JP6171757B2 - Electrophotographic photosensitive member, process cartridge, and image forming apparatus - Google Patents

Description

  The present invention relates to an electrophotographic photosensitive member such as a copying machine, a laser printer, and a normal facsimile, a process cartridge, and an image forming apparatus.

  In recent years, from the viewpoints of saving office space, expanding business opportunities, etc., high speed, downsizing, colorization, high image quality, and easy maintenance have been desired for electrophotographic apparatuses. These are regarded as problems to be solved by developing an electrophotographic photosensitive member because they are related to improvement in characteristics and durability of the electrophotographic photosensitive member. From the viewpoint of improving ease of maintenance, there is a reduction in the replacement frequency of the electrophotographic photosensitive member. This is to reduce image defects derived from the electrophotographic photosensitive member as much as possible over a long period of time, which is nothing but a longer life of the electrophotographic photosensitive member. In addition, in recent years, there have been many reports on development relating to extending the life of electrophotographic photosensitive members because they are related to the improvement of the image quality of output images over a long period of time.

In order to achieve a long life of the electrophotographic photosensitive member, it is an important issue to improve durability against various hazards that the electrophotographic photosensitive member receives from the image forming process. The hazards mentioned here can be broadly divided into two types: mechanical hazards and chemical hazards.
An example of the mechanical hazard is derived from blade cleaning, which is one of means for removing toner remaining on the electrophotographic photosensitive member after transfer of the image forming process (so-called toner cleaning process). Blade cleaning is a means for forcibly removing toner from the electrophotographic photosensitive member by contacting an elastic member (so-called cleaning blade) on the photosensitive member, and has a large toner removing ability in a small space. This is very effective for miniaturization of an electrophotographic apparatus. However, on the other hand, since the elastic member is brought into direct contact with the electrophotographic photosensitive member and rubbed, the mechanical stress on the electrophotographic photosensitive member is very large, and the layer disposed on the outermost surface of the photosensitive member is worn away. The demerit that it is easy is pointed out. For this reason, in an electrophotographic apparatus to which the present cleaning method is applied, wear of the electrophotographic photosensitive member is often a problem for extending the life, and a technique for laminating a high-hardness protective layer is proposed for this problem. (See Patent Documents 1 to 5).

Next, the chemical hazard will be described. In a normal image forming process, an electric charge is applied to the surface of the electrophotographic photosensitive member, and after charging to a predetermined potential, the electric charge applied to the surface via the photosensitive member is removed by exposure to the electrophotographic photosensitive member. At this time, electrostatic stress is applied to the electrophotographic photosensitive member as charges pass through the layers (for example, the surface layer, the charge generation layer, the charge transport layer, and the intermediate layer) of the electrophotographic photosensitive member. Currently, the most widely used electrophotographic photoreceptors are composed of organic materials, and in the current electrophotographic processes in which repeated charging and discharging are repeated, the organics constituting the electrophotographic photoreceptor are included. The material gradually changes in quality due to electrostatic hazards, resulting in the deterioration of electrophotographic characteristics such as the generation of charge traps in the layer and changes in chargeability and light attenuation.
In addition, it is known that acidic gas such as ozone and nitrogen oxide is generated in the vicinity of the charger when an electric charge is applied to the surface of the electrophotographic photosensitive member in the charging process (see Non-Patent Document 6). The photoreceptor is exposed to these acidic gases. Many electrophotographic photoreceptors contain charge transporting materials such as hole transporting materials and electron transporting materials. Depending on the electron donating and accepting properties of these materials and their content in the photosensitive layer, electrophotography is possible. The charge transport function of the photoreceptor is determined. However, many of these materials are known to have a property of being easily altered by acid gas (see Non-Patent Document 7), and the amount of charge transport lumber is oxidized and deteriorated by the acid gas generated in the charging process as described above. Photoconductor characteristics such as the charge transport function change. In the case of using a short-life electrophotographic photosensitive member, the deterioration due to the acid gas is often only the outermost layer of the electrophotographic photosensitive member, and the deterioration component remains in a small amount, causing a large deterioration in the characteristics of the electrophotographic photosensitive member. However, in the case of using a long-life electrophotographic photosensitive member, deterioration due to an acid gas may reach the inside of the electrophotographic photosensitive member, and since there are many deterioration components inside the electrophotographic photosensitive member, Such deterioration of the characteristics of the electrophotographic photosensitive member becomes large. As a result, it is known that the output image has a great influence on the image quality, and causes serious problems such as a decrease in image density, background contamination, and image homogeneity during continuous output.

In order to improve the resistance of the electrophotographic photosensitive member against such chemical hazards, an antioxidant is added to the charge transport layer and the surface layer to reduce the deterioration of the constituent components that greatly contribute to the determination of the characteristics of the electrophotographic photosensitive member. The technique to suppress is proposed (refer patent document 6). In addition, in order to suppress the penetration of acidic gas to the inside of the charge transport layer and the surface layer, and to make the component that oxidizes and deteriorates part of the surface, a technology to reduce the gas permeability of these layers is proposed (See Patent Documents 7 and 8). Further, as a technique for suppressing the oxidative degradation of the electrophotographic photosensitive member itself by an electrophotographic system, for example, a charging technique that generates less discharge products as a charging process has been proposed (see Patent Documents 9 and 10). By applying this charging method to the charging process in the image forming process, it is possible to suppress deterioration of the characteristics of the electrophotographic photosensitive member caused by the discharge product.
However, even when these technologies are used, since there is a relatively large amount of components that cause oxidative degradation inside the electrophotographic photosensitive member, this is not an essential improvement and can be used for long-term use. In such a case, the characteristics of the electrophotographic photosensitive member are gradually changed due to the oxidative deterioration of the constituent components typified by the charge transporting material, and the image quality cannot be maintained over a long period of time. There is.

In addition, a technique has been proposed in which inorganic fine particles are dispersed in the surface layer, and the film resistance is varied depending on the electric field strength (see Patent Document 11). In this technique, the resistance value is maintained at 10 ¹⁴ Ω · cm or more in a relatively high electric field of 1 × 10 ⁵ V / cm, and the resistance of the surface layer is reduced in a high electric field of 2 × 10 ⁵ V / cm. It is disclosed that a good charge transport property and a clear image can be obtained. However, if the resistance value at 1 × 10 ⁵ V / cm is 1 × 10 ¹⁴ Ω · cm or more, sufficient charge transportability cannot be obtained, and the residual potential of the electrophotographic photosensitive member becomes high. As a result, there is a problem that it is impossible to obtain an electrophotographic photosensitive member capable of obtaining high gradation. In addition, in order to obtain the above-described resistance value in the content (10% by mass to 40% by mass) of the inorganic fine particles described in the present invention, it is necessary to use relatively high-resistance inorganic fine particles. There is a problem that the limiting current is likely to be dominant conduction due to the lack of bulk conductivity in the fine particles, and the residual potential rises remarkably in continuous use. Furthermore, since the electrophotographic photosensitive member described in Patent Document 11 has high wear durability and the surface is difficult to be refreshed, in actual use, ions derived from acid gas generated on the outermost surface of the electrophotographic photosensitive member by a charging process or the like. When the substance absorbs moisture, the outermost surface of the photoconductor tends to have a resistance drop, and it is difficult to obtain a desired electrostatic latent image.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention provides an electrophotographic photoreceptor having a surface layer exhibiting excellent electrophotographic photoreceptor characteristics without reducing or using as much as possible the content of a charge transporting material that is easily altered by an acidic gas. In addition, there is very little oxidative degradation due to long-term use of the photoconductor, and in addition, it contributes to the output image quality of the image forming apparatus by suppressing deterioration of image sharpness due to acidic substances deposited on the outermost surface of the electrophotographic photoconductor An object of the present invention is to provide an electrophotographic photosensitive member with few defects and capable of maintaining excellent image quality over a long period of time.

The electrophotographic photosensitive member of the present invention as means for solving the above problems is an electrophotographic photosensitive member having a conductive support and at least a photosensitive layer and a surface layer in this order on the conductive support. ,
The surface layer contains inorganic fine particles and at least one compound selected from compounds represented by the following general formulas (1), (2), and (3),
The inorganic fine particles are zinc oxide fine particles doped with a Group 13 element;
The surface resistivity R ₁ when the electric field strength in the surface layer is 1 × 10 ⁴ V / cm is 1 × 10 ¹³ Ω / cm ² or more,
And the surface resistivity _{R 1,} the ratio of the surface resistivity _{R 15} when the electric field intensity at the surface layer is _{^{1.5 × 10 5 V / cm (}} R 1 / R 15) is 100 to 5 , 000.

<General formula (1)>
In the general formula (1), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. Ar ₁ represents a substituted or unsubstituted aromatic ring group.

<General formula (2)>
However, In the general formula (2), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. m and n represent an integer of 0 to 3, and m and n are not 0 at the same time. R ₄ and R _{5 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 11 carbon atoms, and a substituted or unsubstituted aromatic ring group, and these may be the same or different. Good. Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic ring group, and these may be the same or different.

<General formula (3)>
In the general formula (3), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic ring group. l and m represent an integer of 0 to 3, and l and m are not 0 at the same time. n represents an integer of 1 to 3.

  According to the present invention, the conventional problems can be solved, the object can be achieved, and the content of the charge transporting material that is easily denatured by acid gas is reduced or used as much as possible. An electrophotographic photosensitive member having a surface layer exhibiting electrophotographic photosensitive member characteristics can be obtained, and there is very little oxidative deterioration due to long-term use of the photosensitive member, and in addition, an acidic substance deposited on the outermost surface of the electrophotographic photosensitive member. An object of the present invention is to provide an electrophotographic photosensitive member capable of maintaining excellent image quality over a long period of time with few defects related to the output image quality of an image forming apparatus by suppressing a reduction in image sharpness.

FIG. 1 is a measurement circuit diagram in the method for measuring the surface resistivity of the electrophotographic photosensitive member. FIG. 2 is a schematic view showing an example of the layer structure of the electrophotographic photosensitive member of the present invention. FIG. 3 is a schematic view showing an example of the layer structure of the electrophotographic photosensitive member of the present invention. FIG. 4 is a schematic view showing an example of the layer structure of the electrophotographic photosensitive member of the present invention. FIG. 5 is a schematic view showing an example of the layer structure of the electrophotographic photosensitive member of the present invention. FIG. 6 is a schematic view showing an example of the image forming apparatus of the present invention. FIG. 7 is a schematic view showing an example of the process cartridge of the present invention.

(Electrophotographic photoreceptor)
The electrophotographic photosensitive member of the present invention has at least a photosensitive layer and a surface layer in this order on a conductive support and the conductive support, and further has other layers as necessary. .

  In the present invention, in order to achieve a long life of the electrophotographic photosensitive member, it is important to impart durability to various hazards received from each process in image formation as described above. In particular, there are two hazards: a cleaning process for removing the toner remaining on the surface of the electrophotographic photosensitive member, a mechanical hazard applied by rubbing at the developing unit, and a chemical hazard received from the charging process and the transfer process. It is considered to be a factor that imposes great stress on the body, changes the characteristics of the photoreceptor, and is an impeding factor for extending the life of the photoreceptor. Among these, in the present invention, it relates to an improvement in durability against chemical hazards. More specifically, it is possible to suppress deterioration or deterioration of constituent components near the surface of the electrophotographic photosensitive member even when used for a long period of time. The present invention relates to a technique for suppressing deterioration in image sharpness mainly caused by deposition of an ionic substance derived from an acidic gas in a charging process or the like, which is less likely to cause deterioration in photoreceptor characteristics.

As described above, it is considered that the deterioration of the characteristics of the electrophotographic photosensitive member due to repeated use is mainly caused by deterioration of constituent components due to electrical and chemical hazards in the electrophotographic process. In particular, it is expected that the characteristics of the electrophotographic photosensitive member will be significantly deteriorated when deterioration of the constituent components having a large contribution to the chargeability and charge transporting property of the electrophotographic photosensitive member occurs. It is important to suppress the deterioration of the characteristics of the electrophotographic photosensitive member that the components that contribute greatly are electrostatically and chemically stable.
In general, examples of the material having a large contribution to the chargeability and charge transportability of the electrophotographic photoreceptor include charge transport materials. It is no exaggeration to say that the properties of many electrophotographic photoreceptors are determined by the function of the material, and therefore contain a relatively large amount of charge transport material. While the material has charge transport properties, it is characterized by being easily deteriorated in an acidic gas and alkaline gas atmosphere. Deterioration easily occurs due to gas and alkaline gas, and as a result, the characteristics of the electrophotographic photoreceptor are deteriorated. Many means such as addition of an antioxidant, a light stabilizer, etc. to the photosensitive layer or surface layer of the electrophotographic photosensitive member have been studied in order to exhibit excellent electrophotographic photosensitive member characteristics while suppressing this material deterioration. In addition, by repeating the prescription design, an electrophotographic photosensitive member with little deterioration in characteristics even after long-term use is put to practical use, and a relatively high effect is exhibited. However, it is obvious that the material deteriorated by acid gas and alkaline gas is contained in the electrophotographic photosensitive member, and the characteristic deterioration is gradually caused by long-term use. The side effect caused by this improvement means is another problem. At present, it does not lead to substantial improvement.

  In addition, the electrophotographic process often employs a process in which the electrophotographic photosensitive member is charged by discharging in the charging process, and when this process is repeatedly applied to the electrophotographic photosensitive member, the surface of the electrophotographic photosensitive member is charged. There may be a phenomenon that an ionic substance derived from an acid gas formed during the process is deposited. The substance oxidizes and deteriorates the outermost surface of the electrophotographic photosensitive member, and when the substance absorbs moisture, an extremely thin layer having high ion conductivity is formed. It may cause image quality deterioration that does not originate, and in particular, in an electrophotographic photoreceptor excellent in wear durability, the deposited ionic substance is difficult to be removed and thus is easily manifested.

As a result of intensive studies by the present inventors to achieve the above-mentioned problems, an electrophotographic photoreceptor having at least a photosensitive layer and a surface layer in this order on a conductive support and the conductive support,
The surface layer contains inorganic fine particles and at least one compound selected from compounds represented by the following general formulas (1), (2), and (3),
The inorganic fine particles are zinc oxide doped with a Group 13 element;
The surface resistivity R ₁ when the electric field strength in the surface layer is 1 × 10 ⁴ V / cm is 1 × 10 ¹³ Ω / cm ² or more,
And the surface resistivity _{R 1,} the ratio of the surface resistivity _{R 15} when the electric field intensity at the surface layer is _{^{1.5 × 10 5 V / cm (}} R 1 / R 15) is 100 to 5 Even when the charge transporting material that easily deteriorates by repeated use as described above is reduced as much as possible, it has excellent chargeability and charge transportability and is stable over a long period of time. It has been found that an electrophotographic photoreceptor having characteristics can be obtained.

  In the present invention, the constituents mainly used (inorganic fine particles and resins not having a charge transporting structure) are generally robust against oxidation / reduction of acidic gas / alkaline gas and the like, and the following general formulas (1), (2 ) And at least one compound selected from the compounds represented by (3) renders the ionic substance deposited on the outermost surface of the electrophotographic photoreceptor harmless and also exhibits a charge transport function in the surface layer. Therefore, it is an electrophotographic photoreceptor that exhibits outstanding effects on electrostatic characteristics, has very few components that deteriorate even after long-term use, and can reduce the effects of ionic substance deposition. Therefore, an excellent output image can be obtained over a long period of time.

<General formula (1)>
In the general formula (1), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. Ar ₁ represents a substituted or unsubstituted aromatic ring group.

<General formula (2)>
However, In the general formula (2), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. m and n represent an integer of 0 to 3, and m and n are not 0 at the same time. R ₄ and R _{5 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 11 carbon atoms, and a substituted or unsubstituted aromatic ring group, and these may be the same or different. Good. Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic ring group, and these may be the same or different.

<General formula (3)>
In the general formula (3), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic ring group. l and m represent an integer of 0 to 3, and l and m are not 0 at the same time. n represents an integer of 1 to 3.

In the present invention, even when the charge transport material of the surface layer is reduced as much as possible, in order to provide excellent electrophotographic photoreceptor characteristics, “chargeability”, “ It is important to provide “charge transportability” and “latent image maintenance”. With regard to “chargeability”, it is possible to give the photosensitive layer as an alternative function. Therefore, “charge transportability” and “latent image maintenance” are particularly important as functions required for the surface layer having the above structure. Considered a requirement.
In order to obtain an electrophotographic photosensitive member having sufficient functions even when the charge transport material of the surface layer is reduced as much as possible, the present inventor exhibits a high resistance in a low electric field, a medium electric field to a high electric field. Ascertaining that it is important to show low resistance in the electric field, the present invention has been completed.

First, the electrical characteristics of the electrophotographic photosensitive member of the present invention having a surface layer excellent in latent image maintenance will be described.
In order to obtain an electrophotographic photoreceptor excellent in latent image maintenance, it is important to suppress the deterioration of the electrophotographic photoreceptor and reduce the influence of ionic substances deposited on the outermost surface of the electrophotographic photoreceptor. Regarding the suppression of deterioration of the electrophotographic photosensitive member, the surface resistivity of the electrophotographic photosensitive member at 1 × 10 ⁴ V / cm or more and 3 × 10 ⁴ V / cm or less is 1 × 10 ¹³ Ω / cm ² or more, preferably It was found from various experiments that excellent latent image maintenance is exhibited at 1 × 10 ¹⁴ Ω / cm ² or more. In the surface layer according to the present invention, it is considered that the electric field having a large contribution to the latent image maintenance is derived from the vicinity of the electric field strength, and by making the resistance relatively high in this electric field strength range, It seems that it is possible to inhibit the charge transfer and to improve the latent image maintenance. When the electric field strength is 1 × 10 ⁴ V / cm and is less than 1 × 10 ¹³ Ω / cm ² , the latent image maintaining property is not sufficient, and dot thinning and image blurring of the output image occur.

Furthermore, it is preferable resistance variation is small in the field strength range, in particular the surface resistivity _{R 3} in 1 × ¹⁰ 4 surface resistivity in V / cm _{R 1} and 3 × ¹⁰ 4 V / cm The ratio (R ₁ / R ₃ ) is preferably from 0.1 to 10, and more preferably from 0.1 to 2. If the ratio (R ₁ / R ₃ ) is less than 0.1, there is a concern that the charge transporting property described later is lowered and the residual potential is increased. On the other hand, when the ratio R ₁ / R ₃ exceeds 10, the latent image maintenance property is not sufficient, and the dots of the output image may be thinned, which is not preferable. Regarding the reduction of the influence of ionic substances deposited on the outermost surface of the electrophotographic photoreceptor, it has become clear from various studies that additives such as antioxidants that render the deposited ionic substances harmless are effective, In particular, at least one compound selected from the compounds represented by the general formulas (1), (2), and (3) that hardly deteriorates the charge transport property of the electrophotographic photosensitive member is contained, and the latent image maintaining property is contained. Was found to be extremely effective.

Next, the electrical characteristics of the electrophotographic photoreceptor having a surface layer excellent in charge transportability will be described. The present inventor also shows excellent charge transport properties by sufficiently reducing the surface resistivity at 1.5 × 10 ⁵ V / cm compared to the surface resistivity of 1 × 10 ⁴ V / cm. It became clear from the examination. In the surface layer described in the present invention, it is considered that the electric field strength that greatly contributes to the charge transport function is derived from the range of 1.5 × 10 ⁵ V / cm or more. It seems that smooth charge transport is promoted by using a relatively high resistance. Specifically, the ratio of 1 × ¹⁰ 4 V / cm surface resistivity _{R 1} and the surface resistivity _{R 15} at 1.5 × ¹⁰ 5 V / cm of _(R 1 _{/ R 15)} is 100 5,000, preferably 100 to 1,000. If the ratio (R ₁ / R ₁₅ ) is less than 100, the surface layer has insufficient charge transport properties, and image defects may occur due to an increase in residual potential. On the other hand, if the ratio (R ₁ / R ₁₅ ) exceeds 5,000, it is considered that the electrophotographic photosensitive member is insufficiently charged, and there are concerns such as the occurrence of background stains and a decrease in gradation. Therefore, it is not preferable.

<< Method for measuring surface resistivity of electrophotographic photosensitive member >>
Here, a method for measuring the surface resistivity of the electrophotographic photosensitive member will be described.
The surface specific resistivity of the electrophotographic photosensitive member may be measured by a generally known method, for example, in accordance with JIS-C2139: 2008 (Solid Electrical Insulating Material—Measurement Method of Volume Resistivity and Surface Resistivity) The method of measuring by doing. In general, many electrophotographic photoreceptors have a cylinder shape, and when measurement is difficult by the method of the above-mentioned literature, the measurement may be performed by the following method.

-Electrode shape and manufacturing method-
The electrode shape has a known length and is a counter electrode having a known gap. The electrode length is preferably 10 mm or more and 30 mm or less, and the electrode gap is preferably 25 μm or more and 100 μm or less. The electrode length and the electrode gap may be determined based on the capacity of a DC voltage source used for measurement and the accuracy of an ammeter. The metal constituting the electrode may be appropriately selected as long as the electrode can be formed on the surface of the electrophotographic photosensitive member, and examples thereof include commonly used gold, silver, copper, aluminum, nickel, platinum, chromium, zinc, and carbon. The counter electrodes are preferably made of the same metal. The method for producing the electrode is not particularly limited as long as the constituent components of the electrophotographic photosensitive member do not change in quality, but a vacuum deposition method is preferable because it does not easily change the electrophotographic photosensitive member.

<Measurement method>
The electric field applying power source is not particularly limited as long as it is a sufficiently stable DC voltage source. Further, the measurement of the current passing through the sample when a voltage is applied is not particularly limited as long as a microammeter is used and the measurement accuracy capable of measuring 1 × 10 ⁴ V / cm described in the present invention is obtained.
A measurement circuit diagram is shown in FIG. The voltage application polarity is preferably a negative voltage application when evaluating a negatively charged electrophotographic photosensitive member, and a positive voltage application when evaluating a positively charged electrophotographic photosensitive member. It is preferable to perform measurement for 60 seconds or more and calculate the surface resistivity based on the current value for 60 seconds.

In this invention, it can measure on condition of the following using the above-mentioned method.
Current-voltmeter: Keithley source measure unit type 2410
-Electrode metal: Gold-Electrode length: 10 mm
-Electrode gap: 25 μm
Measurement atmosphere: 50% RH at 25 ° C
・ Measurement time: 70 seconds (surface resistance is calculated from the current value 60 seconds after voltage application)

<Surface layer>
The surface layer contains inorganic fine particles and at least one compound selected from the compounds represented by the general formulas (1), (2), and (3), and has no charge transport property. It preferably contains a resin and a charge transporting compound, and further contains other components as necessary.

<< Inorganic fine particles >>
As the inorganic fine particles, zinc oxide fine particles doped with a Group 13 element are used.
The group 13 element is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include boron, aluminum, gallium, and indium. These may be used alone or in combination of two or more. Among these, gallium is preferable because it is excellent in charge transporting property and latent image maintaining property and can maintain the electrical characteristics of the surface layer.

The method for doping the zinc oxide fine particles with the group 13 element is not particularly limited and may be appropriately selected depending on the intended purpose. For example, “zinc oxide as a bulk matrix” or “by firing” Examples thereof include a firing method in which a “precursor that becomes zinc oxide” and a “dope metal” are mixed in a solid state to prepare a mixture, and the mixture is fired in a high-temperature atmosphere.
Here, doping means adding the group 13 element to the zinc oxide in a controlled concentration.

  The method for confirming that the zinc oxide fine particles are doped with the group 13 element is not particularly limited and may be appropriately selected according to the purpose. For example, X-ray photoelectron spectroscopy (XPS), Examples thereof include a method of confirming by a generally known elemental analysis method such as Auger spectroscopy (AES) and energy dispersive X-ray spectroscopy (EDX).

  There is no restriction | limiting in particular as content in the said zinc oxide microparticles | fine-particles of the said group 13 element, Although it can select suitably according to the objective, For example, in the element conversion with respect to 1 mol if it is zinc oxide, 0.001 mol to 0.2 mol is preferable, 0.01 mol to 0.1 mol is more preferable, and 0.02 mol to 0.1 mol is still more preferable. When the content is less than 0.001 mol, the electrical property stability of zinc oxide may be lowered. On the other hand, when the content exceeds 0.2 mol, the effect of improving electrical property stability and fine particle conductivity is often saturated, and an excessive additive element that is not diffused to an effective position becomes a compound at the grain boundary. Therefore, the characteristics of various electrophotographic photoreceptors may be deteriorated.

  There is no restriction | limiting in particular as a measuring method of content in the zinc oxide of the said group 13 element, According to the objective, it can select suitably, For example, X-ray photoelectron spectroscopy (XPS), Auger spectroscopy (AES) ), A method of measuring by a generally known elemental analysis method such as energy dispersive X-ray spectroscopy (EDX).

  It is more preferable that the zinc oxide fine particles doped with the group 13 element contain a sintering inhibitor having an anti-sintering effect on the surface of the zinc oxide fine particles. By containing the sintering inhibitor, it becomes possible to suppress the extreme particle growth during the production of the particles, to make the zinc oxide fine particles with little variation in the primary particle diameter, and to be able to be fired at a relatively high temperature. Since it exists, it has the characteristic that the spreading | diffusion of the dopant element in a zinc oxide microparticle can be made easy. In addition, by selecting a sintering inhibitor having a sintering temperature higher than that of the main constituent element of the zinc oxide fine particles, it becomes difficult for the inorganic fine particles to coalesce or aggregate when firing the zinc oxide fine particles. When applied to an application for forming a coating film using a liquid dispersion similar to the application, it has a feature that it is easy to obtain a coating film in which zinc oxide fine particles are well dispersed.

As the sintering inhibitor, for example, a compound of at least one element selected from Si, Zr, Mg, Hf, Sn, Sr, Mo, W, Ge, Nb, V, Ca, Ta, and Ba is preferable. Silica is more preferable as the sintering inhibitor having a sintering temperature higher than that of zinc oxide.
As content of the said sintering inhibitor, it is preferable that it is the range of 0.5 mass%-20 mass% with respect to the zinc oxide doped with the said group 13 element.
When the gallium-doped zinc oxide fine particles whose surface is modified as the inorganic fine particles and Si as the sintering inhibitor are used, the content of Si is preferably 2% by mass to 15% by mass in terms of SiO ₂ .
When zinc oxide doped with a Group 13 element having such characteristics is applied to the present invention, it is possible to form a coating film having relatively high transparency and an oxidation having high electrical stability. Zinc can be used, and has the effect of further increasing the electrostatic stability, which is one of the characteristics of the electrophotographic photosensitive member described in the present invention.

