be obtained.

  In the invention of claim 9, a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine is formed as the surface protective layer, and the atomic ratio (F / C ratio) of fluorine to carbon is set to a predetermined value. Since it is limited to the range, an effect superior to that of the invention of claim 7 can be obtained.

  In the inventions according to claims 10 and 11, the surface protective layer is not a laminated film, and the peeling of the film on the surface protective layer film is suppressed, and since there is no clear interface that becomes a charge transport trap, the electrical characteristics are also improved. There is an effect of improving.

  In addition, since the invention according to claims 12 to 22 is an image forming apparatus in which the electrophotographic photosensitive member according to the invention of claims 1 to 11 is arranged, an effect obtained by each electrophotographic photosensitive member can be obtained. An image forming apparatus having high performance can be provided.

  According to the invention of claim 23, the charge generation layer, the charge transport layer and the surface protective layer are laminated in this order as the photosensitive layer, and the effect of the invention of any one of claims 1 to 11 is obtained. An electrophotographic photosensitive member is provided.

According to the invention of claim 24, the electrophotographic photosensitive member and at least one means selected from a charging means, a developing means, and a cleaning means for cleaning the surface of the electrophotographic photosensitive member are integrally supported, and an image is obtained. In the process cartridge that is detachable from the forming apparatus body,
A high-performance process cartridge provided with an electrophotographic photosensitive member that exhibits the effects of the invention according to any one of claims 1 to 11 is provided.

  Further, the invention of claim 25 is an image forming method using a charger having a predetermined configuration and the electrophotographic photosensitive member according to any one of claims 1 to 11 or claim 23. A good image can be formed over a wide range.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
One embodiment of the present invention is configured as follows. That is,
Charging that charges the electrophotographic photosensitive member using at least an electrophotographic photosensitive member and a discharge generated by applying a voltage in which the alternating current component is superimposed on a direct current component that is in contact with or close to the electrophotographic photosensitive member. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In the electrophotographic photosensitive member provided in an image forming apparatus having a container,
An electrophotographic photosensitive film comprising at least a photosensitive layer and a surface protective layer in this order on a conductive support, wherein the surface protective layer is a film containing diamond-like carbon containing hydrogen or an amorphous carbon structure. It is a body (Claim 1).

The diamond-like carbon or amorphous carbon film containing hydrogen in the present invention is a film in which similar structures such as a diamond structure having an SP ³ orbit, a graphite structure having an SP ² orbit, and an amorphous carbon structure are mixed. . A photoreceptor provided with this film on the surface layer is a very good film with respect to mechanical durability. This is one of the effects of the invention of claim 1 (for an electrophotographic photosensitive member in which a film having at least hydrogen and oxygen is formed on the photosensitive layer, see JP-A-7-244394. ).

Furthermore, as a result of intensive studies by the present inventor, when a charger using a charging method based on proximity discharge in which an AC voltage is superimposed on a DC voltage is used, not only mechanical durability but also particles generated by discharge (ozone, electron It has been found that it has very high durability against energy irradiation of excited molecules, ions, plasma, etc. (this is also the effect of the invention of claim 1).
This is probably because the diamond-like carbon or amorphous carbon structure itself has a very high bond density and a very large amount of carbon in the film, which improves plasma resistance and durability. It is thought that it is because.

  In the present invention, when nitrogen (Claim 2) or fluorine (Claim 3) is added to a surface protective layer having a diamond-like carbon or amorphous carbon structure containing hydrogen, the transparency and electrical characteristics of the film. Becomes better. Furthermore, when the content ratio of nitrogen to carbon (N / C ratio) is 0.05 or more (Claim 4), or the ratio of fluorine to carbon content atomic ratio is 0.005 or more (Claim 5), Improved characteristics. A film containing nitrogen and fluorine has higher film transparency and further improved electrical characteristics as compared with a film not containing these elements. Therefore, it is possible to increase the film thickness.

  However, the adhesion with the photosensitive layer is reduced as compared with a film containing no nitrogen and fluorine. As a means for improving the transparency and electrical characteristics of the film, and further the adhesion to the photosensitive layer, the following film is preferred.

  That is, in the present invention, nitrogen is contained in the surface protective layer having a diamond-like carbon or amorphous carbon structure containing hydrogen, and the atomic weight ratio (N / C ratio) of nitrogen to carbon is greater than the vicinity of the photosensitive layer. In the case where the outermost layer is large (claim 6), the transparency and electrical properties of the film are improved by adding nitrogen, and the adhesion between the surface protective layer and the photosensitive layer is improved.

  Similarly, the surface protective layer having hydrogen-containing diamond-like carbon or amorphous carbon structure contains fluorine, and the atomic weight ratio of nitrogen to carbon (F / C ratio) is the outermost layer than the vicinity of the photosensitive layer. Is large (Claim 7), the transparency and electrical properties of the film are improved by the addition of fluorine, and the adhesion between the surface protective layer and the photosensitive layer is improved.

  Furthermore, in the present invention, nitrogen is contained in the surface protective layer having a diamond-like carbon or amorphous carbon structure containing hydrogen, and the atomic weight ratio (N / C ratio) of nitrogen to carbon is such that the surface protective layer has a photosensitive property. A more preferable result is obtained when it is 0.005 or less in the vicinity of the layer and 0.05 or more in the vicinity of the outermost layer (Claim 8).

  Similarly, the surface protective layer having hydrogen-containing diamond-like carbon or amorphous carbon structure contains fluorine, and the atomic weight ratio of fluorine to carbon (F / C ratio) is in the vicinity of the surface protective layer near the photosensitive layer. In the case of 0.001 or less, and in the vicinity of the outermost layer, 0.005 or more, a more preferable effect can be obtained (claim 9).

  As a method of forming a film having different atomic weight ratios in the surface protective layer as described above, a method of stacking films having different atomic weight ratios, and gradually changing the introduced gas and other conditions during film formation, There is a method of changing the ratio. Films formed by stacking films having different atomic content ratios are slightly inferior in adhesiveness at the interface between the stacked films, and may peel off at the interface when used for a long time. Therefore, it is preferable to use a film in which the content atomic ratio is gradually changed.

