# Patent

## Title
Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus

## Abstract

An electrophotographic photosensitive member includes a laminated body, the laminated body including a support, an undercoat layer, and a charge generating layer. The undercoat layer includes a polymerized product of a composition including an electron transport material represented by formula (1), a cross-linking agent, and a thermoplastic resin having a polymerizable functional group, the laminated body satisfying expressions (2) and (3)

Z1—X—Z2  (1)

0.20≦|Vd2−Vd1|≦2.0  (2)

τ≦10  (3)

in which Z1 and Z2 are groups having electron transport property, X is a linker, Vd2 and Vd1 are surface potentials of the charge generating layer after charging and τ is transit time based on a change rate of the surface of the charge generating layer, each as defined in the specification.

## Background
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to an electrophotographic photosensitive member, and a process cartridge and an electrophotographic apparatus each including the electrophotographic photosensitive member.
Description of the Related Art
An electrophotographic photosensitive member containing an organic photoconductive material (hereinafter referred to as “charge generating material”) is currently a major electrophotographic photosensitive member to be used for a process cartridge or an electrophotographic apparatus. The electrophotographic photosensitive member generally includes a support and a photosensitive layer (charge generating layer and hole transporting layer) formed on the support. In addition, an undercoat layer is formed between the support and the photosensitive layer in many cases.
A charge generating material having additionally high sensitivity has been used in recent years. However, as the sensitivity of the charge generating material rises, an amount of charge to be generated increases and hence the charge is liable to reside in the photosensitive layer. Consequently, a positive ghost is liable to occur. As a technology of suppressing such positive ghost, in Japanese Patent Application Laid-Open No. 2014-029480, there is a disclosure that the undercoat layer contains a polymerized product (cured product) obtained by polymerizing a composition containing an electron transport material, a cross-linking agent, and a resin. Further, in Japanese Patent Application Laid-Open Nos. 2007-148294 and 2008-250082, there is disclosed a technology involving incorporating an electron transport material into the undercoat layer. There is also disclosed a technology involving curing the undercoat layer so that, when the electron transport material is incorporated into the undercoat layer, the electron transport material is not eluted into a solvent in an application liquid for a photosensitive layer during the formation of a photosensitive layer serving as an upper layer of the undercoat layer.
SUMMARY OF THE INVENTION
The undercoat layer in the related art currently satisfies required image quality.
In recent years, there is a demand for a further increase in image quality, and as an effective method, there is given thinning of a hole transporting layer. This is because, when the hole transporting layer is thinned, the diffusion of charge during the formation of an electrostatic latent image can be suppressed.
Investigations made by the inventors of the present invention have found that, in the case where the hole transporting layer is thinned and the undercoat layer of Japanese Patent Application Laid-Open No. 2014-029480 is used, the occurrence of an image defect such as a black dot can be suppressed although a phenomenon of an increase in dark attenuation is observed. However, the investigations have found that a phenomenon of a significant decrease in sensitivity may be caused as the hole transporting layer is thinned, and thus the image quality is susceptible to improvement.
Further, the inventors of the present invention have made investigations regarding the reduction in positive ghost, and as a result, have found that, in the technology disclosed in Japanese Patent Application Laid-Open Nos. 2007-148294 and 2008-250082, the suppression (reduction) of the positive ghost, in particular, a fluctuation of a positive ghost level before and after continuous image output is still susceptible to improvement.
An object of the present invention is to provide an electrophotographic photosensitive member in which the occurrence of an image defect such as a black dot is suppressed and the sensitivity is increased even when a hole transporting layer is thinned, and a process cartridge and an electrophotographic apparatus each including the electrophotographic photosensitive member. Another object of the present invention is to provide an electrophotographic photosensitive member in which a positive ghost is suppressed, and a process cartridge and an electrophotographic apparatus each including the electrophotographic photosensitive member.
According to a first embodiment of the present invention, there is provided an electrophotographic photosensitive member, including:
a laminated body; and
a hole transporting layer on the laminated body, in which:
the laminated body includes:
a support;
an undercoat layer having a thickness of d1 (μm), on the support; and
a charge generating layer having a thickness of d2 (μm), on the undercoat layer, and
the hole transporting layer has a thickness of 15 μm or less;
the undercoat layer includes a polymerized product of a composition including an electron transport material represented by the following formula (1), a cross-linking agent, and a thermoplastic resin having a polymerizable functional group:

Z1—X—Z2  (1)

in the formula (1):
Z1 and Z2 each represent a group having an electron transport property;
X represents a linking group, and the linking group is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted heterocyclic group, or a group derived by substituting one of methylene groups in a main chain of the substituted or unsubstituted alkylene group with R1, the R1 representing an oxygen atom, a sulfur atom, SO2, NR2, CO, or a substituted or unsubstituted arylene group, the R2 representing a hydrogen atom, an alkyl group, or an aryl group; and
at least one of Z1, Z2, and X has a polymerizable functional group, and the polymerizable functional group is a hydroxyl group, a thiol group, an amino group, a carboxyl group, or a methoxy group;
the laminated body satisfies the following expressions (2) and (4):

0.20≦|Vd2−Vd1|≦2.0  (2)

Vd1=−100×(d1+d2)  (4)

in which Vd1 represents a potential of a surface of the charge generating layer after 1.0 second from charging of the charge generating layer by corona charging, and Vd2 represents a potential of the surface of the charge generating layer after 0.80 second from the charging of the charge generating layer by the corona charging; and τ satisfies the following expression (3):

τ≦10  (3)

in the expression (3), τ represents transit time (ms) determined based on a time change rate of the potential of the surface of the charge generating layer after the surface of the charge generating layer which has a potential of Vd1 (V) is exposed to light, the light having an intensity adjusted so that the potential of the surface of the charge generating layer after 0.04 second from the exposure decays by 20% with respect to Vd1 (V).
According to a second embodiment of the present invention, there is provided an electrophotographic photosensitive member, including:
a support;
an undercoat layer on the support; and
a photosensitive layer on the undercoat layer,
in which the undercoat layer includes a polymerized product of one of the following (i) and (ii):
(i): a polymerized product of a compound represented by the following formula (11); and
(ii): a polymerized product of a composition containing the compound represented by the formula (11) and a cross-linking agent:




in the formula (11),
X1 and X2 each independently represent a residue obtained by removing four carboxyl groups from a substituted or unsubstituted aromatic tetracarboxylic acid, and when the residue has a substituent, the substituent is a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group;
Y represents a substituted or unsubstituted alkylene group having a polymerizable functional group or a substituted or unsubstituted arylene group having a polymerizable functional group; and
R7 and R8 each independently represent a substituted or unsubstituted alkyl group, a group derived by substituting one of methylene groups of the substituted or unsubstituted alkyl group with an oxygen atom, a group derived by substituting one of the methylene groups of the substituted or unsubstituted alkyl group with a sulfur atom, a group derived by substituting one of the methylene groups of the substituted or unsubstituted alkyl group with NR9, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or an alkoxycarbonyl group, and R7 and R8 may each have a polymerizable functional group,
provided that the oxygen atom, the sulfur atom, and the NR9 are free from being directly bonded to nitrogen atoms to which R7 and R8 are bonded.
The present invention also relates to a process cartridge, including: the electrophotographic photosensitive member; and at least one unit selected from the group consisting of a charging unit, a developing unit, and a cleaning unit, the process cartridge integrally supporting the electrophotographic photosensitive member and the at least one unit, the process cartridge being removably mounted onto an electrophotographic apparatus.
The present invention also relates to an electrophotographic apparatus, including: the electrophotographic photosensitive member; a charging unit; an exposing unit; a developing unit; and a transferring unit.
According to the first embodiment of the present invention, the electrophotographic photosensitive member in which the occurrence of an image defect such as a black dot is suppressed and the sensitivity is increased even when the hole transporting layer is thinned, and the process cartridge and the electrophotographic apparatus each including the electrophotographic photosensitive member can be provided.
According to the second embodiment of the present invention, the electrophotographic photosensitive member in which a positive ghost is suppressed, and the process cartridge and the electrophotographic apparatus each including the electrophotographic photosensitive member can be provided.
Further features of the present invention will become apparent from the following description of exemplary embodiments with reference to the attached drawings.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view for illustrating an example of a schematic configuration of a determination device for performing a determination method of the present invention.
FIG. 2 is a view for illustrating another example of the schematic configuration of the determination device for performing the determination method of the present invention.
FIG. 3A is a graph for showing the expression (2).
FIG. 3B is a graph for showing the expression (3).
FIG. 4A is a graph for showing a comparative example in which charging and light amount setting cannot be performed by the determination method of the present invention.
FIG. 4B is a graph for showing a comparative example in which charging and light amount setting cannot be performed by the determination method of the present invention.
FIG. 5 is a graph for showing the expression (4).
FIG. 6 is a graph for showing a comparative example in which a related-art electrophotographic photosensitive member is subjected to measurement by the determination method of the present invention.
FIG. 7 is a view for illustrating a schematic configuration of an electrophotographic apparatus including a process cartridge including an electrophotographic photosensitive member.
FIG. 8 is a schematic sectional view of a grinding device.
FIG. 9 is a diagram for illustrating an image for ghost evaluation (printing for ghost evaluation).
FIG. 10 is a diagram for illustrating a one-dot knight-jump pattern image.



DESCRIPTION OF THE EMBODIMENTS
Preferred embodiments of the present invention will now be described in detail in accordance with the accompanying drawings.
An electrophotographic photosensitive member according to a first embodiment of the present invention includes a laminated body, and a hole transporting layer on the laminated body. The laminated body includes a support, an undercoat layer on the support, and a charge generating layer on the undercoat layer. The undercoat layer has a thickness of d1 (μm), the charge generating layer has a thickness of d2 (μm), and the hole transporting layer has a thickness of 15 μm or less.
In addition, the undercoat layer includes a polymerized product of a composition including an electron transport material represented by the formula (1), a cross-linking agent, and a thermoplastic resin having a polymerizable functional group.

Z1—X—Z2  (1)

(In the formula (1), Z1 and Z2 each represent a group having an electron transport property.

X represents a linking group, and the linking group is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted heterocyclic group, or a group derived by substituting one of methylene groups in a main chain of the substituted or unsubstituted alkylene group with R1. R1 represents an oxygen atom, a sulfur atom, SO2, NR2, CO, or a substituted or unsubstituted arylene group. R2 represents a hydrogen atom, an alkyl group, or an aryl group.

At least one of Z1, Z2, and X has a polymerizable functional group, and the polymerizable functional group is a hydroxyl group, a thiol group, an amino group, a carboxyl group, or a methoxy group.)

In addition, the electrophotographic photosensitive member has a feature in that the laminated body satisfies the following expressions (2) and (4):

0.20≦|Vd2−Vd1|≦2.0  (2)

Vd1=−100×(d1+d2)  (4)

in which Vd1 represents a potential of a surface of the charge generating layer after 1.0 second from charging of the charge generating layer by corona charging, and Vd2 represents a potential of the surface of the charge generating layer after 0.80 second from the charging of the charge generating layer by the corona charging.
Further, the electrophotographic photosensitive member also has a feature in that τ satisfies the following expression (3).

τ≦10  (3)