  The method for measuring the content of the sintering inhibitor in the zinc oxide fine particles doped with the Group 13 element is not particularly limited as long as it is a known elemental quantitative analysis means, and the analysis means described above may be used depending on the purpose. It can be selected appropriately. Examples thereof include a method of measuring by a generally known elemental analysis method such as X-ray photoelectron spectroscopy (XPS), Auger spectroscopy (AES), energy dispersive X-ray spectroscopy (EDX), and the like.

The volume resistivity of the zinc oxide fine particles doped with the Group 13 element, 1 × is preferably from 10 ⁸ Ω · cm, more preferably at most 1 × 10 ³ Ω · cm or more ^{1 × 10 8 Ω · cm,} 1 × 10 ³ Ω · cm to 1 × 10 ⁶ Ω · cm is more preferable. In an electrophotographic photosensitive member having a surface layer using inorganic fine particles having a volume resistivity of less than 1 × 10 ³ Ω · cm, even if the surface layer electrical property suitability range of the present invention is within the range of fine lines or small dots, This is not preferable because bleeding tends to occur. In addition, when inorganic fine particles having a volume resistivity exceeding 1 × 10 ⁶ Ω · cm are used, the environmental dependency of the charge transport property inside the surface layer increases, and the image density due to the decrease in the charge transport property particularly in a low temperature environment. This is not preferable because it tends to cause a decrease.

<< Method for Measuring Volume Resistivity of Zinc Oxide Fine Particles Doped with Group 13 Element >>
As a method for measuring the volume resistivity of the zinc oxide fine particles doped with the group 13 element, a compact body of a predetermined amount of powder is prepared using a predetermined pressure, and electrodes are provided on the upper and lower ends of the compact body. The method of measuring the electric current value at the time of applying this voltage is mentioned. In the present invention, a specimen is prepared by applying two levels of pressure during the production of a compact, and after calculating the respective compact body porosity and each compact volume resistivity, the resistivity at a porosity of 50 vol% is an exponential function. The volume resistivity of the inorganic fine particles was determined from the approximation. The measurement conditions are described below.
-Amount of fine zinc oxide particles used in the specimen: 1.0 g
-Specimen shape: cylinder (diameter 20mm)
-Pressure at the time of specimen preparation: 10 MPa, 20 MPa
・ Sample electrode: W
・ Applied voltage: 0.1V

Hereinafter, although the manufacturing method of the zinc oxide fine particle doped with the group 13 element containing the said sintering inhibitor is demonstrated, if the same kind of zinc oxide fine particle can be formed, it will not be limited to the method mentioned later.
The method for producing zinc oxide doped with a group 13 element containing the sintering inhibitor is as follows: (1) preparing a mixture in which zinc oxide or a precursor compound that becomes zinc oxide by firing and a group 13 element are mixed in a solid state (2) a step of mixing the mixture prepared in step (1) and the sintering inhibitor, and (3) a step of firing the mixture obtained in step (2) at a predetermined temperature. The firing temperature is preferably set to a relatively high temperature for the purpose of diffusing the Group 13 element in the zinc oxide fine particles, and is preferably fired within a temperature range in which the sintering inhibitor effectively works. Specifically, zinc oxide doped with a Group 13 element suitable for the present invention can be obtained by baking at 600 ° C. or higher and 850 ° C. or lower.

  The average primary particle size of zinc oxide doped with the Group 13 element is not particularly limited and can be appropriately selected according to the purpose, but in terms of excellent light transmittance and wear resistance of the surface layer, 10 nm-50 nm are preferable. When the average primary particle size is less than 10 nm, the aggregation of inorganic fine particles is likely to occur, and problems such as inability to stably control the surface resistivity described in the present invention may occur. . When the average primary particle size exceeds 50 nm, the charge transport function in the surface layer tends to be inhomogeneous, making it difficult to form a desired latent image. Further, since the surface roughness of the surface layer increases and wear of a blade cleaning member, which will be described later, progresses rapidly, toner cleaning failure or the like may occur at an early stage. Further, although depending on the specific gravity of the inorganic fine particles, there may be a problem relating to the life of the coating solution, such as promoting the sedimentation of the inorganic fine particles in the dispersion.

  Measurement of the average primary particle size of the zinc oxide fine particles doped with the Group 13 element is, for example, 200 randomly selected images after obtaining observation images of 3,000 to 10,000 times with a scanning electron microscope These particles can be measured by calculating with the image analysis software.

As the zinc oxide doped with the Group 13 element, those having a volume resistivity of 1 × 10 ⁸ Ω · cm or less in which zinc particles are modified with either primary or secondary amino groups are preferred (hereinafter referred to as “the zinc oxide”). Sometimes referred to as “surface-modified zinc fine particles”).
The method for modifying the zinc particles with either the primary or secondary amino group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a compound having a primary or secondary amino group may be selected. And a method of modifying the zinc particles.

-Compounds having primary or secondary amino groups-
The compound having a primary or secondary amino group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N 2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, p-aminophenyltrimethoxysilane, aminoethylaminomethylphenethyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminomethyl Triethoxysilane, phenylaminomethylmethyl Such as methoxy silane. These may be used individually by 1 type and may use 2 or more types together. Among these, a compound having a phenylamino group is preferable.

-Manufacturing method of surface modified zinc particles-
The method for producing the surface-modified zinc particles is not particularly limited and may be appropriately selected depending on the intended purpose. The zinc particles are modified with a compound having a primary or secondary amino group as described below. The method is given as an example.

  A slurry (a suspension of solid fine particles) containing inorganic fine particles and a compound having a primary or secondary amino group is wet pulverized, whereby the inorganic fine particles are refined and at the same time the surface treatment of the inorganic fine particles proceeds. Thereafter, the solvent is removed, heat treatment is performed, and powderization is performed, whereby uniform and fine surface-modified inorganic fine particles modified with an amino group-containing compound can be obtained.

There is no restriction | limiting in particular as a surface treatment apparatus used for the said surface treatment, Although it can select suitably according to the objective, For example, a wet media dispersion type | mold apparatus is mentioned.
The wet media dispersion type apparatus comprises a step of crushing or dispersing agglomerated particles of inorganic fine particles by filling beads in a container as a medium and rotating an agitation disk attached perpendicularly to a rotation axis at a high speed. It is a device that has. The configuration is not particularly limited as long as the metal oxide particles are sufficiently dispersed when the surface treatment is performed on the inorganic fine particles and can be surface-treated, and can be appropriately selected according to the purpose. Various types such as vertical type or horizontal type, continuous type or batch type can be used.

  Specific examples include a sand grinder mill, an ultra visco mill, a pearl mill, a grain mill, a dyno mill, an agitator mill, and a dynamic mill. In these dispersion-type apparatuses, pulverization and dispersion are performed by impact crushing, friction, shearing, shear stress, and the like using a pulverizing medium (media) such as balls and beads. Examples of the beads used in the sand grinder mill include balls made of glass, alumina, zircon, zirconia, steel, flint stone, and the like, but those made of zirconia or zircon are preferable. The beads preferably have a diameter of 1 mm to 2 mm.

  The material of the disk and container inner wall used in the wet media dispersion type device is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include materials made of stainless steel, nylon, ceramic, and the like. . Among these, ceramic materials such as zirconia and silicon carbide are more preferable.

  Since metal oxide particles such as alumina, titanium oxide, tin oxide, and silica also have a hydroxyl group on the surface in the same manner as zinc oxide, the surface-modified inorganic fine particles are obtained by wet treatment using a compound having an amino group. Can be obtained.

  Another example of the method for producing zinc oxide doped with the group 13 element (surface-modified inorganic fine particles) is to react inorganic fine particles with a silane coupling agent having a primary or secondary amino group. And a method of modifying the inorganic fine particles with primary or secondary amino groups.

  The material used in the method for modifying the inorganic fine particles may include a material having a modifying group other than an amino group, but preferably contains 50% by mass or more of a material having an amino group.

-Volume resistivity of surface-modified inorganic fine particles-
The volume resistivity of the surface-modified inorganic fine particles can be measured by using a measuring device based on JIS-K6911. Examples of the measuring device include MCP-PD51 type, Loresta GP, Hiresta UP (all manufactured by Mitsubishi Chemical Analytech Co., Ltd.) and the like.
The measuring device can measure under any pressure. The volume resistivity of the surface-modified inorganic fine particles is calculated by interpolating or extrapolating the value of the powder resistivity with a cylinder porosity of 50% from a plurality of measurement results, and this value is calculated as the surface-modified inorganic fine particle. The volume resistivity of the fine particles. The approximation uses exponential function approximation. The porosity is obtained by the following calculation formula.
Cylinder porosity (%) = (1−measured fine particle weight ÷ fine particle density ÷ particulate volume during pressurization) × 100

The volume resistivity of the surface-modified inorganic fine particles is not particularly limited as long as it is 1 × 10 ⁸ Ω · cm or less, and can be appropriately selected according to the purpose, but the volume resistivity is 5 × 10 ^4. The thing of ohm * cm or less is preferable and the thing of 1 * 10 < ³ > ohm * cm or less is more preferable.

-Detection method of surface-modified inorganic fine particles-
For the detection of the surface-modified inorganic fine particles in the surface layer, for example, gas chromatograph mass spectrometer (GCMS), time-of-flight mass spectrometer (TOF-SIMS), nuclear magnetic resonance (NMR), infrared spectrophotometer (IR) Common analysis techniques such as Raman spectrophotometer and Auger spectroscopy (AES) can be used.

  There is no restriction | limiting in particular as content in the surface layer of the zinc oxide (surface modification inorganic fine particle) doped with the said group 13 element, Although it can select suitably according to the objective, It does not have the said charge transport property. 10 mass parts-130 mass parts are preferable with respect to 100 mass parts of resin. When the content is less than 10 parts by mass, gas resistance may be deteriorated and an abnormal image may be generated. When the content exceeds 130 parts by mass, coating is caused by aggregation of zinc oxide fine particles doped with a Group 13 element. Defects may occur.

  The method for dispersing the surface-modified inorganic fine particles in the surface layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the dispersion method is generally used for the preparation of the surface layer coating liquid. , A method using a ball mill, a sand mill, a KD mill, a three-roll mill, a pressure homogenizer, and ultrasonic dispersion.

When a surface layer as described in the present invention is used, since it contains a relatively large amount of zinc oxide fine particles doped with a group 13 element, it has high scratch resistance and wear resistance, but ozone generated by a charging process, etc. There is a drawback in that image quality deterioration (image density unevenness) is likely to occur due to deposition of an ionic substance derived from an acidic gas such as NOx. The mechanism of unevenness of image density due to acid gas is that the ionic substance derived from acid gas generated by the charger is deposited on the surface of the photoconductor and absorbs moisture, thereby reducing the resistance of the outermost surface of the photoconductor. It is considered that the charge on the image moves laterally on the surface of the photoreceptor.
The electrophotographic photosensitive member that has been generally used so far has poor mechanical durability, and therefore wear due to a mechanical external force applied by a cleaning blade or the like, and ionic substances deposited on the outermost surface can be easily removed. Further, the image density unevenness was hardly manifested. However, an electrophotographic photosensitive member having a surface layer containing a relatively large amount of inorganic fine particles as described in the present invention is difficult to wear on the surface of the photosensitive member, and it is very difficult to remove ionic substances deposited on the surface. Therefore, image density unevenness is likely to be manifested. In particular, when a surface layer is formed using a crosslinkable material, the free volume of the surface layer becomes large due to volume shrinkage due to crosslinking, and the inside of the layer is relatively susceptible to ionic substances. For this reason, image density unevenness tends to be manifested, and in addition, there is a problem that has not been seen so far, such as slow recovery. In order to solve the problem caused by the ionic substance deposited on the outermost surface of the electrophotographic photosensitive member, the compound is selected from compounds represented by the following general formulas (1), (2), and (3). It is effective to contain at least one compound.

<General formula (1)>
In the general formula (1), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. Ar ₁ represents a substituted or unsubstituted aromatic ring group.

<General formula (2)>
However, In the general formula (2), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. m and n represent an integer of 0 to 3, and m and n are not 0 at the same time. R ₄ and R _{5 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 11 carbon atoms, and a substituted or unsubstituted aromatic ring group, and these may be the same or different. Good. Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic ring group, and these may be the same or different.

<General formula (3)>
In the general formula (3), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic ring group. l and m represent an integer of 0 to 3, and l and m are not 0 at the same time. n represents an integer of 1 to 3.

<Compound represented by the general formula (1)>
The diamine compound represented by the general formula (1) is disclosed in Japanese Patent Publication No. 62-13382, US Pat. No. 4,223,144, US Pat. No. 3,271,383, and US Pat. No. 3,291,788. It is described as a precursor. The compound is effective for maintaining image quality when the photoreceptor is used repeatedly. The reason for this is not clarified at the moment, but the alkylamino group contained in the chemical structure is a strongly basic group. The neutralization effect is estimated. In addition, it is known that the aromatic hydrocarbon ring group-substituted amino group is a functional group having excellent charge transporting ability [Takahashi et al., Electrophotographic Society, Vol. 25, No. 3, page 16, 1986], Since the said diamine compound used for this invention contains this group, it turns out that it is a compound with high charge transport ability. Furthermore, the high sensitivity and the repeated stability are further increased when used in combination with other charge transport materials.

  The diamine compound represented by the general formula (1) can be easily produced by the method described in the literature (E. Elceand AS Hay, Polymer, Vol. 37 No. 9, 1745 (1996)). . That is, a dihalide represented by the following general formula (1-1) and a secondary amine compound represented by the following general formula (1-2) are heated from room temperature to about 100 ° C. in the presence of a basic compound. It can be obtained by reacting at a temperature.

<General formula (1-1)>
However, in the general formula (1-1), Ar ₁ represents a substituted or unsubstituted aromatic hydrocarbon group. X represents a halogen atom.

<General formula (1-2)>
In the general formula (1-2), R ₂ and R ₃ is a substituted or unsubstituted alkyl group, an aromatic hydrocarbon group, may be the same or different. However, any one of R ₂ and R ₃ is a substituted or unsubstituted aromatic hydrocarbon group. R ₂ and R ₃ may be bonded to each other to form a substituted or unsubstituted heterocyclic group containing a nitrogen atom.

  Examples of the basic compound include potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, sodium hydride, sodium methylate, potassium t-butoxide and the like. Examples of the reaction solvent include dioxane, tetrahydrofuran, toluene, xylene, dimethyl sulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, and the like.

Examples of the alkyl group in the description of the general formula (1) and the general formula (1-2) include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an undecanyl group. Examples of the aromatic hydrocarbon group include aromatic rings such as benzene, biphenyl, naphthalene, anthracene, fluorene, and pyrene, and aromatic heterocyclic rings such as pyridine, quinoline, thiophene, furan, oxazole, oxadiazole, and carbazole. The group of is mentioned. These substituents include those exemplified in the specific examples of the alkyl group, alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group, or halogen atoms of fluorine atom, chlorine atom, bromine atom and iodine atom. Atoms, the aromatic hydrocarbon groups, and heterocyclic groups such as pyrrolidine, piperidine, piperazine and the like can be mentioned. Further, when R ₁ and R ₂ are bonded to each other to form a heterocyclic group containing a nitrogen atom, the heterocyclic group is a condensed heterocyclic ring in which an aromatic hydrocarbon group is condensed to a pyrrolidino group, piperidino group, piperazino group or the like. The group can be mentioned.

  Below, the preferable example of a compound represented by the said General formula (1) is given. However, the present invention is not limited to these compounds.

<General formula (1)>

In the present invention, the compound represented by the general formula (1) may be used alone, or two or more kinds may be used in combination.

<Compound represented by formula (2)>
The reason why the compound represented by the general formula (2) is preferable in solving the problem caused by the ionic substance deposited on the outermost surface of the electrophotographic photosensitive member has not been clarified at the present time. For example, R ₂ and R ₃ substituted amino groups in the general formula (2) (R ₂ and R ₃ are substituted or unsubstituted alkylamino groups having 1 to 4 carbon atoms) in the general formula (2) It is presumed that there is effective radical substance generation suppression for oxidizing gas. Since the compound represented by the following general formula (2) also has a charge transport capability, it does not act as a charge carrier trap by itself, and almost no deterioration in electrical characteristics such as an increase in residual potential due to addition is observed. It will not be possible.

<General formula (2)>
However, In the general formula (2), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. m and n represent an integer of 0 to 3, and m and n are not 0 at the same time. R ₄ and R _{5 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 11 carbon atoms, and a substituted or unsubstituted aromatic ring group, and these may be the same or different. Good. Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic ring group, and these may be the same or different.

Therefore, unlike the antioxidants conventionally used as a solution to such problems, the addition of the compound shown in the present invention to the photoreceptor causes a decrease in charge transport ability, inhibition of crosslinking, and a decrease in hardness. Therefore, it is possible to obtain an intended electrophotographic photosensitive member having acid gas durability.
Examples of the arylmethane compound having an alkylamino group represented by the general formula (2) include compounds represented by the following general formulas (2-1) to (2-3).

<General formula (2-1)>
However, the general formula (2-1), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, these May be the same or different, and R ₂ and R ₃ may be bonded to each other to form a heterocyclic group containing a nitrogen atom. m and n represent an integer of 0 to 3. However, m and n are not 0 simultaneously. R ₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 11 carbon atoms, or a substituted or unsubstituted aromatic ring group. Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , and Ar ₅ represent a substituted or unsubstituted aromatic ring group, and may be the same or different. Ar ₄ and Ar ₅ , or Ar ₄ and Ar ₃ may be bonded to each other to form a heterocyclic group containing a nitrogen atom.

<General formula (2-2)>
However, the general formula (2-2), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, these May be the same or different, and R ₂ and R ₃ may be bonded to each other to form a heterocyclic group containing a nitrogen atom. m and n represent an integer of 0 to 3. However, m and n are not 0 simultaneously. Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , and Ar ₅ represent a substituted or unsubstituted aromatic ring group, and may be the same or different. Ar ₄ and Ar ₅ , or Ar ₄ and Ar ₃ may be bonded to each other to form a heterocyclic group containing a nitrogen atom.

<General formula (2-3)>
However, in said general formula (2-3), R < ₂ > and R < ₃ > represents either a substituted or unsubstituted aromatic hydrocarbon group and a substituted or unsubstituted C1-C4 alkyl group, These May be the same or different, and R ₂ and R ₃ may be bonded to each other to form a heterocyclic group containing a nitrogen atom. m and n represent an integer of 0 to 3. However, m and n are not 0 simultaneously. Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ , and Ar ₅ represent a substituted or unsubstituted aromatic ring group, and may be the same or different. Ar ₄ and Ar ₅ , or Ar ₄ and Ar ₃ may be bonded to each other to form a heterocyclic group containing a nitrogen atom.

In the general formula (2) and the general formulas (2-1) to (2-3), specific examples of the alkyl group of R ₂ and R ₃ include a methyl group, an ethyl group, a propyl group, and a butyl group. Etc. Examples of the aromatic ring group of R ₂ , R ₃ and Ar _{1 to} Ar ₅ include monovalent to hexavalent aromatic hydrocarbon groups of aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and pyrene, and pyridine, Examples thereof include monovalent to hexavalent aromatic heterocyclic groups such as quinoline, thiophene, furan, oxazole, oxadiazole, and carbazole. These substituents include those exemplified in the specific examples of the alkyl group, alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group, or halogen atoms of fluorine atom, chlorine atom, bromine atom and iodine atom. An atom, an aromatic ring group, etc. are mentioned. Furthermore, specific examples of the heterocyclic group containing a nitrogen atom in which R ₁ and R ₂ are bonded to each other include a pyrrolidinyl group, a piperidinyl group, and a pyrrolinyl group. In addition, examples of the heterocyclic group jointly containing a nitrogen atom include aromatic heterocyclic groups such as N-methylcarbazole, N-ethylcarbazole, N-phenylcarbazole, indole, and quinoline.

  Specific examples of structures of the compounds represented by the general formula (2) and the general formulas (2-1) to (2-3) are shown below. However, the present invention is not limited to these compounds.

  In the present invention, the compounds represented by the general formula (2) and the general formulas (2-1) to (2-3) may be used alone or in combination of two or more. .

<Compound represented by formula (3)>
In order to solve the problem caused by the ionic substance deposited on the outermost surface of the electrophotographic photosensitive member, it is effective to contain a compound represented by the following general formula (3) and the following general formula (3-1). It is. The reason for this is not clarified at the present time, but it is presumed that the substituted amino group contained in the structure of the compound effectively suppresses the generation of radical substances against the oxidizing gas. Moreover, since the compound represented by the following general formula (3) and the following general formula (3-1) also has a charge transport capability, the compound itself does not act as a trap for the charge carrier and is accompanied by the addition. There is almost no deterioration in electrical characteristics such as increase in residual potential.
Therefore, unlike the antioxidants conventionally used as a solution to such problems, the addition of the compound shown in the present invention to the photoreceptor causes a decrease in charge transport ability, inhibition of crosslinking, and a decrease in hardness. It is possible to obtain an intended electrophotographic photosensitive member having acid gas durability.

<General formula (3)>
In the general formula (3), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic ring group. l and m represent an integer of 0 to 3, and l and m are not 0 at the same time. n represents an integer of 1 to 3.

<General formula (3-1)>
However, in said general formula (3-1), R < ₄ > and R < ₅ > represents either a substituted or unsubstituted aromatic hydrocarbon group and a substituted or unsubstituted alkyl group, and these may be the same. R ₄ and R ₅ may be bonded to each other to form a heterocyclic group containing a nitrogen atom. Ar ₃ and Ar ₄ represent a substituted or unsubstituted aromatic ring group. l ′ and m ′ each represent an integer of 0 to 3, provided that l ′ and m ′ are not 0 at the same time. n ′ represents an integer of 1 to 3.

In the general formula (3) and the general formula (3-1), specific examples of the aromatic hydrocarbon group represented by R _{2 to} R ₅ include aromatic hydrocarbon ring groups such as benzene, naphthalene, anthracene, and pyrene. Specific examples of the alkyl group represented by R _{2 to} R ₅ include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an undecanyl group. Groups are preferred. In addition, examples of the aromatic ring group of Ar _{1 to} Ar ₄ include monovalent to tetravalent aromatic hydrocarbon groups of aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and pyrene, and pyridine, quinoline, thiophene, furan, and oxazole. And monovalent to tetravalent aromatic heterocyclic groups of aromatic heterocyclic rings such as oxadiazole and carbazole. These substituents include those exemplified in the specific examples of the alkyl group, alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group, or halogen atoms of fluorine atom, chlorine atom, bromine atom and iodine atom. An atom, an aromatic ring group, etc. are mentioned. Furthermore, specific examples of the heterocyclic group in which R ₂ and R ₃ , or R ₄ and R ₅ are bonded to each other and contain a nitrogen atom include a pyrrolidinyl group, a piperidinyl group, and a pyrrolinyl group. In addition, examples of the heterocyclic group jointly containing a nitrogen atom include N-methylcarbazole, N-ethylcarbazole, N-phenylcarbazole, indole, and an aromatic heterocyclic group of quinoline.

Below, the preferable example of a compound represented by the said General formula (3) or the said General formula (3-1) is given. However, the present invention is not limited to these compounds.
In addition, the compounds represented by the general formula (3) and the general formula (3-1) include compounds described in Japanese Patent Publication No. 58-5739, Japanese Patent No. 2529299, and the like. The compound represented by the general formula (3-1) is a so-called modified Wittig reaction or Wittig reaction by reaction of a corresponding phosphonic acid ester compound or triphenylphosphonium salt compound with a corresponding aldehyde compound. Further, the compound represented by the general formula (3-1) can be produced by reducing the compound represented by the general formula (3).

<General formula (3)>

<General formula (3-1)>

In this invention, the compound represented by the said General formula (3) and the said General formula (3-1) may be used independently, and may be used in combination of 2 or more types.

At least one compound selected from the compounds represented by the general formulas (1) to (3) may be added to the photosensitive layer or the surface layer, or to both the photosensitive layer and the surface layer. You may add simultaneously. Even when the photosensitive layer has a multilayer structure composed of a charge generation layer and a charge transport layer, it may be applied to any layer, or may be applied to two or more layers.
The content of the compound represented by any one of the general formulas (1) to (3) is not particularly limited as long as it satisfies the desired electrical characteristics and mechanical characteristics of the photoreceptor. The total amount of the layer to be added is preferably 0.01 to 150 parts by mass with respect to 100 parts by mass. When the content is less than 0.01 parts by mass, it may be difficult to obtain desired oxidizing gas durability. On the other hand, if the content exceeds 150 parts by mass, sufficient oxidizing gas durability can be obtained, but desired mechanical durability and electrical characteristics may not be obtained, which is not preferable.

<< Resin without charge transportability >>
Having no charge transporting property means having no hole transporting structure and electron transporting structure. Examples of the hole transporting structure include structures possessed by triarylamine, hydrazone, pyrazoline, carbazole, and the like, and examples of the electron transporting structure include condensed polycyclic quinone, diphenoquinone, cyano group, and nitro group. And electron withdrawing aromatic rings.
The resin having no charge transporting property is not particularly limited and can be appropriately selected depending on the purpose. For example, a thermoplastic resin having no electron transporting structure or a cross-linking polymerization having a cross-linkable functional group. Cross-linked resin of a functional compound. Among these, a crosslinked resin of a crosslinked polymerizable compound is preferable from the viewpoint of mechanical durability.

-Thermoplastic resin without electron transport structure-
The thermoplastic resin having no electron transport structure is not particularly limited and may be appropriately selected depending on the intended purpose. For example, styrene resin, 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 resin, cellulose acetate, ethyl cellulose, polyvinyl butyral, Examples include polyvinyl formal, polyvinyl toluene, and poly-N-vinyl carbazole. These may be used alone or in combination of two or more. Among these, styrene resin, polycarbonate resin, and polyarylate resin are preferable.

-Crosslinked resin of crosslinkable polymerizable compound-
There is no restriction | limiting in particular as crosslinked resin of the said crosslinking | crosslinked polymerizable compound, According to the objective, it can select suitably, For example, resin, such as an acrylic resin, a phenol resin, a urethane resin, an organosilicon resin, an epoxy resin, is mentioned. . These may be used alone or in combination of two or more. Of these cross-linked polymerizable compounds, acrylic resins are preferred from the viewpoint of charge transportability and latent image maintenance of the surface layer.

--Acrylic resin--
The acrylic resin is obtained by mixing and crosslinking an acrylic polymerizable compound and a radical polymerization initiator, and the synthesis method is not particularly limited and may be appropriately selected depending on the intended purpose. A method of synthesizing by mixing an acrylic polymerizable compound and a known radical polymerization initiator, applying energy such as heating and light irradiation, and crosslinking is preferable.