  In the present invention, the surface protective layer having hydrogen-containing diamond-like carbon or amorphous carbon structure contains nitrogen, and the atomic weight ratio of nitrogen to carbon (N / C ratio) is such that the surface protective layer is photosensitive. When the film near the outermost layer is larger than the vicinity of the layer and the N / C ratio is gradually inclined, the surface protective layer is not a laminated film, and the film is peeled off at the surface protective layer film. In addition, since there is no clear interface serving as a charge transport trap, electrical characteristics are also improved (claim 10).

  Similarly, the surface protective layer having hydrogen-containing diamond-like carbon or amorphous carbon structure contains fluorine, and the atomic weight ratio of fluorine to carbon (F / C ratio) is in the vicinity of the surface protective layer near the photosensitive layer. When the film is larger in the vicinity of the outermost layer and the F / C ratio is gradually inclined, the surface protective layer does not become a laminated film, and peeling of the film on the surface protective layer film can be suppressed. In addition, since there is no clear interface that becomes a charge transport trap, electrical characteristics are also improved (claim 11).

As a method for producing the surface protective layer, plasma CVD, glow discharge decomposition method, photo CVD method, or sputtering method using graphite as a target is used.
Although the film forming method is not particularly limited, as a method for forming a carbon-based film having good characteristics as a protective layer, the film is formed with a sputtering effect while being a plasma CVD method. A method (Japanese Patent Laid-Open No. 58-49609) is known.

  In the method of forming a protective layer mainly composed of carbon using the plasma CVD method, it is not necessary to heat the support in particular, and a film can be formed at a low temperature of about 150 ° C. or lower. There is also an advantage that there is no problem when the protective layer is formed on the layer.

When the surface protective layer is produced, a carrier gas such as H ₂ or Ar is used with a hydrocarbon gas (methane, ethane, ethylene, acetylene, etc.) as a main material. Furthermore, any gas can be used for supplying the additive element as long as it can be vaporized under reduced pressure or can be vaporized by heating. For example, NH ₃ , N ₂ , C ₂ F ₆ , CH ₃ F, NF ₃ or the like is used as a gas for supplying nitrogen and fluorine.
The atomic ratio of nitrogen to carbon and the atomic ratio of fluorine to carbon in the film are measured using XPS (X-ray photoelectron spectroscopy).

Hereinafter, the layer structure of the present invention will be described.
<About the layer structure of the electrophotographic photoreceptor>
The electrophotographic photosensitive member used in the present invention will be described with reference to the drawings.
FIG. 3 is a cross-sectional view showing the electrophotographic photosensitive member of the present invention. A photosensitive layer 12 having a charge generation function and a charge transport function at the same time on a conductive support 11, and a surface protective layer 13 thereon. The provided photosensitive layer 12 is an electrophotographic photoreceptor 10 having a single layer structure.
FIG. 4 shows a photosensitive layer 12 in which a charge generation layer 12a having a charge generation function, a charge transport layer 12b having a charge transport function, and a surface protective layer 13 are laminated on the conductive support 11. Is an electrophotographic photoreceptor 10A having a laminated structure, and the charge generation layer 12a and the charge transport layer 12b constitute the photosensitive layer 12.

<About conductive support>
Examples of the conductive support include those having a volume resistance of 10 ¹⁰ · cm or less, for example, metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver and platinum, metals such as tin oxide and indium oxide Oxide is deposited or sputtered, film or cylindrical plastic, paper coated, or aluminum, aluminum alloy, nickel, stainless steel, etc. It is possible to use a tube which has been subjected to surface treatment such as super finishing or polishing. Further, endless nickel belts and endless stainless steel belts disclosed in JP-A-52-36016 can also be used as the conductive support.

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

  Furthermore, it is electrically conductive by a heat-shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, Teflon (registered trademark) on a suitable cylindrical substrate. Those provided with a conductive layer can also be used favorably as the conductive support of the present invention.

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

Hereinafter, each of the photosensitive layer having a laminated structure and the photosensitive layer having a single layer structure will be described.
<Photosensitive layer having a laminated structure>
(Charge generation layer)
The charge generation layer is a layer mainly composed of a charge generation material having a charge generation function, and a binder resin can be used in combination as necessary. As the charge generation material, inorganic materials and organic materials can be used.

Inorganic materials include crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compounds, and amorphous silicon. In amorphous silicon, dangling bonds that are terminated with hydrogen atoms or halogen atoms, or those that are doped with boron atoms, phosphorus atoms, or the like are preferably used.
On the other hand, a known material can be used as the organic material. For example, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azulenium salt pigments, squaric acid methine pigments, azo pigments having a carbazole skeleton, azo pigments having a triphenylamine skeleton, azo pigments having a diphenylamine skeleton, dibenzothiophene skeleton Azo pigments having a fluorenone skeleton, azo pigments having an oxadiazole skeleton, azo pigments having a bis-stilbene skeleton, azo pigments having a distyryl oxadiazole skeleton, azo pigments having a distyrylcarbazole skeleton, perylene Pigments, anthraquinone or polycyclic quinone pigments, quinoneimine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, Goido based pigments, and bisbenzimidazole pigments. These charge generation materials can be used alone or as a mixture of two or more.

  As a binder resin used as necessary for the charge generation layer, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-vinylcarbazole, Examples include polyacrylamide. These binder resins can be used alone or as a mixture of two or more. In addition to the binder resin described above as a binder resin for the charge generation layer, a polymer charge transport material having a charge transport function, such as an arylamine skeleton, benzidine skeleton, hydrazone skeleton, carbazole skeleton, stilbene skeleton, pyrazoline skeleton, etc. Polymer materials such as polycarbonate, polyester, polyurethane, polyether, polysiloxane, and acrylic resin, polymer materials having a polysilane skeleton, and the like can be used.