τ represents transit time (ms) determined based on a time change rate of the potential of the surface of the charge generating layer after the surface of the charge generating layer which has a potential of Vd1 (V) is exposed to light, the light having an intensity adjusted so that the potential of the surface of the charge generating layer after 0.04 second from the exposure decays by 20% with respect to Vd1 (V).
The inventors of the present invention have assumed the reason why a decrease in sensitivity is suppressed while the occurrence of a black dot is suppressed by incorporating the above-mentioned polymerized product into the undercoat layer and causing the laminated body to satisfy the expressions (2) and (3) when the thickness of the hole transporting layer is reduced as follows.
In the case of the electrophotographic photosensitive member including the support, and the undercoat layer, the charge generating layer, and the hole transporting layer which are formed on the support in the stated order, in a part irradiated with exposure light (image exposure light), holes are injected into the hole transporting layer and electrons are injected into the undercoat layer among charges (holes and electrons) generated in the charge generating layer. Then, the electrons injected into the undercoat layer are considered to be further transferred to the support. Thus, the intensity of an electric field applied to the undercoat layer, the charge generating layer, and the hole transporting layer is increased by thinning the hole transporting layer. In the undercoat layer that contains the polymerized product of the composition including the electron transport material having a polymerizable functional group, the cross-linking agent, and the resin disclosed in Japanese Patent Application Laid-Open No. 2014-029480, a uniform film is formed, and hence an image defect such as a black dot does not occur. However, as the hole transporting layer is thinned, the intensity of the electric field increases, and a phenomenon of a significant decrease in sensitivity occurs in some cases. In particular, such phenomenon tends to occur remarkably when the hole transporting layer has a thickness of 15 μm or less.
When the time change rate of the potential of a surface is observed in the case where the electric field per unit thickness is increased as in the expression (4), dark attenuation increases as shown in FIG. 5. The inventors of the present invention have considered that the increase in dark attenuation influences the attenuation after exposure. As the reason why the sensitivity is decreased due to the large dark attenuation, the inventors of the present invention have assumed that the influence of heat carriers generated in the charge generating layer becomes nonnegligible to inhibit the transfer of optical carriers. Meanwhile, the inventors of the present invention have assumed that the undercoat layer having a decrease in sensitivity suppressed even under the generation of the heat carriers is obtained by satisfying the expressions (2) and (3).
Further, the inventors of the present invention have assumed the reason why the expressions (2) and (3) can be satisfied by virtue of the undercoat layer containing the polymerized product of the composition including the electron transport material represented by the formula (1), the cross-linking agent, and the thermoplastic resin having a polymerizable functional group as follows. As one factor for inhibiting the transfer of electrons, there is known the formation of a deep trap between adjacent molecules of an electron transfer material (electron transport material). A large amount of the heat carriers enter the trap under a high electric field to exist in the undercoat layer. That is, it is considered that the heat carriers having entered the trap in the undercoat layer inhibit the transfer of the optical carriers. Then, it is considered that the trap is derived from a resin or an impurity not having an electron transfer function, and hence how a site having an electron transfer function and a site not having an electron transfer function are formed in the undercoat layer is important for the presence of the trap and the transfer of electrons in the presence of the trap. Thus, the inventors of the present invention have considered that, by virtue of the configuration of the undercoat layer of the present invention, the formation of the polymerized product and the structurally appropriate distance between the adjacent molecules of the electron transport material can prevent the heat carriers from entering the trap and suppress the inhibition of the transfer of electrons even in the presence of the trap.
Now, the configuration of the undercoat layer and the expressions (2) and (3) are described. First, a determination method of determining whether or not the electrophotographic photosensitive member satisfies the expressions (2) and (3) of the present invention (hereinafter sometimes referred to as “determination method of the present invention”) is described.
It is sufficient that the temperature and humidity conditions for performing the determination method of the present invention be under an environment in which an electrophotographic apparatus including the electrophotographic photosensitive member is used. The temperature and humidity conditions are preferably under an ordinary temperature and ordinary humidity environment (23±3° C., 50±2% RH).
The above-mentioned measurement method is performed through use of the laminated body including the support, the undercoat layer on the support, and the charge generating layer on the undercoat layer.
In the case where the undercoat layer contains the electron transport material, when the charge generating layer and the hole transporting layer each serving as an upper layer are formed by applying an application liquid for a charge generating layer and an application liquid for a hole transporting layer, the electron transport material may be eluted out. In such electrophotographic photosensitive member, the electron transport material is eluted, and hence it is considered that the original transfer of electrons in the undercoat layer cannot be sufficiently evaluated.
Thus, it is necessary that the charge generating layer and the hole transporting layer be formed on the undercoat layer, then the hole transporting layer be peeled to obtain a laminated body including the undercoat layer and the charge generating layer, and the laminated body be subjected to determination.
Further, a black dot is liable to occur in undercoat layers having low uniformity such as an undercoat layer containing an electron transport material as a pigment and an undercoat layer in which metal oxide particles are dispersed. The undercoat layer in which a black dot occurs as described above may not be charged to Vd1 in the determination method of the present invention. Based on this, it is considered that a black dot can be suppressed when the laminated body after the peeling of the hole transporting layer can be charged to Vd1.
Therefore, it is preferred that the hole transporting layer be peeled from the electrophotographic photosensitive member including the laminated body and the hole transporting layer on the laminated body and the resultant be subjected to determination. As a method of peeling the hole transporting layer, there are given, for example, a method involving immersing the electrophotographic photosensitive member in a solvent which dissolves the hole transporting layer and is unlikely to dissolve the undercoat layer and the charge generating layer, to thereby peel the hole transporting layer and a method involving grinding the hole transporting layer.
As the solvent which dissolves the hole transporting layer and is unlikely to dissolve the undercoat layer and the charge generating layer, it is preferred to use a solvent to be used for the application liquid for a hole transporting layer. The kind of the solvent is described later. The electrophotographic photosensitive member is immersed in the solvent to dissolve the hole transporting layer, followed by being dried, and thus the above-mentioned laminated body can be obtained. It can be confirmed that the hole transporting layer has been peeled, for example, based on the fact that a resin component of the hole transporting layer is not observed by an attenuated total reflection method (ATR method) in a FTIR measurement method.
Further, the method involving grinding the hole transporting layer is performed, for example, through use of a wrapping tape (C2000, manufactured by Fujifilm Corporation) in a drum grinding device. A schematic sectional view of the grinding device is illustrated in FIG. 8. A wrapping tape 802 is fed from a feed roller 803 to be taken up by a take-up roller 804 and is moved at a constant speed. The wrapping tape 802 is pressed with a rubber roller 805 to grind an electrophotographic photosensitive member 801. An entire surface of the electrophotographic photosensitive member 801 can be uniformly ground within a short period of time by vibrating the rubber roller 805. In this case, it is preferred to: successively measure the thickness so as to prevent the hole transporting layer from being ground excessively to grind the charge generating layer; and perform the measurement at a site where the hole transporting layer is entirely eliminated while observing the surface of the electrophotographic photosensitive member. Further, it has been confirmed that when the thickness of the charge generating layer is 0.10 μm or more after the grinding is performed to the charge generating layer, substantially the same value is obtained in the above-mentioned measurement method as compared to the case where the charge generating layer is not ground. Therefore, even when the charge generating layer as well as the hole transporting layer is ground, in the case where the thickness of the charge generating layer is 0.10 μm or more, the above-mentioned measurement method can be used.
FIG. 1 is a view for illustrating an example of a schematic configuration of a determination device for performing the determination method of the present invention. A cylindrical laminated body 101 is driven to rotate in the arrow direction and is stopped at a position of a transparent probe 104P that transmits pulse light 103L. At the time of the stop, the potential of a surface of the laminated body 101 is started to be measured with a potentiometer 104 which measures the potential of a surface of the charge generating layer of the laminated body 101 and the transparent probe 104P. After that, the pulse light (image exposure light) 103L oscillated from a device configured to oscillate pulse laser light (image exposure oscillation device) 103 passes through the transparent probe 104P to expose the laminated body 101 to light, and thus the time change rate of the potential of the surface of the charge generating layer is measured.
FIG. 2 is a view for illustrating another example of the schematic configuration of the determination device for performing the determination method of the present invention. A sheet-shaped laminated body 201 is driven in the arrow direction and is stopped at a position of a transparent probe 204P that transmits pulse light 203L. At the time of the stop, the potential of a surface of the laminated body 201 is started to be measured with a potentiometer 204 which measures the potential of a surface of the charge generating layer of the laminated body 201 and the transparent probe 204P. After that, the pulse light (image exposure light) 203L oscillated from a device configured to oscillate pulse laser light (image exposure oscillation device) 203 passes through the transparent probe 204P to expose the laminated body 201 to light, and thus the time change rate of the potential of the surface of the charge generating layer is measured.
The position of a corona charger 102 (202), the position of exposure, and the movement speed of the laminated body are set so that a period of time between the charging by the corona charger 102 (202) and the light irradiation (also referred to as exposure) with the pulse light 103L (203L) is 1.00 second. As the corona charger 102 (202), a scorotron charger having a characteristic of applying a constant potential is preferably used. It is preferred that laser pulse light having a wavelength of 780 nm and a pulse width of 1 μs be used as the pulse light 103L (203L), and the light amount be adjusted with an ND filter. That is, exposure time is 1 μs (microsecond).
Next, the expressions (2) to (4) are described.
FIG. 3A and FIG. 3B are graphs for showing Vd1, Vd2, and τ in the expressions (2) and (3).
The following charging conditions C and light E are determined before determining whether or not the electrophotographic photosensitive member satisfies the expressions (2) and (3).
<Charging Conditions C>
The conditions for charging the surface of the charge generating layer of the laminated body are set as follows. The value of a grid voltage to be applied to the corona charger and the value of a current of a discharge wire are adjusted so that the potential of a surface of the charge generating layer after 1.00 second from the charging by the corona charger is Vd1 (V) represented by the expression (4). The value of the grid voltage and the value of the current of the discharge wire are defined as the charging conditions C.

Vd1=−100×(d1+d2)  (4)

<Light E>
The surface of the charge generating layer is charged so that the potential of a surface of the charge generating layer is Vd1 (V) represented by the expression (4) under the charging conditions C. Then, the intensity of light is adjusted with the ND filter so that the potential of a surface of the electrophotographic photosensitive member after 0.04 second from the exposure to laser light having a wavelength of 780 nm for 1 microsecond decays by 20% with respect to Vd1 (V). Light set to this intensity is defined as light E.
FIG. 3A is a graph of an attenuation curve for showing a time change rate of the potential of a surface of the charge generating layer of the laminated body 101 when charged under the charging conditions C and irradiated with the light E after 1.00 second from the charging. Vd2 represents the potential of a surface of the charge generating layer after 0.80 second from the charging, that is, the potential of the surface of the charge generating layer before 0.20 second from the time when the charge generating layer is charged to a potential of a surface of Vd1 (V). Vd2 also represents the potential of the surface of the charge generating layer before 0.20 second from the exposure of the surface of the charge generating layer to the light E. In the present invention, the potential of the surface of the charge generating layer of the laminated body 101 is measured after the laminated body 101 is stopped by the method illustrated in FIG. 1 and FIG. 2. Therefore, the laminated body 101 is driven immediately after the charging by the corona charger, and hence the potential of the surface of the charge generating layer of the laminated body 101 cannot be measured. Thus, it is necessary to measure the amount of dark attenuation represented by the expression (2) under a state in which the laminated body 101 is stopped. In the present invention, the potential of a surface is measured during 0.20 second from 0.80 second to 1.00 second after the charging by the corona charger.
Vd2 and τ can be measured by setting the charging conditions C and the intensity of the light E as described above.
In the case where the charging conditions C and the intensity of the light E cannot be set, the determination method of the present invention cannot be satisfied. FIG. 4A is a graph for showing an example in which the charging conditions C cannot be set, and in a comparative example represented by the solid line, the charging conditions C cannot be set. This is an example in which the charging ability of the charge generating layer is not sufficient, and hence the charge generating layer after 1.00 second from the charging cannot be charged to a potential of a surface of Vd1 (V) represented by the expression (4).
FIG. 4B is a graph for showing an example in which the light E cannot be set, and in a comparative example represented by the solid line, the light E cannot be set. This is an example in which the electron transfer function is not sufficient, and hence the potential of a surface of the charge generating layer after 0.04 second after the exposure cannot decay by 20% with respect to Vd1 (V) even when the intensity of light is increased.
Vd1 (V) represented by the expression (4) means that the potential of the surface of the charge generating layer is set so as to be −100 V per unit thickness (μm) with respect to the total thickness (μm) of the undercoat layer having a thickness d1 and the charge generating layer having a thickness d2.
|Vd2-Vd1| in the expression (2) represents a dark attenuation amount in the case where a sufficiently strong electric field is applied to the laminated body. FIG. 5 is a graph for showing an electric field per unit thickness and a dark attenuation amount during 0.2 second (0.2 s). It is understood that the dark attenuation amount abruptly increases at an electric field intensity of from about −70 V/μm to −80 V/μm.

0.2≦|Vd2−Vd1|≦2.0  (2)

The potential of a surface of −100 V per unit thickness is a sufficiently strong electric field in the case where an increase in electric field applied to the laminated body caused by thinning of the hole transporting layer is assumed.
The expression (3) represents transit time τ (ms) determined based on a time change rate of the potential of the surface of the charge generating layer after the surface of the charge generating layer which has a potential of a surface of Vd1 (V) is exposed to the light E. The transit time τ is determined with reference to a Xerographic TOF (XTOF) method disclosed in, for example, Japanese Patent Application Laid-Open No. 2006-251554 and Journal of Society of Electrophotography of Japan, Vol. 22, No. 1 (1983), page 69 to 76. Specifically, the attenuation curve (FIG. 3A) for showing a time change rate of the potential of the surface of the charge generating layer is subjected to logarithmic conversion with respect to the relationship with temporal differentiation of the potential of a surface during a period of time from the exposure (0 seconds) to 0.1 second (100 milliseconds) thereafter to obtain a waveform shown in FIG. 3B. The waveform shown in FIG. 3B is assumed to be formed of two straight lines, and the two straight lines are obtained by straight-line approximation through use of a least-square method. Time elapsed from the exposure of the intersection of the two straight lines obtained by the straight-line approximation through use of the least-square method is defined as τ (transit time). If the obtained waveform does not clearly have a bending point, the transit time can be defined by the logarithmic conversion of the attenuation curve after 0.1 second after the exposure.
The transit time τ in the expression (3) represents a value showing time required for an electron generated in the charge generating layer immediately after the exposure to be injected into the undercoat layer and transferred therein to reach the support. In the case where τ is small, the time required for the electron to reach the support is short, which means that the sensitivity of the electrophotographic photosensitive member is high. In the case where τ is large, the time required for the electron to reach the support is long, which means that the sensitivity of the electrophotographic photosensitive member is low. In the present invention, when τ is 10 or less, high sensitivity is obtained. Further, τ that satisfies the expression (5) is more preferred.

0.01≦τ≦2  (5)

From the foregoing, when the expressions (2) and (3) are satisfied, even when dark attenuation is increased due to the application of a strong electric field, the electrons are transferred fast, and sufficiently high sensitivity is obtained.
A second embodiment of the present invention relates to an electrophotographic photosensitive member, including: a support; an undercoat layer on the support; and a photosensitive layer on the undercoat layer. In addition, the electrophotographic photosensitive member has a feature in that the undercoat layer includes a polymerized product of one of the following (i) and (ii):
(i): a polymerized product of a compound represented by the following formula (11); and
(ii): a polymerized product of a composition containing the compound represented by the formula (11) and a cross-linking agent.




In the formula (11), X1 and X2 each independently represent a residue obtained by removing four carboxyl groups from a substituted or unsubstituted aromatic tetracarboxylic acid. When the residue has a substituent, the substituent is a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted, linear or branched alkyl group, or a substituted or unsubstituted aryl group.
Y represents a substituted or unsubstituted alkylene group having a polymerizable functional group or a substituted or unsubstituted arylene group having a polymerizable functional group.
R7 and R8 each independently represent a substituted or unsubstituted, linear or branched alkyl group, a group derived by substituting one of methylene groups of the substituted or unsubstituted, linear or branched alkyl group with an oxygen atom, a group derived by substituting one of the methylene groups of the substituted or unsubstituted, linear or branched alkyl group with a sulfur atom, a group derived by substituting one of the methylene groups of the substituted or unsubstituted, linear or branched alkyl group with NR9, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or an alkoxycarbonyl group. R7 and R8 may each have a polymerizable functional group. It should be noted that the oxygen atom, the sulfur atom, and the NR9 are free from being directly bonded to nitrogen atoms to which R7 and R8 are bonded.
The inventors of the present invention have assumed the reason why the electrophotographic photosensitive member including the undercoat layer containing the polymerized product according to the present invention is particularly excellent in the effect of suppressing a positive ghost as follows. The compound of the present invention includes a spacer between two electron transporting sites. Further, the spacer has a polymerizable functional group. Therefore, it is considered that polymerization is performed with respect to the center of the compound, two electron transporting sites exist at an equal interval, and the electron transporting sites exist uniformly in the polymerized product. Therefore, it is considered that the transport of electrons by intermolecular hopping is enhanced, and the high effect of suppressing a positive ghost that is caused by the residence of the electrons is obtained.
[Undercoat Layer]
The undercoat layer contains the polymerized product of the composition including the electron transport material represented by the formula (1), the cross-linking agent, and the thermoplastic resin having a polymerizable functional group. In the polymerized product, the electron transport material represented by the formula (1) may contain the above-mentioned polymerized product of (i) or (ii).
In Z1 and Z2 of the electron transport material represented by the formula (1), the group having an electron transport property refers to a group having a structure having an electron transport property. Examples of the structure having an electron transport property include a quinone structure, an imide structure, a benzimidazole structure, and a cyclopentadienylidene structure.
Now, specific examples of the group having an electron transport property are shown. There are given groups each represented by any one of the following formulae (A1) to (A10).