  The polymerizable functional group in the acrylic polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of crosslinking reactivity, an acryloyloxy group, a methacryloyloxy group, and the like are preferable.

  The number of polymerizable functional groups of the acrylic polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2 or more in terms of surface layer strength and film formability.

  The compound having two polymerizable functional groups of the acrylic polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,3-butanediol diacrylate, 1,4- Butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, EO-modified bisphenol A diacrylate, EO Examples thereof include modified bisphenol F diacrylate and neopentyl glycol diacrylate.

  The compound having 3 or more polymerizable functional groups of the acrylic polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trimethylolpropane triacrylate (TMPTA) and trimethylolpropane. Trimethacrylate, trimethylolpropane alkylene-modified triacrylate, trimethylolpropane ethyleneoxy-modified (hereinafter EO-modified) triacrylate, trimethylolpropane propyleneoxy-modified (hereinafter PO-modified) triacrylate, trimethylolpropane caprolactone-modified triacrylate, trimethylolpropane Alkylene-modified trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate (PETTA), glycerol triacrylate Glycerol epichlorohydrin modified (ECH modified) triacrylate, glycerol EO modified triacrylate, glycerol PO modified triacrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol caprolactone modified hexaacrylate , Dipentaerythritol hydroxypentaacrylate, alkylated dipentaerythritol pentaacrylate, alkylated dipentaerythritol tetraacrylate, alkylated dipentaerythritol triacrylate, dimethylolpropane tetraacrylate (DTMPTA), pentaerythritol ethoxytetraacrylate, phosphoric acid EO Modified triacrylate, 2,2,5,5-te And La hydroxymethyl cyclopentanone tetraacrylate and the like. These may be used alone or in combination of two or more.

  The radical polymerization initiator used in combination with the acrylic polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, thermal polymerization of a peroxide initiator, an azo initiator, etc. Initiator; acetophenone photopolymerization initiator, ketal photopolymerization initiator, benzoin ether photopolymerization initiator, benzophenone photopolymerization initiator, thioxanthone photopolymerization initiator, titanocene photopolymerization initiator, acridine compound, Examples include photopolymerization initiators such as triazine compounds and imidazole compounds. These may be used alone or in combination of two or more. Among these, a photopolymerization initiator is preferable.

  The radical polymerization initiator may be used alone or in combination with a radical polymerization accelerator. The radical polymerization accelerator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid. Examples include acid (2-dimethylamino) ethyl, 4,4′-dimethylaminobenzophenone, and the like.

  There is no restriction | limiting in particular as content of the said radical polymerization initiator, Although it can select suitably according to the objective, 0.5 mass part-40 mass parts are preferable with respect to 100 mass parts of acrylic polymerizable compounds. 1 mass part-20 mass parts are more preferable.

--- Phenolic resin--
There is no restriction | limiting in particular as said phenol resin, According to the objective, it can select suitably, For example, a novolak resin, a resole resin, etc. are mentioned. Among these, a resole resin is preferable in that it is excellent in latent image maintenance and can be crosslinked without using the initiator as compared with a novolak resin in which an initiator such as an acid catalyst is essential.

  The phenolic crosslinkable compound is not particularly limited and may be appropriately selected depending on the intended purpose. By heating and crosslinking a phenol derivative having one or more methylol groups in the unit structure. Those synthesized are preferred.

  As said phenol resin, a commercial item may be used and what was synthesize | combined suitably may be used. The synthesis method is not particularly limited and may be appropriately selected depending on the intended purpose. However, the synthesis method is performed by heating and crosslinking a phenol derivative having one or more methylol groups in the unit structure. Is preferred.

  The phenol derivative having one or more methylol groups in the unit structure is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dimethylol compounds of phenolic monomers, trimethylol of phenolic monomers. Examples thereof include high molecular weight compounds such as compounds and phenolic dimers. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as a dimethylol compound of the said phenols monomer, According to the objective, it can select suitably, For example, 2, 6- dihydroxymethyl-4-methylphenol, 2, 4- dihydroxymethyl-6-methyl Phenol, 2,6-dihydroxymethyl-3,4-dimethylphenol, 4,6-dihydroxymethyl-2,3-dimethylphenol, 4-t-butyl-2,6-dihydroxymethylphenol, 4-cyclohexyl-2, 6-dihydroxymethylphenol, 2-cyclohexyl-4,6-dihydroxymethylphenol, 2,6-dihydroxymethyl-4-ethylphenol, 4,6-dihydroxymethyl-2-ethylphenol, 4,6-dihydroxymethyl-2 -Isopropylphenol, 6-cyclohex Etc. Le-2,4-dihydroxy-3-methyl phenol.

  The trimethylol compound of the phenolic monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 2,4,6-trihydroxymethylphenol.

-Urethane resin-
There is no restriction | limiting in particular as said urethane resin, According to the objective, it can select suitably, For example, ester type urethane resin, ether type urethane resin, etc. are mentioned. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as said urethane resin, A commercial item may be used and what was synthesize | combined suitably may be used. The method for synthesizing is not particularly limited and may be appropriately selected depending on the intended purpose. However, a known polyol compound and a known isocyanate compound are mixed and subjected to crosslinking by applying energy such as heating and light irradiation. Thus, a method of synthesizing is preferable.

There is no restriction | limiting in particular as said polyol compound, Although it can select suitably according to the objective, A bifunctional or more functional polyol compound is preferable at the point which is excellent in surface strength and film forming property.
The bifunctional or higher functional polyol compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkylene glycol, alkylene ether glycol, alicyclic diol, and alkylene oxide adduct of alicyclic diol, Diol compounds such as alkylene oxide adducts of bisphenols; polyhydric aliphatic alcohols (eg glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitol, etc.), trivalent or higher phenols (eg phenol novolac, cresol) Novolak, etc.) and trivalent or higher polyol compounds such as alkylene oxide adducts of trivalent or higher phenols. These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as said isocyanate compound, Although it can select suitably according to the objective, A bifunctional or more isocyanate compound is preferable at the point which is excellent in surface layer intensity | strength and film forming property.
The bifunctional or higher functional isocyanate compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, bis ( Isocyanatomethyl) cyclohexane, trimethylhexamethylene diisocyanate, HDI isocyanurate, HDI biuret, XDI trimethylolpropane adduct, IPDI trimethylolpropane adduct, IPDI isocyanurate, and the like. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as content of the said isocyanate compound, Although it can select suitably according to the objective, 0.5 mass part-40 mass parts are preferable with respect to 100 mass parts of said polyol compounds, 1 mass part -20 mass parts is more preferable, and it is preferable to mix | blend an appropriate quantity based on OH value and NCO value.

--- Epoxy resin--
There is no restriction | limiting in particular as said epoxy resin, According to the objective, it can select suitably, For example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a cresol novolak type epoxy resin, a phenol novolak type epoxy resin etc. are mentioned. It is done. These may be used alone or in combination of two or more.

  As said epoxy resin, a commercial item may be used and what was synthesize | combined suitably may be used. The method of synthesizing is not particularly limited and may be appropriately selected depending on the purpose. However, an epoxy ring-containing compound having two or more epoxy rings in one molecule and a curing agent are mixed, heated, A method of synthesizing by applying energy such as light irradiation and crosslinking is preferable.

  The epoxy ring-containing compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyalkylene glycol diglycidyl ether, bisphenol A diglycidyl ether, glycerin triglycidyl ether, diglycerol triglycidyl ether, Examples thereof include diglycidyl hexahydrophthalate, trimethylolpropane diglycidyl ether, allyl glycidyl ether, and phenyl glycidyl ether. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as said hardening | curing agent, According to the objective, it can select suitably, For example, a thermal acid generator, a photo-acid generator, etc. are mentioned, Specifically, an aliphatic amine compound, an alicyclic ring, etc. Group amine compounds, aromatic amine compounds, modified amine compounds, polyamidoamines, imidazoles, polymercaptans, acid anhydrides and the like. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as content of the said hardening | curing agent, Although it can select suitably according to the objective, 0.5 mass part-20 mass parts are preferable with respect to 100 mass parts of said epoxy ring containing compounds, 1 mass part-10 mass parts are more preferable.

--- Organic silicon resin--
The organosilicon resin (silicone resin) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, dimethylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, Vinyl silicone, polyether modified silicone, polyglycerin modified silicone, amino modified silicone, epoxy modified silicone, mercapto modified silicone, methacryl modified silicone, carboxylic acid modified silicone, fatty acid ester modified silicone, alcohol modified silicone, alkyl modified silicone, fluoroalkyl modified Examples include silicone. These may be used alone or in combination of two or more.

  As said organosilicon resin, a commercial item may be used and what was synthesize | combined suitably may be used. The synthesis method is not particularly limited and may be appropriately selected depending on the intended purpose. However, a reactive organosilicon compound having one or more hydrolyzable groups on a silicon atom may be used alone or mixed with a condensation catalyst. A method of synthesizing by crosslinking by applying energy such as heating is preferable.

  The reactive organosilicon compound is not particularly limited and may be appropriately selected depending on the purpose. For example, two or more hydrolyzable groups are bonded to a silicon atom in terms of excellent surface layer strength. A reactive organosilicon compound having a structure is preferred. The hydrolyzable group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, methoxy group, ethoxy group, methyl ethyl ketoxime group, diethylamino group, acetoxy group, propenoxy group, propoxy group, butoxy group And a methoxyethoxy group.

  The condensation catalyst is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a catalyst that acts catalytically in a condensation reaction, a catalyst that moves a reaction equilibrium of a condensation reaction to a production system, etc. Specifically, alkali metal salts such as organic carboxylic acid, nitrous acid, sulfurous acid, aluminate, carbonic acid and thiocyanic acid; organic amine salts such as tetramethylammonium hydroxide and tetramethylammonium acetate; stanna octo And tin organic acid salts such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, and dibutyltin malate.

  There is no restriction | limiting in particular as content of the said condensation catalyst, Although it can select suitably according to the objective, 0.5 mass part-20 mass parts are preferable with respect to 100 mass parts of said reactive organosilicon compounds. 1 mass part-10 mass parts are more preferable.

-Charge transporting compounds-
The charge transporting compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a known hole transporting material having a hole transporting structure such as triarylamine, hydrazone, pyrazoline, and carbazole. A known electron transport material having an electron transport structure such as an electron-withdrawing aromatic ring (condensed polycyclic quinone, diphenoquinone, cyano group, nitro group, etc.) and the like. These may be used alone or in combination of two or more.
Further, when the cross-linked resin is used as the resin having no charge transport property, the charge having a functional group having reactivity with the cross-linked resin, for example, a hydroxyl group, an acryloyloxy group, a methacryloyloxy group, etc. A transport compound may be used.

  The content of the charge transporting compound is not particularly limited and may be appropriately selected according to the purpose. However, it is possible to reduce the influence of deterioration of the electrophotographic photoreceptor characteristics due to deterioration of the charge transporting compound. In this respect, 20 parts by mass or less is preferable with respect to 100 parts by mass of the resin having no charge transporting property.

  The method for measuring the content of the charge transporting compound in the surface layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray Spectroscopic method (EDX), method of measuring by elemental analysis such as wavelength dispersive X-ray analyzer (WDX), method of measuring based on dyeing amount stained with reagent, Fourier transform infrared spectroscopy (FT-IR) The method of measuring is mentioned. Among these, quantification is simple and highly versatile, and it is possible to perform quantification based on a calibration curve created based on the ratio of peak intensities measured by Fourier transform infrared spectroscopy (FT-IR). preferable.

  As the calibration curve, for example, the surface layer is prepared by blending a known amount of the charge transporting compound, and the vibration peak intensity (peak height or peak area) characteristic of the charge transporting compound is expressed as the FT. -Measured by -IR and prepared based on the ratio of the obtained vibration peak intensities. In order to improve the accuracy of the calibration curve, a surface layer prepared with a blending amount of 2 to 5 levels is prepared, and a calibration curve is created based on the vibration peak intensity obtained by measurement by the FT-IR. May be. As the vibration peak intensity, it is preferable to use the vibration peak intensity (peak height or peak area) characteristic of the charge transporting compound, which has poor reactivity and has a known compounding ratio in the film. It is more preferable to use the vibration peak intensity.

<< Other ingredients >>
There is no restriction | limiting in particular as said additive, According to the objective, it can select suitably, For example, a dispersing agent, surfactant, a plasticizer, a leveling agent, antioxidant, etc. are mentioned.

-Dispersant-
When the surface-modified inorganic fine particles are favorably dispersed in the surface layer, a dispersant may be used. There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably.
The content of the dispersant is not particularly limited and may be appropriately selected depending on the particle size of the inorganic fine particles, but is preferably 0.5% by mass to 30% by mass with respect to the total amount of the inorganic fine particles, 1 mass%-15 mass% are more preferable. When the content is less than 0.5% by mass, the dispersion effect of the inorganic fine particles may not be obtained. is there.

-Surfactant-
When the surface-modified inorganic fine particles are favorably dispersed in the surface layer, a surfactant may be used. There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably.
There is no restriction | limiting in particular as content of the said surfactant, Although it can select suitably according to the particle size etc. of inorganic fine particles, 0.5 mass%-30 mass% are with respect to the said inorganic fine particle whole quantity. Preferably, 1% by mass to 15% by mass is more preferable. When the content is less than 0.5% by mass, the dispersion effect of the inorganic fine particles may not be obtained. is there.

-Plasticizer-
The plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dibutyl phthalate and dioctyl phthalate. These may be used alone or in combination of two or more. There is no restriction | limiting in particular as content of the said plasticizer, Although it can select suitably according to the objective, 0 mass part-30 mass parts are with respect to 100 mass parts of resin which does not have the said charge transportability. preferable.

-Leveling agent-
The leveling agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include silicone oils such as dimethyl silicone oil and methylphenyl silicone oil; polymers or oligomers having a perfluoroalkyl group in the side chain. Etc. There is no restriction | limiting in particular as content of the said leveling agent, Although it can select suitably according to the objective, 0 mass part-1 mass part are with respect to 100 mass parts of resin which does not have the said charge transportability. preferable.

-Antioxidant-
The antioxidant is not particularly limited, and examples thereof include phenol compounds, paraphenylenediamines, hydroquinones, organic sulfur compounds, organic phosphorus compounds, hindered amines, and the like. There is no restriction | limiting in particular as content of the said antioxidant, Although it can select suitably according to the objective, 0 mass part-5 mass parts with respect to 100 mass parts of resin which does not have the said charge transportability. Is preferred.

<< Method for forming surface layer >>
The method for forming the surface layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a coating containing the resin having no charge transport property, the surface-modified inorganic fine particles, and the additive may be used. Examples of the method include a method in which the working solution is applied to the surface of the photosensitive layer of the electrophotographic photosensitive member, and then is formed by UV irradiation or heat drying and curing.

  The coating method of the coating liquid is not particularly limited and can be appropriately selected according to the purpose such as the viscosity of the coating liquid and the desired film thickness of the surface layer. For example, dip coating, spraying Examples thereof include a coating method, a bead coating method, and a ring coating method.

  Since the coating liquid is a solid or a relatively highly viscous liquid at normal temperature, it is preferably prepared by dissolving in a solvent. The solvent is not particularly limited as long as it can dissolve or disperse the above-described components constituting the surface layer, and can be appropriately selected according to the purpose. For example, methanol, ethanol, propanol Alcohol solvents such as butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as tetrahydrofuran, dioxane and propyl ether; dichloromethane, dichloroethane, Halogen solvents such as trichloroethane and chlorobenzene; aromatic solvents such as benzene, toluene and xylene; cellosolv solvents such as methyl cellosolve, ethyl cellosolve and cellosolve acetate. These may be used alone or in combination of two or more.

In order to remove the solvent remaining in the surface layer, it is preferable to perform a heat drying treatment after forming the surface layer by the method.
The heating method is not particularly limited and may be appropriately selected depending on the purpose. For example, air, gas such as nitrogen, steam, various heat media, infrared energy, heat energy such as electromagnetic waves, etc. The method etc. which heat from the said electroconductive support body side are mentioned.
There is no restriction | limiting in particular as temperature at the time of the said heating, Although it can select suitably according to the objective, 100 to 170 degreeC is preferable. When the temperature is less than 100 ° C., the amount of the solvent remaining in the surface layer tends to increase, which may affect the characteristics of the electrophotographic photosensitive member. On the other hand, when the temperature exceeds 170 ° C., the low molecular weight component in the photosensitive layer adjacent to the surface layer is likely to migrate to the surface layer, and the surface resistivity control and other characteristics described in the present invention are performed. May cause decline.

  When using a photocurable resin as the resin having no charge transporting property, a lamp capable of irradiating energy rays used for curing is used. The lamp is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a low pressure, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a (pulse) xenon lamp, and an electrodeless discharge lamp. Can be mentioned.

  There is no restriction | limiting in particular as thickness of the said surface layer, Although it can select suitably according to the objective, 10 micrometers or less are preferable and 8 micrometers or less are more preferable at the point which is excellent in the resolution and responsiveness. The lower limit value varies depending on the system to be used (particularly charging potential), but is preferably 3 μm or more from the viewpoint of chargeability and wear durability.

<Photosensitive layer>
The photosensitive layer may be a laminated type photosensitive layer or a single layer type photosensitive layer.

<< Single-layer type photosensitive layer >>
The single-layer type photosensitive layer is a layer having a charge generation function and a charge transport function at the same time.
The single-layer type photosensitive layer contains a charge generating substance, a charge transporting substance, and a binder resin, and further contains other components as necessary.

-Charge generation material-
The charge generating material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the same materials as those used in the laminated photosensitive layer described later. There is no restriction | limiting in particular as content of the said charge generation substance, Although it can select suitably according to the objective, 5 mass parts-40 mass parts are preferable with respect to 100 mass parts of said binder resins.

-Charge transport material-
There is no restriction | limiting in particular as said charge transport substance, According to the objective, it can select suitably, For example, the substance similar to what is used by the laminated type photosensitive layer mentioned later etc. are mentioned. There is no restriction | limiting in particular as content of the said charge transport material, Although it can select suitably according to the objective, 190 mass parts or less are preferable with respect to 100 mass parts of said binder resin, and 50 mass parts-150 mass parts. Part by mass is more preferable.

-Binder resin-
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably, For example, the binder resin similar to what is used by the laminated type photosensitive layer mentioned later etc. are mentioned.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, the same low molecular charge transport material, the same solvent, and the same as those used in the laminated photosensitive layer described later A leveling agent, the above-mentioned antioxidant, etc. are mentioned.

-Method for forming a single-layer type photosensitive layer-
The method for forming the single-layer photosensitive layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a charge generating material, a charge transporting material, a binder resin, other components, etc. Examples thereof include a method of forming a coating liquid obtained by dissolving or dispersing in a suitable solvent (for example, tetrahydrofuran, dioxane, dichloroethane, cyclohexane, etc.) by coating or drying.

  There is no restriction | limiting in particular as a method to apply the said coating liquid, According to the objective, it can select suitably, For example, a dip coating method, a spray coat, a bead coat, a ring coat etc. are mentioned. Moreover, you may add a plasticizer, a leveling agent, antioxidant, etc. as needed.

  There is no restriction | limiting in particular as thickness of the said single layer type photosensitive layer, Although it can select suitably according to the objective, 5 micrometers-25 micrometers are preferable.

<< Laminated Photosensitive Layer >>
Since the layered photosensitive layer has independent charge generation functions and charge transport functions, it has at least a charge generation layer and a charge transport layer in this order. In addition, a conventionally well-known thing can be used for the said charge generation layer and the said charge transport layer.

  In the stacked photosensitive layer, the stacking order of the charge generation layer and the charge transport layer is not particularly limited and can be appropriately selected according to the purpose. Many charge generation materials are chemically stable. However, exposure to an acidic gas such as a discharge product around a charger in an electrophotographic imaging process causes a reduction in charge generation efficiency. For this reason, it is preferable to laminate the charge transport layer on the charge generation layer.

-Charge generation layer-
The charge generation layer includes a charge generation material, preferably includes a binder resin, and further includes other components such as the above-described antioxidant as necessary.

-Charge generation material-
There is no restriction | limiting in particular as said charge generation substance, According to the objective, it can select suitably, For example, an inorganic material, an organic material, etc. are mentioned.

---- Inorganic material ---
The inorganic material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, crystalline selenium, amorphous selenium, selenium-tellurium, selenium-tellurium-halogen, selenium-arsenic compound, amorphous silicon (For example, a dangling bond that is terminated with a hydrogen atom, a halogen atom, or the like; a boron atom, a phosphorus atom, or the like is preferred).

---- Organic materials ---
The organic material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine; azulenium salt pigments, squaric acid methine pigments, and carbazole skeletons. Azo pigments having a triphenylamine skeleton, azo pigments having a diphenylamine skeleton, azo pigments having a dibenzothiophene skeleton, azo pigments having a fluorenone skeleton, azo pigments having an oxadiazole skeleton, azo having a bisstilbene skeleton Pigment, azo pigment having distyryl oxadiazole skeleton, azo pigment having distyryl carbazole skeleton, perylene pigment, anthraquinone or polycyclic quinone pigment, quinoneimine pigment, diphenylmethane and triphenylmethane face , Benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, indigoid pigments, and bis-benzimidazole-based pigments. These may be used individually by 1 type and may use 2 or more types together.

--Binder resin--
The binder resin is not particularly limited and can be appropriately selected according to the purpose. For example, polyamide resin, polyurethane resin, epoxy resin, polyketone resin, polycarbonate resin, silicone resin, acrylic resin, polyvinyl butyral resin, Examples thereof include polyvinyl formal resin, polyvinyl ketone resin, polystyrene resin, poly-N-vinyl carbazole resin, polyacrylamide resin and the like. These may be used individually by 1 type and may use 2 or more types together.

  As the binder resin, in addition to the above-mentioned binder resin, a charge transporting polymer material having a charge transport function may be included.For example, an arylamine skeleton, a benzidine skeleton, a hydrazone skeleton, a carbazole skeleton, a stilbene skeleton, A polymer material having a pyrazoline skeleton or the like, such as a polycarbonate, polyester, polyurethane, polyether, polysiloxane, or acrylic resin, or a polymer material having a polysilane skeleton can be used.

-Other ingredients-
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a low molecular charge transport material, a solvent, a leveling agent etc. are mentioned, You may contain the above-mentioned antioxidant.
There is no restriction | limiting in particular as content of the said other component, Although it can select suitably according to the objective, 0.01 mass%-10 mass% are preferable with respect to the total mass of the layer to add.

--- Low molecular charge transport material ---
There is no restriction | limiting in particular as said low molecular charge transport material, According to the objective, it can select suitably, For example, an electron transport material, a hole transport material, etc. are mentioned.

  The electron transport material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, chloroanil, bromilyl, 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-trinitrodibenzothiophene-5,5-dioxide, diphenoquinone derivatives and the like. These may be used individually by 1 type and may use 2 or more types together.

  The hole transport material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, and triarylamine derivatives. , Stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triarylmethane derivatives, 9-styrylanthracene derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, etc. Derivatives, enamine derivatives and the like. These may be used individually by 1 type and may use 2 or more types together.

--- Solvent ---
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose.For example, tetrahydrofuran, dioxane, dioxolane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, cyclopentanone, anisole, xylene, methyl ethyl ketone, Acetone, ethyl acetate, butyl acetate and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

--- Leveling agent ---
There is no restriction | limiting in particular as said leveling agent, According to the objective, it can select suitably, For example, silicone oils, such as dimethyl silicone oil and methylphenyl silicone oil, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

--Method of forming charge generation layer--
The method for forming the charge generation layer is not particularly limited and may be appropriately selected depending on the purpose. For example, the charge generation material and the binder resin are dissolved or dispersed in the other components such as the solvent. For example, a method of forming the coating liquid obtained by applying the coating liquid on the conductive support and drying it may be used. In addition, the said coating liquid can be apply | coated by the casting method etc.

  There is no restriction | limiting in particular as thickness of the said charge generation layer, Although it can select suitably according to the objective, 0.01 micrometer-5 micrometers are preferable, and 0.05 micrometer-2 micrometers are more preferable.

-Charge transport layer-
The charge transport layer is a layer intended to hold a charged charge and to couple the charge generated and separated in the charge generation layer by exposure to the charged charge held by movement. In order to achieve the purpose of holding the charged charge, it is required that the electric resistance is high. Further, in order to achieve the purpose of obtaining a high surface potential with the charged charge that has been held, it is required that the dielectric constant is small and the charge mobility is good.

  The charge transport layer preferably includes a charge transport material, preferably includes a binder resin, and further includes other components as necessary.

-Charge transport material-
The charge transport material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include an electron transport material, a hole transport material, and a polymer charge transport material.

  There is no restriction | limiting in particular as content in the charge transport layer whole quantity of the said charge transport material, Although it can select suitably according to the objective, 20 mass%-80 mass% are preferable, and 30 mass%-70 mass% are preferable. More preferred. If the content is less than 20% by mass, the charge transporting property of the charge transport layer may be reduced, so that desired light attenuation characteristics may not be obtained. The body may wear more than necessary due to various hazards. On the other hand, when the content of the charge transport material in the charge transport layer is within the more preferable range, a desired light attenuation can be obtained, and an electrophotographic photoreceptor with less wear can be obtained by use. This is advantageous.

---- Electron transport material ---
The electron transport material (electron-accepting material) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, chloroanil, bromoanil, 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] thiophene-4-one, 1,3,7-trinitrodibenzothiophene-5,5-dioxide, and the like. These may be used alone or in combination of two or more.

--- Hole transport material ---
The hole transport material (electron donating material) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, 9- (P-diethylaminostyrylanthracene), 1,1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, Examples include acridine derivatives, benzofuran derivatives, benzimidazole derivatives, thiophene derivatives, and the like. These may be used alone or in combination of two or more.

--- Polymer charge transport material ---
The polymer charge transport material is a material having both the functions of a binder resin and a charge transport material described later.

  The polymer charge transport material is not particularly limited and may be appropriately selected depending on the intended purpose.For example, a polymer having a carbazole ring, a polymer having a hydrazone structure, a polysilylene polymer, or a triarylamine structure may be used. For example, a polymer having a triarylamine structure described in Japanese Patent No. 3852812, Japanese Patent No. 3990499, and the like, a polymer having an electron donating group, and other polymers. These may be used individually by 1 type, may use 2 or more types together, and may use together with the binder resin mentioned later at the point of abrasion durability or film forming property.

  The content of the polymer charge transport material in the total mass of the charge transport layer is not particularly limited and may be appropriately selected depending on the intended purpose. The polymer charge transport material and the binder resin are used in combination. In the case, 40 mass%-90 mass% is preferable, and 50 mass%-80 mass% is more preferable.