  Specific examples of the former include JP-A-01-001728, JP-A-01-009964, JP-A-01-013061, JP-A-01-019049, JP-A-01-241559, Japanese Unexamined Patent Publication Nos. 04-011627, 04-175337, 04-183719, 04-2225014, 04-230767, 04-320420, 05 -232727, JP-A 05-310904, JP-A 06-234836, JP-A 06-234837, JP-A 06-234838, JP-A 06-234839, JP-A 06-234840. No. 1, JP-A 06-234841, JP-A 06-239049, Japanese Unexamined Patent Publication Nos. 06-236050, 06-236051, 06-295077, 07-0756374, 08-176293, 08-208820, 08 No. -21640, JP 08-252868, JP 08-269183, JP 09-062019, JP 09-038883, JP 09-71642, JP 09-87376. JP-A 09-104746, JP-A 09-110974, JP-A 09-110976, JP-A 09-157378, JP-A 09-221544, JP-A 09-227669. JP-A 09-228367, JP-A 09-241369 Charge transporting polymer materials described in JP 09-268226 A, JP 09-272728 A, JP 09-302084 A, JP 09-302085 A, JP 09-328539 A, etc. Can be mentioned.

  Specific examples of the latter include polysilylene polymers described in, for example, JP-A No. 63-285552, JP-A No. 05-19497, JP-A No. 05-70595, JP-A No. 10-73944, and the like. Illustrated.

  The charge generation layer may contain a low molecular charge transport material. Low molecular charge transport materials that can be used in the charge generation layer include hole transport materials and electron transport materials.

  Examples of the electron transporting material include chloroanil, bromanyl, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-tri Examples thereof include electron-accepting substances such as nitrodibenzothiophene-5,5-dioxide and diphenoquinone derivatives. These electron transport materials can be used alone or as a mixture of two or more.

  Examples of the hole transporting material include the electron donating materials shown below and are used favorably. As hole transport materials, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triaryls Other known materials such as methane derivatives, 9-styrylanthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives, and the like can be given. These hole transport materials can be used alone or as a mixture of two or more.

Methods for forming the charge generation layer include a vacuum thin film preparation method and a casting method from a solution dispersion system.
As the former method, a vacuum deposition method, a glow discharge decomposition method, an ion plating method, a sputtering method, a reactive sputtering method, a CVD method, or the like is used, and the above-described inorganic materials and organic materials can be satisfactorily formed.

  In order to provide a charge generation layer by a casting method described later, the inorganic or organic charge generation material described above, together with a binder resin, if necessary, tetrahydrofuran, dioxane, dioxolane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, Formed by dispersing with a ball mill, attritor, sand mill, bead mill, etc. using a solvent such as cyclopentanone, anisole, xylene, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, etc. it can. Moreover, leveling agents, such as a dimethyl silicone oil and a methylphenyl silicone oil, can be added as needed. The coating can be performed using a dip coating method, spray coating, bead coating, ring coating method or the like.

  The thickness of the charge generation layer provided as described above is suitably about 0.01 to 5 μm, preferably 0.05 to 2 μm.

(About charge transport layer)
The charge transport layer is a layer having a charge transport function.
The charge transport layer is formed by dissolving or dispersing a charge transport material having a charge transport function and a binder resin in an appropriate solvent, and coating and drying the solution on the charge generation layer.
As the charge transport material, the electron transport material, hole transport material and polymer charge transport material described in the charge generation layer can be used.

  As the binder resin, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, Polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin And thermoplastic or thermosetting resins such as phenol resins and alkyd resins.

  The amount of the charge transport material is appropriately 20 to 300 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder resin. However, when a polymer charge transport material is used, it can be used alone or in combination with a binder resin.

  As the solvent used for the charge transport layer, the same solvent as that used for the charge generation layer can be used, but a solvent that dissolves the charge transport material and the binder resin well is suitable. These solvents may be used alone or in combination of two or more. The charge transport layer can be formed by the same coating method as that for the charge generation layer. If necessary, a plasticizer and a leveling agent can be added.

As a plasticizer that can be used in combination with the charge transport layer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is 0 with respect to 100 parts by weight of the binder resin. About 30 parts by weight is appropriate.
Leveling agents that can be used in combination with the charge transport layer include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, and polymers or oligomers having a perfluoroalkyl group in the side chain. The amount used is a binder resin. About 0 to 1 part by weight is appropriate for 100 parts by weight.
The thickness of the charge transport layer is suitably about 5 to 40 μm, preferably about 10 to 30 μm.

<Single photosensitive layer>
A photosensitive layer having a single layer structure is a layer having both a charge generation function and a charge transport function.
The photosensitive layer can be formed by dissolving or dispersing a charge generation material having a charge generation function, a charge transport material having a charge transport function, and a binder resin in an appropriate solvent, and applying and drying the solution. Moreover, a plasticizer, a leveling agent, etc. can also be added as needed. As the charge generation material dispersion method, the charge generation material, the charge transport material, the plasticizer, and the leveling agent may be the same as those already described in the charge generation layer and the charge transport layer. As the binder resin, in addition to the binder resin previously mentioned in the section of the charge transport layer, the binder resin mentioned in the charge generation layer may be mixed and used. In addition, the polymer charge transport materials mentioned above can also be used. The film thickness of the photosensitive layer is suitably about 5 to 30 μm, preferably about 10 to 25 μm.
The charge generation material contained in the photosensitive layer having a single layer structure is preferably 1 to 30% by weight based on the total amount of the photosensitive layer, the binder resin contained in the photosensitive layer is 20 to 80% by weight of the total amount, and the charge transport material is 10 to 70 parts by weight are preferably used.

<About the undercoat layer>
In the electrophotographic photoreceptor of the present invention, an undercoat layer can be provided between the conductive support and the photosensitive layer. In general, the undercoat layer is mainly composed of a resin. However, considering that the photosensitive layer is coated with a solvent on these resins, the resin may be a resin having high solvent resistance with respect to a general organic solvent. desirable. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. Further, a metal oxide fine powder pigment exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the undercoat layer in order to prevent moire and reduce residual potential.

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

<Addition of antioxidant to each layer>
In the present invention, in order to improve the environmental resistance, in order to prevent a decrease in sensitivity and an increase in residual potential, in particular, a crosslinked surface layer, a charge generation layer, a charge transport layer, an undercoat layer, an intermediate layer, etc. Antioxidants can be added to each layer.