In the formulae (A1) to (A10), any one of R101 to R106, any one of R201 to R210, any one of R301 to R308, any one of R401 to R408, any one of R501 to R510, any one of R601 to R606, any one of R701 to R708, any one of R801 to R80, any one of R901 to R910, or any one of R1001 to R1008 represents a bonding site (single bond) for bonding to X.
In the formulae (A1) to (A10), R101 to R106, R201 to R210, R301 to R308, R401 to R408, R501 to R510, R601 to R606, R701 to R708, R801 to R810, R901 to R910, and R1001 to R1008 each independently represent a single bond, a group represented by the following formula (A), a hydrogen atom, a cyano group, a nitro group, a halogen atom, an alkoxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a group derived by substituting one of methylene groups in a main chain of the substituted or unsubstituted alkyl group with R3. R3 represents an oxygen atom, a sulfur atom, or NR1101 (R1101 represents a hydrogen atom or an alkyl group).
A substituent of the substituted alkyl group is an alkyl group, an aryl group, a halogen atom, or an alkoxycarbonyl group. A substituent of the substituted aryl group and a substituent of the substituted heterocyclic group are each a halogen atom, a nitro group, a cyano group, an alkyl group, a halogen-substituted alkyl group, or an alkoxy group.
Z201, Z301, Z401, and Z501 each independently represent a carbon atom, a nitrogen atom, or an oxygen atom. R209 and R210 are absent when Z201 represents the oxygen atom, and R210 is absent when Z201 represents the nitrogen atom. R307 and R308 are absent when Z301 represents the oxygen atom, and R308 is absent when Z301 represents the nitrogen atom. R407 and R408 are absent when Z401 represents the oxygen atom, and R408 is absent when Z401 represents the nitrogen atom. R509 and R510 are absent when Z501 represents the oxygen atom, and R510 is absent when Z501 represents the nitrogen atom.

αlβmγ  (A)

In the formula (A), at least one of α, β, and γ represents a group having a polymerizable functional group. As described above, the polymerizable functional group is a hydroxyl group, a thiol group, an amino group, a carboxyl group, or a methoxy group. 1 and m each independently represent 0 or 1, and the sum of 1 and m is 0 or more and 2 or less.
α represents a substituted or unsubstituted alkylene group having in its main chain 1 to 6 atoms or a group derived by substituting one of methylene groups in the main chain of the substituted or unsubstituted alkylene group with R4, and these groups may each have a polymerizable functional group. R4 represents an oxygen atom, a sulfur atom, or NR1102 (R1102 represents a hydrogen atom or an alkyl group). A substituent of the substituted alkylene group is an alkyl group having 1 to 6 carbon atoms, a benzyl group, an alkoxycarbonyl group, or a phenyl group.
β represents a phenylene group, a phenylene group substituted with an alkyl having 1 to 6 carbon atoms, a nitro-substituted phenylene group, a halogen atom-substituted phenylene group, or an alkoxy group-substituted phenylene group. These groups may each have a polymerizable functional group.
γ represents a hydrogen atom, a substituted or unsubstituted alkyl group having in its main chain 1 to 6 atoms, or a group derived by substituting one of methylene groups in the main chain of the substituted or unsubstituted alkyl group with R5. These groups may each have a polymerizable functional group. A substituent of the substituted alkyl group is an alkyl group having 1 to 6 carbon atoms. R5 represents an oxygen atom, a sulfur atom, or NR1103 (R1103 represents a hydrogen atom or an alkyl group).
Now, specific examples of the groups each represented by any one of the formulae (A1) to (A10) are shown. In Table 1, A1 and A2 are groups each represented by the formula (A). In Table 1, in the case where γ is “-”, γ represents a hydrogen atom, and the hydrogen atom of γ is shown in a state of being included in a structure in the column of “α” or “β”. In Table 1, “*” represents a bonding site (single bond) for bonding to X.













TABLE 1







Exemplified








Compound
R101
R102
R103
R104
R105
R106





A101
H
H
H
H
*
A1


 


A102
*
H
H
H




A1


 


A103
H
H
H
H
*
A1


A104
H
H
H
H
*
A1


A105
H
H
H
H
*
A1


A106
H
A
H
H
*
H


A107
H
H
H
H
*
A1


A108
H
*
H
H
H
A1


A109
H
H
H
H
*
A1


A110
H
H
H
H
*
A1


A111
H
H
H
H
*
A1


A112
H
H
H
H
*
A1


A113
H
H
H
H
*
A1


A114
H
H
H
H
*
A1


A115
H
H
H
H
*
A1


A116
H
*
H
H
A1
A2


A117
*
H
H
H
A1
A2


A118
H
H
H
H
*
A1


A119
H
H
H
H
*
A1


A120
H
H
H
H
*
A1


A121
H
H
H
H
*
H


 


A122
H
H
H
H
*






 


A123
H
H
H
H
*
















Exemplified
A1
A2













Compound
α
β
Υ
α
β
Υ





A101




—
—
—
—
—


 


A102




—
—
—
—
—


 


A103
—




—
—
—
—


 


A104
—




—
—
—
—


 


A105




—
—
—
—
—


 


A106
—








—
—
—


 


A107




—
—
—
—
—


 


A108




—
—
—
—
—


 


A109




—
—
—
—
—


 


A110




—
—
—
—
—


 


A111
—








—
—
—


 


A112
—CH2—OH
—
—
—
—
—


 


A113




—
—
—
—
—


 


A114




—
—
—
—
—


 


A115
—C2H4—S—C2H4—OH
—
—
—
—
—


 


A116




—
—




—
—


 


A117
—












—
—


 


A118




—
—
—
—
—


 


A119




—
—
—
—
—


 


A120




—
—
—
—
—


 


A121
—
—
—
—
—
—


A122
—
—
—
—
—
—


A123
—
—
—
—
—
—






























TABLE 2







Exem-
















plified

































Com-











A1





















pound
R201
R202
R203
R204
R205
R206
R207
R208
R209
R210
R201
α
β
Υ





A201
H
H
A1
H
H
*
H
H
—
—
O
—










 


A202
H
H
*
H
H
H
H
H
A1
—
N
—










 


A203
H
H




H
H
A1
H
H
*
—
N
—










 


A204
H
H




H
*




H
H
A1
—
N
—










 


A205
H
H
A1
H
H
*
H
H
—
—
O
—










 


A206
H
A1
H
H
H
H
*
H
—
—
O
—










 


A207
H
*
H
H
H
H
H
H
A1
—
N



































TABLE 3







Exemplified









A1



















Compound
R301
R302
R303
R304
R305
R306
R307
R308
Z301
α
β
Υ





A301
H
A1
H
H
*
H
—
—
O
—










 


A302
H
H
*
H
H
H
A1
—
N
—










 


A303
H
*
H
H
H
H
A1
—
N




—
—


 


A304
H
*
Cl
Cl
H
H
A1
—
N
—










 


A305
H
*
H
H
A1
H
CN
CN
C
—


































TABLE 4







Exemplified









A1



















Compound
R401
R402
R403
R404
R405
R406
R407
R408
Z401
α
β
Υ





A401
H
H
A1
H
H
*
CN
CN
C
—










 


A402
H
*
H
H
H
H
A1
—
N
—










 


A403
H
H
A1
H
H
H
*
CN
C
—










 


A404
H
H
H
A1
H
H
*
CN
C
—




—


 


A405
H
H
A1
H
H
*
—
—
O
—




































TABLE 5







Exem-














plified














Com-











A1





















pound
R501
R502
R503
R504
R505
R506
R507
R508
R509
R510
Z501
α
β
Υ





A501
H
A1
H
H
H
H
*
H
CN
CN
C
—










 


A502
H
NO2
H
H
*
H
NO2
H
A1
—
N
—










 


A503
H
A1
H
H
H
H
*
H
CN
CN
C




—
—


 


A504
H
*
H
H
H
A1
H
H
CN
CN
C
—










 


A505
H
H
*
H
H
A1
H
H
CN
CN
C




—
—























TABLE 6







Exemplified






A1
















Compound
R601
R602
R603
R604
R605
R606
α
β
Υ





A601
A1
H
H
*
H
H
—










 


A602
A1
H
H
H
*
H
—










 


A603
A1
H
*
H
H
H




—
—


 


A604
A1
*
H
H
H
H
—










 


A605
*
A1
H
H
H
H




—
—

























TABLE 7







Exemplified








A1


















Compound
R701
R702
R703
R704
R705
R706
R707
R708
α
β
Υ





A701
A1
H
H
H
*
H
H
H
—










 


A702
A1
H
H
H
H
*
H
H




—
—


 


A703
A1
H
H
H
H
*
H
H
—










 


A704
A1
*
H
H
A2
H
H
H




—
—


 


A705
A1
H
H
H
A2
*
H
H
—




















   
Exemplified
A2












Compound
α
β
Υ






A701
—
—
—



A702
—
—
—



A703
—
—
—


 



A704
—










 



A705




—
—



























TABLE 8







Exemplified










A1




















Compound
R801
R802
R803
R804
R805
R806
R807
R808
R809
R810
α
β
Υ





A801
H
H
H
H
H
H
H
H
*
A1




—
—


 


A802
H
H
H
H
H
H
H
H
*
A1
—




—


 


A803
H
CN
H
H
H
H
CN
H
*
A1




—
—


 


A804
*
H
H
H
H
H
H
H
H
A1




—
—


 


A805
H
H
H
H
H
H
H
H
*
A1
—



































TABLE 9







Exem-













plified













Com-










A1




















pound
R901
R902
R903
R904
R905
R906
R907
R908
R909
R910
α
β
Υ





A901




H
H
H
*
H
H
H
H
A1
—CH2—OH
—
—


 


A902
*
H
H
H
A1
H
H
H
H




—




—


 


A903
A1
H
H
H
*
H
H
H
H




—




—


 


A904




A1
H
H
*
H
H
H
H




—




—


 


A905
A1
H
H
H
*
H
H
H
H




—CH2—OH
—
—

























TABLE 10







Exemplified








A1


















Compound
R1001
R1002
R1003
R1004
R1005
R1006
R1007
R1008
α
β
Υ





A1001
A1
H
H
H
*
H
H
H
—CH2—OH
—
—


 


A1002
A1
H
H
H
*
H
H
H




—
—


 


A1003
H
H
H
*
H
H
H
A1
—CH2—OH
—
—


 


A1004
H
H
*
H
H
H
H
A1




—
—


 


A1005
H
CN
H
*
H
H
CN
A1
—




—


 


A1006
A1
A1
H
NO2
*
H
NO2
H




—
—


 


A1007
H
A1
A1
H
H
H
*
H
—CH2—OH
—
—









X represents a linking group, and the linking group is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted heterocyclic group, or a group derived by substituting one of methylene groups in a main chain of the substituted or unsubstituted alkylene group with R1. R1 represents an oxygen atom, a sulfur atom, SO2, NR2, CO, or a substituted or unsubstituted arylene group. R2 represents a hydrogen atom, an alkyl group, or an aryl group. For example, an alkyl group, an aryl group, a hydroxyl group, an amino group, and a halogen group are given as a substituent of the substituted alkylene group, a substituent of the substituted arylene group, and a substituent of the substituted heterocyclic group.
Now, specific examples of X are shown. In Table 11, dotted lines represent bonding sites for bonding to Z1 and Z2.








TABLE 11







X1 






 


X2 






 


X3 






 


X4 






 


X5 






 


X6 






 


X7 






 


X8 






 


X9 






 


X10






 


X11






 


X12






 


X13






 


X14






 


X15






 


X16






 


X17






 


X18






 


X19






 


X20






 


X21






 


X22






 


X23






 


X24






 


X25






 


X26






 


X27






 


X28






 


X29






 


X30






 


X31






 


X32






 


X33






 


X34






 


X35






 


X36






 


X37






 


X38






 


X39






 


X40






 


X41






 


X42






 


X43






 


X44






 


X45






 


X46






 


X47






 


X48






 


X49






 


X50






 


X51






 


X52






 


X53






 


X54






 


X55






 


X56






 


X57






 


X58






 


X59






 


X60






 


X61






 


X62






 


X63






 


X64






 


X65






 


X66






 


X67






 


X68






 


X69






 


X70













Now, specific examples of the electron transport material represented by the formula (1) are shown in Table 12. In Table 12, in the case where X is “-”, X represents a single bond.