--Binder resin--
The binder resin is not particularly limited and can be appropriately selected depending on the purpose. For example, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyethylene resin, polyvinyl chloride resin, polyvinyl acetate resin, Polystyrene resin, phenol resin, epoxy resin, polyurethane resin, polyvinylidene chloride resin, alkyd resin, silicone resin, polyvinyl carbazole resin, polyvinyl butyral resin, polyvinyl formal resin, polyacrylate resin, polyacrylamide resin, phenoxy resin, and the like are used. These may be used alone or in combination of two or more.
The charge transport layer may also contain a copolymer of a crosslinkable binder resin and a crosslinkable charge transport material.

-Other ingredients-
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a solvent, a plasticizer, a leveling agent, etc. are mentioned, You may contain antioxidant mentioned above.
There is no restriction | limiting in particular as content of the said other component, Although it can select suitably according to the objective, 0.01 mass%-10 mass% are preferable with respect to the total mass of the layer to add.

--- Solvent ---
The solvent is not particularly limited and may be appropriately selected depending on the purpose. The same solvent as the charge generation layer can be used, but a solvent that dissolves the charge transport material and the binder resin satisfactorily. preferable. These may be used singly or in combination of two or more.

---- Plasticizer ---
The plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate.

--- Leveling agent ---
The leveling agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include silicone oils such as dimethyl silicone oil and methyl phenyl silicone oil; polymers or oligomers having a perfluoroalkyl group in the side chain. Etc.

--Method of forming charge transport layer--
The method for forming the charge transport layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the charge transport material and the binder resin are dissolved or dispersed in the other components such as the solvent. And a method of forming the coating liquid obtained by applying the coating liquid on the charge generation layer and heating or drying.

  The method for applying the coating liquid used for forming the charge transport layer is not particularly limited, and may be appropriately selected according to the purpose such as the viscosity of the coating liquid and the desired thickness of the charge transport layer. Examples thereof include a dip coating method, a spray coating method, a bead coating method, and a ring coating method.

From the viewpoint of electrophotographic characteristics and film viscosity, the charge transport layer needs to be heated by some means to remove the solvent from the charge transport layer.
Examples of the heating method include a method of heating heat energy such as air, nitrogen and other gases, steam, various heat media, infrared rays, and electromagnetic waves from the coated surface side or the support side.
There is no restriction | limiting in particular as temperature at the time of the said heating, Although it can select suitably according to the objective, 100 to 170 degreeC is preferable. When the temperature is less than 100 ° C., the organic solvent in the film cannot be sufficiently removed, and electrophotographic characteristics and wear durability may be deteriorated. On the other hand, when the temperature exceeds 170 ° C., not only the surface of the surface is distorted and cracks are generated, peeling occurs at the interface with the adjacent layer, etc., but volatile components in the photosensitive layer are scattered to the outside. In this case, desired electrical characteristics may not be obtained.

  There is no restriction | limiting in particular as thickness of the said charge transport layer, Although it can select suitably according to the objective, From the point of resolution thru | or response, 50 micrometers or less are preferable and 45 micrometers or less are more preferable. The lower limit varies depending on the system to be used (particularly charging potential), but is preferably 5 μm or more.

<Other layers>
There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, an undercoat layer, an intermediate | middle layer, etc. are mentioned.

-Undercoat layer-
The undercoat layer can be provided between the conductive support and the photosensitive layer.
The undercoat layer contains a resin and, if necessary, further contains other components such as the above-mentioned antioxidant, fine powder pigment, and coupling agent.

The resin contained in the undercoat layer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include water-soluble resins such as polyvinyl alcohol, casein and sodium polyacrylate, copolymer nylon, and methoxymethyl. Examples thereof include alcohol-soluble resins such as nylon fluoride, curable resins that form a three-dimensional network structure, such as polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy resin.
Among these, a resin having a high solvent resistance with respect to a general organic solvent is preferable in that a photosensitive layer is coated on the resin with a solvent.

  The fine powder pigment contained in the undercoat layer is not particularly limited as long as it is a pigment that can prevent moire, reduce residual potential, etc., and can be appropriately selected according to the purpose. Examples thereof include metal oxides such as titanium, silica, alumina, zirconium oxide, tin oxide, and indium oxide.

  There is no restriction | limiting in particular as a coupling agent contained in the said undercoat layer, According to the objective, it can select suitably, For example, a silane coupling agent, a titanium coupling agent, a chromium coupling agent etc. are mentioned.

  There is no restriction | limiting in particular as said undercoat layer, According to the objective, it can select suitably, For example, a single layer may be sufficient and the lamination | stacking of two or more layers may be sufficient.

A method for forming the undercoat layer is not particularly limited, and can be formed by using an appropriate solvent and a coating method as in the above-described photosensitive layer. For example, a method of forming by anodizing Al ₂ O ₃ And an organic material such as polyparaxylylene (parylene); an inorganic material such as SiO ₂ , SnO ₂ , TiO ₂ , ITO, and CeO ₂ ; by a vacuum thin film manufacturing method.

  There is no restriction | limiting in particular as thickness of the said undercoat layer, Although it can select suitably according to the objective, 1 micrometer-5 micrometers are preferable.

-Intermediate layer-
The intermediate layer can be provided between the charge transport layer and the surface layer for the purpose of suppressing mixing of charge transport layer components into the surface layer or improving adhesion between the two layers.

  The intermediate layer includes a binder resin, and further includes other components such as the above-described antioxidant as necessary. The intermediate layer coating solution is preferably insoluble or sparingly soluble in the surface layer coating solution.

  There is no restriction | limiting in particular as binder resin contained in the said intermediate | middle layer, According to the objective, it can select suitably, For example, polyamide, alcohol soluble nylon, polyvinyl butyral, polyvinyl alcohol, etc. are mentioned.

  There is no restriction | limiting in particular as a formation method of the said intermediate | middle layer, According to the objective, it can select suitably, For example, the method etc. which form using the suitable solvent and coating method similar to the said photosensitive layer are mentioned.

  There is no restriction | limiting in particular as thickness of the said intermediate | middle layer, Although it can select suitably according to the objective, 0.05 micrometer-2 micrometers are preferable.

<Conductive support>
The conductive support is not particularly limited as long as it has a volume resistivity of 1 × 10 ¹⁰ Ω · cm or less, and can be appropriately selected according to the purpose. An endless belt (such as an endless nickel belt or an endless stainless steel belt) disclosed in Japanese Patent Laid-Open No. 52-36016 may be used.

  There is no restriction | limiting in particular as a formation method of the said electroconductive support body, According to the objective, it can select suitably, For example, a metal (aluminum, nickel, chromium, nichrome, copper, gold | metal | money, silver, platinum etc.) or a metal A method of forming an oxide (tin oxide, indium oxide, etc.) by depositing or sputtering and coating a support (film, cylindrical plastic, paper, etc.); metal (aluminum, aluminum alloy, nickel, For example, a method of extruding a plate of stainless steel, etc., performing drawing, etc., and performing surface treatment (cutting, superfinishing, polishing, etc. after forming a blank), and the like.

The conductive support may be provided with a conductive layer on the conductive support.
The method for forming the conductive layer is not particularly limited and may be appropriately selected depending on the purpose. For example, the conductive layer and the binder resin may be dispersed or dissolved in a solvent as necessary. A method of forming the applied coating liquid on the conductive support, such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, and Teflon (registered trademark) Examples include a method of forming using a heat-shrinkable tube containing conductive powder.

  There is no restriction | limiting in particular as said electroconductive powder, According to the objective, it can select suitably, For example, carbon fine particles, such as carbon black and acetylene black; Aluminum, nickel, iron, nichrome, copper, zinc, silver, etc. And metal oxide powders such as conductive tin oxide and ITO.

  There is no restriction | limiting in particular as binder resin used for the said electroconductive layer, According to the objective, it can select suitably, For example, a thermoplastic resin, a thermosetting resin, a photocurable resin etc. are mentioned, Specifically, Are polystyrene resin, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester resin, polyvinyl chloride resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate resin, Polyvinylidene chloride resin, polyarylate resin, phenoxy resin, polycarbonate resin, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral resin, polyvinyl formal resin, polyvinyl toluene resin, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, Melamine resin, Ureta Resins, phenol resins, and alkyd resins.

  There is no restriction | limiting in particular as a solvent used for the said electroconductive layer, According to the objective, it can select suitably, For example, tetrahydrofuran, a dichloromethane, methyl ethyl ketone, toluene etc. are mentioned.

[Embodiment of electrophotographic photosensitive member]
Hereinafter, embodiments of the electrophotographic photosensitive member of the present invention will be described.

<First Embodiment>
The layer structure of the electrophotographic photosensitive member according to the first embodiment will be described with reference to FIG.
FIG. 2 is a diagram showing a layer structure of an electrophotographic photosensitive member having a single-layer type photosensitive layer, in which a single-layer type photosensitive layer 26 and a surface layer 25 are sequentially laminated on a conductive support 21. .

<Second Embodiment>
The layer structure of the electrophotographic photosensitive member according to the second embodiment will be described with reference to FIG.
FIG. 3 shows a structure having a laminated photosensitive layer, and shows a layer structure of an electrophotographic photosensitive member in which a charge generation layer 23, a charge transport layer 24, and a surface layer 25 are sequentially laminated on a conductive support 21. FIG. The charge generation layer 23 and the charge transport layer 24 correspond to the photosensitive layer.

<Third Embodiment>
The layer structure of the electrophotographic photosensitive member according to the third embodiment will be described with reference to FIG.
4 has a configuration in which an intermediate layer is further provided on the electrophotographic photosensitive member having the configuration of FIG.
FIG. 4 is a diagram showing a layer structure of an electrophotographic photosensitive member in which an undercoat layer 22, a charge generation layer 23, a charge transport layer 24, and a surface layer 25 are sequentially laminated on a conductive support 21. The charge generation layer 23 and the charge transport layer 24 correspond to the photosensitive layer.

<Fourth Embodiment>
The layer structure of the electrophotographic photosensitive member according to the fourth embodiment will be described with reference to FIG.
FIG. 5 shows a structure having a laminated photosensitive layer, and shows a layer structure of an electrophotographic photoreceptor in which a charge transport layer 24, a charge generation layer 23, and a surface layer 25 are sequentially laminated on a conductive support 21. FIG. The charge generation layer 23 and the charge transport layer 24 correspond to the photosensitive layer.

(Image forming device)
The image forming apparatus includes: an electrophotographic photosensitive member; a charging unit that charges a surface of the electrophotographic photosensitive member; an exposure unit that exposes the charged surface of the electrophotographic photosensitive member to form an electrostatic latent image; It has at least developing means for developing the latent image with toner to form a visible image, and transfer means for transferring the visible image to a recording medium, and further has other means if necessary. Do it. The electrophotographic photosensitive member used in the image forming apparatus is the above-described electrophotographic photosensitive member of the present invention. The charging unit and the exposure unit may be collectively referred to as an electrostatic latent image forming unit.

<Charging means>
The charging means is not particularly limited and may be appropriately selected according to the purpose. For example, a known contact charger including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotron and scorotron (including proximity-type non-contact chargers having a gap of 100 μm or less between the surface of the electrophotographic photosensitive member and the charger).

<Exposure means>
The exposure means is not particularly limited as long as the surface of the electrophotographic photosensitive member charged by the charging means can be exposed like an image to be formed, and can be appropriately selected according to the purpose. Examples include various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, a liquid crystal shutter optical system, and an LED optical system, and examples of the light source in the exposure device include a light emitting diode (LED) and a semiconductor laser. (LD), electroluminescence (EL), etc. and the light source etc. which can ensure high brightness | luminance are mentioned. In the present invention, an optical backside system that performs imagewise exposure from the backside of the electrophotographic photosensitive member may be employed.

<Developing means>
The developing means is not particularly limited and may be appropriately selected depending on the purpose. For example, as long as development can be performed using the toner or developer, there is no particular limitation, and the developing means is appropriately selected according to the purpose. However, it is preferable to have at least a developing unit that accommodates the developer and can apply the developer to the electrostatic latent image in a contact or non-contact manner. The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multicolor developing unit. Also good. For example, a developer having a stirrer that charges the developer by frictional stirring and a rotatable magnet roller is preferable. In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrophotographic photosensitive member, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted to the electrophotographic photosensitive member. Move to the surface of the body. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrophotographic photosensitive member.

<Transfer means>
The transfer means is a means for transferring the visible image to a recording medium, and uses a method for directly transferring a visible image from the surface of the electrophotographic photosensitive member to a recording medium, and an intermediate transfer member. There is a method in which a visible image is primarily transferred onto the recording medium, and then the visible image is secondarily transferred onto the recording medium. Either aspect can be used satisfactorily, but the former (direct transfer) method with a small number of transfers is preferred when the adverse effect of the transfer is great when the image quality is improved. The transfer can be performed, for example, by charging the electrophotographic photosensitive member with the transfer charger using the visible image, and can be performed by the transfer unit.

<Other means>
The other means is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a fixing means, a static elimination means, a cleaning means, a recycling means, and a control means.

-Fixing means-
The fixing unit is not particularly limited and may be appropriately selected depending on the purpose. However, a known heating and pressing unit is preferable, and the heating and pressing unit includes a combination of a heating roller and a pressing roller, A combination of a heating roller, a pressure roller, and an endless belt can be mentioned. The fixing may be performed, for example, every time the toner of each color is transferred to the recording medium, or may be performed simultaneously in a state where the toner of each color is stacked.

-Static elimination means-
The neutralizing means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralizing bias to the electrophotographic photosensitive member. For example, a neutralizing lamp is preferable. Can be mentioned.

-Cleaning means-
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrophotographic photosensitive member, and can be appropriately selected from known cleaners. For example, a magnetic brush cleaner Suitable examples include electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, and web cleaners.

-Recycling means-
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

-Control means-
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

[Embodiment of Image Forming Apparatus]
Hereinafter, embodiments of the image forming apparatus of the present invention will be described.
FIG. 6 is a schematic diagram for explaining the image forming apparatus of the present invention. A charging unit 3, an exposing unit 5, a developing unit 6, a transfer unit 10 and the like are arranged around the electrophotographic photosensitive member 1. FIG.

  First, the electrophotographic photosensitive member 1 is charged on average by the charging means 3 shown in FIG. As the charging means 3, a corotron device, a scorotron device, a solid discharge element, a needle electrode device, a roller charging device, a conductive brush device, or the like is used, and a known system can be used.

  Next, an electrostatic latent image is formed on the uniformly charged electrophotographic photosensitive member 1 by the exposure means 5 shown in FIG. As this light source, all luminescent materials such as fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light emitting diodes (LEDs), semiconductor lasers (LD), and electroluminescence (EL) can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.

  Next, the electrostatic latent image formed on the electrophotographic photoreceptor 1 is visualized by the developing means 6 shown in FIG. Examples of the developing method include a one-component developing method using a dry toner, a two-component developing method, and a wet developing method using a wet toner. When the electrophotographic photoreceptor 1 is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photoreceptor. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner.

  Next, the toner image visualized on the electrophotographic photoreceptor 1 is transferred onto the recording medium 9 by the transfer means 10 shown in FIG. In addition, a pre-transfer charger 7 may be used for better transfer. As the transfer means 10, an electrostatic transfer method using a transfer charger, a bias roller, or the like; a mechanical transfer method such as an adhesive transfer method or a pressure transfer method; a magnetic transfer method or the like can be used.

  Further, if necessary, a separation charger 11 and a separation claw 12 may be used as means for separating the recording medium 9 shown in FIG. 6 from the electrophotographic photosensitive member 1. As other separation means, electrostatic adsorption induction separation, side end belt separation, tip grip conveyance, curvature separation, and the like are used. As the separation charger 11, the charging means can be used. In addition, cleaning means such as a fur brush 14 and a cleaning blade 15 are used to clean the toner remaining on the photoconductor after transfer, and the pre-cleaning charger 13 may be used for more efficient cleaning. Good. Other cleaning means include a web method, a magnet brush method, and the like, but each may be used alone or in combination. Further, in order to remove the latent image on the electrophotographic photosensitive member 1, the charge eliminating means 2 may be used. As the charge removal means 2, a charge removal lamp, a charge removal charger or the like is used, and the exposure light source and the charging means can be used, respectively. In addition, known processes can be used for reading, feeding, fixing, paper discharge and the like that are not close to the photoconductor.

(Process cartridge)
The process cartridge of the present invention includes an electrophotographic photosensitive member, a charging unit that charges the surface of the electrophotographic photosensitive member, an exposure unit that exposes the charged surface of the electrophotographic photosensitive member to form an electrostatic latent image, It comprises at least one of developing means for developing the electrostatic latent image with toner to form a visible image and transfer means for transferring the visible image to a recording medium. And other means. The electrophotographic photosensitive member used in the process cartridge of the present invention is the above-described electrophotographic photosensitive member of the present invention.

  For example, as shown in FIG. 7, the process cartridge includes an electrophotographic photosensitive member 101, and at least a charging unit 102, a developing unit 104, a transfer unit 106, a cleaning unit 107, and a discharging unit (not shown). This is an apparatus (part) that includes one and is detachable from the image forming apparatus main body. Referring to the image forming process using the process cartridge of FIG. 7, the photosensitive member 101 is charged in the direction of the arrow while being charged by the charging unit 102 and exposed by the exposure unit 103. The electrostatic latent image is developed with toner by the developing unit 104, and the toner development is transferred to the recording medium 105 by the transfer unit 106 and printed out. Next, the surface of the photoconductor after the image transfer is cleaned by the cleaning unit 107 and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to a following example. In addition, a mass part is abbreviated as a part.

Example 1
A coating solution for an undercoat layer, a coating solution for a charge generation layer, and a coating solution for a charge transport layer, which are described below, are sequentially applied onto an aluminum cylinder having a diameter of 40 mm and dried to obtain a thickness of 3.5 μm. An undercoat layer, a charge generation layer having a thickness of 0.2 μm, and a charge transport layer having a thickness of 20 μm were formed.

[Coating liquid for undercoat layer]
・ Alkyd resin (Beccosol 1307-60-EL, manufactured by DIC Corporation) ・ ・ ・ 12 parts ・ Melamine resin (Super Becamine G-821-60, manufactured by DIC Corporation) ・ ・ ・ 8 parts ・ Titanium oxide (CR- EL, manufactured by Ishihara Sangyo Co., Ltd.) ... 80 parts Methyl ethyl ketone ... 250 parts

[Coating liquid for charge generation layer]
-Bisazo pigment of the following structural formula (1): 2.5 parts <Structural formula (1)>
・ Polyvinyl butyral (XYHL, manufactured by UCC): 0.5 part ・ Cyclohexanone: 200 parts ・ Methyl ethyl ketone: 80 parts

[Coating liquid for charge transport layer]
-Bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals Ltd.) ... 10 parts-Charge transporting compound of the following structural formula (2) ... 7 parts <Structural formula (2)>
Tetrahydrofuran: 100 parts Tetrahydrofuran solution of 1% silicone oil (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part

Next, a surface layer coating solution having the following composition is sprayed onto the laminate comprising the conductive support, the undercoat layer, the charge generation layer, and the charge transport layer using the following surface layer coating solution. A surface layer having a thickness of 4.5 μm is formed by a coating method, and light irradiation is performed using a metal halide lamp while rotating the electrophotographic photosensitive member under the conditions of illuminance: 900 mW / cm ² and irradiation time: 120 seconds. After the surface layer was crosslinked by performing, drying was performed at 130 ° C. for 30 minutes.

  The surface layer coating solution was prepared as follows. First, in a 50 mL container charged with 110 g of zirconia beads (average particle size: 0.1 mm), Al-doped zinc oxide, a surfactant, and cyclohexanone are placed, and vibration dispersion is performed for 2 hours under a vibration condition of 1,500 rpm. Then, a dispersion liquid in which Al-doped zinc oxide was dispersed was prepared. Next, the dispersion was transferred to a 50 mL container charged with 60 g of sirconia beads (average particle size: particle size 5 mm), and dispersed for 24 hours at a rotation speed of 200 rpm to prepare a mill base. And the said mill base was added to the tetrahydrofuran solution which melt | dissolved the trimethylol propane triacrylate, and the coating liquid for surface layers of the following composition was prepared.

[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Al-doped zinc oxide fine particles (Pazet CK, average particle size 35 nm, Hakusui Tech Co., Ltd. 10 ³ Ω · cm) 35.7 parts ・ General formula (2 ) Compound (Exemplary Compound No. 17) ... 7.1 parts Surfactant (BYK-P105, manufactured by BYK Chemie) ... 1.8 parts Tetrahydrofuran ... 952 parts Cyclohexanone・ 238 parts

(Example 2)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the content ratio of zinc oxide contained in the surface layer coating solution of Example 1 was changed to the following compounding ratio.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Al-doped zinc oxide fine particles (Pazet CK, average particle size 35 nm, manufactured by Hakusui Tech Co., Ltd., 10 ³ Ω · cm) 111.1 parts ・ General formula (1 ) (Exemplary Compound No. 17) ... 11.1 parts -Surfactant (BYK-P105, manufactured by Big Chemie) -5.6 parts -Tetrahydrofuran ... 1778 parts -Cyclohexanone-・ 444 parts

(Example 3)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the content ratio of zinc oxide contained in the surface layer coating solution of Example 1 was changed to the following compounding ratio.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Al-doped zinc oxide fine particles (Pazet CK, average particle size 35 nm, manufactured by Hakusui Tech Co., Ltd., 10 ³ Ω · cm) 171.4 parts ・ General formula (1 ) (Exemplary Compound No. 17) 14.3 parts Surfactant (BYK-P105, manufactured by BYK Chemie) 8.6 parts Tetrahydrofuran 2438 parts Cyclohexanone・ 610 parts

Example 4
An electrophotographic photosensitive member was produced in the same manner as in Example 2 except that the zinc oxide contained in the surface layer coating solution of Example 2 was changed to the following.
・ Al-doped zinc oxide fine particles (23-K, average particle size 152 nm, manufactured by Hakusui Tech Co., 10 ³ Ω · cm)

(Example 5)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the zinc oxide used in the surface layer coating solution of Example 1 was changed to the following.
Ga-doped zinc oxide fine particles (Pazet GK-40, average particle size 32 nm), manufactured by Hakusui Tech Co., 10 ³ Ω · cm)

(Example 6)
An electrophotographic photosensitive member was produced in the same manner as in Example 5 except that the surface layer coating solution in Example 5 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles (Pazet GK-40, average particle size 32 nm, manufactured by Hakusui Tech Co., Ltd., 10 ³ Ω · cm) 58.3 parts (1) Compound (Exemplary Compound No. 17) 8.3 parts Surfactant (BYK-P105, manufactured by Big Chemie) 2.9 parts Tetrahydrofuran 1200 parts Cyclohexanone ... 300 copies

(Example 7)
An electrophotographic photosensitive member was produced in the same manner as in Example 2 except that the zinc oxide used in the surface layer coating solution of Example 2 was changed to the following.
Ga-doped zinc oxide fine particles (Pazet GK-40, average particle size 32 nm, manufactured by Hakusui Tech Co., 10 ³ Ω · cm)

(Example 8)
An electrophotographic photosensitive member was produced in the same manner as in Example 3 except that the zinc oxide used in the surface layer coating solution of Example 3 was changed to the following.
Ga-doped zinc oxide fine particles (Pazet GK-40, average particle size 32 nm, manufactured by Hakusui Tech Co., 10 ³ Ω · cm)

Example 9
An electrophotographic photosensitive member was produced in the same manner as in Example 5, except that zinc oxide used in Example 5 was surface-treated by the following procedure and that the following surface layer coating solution was used.
The surface layer coating solution was prepared as follows. First, in a 50 mL container charged with 110 g of zirconia beads (average particle size: 0.1 mm), Ga-doped zinc oxide and cyclohexanone surface-treated by the surface treatment method described later are placed, and the vibration condition of 1,500 rpm is 2 hours. The dispersion liquid in which Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane were dispersed was prepared. Next, the dispersion was transferred to a 50 mL container charged with 60 g of sirconia beads (average particle size: 5 mm), and dispersed for 24 hours at a rotation speed of 200 rpm to prepare a mill base. And the said mill base was added to the tetrahydrofuran solution which melt | dissolved the trimethylol propane triacrylate, and the coating liquid for surface layers of the following composition was prepared.
[Surface treatment method]
2.5 g of N-phenyl-3-aminopropyltrimethoxysilane (KBM-573, manufactured by Shin-Etsu Silicone) was added to 100 g of methanol, and Ga-doped zinc oxide fine particles (Pazet GK-40, average particle diameter of 32 nm, manufactured by Hakusui Tech Co., Ltd.) ) 25 g was added, refluxed at 95 ° C. for 2 hours, and then the solvent was removed under reduced pressure. When the solvent was exhausted, the temperature was raised to 150 ° C. and held for 2 hours to maintain N-phenyl-3-aminopropyltri Ga-doped zinc oxide fine particles modified with methoxysilane were obtained.