The following are mentioned as antioxidant which can be used for this invention.
(Phenolic compounds)
2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (28-di-t-butyl-4-hydroxy Phenyl) propionate, 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4 ′ -Thiobis- (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis- (3-methyl-6-tert-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy) -5-tert-butylphenyl) butane, 1,28-trimethyl-2,4,6-tris (28-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- ( ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] clico- Luester, tocopherols, etc.
(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.
(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.
(Organic sulfur compounds)
Dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like.
(Organic phosphorus compounds)
Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine, and the like.

These compounds are known as antioxidants such as rubbers, plastics and fats and oils, and commercially available products can be easily obtained.
The addition amount of the antioxidant in the present invention is 0.01 to 10% by weight based on the total weight of the layer to be added.

<Image Forming Method and Apparatus>
Embodiments of an image forming apparatus to which the present invention is applied will be described below. However, these are just examples, and the present invention is not limited to these. FIG. 5 shows an example of an image forming apparatus having a configuration common to the embodiments described later. This image forming apparatus includes an electrophotographic photosensitive member made of an organic photosensitive member. The electrophotographic photosensitive member 1 has at least a photosensitive layer and a surface protective layer, and the surface protective layer is a film having a diamond-like carbon containing hydrogen or an amorphous carbon structure.

<About the overall configuration>
In FIG. 5, the electrophotographic photosensitive member 10 (10A) is rotationally driven by a driving device (not shown), and the surface thereof is charged to a predetermined polarity by a charging roller 21a of a charging device 21 of a proximity charging system. The surface of the charged electrophotographic photosensitive member 10 is exposed by the exposure device 22 to form an electrostatic latent image corresponding to the image information. This electrostatic latent image is developed with toner as a developer supplied from the developing device 23 to the surface of the electrophotographic photosensitive member 10 to be visualized as a toner image.

  On the other hand, a transfer sheet as a recording medium is fed toward the electrophotographic photosensitive member 10 from a paper supply unit (not shown). The toner image on the electrophotographic photosensitive member 10 is transferred onto the transfer paper by the transfer device 24 disposed opposite to the electrophotographic photosensitive member 10 on the transfer paper. The transfer paper on which the toner image has been transferred is separated from the electrophotographic photosensitive member 10 and then conveyed to the fixing device 25 along the transfer material conveyance path 29 to fix the toner image. Transfer residual toner as residual toner remaining on the electrophotographic photosensitive member 10 after the toner image is transferred to the transfer paper is removed from the electrophotographic photosensitive member 10 by the cleaning device 26. Further, the residual charge on the surface of the electrophotographic photosensitive member after the transfer residual toner is removed is removed by the static eliminator 28. In this way, the electrophotographic photoreceptor 10 is repeatedly used. In FIG. 5, reference numeral 27 denotes a cleaning blade.

  In the image forming apparatus according to the present embodiment, the electrophotographic photosensitive member, the charging member, the developing device, and the cleaning device are integrally configured as a process cartridge that is detachable from the image forming apparatus main body.

<About charging>
Next, the charging device 21 used in the image forming apparatus will be described. The charging device 21 charges the electrophotographic photosensitive member using proximity discharge. As a method of charging the electrophotographic photosensitive member using proximity discharge, a contact charging method in which a rotatable roller-shaped charging member (hereinafter referred to as a charging roller) 21a is placed in contact with the electrophotographic photosensitive member, and charging is performed. There is a non-contact charging method in which a roller is disposed in a non-contact manner on an electrophotographic photosensitive member. In this embodiment, a non-contact charging method is used.

  The present invention can also be applied to a contact charging method. However, in the contact charging method, it is preferable to use an elastic member that improves the contact property with the surface of the electrophotographic photosensitive member and does not apply mechanical stress to the electrophotographic photosensitive member. However, when an elastic member is used, the charging nip width is widened, which may cause the protective material to easily adhere to the charging roller side. Therefore, it is more advantageous to adopt a non-contact charging method for high durability. In the present embodiment, a non-contact charging method is employed in which the charging roller 21a is disposed so as to face at least an image forming area on the surface of the electrophotographic photosensitive member with a predetermined charging gap.

FIG. 6 is an explanatory diagram of the charging device 21 used in the image forming apparatus of the present embodiment.
The charging roller 61 includes a shaft portion 61a and a roller portion 61b. The roller portion 61b can be rotated by the rotation of the shaft portion 61a, and a portion of the surface of the electrophotographic photosensitive member 10 (10A) facing the image forming region 51 where an image is formed is not in contact with the electrophotographic photosensitive member 10. is there. The charging roller 61 is set to have a length in the longitudinal direction (axial direction) slightly longer than that of the image forming area 51, and spacers 62 are provided at both ends in the longitudinal direction. These two spacers are brought into contact with the non-image forming regions 52 at both ends of the surface of the electrophotographic photosensitive member, thereby forming a minute gap 54 between the electrophotographic photosensitive member 10 and the charging roller 61. The minute gap 54 is configured such that the distance at the closest portion between the charging roller 61 and the electrophotographic photosensitive member 10 can be maintained at 1 to 100 μm. A more preferable range of the gap 54 is 10 to 80 μm, and more preferably 30 to 65 μm. In the apparatus of this embodiment, the gap 54 is set to 50 μm. Further, the shaft portion 61a is pressed against the electrophotographic photosensitive member side by a pressing spring 55 made of a spring. Thereby, the minute gap 54 can be accurately maintained. Further, the charging roller 61 rotates along with the surface of the electrophotographic photosensitive member via the spacer 62.

  A charging power source 56 is connected to the charging roller 61. As a result, the surface of the electrophotographic photosensitive member is uniformly charged by proximity discharge in a minute gap between the surface of the electrophotographic photosensitive member and the surface of the charging roller. As the applied voltage, an AC voltage is superimposed on a DC voltage. When an alternating voltage obtained by superimposing an AC voltage on a DC voltage is used as the applied voltage, the effect of variations in charging potential due to minute gap fluctuations is suppressed, and uniform charging becomes possible. In this embodiment, an alternating voltage obtained by superimposing an AC voltage that is an AC component on a DC voltage that is a DC component is used.