TABLE 12







Formula (1)
Z1
Z2
X









(1-1)-1
A101
A101
X42



(1-1)-2
A102
A102
X42



(1-1)-3
A103
A103
—



(1-1)-4
A114
A114
X5



(1-1)-5
A101
A101
X8



(1-1)-6
A105
A105
X24



(1-1)-7
A119
A119
X15



(1-1)-8
A115
A119
X36



(1-1)-9
A112
A112
X42



(1-1)-10
A109
A121
X9



(1-2)-1
A201
A201
X11



(1-2)-2
A202
A202
X8



(1-2)-3
A201
A201
X12



(1-2)-4
A201
A201
X23



(1-2)-5
A205
A205
—



(1-3)-1
A301
A301
X16



(1-3)-2
A302
A302
X41



(1-3)-3
A303
A303
X56



(1-3)-4
A304
A304
X2



(1-3)-5
A305
A305
X15



(1-4)-1
A401
A401
X18



(1-4)-2
A402
A402
X59



(1-4)-3
A403
A403
X21



(1-4)-4
A404
A404
X4



(1-4)-5
A405
A405
X69



(1-5)-1
A501
A501
X8



(1-5)-2
A502
A502
X3



(1-5)-3
A503
A503
X2



(1-5)-4
A504
A504
X17



(1-5)-5
A505
A505
X22



(1-6)-1
A601
A601
X13



(1-6)-2
A602
A602
X52



(1-6)-3
A603
A603
X15



(1-6)-4
A605
A605
X32



(1-6)-5
A604
A605
X21



(1-7)-1
A701
A701
X35



(1-7)-2
A702
A702
X31



(1-7)-3
A703
A703
X11



(1-7)-4
A704
A704
X44



(1-7)-5
A705
A705
X17



(1-8)-1
A801
A801
—



(1-8)-2
A802
A802
—



(1-8)-3
A801
A801
X21



(1-8)-4
A802
A802
X15



(1-8)-5
A802
A805
X42



(1-8)-6
A803
A803
X61



(1-8)-7
A803
A803
X7



(1-8)-8
A804
A804
X34



(1-8)-9
A804
A804
X41



(1-8)-10
A805
A805
X29



(1-8)-11
A805
A805
X27



(1-9)-1
A901
A901
X66



(1-9)-2
A901
A901
X3



(1-9)-3
A902
A903
X12



(1-9)-4
A904
A904
X14



(1-9)-5
A905
A905
X23



(1-10)-1
A1001
A1007
X1



(1-10)-2
A1002
A1002
X50



(1-10)-3
A1005
A1005
X53



(1-10)-4
A1006
A1006
X19



(1-1)-11
A122
A122
X20



(1-1)-12
A123
A123
X17










The electron transport material represented by the formula (1) has at least one polymerizable functional group, and preferably has two or more polymerizable functional groups because the formation of a network structure is accelerated particularly at a time of polymerization.
A partial structure of the electron transport material represented by the formula (1) having the group represented by the formula (A1) can be synthesized through use of a known synthesis method disclosed in, for example, U.S. Pat. No. 4,442,193, U.S. Pat. No. 4,992,349, U.S. Pat. No. 5,468,583, or Chemistry of materials, Vol. 19, No. 11, 2703-2705 (2007). Further, the partial structure can be synthesized by a reaction between naphthalenetetracarboxylic acid dianhydride available from Tokyo Chemical Industry Co. Ltd., Sigma-Aldrich Japan, or Johnson Matthey Japan Inc. and a monoamine derivative.
A partial structure of the electron transport material represented by the formula (1) having the group represented by the formula (A2) is available from, for example, Tokyo Chemical Industry Co. Ltd., Sigma-Aldrich Japan, or Johnson Matthey Japan Inc. Further, the partial structure can be synthesized through use of a synthesis method disclosed in Chem. Educator No. 6, 227-234 (2001), Journal of Synthetic Organic Chemistry, Japan, vol. 15, 29-32 (1957), or Journal of Synthetic Organic Chemistry, Japan, vol. 15, 32-34 (1957) based on a phenanthrene derivative or a phenanthroline derivative. A dicyanomethylene group can also be introduced through a reaction with malononitrile.
A partial structure of the electron transport material represented by the formula (1) having the group represented by the formula (A3) is available from Tokyo Chemical Industry Co. Ltd., Sigma-Aldrich Japan, or Johnson Matthey Japan Inc. Further, the partial structure can be synthesized through use of a synthesis method disclosed in Bull. Chem. Soc. Jpn., Vol. 65, 1006-1011 (1992) based on a phenanthrene derivative or a phenanthroline derivative. A dicyanomethylene group can also be introduced through a reaction with malononitrile.
A partial structure of the electron transport material represented by the formula (1) having the group represented by the formula (A4) is available from, for example, Tokyo Chemical Industry Co. Ltd., Sigma-Aldrich Japan, or Johnson Matthey Japan Inc. Further, the partial structure can be synthesized through use of a synthesis method disclosed in Tetrahedron Letters, 43(16), 2991-2994 (2002) or Tetrahedron Letters, 44(10), 2087-2091 (2003) based on an acenaphthenequinone derivative. A dicyanomethylene group can also be introduced through a reaction with malononitrile.
A partial structure of the electron transport material represented by the formula (1) having the group represented by the formula (A5) is available from, for example, Tokyo Chemical Industry Co. Ltd., Sigma-Aldrich Japan, or Johnson Matthey Japan Inc. Further, the partial structure can be synthesized through use of a synthesis method disclosed in U.S. Pat. No. 4,562,132 with a fluorenone derivative and malononitrile. Further, the partial structure can also be synthesized through use of a synthesis method disclosed in Japanese Patent Application Laid-Open No. H05-279582 or Japanese Patent Application Laid-Open No. H07-070038 with a fluorenone derivative and an aniline derivative.
A partial structure of the electron transport material represented by the formula (1) having the group represented by the formula (A6) can be synthesized through use of a synthesis method disclosed in, for example, Chemistry Letters, 37(3), 360-361 (2008) or Japanese Patent Application Laid-Open No. H09-151157. Further, the partial structure is available from Tokyo Chemical Industry Co. Ltd., Sigma-Aldrich Japan, or Johnson Matthey Japan Inc.
A partial structure of the electron transport material represented by the formula (1) having the group represented by the formula (A7) can be synthesized through use of a synthesis method disclosed in Japanese Patent Application Laid-Open No. H01-206349 or PPCI/Japan Hard Copy '98, proceedings p. 207 (1998). Further, the partial structure can be synthesized using as a raw material a phenol derivative available from Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich Japan.
A partial structure of the electron transport material represented by the formula (1) having the group represented by the formula (A8) can be synthesized through use of a known synthesis method disclosed in, for example, Journal of the American chemical society, Vol. 129, No. 49, 15259-78 (2007). Further, the partial structure can be synthesized by a reaction between perylenetetracarboxylic acid dianhydride available from Tokyo Chemical Industry Co. Ltd., Sigma-Aldrich Japan, or Johnson Matthey Japan Inc. and a monoamine derivative.
A partial structure of the electron transport material represented by the formula (1) having the group represented by the formula (A9) can be synthesized, for example, as follows through use of a compound available from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan, or Johnson Matthey Japan Inc. That is, the partial structure can be synthesized by oxidizing the compound with an oxidant in an organic solvent. As the oxidant, there is given potassium permanganate, and as the organic solvent, there is given chloroform.
A partial structure of the electron transport material represented by the formula (1) having the group represented by the formula (A10) can be synthesized through use of a known synthesis method disclosed in, for example, Bulletin of Tokai Women's Junior College, 7, 1-11 (1980) and is available from, for example, Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan, or Johnson Matthey Japan Inc. A cyanated methylene structure or an imine structure may be introduced through the action of a cyanated methylene derivative or an aniline derivative.
Then, the partial structures of the electron transport material represented by the formula (1) having the group represented by any one of the formulae (A1) to (A10) are linked to each other, and thus the intended electron transport material represented by the formula (1) can be obtained. In order to link the partial structures of the electron transport material represented by the formula (1), a known method can be used, which involves, based on the partial structure of the electron transport material represented by the formula (1) having a functional group introduced therein, reacting a compound having a plurality of functional groups capable of being bonded to the introduced functional group, or the like. Specifically, the functional group can be introduced through the reactions described below.
For example, there are given: a method involving introducing an arylene group by means of a cross-coupling reaction based on a halide of the partial structure of the electron transport material represented by the formula (1), the reaction involving using a palladium catalyst and a base; a method involving introducing an alkylene group by means of a cross-coupling reaction based on a halide of the partial structure of the electron transport material represented by the formula (1), the reaction involving using a FeCl3 catalyst and a base; a method involving introducing a linking group through an ester bond or an amide bond by reacting a diol compound or a diamino compound based on the partial structure of the electron transport material represented by the formula (1) having a carboxyl group introduced therein; a method involving introducing a linking group through an ester bond or a urethane bond by reacting a dicarboxyl compound or a diisocyanate compound based on the partial structure of the electron transport material represented by the formula (1) having a hydroxyl group introduced therein; and a method involving introducing a linking group through an amide bond or a urea bond by reacting a dicarboxyl compound or a diisocyanate compound based on the partial structure of the electron transport material represented by the formula (1) having an amino group introduced therein.
Compounds that can be used in the above-mentioned reactions are available from Tokyo Chemical Industry Co. Ltd., Sigma-Aldrich Japan, or Johnson Matthey Japan Inc.
The electron transport material represented by the formula (1) has a polymerizable functional group (a hydroxyl group, a thiol group, an amino group, or a carboxyl group) capable of reacting with the cross-linking agent. As a method of introducing the polymerizable functional group into the main skeleton of the electron transport material represented by the formula (1), there is given a method involving introducing the polymerizable functional group directly into the main skeleton of the electron transport material represented by the formula (1). Also available is a method involving introducing a structure having the polymerizable functional group or a functional group that may serve as a precursor of the polymerizable functional group into the main skeleton of the electron transport material represented by the formula (1). As the latter method, there is given a method involving introducing an aryl group having the polymerizable functional group by means of a cross-coupling reaction based on a halide of the partial structure of the electron transport material represented by the formula (1), the reaction involving using a palladium catalyst and a base. Also available is a method involving introducing an alkyl group having the polymerizable functional group by means of a cross-coupling reaction based on the halide, the reaction involving using a FeCl3 catalyst and a base. Also available is a method involving subjecting a halide of the partial structure of the electron transport material represented by the formula (1) to lithiation, and causing an epoxy compound or carbon dioxide to act on the resultant to introduce a hydroxyalkyl group or a carboxyl group.
Further, the electron transport material represented by the formula (1) may be a compound represented by the formula (11). In this case, it is preferred that the polymerizable functional group be a hydroxyl group, a thiol group, an amino group, a carboxyl group, or a methoxy group.




In the formula (11), X1 and X2 each independently represent a residue obtained by removing four carboxyl groups from a substituted or unsubstituted aromatic tetracarboxylic acid. When the residue has a substituent, the substituent is a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.
Y represents a substituted or unsubstituted alkylene group having a polymerizable functional group or a substituted or unsubstituted arylene group having a polymerizable functional group.
R7 and R8 each independently represent a substituted or unsubstituted alkyl group, a group derived by substituting one of methylene groups of the substituted or unsubstituted alkyl group with an oxygen atom, a group derived by substituting one of the methylene groups of the substituted or unsubstituted alkyl group with a sulfur atom, a group derived by substituting one of the methylene groups of the substituted or unsubstituted alkyl group with NR9, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or an alkoxycarbonyl group. R7 and R8 may each have a polymerizable functional group.
It should be noted that the oxygen atom, the sulfur atom, and the NR9 are free from being directly bonded to nitrogen atoms to which R7 and R8 are bonded.
Examples of the residue obtained by removing four carboxyl groups from an aromatic tetracarboxylic acid represented by X1 or X2 in the compound represented by the formula (11) include a phenyl group, a biphenyl group, a p-terphenyl group, a naphthyl group, an anthryl group, and a perylenyl group. Specific examples of the aromatic tetracarboxylic acid include, but not limited to, 1,2,3,4-benzenetetracarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, 2,2′,3,3′-biphenyltetracarboxylic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 2,3,3′,4′-biphenyltetracarboxylic acid, 3,3′,4,4′-p-terphenyltetracarboxylic acid, 2,2′,3,3′-p-terphenyltetracarboxylic acid, 2,3,3′,4′-p-terphenyltetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, and 3,4,9,10-perylenetetracarboxylic acid.
Substituents of the X1 and X2 are exemplified by, but not limited to: a halogen atom such as a fluorine, chlorine, bromine, or iodine atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group; and an aryl group such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, or a fluorenyl group. In addition, the alkyl group may be further substituted with the halogen atom or the aryl group, and the aryl group may be further substituted with the halogen atom or the alkyl group. Further, the X1 and X2 may each be substituted with one or two or more substituents.
Examples of the alkylene group represented by Y in the compound represented by the formula (11) include, but not limited to, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclohexylene group, a heptylene group, an octylene group, a nonylene group, and a decylene group.
Examples of the arylene group represented by Y in the compound represented by the formula (11) include, but not limited to, a phenylene group, a naphthylene group, a biphenylylene group, a fluorenylylene group, a spirofluorenylylene group, an anthranyl group, and a phenanthrenyl group.
Examples of the polymerizable functional group that Y has include an active hydrogen group, an unsaturated hydrocarbon group, and a methoxy group. The active hydrogen group is preferably a hydroxyl group, a hydroxyalkyl group, a carboxyl group, an amino group, and a thiol group. Of those, a hydroxyl group and a carboxyl group are more preferred. In addition, the unsaturated hydrocarbon group is preferably an ethylene group, an acryloyloxy group, or a methacryloyloxy group which are substituents of the arylene group.
As a substituent of the Y, there are given, for example, a methyl group, an ethyl group, a propyl group, and a butyl group. The compound represented by the formula (11) may have one or two or more of the polymerizable functional groups that Y has, and may have one kind or two or more kinds thereof.
Examples of the alkyl group represented by R7 or R8 in the compound represented by the formula (11) include, but not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a cyclohexyl group.
Examples of the group derived by substituting one of the methylene groups of the alkyl group with an oxygen atom represented by R7 or R8 in the compound represented by the formula (11) include, but not limited to, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group.
Examples of the group derived by substituting one of the methylene groups of the alkyl group with a sulfur atom represented by R7 or R8 in the compound represented by the formula (11) include, but not limited to, a methylthiomethyl group, a methylthioethyl group, a methylthiopropyl group, a methylthiobutyl group, an ethylthiomethyl group, an ethylthioethyl group, an ethylthiopropyl group, and an ethylthiobutyl group as well as a mercaptomethyl group, a mercaptoethyl group, a mercaptopropyl group, a mercaptobutyl group, a mercaptopentyl group, a mercaptohexyl group, a mercaptoheptyl group, a mercaptooctyl group, a mercaptononyl group, a mercaptodecyl group, and a mercaptocyclohexyl group.
Examples of the group derived by substituting one of the methylene groups of the alkyl group with NR9 represented by R7 or R8 in the compound represented by the formula (11) include, but not limited to, a dimethylaminomethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a methylethylaminomethyl group, a methylethylaminoethyl group, a methylethylaminopropyl group, a diethylaminomethyl group, a diethylaminoethyl group, a diethylaminopropyl group, an ethylpropylaminomethyl group, an ethylpropylaminoethyl group, an ethylpropylaminopropyl group, a dipropylaminomethyl group, a dipropylaminoethyl group, and a dipropylaminopropyl group.
Examples of the aryl group represented by R7 or R8 in the compound represented by the formula (11) include, but not limited to, a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, and a fluorenyl group.
Examples of the heterocyclic group represented by R7 or R8 in the compound represented by the formula (11) include, but not limited to, thiophene, pyrrole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, oxazole, oxadiazole, phenanthridine, acridine, naphthyridine, quinoxaline, quinazoline, cinnoline, phthalazine, phenanthroline, phenazine, dibenzofuran, dibenzothiophene, carbazole, benzofuran, benzothiophene, indole, benzimidazole, benzothiazole, and benzothiadiazole.
Examples of the alkoxycarbonyl group represented by R7 or R8 in the compound represented by the formula (11) include, but not limited to, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group.
As substituents of the alkyl group, the group derived by substituting one of the methylene groups of the alkyl group with an oxygen atom, the group derived by substituting one of the methylene groups of the alkyl group with a sulfur atom, and the group derived by substituting one of the methylene groups of the alkyl group with NR9, there are given, for example: an aralkyl group such as a benzyl group; aryl groups such as a phenyl group and a biphenyl group; heterocyclic groups such as a pyridyl group, a pyrrolyl group, a benzimidazolyl group, and a benzothiazolyl group; alkoxyl groups such as a methoxyl group, an ethoxyl group, a propoxyl group, and a phenoxyl group; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; a cyano group; a nitro group; a carbonyl group; a carboxyl group; and an alkoxycarbonyl group.
As substituents of the aryl group and the heterocyclic group, there are given, for example: alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group; an aralkyl group such as a benzyl group; aryl groups such as a phenyl group and a biphenyl group; heterocyclic groups such as a pyridyl group, a pyrrolyl group, a benzimidazolyl group, and a benzothiazolyl group; alkoxyl groups such as a methoxyl group, an ethoxyl group, a propoxyl group, and a phenoxyl group; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; a cyano group; a nitro group; an alkoxycarbonyl group; an alkoxy group; and a halogenated alkyl group.
In addition, when R7 and R8 each have a polymerizable functional group, examples of the polymerizable functional group include the same functional groups as the examples of the polymerizable functional group that Y has. As in the case of Y, the compound may have one or two or more of the polymerizable functional groups that R7 and R8 have, and may have one kind or two or more kinds thereof.
In the second embodiment of the present invention, the compound represented by the formula (11) is used as (i) a polymerized product of the compound represented by the formula (11) or (ii) a polymerized product of a composition containing the compound represented by the formula (11) and a cross-linking agent. It should be noted that, in the case where the compound represented by the formula (11) is used as (i) the polymerized product of the compound represented by the formula (11), the polymerizable functional group of Y is preferably an unsaturated hydrocarbon group. The unsaturated hydrocarbon group is preferably an ethylene group, an acryloyloxy group, or a methacryloyloxy group which are substituents of the arylene group.
Examples of the compound represented by the formula (11) according to the present invention are shown in Tables 13 to 16, but the present invention is not limited thereto. A plurality of compounds each represented by the formula (11) may be used in combination.