[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) ・ ・ ・ 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) ・ ・ ・ 35.7 parts Compound represented by formula (1) (Exemplary Compound No. 17) ... 7.1 parts Tetrahydrofuran ... 952 parts Cyclohexanone ... 238 parts

(Example 10)
An electrophotographic photosensitive member was produced in the same manner as in Example 5 except that the surface layer coating solution used in Example 5 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 58.3 parts Compound represented by formula (1) (Exemplary Compound No. 17) 8.3 parts Tetrahydrofuran 1200 parts Cyclohexanone 300 parts

(Example 11)
An electrophotographic photosensitive member was produced in the same manner as in Example 5 except that the surface layer coating solution used in Example 5 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 111.1 parts Compound represented by formula (1) (Exemplary Compound No. 17) ... 11.1 parts-Tetrahydrofuran ... 1,778 parts-Cyclohexanone ... 444 parts

(Example 12)
An electrophotographic photosensitive member was produced in the same manner as in Example 5 except that the surface layer coating solution used in Example 5 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 171.4 parts Compound represented by formula (1) (Exemplary Compound No. 17) 14.3 parts Tetrahydrofuran 2,438 parts Cyclohexanone 610 parts

(Example 13)
An electrophotographic photosensitive member was produced in the same manner as in Example 5 except that the surface layer coating solution used in Example 5 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 38.5 parts Compound represented by formula (1) (Exemplary Compound No. 17) ... 15.4 parts Tetrahydrofuran ... 1,026 partsCyclohexanone ... 256 parts

(Example 14)
An electrophotographic photosensitive member was produced in the same manner as in Example 5 except that the surface layer coating solution used in Example 5 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 63.6 parts Compound represented by formula (1) (Exemplary Compound No. 17) ... 18.2 parts-Tetrahydrofuran ... 1,309 parts-Cyclohexanone ... 327 parts

(Example 15)
An electrophotographic photosensitive member was produced in the same manner as in Example 5 except that the surface layer coating solution used in Example 5 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 125.0 parts ・ General Compound represented by formula (1) (Exemplary Compound No. 17) 25.0 parts Tetrahydrofuran 2,000 parts Cyclohexanone 500 parts

(Example 16)
An electrophotographic photosensitive member was produced in the same manner as in Example 5 except that the surface layer coating solution used in Example 5 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 200.0 parts Compound represented by formula (1) (Exemplary Compound No. 17) 33.3 parts Tetrahydrofuran 2,844 parts Cyclohexanone 711 parts

(Example 17)
An electrophotographic photosensitive member was produced in the same manner as in Example 9, except that the compound represented by the general formula (1) used in the surface layer coating solution of Example 9 was changed to the following.
Compound represented by the general formula (1) (Exemplary Compound No. 2)

(Example 18)
An electrophotographic photosensitive member was produced in the same manner as in Example 11 except that the compound represented by the general formula (1) used in the surface layer coating solution of Example 11 was changed to the following.
Compound represented by the general formula (1) (Exemplary Compound No. 2)

(Example 19)
An electrophotographic photosensitive member was produced in the same manner as in Example 12 except that the compound represented by the general formula (1) used in the surface layer coating solution of Example 12 was changed to the following.
Compound represented by the general formula (1) (Exemplary Compound No. 2)

(Example 20)
An electrophotographic photosensitive member was produced in the same manner as in Example 9, except that the compound represented by the general formula (1) used in the surface layer coating solution of Example 9 was changed to the following.
Compound represented by the general formula (1) (Exemplary Compound No. 4)

(Example 21)
An electrophotographic photosensitive member was produced in the same manner as in Example 11 except that the compound represented by the general formula (1) used in the surface layer coating solution of Example 11 was changed to the following.
Compound represented by the general formula (1) (Exemplary Compound No. 4)

(Example 22)
An electrophotographic photosensitive member was produced in the same manner as in Example 12 except that the compound represented by the general formula (1) used in the surface layer coating solution of Example 12 was changed to the following.
Compound represented by the general formula (1) (Exemplary Compound No. 4)

(Example 23)
An electrophotographic photosensitive member was produced in the same manner as in Example 11 except that the surface layer coating solution used in Example 11 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 142.9 parts Compound represented by formula (1) (Exemplary Compound No. 17) 14.3 parts Compound represented by the structural formula (2) 28.6 parts Tetrahydrofuran 2,286 parts Cyclohexanone: 571 parts

(Example 24)
An electrophotographic photosensitive member was produced in the same manner as in Example 11 except that the surface layer coating solution used in Example 11 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 200.0 parts Compound represented by formula (1) (exemplary compound No. 17) 20.0 parts Compound represented by the structural formula (2) 80.0 parts Tetrahydrofuran 3200 parts Cyclohexanone: 800 parts

(Example 25)
An electrophotographic photosensitive member was produced in the same manner as in Example 11 except that the surface layer coating solution used in Example 11 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 333.3 parts Compound represented by formula (1) (Exemplary Compound No. 17) 33.3 parts Compound represented by the structural formula (2) 200 parts Tetrahydrofuran 5333 parts Cyclohexanone ..1,333 parts

(Example 26)
An electrophotographic photosensitive member was produced in the same manner as in Example 7, except that the surface layer coating solution used in Example 7 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 142.9 parts Compound represented by formula (1) (Exemplary Compound No. 17) ... 14.3 parts-Compound represented by the following structural formula (3) ... 28.6 parts <Structural formula (3)>
Surfactant (BYK-P105, manufactured by Big Chemie) 7.1 parts Tetrahydrofuran 2,286 parts Cyclohexanone 571 parts

(Example 27)
An electrophotographic photosensitive member was produced in the same manner as in Example 7, except that the surface layer coating solution used in Example 7 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 200.0 parts Compound represented by formula (1) (Exemplary Compound No. 17) 20.0 parts Compound represented by Structural Formula (3) 80.0 parts Surfactant (BYK-P105, Big Chemie 10 parts) · Tetrahydrofuran ... 3,200 parts · Cyclohexanone ... 800 parts

(Example 28)
An electrophotographic photosensitive member was produced in the same manner as in Example 7, except that the surface layer coating solution used in Example 7 was changed to the following.
[Coating liquid for surface layer]
Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts Photoinitiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 333.3 parts Compound represented by Formula (1) (Exemplary Compound No. 17) 33.3 parts Compound represented by Structural Formula (3) 200 parts Surfactant (BYK-P105, manufactured by Big Chemie) ) ... 16.7 parts Tetrahydrofuran ... 5,333 partsCyclohexanone ... 1,333 parts

(Example 29)
An electrophotographic photosensitive member was produced in the same manner as in Example 7, except that the surface layer coating solution used in Example 7 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 142.9 parts Compound represented by formula (1) (Exemplary Compound No. 17) 14.3 parts Compound represented by the structural formula (3) 28.6 parts Tetrahydrofuran 2,286 parts Cyclohexanone: 571 parts

(Example 30)
An electrophotographic photosensitive member was produced in the same manner as in Example 7, except that the surface layer coating solution used in Example 7 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 200.0 parts Compound represented by formula (1) (Exemplary compound No. 17) 20.0 parts Compound represented by the structural formula (3) 80.0 parts Tetrahydrofuran 3200 parts Cyclohexanone: 800 parts

(Example 31)
An electrophotographic photosensitive member was produced in the same manner as in Example 7, except that the surface layer coating solution used in Example 7 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 333.3 parts Compound represented by formula (1) (Exemplary Compound No. 17) 33.3 parts Compound represented by the structural formula (3) 200 parts Tetrahydrofuran 5333 parts Cyclohexanone ..1,333 parts

(Example 32)
A surface layer coating solution having the following composition was spray coated onto a laminate comprising a conductive support, an undercoat layer, a charge generation layer, and a charge transport layer prepared according to the procedure of Example 1, with a thickness of 4.5 μm. The surface layer was formed and dried at 130 ° C. for 30 minutes to prepare an electrophotographic photosensitive member.
[Coating liquid for surface layer]
Bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals) ... 100 parts Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm)・ 35.7 parts ・ Compound represented by the above general formula (1) (Exemplary Compound No. 17)... 7.1 parts ・ Tetrahydrofuran ... 952 parts ・ Cyclohexanone ... 238 parts

(Example 33)
An electrophotographic photosensitive member was produced in the same manner as in Example 32 except that the surface layer coating solution used in Example 32 was changed to the following.
[Coating liquid for surface layer]
Bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals) ... 100 parts Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm)・ 111.1 parts ・ Compound represented by the above general formula (1) (Exemplary Compound No. 17) ... 11.1 parts ・ Tetrahydrofuran ... 1,779 parts ・ Cyclohexanone ... 444 parts

(Example 34)
An electrophotographic photosensitive member was produced in the same manner as in Example 32 except that the surface layer coating solution used in Example 32 was changed to the following.
[Coating liquid for surface layer]
Bisphenol Z polycarbonate (Panlite TS-2050, manufactured by Teijin Chemicals) ... 100 parts Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ³ Ω · cm) 171.4 parts Compound represented by general formula (1) (Exemplary Compound No. 17) 14.3 parts Tetrahydrofuran 2,438 parts Cyclohexanone 610 parts

(Examples 35-37)
Electrophotographic photosensitive members were produced in the same manner as in Examples 32-34, except that the bisphenol Z polycarbonate used in the surface layer coating solutions of Examples 32-34 was changed to the following.
-The following two compounds were adjusted so that the OH value / NCO value = 1.0 (1) Polyol compound of the following structural formula (3) <Structural formula (3)>
(2) Isocyanate compound (Takenate D140N, manufactured by Mitsui Takeda Chemical Co., Ltd.)

(Example 38)
An electrophotographic photosensitive member was produced in the same manner as in Example 33 except that the bisphenol Z polycarbonate used in the surface layer coating solution of Example 33 was changed to the following.
・ Polyarylate resin (U-100, manufactured by Unitika)

(Example 39)
An electrophotographic photosensitive member was produced in the same manner as in Example 33 except that the bisphenol Z polycarbonate used in the surface layer coating solution of Example 33 was changed to the following.
・ Styrene resin (Product name: Septon 2043, manufactured by Kuraray Co., Ltd.)

(Example 40)
An electrophotographic photosensitive member was produced in the same manner as in Example 33 except that the bisphenol Z polycarbonate used in the surface layer coating solution of Example 33 was changed to the following.
・ Phenolic resin (Product name: PR9480, manufactured by Sumitomo Bakelite)

(Example 41)
An electrophotographic photosensitive member was produced in the same manner as in Example 33 except that the bisphenol Z polycarbonate used in the surface layer coating solution of Example 33 was changed to the following.
- After 2 hours stirring was carried out at a temperature of the liquid to 60 ° C. the following formulation, it was added 0.016 parts of tin organic acid salt _{(nBu 2 · Sn (OAc)} 2), 3 at a temperature of 40 ° C. Compound stirred for hours.
・ Methyltrimethoxysilane ・ ・ ・ 10 parts ・ 1% acetic acid aqueous solution ・ ・ ・ 5 parts ・ n-butanol ・ ・ ・ 15 parts

(Comparative Example 1)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) ... 5 parts ・ Tetrahydrofuran ... 533 parts ・ Cyclohexanone ... 133 parts

(Comparative Example 2)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Compound represented by the above structural formula (3) 5.3 parts ・ Tetrahydrofuran 561 parts ・ Cyclohexanone 140 parts

(Comparative Example 3)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.): 5 parts ・ Zinc oxide fine particles (Nanotek ZnO, average particle size: 34 nm, manufactured by CI Kasei Co., Ltd., 10 ⁹ Ω · cm): 5.3 parts ・ Surfactant (BYK- P105, manufactured by Big Chemie) ... 0.3 part Tetrahydrofuran ... 590 parts Cyclohexanone ... 147 parts

(Comparative Example 4)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Zinc oxide fine particles (Nanotek ZnO, average particle size 34 nm, manufactured by CI Chemical Co., Ltd., 10 ⁹ Ω · cm) 100 parts ・ Surfactant (BYK-P105, (Made by Big Chemie) ... 5 parts-Tetrahydrofuran ... 1,600 parts-Cyclohexanone ... 400 parts

(Comparative Example 5)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.): 5 parts ・ Zinc oxide fine particles (Nanotek ZnO, average particle size: 34 nm, manufactured by CI Chemical Co., Ltd., 10 ⁹ Ω · cm): 233.3 parts ・ Surfactant (BYK- P105, manufactured by Big Chemie) ... 11.7 parts-Tetrahydrofuran ... 3,022 parts-Cyclohexanone ... 756 parts

(Comparative Example 6)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Zinc oxide fine particles (Nanotek ZnO, average particle size 34 nm, manufactured by CI Kasei Co., Ltd., 10 ⁹ Ω · cm) 5.6 parts ・ General formula (1) Compound (Exemplary Compound No. 17) represented by: 5.6 parts Surfactant (BYK-P105, manufactured by Big Chemie): 0.3 part Tetrahydrofuran: 622 parts Cyclohexanone: 156 parts

(Comparative Example 7)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) ... 5 parts ・ Zinc oxide fine particles (Nanotek ZnO, average particle size 34 nm, manufactured by CI Kasei Co., Ltd., 10 ⁹ Ω · cm) 111.1 parts ・ General formula (1) Compound (Exemplary Compound No. 17) shown in FIG. 11.1 part. Surfactant (BYK-P105, manufactured by Big Chemie). 5.6 parts. Tetrahydrofuran ... 1,778 parts. Cyclohexanone. ..444 parts

(Comparative Example 8)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Zinc oxide fine particles (Nanotek ZnO, average particle size 34 nm, manufactured by C.I. Kasei Co., Ltd., 10 ⁹ Ω · cm) 280 parts ・ Indicated by the above general formula (1) Compound (Exemplary Compound No. 17) 20 parts Surfactant (BYK-P105, manufactured by BYK Chemie) 14 parts Tetrahydrofuran 3,627 parts Cyclohexanone 907 parts

(Comparative Examples 9-11)
Electrophotographic photosensitive members were produced in the same manner as in Examples 6-8, except that the zinc oxide fine particles used in the surface layer coating liquids of Examples 6-8 were changed to the following.
・ Zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (10 ⁹ Ω · cm)
[Surface treatment method]
2.5 g of N-phenyl-3-aminopropyltrimethoxysilane (KBM-573, manufactured by Shin-Etsu Silicone) was added to 100 g of methanol, and 25 g of zinc oxide fine particles (Nanotek ZnO, average particle size of 34 nm, manufactured by CI Kasei Co., Ltd.). In addition, the mixture was refluxed at 95 ° C. for 2 hours, and then the solvent was removed under reduced pressure. When the solvent was exhausted, the temperature was raised to 150 ° C. and held for 2 hours. Modified zinc oxide fine particles were obtained.

(Comparative Example 12)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane 7.1 parts ・ Compound represented by the general formula (1) ( Exemplified compound No. 17)... 7.1 parts ・ Compound represented by the structural formula (3)... 28.6 parts. ・ Tetrahydrofuran ..622 parts.

(Comparative Example 13)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane 200 parts ・ Compound represented by the above general formula (1) (exemplary compound) No. 17) ... 20 parts-Compound represented by the structural formula (3) ... 80 parts-Tetrahydrofuran ... 3,200 parts-Cyclohexanone ... 800 parts

(Comparative Examples 14-19)
Electrophotographic photosensitive members were produced in the same manner as in Comparative Examples 4 to 9, except that the zinc oxide fine particles used in the surface layer coating solutions of Comparative Examples 4 to 9 were changed to the following.
・ Titanium oxide fine particles (Nanotek TiO ₂ , average particle size 36 nm, manufactured by CI Kasei Co., Ltd., 10 ⁷ Ω · cm)

(Comparative Examples 20-22)
Electrophotographic photosensitive members were produced in the same manner as in Comparative Examples 4 to 6 except that the zinc oxide fine particles used in the surface layer coating solutions of Comparative Examples 4 to 6 were changed to the following.
Tin oxide fine particles (Nanotek SnO ₂ , average particle size 21 nm, manufactured by CI Kasei Co., 10 ³ Ω · cm)

(Comparative Examples 23-25)
Electrophotographic photosensitive members were produced in the same manner as in Comparative Examples 4 to 6 except that the zinc oxide fine particles used in the surface layer coating solutions of Comparative Examples 4 to 6 were changed to the following.
Ga-doped zinc oxide fine particles (Pazet GK-40, average particle size 32 nm, manufactured by Hakusui Tech Co., 10 ³ Ω · cm)

(Comparative Example 26)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Al-doped zinc oxide fine particles (Pazet CK, average particle size 35 nm, manufactured by Hakusui Tech Co., Ltd., 10 ³ Ω · cm) 5.6 parts ・ General formula (1 ) Compound (Exemplary Compound No. 17) 5.6 parts Surfactant (BYK-P105, manufactured by BYK Chemie) 0.3 parts Tetrahydrofuran 622 parts Cyclohexanone・ 156 parts

(Comparative Example 27)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) ・ ・ ・ 5 parts ・ Al-doped zinc oxide fine particles (Pazet CK, average particle size 35 nm, Hakusitek Co., 10 ³ Ω · cm) 280 parts ・ In the general formula (2) Compound shown (Exemplary Compound No. 17) ... 20 parts Surfactant (BYK-P105, manufactured by BYK Chemie) ... 14 partsTetrahydrofuran ... 3,627 parts Cyclohexanone ... 907 parts

(Comparative Examples 28-29)
Electrophotographic photosensitive members were produced in the same manner as in Comparative Examples 26 to 27 except that the zinc oxide fine particles used in the surface layer coating liquids of Comparative Examples 26 to 27 were changed to the following.
Ga-doped zinc oxide fine particles (Pazet GK-40, average particle size 32 nm, manufactured by Hakusui Tech Co., 10 ³ Ω · cm)

(Comparative Examples 30-31)
Electrophotographic photosensitive members were produced in the same manner as in Comparative Examples 26 to 27 except that the zinc oxide fine particles used in the surface layer coating liquids of Comparative Examples 26 to 27 were changed to the following.
Ga-doped zinc oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane

(Comparative Example 32)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Compound represented by the above general formula (1) (Exemplary Compound No. 17) 5.3 parts ・ Tetrahydrofuran 561 parts ・ Cyclohexanone 140 Part

(Comparative Example 33)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Compound represented by the above general formula (1) (Exemplary Compound No. 17) 11.1 parts ・ Tetrahydrofuran 593 parts ・ Cyclohexanone 148 Part

(Comparative Example 34)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Compound represented by the above general formula (1) (Exemplary Compound No. 17) 25 parts ・ Tetrahydrofuran 667 parts ・ Cyclohexanone 167 parts

(Comparative Example 35)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Compound represented by the above general formula (1) (Exemplary Compound No. 17) 5.9 parts ・ Compound represented by the above structural formula (3) 11.8 parts Tetrahydrofuran ... 628 parts Cyclohexanone 157 parts

(Comparative Example 36)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Compound represented by the above general formula (1) (Exemplary Compound No. 17) 6.7 parts ・ Compound represented by the above structural formula (3) -26.7 parts-Tetrahydrofuran ... 711 parts-Cyclohexanone ... 178 parts

(Comparative Example 37)
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the surface layer coating solution of Example 1 was changed to the following.
[Coating liquid for surface layer]
-Resin not having a charge transporting structure (trimethylolpropane triacrylate, TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 100 parts-Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure I-184, Ciba・ Specialty Chemicals Co., Ltd.) 5 parts ・ Compound represented by the general formula (1) (Exemplary Compound No. 17) 7.7 parts ・ Compound represented by the structural formula (3) -46.2 parts-Tetrahydrofuran ... 821 parts-Cyclohexanone ... 205 parts

  Next, the following tests were carried out on the electrophotographic photoreceptors of Examples 1-41 and Comparative Examples 1-37 produced as described above. The results are shown in Table 1-1 and Table 1-2.

<Surface specific resistivity measurement>
The surface resistivity of the electrophotographic photosensitive member at each electric field strength was measured as follows.
The surface specific resistivity of the electrophotographic photosensitive member according to the present invention may be measured by a generally known method. ) And the like. In general, many electrophotographic photoreceptors have a cylinder shape, and when measurement is difficult by the method of the above-mentioned literature, the measurement may be performed by the following method.

<Electrode shape and production method>
The electrode shape has a known length, a counter electrode having a known gap, an electrode length of 10 mm, and an electrode gap of 25 μm. The electrode length and electrode gap may be determined based on the capacity of the DC voltage source used for measurement and the accuracy of the ammeter. The metal constituting the electrode may be appropriately selected as long as the electrode can be formed on the surface of the electrophotographic photosensitive member, and examples thereof include commonly used gold, silver, copper, aluminum, nickel, platinum, chromium, zinc, and carbon. The counter electrodes are preferably made of the same metal. The method for producing the electrode is not particularly limited as long as the constituent components of the electrophotographic photosensitive member do not change in quality, but a vacuum deposition method is preferable because it does not easily change the electrophotographic photosensitive member.

From the results of Table 1-1 and Table 1-2, the electrophotographic photosensitive member described in the examples has a surface resistivity of 1 × 10 ^{13 at a} low electric field (1 × 10 ^{4 to} 3 × 10 ⁴ V / cm ² ). It shows Ω / cm ² or more, and shows high resistance in a low electric field. About 1 × ¹⁰ 4 the ratio of the surface resistivity _{R 3} in the surface resistivity _{R 1} and 3 × ¹⁰ 4 V / cm ² in V / cm ² _R 1 / _{R 3} is a result showing 10 below The surface resistivity in the low electric field strength region was shown to be extremely stable. On the other hand, Comparative Examples 1-2 to 32-37 are surface layers that do not contain inorganic fine particles, and the surface resistivity is large and the change is small in a low electric field to a high electric field. It is estimated that the charge transporting property is low. Further, even when the particles are contained, if the particle content is too small (Comparative Examples 3, 6, 9, 12, 14, 17, 20, 23, 26, 28, 30), the surface Although the surface specific resistivity of the layer is kept high, the ratio R ₁ / R ₁₅ between the surface specific resistivity R ₁ and the surface specific resistivity R _{15 at} 1.5 × 10 ⁵ V / cm ² is 100 or less. The results show that the change in resistivity of the surface layer due to the change in electric field is small, and it is estimated that such a surface layer also has poor charge transportability. In contrast, when the particle content is too high (Comparative Examples 5, 8, 11, 16, 19, 22, 25, 27, 29, 31), the surface resistivity of the surface layer is very high. Get smaller. In addition, the ratio R ₁ / R ₁₅ between the surface specific resistivity R ₁ and the surface specific resistivity R _{15 at} 1.5 × 10 ⁵ V / cm ² is 5,000 or more, and the electric field change It can be seen that the change in resistivity of the surface layer due to the surface layer is large, and in contrast to the above surface layer, these surface layers have high charge transport properties, but when dot reproducibility is poor due to low surface resistivity. Guessed.
When the particle content is appropriately contained (Comparative Examples 4, 7, 10, 13, 15, 18, 21, 24), the surface resistivity and electric field strength of the surface layer are the same as in the examples. It can be seen that the change in surface resistivity due to the change is in an ideal form.

<Electrical photoconductor characteristics and output image evaluation before and after long-term use>
It was used for a running test using a modified photoconductor unit in which a member (cleaning blade, etc.) excluding the charging unit was removed from a photoconductor unit of Imagio MP C5000 manufactured by Ricoh Co., Ltd. The modified photoreceptor unit to which the photoreceptors produced in the examples and comparative examples were attached was set in an Imagio MP C5000 modified machine so that only charging and development could be repeated without passing paper. As charging conditions, a charging roller is used, an alternating voltage obtained by superimposing an AC voltage on a DC voltage is applied, a peak-to-peak voltage Vpp of the AC voltage is about 1.9 [kV], and a frequency f is about 900 [Hz]. The DC voltage was set to -650 [V], and the rotational speed of the electrophotographic photosensitive member was set to 230 mm / sec. As development conditions, a 655 nm LD was used, and the writing pattern was a 100% writing pattern (all solid). In order to load the electrophotographic photoreceptor with an electrostatic fatigue equivalent to 150,000 sheets running (5% test pattern / charge-exposure potential difference 550 V / electrophotographic photoreceptor capacitance 110 pF / cm ² ) under these conditions, Passage charge calculations show that it can be achieved by running for about 3.8 hours. In this evaluation, an electrostatic fatigue test corresponding to 150,000 sheets of running was performed using the above-described modified machine, and image evaluation was performed using the following evaluation machine.
For the image evaluation, a modified IPSiO MP C5000 was used so as to eliminate the initial idling process during image output. Imagio toner type 27 was used as the toner, and MyPaper (A4 size) manufactured by NBS Ricoh was used as the paper. The photoreceptor surface potential at the start was −650 V, and the in-machine potential (post-charge potential and exposed portion potential) before and after the electrostatic fatigue was evaluated. As an output image, three halftone outputs were performed continuously, and the dot reproduction state of the output image was confirmed visually and with a microscope. The measurement results of the in-machine potential and the image evaluation results are shown in Table 2-1 and Table 2-2.

* Running was stopped due to abnormal noise during running.

About Comparative Examples 1-2 thru | or Comparative Examples 32-36, since abnormal noise generate | occur | produced during running, running was stopped. As a result of investigating the cause, it is considered that abnormal noise was generated in the developing unit or the cleaning unit because the increase in the bright portion potential was large and the toner supply amount decreased during the running.
From the other results, it can be seen that in Examples 1 to 41, the changes in the dark part potential and the bright part potential before and after running are extremely small, and the electrophotographic photosensitive member is satisfactory. Among them, when using aluminum-doped zinc oxide and gallium-doped zinc oxide, the stability of the bright part potential is high, and particularly when using gallium-doped zinc oxide, it shows very high stability, It was found that there was very little fluctuation in both the dark part potential and the light part potential. This is because zinc oxide itself contains a large amount of oxygen vacancies in its particle bulk and surface, and its resistance value is likely to fluctuate due to oxidation in the atmosphere, but by doping a group 13 element to compensate for the oxygen vacancies. It is thought that this is because the stability in the atmosphere is increased, and in addition, the gallium element itself is less likely to participate in the atmosphere, and is considered to be derived from exhibiting very stable characteristics. In addition, since each of the examples contains the compound represented by the general formula (1), it has a high resistance to acid gas in the charging process in the electrophotographic imaging process and has been used for a long time. Even in this case, it can be seen that good image quality is obtained. On the other hand, Comparative Examples 3, 6, 9, 12, 14, 17, 20, 23, 26 having a surface layer having a small particle content and a small surface specific resistance and a small electric field strength dependency of the surface specific resistivity. 28, 30, the bright part potential is high from the beginning, and the rise of the bright part potential is relatively large. This is probably because the surface transport resistivity is relatively high at a high electric field strength, so that the charge transportability is not sufficient, and the charge transportability is greatly reduced during use. In particular, in Comparative Examples 26, 28, and 30 exceeding 1 × 10 ¹⁴ Ω / cm ² even in a high electric field, the bright part potential is very large, and the image density is significantly reduced. The potential and the bright part potential were large, and sufficient stability could not be obtained. As for Comparative Examples 3 to 22 and Comparative Examples 26 to 27 using zinc oxide fine particles containing no Group 13 element and other oxide metal fine particles, the surface resistivity of the surface layer was good from the results of Table 1. However, the fluctuation of the dark part potential and the bright part potential before and after running tends to be very large as compared with the example. Further, the density of the output image after running is also reduced, but this is considered to be caused by the increase of the bright part potential after running. Further, in Comparative Examples 5, 8, 11, 16, 19, 22, 25, 27, 29, and 31 having a surface layer having a large particle content, the dark portion potential, the bright portion potential, and the variation amount thereof are not so large. However, dot reproducibility was poor for any of the photoreceptors. This is because the surface resistivity at a low electric field is as small as 1 × 10 ¹³ Ω / cm or less, and the ratio R between the surface resistivity R ₁ and the surface resistivity R _{15 at} 1.5 × 10 ⁵ V / cm ² . _{Since 1} / R ₁₅ is 5,000 or more, it can be considered as a phenomenon derived from the fact that the latent image is easily broken. In contrast, among Comparative Examples 4, 7, 10, 13, 15, 18, 21, and 24 that are considered appropriate for the surface resistivity and the change in electric field strength, Comparative Examples 4 and 15 21 and 24, image density reduction or image blurring occurred. This is considered to be a phenomenon that occurs because the surface resistance is reduced by the acidic gas generated in the charging process because the surface layer containing an unstable material in the atmosphere is used as particles. Further, since Comparative Examples 7, 10, 13, and 18 contain the compound represented by the general formula (1), generation of image blur was suppressed because resistance to the acidic gas was increased. Although it is considered that the inorganic fine particles used in the surface layer are unstable in atmospheric oxygen, it is considered that the resistance to acidic gas is insufficient.
From the above results, the electrophotographic photosensitive member of the present invention has excellent charge transportability and latent image retention, and has extremely high charge transportability and latent image retention even when running for a long time. As a result, it was found that the electrophotographic photosensitive member has few defects relating to image quality over a long period of time.