  The charging roller 61 has a cored bar as a conductive support having a cylindrical shape and a resistance adjusting layer formed on the outer peripheral surface of the cored bar. The surface of the charging roller 61 is preferably hard. A rubber member can also be used as the roller member. However, if the member is easily deformed, such as a rubber member, it is difficult to maintain the minute gap 54 with the electrophotographic photosensitive member 10 uniformly. There is a possibility that only the central portion suddenly contacts the surface of the electrophotographic photosensitive member. The charging roller 61 is preferably a hard member with less deflection when the non-contact charging method is used.

  Specific examples of the charging roller 61 having a hard surface include, for example, a resistance adjustment layer, a thermoplastic resin composition in which a polymer ion conductive agent is dispersed (polyethylene, polypropylene, polymethyl methacrylate, polystyrene, and copolymers thereof) Etc.), and the surface of the resistance adjustment layer is treated with a curing film with a curing agent. The cured film treatment is performed, for example, by immersing the resistance adjustment layer in a treatment solution containing an isocyanate-containing compound, but may be performed by forming a cured treatment film layer on the surface of the resistance adjustment layer. In the present embodiment, the charging roller 61 is formed with a diameter of 10 mm (diameter 10 mm).

  As is apparent from the above description, the electrophotographic photosensitive member of the present invention can be used not only for electrophotographic copying machines but also for electrophotographic applications such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making. It can be widely used in the field.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, the technical scope of this invention is not limited at all by this. In the following, all “parts” are based on weight.
[Example 1]
An undercoat layer was formed on an Al support (outer diameter 30 mmφ) by dipping so that the film thickness after drying was 28 μm.

[Coating liquid for undercoat layer]
Alkyd resin 6 parts (Beckosol 1307-60-EL, manufactured by Dainippon Ink & Chemicals, Inc.)
Melamine resin 4 parts (Super Becamine G-821-60, manufactured by Dainippon Ink & Chemicals, Inc.)
Titanium oxide 40 parts (CR-EL: Ishihara Sangyo)
50 parts of methyl ethyl ketone On this undercoat layer, a charge generation layer coating solution containing a bisazo pigment having the following structure was dip coated and dried by heating to form a charge generation layer having a thickness of 0.2 μm.

[Coating liquid for charge generation layer]
2.5 parts of bisazo pigment having the structure shown in the following chemical formula (1)

Polyvinyl butyral (XYHL, manufactured by UCC) 0.5 part Cyclohexanone 200 parts Methyl ethyl ketone 80 parts

On this charge generation layer, dip coating was performed using a coating liquid for a charge transport layer having the following composition, followed by drying by heating to obtain a charge transport layer having a thickness of 22 μm.
[Coating liquid for charge transport layer]
10 parts of bisphenol Z type polycarbonate 10 parts of low molecular charge transport material having the structure shown in the following chemical formula (2)

Tetrahydrofuran 80 parts 1% silicone oil in tetrahydrofuran 0.2 parts (KF50, manufactured by Shin-Etsu Chemical Co., Ltd.)

  The organic photoreceptor thus formed was set in a plasma CVD apparatus as shown in FIG. 7, and a surface protective layer was further formed. Here, in FIG. 7, reference numeral 107 denotes a vacuum chamber of a plasma CVD apparatus, which is partitioned from a load / unload spare chamber 117 by a gate valve 109. The inside of the vacuum chamber 107 is evacuated by an exhaust system 120 (comprising a pressure adjusting valve 121, a turbo molecular pump 122, and a rotary pump 123), and is kept at a constant pressure.

  A reaction tank 150 is provided in the vacuum tank 107. This reaction tank has a frame-like structure 102 (having a square shape (FIG. 8) or a hexagonal shape (FIG. 9) as viewed from the electrode side) as shown in FIG. 8 or FIG. The hoods 108 and 118 are configured to cover the first and second electrodes 103 and 113 (a metal mesh such as aluminum) having the same shape and disposed on the hoods 108 and 118. Has been. Reference numeral 130 denotes a gas line to be introduced into the reaction tank 150. Various material gas containers are connected to each other, and are introduced into the reaction tank 150 from the nozzle 125 via the flowmeter 129, respectively.

  In the frame-like structure 102, supports 101 (101-1, 101-2,... 101-n) on which the photosensitive layer is formed are arranged as shown in FIG. In addition, each support body is arrange | positioned as a 3rd electrode so that it may mention later. For the electrodes 103 and 113, a pair of power sources 115 (115-1 and 115-2) for applying a first alternating voltage is prepared. The frequency of the first alternating voltage is 1 to 100 MHz. These power sources are connected to matching transformers 116-1 and 116-2, respectively. The phase in the matching transformer is adjusted by the phase adjuster 126 and can be supplied with a shift of 180 ° or 0 ° from each other. That is, it has a symmetrical or in-phase output. The one end 104 and the other end 114 of the match transformer are connected to the first and second electrodes 103 and 113, respectively. Further, the output-side midpoint 105 of the transformer is held at the ground level. Further, a second alternating voltage is applied between the midpoint 105 and the third electrode, that is, the support 101 (101-1, 101-2... 101-n) or the holder 102 electrically connected thereto. A power source 119 is provided. The frequency of the second alternating voltage is 1 to 500 kHz. The output of the first alternating voltage applied to the first and second electrodes is 0.1 to 1 kW at a frequency of 13.56 MHz, and the second alternating voltage applied to the third electrode, that is, the support. Is about 100 W for a frequency of 150 kHz.

  7 to 9, reference numeral 111 (111-1 to 111-n) is a third electrode, reference numeral 140 is an alternating power supply system, reference numeral 160 is a drum installation board, and reference numeral 170 is an electrode.

A surface protective layer was formed under the following conditions.
[Surface protection layer deposition conditions]
C ₂ H ₄ flow rate: 100 sccm
H ₂ flow rate: 200 sccm
Reaction pressure: 0.02 torr
First alternating voltage output: 100 W 13.56 MHz
Bias voltage (DC component): -150V
Film thickness: 0.8μm

[Example 2]
It was produced in the same manner as in Example 1 except that the thickness of the surface protective layer was 1.5 μm.