TABLE 13





Exem-







plified







Com-







pound
R7
X1
Y
X2
R8







E101






















 


E102






















 


E103






















 


E104






















 


E105






















 


E106






















 


E107






















 


E108






















 


E109






















 


E110






















 


E111






















 


E112






















 


E113






















 


E114






















 


E115






















 


E116






















 


E117






















 


E118






















 


E119






















 


E120






















 


E121






















 


E122






















 


E123






















 


E124






















 


E125






















 


E126






















 


E127






















 


E128






















 


E129






















 


E130






















 


E131






















 


E132






















 


E133






















 


E134






















 


E135






















 


E136






















 


E137






















 


E138






















 


E139






















 


E140






















 


E141






















 


E142






















 


E143






















 


E144






















 


E145






















 


E146






















 


E147









































TABLE 14





Exem-







plified







Com-







pound
R7
X1
Y
X2
R8







E201






















 


E202






















 


E203






















 


E204






















 


E205






















 


E206






















 


E207






















 


E208






















 


E209






















 


E210






















 


E211






















 


E212









































TABLE 15





Exem-







plified







Com-







pound
R7
X1
Y
X2
R8







E301






















 


E302






















 


E303






















 


E304






















 


E305






















 


E306






















 


E307






















 


E308






















 


E309






















 


E310






















 


E311






















 


E312






















 


E313






















 


E314






















 


E315






















 


E316






















 


E317






















 


E318






















 


E319






















 


E320









































TABLE 16





Exem-







plified







Com-







pound
R7
X1
Y
X2
R8







E401






















 


E402






















 


E403






















 


E404






















 


E405






















 


E406






















 


E407






















 


E408






















 


E409






















 


E410






















 


E411






















 


E412






















 


E413






















 


E414






















 


E415






















 


E416






















 


E417






















 


E418






















 


E419






















 


E420





























The compound represented by the formula (11) in the present invention can be synthesized through use of a known synthesis method disclosed in, for example, Japanese Patent Application Laid-Open No. 2007-108670 or Journal of the Imaging Society of Japan, 45(6), 521-525, (2006). In addition, the compound is also available as a reagent from, for example, Tokyo Chemical Industry Co. Ltd., Sigma-Aldrich Japan, or Johnson Matthey Japan Inc.
As a method of introducing a polymerizable functional group when synthesizing the compound represented by the formula (11), there are two methods. One of the methods is (i) a method involving directly introducing the polymerizable functional group when synthesizing the compound represented by the formula (11). The other is (ii) a method involving forming a skeleton of the compound represented by the formula (11) having a group that is to serve as a basis for introducing the polymerizable functional group and then introducing a structure having the polymerizable functional group when synthesizing the compound represented by the formula (11). As the method of (ii), there is given, for example, a method involving introducing an aryl group containing a functional group into the compound represented by the formula (11) in which R7, R8, or Y represents a halogen-substituted naphthyl group by means of a cross-coupling reaction using a palladium catalyst and a base. Further, a FeCl3 catalyst may be used in place of the palladium catalyst. Further, also available is a method involving subjecting the compound represented by the formula (11) in which R7, R8, or Y represents a halogen-substituted naphthyl group to lithiation, and causing an epoxy compound or CO2 to act on the resultant to introduce a hydroxyalkyl group or a carboxyl group.
Further, as a method of introducing an unsaturated hydrocarbon group (for example, acryloyl, methacryloyl, or styrene) when synthesizing the compound represented by the formula (11), there is given the following method. That is, there is given a method involving using a monoamine having the unsaturated hydrocarbon group as a structure for R7 or R8 or as a structure for the Y moiety which is a diamine when synthesizing the compound represented by the formula (11). There is also given a method involving deriving an ester of acrylic acid or methacrylic acid from a hydroxyl group of the compound represented by the formula (11) having a hydroxyl group to introduce an acryloyl group or a methacryloyl group.
The compound and the like according to the present invention were confirmed by the following method.
Mass Analysis
A molecular weight was measured under the conditions of an acceleration voltage of 20 kV, a mode of Reflector, and a molecular weight standard product of fullerene C60 through use of a mass spectrometer (MALDI-TOF MS, ultraflex, manufactured by Bruker Daltonics Inc.). The molecular weight was confirmed based on the obtained peak-top value.
A synthesis example of the compound represented by the formula (11) is described.
(Synthesis Example)
13.4 g (50 mmol) of 1,4,5,8-naphthalenetetracarboxylic acid dianhydride and 70 ml of dimethylacetamide were loaded into a 300-ml three-necked flask under a nitrogen stream at room temperature. A mixture of 5.7 g (50 mmol) of 4-heptylamine and 30 ml of dimethylacetamide was dropped into the three-necked flask under stirring. After the completion of dropping, the resultant was heated to 50° C. and then stirred at this temperature for 2 hours. Further, 5.4 g (25 mmol) of 3,3′-dihydroxybenzidine and 30 ml of dimethylacetamide were added to the resultant and the mixture was refluxed by heating for 6 hours. After the completion of the reaction, the vessel was cooled and the resultant was concentrated under reduced pressure. The residue was purified by silica gel column chromatography. Further, the recovered product was recrystallized with toluene/ethyl acetate to obtain 2.4 g of Exemplified Compound (E106).
Next, the cross-linking agent is described. A compound having a reactive group that polymerizes or cross-links with the electron transport material having a polymerizable functional group and the thermoplastic resin having a polymerizable functional group can be used as the cross-linking agent. Specifically, for example, a compound described in the “Cross-linking Agent Handbook” edited by Shinzo Yamashita and Tosuke Kaneko, and published by TAISEISHA LTD. (1981) can be used.
The cross-linking agent to be used in the undercoat layer is preferably a compound having 2 to 6 isocyanate groups, 2 to 6 blocked isocyanate groups, or 2 to 6 groups each represented by —CH2—OR6 (R6 represents an alkyl group). The compound is specifically an isocyanate compound having isocyanate groups or blocked isocyanate groups or an amine compound having groups each represented by —CH2—OR6. Of those, an isocyanate compound having 2 to 6 isocyanate groups or 2 to 6 blocked isocyanate groups is preferred. Examples of the isocyanate compound include triisocyanatobenzene, triisocyanatomethylbenzene, triphenylmethane triisocyanate, lysine triisocyanate, and an isocyanurate modified product, biuret modified product, allophanate modified product, and trimethylolpropane or pentaerythritol adduct modified product of a diisocyanate such as tolylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, methyl 2,6-diisocyanatohexanoate, or norbornane diisocyanate. Of those, an isocyanurate modified product and an adduct modified product are more preferred.
The blocked isocyanate group is a group having a structure represented by —NHCOX3 (where X3 represents a protective group). Although X3 may represent any protective group as long as the protective group can be introduced into an isocyanate group, X3 preferably represents a group represented by any one of the following formulae (H1) to (H7).




Specific examples (B1) to (B21) of the isocyanate compound are shown below.










As the amine compound, for example, an amine compound having 2 to 6 groups each represented by —CH2—OR6 is preferred. As the amine compound, for example, there are given a melamine compound, a guanamine compound, and a urea compound. Preferred specific examples of the amine compound include a compound represented by any one of the following formulae (C1) to (C5) and an oligomer of the compound represented by any one of the following formulae (C1) to (C5).




In the formulae (C1) to (C5), R11 to R16, R22 to R25, R31 to R34, R41 to R44, and R51 to R54 each independently represent a hydrogen atom, a hydroxyl group, an acyl group, or a monovalent group represented by —CH2—OR6. At least one of R11 to R16, at least one of R22 to R25, at least one of R31 to R34, at least one of R41 to R44, and at least one of R51 to R54 each represent a monovalent group represented by —CH2—OR6. R6 represents a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms. The alkyl group is preferably a methyl group, an ethyl group, a propyl group (n-propyl group or iso-propyl group), a butyl group (n-butyl group, iso-butyl group, or tert-butyl group), or the like from the viewpoint of polymerizability. R21 represents an aryl group, an aryl group substituted with alkyl group, a cycloalkyl group, or a cycloalkyl group substituted with an alkyl group.
Specific examples of the compound represented by any one of the formulae (C1) to (C5) are shown below. Further, the amine compound may contain an oligomer (multimer) of the compound represented by any one of the formulae (C1) to (C5).
The polymerization degree of the multimer is preferably 2 or more and 100 or less. Further, the above-mentioned multimer and monomer can also be used as a mixture of two or more kinds.
A compound that can be generally purchased as the compound represented by the formula (C1) is exemplified by SUPER MELAMI No. 90 (manufactured by NOF CORPORATION), SUPER BECKAMINE (trademark) TD-139-60, L-105-60, L127-60, L110-60, J-820-60, or G-821-60 (manufactured by DIC Corporation), U-VAN 2020 (Mitsui Chemicals, Inc.), Sumitex Resin M-3 (Sumitomo Chemical Company), or NIKALAC MW-30, MW-390, or MX-750LM (manufactured by NIPPON CARBIDE INDUSTRIES CO., INC.).
A compound that can be generally purchased as the compound represented by the formula (C2) is exemplified by SUPER BECKAMINE (trademark) L-148-55, 13-535, L-145-60, or TD-126 (manufactured by DIC Corporation) or NIKALAC BL-60 or BX-4000 (manufactured by NIPPON CARBIDE INDUSTRIES CO., INC.).
A compound that can be generally purchased as the compound represented by the formula (C3) is exemplified by NIKALAC MX-280 (manufactured by NIPPON CARBIDE INDUSTRIES CO., INC.).
A compound that can be generally purchased as the compound represented by the formula (C4) is exemplified by NIKALAC MX-270 (manufactured by NIPPON CARBIDE INDUSTRIES CO., INC.).
A compound that can be generally purchased as the compound represented by the formula (C5) is exemplified by NIKALAC MX-290 (manufactured by NIPPON CARBIDE INDUSTRIES CO., INC.).
Specific examples of the compound represented by the formula (C1) are shown below.







Specific examples of the compound represented by the formula (C2) are shown below.










Specific examples of the compound represented by the formula (C3) are shown below.




Specific examples of the compound represented by the formula (C4) are shown below.




Specific examples of the compound represented by the formula (C5) are shown below.




Next, the thermoplastic resin having a polymerizable functional group is described. The thermoplastic resin having a polymerizable functional group is preferably a thermoplastic resin having a structural unit represented by the following formula (D).




In the formula (D), R61 represents a hydrogen atom or an alkyl group, Y1 represents a single bond, an alkylene group, or a phenylene group, and W1 represents a hydroxyl group, a thiol group, an amino group, a carboxyl group, or a methoxy group.
Examples of the thermoplastic resin having a structural unit represented by the formula (D) include an acetal resin, a polyolefin resin, a polyester resin, a polyether resin, a polyamide resin, and a cellulose resin. The structural unit represented by the formula (D) may be present in a characteristic structure represented below, or may be present separately from the characteristic structure. The characteristic structures are represented in the following formulae (E-1) to (E-6). The formula (E-1) represents the structural unit of the acetal resin. The formula (E-2) represents the structural unit of the polyolefin resin. The formula (E-3) represents the structural unit of the polyester resin. The formula (E-4) represents the structural unit of the polyether resin. The formula (E-5) represents the structural unit of the polyamide resin. The formula (E-6) represents the structural unit of the cellulose resin.




In the formulae, R2001 to R2005 each independently represent a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R2006 to R2010 each independently represent a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group. When R2001 represents C3H7, the resin represented by E-1 includes butyral moiety. R2011 to R2016 each represent an acetyl group, a hydroxyethyl group, a hydroxypropyl group, or a hydrogen atom.
The resin having a structural unit represented by the formula (D) (hereinafter sometimes referred to as “resin D”) is obtained by, for example, polymerizing a monomer having a polymerizable functional group (hydroxyl group, thiol group, amino group, carboxyl group, or methoxy group) that can be purchased from Sigma-Aldrich Japan or Tokyo Chemical Industry Co., Ltd.
In addition, the resin D can be generally purchased. Examples of the resin that can be purchased include: a polyether polyol-based resin such as AQD-457 or AQD-473 manufactured by Nippon Polyurethane Industry Co., Ltd., or SANNIX GP-400 or GP-700 manufactured by Sanyo Chemical Industries, Ltd.; a polyester polyol-based resin such as PHTHALKYD W2343 manufactured by Hitachi Chemical Co., Ltd., WATERSOL S-118 or CD-520 or BECKOLITE M-6402-50 or M-6201-40IM manufactured by DIC Corporation, HARIDIP WH-1188 manufactured by Harima Chemicals, Inc., or ES3604 or ES6538 manufactured by Japan U-Pica Company Ltd.; an polyacrylic polyol-based resin such as BURNOCK WE-300 or WE-304 manufactured by DIC Corporation; a polyvinyl alcohol-based resin such as KURARAY POVAL PVA-203 manufactured by KURARAY CO., LTD.; a polyvinyl acetal-based resin such as BX-1 or BM-1 manufactured by Sekisui Chemical Co., Ltd.; a polyamide-based resin such as TORESIN FS-350 manufactured by Nagase ChemteX Corporation; a carboxyl group-containing resin such as AQUALIC manufactured by Nippon Shokubai CO., LTD. or FINELEX SG2000 manufactured by Namariichi Co., Ltd.; a polyamine resin such as LUCKAMIDE manufactured by DIC Corporation; and a polythiol resin such as QE-340M manufactured by Toray Fine Chemicals Co., Ltd. Of those, a polyvinyl acetal-based resin, a polyester polyol-based resin, and the like are more preferred from the viewpoints of polymerizability and uniformity of the undercoat layer.
The weight-average molecular weight (Mw) of the resin D preferably falls within the range of from 5,000 to 400,000.
Examples of a method of quantifying the polymerizable functional group in the resin include: the titration of a carboxyl group with potassium hydroxide; the titration of an amino group with sodium nitrite; the titration of a hydroxyl group with acetic anhydride and potassium hydroxide; the titration of a thiol group with 5,5′-dithiobis(2-nitrobenzoic acid); and a calibration curve method involving obtaining the amount of the polymerizable functional group from the IR spectrum of a sample whose polymerizable functional group introduction ratio has been changed.
Specific examples of the resin D are shown in Table 17 below. In the column “characteristic structure” of Table 17, a structural unit represented by any one of the formulae (E-1) to (E-6), and major structures in the structural units in the cases of “butyral”, “polyolefin”, “polyester”, “polyether”, “cellulose”, “polyamide”, and “acetal” are “polyvinyl butyral”, “polyethylene”, “polybutylene succinate”, “polyoxyphenylene”, “cellulose triacetate”, “polyhexamethylene adipamide”, and “polyvinyl formal”, respectively.