(Production Example 1: Production of Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane)
In 100 g of methanol, 2.5 g of N-phenyl-3-aminopropyltrimethoxysilane (KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) and Ga-doped zinc oxide fine particles (Pazet GK-40, average primary particle diameter of 32 nm) , Hakusuitec Co., Ltd.) was added. The mixture was refluxed at 95 ° C. for 2 hours, and then the solvent was removed under reduced pressure. When the solvent was exhausted, the temperature was raised to 150 ° C. and held for 2 hours, whereby N-phenyl-3-aminopropyltrimethoxysilane was used. Modified Ga-doped zinc oxide fine particles (volume resistivity 9.2 × 10 ¹ Ω · cm) were obtained.

<Measurement of volume resistivity>
The volume resistivity of the Ga-doped zinc oxide fine particles modified with the produced N-phenyl-3-aminopropyltrimethoxysilane is a combination of MCP-PD51 type and Loresta GP, or MCP-PD51 type and Hiresta UP. It measured based on JIS-K6911 using the combination (all are Mitsubishi Chemical Analytech make). The powder resistivity value in a state where the cylinder porosity is 50% was calculated by interpolating from the measurement results of three times, and this value was modified with the N-phenyl-3-aminopropyltrimethoxysilane. The volume resistivity of the Ga-doped zinc oxide fine particles was used. The approximation uses exponential function approximation. The porosity was determined by the following calculation formula.
Cylinder porosity (%) = (1−measured fine particle weight ÷ fine particle density ÷ particulate volume during pressurization) × 100

(Production Example 2: Production of fine zinc oxide particles modified with N-phenyl-3-aminopropyltrimethoxysilane)
N-phenyl-3-like in the same manner as in Production Example 1, except that the Ga-doped zinc oxide fine particles were changed to zinc oxide fine particles (Nanotek (registered trademark) ZnO, primary particle average particle size 28 nm, manufactured by CI Kasei Co., Ltd.). Zinc oxide fine particles (volume resistivity: 3.0 × 10 ⁴ Ω · cm) modified with aminopropyltrimethoxysilane were obtained.

(Production Example 3: Production of titanium oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane)
N-phenyl-3-aminopropyltrimethyl trioxide was changed in the same manner as in Production Example 1 except that the Ga-doped zinc oxide fine particles were changed to titanium oxide fine particles (ET-300, primary particle average particle size 40 nm, manufactured by Ishihara Sangyo Co., Ltd.). Titanium oxide fine particles (volume resistivity 5.0 × 10 ¹ Ω · cm) modified with methoxysilane were obtained.

(Production Example 4: Production of tin oxide fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane)
N-phenyl-3-aminopropyltrimethyl trioxide was the same as Production Example 1 except that the Ga-doped zinc oxide fine particles were changed to tin oxide fine particles (S-2000, primary particle average particle size 30 nm, manufactured by Mitsubishi Materials Corporation). Tin oxide fine particles (volume resistivity 2.0 × 10 ² Ω · cm) modified with methoxysilane were obtained.

(Production Example 5: Production of fine tin oxide particles modified with N-phenyl-3-aminopropyltrimethoxysilane)
N-phenyl-3-aminopropyltrimethyl trioxide is the same as Production Example 1 except that the Ga-doped zinc oxide fine particles are changed to tin oxide fine particles (S-1, primary particle average particle size 43 nm, manufactured by Mitsubishi Materials Corporation). Tin oxide fine particles (volume resistivity: 7.0 × 10 ⁷ Ω · cm) modified with methoxysilane were obtained.

(Production Example 6: Production of Ga-doped zinc oxide fine particles modified with N-2- (aminoethyl) -3-aminopropyltrimethoxysilane)
Production Example 1 except that N-phenyl-3-aminopropyltrimethoxysilane was changed to N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) Similarly, Ga-doped zinc oxide fine particles (volume resistivity 7.2 × 10 ¹ Ω · cm) modified with N-2- (aminoethyl) -3-aminopropyltrimethoxysilane were obtained.

(Production Example 7: Production of Ga-doped zinc oxide fine particles modified with 3-aminopropyltrimethoxysilane)
3-aminopropyltrimethoxysilane was prepared in the same manner as in Production Example 1, except that N-phenyl-3-aminopropyltrimethoxysilane was changed to 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.). Ga-doped zinc oxide fine particles (volume resistivity 8.4 × 10 ¹ Ω · cm) modified with methoxysilane were obtained.

(Production Example 8: Production of silica fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane)
N-phenyl-3-aminopropyltrimethoxysilane was used in the same manner as in Production Example 1 except that the Ga-doped zinc oxide fine particles were changed to silica fine particles (R972CF, primary particle average particle size 20 nm, manufactured by Nippon Aerosil Co., Ltd.). Modified silica fine particles (volume resistivity 4.0 × 10 ¹² Ω · cm) were obtained.

(Production Example 9: Production of Ga-doped zinc oxide fine particles modified with 3-methacryloxypropyltrimethoxysilane)
In the same manner as in Production Example 1, except that N-phenyl-3-aminopropyltrimethoxysilane was changed to 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxy Ga-doped zinc oxide fine particles (volume resistivity 8.0 × 10 ¹ Ω · cm) modified with propyltrimethoxysilane were obtained.

(Production Example 10: Production of Ga-doped zinc oxide fine particles modified with 4- [2- (triethoxysilyl) ethyl] triphenylamine)
4- [2- (Triethoxysilyl) was prepared in the same manner as in Production Example 1 except that N-phenyl-3-aminopropyltrimethoxysilane was changed to 4- [2- (triethoxysilyl) ethyl] triphenylamine. ) Ethyl] triphenylamine modified Ga-doped zinc oxide fine particles (volume resistivity 5.0 × 10 ¹ Ω · cm) were obtained.

(Production Example 11: Production of silica fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane)
N-phenyl-3-aminopropyl was prepared in the same manner as in Production Example 1 except that the Ga-doped zinc oxide fine particles were changed to silica fine particles (Sciquas 0.05 μm, primary particle average particle size 50 nm, manufactured by Sakai Chemical Industry Co., Ltd.). Silica fine particles (volume resistivity 3.0 × 10 ⁹ Ω · cm) modified with trimethoxysilane were obtained.

(Production Example 12: Production of tin oxide fine particles modified with compound A-1)
Ga-doped zinc oxide fine particles are changed to tin oxide fine particles (S-2000, primary particle average particle size 30 nm, manufactured by Mitsubishi Materials Corporation), N-phenyl-3-aminopropyltrimethoxysilane is represented by the following structural formula (1). Tin oxide fine particles (volume resistivity 2.0 × 10 ² Ω · cm) modified with compound A-1 were obtained in the same manner as in Production Example 1 except that the compound A-1 was changed.
However, in the structural formula (1), Rs1 is a functional group represented by —Si (OCH ₃ ) ₃ .

(Production Example 13: Production of titanium oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane)
N-Phenyl-3-aminopropyltrimethyl was prepared in the same manner as in Production Example 1 except that the Ga-doped zinc oxide fine particles were changed to titanium oxide fine particles (PT-401M, primary particle average particle size 70 nm, manufactured by Ishihara Sangyo Co., Ltd.). Titanium oxide fine particles (volume resistivity 7.4 × 10 ⁶ Ω · cm) modified with methoxysilane were obtained.

(Production Example 14: Production of Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane)
In 100 g of methanol, 2.5 g of N-phenyl-3-aminopropyltrimethoxysilane (KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) and Ga-doped zinc oxide fine particles (inorganic fine particles A, primary particle average particle size 31 nm) 25 g was added. The mixture was refluxed at 95 ° C. for 2 hours, and then the solvent was removed under reduced pressure. When the solvent was exhausted, the temperature was raised to 150 ° C. and held for 2 hours, whereby N-phenyl-3-aminopropyltrimethoxysilane was used. Modified Ga-doped zinc oxide fine particles 2 (volume resistivity 5.8 × 10 ⁴ Ω · cm) were obtained.

<< Preparation Method of Inorganic Fine Particle A (Zinc Oxide Doped with Group 13 Element) >>
A zinc chloride aqueous solution was prepared by adding 100 g of zinc oxide to a hydrochloric acid aqueous solution consisting of 250 g of 35 mass% hydrochloric acid and 350 g of pure water, and dissolving the zinc oxide. Next, 14.7 g of gallium nitrate octahydrate was added to the prepared aqueous zinc chloride solution. Separately, 230 g of ammonium bicarbonate (special grade reagent) was dissolved in 1500 g of purified water to prepare an aqueous ammonium bicarbonate solution separately. The zinc chloride aqueous solution in which the gallium nitrate was dissolved was slowly added to the ammonium bicarbonate aqueous solution to form a precipitate. Next, 150 mL of an aqueous solution containing 23.5 g of sodium metasilicate nonahydrate and 10% by mass sulfuric acid were added while adjusting the flow rate so that the pH was in the range of 7 to 9, and simultaneously added over 90 minutes. Thereafter, the precipitate was sufficiently washed, separated from the liquid phase, and dried at 130 ° C. for 5 hours. Finally, the dried powder is crushed in an agate mortar to form a calcined precursor, and this precursor is put into an alumina boat, and nitrogen gas is 0.2 liters / minute, hydrogen gas is 0.1 using a tubular furnace. The temperature was raised to 700 ° C. at 200 ° C./hour while flowing a mixed gas of liter / minute. The inorganic fine particles A having an average particle diameter of 31 nm suitable for the present invention were obtained by maintaining the state as it was for 2 hours and then allowing to cool to room temperature.

(Production Example 15: Production of Ga-doped zinc oxide fine particles 2 modified with N-2- (aminoethyl) -3-aminopropyltrimethoxysilane)
Except for changing N-phenyl-3-aminopropyltrimethoxysilane to N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), Production Example 14 and Similarly, Ga-doped zinc oxide fine particles 2 (volume resistivity 5.8 × 10 ⁴ Ω · cm) modified with N-2- (aminoethyl) -3-aminopropyltrimethoxysilane were obtained.

(Production Example 16: Production of Ga-doped zinc oxide fine particles 2 modified with 3-aminopropyltrimethoxysilane)
3-aminopropyltrimethoxysilane was prepared in the same manner as in Production Example 14 except that N-phenyl-3-aminopropyltrimethoxysilane was changed to 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.). Ga-doped zinc oxide fine particles 2 (volume resistivity 3.8 × 10 ⁴ Ω · cm) modified with methoxysilane were obtained.

(Production Example 17: Production of Ga-doped zinc oxide fine particles modified with 3-methacryloxypropyltrimethoxysilane)
3-Methacryloxy in the same manner as in Production Example 14 except that N-phenyl-3-aminopropyltrimethoxysilane was changed to 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.). Ga-doped zinc oxide fine particles (volume resistivity 6.9 × 10 ⁴ Ω · cm) modified with propyltrimethoxysilane were obtained.

(Production Example 18: Production of Ga-doped zinc oxide fine particles modified with 4- [2- (triethoxysilyl) ethyl] triphenylamine)
4- [2- (Triethoxysilyl) was prepared in the same manner as in Production Example 14 except that N-phenyl-3-aminopropyltrimethoxysilane was changed to 4- [2- (triethoxysilyl) ethyl] triphenylamine. ) Ethyl] Triphenylamine modified Ga-doped zinc oxide fine particles (volume resistivity 1.3 × 10 ⁴ Ω · cm) were obtained.

(Example A1)
On an aluminum cylinder having a diameter of 40 mm, an undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following composition were sequentially applied and dried to obtain an average thickness of 3.5 μm. An undercoat layer, a charge generation layer having an average thickness of 0.2 μm, and a charge transport layer having an average thickness of 20 μm were formed.

[Coating liquid for undercoat layer]
・ Alkyd resin: 12 parts (Beccosol 1307-60-EL, manufactured by DIC Corporation)
Melamine resin: 8 parts (Super Becamine G-821-60, manufactured by DIC Corporation)
・ Titanium oxide: 80 parts (CR-EL, manufactured by Ishihara Sangyo Co., Ltd.)
・ Methyl ethyl ketone: 250 parts

[Coating liquid for charge generation layer]
-Bisazo pigment of the following structural formula (2): 2.5 parts-Polyvinyl butyral (XYHL, manufactured by UCC): 0.5 part-Cyclohexanone: 200 parts-Methyl ethyl ketone: 80 parts

[Coating liquid for charge transport layer]
-Bisphenol Z polycarbonate: 10 parts (Panlite TS-2050, manufactured by Teijin Chemicals Ltd.)
・ Charge transporting compound of the following structural formula (3): 7 parts ・ Tetrahydrofuran: 100 parts ・ Tetrahydrofuran solution of 1 mass% silicone oil: 1 part (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Coating process of surface layer]
Spray coating method using the following surface layer coating solution on a laminate having the conductive layer, the undercoat layer, the charge generation layer, and the charge transport layer in this order, the surface layer coating solution having the following composition A surface layer having an average thickness of 4.5 μm was formed.
[Coating liquid for surface layer 1]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 × 10 ¹ Ω · cm) 100 parts ・ Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts-Compound represented by the general formula (2) (Exemplary Compound No. 2- 1) ・ ・ ・ 5 parts ・ Methyl ethyl ketone ・ ・ ・ 1,845 parts

[Ultraviolet irradiation and drying process]
While rotating the laminate on which the surface layer was formed, using a metal halide lamp, the surface layer was crosslinked by irradiating light under the conditions of an illuminance of 900 mW / cm ² and an irradiation time of 120 seconds. The electrophotographic photosensitive member was obtained by drying for 30 minutes.

(Example A2)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 2.
[Coating liquid for surface layer 2]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 × 10 ¹ Ω · cm) 33.3 parts Photopolymerization Initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)... 5 parts 2-1) ... 5 parts-Methyl ethyl ketone ... 1,245 parts

(Example A3)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 3.
[Coating liquid 3 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 × 10 ¹ Ω · cm) 150 parts ・ Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts-Compound represented by the general formula (2) (Exemplary Compound No. 2- 1) ... 5 parts ・ Methyl ethyl ketone ... 2,295 parts

(Example A4)
The surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 4, and the conductive support, undercoat layer, charge generation layer, and charge transport layer described in Example A1 were used. A surface layer having an average thickness of 4.5 μm was formed on the laminated body in this order by spray coating, and dried at 150 ° C. for 30 minutes to obtain an electrophotographic photosensitive member.
[Coating fluid for surface layer 4]
-The following two compounds adjusted to have an OH value / NCO value = 1.0: 100 parts Polyol compound of the following structural formula (4)
2. Isocyanate compound (Takenate (registered trademark) D140N, manufactured by Mitsui Takeda Chemical Co., Ltd.)
・ Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 × 10 ¹ Ω · cm) 100 parts ・ The above general formula ( 2) Compound (Exemplary Compound No. 2-1) ... 5 parts Methyl ethyl ketone ... 1,845 parts

(Example A5)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 5.
[Surface layer coating solution 5]
-The following two compounds adjusted to have an OH value / NCO value = 1.0: 100 parts 1. Polyol compound of the structural formula (4) Isocyanate compound (Takenate (registered trademark) D140N, manufactured by Mitsui Takeda Chemical Co., Ltd.)
Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 × 10 ¹ Ω · cm) 33.3 parts Compound represented by formula (2) (Exemplary Compound No. 2-1) ... 5 parts Methyl ethyl ketone ... 1,245 parts

(Example A6)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 6.
[Surface layer coating solution 6]
-The following two compounds adjusted to have an OH value / NCO value = 1.0: 100 parts 1. Polyol compound of the structural formula (4) Isocyanate compound (Takenate (registered trademark) D140N, manufactured by Mitsui Takeda Chemical Co., Ltd.)
-Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 x 10 < ¹ > [Omega] .cm) ... 150 parts-General formula ( 2) Compound (Exemplary Compound No. 2-1): 5 parts Methyl ethyl ketone: 2,295 parts

(Example A7)
The surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 7, and the conductive support, undercoat layer, charge generation layer, and charge transport layer described in Example A1 were used. A surface layer having an average thickness of 4.5 μm was formed on the laminated body in this order by spray coating, and dried at 150 ° C. for 30 minutes to obtain an electrophotographic photosensitive member.
[Surface layer coating solution 7]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
・ Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 × 10 ¹ Ω · cm) 100 parts ・ The above general formula ( 2) Compound (Exemplary Compound No. 2-1) ... 5 parts Tetrahydrofuran ... 4,612 parts

(Example A8)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 8.
[Surface layer coating solution 8]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 × 10 ¹ Ω · cm) 33.3 parts Compound represented by formula (2) (Exemplary Compound No. 2-1) ... 5 parts Tetrahydrofuran ... 3,113 parts

(Example A9)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 9.
[Coating liquid for surface layer 9]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
-Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 x 10 < ¹ > [Omega] .cm) ... 150 parts-General formula ( 2) Compound (Exemplary Compound No. 2-1) ... 5 parts Tetrahydrofuran ... 5,738 parts

(Example A10)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 10.
[Coating liquid 10 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga doped zinc oxide fine particles modified with N-2- (aminoethyl) -3-aminopropyltrimethoxysilane of Production Example 6 (volume resistivity 7.2 × 10 ¹ Ω · cm) 100 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts-Compound represented by the general formula (2) (exemplary compound) No. 2-1) ... 5 parts Methyl ethyl ketone ... 1,845 parts

(Example A11)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 11.
[Coating liquid 11 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles modified with 3-aminopropyltrimethoxysilane of Production Example 7 (volume resistivity 8.4 × 10 ¹ Ω · cm) 100 parts ・ Photopolymerization initiator (1-hydroxy- Cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 parts-Compound represented by the general formula (2) (Exemplary Compound No. 2-1) ... 5 parts ・ Methyl ethyl ketone ・ ・ ・ 1,845 parts

(Example A12)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 12.
[Coating liquid 12 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts ・ Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts-Compound represented by the general formula (2) (Exemplary Compound No. 2- 1) ・ ・ ・ 5 parts ・ Methyl ethyl ketone ・ ・ ・ 1,845 parts

(Example A13)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 13.
[Surface layer coating solution 13]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 33 parts ・ Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts-Compound represented by the general formula (2) (Exemplary Compound No. 2- 1) ・ ・ ・ 5 parts ・ Methyl ethyl ketone ・ ・ ・ 1,245 parts

(Example A14)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 14.
[Coating liquid for surface layer 14]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 150 parts ・ Photopolymerization initiator (1-Hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)... 5 parts 1) ... 5 parts ・ Methyl ethyl ketone ... 2,295 parts

(Example A15)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 15.
[Surface layer coating solution 15]
-The following two compounds adjusted to have an OH value / NCO value = 1.0: 100 parts 1. Polyol compound of the structural formula (4) Isocyanate compound (Takenate (registered trademark) D140N, manufactured by Mitsui Takeda Chemical Co., Ltd.)
-Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 x 10 ⁴ Ω-cm) ... 100 parts-General formula ( 2) Compound (Exemplary Compound No. 2-1) ... 5 parts Methyl ethyl ketone ... 1,845 parts

(Example A16)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 16.
[Coating liquid 16 for surface layer]
-The following two compounds adjusted to have an OH value / NCO value = 1.0: 100 parts 1. Polyol compound of the structural formula (4) Isocyanate compound (Takenate (registered trademark) D140N, manufactured by Mitsui Takeda Chemical Co., Ltd.)
Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 33.3 parts Compound represented by formula (2) (Exemplary Compound No. 2-1) ... 5 parts Methyl ethyl ketone ... 1,245 parts

(Example A17)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 17.
[Coating liquid 17 for surface layer]
The following two compounds were adjusted so that the OH value / NCO value = 1.0. 100 parts 1. Polyol compound of the structural formula (4) Isocyanate compound (Takenate (registered trademark) D140N, manufactured by Mitsui Takeda Chemical Co., Ltd.)
-Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 x 10 ⁴ Ω-cm) ... 150 parts-General formula ( 2) Compound (Exemplary Compound No. 2-1): 5 parts Methyl ethyl ketone: 2,295 parts

(Example A18)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 18.
[Surface layer coating solution 18]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
-Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 x 10 ⁴ Ω-cm) ... 100 parts-General formula ( 2) Compound (Exemplary Compound No. 2-1) ... 5 parts Tetrahydrofuran ... 4,612 parts

(Example A19)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 19.
[Coating liquid 19 for surface layer]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 33.3 parts Compound represented by formula (2) (Exemplary Compound No. 2-1) ... 5 parts Tetrahydrofuran ... 3,113 parts

(Example A20)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 20.
[Coating liquid 20 for surface layer]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
-Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 x 10 ⁴ Ω-cm) ... 150 parts-General formula ( 2) Compound (Exemplary Compound No. 2-1) ... 5 parts Tetrahydrofuran ... 5,738 parts

(Example A21)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 21.
[Surface layer coating solution 21]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
-Ga-doped zinc oxide fine particles 2 modified with N-2- (aminoethyl) -3-aminopropyltrimethoxysilane in Production Example 15 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Compound represented by the above general formula (2) (exemplary) Compound No. 2-1) 5 parts Methyl ethyl ketone 845 parts

(Example A22)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 22.
[Surface layer coating solution 22]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with 3-aminopropyltrimethoxysilane in Production Example 16 (volume resistivity 3.8 × 10 ⁴ Ω · cm) 100 parts ・ Photopolymerization initiator (1-hydroxy -Cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 parts-Compound represented by the general formula (2) (Exemplary Compound No. 2-1)-・ 5 parts ・ Methyl ethyl ketone ・ ・ ・ 1,845 parts

(Example A23)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 23.
[Surface layer coating solution 23]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts ・ The following structural formula ( A) charge transporting material: 10 parts <Structural formula A>
Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Compound represented by the above general formula (2) (exemplary) Compound No. 2-1) 5 parts Methyl ethyl ketone 1,845 parts

(Example A24)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 24.
[Surface layer coating solution 24]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts ・ The above structural formula ( A) charge transporting material: 20 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals) ... 5 parts Compound represented by the general formula (2) (Exemplary Compound No. 2-1) ... 5 parts Methyl ethyl ketone ... 2,025 parts

(Example A25)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 25.
[Coating liquid for surface layer 25]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts ・ The above structural formula ( A) charge transport material: 40 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Compound represented by general formula (2) (Exemplary Compound No. 2-1) 5 parts Methyl ethyl ketone 2,205 parts

(Example A26)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 26.
[Coating liquid for surface layer 26]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts ・ The following structural formula ( B) Charge transport material: 10 parts <Structural formula (B)>
-Compound represented by the general formula (2) (Exemplary Compound No. 2-1) ... 5 parts-Tetrahydrofuran ... 4,838 parts

(Example A27)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 27.
[Coating liquid for surface layer 27]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts ・ The above structural formula ( B) Charge transport material: 20 parts Compound (exemplary compound No. 2-1) represented by general formula (2): 5 parts Tetrahydrofuran: 5,062 parts

(Example A28)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 28.
[Coating liquid 28 for surface layer]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts ・ The above structural formula ( B) Charge transport material: 40 parts-Compound represented by the general formula (2) (Exemplary Compound No. 2-1)-5 parts-Tetrahydrofuran ... 5,513 parts

(Example A29)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 29.
[Coating liquid for surface layer 29]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9 × 10 ¹ Ω · cm) 105 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (2) (Exemplary Compound No. (2) -1) ... 5 parts-Methyl ethyl ketone ... 1,067 parts-Cyclohexanone ... 267 parts

(Example A30)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 30.
[Surface layer coating solution 30]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 105 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (2) (Exemplary Compound No. (2) -1) ... 5 parts-Methyl ethyl ketone ... 1,067 parts-Cyclohexanone ... 267 parts

(Example A31)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 31.
[Coating liquid 31 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 110 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (2) (Exemplary Compound No. (2) -1) ... 5 parts-Methyl ethyl ketone ... 1,120 parts-Cyclohexanone ... 280 parts

(Example A32)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 32.
[Surface layer coating solution 32]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 130 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (2) (Exemplary Compound No. (2) -1) ... 5 parts-Methyl ethyl ketone ... 1,067 parts-Cyclohexanone ... 267 parts

(Example A33)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 33.
[Coating liquid for surface layer 33]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 105 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (2) (Exemplary Compound No. (2) -1) ... 5 parts-Methyl ethyl ketone ... 1,067 parts-Cyclohexanone ... 267 parts

(Example A34)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 34.
[Coating liquid for surface layer 34]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 110 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (2) (Exemplary Compound No. (2) -1) ... 5 parts-Methyl ethyl ketone ... 1,120 parts-Cyclohexanone ... 280 parts

(Example A35)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 35.
[Coating liquid for surface layer 35]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 110 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (2) (Exemplary Compound No. (2) -1) ... 5 parts-Charge transport material of the following structural formula (A) ... 10 parts <Structural formula (A)>
・ Methyl ethyl ketone ・ ・ ・ 1,227 parts ・ Cyclohexanone ... 307 parts

(Example A36)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 36.
[Coating liquid for surface layer 36]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 125 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (2) (Exemplary Compound No. (2) -1) ... 5 parts-Charge transport material of the structural formula (A) ... 20 parts-Methyl ethyl ketone ... 1, 333 parts ・ Cyclohexanone ... 333 parts

(Example A37)
An electrophotographic photoreceptor was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 37.
[Coating liquid 37 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 120 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Compound represented by the general formula (2) (Exemplary Compound No. (2) -1) ... 10 parts Charge transport material of the structural formula (A) ... 10 parts Methyl ethyl ketone ... 1, 280 parts ・ Cyclohexanone: 320 parts

(Example A38)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 38.
[Coating liquid 38 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 130 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (2) (Exemplary Compound No. (2) -1) ... 20 parts-Charge transport material of the structural formula (A) ... 10 parts-Methyl ethyl ketone ... 1, 387 parts ・ Cyclohexanone: 347 parts

(Example A39)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 39.
[Surface layer coating liquid 39]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 105 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (2) (Exemplary Compound No. (3) -1) ... 5 parts-Methyl ethyl ketone ... 1,067 parts-Cyclohexanone ... 267 parts

(Example A40)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 40.
[Surface layer coating solution 40]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 110 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (2) (Exemplary Compound No. (3) -1) ... 10 parts-Methyl ethyl ketone ... 1,120 parts-Cyclohexanone ... 280 parts