[Example 3]
The surface protective layer was produced in the same manner as in Example 1 except that the production conditions were as follows.
C ₂ H ₄ flow rate: 100 sccm
H ₂ flow rate: 150 sccm
N ₂ flow rate: 5 sccm
Reaction pressure: 0.03 torr
First alternating voltage output: 100 W 13.56 MHz
Bias voltage (DC component): -150V
Film thickness: 2.1μm

[Example 4]
The surface protective layer was produced in the same manner as in Example 1 except that the production conditions were as follows.
C ₂ H ₄ flow rate: 100 sccm
H ₂ flow rate: 150 sccm
N ₂ flow rate: 45sccm
Reaction pressure: 0.03 torr
First alternating voltage output: 100 W 13.56 MHz
Bias voltage (DC component): -150V
Film thickness: 2.1μm

[Example 5]
The surface protective layer was produced in the same manner as in Example 1 except that the production conditions were as follows.
C ₂ H ₄ flow rate: 100 sccm
H ₂ flow rate: 200 sccm
C ₂ F ₆ flow rate: 5 sccm
Reaction pressure: 0.01 torr
First alternating voltage output: 150 W 13.56 MHz
Bias voltage (DC component): -200V
Film thickness: 2.0μm

[Example 6]
The surface protective layer was produced in the same manner as in Example 1 except that the production conditions were as follows.
C ₂ H ₄ flow rate: 100 sccm
H ₂ flow rate: 200 sccm
C ₂ F ₆ flow rate: 50 sccm
Reaction pressure: 0.01 torr
First alternating voltage output: 150 W 13.56 MHz
Bias voltage (DC component): -200V
Film thickness: 2.0μm

[Example 7]
It was produced in the same manner as in Example 1 except that the surface protective layers 1 and 2 were formed on the charge transport layer under the following conditions.
[Surface protection layer 1 film-forming conditions]
C ₂ H ₄ flow rate: 100 sccm
H ₂ flow rate: 100 sccm
Reaction pressure: 0.02 torr
First alternating voltage output: 200W 13.56 MHz
Bias voltage (DC component): -200V
Film thickness: 0.2μm
[Surface protection layer 2 film-forming conditions]
C ₂ H ₄ flow rate: 100 sccm
H ₂ flow rate: 150 sccm
N ₂ flow rate: 45sccm
Reaction pressure: 0.03 torr
First alternating voltage output: 100 W 13.56 MHz
Bias voltage (DC component): -150V
Film thickness: 1.9 μm

[Example 8]
It was produced in the same manner as in Example 1 except that the surface protective layers 1 and 2 were formed on the charge transport layer under the following conditions.
[Surface protection layer 1 film-forming conditions]
C ₂ H ₄ flow rate: 100 sccm
H ₂ flow rate: 100 sccm
Reaction pressure: 0.02 torr
First alternating voltage output: 200W 13.56 MHz
Bias voltage (DC component): -200V
Film thickness: 0.2μm
[Surface protection layer 2 film-forming conditions]
C ₂ H ₄ flow rate: 100 sccm
H ₂ flow rate: 200 sccm
C ₂ F ₆ flow rate: 50 sccm
Reaction pressure: 0.03 torr
First alternating voltage output: 150 W 13.56 MHz
Bias voltage (DC component): -200V
Film thickness: 1.8μm

[Example 9]
It was produced in the same manner as in Example 1 except that after the surface protective layer 1 was formed on the charge transport layer, the film was formed while gradually changing the surface protective layer 2 to the conditions.
[Surface protection layer 1 film-forming conditions]
C ₂ H ₄ flow rate: 100 sccm
H ₂ flow rate: 100 sccm
Reaction pressure: 0.02 torr
First alternating voltage output: 200W 13.56 MHz
Bias voltage (DC component): -200V
Film thickness: 0.2μm
[Surface protection layer 2 film-forming conditions]
C ₂ H ₄ flow rate: 100 sccm
H ₂ flow rate: 150 sccm
N ₂ flow rate: 45sccm
Reaction pressure: 0.03 torr
First alternating voltage output: 100 W 13.56 MHz
Bias voltage (DC component): -150V
Film thickness: 1.9 μm

[Example 10]
It was produced in the same manner as in Example 1 except that after the surface protective layer 1 was formed on the charge transport layer, the film was formed while gradually changing the surface protective layer 2 to the conditions.
[Surface protection layer 1 film-forming conditions]
C ₂ H ₄ flow rate: 100 sccm
H ₂ flow rate: 100 sccm
Reaction pressure: 0.02 torr
First alternating voltage output: 200W 13.56 MHz
Bias voltage (DC component): -200V
Film thickness: 0.2μm
[Surface protection layer 2 film-forming conditions]
C ₂ H ₄ flow rate: 100 sccm
H ₂ flow rate: 200 sccm
C ₂ F ₆ flow rate: 50 sccm
Reaction pressure: 0.03 torr
First alternating voltage output: 150 W 13.56 MHz
Bias voltage (DC component): -200V
Film thickness: 1.8μm

[Example 11]
It was produced in the same manner as in Example 1 except that after the surface protective layer 1 was formed on the charge transport layer, the film was formed while gradually changing the surface protective layer 2 to the conditions.
[Surface protection layer 1 film-forming conditions]
C ₂ H ₄ flow rate: 100 sccm
H ₂ flow rate: 100 sccm
Reaction pressure: 0.02 torr
First alternating voltage output: 200W 13.56 MHz
Bias voltage (DC component): -200V
Film thickness: 0.2μm
[Surface protection layer 2 film-forming conditions]
C ₂ H ₄ flow rate: 100 sccm
H ₂ flow rate: 150 sccm
NF ₃ flow rate: 50 sccm
Reaction pressure: 0.02 torr
First alternating voltage output: 100 W 13.56 MHz
Bias voltage (DC component): -150V
Film thickness: 2.3 μm

[Comparative Example 1]
It was produced in the same manner as in Example 1 except that the surface protective layer was not provided.