TABLE 17









Number of






moles of

Substituent of













Structure
functional
Characteristic
characteristic
Molecular















R61
Y1
W1
group per g
structure
structure
weight


















D1
H
Single bond
OH
3.3 mmol
Butyral
R2001═C3H8
1 × 105


D2
H
Single bond
OH
3.3 mmol
Butyral
R2001═C3H8
4 × 104


D3
H
Single bond
OH
3.3 mmol
Butyral
R2001═C3H8
2 × 104


D4
H
Single bond
OH
1.0 mmol
Polyolefin
R2002 to R2005═H
1 × 105


D5
H
Single bond
OH
3.0 mmol
Polyester
R2006═R2007═C2H4
8 × 104


D6
H
Single bond
OH
2.5 mmol
Polyether
R208═C4H8
5 × 104


D7
H
Single bond
OH
2.1 mmol
Polyether
R2008═C4H9
2 × 105


D8
H
Single bond
COOH
3.5 mmol
Polyolefin
R102 to R105═H
6 × 104


D9
H
Single bond
NH2
1.2 mmol
Polyamide
R2009═C10H20,
2 × 105








R2010═C6H12


D10
H
Single bond
SH
1.3 mmol
Polyolefin
R2002 to R2005═H
9 × 103


D11
H
Phenylene
OH
2.8 mmol
Polyolefin
R2002 to R2005═H
4 × 103


D12
H
Single bond
OH
3.0 mmol
Butyral
R2001═C3H8
7 × 104


D13
H
Single bond
OH
2.9 mmol
Polyester
R2006═Ph,
2 × 104








R2007═C2H4


D14
H
Single bond
OH
2.5 mmol
Polyester
R2006═R2007═C2H4
6 × 103


D15
H
Single bond
OH
2.7 mmol
Polyester
R2006═R2007═C2H4
8 × 104


D16
H
Single bond
COOH
1.4 mmol
Polyolefin
R2002 to R2004═H,
2 × 105








R2005═CH3


D17
H
Single bond
COOH
2.2 mmol
Polyester
R2006═Ph,
9 × 103








R2007═C2H4


D18
H
Single bond
COOH
2.8 mmol
Polyester
R2006═R2007═C2H4
8 × 102


D19
CH3
CH2
OH
1.5 mmol
Polyester
R2006═R2007═C2H5
2 × 104


D20
C2H5
CH2
OH
2.1 mmol
Polyester
R2006═R2007═C2H6
1 × 104


D21
C2H5
CH2
OH
3.0 mmol
Polyester
R2006═R2007═C2H7
5 × 104


D22
H
Single bond
OCH3
1.2 mmol
Polyolefin
R2002 to R2005═H
7 × 103


D23
H
Single bond
OH
3.3 mmol
Butyral
R2001═C3H8
2.7 × 105 


D24
H
Single bond
OH
3.3 mmol
Butyral
R2001═C3H8
4 × 105


D25
H
Single bond
OH
2.5 mmol
Acetal
R2001═H
3.4 × 105 


D26
H
Single bond
OH
2.8 mmol
Cellulose
R2011═R2016═H, R2012
3 × 104








to R2015═COCH3









The content of the electron transport material having a polymerizable functional group is preferably 50 mass % or more and 85 mass % or less with respect to the total mass of the composition including the electron transport material having a polymerizable functional group, the cross-linking agent, and the resin having a polymerizable functional group. When the content of the electron transport material is 50 mass % or more and 85 mass % or less, a black dot does not occur, and the sensitivity further increases. When the content of the electron transport material is 50 mass % or more, the structurally appropriate distance can be kept between adjacent molecules of the electron transport material, and hence the sensitivity further increases. Further, when the content of the electron transport material is 85 mass % or less, it is considered that the electron transport material is polymerized to accelerate the formation of a network structure, and the effect of suppressing a black dot is further enhanced.
The content of the polymerized product according to the present invention in the undercoat layer is preferably 50 mass % or more and 100 mass % or less, more preferably 80 mass % or more and 100 mass % or less with respect to the total mass of the undercoat layer.
The thickness d1 of the undercoat layer is preferably 0.7 μm or more and 3.0 μm or less. When the thickness d1 is 0.7 μm or more and 3.0 μm or less, the expressions (2) and (3) are likely to be satisfied, and the sensitivity under a high electric field further increases. When the thickness d1 is 0.7 μm or more, an increase in dark attenuation is suppressed, and hence the sensitivity further increases. Further, when the thickness d1 is 3.0 μm or less, the expression (3) is likely to be satisfied, and hence the sensitivity further increases.
In the polymerized product of (ii), the mass ratio between the compound represented by the formula (11) and the cross-linking agent in the composition of the undercoat layer is preferably 100:50 or more and 100:750 or less. Further, the mass ratio is more preferably 100:50 or more and 100:500 or less. When the mass ratio falls within the above-mentioned range, it is considered that the aggregation of the cross-linking agent is suppressed, and as a result, a trap site in the undercoat layer decreases, to thereby further enhance the effect of suppressing a ghost.
Further, in the case where the undercoat layer contains the polymerized product of (i) or (ii), the thickness of the undercoat layer is preferably 0.5 μm or more and 15 μm or less from the viewpoint of the effect of suppressing a ghost. The thickness of the undercoat layer is more preferably 0.5 μm or more and 5 μm or less.
Now, the support, the hole transporting layer, and the other layers of the laminated body are described.
[Support]
The support is preferably a support having conductivity (conductive support). For example, a support made of a metal such as aluminum, nickel, copper, gold, or iron, or an alloy thereof can be used. Examples thereof include: a support obtained by forming a thin film of a metal such as aluminum, silver, or gold on an insulating support such as a polyester resin, a polycarbonate resin, a polyimide resin, or a glass; and a support having formed thereon a thin film of an electroconductive material such as indium oxide or tin oxide.
The surface of the support may be subjected to electrochemical treatment such as anodization, wet honing treatment, blast treatment, or cutting treatment in order that the electrical characteristics of the electrophotographic photosensitive member may be improved and interference fringes may be suppressed.
An electroconductive layer may be formed between the support and the undercoat layer of the laminated body. The electroconductive layer is obtained by: forming, on the support, a coating film of an application liquid for the electroconductive layer obtained by dispersing electroconductive particles in a resin; and drying the coating film.
Examples of the electroconductive particles include carbon black, acetylene black, powder of a metal such as aluminum, nickel, iron, nichrome, copper, zinc, or silver, and powder of a metal oxide such as electroconductive tin oxide or ITO.
In addition, examples of the resin include a polyester resin, a polycarbonate resin, a polyvinyl butyral resin, an acrylic resin, a silicone resin, an epoxy resin, a melamine resin, a urethane resin, a phenol resin, and an alkyd resin.
Examples of the solvent of the application liquid for the electroconductive layer include an ether-based solvent, an alcohol-based solvent, a ketone-based solvent, and an aromatic hydrocarbon solvent. The thickness of the electroconductive layer is preferably 0.2 μm or more and 40 μm or less, more preferably 1 μm or more and 35 μm or less, still more preferably 5 μm or more and 30 μm or less.
[Charge Generating Layer]
In the laminated body, the photosensitive layer is formed on the undercoat layer. The photosensitive layer includes the charge generating layer containing a charge generating material and a binder resin. Further, it is preferred that the photosensitive layer be a laminated photosensitive layer including the charge generating layer and the hole transporting layer containing a hole transporting material.
Examples of the charge generating material include an azo pigment, a perylene pigment, an anthraquinone derivative, an anthanthrone derivative, a dibenzpyrenequinone derivative, a pyranthrone derivative, a violanthrone derivative, an isoviolanthrone derivative, an indigo derivative, a thioindigo derivative, phthalocyanine pigments such as a metal phthalocyanine and a metal-free phthalocyanine, and a bisbenzimidazole derivative. Of those, at least one kind selected from the group consisting of an azo pigment and phthalocyanine pigments is preferred. Of the phthalocyanine pigments, oxytitanium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine are preferred.
Examples of the binder resin to be used for the charge generating layer include: a polymer and copolymer of a vinyl compound such as styrene, vinyl acetate, vinyl chloride, an acrylic acid ester, a methacrylic acid ester, vinylidene fluoride, or trifluoroethylene; a polyvinyl alcohol resin; a polyvinyl acetal resin; a polycarbonate resin; a polyester resin; a polysulfone resin; a polyphenylene oxide resin; a polyurethane resin; a cellulose resin; a phenol resin; a melamine resin; a silicone resin; and an epoxy resin. Of those, a polyesterresin, a polycarbonate resin, and a polyvinyl acetal resin are preferred, and polyvinyl acetal is more preferred.
In the charge generating layer, the mass ratio (charge generating material/binder resin) of the charge generating material to the binder resin falls within the range of preferably from 10/1 to 1/10, more preferably from 5/1 to 1/5. A solvent to be used in an application liquid for the charge generating layer is, for example, an alcohol-based solvent, a sulfoxide-based solvent, a ketone-based solvent, an ether-based solvent, an ester-based solvent, or an aromatic hydrocarbon solvent.
The thickness of the charge generating layer is preferably 0.05 μm or more and 5 μm or less.
[Hole Transporting Layer]
The hole transporting layer is formed on the charge generating layer. The hole transporting layer contains a hole transporting material and a binder resin.
Examples of the hole transporting material include a polycyclic aromatic compound, a heterocyclic compound, a hydrazone compound, a styryl compound, a benzidine compound, a triarylamine compound, a triphenylamine, and a polymer having in its main chain or side chain a group derived from any one of these compounds. Of those, at least one kind selected from the group consisting of a triarylamine compound, a benzidine compound, and a styryl compound is preferred.
Examples of the binder resin to be used for the hole transporting layer include a polyester resin, a polycarbonate resin, a polymethacrylic acid ester resin, a polyarylate resin, a polysulfone resin, and a polystyrene resin. Of those, a polycarbonate resin and a polyarylate resin are preferred. In addition, it is preferred that the weight-average molecular weight (Mw) of any such binder resin fall within the range of from 10,000 to 300,000.
In the hole transporting layer, the ratio (hole transporting material/binder resin) of the hole transporting material to the binder resin is preferably from 10/5 to 5/10, more preferably from 10/8 to 6/10.
When the thickness of the hole transporting layer according to the present invention is 15 μm or less, the effects are obtained effectively. When the thickness of the hole transporting layer is 3 μm or more and 10 μm or less, the effects of the present invention are obtained more effectively. When the thickness is 3 μm or more, the expression (2) is likely to be satisfied. When the thickness is 10 μm or less, the intensity of an electric field applied to the undercoat layer becomes high, and hence the effects of the present invention are more significantly obtained as compared to the undercoat layer in the related art. Further, in the case where the undercoat layer contains the polymerized product of (i) or (ii), even when the thickness of the hole transporting layer is more than 15 μm, the effect of suppressing a ghost is obtained. The thickness of the hole transporting layer in this case is preferably more than 15 μm and 40 μm or less.
A solvent to be used in an application liquid for the hole transporting layer is, for example, an alcohol-based solvent, a sulfoxide-based solvent, a ketone-based solvent, an ether-based solvent, an ester-based solvent, or an aromatic hydrocarbon solvent.
It should be noted that another layer such as a second undercoat layer free of the polymerized product relating to the present invention may be formed between the undercoat layer and the charge generating layer.
In addition, a surface protective layer may be formed on the hole transporting layer. The surface protective layer contains electroconductive particles or a charge transporting material and a binder resin. In addition, the surface protective layer may further contain an additive such as a lubricant. In addition, the binder resin itself of the protective layer may be provided with conductivity or a charge transport property, and in this case, the electroconductive particles or the charge transporting material except the resin may not be incorporated into the protective layer. In addition, the binder resin of the protective layer may be a thermoplastic resin, or may be a curable resin polymerised with heat, light, or a radiation (such as an electron beam).
The following method is preferred as a method of forming each layer: an application liquid obtained by dissolving and/or dispersing a material constituting each layer in a solvent is applied, and the resultant coating film is dried and/or cured to form the layer. A method of applying the application liquid is, for example, an immersion application method (immersion coating method), a spray coating method, a curtain coating method, or a spin coating method. Of those, an immersion application method is preferred from the viewpoints of efficiency and productivity.
[Process Cartridge and Electrophotographic Apparatus]
FIG. 7 is a view for illustrating the schematic configuration of an electrophotographic apparatus including a process cartridge including an electrophotographic photosensitive member.
In FIG. 7, an electrophotographic photosensitive member 1 having a cylindrical shape is rotationally driven about an axis 2 in a direction indicated by an arrow at a predetermined peripheral speed. The surface (peripheral surface) of the electrophotographic photosensitive member 1 to be rotationally driven is uniformly charged to a predetermined positive or negative potential by a charging unit 3 (primary charging unit such as a charging roller). Next, the surface receives exposure light (image exposure light) 4 from an exposing unit (not shown) such as slit exposure or laser beam scanning exposure. Thus, electrostatic latent images corresponding to the target image are sequentially formed on the surface of the electrophotographic photosensitive member 1.
The electrostatic latent images formed on the surface of the electrophotographic photosensitive member 1 are then developed with toner in the developer of a developing unit 5 to become toner images. Next, the toner images formed on and carried by the surface of the electrophotographic photosensitive member 1 are sequentially transferred onto a transfer material P (such as paper) by a transfer bias from a transferring unit 6 (such as a transfer roller). It should be noted that the transfer material P is taken out and supplied from a transfer material-supplying unit (not shown) to a space (abutment portion) between the electrophotographic photosensitive member 1 and the transferring unit 6 in synchronization with the rotation of the electrophotographic photosensitive member 1.
The transfer material P onto which the toner images have been transferred is separated from the surface of the electrophotographic photosensitive member 1 and introduced into a fixing unit 8, where the images are fixed. Thus, the transfer material is printed out as an image-formed product (print or copy) to the outside of the apparatus.
The surface of the electrophotographic photosensitive member 1 after the transfer of the toner images is cleaned through the removal of a transfer residual developer (toner) by a cleaning unit 7 (such as a cleaning blade). Next, the surface is subjected to antistatic treatment by pre-exposure light 11 from a pre-exposing unit (not shown), and is then repeatedly used in image formation. It should be noted that, when the charging unit 3 is a contact charging unit using a charging roller or the like as illustrated in FIG. 7, pre-exposure is not necessarily needed.
Two or more of components such as the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, and the cleaning unit 7 may be selected, stored in a container, and integrally coupled to form a process cartridge. In this case, the process cartridge is preferably removably mounted onto the main body of the electrophotographic apparatus such as a copying machine or a laser beam printer. In FIG. 7, the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, and the cleaning unit 7 are integrally supported to from a cartridge. In addition, the cartridge serves as a process cartridge 9 removably mounted onto the main body of the electrophotographic apparatus by using a guiding unit 10 such as the rail of the main body of the electrophotographic apparatus.
EXAMPLES
Next, the production and evaluation of the electrophotographic photosensitive member are described.
Example 1
An aluminum cylinder (JIS-A3003, aluminum alloy) having a length of 260.5 mm and a diameter of 30 mm was used as a support (conductive support).
Then, 50 parts of titanium oxide particles (powder resistivity: 120 Ω·cm, coverage ratio of tin oxide: 40%) each covered with oxygen-deficient tin oxide, 40 parts of a phenol resin (Plyophen J-325, manufactured by DIC Corporation, resin solid content: 60%), and 50 parts of methoxypropanol serving as a solvent (dispersion medium) were loaded into a sand mill using glass beads each having a diameter of 1 mm and subjected to dispersion treatment for 3 hours to prepare an application liquid (dispersion liquid) for an electroconductive layer. The application liquid for an electroconductive layer was applied onto the support by immersion to obtain a coating film. The coating film thus obtained was subjected to drying and thermal polymerization at 150° C. for 30 minutes to form an electroconductive layer having a thickness of 16 μm.
The average particle diameter of the titanium oxide particles each covered with oxygen-deficient tin oxide in the application liquid for an electroconductive layer was measured by a centrifugal sedimentation method at a number of revolutions of 5,000 rpm using tetrahydrofuran as a dispersion medium with a particle size distribution analyzer (trade name: CAPA 700, manufactured by Horiba, Ltd.). As a result, the average particle diameter was 0.31 μm.
Next, 6.1 parts of an electron transport material (1-1)-1, 5.2 parts of an isocyanate compound (B1, protective group (H1)=5.1:2.2 (mass ratio)), 0.3 part of a resin (D1), and 0.05 part of dioctyltin laurate serving as a catalyst were dissolved in a mixed solvent of 100 parts of dimethylacetamide and 100 parts of methyl ethyl ketone to prepare an application liquid for an undercoat layer. The application liquid for an undercoat layer was applied onto the electroconductive layer by immersion to obtain a coating film. The coating film thus obtained was heated to be polymerized at 160° C. for 40 minutes, to thereby form an undercoat layer having a thickness (UC thickness) of 1.25 μm.
The content of the electron transport material with respect to the total mass of the composition containing the electron transport material, the cross-linking agent, and the resin was 52 mass %.
Next, a hydroxygallium phthalocyanine crystal (charge generating material) of a crystal form having peaks at Bragg angles)(2θ±0.2° in CuKα characteristic X-ray diffraction of 7.5°, 9.9°, 12.5°, 16.3°, 18.6°, 25.1°, and 28.3° was prepared. 10 Parts of the hydroxygallium phthalocyanine crystal, 5 parts of a polyvinyl butyral resin (trade name: S-LEC BX-1, manufactured by Sekisui Chemical Co., Ltd.), and 250 parts of cyclohexanone were loaded into a sand mill using glass beads each having a diameter of 1 mm, and the mixture was subjected to dispersion treatment for 1.5 hours. Next, 250 parts of ethyl acetate was added to the resultant to prepare an application liquid for a charge generating layer. The application liquid for a charge generating layer was applied onto the undercoat layer by immersion to obtain a coating film. The coating film thus obtained was dried at 100° C. for 10 minutes to form a charge generating layer having a thickness of 0.15 μm.
Next, 8 parts of a compound (hole transporting material) represented by the formula (12-1) and 10 parts of polyarylate having a structural unit represented by the formula (13-1) and a structural unit represented by the formula (13-2) in a ratio of 5/5 and having a weight-average molecular weight (Mw) of 100,000 were dissolved in a mixed solvent of 40 parts of dimethyoxymethane and 60 parts of chlorobenzene to prepare an application liquid for a hole transporting layer. The application liquid for a hole transporting layer was applied onto the charge generating layer by immersion to obtain a coating film. The coating film thus obtained was dried at 120° C. for 40 minutes to form a hole transporting layer having a thickness (CT thickness) of 7 μm.