(Example A41)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 41.
[Coating liquid 41 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 105 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Compound represented by the general formula (2) (Exemplary Compound No. (4) -1) 5 parts Methyl ethyl ketone 1067 parts Cyclohexanone 267 parts

(Example A42)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 42.
[Surface Layer Coating Liquid 42]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 110 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Compound represented by the general formula (2) (Exemplary Compound No. (4) -1) ... 10 parts Methyl ethyl ketone ... 1,120 partsCyclohexanone ... 280 parts

(Example A43)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 43.
[Surface layer coating solution 43]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 105 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Compound represented by the general formula (2) (Exemplary Compound No. (5) -1) ... 5 parts Methyl ethyl ketone ... 1,067 partsCyclohexanone ... 267 parts

(Example A44)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 44.
[Coating liquid for surface layer 44]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 110 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (2) (Exemplary Compound No. (5) -1) ... 10 parts-Methyl ethyl ketone ... 1,120 parts-Cyclohexanone ... 280 parts

(Comparative Example A1)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 45.
[Surface layer coating solution 45]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Charge transport agent (N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′] biphenyl-4,4′-diamine) 67 parts Silica fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (volume resistivity: 4.0 × 10 ¹² Ω · cm): 5 parts • Tetrafluoroethylene resin particles: 10 parts (AD911L Average particle size 0.25 μm, manufactured by Asahi Glass Co., Ltd.)
・ Fluorinated alkyl group-containing methacrylic copolymer ... 0.25 part (weight average molecular weight 30,000)
Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Antioxidant (2,6-di-t- Butyl-4-methylphenol, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 1.6 parts Tetrahydrofuran ... 1,486 parts Toluene ... 200 parts

(Comparative Example A2)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 46.
[Coating liquid for surface layer 46]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Silica fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 8 (volume resistivity 4.0 × 10 ¹² Ω · cm) 5 parts Tetrafluoroethylene resin particles 10 parts (AD911L, average particle size 0.25 μm, manufactured by Asahi Glass Co., Ltd.)
・ Fluorinated alkyl group-containing methacrylic copolymer ... 0.25 part (weight average molecular weight 30,000)
Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Antioxidant (2,6-di-t- Butyl-4-methylphenol, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 1.6 parts Tetrahydrofuran ... 880 parts Toluene ... 200 parts

(Comparative Example A3)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 47.
[Surface layer coating solution 47]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga-doped zinc oxide fine particles 1 (volume resistivity 2.4 × 10 ¹ Ω · cm)... 100 parts (Pazet GK-40, primary particle average particle size 32 nm, manufactured by Hux Itec Corp.)
Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Methyl ethyl ketone ... 1,845 parts

(Comparative Example A4)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 48.
[Coating liquid 48 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga-doped zinc oxide fine particles 1 (volume resistivity 2.4 × 10 ¹ Ω · cm)... 100 parts (Pazet GK-40, primary particle average particle size 32 nm, manufactured by Hux Itec Corp.)
Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Antioxidant (2,6-di-t- (Butyl-4-methylphenol, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 1.7 parts ・ Methyl ethyl ketone ... 1,845 parts

(Comparative Example A5)
An electrophotographic photoreceptor was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 49.
[Coating liquid for surface layer 49]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
Ga-doped zinc oxide fine particles 1 (volume resistivity 2.4 × 10 ¹ Ω · cm)... 100 parts (Pazet GK-40, primary particle average particle size 32 nm, manufactured by Hux Itec Corp.)
Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Antioxidant (2,6-di-t- (Butyl-4-methylphenol, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 1.7 parts Tetrahydrofuran ... 4,612 parts Tetrahydrofuran ... 4,612 parts

(Comparative Example A6)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 50.
[Surface layer coating solution 50]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga doped zinc oxide fine particles modified with 3-methacryloxypropyltrimethoxysilane of Production Example 9 (volume resistivity 8.0 × 10 ¹ Ω · cm) 100 parts ・ Photopolymerization initiator (1-hydroxy -Cyclohexyl-phenyl-ketone, Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Methyl ethyl ketone ... 1,845 parts

(Comparative Example A7)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 51.
[Surface layer coating solution 51]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga-doped zinc oxide fine particles modified with 4- [2- (triethoxysilyl) ethyl] triphenylamine in Production Example 10 (volume resistivity 5.0 × 10 ¹ Ω · cm) 100 parts Polymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure 184, manufactured by Ciba Specialty Chemicals) ··· 5 parts · Methyl ethyl ketone · · · 1,845 parts

(Comparative Example A8)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 52.
[Surface layer coating solution 52]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga doped zinc oxide fine particles (inorganic fine particles A, volume resistivity 3.2 × 10 ⁴ Ω · cm) 100 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Methyl ethyl ketone ... 1,845 parts

(Comparative Example A9)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 53.
[Surface layer coating solution 53]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga doped zinc oxide fine particles (inorganic fine particles A, volume resistivity 3.2 × 10 ⁴ Ω · cm) 100 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Antioxidant (2,6-di-t-butyl-4-methylphenol, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 1.7 parts・ Methyl ethyl ketone ・ ・ ・ 1,845 parts

(Comparative Example A10)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 54.
[Coating liquid for surface layer 54]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga-doped zinc oxide fine particles 2 modified with 3-methacryloxypropyltrimethoxysilane of Production Example 17 (volume resistivity 6.9 × 10 ⁴ Ω · cm) 100 parts Photopolymerization initiator (1- Hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Methyl ethyl ketone ... 1,845 parts

(Comparative Example A11)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 55.
[Surface layer coating solution 55]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga doped zinc oxide fine particles 2 modified with 4- [2- (triethoxysilyl) ethyl] triphenylamine in Production Example 18 (volume resistivity 1.3 × 10 ⁴ Ω · cm) 100 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Methyl ethyl ketone ... 1,845 parts

(Comparative Example A12)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 56.
[Coating liquid 56 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Silica fine particles modified with N-phenyl-3-aminopropylmethoxysilane in Production Example 11 (volume resistivity 3.0 × 10 ⁹ Ω · cm) 100 parts Photopolymerization initiator (1-hydroxy- Cyclohexyl-phenyl-ketone, Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Methyl ethyl ketone ... 1,845 parts

(Comparative Example A13)
An electrophotographic photosensitive member was produced in the same manner as in Example A1, except that the surface layer coating solution 1 used in Example A1 was changed to the following surface layer coating solution 57.
[Coating fluid 57 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Tin oxide fine particles modified with Compound A-1 of Production Example 12 (volume resistivity 2.0 × 10 ² Ω · cm) 100 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone , Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts ・ Methyl ethyl ketone ... 1,845 parts

<Characteristics of electrophotographic photoreceptor>
The electrophotographic photoreceptors produced in the examples and comparative examples are shown in Table A1 to Table A3.

In the numerical values of the surface resistivity shown in the table, the symbol “E” indicates that the next numerical value is a “power index” with 10 as the base, and is expressed as an exponential function with 10 as the base. Indicates that the numerical value to be multiplied with the numerical value before "E". For example, “1.0E + 14” indicates “1.0 × 10 ¹⁴ ”.

In the numerical values of the surface resistivity shown in the table, the symbol “E” indicates that the next numerical value is a “power index” with 10 as the base, and is expressed as an exponential function with 10 as the base. Indicates that the numerical value to be multiplied with the numerical value before "E". For example, “1.0E + 14” indicates “1.0 × 10 ¹⁴ ”.

* The Si content of the inorganic fine particles used in the Ga-doped zinc oxide fine particles 1 (Ga-doped ZnO 1) is 0.8%, and the inorganic fine particles used in the Ga-doped zinc oxide fine particles 2 (Ga-doped ZnO 2). The Si content is 3.2%.

* Antioxidant BHT: 2,6-di-t-butyl-4-methylphenol * The surface layer material of Comparative Example A1 is tetrafluoroethylene resin, fluorinated alkyl group-containing methacrylic copolymer, charge transporting material (N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1 '] biphenyl-4,4'-diamine).
* The surface layer material of Comparative Example B2 includes a tetrafluoroethylene resin and a fluorinated alkyl group-containing methacrylic copolymer.
* Structural formula (1) of the surface modification functional group of Comparative Example A13 is as follows.
However, in the structural formula (1), Rs1 is a functional group represented by —Si (OCH ₃ ) ₃ .
* The Si content of the inorganic fine particles used in the Ga-doped zinc oxide fine particles 1 (Ga-doped ZnO 1) is 0.8%, and the inorganic fine particles used in the Ga-doped zinc oxide fine particles 2 (Ga-doped ZnO 2). The Si content is 3.2%.

(Evaluation)
The following evaluations were performed on the electrophotographic photoreceptors produced in the examples and comparative examples.

<Evaluation of electrical characteristics (exposed portion potential)>
After disassembling the development unit of imgio Neo 270 (manufactured by Ricoh Co., Ltd.) and attaching the probe connected to the surface potential meter MODEL 344 (manufactured by TREK) to the developing unit, each of the photoreceptors of the examples and comparative examples is mounted. did. After adjusting the potential applied to the photoconductor so that the charging potential was −800 V in an environment of 23 ° C. and 55% RH, a black solid image was output, and the exposed portion potential before the paper passing test was measured.
Next, the following wear durability was evaluated, and then the potential of the exposed portion after the paper passing test was measured by the same method using the photoreceptors of the examples and comparative examples. The change of the exposure part potential before and after paper passing and the exposure part potential before and after paper passing is shown. The results are shown in Table A4-1 and Table A4-2.
The smaller the variation of the exposed portion potential before and after the actual machine paper passing test, the better the chemical durability.

<Evaluation of wear durability>
In the wear durability test, image Neo Neo 270 (manufactured by Ricoh Co., Ltd.) was used as an image forming apparatus.
As the paper, MyPaper (A4 size, manufactured by NBS Ricoh Co., Ltd.) was used. In a normal temperature and normal humidity (23 ° C., 55% RH) environment, 30,000 sheets of 50% halftone (black) images were formed with the short direction as the feeding direction. Next, 30,000 sheets of images were formed in the same manner under an environment of high temperature and high humidity (28 ° C., 75% RH). Finally, 30,000 sheets of images were similarly formed in a low-temperature and low-humidity environment (10 ° C., 15% RH), and a total of 90,000 sheets were tested. The film thickness of the photoconductor before and after the actual machine paper passing test was measured using an eddy current film thickness meter Fischer scope MMS (manufactured by Fischer), and the amount of wear was determined and evaluated according to the following criteria. The results are shown in Table A4-1 and Table A4-2.
〔Evaluation criteria〕
A: Wear amount is 0.2 μm or less B: Wear amount is greater than 0.2 μm and 0.5 μm or less C: Wear amount is greater than 0.5 μm and 1 μm or less D: Wear amount is greater than 1 μm

<Evaluation of image quality>
After attaching the photoconductors of Examples and Comparative Examples to imagio Neo 270 (manufactured by Ricoh Co., Ltd.), using A4 size paper MyPaper (manufactured by NBS Ricoh Co., Ltd.), 3 After forming 10,000 images, the Japanese Society of Imaging Society test chart no. 3 was output, and the image quality was evaluated according to the following criteria. The results are shown in Table A4-1 and Table A4-2.
〔Evaluation criteria〕
A: Level at which image quality is hardly degraded B: Image quality is slightly degraded, but there is no problem with visual observation C: Level at which degradation of image quality can be seen even with visual observation D: Level at which there is a serious problem with image quality

From the results of Table A4-1 and Table A4-2, the electrophotographic photoreceptors of Examples A1 to A44 have a surface layer containing a resin having no charge transporting property and any of primary and secondary amino groups. It can be seen that the inclusion of inorganic fine particles having a volume resistivity of 1 × 10 ⁸ Ω · cm or less, which is modified by a compound having high durability against mechanical and chemical hazards, and image quality can be maintained.
On the other hand, the electrophotographic photosensitive member of Comparative Example A1 contains a charge transport material and an antioxidant in the surface layer, so that the chemical durability is at a level that can withstand practical use. However, inorganic fine particles having a volume resistivity greater than 1 × 10 ⁸ Ω · cm modified with a compound having tetrafluoroethylene resin particles, a fluorinated alkyl group-containing methacrylic copolymer, and a secondary amino group as a filler are used as a surface layer. It can be seen that even when added, the mechanical durability is low and the image quality is poorly maintained.
Unlike Comparative Example A1, the electrophotographic photosensitive member of Comparative Example A2 had a higher exposed area potential and an abnormal image because the charge transport material was not present in the surface layer. Therefore, the wear durability test and the image quality test in the environment of low temperature and low humidity and high temperature and high humidity were not performed.
The electrophotographic photoreceptors of Comparative Examples A4, A5, and A9 have chemical durability at a level that can withstand practical use because the surface layer contains an antioxidant. The volume resistivity of the inorganic fine particles in the surface layer is 1 × 10 ⁸ Ω · cm or less, but since it is not coated with a compound having either primary or secondary amino groups, the mechanical durability is improved. It can be seen that the image quality is poor and the image quality is poor.
The electrophotographic photoreceptors of Comparative Examples A3, A6, A7, A8, A10, and A11 have sufficient mechanical durability because the surface layer does not contain an antioxidant and a charge transport material. The volume resistivity of the inorganic fine particles in the surface layer is 1 × 10 ⁸ Ω · cm or less. However, the surface of the fine particles is not modified (Comparative Example A3), modified with a compound having no amino group (Comparative Example A6), and modified with a compound having a tertiary amino group (Comparative Example). A7) Therefore, it can be seen that the chemical durability is poor and the image quality is poorly maintained.
The electrophotographic photoreceptor of Comparative Example A12 has sufficient mechanical durability because the surface layer does not contain an antioxidant and a charge transport material. In addition, since the inorganic fine particles are modified with a compound having an amino group, fluctuations in the post-exposure potential before and after paper passing are small. However, the volume resistivity of the inorganic fine particles in the surface layer is as large as 3 × 10 ⁹ Ω · cm, and there was no problem at 23 ° C. and 55% RH, but there was no image in the environment of 10 ° C., 20% RH, 28 ° C., 75% RH. It turns out that quality cannot be maintained.
The electrophotographic photoreceptor of Comparative Example A13 has sufficient mechanical durability because the surface layer does not contain an antioxidant and a charge transport material. However, although the inorganic fine particles are modified with a material that exhibits a function as an antioxidant, the characteristics are not sufficient. For this reason, the image quality is not sufficiently maintained, and the fluctuation of the post-exposure potential before and after the sheet passing is large.

  Next, with respect to Examples A1 to A44, the wear durability evaluation was continuously performed up to 200,000 sheets, and the electrical characteristic evaluation was performed. The results are shown in Table A5.

From the results of Table A5, the electrophotographic photoreceptors of Examples A1 to A11 have a relatively large amount of fluctuation of the exposed portion potential after running 200,000 sheets, whereas the electrophotographic photoreceptors of Examples A12 to A44 are The amount of fluctuation of the exposed area potential after running 200,000 sheets is small, comparable to the exposed area potential after running 90,000 sheets, and the volume resistivity of the inorganic fine particles is 1 × 10 ⁴ or more, or the Si content is 2%. It was shown that when the Ga-doped zinc oxide fine particles as described above were used, the electrostatic stability was very high.

(Example B1)
On an aluminum cylinder having a diameter of 40 mm, an undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following composition were sequentially applied and dried to obtain an average thickness of 3.5 μm. An undercoat layer, a charge generation layer having an average thickness of 0.2 μm, and a charge transport layer having an average thickness of 20 μm were formed.

[Coating liquid for undercoat layer]
・ Alkyd resin: 12 parts (Beccosol 1307-60-EL, manufactured by DIC Corporation)
Melamine resin: 8 parts (Super Becamine G-821-60, manufactured by DIC Corporation)
・ Titanium oxide: 80 parts (CR-EL, manufactured by Ishihara Sangyo Co., Ltd.)
・ Methyl ethyl ketone: 250 parts

[Coating liquid for charge generation layer]
-Bisazo pigment of the following structural formula (2): 2.5 parts-Polyvinyl butyral (XYHL, manufactured by UCC): 0.5 part-Cyclohexanone: 200 parts-Methyl ethyl ketone: 80 parts

[Coating liquid for charge transport layer]
-Bisphenol Z polycarbonate: 10 parts (Panlite TS-2050, manufactured by Teijin Chemicals Ltd.)
・ Charge transporting compound of the following structural formula (3): 7 parts ・ Tetrahydrofuran: 100 parts ・ Tetrahydrofuran solution of 1 mass% silicone oil: 1 part (KF50-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Coating process of surface layer]
Spray coating method using the following surface layer coating solution on a laminate having the conductive layer, the undercoat layer, the charge generation layer, and the charge transport layer in this order, the surface layer coating solution having the following composition A surface layer having an average thickness of 4.5 μm was formed.
[Coating liquid for surface layer 1]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 × 10 ¹ Ω · cm) 100 parts ・ Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts-Compound represented by the general formula (3) (Exemplary Compound No. 2- 1) ・ ・ ・ 5 parts ・ Methyl ethyl ketone ・ ・ ・ 1,845 parts

[Ultraviolet irradiation and drying process]
While rotating the laminate on which the surface layer was formed, using a metal halide lamp, the surface layer was crosslinked by irradiating light under the conditions of an illuminance of 900 mW / cm ² and an irradiation time of 120 seconds. The electrophotographic photosensitive member was obtained by drying for 30 minutes.

(Example B2)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 2.
[Coating liquid for surface layer 2]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 × 10 ¹ Ω · cm) 33.3 parts Photopolymerization Initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts-Compound represented by the above general formula (3) Compound No. 2-1) ... 5 parts Methyl ethyl ketone ... 1,245 parts

(Example B3)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 3.
[Coating liquid 3 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 × 10 ¹ Ω · cm) 150 parts ・ Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts-Compound represented by the general formula (3) (Exemplary Compound No. 2- 1) ... 5 parts ・ Methyl ethyl ketone ... 2,295 parts

(Example B4)
The surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 4, and the conductive support, undercoat layer, charge generation layer, and charge transport layer described in Example B1 were used. A surface layer having an average thickness of 4.5 μm was formed on the laminated body in this order by spray coating, and dried at 150 ° C. for 30 minutes to obtain an electrophotographic photosensitive member.
[Coating fluid for surface layer 4]
-The following two compounds adjusted to have an OH value / NCO value = 1.0: 100 parts Polyol compound of the following structural formula (4)
2. Isocyanate compound (Takenate (registered trademark) D140N, manufactured by Mitsui Takeda Chemical Co., Ltd.)
・ Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 × 10 ¹ Ω · cm) 100 parts ・ The above general formula ( 3) Compound (Exemplary Compound No. 2-1): 5 parts Methyl ethyl ketone: 1,845 parts

(Example B5)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 5.
[Surface layer coating solution 5]
-The following two compounds adjusted to have an OH value / NCO value = 1.0: 100 parts 1. Polyol compound of the structural formula (4) Isocyanate compound (Takenate (registered trademark) D140N, manufactured by Mitsui Takeda Chemical Co., Ltd.)
Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 × 10 ¹ Ω · cm) 33.3 parts Compound represented by formula (3) (Exemplary Compound No. 2-1) ... 5 parts · Methyl ethyl ketone ... 1,245 parts

(Example B6)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 6.
[Surface layer coating solution 6]
-The following two compounds adjusted to have an OH value / NCO value = 1.0: 100 parts 1. Polyol compound of the structural formula (4) Isocyanate compound (Takenate (registered trademark) D140N, manufactured by Mitsui Takeda Chemical Co., Ltd.)
-Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 x 10 < ¹ > [Omega] .cm) ... 150 parts-General formula ( 3) Compound (Exemplary Compound No. 2-1): 5 parts Methyl ethyl ketone: 2,295 parts

(Example B7)
The surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 7, and the conductive support, undercoat layer, charge generation layer, and charge transport layer described in Example B1 were used. A surface layer having an average thickness of 4.5 μm was formed on the laminated body in this order by spray coating, and dried at 150 ° C. for 30 minutes to obtain an electrophotographic photosensitive member.
[Surface layer coating solution 7]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
・ Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 × 10 ¹ Ω · cm) 100 parts ・ The above general formula ( 3) Compound (Exemplary Compound No. 2-1) ... 5 parts Tetrahydrofuran ... 4,612 parts

(Example B8)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 8.
[Surface layer coating solution 8]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 × 10 ¹ Ω · cm) 33.3 parts Compound represented by formula (3) (Exemplary Compound No. 2-1) ... 5 parts Tetrahydrofuran ... 3,113 parts

(Example B9)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 9.
[Coating liquid for surface layer 9]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
Ga doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9.2 × 10 ¹ Ω · cm) 150 parts 3) Compound (Exemplary Compound No. 2-1) ... 5 parts Tetrahydrofuran ... 5,738 parts

(Example B10)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 10.
[Coating liquid 10 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga doped zinc oxide fine particles modified with N-2- (aminoethyl) -3-aminopropyltrimethoxysilane of Production Example 6 (volume resistivity 7.2 × 10 ¹ Ω · cm) 100 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts-Compound represented by the above general formula (3) No. 2-1) ... 5 parts -Methyl ethyl ketone ... 1,845 parts

(Example B11)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 11.
[Coating liquid 11 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles modified with 3-aminopropyltrimethoxysilane of Production Example 7 (volume resistivity 8.4 × 10 ¹ Ω · cm) 100 parts ・ Photopolymerization initiator (1-hydroxy- Cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 parts 5 parts ・ Methyl ethyl ketone ・ ・ ・ 1,845 parts

(Example B12)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 12.
[Coating liquid 12 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts ・ Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts 1) ・ ・ ・ 5 parts ・ Methyl ethyl ketone ・ ・ ・ 1,845 parts

(Example B13)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 13.
[Surface layer coating solution 13]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 33 parts ・ Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts-Compound represented by the general formula (3) (Exemplary Compound No. 2- 1) ・ ・ ・ 5 parts ・ Methyl ethyl ketone ・ ・ ・ 1,245 parts

(Example B14)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 14.
[Coating liquid for surface layer 14]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 150 parts ・ Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts-Compound represented by the general formula (3) (Exemplary Compound No. 2- 1) ... 5 parts ・ Methyl ethyl ketone ... 2,295 parts

(Example B15)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 15.
[Surface layer coating solution 15]
-The following two compounds adjusted to have an OH value / NCO value = 1.0: 100 parts 1. Polyol compound of the structural formula (4) Isocyanate compound (Takenate (registered trademark) D140N, manufactured by Mitsui Takeda Chemical Co., Ltd.)
-Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 x 10 ⁴ Ω-cm) ... 100 parts-General formula ( 3) Compound (Exemplary Compound No. 2-1): 5 parts Methyl ethyl ketone: 1,845 parts

(Example B16)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 16.
[Coating liquid 16 for surface layer]
-The following two compounds adjusted to have an OH value / NCO value = 1.0: 100 parts 1. Polyol compound of the structural formula (4) Isocyanate compound (Takenate (registered trademark) D140N, manufactured by Mitsui Takeda Chemical Co., Ltd.)
Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 33.3 parts Compound represented by formula (3) (Exemplary Compound No. 2-1) ... 5 parts · Methyl ethyl ketone ... 1,245 parts

(Example B17)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 17.
[Coating liquid 17 for surface layer]
The following two compounds were adjusted so that the OH value / NCO value = 1.0. 100 parts 1. Polyol compound of the structural formula (4) Isocyanate compound (Takenate (registered trademark) D140N, manufactured by Mitsui Takeda Chemical Co., Ltd.)
-Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 x 10 ⁴ Ω-cm) ... 150 parts-General formula ( 3) Compound (Exemplary Compound No. 2-1): 5 parts Methyl ethyl ketone: 2,295 parts

(Example B18)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 18.
[Surface layer coating solution 18]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
-Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 x 10 ⁴ Ω-cm) ... 100 parts-General formula ( 3) Compound (Exemplary Compound No. 2-1) ... 5 parts Tetrahydrofuran ... 4,612 parts

(Example B19)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 19.
[Coating liquid 19 for surface layer]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 33.3 parts Compound represented by formula (3) (Exemplary Compound No. 2-1) ... 5 parts Tetrahydrofuran ... 3,113 parts

(Example B20)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 20.
[Coating liquid 20 for surface layer]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
-Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 x 10 ⁴ Ω-cm) ... 150 parts-General formula ( 3) Compound (Exemplary Compound No. 2-1) ... 5 parts Tetrahydrofuran ... 5,738 parts

(Example B21)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 21.
[Surface layer coating solution 21]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
-Ga-doped zinc oxide fine particles 2 modified with N-2- (aminoethyl) -3-aminopropyltrimethoxysilane of Production Example 15 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Compound represented by the general formula (3) (exemplary) Compound No. 2-1) 5 parts Methyl ethyl ketone 845 parts

(Example B22)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 22.
[Surface layer coating solution 22]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with 3-aminopropyltrimethoxysilane in Production Example 16 (volume resistivity 3.8 × 10 ⁴ Ω · cm) 100 parts ・ Photopolymerization initiator (1-hydroxy -Cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts・ 5 parts ・ Methyl ethyl ketone ・ ・ ・ 1,845 parts

(Example B23)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 23.
[Surface layer coating solution 23]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts ・ The following structural formula ( A) charge transporting material: 10 parts <Structural formula A>
Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Compound represented by the general formula (3) Compound No. 2-1) 5 parts Methyl ethyl ketone 1,845 parts

(Example B24)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 24.
[Surface layer coating solution 24]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts ・ The above structural formula ( A) charge transporting material: 20 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals) ... 5 parts Compound represented by the general formula (3) (Exemplary Compound No. 2-1) ... 5 parts Methyl ethyl ketone ... 2,025 parts

(Example B25)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 25.
[Coating liquid for surface layer 25]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts ・ The above structural formula ( A) charge transport material: 40 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Compound represented by the general formula (3) (Exemplary Compound No. 2-1) 5 parts Methyl ethyl ketone 2,205 parts

(Example B26)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 26.
[Coating liquid for surface layer 26]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts ・ The following structural formula ( B) Charge transport material: 10 parts <Structural formula (B)>
-Compound represented by the above general formula (3) (Exemplary Compound No. 2-1) ... 5 parts-Tetrahydrofuran ... 4,838 parts

(Example B27)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 27.
[Coating liquid for surface layer 27]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts ・ The above structural formula ( B) Charge transporting material: 20 parts Compound (exemplary compound No. 2-1) represented by general formula (3): 5 parts Tetrahydrofuran: 5,062 parts

(Example B28)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 28.
[Coating liquid 28 for surface layer]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 5.8 × 10 ⁴ Ω · cm) 100 parts ・ The above structural formula ( B) Charge transporting material: 40 parts Compound (exemplary compound No. 2-1) represented by general formula (3): 5 parts Tetrahydrofuran: 5,513 parts