[Comparative Example 2]
Prepared in the same manner as in Example 1 except that the above-described charge transport layer was spray-coated using a coating liquid having the following composition, dried by heating at 150 ° C. to form a surface protective layer having a thickness of 2.5 μm. did.
[Coating liquid for surface protective layer]
Isocyanate (Takenate D140N <IPDI adduct>: Mitsui Takeda Chemical Co., Ltd.)
Polyol (polyol having a structure represented by the following chemical formula (3): molecular weight 334.16)
Isocyanate + polyol 10 parts (NCO / OH ratio: 1.0)

Acetone 40 parts Cellosolve acetate 40 parts Methyl isobutyl ketone 10 parts

[Comparative Example 3]
The charge transport layer is spray-coated using a coating liquid having the following composition, irradiated with light under the conditions of a metal halide lamp, irradiation light intensity: 700 mW / cm ² , irradiation time: 120 seconds, and further at 130 ° C. for 30 It was produced in the same manner as Example 1 except that partial drying was applied to form a surface protective layer with a film thickness of 2.1 μm.

[Surface protective layer coating solution]
(1) Trifunctional or higher-functional radical polymerizable monomer having no charge transporting property 10 parts Trimethylolpropane acrylate lot (KAYARAD TMPTA, manufactured by Nippon Kayaku)
(2) Photopolymerization initiator 1 part 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals)
(3) 80 parts of tetrahydrofuran

[XPS analysis]
The surface protective layers of Examples 1 to 11 were subjected to XPS analysis (X-ray photoelectron spectroscopy), and the atomic weight ratio of nitrogen to carbon and the atomic ratio of fluorine to carbon were determined. The results are shown in Tables 1 and 2 below.

[Actual paper feeding test]
Using the Ricoh IPSiO Color CX8200 equipped with a charger that applies a voltage in which the alternating current component is superimposed on the direct current component, the produced electrophotographic photosensitive member was tested for 300,000 actual papers (A4, My Paper made by NBS Ricoh). The charging potential at start-650 V) was carried out, and the wear characteristics and the in-machine potential were evaluated. The results are shown in Tables 3 and 4 below.

From the results of Tables 3 and 4, the following can be understood.
(1) In Examples 1 to 11 of the present invention, high durability and high performance electrons having higher wear resistance than Comparative Examples 1 to 3, less photoconductor deterioration due to charging, and good electrical characteristics. A photographic photoreceptor was obtained.
(2) Among Examples 1 to 11 of the present invention, the electrophotographic photoreceptors of Examples 9 to 11 exhibit particularly excellent wear resistance and electrical characteristics.
Therefore, a high-performance and highly reliable image forming process, image forming apparatus, and process cartridge for an image forming apparatus capable of forming a good image over a long period of time by using the electrophotographic photosensitive member according to the present invention. It can be provided.

3 is a graph showing a change in film thickness due to a charging load in an electrophotographic photosensitive member. FIG. 4 is an explanatory diagram showing the state of the electrophotographic photosensitive member surface when the surface of the electrophotographic photosensitive member deteriorates due to proximity discharge, in which the charging roller is opposed to the electrophotographic photosensitive member surface with a minute gap. FIG. 3 is a schematic cross-sectional view showing an example of a layer configuration of the electrophotographic photosensitive member according to the present invention. It is a schematic cross section which shows another example of the layer structure of the electrophotographic photoreceptor which concerns on this invention. It is explanatory drawing which shows an example of the image forming apparatus which concerns on this invention. It is explanatory drawing which shows an example of the charging device which concerns on this invention. It is explanatory drawing which shows the specific example of a plasma CVD apparatus used when forming the protective layer which consists of the diamond-like carbon containing hydrogen, or an amorphous carbon structure. It is a top view which shows the frame-shaped structure of the plasma CVD apparatus of FIG. It is a top view which shows the frame-shaped structure of another plasma CVD apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Electrophotographic photoreceptor 10A Electrophotographic photoreceptor 11 Conductive support 12 Photosensitive layer 12a Charge generation layer 12b Charge transport layer 13 Surface protective layer 21 Charging device 21a Charging roller 22 Exposure device 23 Developing device 24 Transfer device 25 Fixing device 26 Cleaning Device 27 Cleaning blade 28 Static elimination device 29 Transfer material conveyance path 51 Image forming region 52 Non-image forming region 54 Minute gap 55 Pressure spring 56 Power source 61 Charging roller 61a Shaft portion 61b Roller portion 62 Spacer 81 Electrophotographic photosensitive member 81a Charge transport Layer 82a Charging roller 101, 101-1 to 101-n Support body 102 Frame-shaped structure 103 First electrode 104 Matching transformer end 105 Output side midpoint 107 Vacuum tank 108 Hood 109 Gate valve 111, 111-1 111-nth Electrode 113 second electrode 114 matching transformer end 115, 115-1, 115-2 power source 116-1, 116-2 matching transformer 117 load / unload spare chamber 118 hood 119 power source 120 exhaust system 121 adjustment valve 122 turbo molecular pump 123 rotary pump 125 nozzle 126 phase adjuster 129 flow meter 130-134 gas line 140 alternating power system 150 reaction tank 160 drum installation substrate 170 power supply

Claims (25)