Thus, an electrophotographic photosensitive member for evaluating a positive ghost and a fluctuation in potential was produced. Further, another electrophotographic photosensitive member was produced in the same manner as described above, and the above-mentioned laminated body was prepared therefrom and subjected to the measurement method of the present invention.
(Determination Test)
The electrophotographic photosensitive member was immersed in a mixed solvent of 40 parts of dimethoxymethane and 60 parts of chlorobenzene for 5 minutes to peel the hole transporting layer. Then, the resultant was dried at 100° C. for 10 minutes to obtain a laminated body. It was confirmed that the hole transporting layer did not exist on the surface by a FTIR-ATR method.
Next, the laminated body was left under an environment having a temperature of 25° C. and a humidity of 50% RH for 24 hours, and then |Vd2−Vd1| (expression (2)) and transit time τ (expression (3)) were calculated by the above-mentioned determination method as described above. The measurement results are shown in Table 18.
(Evaluation of Black Dot)
The above-mentioned electrophotographic photosensitive member was mounted onto a process cartridge of the above-mentioned laser beam printer, and the process cartridge was mounted onto a station for a cyan process cartridge. A solid white image was output. The determination was performed by visual inspection.
(Evaluation of Sensitivity and Dark Attenuation)
The sensitivity was evaluated based on a light portion potential at a time of irradiation with the same light. It can be evaluated that, when the light portion potential is low, the sensitivity is high, and when the light portion potential is high, the sensitivity is low. The dark attenuation was evaluated based on a dark portion potential at a time of the application of the same voltage. It was determined that, when the dark portion potential was low, the dark attenuation was large, and when the dark portion potential was high, the dark attenuation was small. The evaluation was made by mounting the electrophotographic photosensitive member onto a reconstructed machine of a laser beam printer (trade name: LaserJet P4510, manufactured by Hewlett-Packard Japan, Ltd.).
The reconstruction was performed so that an external power source was used for charging to set Vpp of AC to 1,800 V and a frequency to 870 Hz and set the application voltage of DC to −700 V, and the light amount of exposure light (image exposure light) became variable.
The potential of a surface of the electrophotographic photosensitive member was measured by removing a cartridge for development from the evaluation machine and inserting a potential measurement device therein. The potential measurement device has a configuration in which a potential measurement probe is arranged at a development position of the cartridge for development, and the position of the potential measurement probe with respect to the electrophotographic photosensitive member was set to the center in a drum axis direction.
First, a dark portion potential (Vd) was measured without irradiation with light. As a result, the dark potion potential (Vd) was −670 V. Then, the light E was set to 0.40 μJ/cm2, and a light portion potential (Vl) was measured. As a result, the light portion potential (Vl) was −180 V.
Examples 2 to 15
Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that the electron transport material (1-1)-1 of Example 1 was changed to an electron transport material shown in Table 18 and the electrophotographic photosensitive members were evaluated similarly. The results are shown in Table 18.
Examples 16 to 19
Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that the resin (D1) of Example 1 was changed to a resin shown in Table 18 and the electrophotographic photosensitive members were evaluated similarly. The results are shown in Table 18.
Example 20
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the undercoat layer was formed as follows and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 18.
5.2 Parts of an electron transport material (1-1)-10, 5.6 parts of the cross-linking agent (B1, protective group (H1)=5.1:2.2 (mass ratio)), 0.9 part of the resin (D1), and 0.05 part of dioctyltin laurate were dissolved in a mixed solvent of 100 parts of dimethylacetamide and 100 parts of methyl ethyl ketone to prepare an application liquid for an undercoat layer. The application liquid for an undercoat layer was applied onto the electroconductive layer by immersion to obtain a coating film. The coating film thus obtained was heated at 160° C. for 40 minutes to be polymerized, to thereby form an undercoat layer having a thickness of 1.25 μm.
The content of the electron transport material with respect to the total mass of the composition containing the electron transport material, the cross-linking agent, and the resin was 44 mass %.
Example 21
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the undercoat layer was formed as follows and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 18.
5.9 Parts of the electron transport material (1-1)-1, 5.4 parts of the isocyanate compound (B1, protective group (H1)=5.1:2.2 (mass ratio)), 0.5 part of the resin (D1), and 0.03 part of dioctyltin laurate were dissolved in a mixed solvent of 100 parts of dimethylacetamide and 100 parts of methyl ethyl ketone to prepare an application liquid for an undercoat layer. The application liquid for an undercoat layer was applied onto the electroconductive layer by immersion to obtain a coating film. The coating film thus obtained was heated at 160° C. for 40 minutes to be polymerized, to thereby form an undercoat layer having a thickness of 1.25 μm.
The content of the electron transport material with respect to the total mass of the composition containing the electron transport material, the cross-linking agent, and the resin was 50 mass %.
Example 22
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the undercoat layer was formed as follows and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 18.
6.7 Parts of the electron transport material (1-1)-1, 4.3 parts of the isocyanate compound (B1, protective group (H1)=5.1:2.2 (mass ratio)), 0.3 part of the resin (D1), and 0.03 part of dioctyltin laurate were dissolved in a mixed solvent of 100 parts of dimethylacetamide and 100 parts of methyl ethyl ketone to prepare an application liquid for an undercoat layer. The application liquid for an undercoat layer was applied onto the electroconductive layer by immersion to obtain a coating film. The coating film thus obtained was heated at 160° C. for 40 minutes to be polymerized, to thereby form an undercoat layer having a thickness of 1.25 μm.
The content of the electron transport material with respect to the total mass of the composition containing the electron transport material, the cross-linking agent, and the resin was 59 mass %.
Example 23
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the undercoat layer was formed as follows and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 18.
6.8 Parts of an electron transport material (1-1)-4, 1.4 parts of an amino compound (C1-3) as a cross-linking agent, 1.8 parts of the resin (D1), and 0.1 part of dodecylbenzenesulfonic acid serving as a catalyst were dissolved in a mixed solvent of 100 parts of dimethylacetamide and 100 parts of methyl ethyl ketone to prepare an application liquid for an undercoat layer. The application liquid for an undercoat layer was applied onto the electroconductive layer by immersion to obtain a coating film. The coating film thus obtained was heated at 160° C. for 40 minutes to be polymerized, to thereby form an undercoat layer having a thickness of 1.50 μm.
The content of the electron transport material with respect to the total mass of the composition containing the electron transport material, the cross-linking agent, and the resin was 68 mass %.
Examples 24 to 36
Electrophotographic photosensitive members were each produced in the same manner as in Example 23 except that the electron transport material (1-1)-4 of Example 23 was changed to an electron transport material shown in Table 18 and the electrophotographic photosensitive members were evaluated similarly. The results are shown in Table 18.
Examples 37 to 40
Electrophotographic photosensitive members were each produced in the same manner as in Example 23 except that the resin (D1) of Example 1 was changed to a resin shown in Table 18 and the electrophotographic photosensitive members were evaluated similarly. The results are shown in Table 18.
Example 41
An electrophotographic photosensitive member was produced in the same manner as in Example 23 except that the undercoat layer was formed as follows and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 18.
7.3 Parts of the electron transport material (1-1)-4, 1.3 parts of the amino compound (C1-3), 1.4 parts of the resin (D1), and 0.1 part of dodecylbenzenesulfonic acid serving as a catalyst were dissolved in a mixed solvent of 100 parts of dimethylacetamide and 100 parts of methyl ethyl ketone to prepare an application liquid for an undercoat layer. The application liquid for an undercoat layer was applied onto the electroconductive layer by immersion to obtain a coating film. The coating film thus obtained was heated at 160° C. for 40 minutes to be polymerized, to thereby form an undercoat layer having a thickness of 1.50 μm.
The content of the electron transport material with respect to the total mass of the composition containing the electron transport material, the cross-linking agent, and the resin was 73 mass %.
Example 42
An electrophotographic photosensitive member was produced in the same manner as in Example 23 except that the undercoat layer was formed as follows and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 18.
7.8 Parts of the electron transport material (1-1)-4, 1.2 parts of the amino compound (C1-3), 1.0 part of the resin (D1), and 0.1 part of dodecylbenzenesulfonic acid serving as a catalyst were dissolved in a mixed solvent of 100 parts of dimethylacetamide and 100 parts of methyl ethyl ketone to prepare an application liquid for an undercoat layer. The application liquid for an undercoat layer was applied onto the electroconductive layer by immersion to obtain a coating film. The coating film thus obtained was heated at 160° C. for 40 minutes to be polymerized, to thereby form an undercoat layer having a thickness of 1.50 μm.
The content of the electron transport material with respect to the total mass of the composition containing the electron transport material, the cross-linking agent, and the resin was 78 mass %.
Example 43
An electrophotographic photosensitive member was produced in the same manner as in Example 23 except that the undercoat layer was formed as follows and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 18.
8.3 Parts of the electron transport material (1-1)-4, 1.0 part of the amino compound (C1-3), 0.5 part of the resin (D1), and 0.1 part of dodecylbenzenesulfonic acid serving as a catalyst were dissolved in a mixed solvent of 100 parts of dimethylacetamide and 100 parts of methyl ethyl ketone to prepare an application liquid for an undercoat layer. The application liquid for an undercoat layer was applied onto the electroconductive layer by immersion to obtain a coating film. The coating film thus obtained was heated at 160° C. for 40 minutes to be polymerized, to thereby form an undercoat layer having a thickness of 1.50 μm.
The content of the electron transport material with respect to the total mass of the composition containing the electron transport material, the cross-linking agent, and the resin was 85 mass %.
Example 44
An electrophotographic photosensitive member was produced in the same manner as in Example 23 except that the undercoat layer was formed as follows and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 18.
8.8 Parts of the electron transport material (1-1)-4, 1.0 part of the amino compound (C1-3), 0.2 part of the resin (D1), and 0.1 part of dodecylbenzenesulfonic acid serving as a catalyst were dissolved in a mixed solvent of 100 parts of dimethylacetamide and 100 parts of methyl ethyl ketone to prepare an application liquid for an undercoat layer. The application liquid for an undercoat layer was applied onto the electroconductive layer by immersion to obtain a coating film. The coating film thus obtained was heated at 160° C. for 40 minutes to be polymerized, to thereby form an undercoat layer having a thickness of 1.50 μm.
The content of the electron transport material with respect to the total mass of the composition containing the electron transport material, the cross-linking agent, and the resin was 88 mass %.
Examples 45 to 49
Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that the cross-linking agent (B1, protective group (H1)) of Example 1 was changed to a cross-linking agent shown in Table 18 and the electrophotographic photosensitive members were evaluated similarly. The results are shown in Table 18.
Examples 50 to 54
Electrophotographic photosensitive members were each produced in the same manner as in Example 23 except that the cross-linking agent (C1-3) of Example 23 was changed to a cross-linking agent shown in Table 18 and the electrophotographic photosensitive members were evaluated similarly. The results are shown in Table 18.
Examples 55 to 59
Electrophotographic photosensitive members were each produced in the same manner as in Example 23 except that the thickness of the undercoat layer of Example 23 was changed from 1.50 μm to 0.63 μm (Example 55), 0.77 μm (Example 56), 2.00 μm (Example 57), 3.00 μm (Example 58), and 3.50 μm (Example 59) and the electrophotographic photosensitive members were evaluated similarly. The results are shown in Table 18.
Example 60
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the charge generating layer was formed as follows and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 18.
An oxytitanium phthalocyanine crystal having peaks at Bragg angles)(2θ±0.2° in CuKα X-ray diffraction of 9.0°, 14.2°, 23.9°, and 27.1° was prepared. 10 Parts of the oxytitanium phthalocyanine crystal and polyvinyl butyral (trade name: S-LEC BX-1, manufactured by Sekisui Chemical Co., Ltd.) were dissolved in a mixed solvent of cyclohexanone and water (97:3) to prepare 166 parts of a 5 mass % solution. The solution and 150 parts of the mixed solvent of cyclohexanone and water (97:3) were each dispersed in a sand mill device for 4 hours through use of 400 parts of glass beads each having a diameter of 1 mmφ. Then, 210 parts of the mixed solvent of cyclohexanone and water (97:3) and 260 parts of cyclohexanone were added to the resultant to prepare an application liquid for a charge generating layer. The application liquid for a charge generating layer was applied onto the undercoat layer by immersion to obtain a coating film. The coating film thus obtained was dried at 80° C. for 10 minutes to form a charge generating layer having a thickness of 0.20 μm.
Example 61
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the charge generating layer was formed as follows and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 18.
20 Parts of a bisazo pigment represented by the formula (14) and 10 parts of a polyvinyl butyral resin (trade name: S-LEC BX-1, manufactured by Sekisui Chemical Co., Ltd.) were mixed and dispersed together with 150 parts of tetrahydrofuran to prepare an application liquid for a charge generating layer. The application liquid for a charge generating layer was applied onto the undercoat layer by a dip coating method, and the resultant was dried by heating at 110° C. for 30 minutes to form a charge generating layer having a thickness of 0.30 μm.