(Example B29)
An electrophotographic photoreceptor was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 29.
[Coating liquid for surface layer 29]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 1 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 1 (volume resistivity 9 × 10 ¹ Ω · cm) 105 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (3) (Exemplary Compound No. 2-1) ... 5 parts-Methyl ethyl ketone ... 1,067 parts-Cyclohexanone ... 267 parts

(Example B30)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 30.
[Surface layer coating solution 30]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 105 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (3) (Exemplary Compound No. 2-1) ... 5 parts-Methyl ethyl ketone ... 1,067 parts-Cyclohexanone ... 267 parts

(Example B31)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 31.
[Coating liquid 31 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 110 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (3) (Exemplary Compound No. 2-1) ... 5 parts-Methyl ethyl ketone ... 1,120 parts-Cyclohexanone ... 280 parts

(Example B32)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 32.
[Surface layer coating solution 32]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 130 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (3) (Exemplary Compound No. 2-1) ... 5 parts-Methyl ethyl ketone ... 1,067 parts-Cyclohexanone ... 267 parts

(Example B33)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 33.
[Coating liquid for surface layer 33]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 105 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (3) (Exemplary Compound No. 2-1) ... 5 parts-Methyl ethyl ketone ... 1,067 parts-Cyclohexanone ... 267 parts

(Example B34)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 34.
[Coating liquid for surface layer 34]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 110 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (3) (Exemplary Compound No. 2-1) ... 5 parts-Methyl ethyl ketone ... 1,120 parts-Cyclohexanone ... 280 parts

(Example B35)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 35.
[Coating liquid for surface layer 35]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 110 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (3) (Exemplary Compound No. 2-1) ... 5 parts-Charge transport material of the following structural formula (A) ... 10 parts <Structural formula (A)>
・ Methyl ethyl ketone ・ ・ ・ 1,227 parts ・ Cyclohexanone ... 307 parts

(Example B36)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 36.
[Coating liquid for surface layer 36]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 125 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (3) (Exemplary Compound No. 2-1) ... 5 parts-Charge transport material of the above structural formula (A) ... 20 parts-Methyl ethyl ketone ... 1,333 parts・ Cyclohexanone: 333 parts

(Example B37)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 37.
[Coating liquid 37 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 120 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (3) (Exemplary Compound No. 2-1) ... 10 parts-Charge transport material of the structural formula (A) ... 10 parts-Methyl ethyl ketone ... 1,280 parts・ Cyclohexanone: 320 parts

(Example B38)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 38.
[Coating liquid 38 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 130 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (3) (Exemplary Compound No. 2-1) ... 20 parts-Charge transport material of the above structural formula (A) ... 10 parts-Methyl ethyl ketone ... 1,387 parts・ Cyclohexanone: 347 parts

(Example B39)
An electrophotographic photoreceptor was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 39.
[Surface layer coating liquid 39]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 105 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (3) (Exemplary Compound No. 3-1) ... 5 parts-Methyl ethyl ketone ... 1,067 parts-Cyclohexanone ... 267 parts

(Example B40)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 40.
[Surface layer coating solution 40]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 110 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
-Compound represented by the general formula (3) (Exemplary Compound No. 3-1) ... 10 parts-Methyl ethyl ketone ... 1,120 parts-Cyclohexanone ... 280 parts

(Example B41)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 41.
[Coating liquid 41 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 105 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Compound represented by the general formula (3) (Exemplary Compound No. 2-1: Exemplified Compound 3-1 = 1: 1 (mass ratio)) ... 5 parts Methyl ethyl ketone ... 1,067 parts Cyclohexanone ... 267 parts

(Example B42)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 42.
[Surface Layer Coating Liquid 42]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga-doped zinc oxide fine particles 2 modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 14 (volume resistivity 6 × 10 ⁴ Ω · cm) 110 parts ・ Photopolymerization initiator (1 -Hydroxy-cyclohexyl-phenyl-ketone) 5 parts (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.)
Compound represented by the general formula (3) (Exemplary Compound No. 2-1: Exemplified Compound 3-1 = 1: 1 (mass ratio)) ... 10 parts Methyl ethyl ketone ... 1,120 partsCyclohexanone ... 280 parts

(Comparative Example B1)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 43.
[Surface layer coating solution 43]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Charge transport agent (N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1 ′] biphenyl-4,4′-diamine) 67 parts Silica fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane (volume resistivity: 4.0 × 10 ¹² Ω · cm): 5 parts • Tetrafluoroethylene resin particles: 10 parts (AD911L Average particle size 0.25 μm, manufactured by Asahi Glass Co., Ltd.)
・ Fluorinated alkyl group-containing methacrylic copolymer ... 0.25 part (weight average molecular weight 30,000)
Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Antioxidant (2,6-di-t- Butyl-4-methylphenol, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 1.6 parts Tetrahydrofuran ... 1,486 parts Toluene ... 200 parts

(Comparative Example B2)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 44.
[Coating liquid for surface layer 44]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Silica fine particles modified with N-phenyl-3-aminopropyltrimethoxysilane of Production Example 8 (volume resistivity 4.0 × 10 ¹² Ω · cm) 5 parts Tetrafluoroethylene resin particles 10 parts (AD911L, average particle size 0.25 μm, manufactured by Asahi Glass Co., Ltd.)
・ Fluorinated alkyl group-containing methacrylic copolymer ... 0.25 part (weight average molecular weight 30,000)
Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Antioxidant (2,6-di-t- Butyl-4-methylphenol, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 1.6 parts Tetrahydrofuran ... 880 parts Toluene ... 200 parts

(Comparative Example B3)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 45.
[Surface layer coating solution 45]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga-doped zinc oxide fine particles 1 (volume resistivity 2.4 × 10 ¹ Ω · cm)... 100 parts (Pazet GK-40, primary particle average particle size 32 nm, manufactured by Hux Itec Corp.)
Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Methyl ethyl ketone ... 1,845 parts

(Comparative Example B4)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 46.
[Coating liquid for surface layer 46]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga-doped zinc oxide fine particles 1 (volume resistivity 2.4 × 10 ¹ Ω · cm)... 100 parts (Pazet GK-40, primary particle average particle size 32 nm, manufactured by Hux Itec Corp.)
Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Antioxidant (2,6-di-t- (Butyl-4-methylphenol, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 1.7 parts ・ Methyl ethyl ketone ... 1,845 parts

(Comparative Example B5)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 47.
[Surface layer coating solution 47]
Bisphenol Z polycarbonate: 100 parts (Panlite (registered trademark) TS-2050, manufactured by Teijin Chemicals Limited)
Ga-doped zinc oxide fine particles 1 (volume resistivity 2.4 × 10 ¹ Ω · cm)... 100 parts (Pazet GK-40, primary particle average particle size 32 nm, manufactured by Hux Itec Corp.)
Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Antioxidant (2,6-di-t- (Butyl-4-methylphenol, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 1.7 parts Tetrahydrofuran ... 4,612 parts

(Comparative Example B6)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 48.
[Coating liquid 48 for surface layer]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Ga doped zinc oxide fine particles modified with 3-methacryloxypropyltrimethoxysilane of Production Example 9 (volume resistivity 8.0 × 10 ¹ Ω · cm) 100 parts ・ Photopolymerization initiator (1-hydroxy -Cyclohexyl-phenyl-ketone, Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Methyl ethyl ketone ... 1,845 parts

(Comparative Example B7)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 49.
[Coating liquid for surface layer 49]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga-doped zinc oxide fine particles modified with 4- [2- (triethoxysilyl) ethyl] triphenylamine in Production Example 10 (volume resistivity 5.0 × 10 ¹ Ω · cm) 100 parts Polymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure 184, manufactured by Ciba Specialty Chemicals) ··· 5 parts · Methyl ethyl ketone · · · 1,845 parts

(Comparative Example B8)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 50.
[Surface layer coating solution 50]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga doped zinc oxide fine particles (inorganic fine particles A, volume resistivity 3.2 × 10 ⁴ Ω · cm) 100 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Methyl ethyl ketone ... 1,845 parts

(Comparative Example B9)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 51.
[Surface layer coating solution 51]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga doped zinc oxide fine particles (inorganic fine particles A, volume resistivity 3.2 × 10 ⁴ Ω · cm) 100 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Antioxidant (2,6-di-t-butyl-4-methylphenol, manufactured by Tokyo Chemical Industry Co., Ltd.) ... 1.7 parts・ Methyl ethyl ketone ・ ・ ・ 1,845 parts

(Comparative Example B10)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 52.
[Surface layer coating solution 52]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga-doped zinc oxide fine particles 2 modified with 3-methacryloxypropyltrimethoxysilane of Production Example 17 (volume resistivity 6.9 × 10 ⁴ Ω · cm) 100 parts Photopolymerization initiator (1- Hydroxy-cyclohexyl-phenyl-ketone, Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Methyl ethyl ketone ... 1,845 parts

(Comparative Example B11)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 53.
[Surface layer coating solution 53]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga doped zinc oxide fine particles 2 modified with 4- [2- (triethoxysilyl) ethyl] triphenylamine in Production Example 18 (volume resistivity 1.3 × 10 ⁴ Ω · cm) 100 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Methyl ethyl ketone ... 1,845 parts

(Comparative Example B12)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 54.
[Coating liquid for surface layer 54]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Silica fine particles modified with N-phenyl-3-aminopropylmethoxysilane in Production Example 11 (volume resistivity 3.0 × 10 ⁹ Ω · cm) 100 parts Photopolymerization initiator (1-hydroxy- Cyclohexyl-phenyl-ketone, Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts Methyl ethyl ketone ... 1,845 parts

(Comparative Example B13)
An electrophotographic photosensitive member was produced in the same manner as in Example B1, except that the surface layer coating solution 1 used in Example B1 was changed to the following surface layer coating solution 55.
[Surface layer coating solution 55]
・ Trimethylolpropane triacrylate: 100 parts (TMPTA, manufactured by Tokyo Chemical Industry Co., Ltd.)
Tin oxide fine particles modified with Compound A-1 of Production Example 12 (volume resistivity 2.0 × 10 ² Ω · cm) 100 parts Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone , Irgacure (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) ... 5 parts ・ Methyl ethyl ketone ... 1,845 parts

<Characteristics of electrophotographic photoreceptor>
The electrophotographic photoreceptors produced in the examples and comparative examples are shown in Table B1-1 to Table B3-2.

In the numerical values of the surface resistivity shown in the table, the symbol “E” indicates that the next numerical value is a “power index” with 10 as the base, and is expressed as an exponential function with 10 as the base. Indicates that the numerical value to be multiplied with the numerical value before "E". For example, “1.0E + 14” indicates “1.0 × 10 ¹⁴ ”.

In the numerical values of the surface resistivity shown in the table, the symbol “E” indicates that the next numerical value is a “power index” with 10 as the base, and is expressed as an exponential function with 10 as the base. Indicates that the numerical value to be multiplied with the numerical value before "E". For example, “1.0E + 14” indicates “1.0 × 10 ¹⁴ ”.

* The Si content of the inorganic fine particles used in the Ga-doped zinc oxide fine particles 1 (Ga-doped ZnO 1) is 0.8%, and the inorganic fine particles used in the Ga-doped zinc oxide fine particles 2 (Ga-doped ZnO 2). The Si content is 3.2%.

* Antioxidant BHT: 2,6-di-t-butyl-4-methylphenol * The surface layer material of Comparative Example B1 is tetrafluoroethylene resin, fluorinated alkyl group-containing methacrylic copolymer, charge transport material (N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1 '] biphenyl-4,4'-diamine).
* The surface layer material of Comparative Example B2 includes a tetrafluoroethylene resin and a fluorinated alkyl group-containing methacrylic copolymer.
* Structural formula (1) of the surface modification functional group of Comparative Example B13 is as follows.
However, in the structural formula (1), Rs1 is a functional group represented by —Si (OCH ₃ ) ₃ .
* The Si content of the inorganic fine particles used in the Ga-doped zinc oxide fine particles 1 (Ga-doped ZnO 1) is 0.8%, and the inorganic fine particles used in the Ga-doped zinc oxide fine particles 2 (Ga-doped ZnO 2). The Si content is 3.2%.

(Evaluation)
The following evaluations were performed on the electrophotographic photoreceptors produced in the examples and comparative examples.

<Evaluation of electrical characteristics (exposed portion potential)>
After disassembling the development unit of imgio Neo 270 (manufactured by Ricoh Co., Ltd.) and attaching the probe connected to the surface potential meter MODEL 344 (manufactured by TREK) to the developing unit, each of the photoreceptors of the examples and comparative examples is mounted. did. After adjusting the potential applied to the photoconductor so that the charging potential was −800 V in an environment of 23 ° C. and 55% RH, a black solid image was output, and the exposed portion potential before the paper passing test was measured.
Next, the following wear durability was evaluated, and then the potential of the exposed portion after the paper passing test was measured by the same method using the photoreceptors of the examples and comparative examples. The change of the exposure part potential before and after paper passing and the exposure part potential before and after paper passing is shown. The results are shown in Table B4-1 and Table 4-2.
The smaller the variation of the exposed portion potential before and after the actual machine paper passing test, the better the chemical durability.

<Evaluation of wear durability>
In the wear durability test, image Neo Neo 270 (manufactured by Ricoh Co., Ltd.) was used as an image forming apparatus.
As the paper, MyPaper (A4 size, manufactured by NBS Ricoh Co., Ltd.) was used. In a normal temperature and normal humidity (23 ° C., 55% RH) environment, 30,000 sheets of 50% halftone (black) images were formed with the short direction as the feeding direction. Next, 30,000 sheets of images were formed in the same manner under an environment of high temperature and high humidity (28 ° C., 75% RH). Finally, 30,000 sheets of images were similarly formed in a low-temperature and low-humidity environment (10 ° C., 15% RH), and a total of 90,000 sheets were tested. The film thickness of the photoconductor before and after the actual machine paper passing test was measured using an eddy current film thickness meter Fischer scope MMS (manufactured by Fischer), and the amount of wear was determined and evaluated according to the following criteria. The results are shown in Tables B4-1 and B4-2.
〔Evaluation criteria〕
A: Wear amount is 0.2 μm or less B: Wear amount is greater than 0.2 μm and 0.5 μm or less C: Wear amount is greater than 0.5 μm and 1 μm or less D: Wear amount is greater than 1 μm

<Evaluation of image quality>
After attaching the photoconductors of Examples and Comparative Examples to imagio Neo 270 (manufactured by Ricoh Co., Ltd.), using A4 size paper MyPaper (manufactured by NBS Ricoh Co., Ltd.), 3 After forming 10,000 images, the Japanese Society of Imaging Society test chart no. 3 was output, and the image quality was evaluated according to the following criteria. The results are shown in Tables B4-1 and B4-2.
〔Evaluation criteria〕
A: Level at which there is almost no degradation in image quality B: Level at which image quality is slightly degraded but no problem with visual observation C: Level at which degradation in image quality can be seen through visual observation D: Level at which there is a serious problem with image quality

From the results of Table B4-1 and Table B4-2, the electrophotographic photoreceptors of Examples B1 to B42 have a surface layer containing a resin having no charge transporting property and any of primary and secondary amino groups. It can be seen that the inclusion of inorganic fine particles having a volume resistivity of 1 × 10 ⁸ Ω · cm or less, which is modified by a compound having high durability against mechanical and chemical hazards, and image quality can be maintained.
On the other hand, since the electrophotographic photosensitive member of Comparative Example B1 contains a charge transport material and an antioxidant in the surface layer, the chemical durability is at a level that can withstand practical use. However, inorganic fine particles having a volume resistivity greater than 1 × 10 ⁸ Ω · cm modified with a compound having tetrafluoroethylene resin particles, a fluorinated alkyl group-containing methacrylic copolymer, and a secondary amino group as a filler are used as a surface layer. It can be seen that even when added, the mechanical durability is low and the image quality is poorly maintained.
Unlike the comparative example 1, the electrophotographic photosensitive member of the comparative example B2 had a higher exposure area potential than the initial stage and an abnormal image was observed because no charge transport material was present in the surface layer. Therefore, the wear durability test and the image quality test in the environment of low temperature and low humidity and high temperature and high humidity were not performed.
The electrophotographic photoreceptors of Comparative Examples B4, B5, and B9 have chemical durability at a level that can withstand practical use because the surface layer contains an antioxidant. The volume resistivity of the fine particles in the surface layer is 1 × 10 ⁸ Ω · cm or less, but it is not covered with a compound having either a primary or secondary amino group, and therefore has poor mechanical durability. It can be seen that the image quality is poor.
The electrophotographic photoreceptors of Comparative Examples B3, B6, B7, B8, B10, and B11 have sufficient mechanical durability because the surface layer does not contain an antioxidant and a charge transport material. The volume resistivity of the inorganic fine particles in the surface layer is 1 × 10 ⁸ Ω · cm or less. However, the surface of the fine particles is not modified (Comparative Example B3), modified with a compound having no amino group (Comparative Example B6), and modified with a compound having a tertiary amino group (Comparative Example). B7) Therefore, it can be seen that the chemical durability is poor and the image quality is poorly maintained.
The electrophotographic photoreceptor of Comparative Example B12 has sufficient mechanical durability because the surface layer does not contain an antioxidant and a charge transport material. In addition, since the fine particles are modified with a compound having an amino group, the variation in the post-exposure potential before and after paper passing is small. However, the volume resistivity of the fine particles in the surface layer is as large as 3 × 10 ⁹ Ω · cm, and although there was no problem at 23 ° C. and 55% RH, the image quality was 10 ° C., 20% RH, 28 ° C., and 75% RH. It can be seen that it cannot be maintained.
The electrophotographic photoreceptor of Comparative Example B13 has sufficient mechanical durability because the surface layer does not contain an antioxidant and a charge transport material. However, although the inorganic fine particles are modified with a material that exhibits a function as an antioxidant, the characteristics are not sufficient. For this reason, the image quality is not sufficiently maintained, and the fluctuation of the post-exposure potential before and after the sheet passing is large.

  Next, with respect to Examples B1 to B42, the wear durability evaluation was continuously performed up to 200,000 sheets, and the electrical characteristic evaluation was performed. The results are shown in Table B5.

From the results of Table B5, the electrophotographic photoreceptors of Examples B1 to B11 have a relatively large amount of fluctuation in the exposed portion potential after running 200,000 sheets, whereas the electrophotographic photoreceptors of Examples B12 to B42 The amount of fluctuation of the exposed area potential after 200,000 sheets running is small, comparable to the exposed area potential after 90,000 sheets running, and the volume resistivity of fine particles is 1 × 10 ⁴ or more, or the Si content is 2% or more. When using Ga-doped zinc oxide fine particles, it has been shown that it has very high electrostatic stability.

As an aspect of this invention, it is as follows, for example.
<1> An electrophotographic photosensitive member having a conductive support and at least a photosensitive layer and a surface layer in this order on the conductive support,
The surface layer contains inorganic fine particles and at least one compound selected from compounds represented by the following general formulas (1), (2), and (3),
The inorganic fine particles are zinc oxide fine particles doped with a Group 13 element;
The surface resistivity R ₁ when the electric field strength in the surface layer is 1 × 10 ⁴ V / cm is 1 × 10 ¹³ Ω / cm ² or more,
And the surface resistivity _{R 1,} the ratio of the surface resistivity _{R 15} when the electric field intensity at the surface layer is _{^{1.5 × 10 5 V / cm (}} R 1 / R 15) is 100 to 5 The electrophotographic photosensitive member is characterized in that it is 1,000,000.
<General formula (1)>
In the general formula (1), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. Ar ₁ represents a substituted or unsubstituted aromatic ring group.
<General formula (2)>
However, In the general formula (2), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. m and n represent an integer of 0 to 3, and m and n are not 0 at the same time. R ₄ and R _{5 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 11 carbon atoms, and a substituted or unsubstituted aromatic ring group, and these may be the same or different. Good. Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic ring group, and these may be the same or different.
<General formula (3)>
In the general formula (3), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic ring group. l and m represent an integer of 0 to 3, and l and m are not 0 at the same time. n represents an integer of 1 to 3.
<2> the surface resistivity _{R 1} in _the 1 × ¹⁰ 4 V / cm of the surface layer, the ratio of the surface resistivity _{R 3} in _{the ^{3 × 10 4 V / cm (}} R 1 / R 3) are 0. The electrophotographic photosensitive member according to <1>, wherein the electrophotographic photosensitive member is 1 to 10.
<3> The electrophotographic photosensitive member according to any one of <1> to <2>, wherein the zinc oxide fine particles doped with a Group 13 element are zinc oxide doped with a gallium element.
<4> The electrophotographic photosensitive member according to any one of <1> to <3>, wherein the content of the zinc oxide fine particles doped with the Group 13 element in the surface layer is 7% by volume to 40% by volume. .
<5> The electrophotographic photosensitive member according to any one of <1> to <4>, wherein the inorganic fine particles are coated with a compound having a primary or secondary amino group.
<6> The electrophotographic photosensitive member according to any one of <1> to <5>, wherein the inorganic fine particles have a volume resistivity of 1 × 10 ⁸ Ω · cm or less.
<7> The surface layer contains a resin having no charge transporting property, and the resin not having the charge transporting property is selected from a polycarbonate resin, an acrylic resin, a polyarylate resin, a styrene resin, a phenol resin, and a urethane resin. The electrophotographic photosensitive member according to any one of <1> to <6>, which is at least one kind.
<8> In the above <7>, the surface layer further contains a charge transporting compound, and the content of the charge transporting compound is 20 parts by mass or less with respect to 100 parts by mass of the resin having no charge transporting property. The electrophotographic photosensitive member described.
<9> An electrophotographic photosensitive member, a charging unit that charges the surface of the electrophotographic photosensitive member, an exposure unit that exposes the charged surface of the electrophotographic photosensitive member to form an electrostatic latent image, and the electrostatic latent image An image forming apparatus having at least developing means for developing a visible image by developing with toner, and transfer means for transferring the visible image to a recording medium,
An electrophotographic photosensitive member according to any one of <1> to <8>, wherein the electrophotographic photosensitive member is an image forming apparatus.
<10> A process cartridge having at least an electrophotographic photosensitive member and developing means for developing a latent image formed on the electrophotographic photosensitive member using a toner to form a visible image,
A process cartridge, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of <1> to <8>.

DESCRIPTION OF SYMBOLS 1 Electrophotographic photosensitive member 3 Charging means 5 Exposure means 6 Developing means 10 Transfer means 21 Conductive support body 23 Charge generation layer 24 Charge transport layer 25 Surface layer 26 Single layer type photosensitive layer 101 Electrophotographic photosensitive member 102 Charging means 104 Developing means 106 Transfer means

JP-A-5-181299 JP 2002-6526 A JP 2002-82465 A JP 2000-284514 A JP 2001-194413 A JP 2006-99028 A Japanese Patent Laid-Open No. 3-45762 Japanese Patent Laid-Open No. 7-281463 Japanese Patent Laid-Open No. 9-26685 JP 2002-229241 A Japanese Patent No. 2795566

KONICA Technology Report Vol. 13 (2000) Journal of Imaging Science 32: 205-210 (1988)

Claims (10)

An electrophotographic photosensitive member having a conductive support and at least a photosensitive layer and a surface layer in this order on the conductive support,
The surface layer contains inorganic fine particles and at least one compound selected from compounds represented by the following general formulas (1), (2), and (3),
The inorganic fine particles are zinc oxide fine particles doped with a Group 13 element;
The surface resistivity R ₁ when the electric field strength in the surface layer is 1 × 10 ⁴ V / cm is 1 × 10 ¹³ Ω / cm ² or more,
And the surface resistivity _{R 1,} the ratio of the surface resistivity _{R 15} when the electric field intensity at the surface layer is _{^{1.5 × 10 5 V / cm (}} R 1 / R 15) is 100 to 5 An electrophotographic photosensitive member, wherein
<General formula (1)>
In the general formula (1), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. Ar ₁ represents a substituted or unsubstituted aromatic ring group.
<General formula (2)>
However, In the general formula (2), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. m and n represent an integer of 0 to 3, and m and n are not 0 at the same time. R ₄ and R _{5 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 11 carbon atoms, and a substituted or unsubstituted aromatic ring group, and these may be the same or different. Good. Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic ring group, and these may be the same or different.
<General formula (3)>
In the general formula (3), R ₂ and R ₃ represents either a substituted or unsubstituted aromatic hydrocarbon group, and a substituted or unsubstituted alkyl groups, they have be the same or different R ₂ and R ₃ may combine with each other to form a heterocyclic group containing a nitrogen atom. Ar ₁ and Ar ₂ represent a substituted or unsubstituted aromatic ring group. l and m represent an integer of 0 to 3, and l and m are not 0 at the same time. n represents an integer of 1 to 3. The surface resistivity _{R 1} in _the 1 × ¹⁰ 4 V / cm of the surface layer, the ratio of the surface resistivity _{R 3} in _{the ^{3 × 10 4 V / cm (}} R 1 / R 3) is 0.1 to 10 The electrophotographic photosensitive member according to claim 1.   3. The electrophotographic photosensitive member according to claim 1, wherein the zinc oxide fine particles doped with a group 13 element are zinc oxide doped with a gallium element.   4. The electrophotographic photosensitive member according to claim 1, wherein the content of zinc oxide fine particles doped with a Group 13 element in the surface layer is 7% by volume to 40% by volume.   The electrophotographic photosensitive member according to claim 1, wherein the inorganic fine particles are coated with a compound having a primary or secondary amino group. The electrophotographic photosensitive member according to claim 1, wherein the inorganic fine particles have a volume resistivity of 1 × 10 ⁸ Ω · cm or less.   The surface layer contains a resin having no charge transporting property, and the resin having no charge transporting property is selected from polycarbonate resin, acrylic resin, polyarylate resin, styrene resin, phenol resin, and urethane resin. The electrophotographic photosensitive member according to any one of claims 1 to 6.   The electrophotographic image according to claim 7, wherein the surface layer further contains a charge transporting compound, and the content of the charge transporting compound is 20 parts by mass or less with respect to 100 parts by mass of the resin having no charge transporting property. Photoconductor. An electrophotographic photosensitive member, a charging means for charging the surface of the electrophotographic photosensitive member, an exposure means for exposing the charged surface of the electrophotographic photosensitive member to form an electrostatic latent image, and the electrostatic latent image using toner An image forming apparatus including at least a developing unit that forms a visible image by developing the image and a transfer unit that transfers the visible image to a recording medium,
An image forming apparatus, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to claim 1. A process cartridge having at least an electrophotographic photosensitive member and developing means for developing an electrostatic latent image formed on the electrophotographic photosensitive member using a toner to form a visible image;
A process cartridge, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to claim 1.