At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In the electrophotographic photosensitive member provided in an image forming apparatus having a container,
An electrophotographic photosensitive film comprising at least a photosensitive layer and a surface protective layer in this order on a conductive support, wherein the surface protective layer is a film containing diamond-like carbon containing hydrogen or an amorphous carbon structure. body. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In the electrophotographic photosensitive member provided in an image forming apparatus having a container,
An electron having at least a photosensitive layer and a surface protective layer in this order on a conductive support, wherein the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen Photoconductor. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In the electrophotographic photosensitive member provided in an image forming apparatus having a container,
An electron having at least a photosensitive layer and a surface protective layer in this order on a conductive support, wherein the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. Photoconductor. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In the electrophotographic photosensitive member provided in an image forming apparatus having a container,
It has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen, and further, nitrogen with respect to carbon An electrophotographic photosensitive member characterized by being a film having a content atomic weight ratio (N / C ratio) of 0.05 or more. Provided at least in contact with or in proximity to the electrophotographic photosensitive member,
A charger that charges the electrophotographic photosensitive member using a discharge generated by applying a voltage in which the alternating current component is superimposed on the direct current component, and forms an electrostatic latent image on the surface of the electrophotographic photosensitive member that is charged by the charger. In the electrophotographic photosensitive member provided in an image forming apparatus having a latent image forming device and a developing device for attaching toner to an image portion of an electrostatic latent image formed by the latent image forming device,
It has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine, and further fluorine with respect to carbon. An electrophotographic photosensitive member characterized by being a film having a content atomic weight ratio (F / C ratio) of 0.005 or more. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In the electrophotographic photosensitive member provided in an image forming apparatus having a container,
It has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen, and further, nitrogen with respect to carbon An electrophotographic photosensitive member characterized in that the content atomic ratio (N / C ratio) is a film in the vicinity of the outermost layer larger than that in the vicinity of the photosensitive layer of the surface protective layer. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In the electrophotographic photosensitive member provided in an image forming apparatus having a container,
It has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine, and further fluorine with respect to carbon. An electrophotographic photosensitive member characterized in that the content atomic ratio (F / C ratio) is a film in the vicinity of the outermost layer, which is larger than that in the vicinity of the photosensitive layer in the surface protective layer. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In the electrophotographic photosensitive member provided in an image forming apparatus having a container,
It has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen, and further, nitrogen with respect to carbon An electrophotographic photosensitive member characterized in that the content atomic weight ratio (N / C ratio) is 0.005 or less in the vicinity of the photosensitive layer of the surface protective layer and 0.05 or more in the vicinity of the outermost layer. . At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In the electrophotographic photosensitive member provided in an image forming apparatus having a container,
It has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine, and further fluorine with respect to carbon. An electrophotographic photosensitive member characterized in that the content atomic weight ratio (F / C ratio) is 0.001 or less in the vicinity of the photosensitive layer of the surface protective layer and 0.005 or more in the vicinity of the outermost layer. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In the electrophotographic photosensitive member provided in an image forming apparatus having a container,
It has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen, and further, nitrogen with respect to carbon It is characterized in that the content atomic ratio (N / C ratio) is larger in the vicinity of the outermost layer than in the vicinity of the photosensitive layer of the surface protective layer, and the N / C ratio is a concentration gradient gradually. Electrophotographic photoreceptor. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In the electrophotographic photosensitive member provided in an image forming apparatus having a container,
It has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine, and further fluorine with respect to carbon. The content atomic weight ratio (F / C ratio) is larger in the vicinity of the outermost layer than in the vicinity of the photosensitive layer of the surface protective layer, and the F / C ratio is a film whose concentration is gradually inclined. Electrophotographic photoreceptor. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In an image forming apparatus having a container,
The electrophotographic photoreceptor has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film containing diamond-like carbon containing hydrogen or an amorphous carbon structure. An image forming apparatus. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In the image forming apparatus having a container, the electrophotographic photosensitive member has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer contains diamond-like carbon or amorphous material containing hydrogen and nitrogen. An image forming apparatus comprising a film having a carbon structure. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In an image forming apparatus having a container,
The electrophotographic photoreceptor has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. An image forming apparatus. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In an image forming apparatus having a container,
The electrophotographic photoreceptor has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen. Furthermore, the image forming apparatus is characterized in that the atomic ratio (N / C ratio) of nitrogen to carbon is 0.05 or more. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In an image forming apparatus having a container,
The electrophotographic photoreceptor has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. Furthermore, the image forming apparatus is characterized in that the film has a fluorine-to-carbon content atomic ratio (F / C ratio) of 0.005 or more. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In an image forming apparatus having a container,
The electrophotographic photoreceptor has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen. Further, the image forming apparatus is characterized in that the atomic ratio (N / C ratio) of nitrogen to carbon is larger in the vicinity of the outermost layer than in the vicinity of the photosensitive layer of the surface protective layer. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In an image forming apparatus having a container,
The electrophotographic photoreceptor has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. Further, the image forming apparatus is characterized in that the atomic ratio of fluorine to carbon (F / C ratio) is larger in the vicinity of the outermost layer than in the vicinity of the photosensitive layer of the surface protective layer. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In an image forming apparatus having a container,
The electrophotographic photoreceptor has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen. Further, the atomic ratio of nitrogen to carbon (N / C ratio) is 0.005 or less in the vicinity of the photosensitive layer of the surface protective layer, and 0.05 or more in the vicinity of the outermost layer. Image forming apparatus. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In an image forming apparatus having a container,
The electrophotographic photoreceptor has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. Furthermore, the atomic ratio of fluorine to carbon (F / C ratio) is 0.001 or less near the photosensitive layer in the vicinity of the surface protective layer and 0.005 or more near the outermost layer. Image forming apparatus. At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In an image forming apparatus having a container,
The electrophotographic photoreceptor has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and nitrogen. Furthermore, the ratio of the atomic content of nitrogen to carbon (N / C ratio) is greater in the vicinity of the outermost layer than in the vicinity of the photosensitive layer of the surface protective layer, and the N / C ratio is a concentration gradient. An image forming apparatus, comprising: At least an electrophotographic photosensitive member and a charge that is provided in contact with or close to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. , A latent image forming device for forming an electrostatic latent image on the surface of the electrophotographic photosensitive member charged by the charging device, and development for attaching toner to an image portion of the electrostatic latent image formed by the latent image forming device. In an image forming apparatus having a container,
The electrophotographic photoreceptor has at least a photosensitive layer and a surface protective layer in this order on a conductive support, and the surface protective layer is a film having a diamond-like carbon or amorphous carbon structure containing hydrogen and fluorine. Furthermore, the ratio of the atomic content of fluorine to carbon (F / C ratio) is larger in the vicinity of the outermost layer than in the vicinity of the photosensitive layer of the surface protective layer, and the F / C ratio is a concentration gradient gradually. An image forming apparatus, comprising:   The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer has a structure in which a charge generation layer, a charge transport layer, and a surface protective layer are laminated in this order. In a process cartridge that integrally supports an electrophotographic photosensitive member and at least one means selected from a charging unit, a developing unit, and a cleaning unit that cleans the surface of the electrophotographic photosensitive member, and is detachable from an image forming apparatus main body. ,
A process cartridge, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 1 to 11 or claim 23. A charger that is provided in contact with or in proximity to the electrophotographic photosensitive member and charges the electrophotographic photosensitive member by using a discharge generated by applying a voltage in which an alternating current component is superimposed on a direct current component. An image forming method using the electrophotographic photosensitive member according to any one of claims 11 to 23.

Images