Example 62
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the compound (hole transporting material) represented by the formula (12-1) of Example 1 was changed to a benzidine compound (hole transporting material) represented by the formula (12-2) and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 18.




Example 63
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the compound (hole transporting material) represented by the formula (12-1) of Example 1 was changed to a styryl compound (hole transporting material) represented by the formula (12-3) and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 18.























TABLE 18







Electron
Cross-

Ratio of electron
UC
CT








transport
linking

transport
thickness
thickness
Expression
Expression


Black



material
agent
Resin
material
(μm)
(μm)
(2)
(3)
Vd (−V)
Vl (−V)
dot



























Example 1
(1-1)-1
B1:H1
D1
52%
1.25
7
0.6
5.8
670
180
Absent


Example 2
(1-1)-2
↑
↑
↑
↑
↑
0.6
3.5
674
160
↑


Example 3
(1-1)-3
↑
↑
↑
↑
↑
0.4
8.0
672
182
↑


Example 4
(1-2)-4
↑
↑
↑
↑
↑
0.7
3.1
675
161
↑


Example 5
(1-2)-5
↑
↑
↑
↑
↑
0.4
2.8
676
169
↑


Example 6
(1-3)-1
↑
↑
↑
↑
↑
0.6
3.7
671
164
↑


Example 7
(1-3)-3
↑
↑
↑
↑
↑
0.3
9.0
670
173
↑


Example 8
(1-4)-1
↑
↑
↑
↑
↑
0.7
2.0
674
168
↑


Example 9
(1-4)-5
↑
↑
↑
↑
↑
0.9
1.0
678
173
↑


Example 10
(1-5)-3
↑
↑
↑
↑
↑
0.3
4.9
674
172
↑


Example 11
(1-5)-4
↑
↑
↑
↑
↑
0.7
9.0
671
180
↑


Example 12
(1-6)-2
↑
↑
↑
↑
↑
1.2
8.0
677
178
↑


Example 13
(1-7)-3
↑
↑
↑
↑
↑
0.8
8.3
677
172
↑


Example 14
(1-8)-4
↑
↑
↑
↑
↑
0.7
2.5
676
169
↑


Example 15
(1-9)-1
↑
↑
↑
↑
↑
1.3
5.5
673
165
↑


Example 16
(1-1)-1
↑
D3
↑
↑
↑
0.6
1.5
676
177
↑


Example 17
↑
↑
D5
↑
↑
↑
0.9
8.5
671
178
↑


Example 18
↑
↑
D19
↑
↑
↑
0.8
5.5
671
176
↑


Example 19
↑
↑
D20
↑
↑
↑
0.5
4.0
675
163
↑


Example 20
(1-1)-10
↑
D1
44%
↑
↑
0.3
9.5
685
195
↑


Example 21
(1-1)-1
↑
↑
50%
↑
↑
0.6
6.8
674
185
↑


Example 22
↑
↑
↑
59%
↑
↑
0.6
3.8
673
173
↑


Example 23
(1-1)-4
C1-3
↑
68%
1.50
↑
0.8
1.2
679
160
↑


Example 24
(1-1)-9
↑
↑
↑
↑
↑
0.7
0.7
677
163
↑


Example 25
(1-2)-1
↑
↑
↑
↑
↑
0.5
0.9
674
167
↑


Example 26
(1-2)-3
↑
↑
↑
↑
↑
1.0
1.2
678
166
↑


Example 27
(1-3)-4
↑
↑
↑
↑
↑
0.9
3.6
674
162
↑


Example 28
(1-3)-5
↑
↑
↑
↑
↑
0.7
2.0
675
161
↑


Example 29
(1-4)-2
↑
↑
↑
↑
↑
0.6
3.0
676
174
↑


Example 30
(1-4)-3
↑
↑
↑
↑
↑
0.8
2.5
670
172
↑


Example 31
(1-5)-1
↑
↑
↑
↑
↑
1.1
4.2
672
176
↑


Example 32
(1-5)-5
↑
↑
↑
↑
↑
0.6
4.5
678
168
↑


Example 33
(1-6)-1
↑
↑
↑
↑
↑
0.7
3.5
671
168
↑


Example 34
(1-7)-2
↑
↑
↑
↑
↑
0.8
2.1
675
176
↑


Example 35
(1-8)-3
↑
↑
↑
↑
↑
0.4
5.8
676
161
↑


Example 36
(1-9)-5
↑
↑
↑
↑
↑
0.9
1.6
677
171
↑


Example 37
(1-1)-4
↑
D2
↑
↑
↑
0.5
3.2
672
165
↑


Example 38
↑
↑
D4
↑
↑
↑
0.7
1.4
674
168
↑


Example 39
↑
↑
D6
↑
↑
↑
0.8
4.6
679
166
↑


Example 40
↑
↑
D23
↑
↑
↑
0.6
7.0
677
166
↑


Example 41
↑
↑
D1
73%
↑
↑
0.8
0.7
676
155
↑


Example 42
↑
↑
↑
78%
↑
↑
0.9
0.5
673
151
↑


Example 43
↑
↑
↑
85%
↑
↑
1.1
1.0
678
163
↑


Example 44
↑
↑
↑
88%
↑
↑
1.5
10.0
650
185
↑


Example 45
(1-1)-1
B1:H2
↑
52%
1.25
↑
0.9
5.0
674
177
↑


Example 46
↑
B1:H3
↑
↑
↑
↑
0.9
6.0
672
161
↑


Example 47
↑
B4:H1
↑
↑
↑
↑
1.5
2.0
673
175
↑


Example 48
↑
B7:H1
↑
↑
↑
↑
1.1
6.0
678
173
↑


Example 49
↑
B12:H1
↑
↑
↑
↑
1.3
3.0
679
167
↑


Example 50
(1-1)-4
C1-1
↑
68%
1.50
↑
1.3
1.0
672
174
↑


Example 51
↑
C1-7
↑
↑
↑
↑
1.0
2.0
674
170
↑


Example 52
↑
C1-9
↑
↑
↑
↑
1.3
7.0
676
174
↑


Example 53
↑
C2-1
↑
↑
↑
↑
1.5
6.0
676
175
↑


Example 54
↑
C3-3
↑
↑
↑
↑
1.0
9.0
674
176
↑


Example 55
↑
C1-3
↑
↑
0.63
↑
1.9
0.6
640
189
↑


Example 56
↑
↑
↑
↑
0.77
↑
1.2
0.7
672
169
↑


Example 57
↑
↑
↑
↑
2.00
↑
1.0
1.5
676
161
↑


Example 58
↑
↑
↑
↑
3.00
↑
0.3
3.4
671
179
↑


Example 59
↑
↑
↑
↑
3.50
↑
0.2
6.5
680
205
↑


Example 60
(1-1)-1
B1:H1
D1
52%
1.25
7
0.7
3.3
670
180
↑


Example 61
↑
↑
↑
↑
↑
↑
0.5
3.4
675
175
↑


Example 62
↑
↑
↑
↑
↑
↑
0.6
3.4
675
173
↑


Example 63
↑
↑
↑
↑
↑
↑
0.6
3.4
675
173
↑









Comparative Example 1
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the electron transport material (1-1)-1 of Example 1 was changed to an electron transport material represented by the formula (15) and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 19.




Comparative Example 2
An electrophotographic photosensitive member was produced in the same manner as in Comparative Example 1 except that the thickness of the undercoat layer of Comparative Example 1 was changed from 1.25 μm to 0.58 μm and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 19.
Comparative Example 3
An electrophotographic photosensitive member was produced in the same manner as in Comparative Example 1 except that the undercoat layer was formed as follows and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 19.
4.0 Parts of the electron transport material represented by the formula (15), 7.3 parts of the isocyanate compound (B1, protective group (H1)=5.1:2.2 (mass ratio)), 0.9 part of the resin (D1), and 0.05 part of dioctyltin laurate were dissolved in a mixed solvent of 100 parts of dimethylacetamide and 100 parts of methyl ethyl ketone to prepare an application liquid for an undercoat layer. The application liquid for an undercoat layer was applied onto the electroconductive layer by immersion to obtain a coating film. The coating film thus obtained was heated at 160° C. for 40 minutes to be polymerized, to thereby form an undercoat layer having a thickness of 0.58 μm.
The content of the electron transport material with respect to the total mass of the composition containing the electron transport material, the cross-linking agent, and the resin was 33 mass %.
Comparative Example 4
An electrophotographic photosensitive member was produced in the same manner as in Comparative Example 1 except that the undercoat layer was formed as follows and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 19.
3.6 Parts of an electron transport material (1-6)-3, 7.5 parts of the isocyanate compound (B1, protective group (H1)=5.1:2.2 (mass ratio)), 1.1 parts of the resin (D1), and 0.05 part of dioctyltin laurate were dissolved in a mixed solvent of 100 parts of dimethylacetamide and 100 parts of methyl ethyl ketone to prepare an application liquid for an undercoat layer. The application liquid for an undercoat layer was applied onto the electroconductive layer by immersion to obtain a coating film. The coating film thus obtained was heated at 160° C. for 40 minutes to be polymerized, to thereby form an undercoat layer having a thickness of 0.58 μm.
The content of the electron transport material with respect to the total mass of the composition containing the electron transport material, the cross-linking agent, and the resin was 30 mass %.
Comparative Example 5
An electrophotographic photosensitive member was produced in the same manner as in Comparative Example 1 except that the undercoat layer was formed as follows and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 19.
9.0 parts of the electron transport material (1-6)-3, 0.7 part of the isocyanate compound (B1, protective group (H1)=5.1:2.2 (mass ratio)), 0.3 part of the resin (D1), and 0.05 part of dioctyltin laurate were dissolved in a mixed solvent of 100 parts of dimethylacetamide and 100 parts of methyl ethyl ketone to prepare an application liquid for an undercoat layer. The application liquid for an undercoat layer was applied onto the electroconductive layer by immersion to obtain a coating film. The coating film thus obtained was heated at 160° C. for 40 minutes to be polymerized, to thereby form an undercoat layer having a thickness of 1.25 μm.
The content of the electron transport material with respect to the total mass of the composition containing the electron transport material, the cross-linking agent, and the resin was 90 mass %.
Comparative Example 6
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the undercoat layer was formed as follows and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 19.
10.0 Parts of the electron transport material (1-1)-3 and 12.0 parts of a polycarbonate resin serving as a binder resin (Iupilon 2400, manufactured by Mitsubishi Gas Chemical Company Inc.) were dissolved in 80 parts of tetrahydrofuran (THF) to prepare an application liquid for an undercoat layer. The application liquid for an undercoat layer was applied onto the electroconductive layer by immersion to obtain a coating film. The coating film thus obtained was heated at 160° C. for 40 minutes to be polymerized, to thereby form an undercoat layer having a thickness of 1.25 μm.
The content of the electron transport material with respect to the total mass of the composition containing the electron transport material, the cross-linking agent, and the resin was 45 mass %.
Comparative Example 7
An electrophotographic photosensitive member was produced in the same manner as in Example 9 except that the resin (D1) of Example 9 was not added to the undercoat layer and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 19.



















TABLE 19










Ratio of










Electron
Cross-

electron
UC
CT



transport
linking

transport
thickness
thickness
Expression
Expression


Black



material
agent
Resin
material
(μm)
(μm)
(2)
(3)
Vd (−V)
Vl (−V)
dot



























Comparative
Formula (15)
B1:H1
D1
52%
1.25
7
1.8
16
670
280
Absent


Example 1


Comparative
↑
↑
↑
↑
0.58
7
5.2
55
650
245
Absent


Example 2


Comparative
↑
↑
↑
33%
0.58
7
0.1
210 
680
480
Absent


Example 3


Comparative
(1-6)-3
↑
↑
30%
0.58
7
0.1
80
685
380
Absent


Example 4


Comparative
↑
↑
↑
90%
1.25
7
Unmeasurable
Unmeasurable
640
228
Occurred


Example 5


Comparative
(1-1)-3
Absent
Polycar-
45%
1.25
7
Unmeasurable
Unmeasurable
630
255
Occurred


Example 6


bonate


Comparative
(1-4)-5
B1:H1
Absent
54%
1.25
7
2.8
20
660
230
Occurred


Example 7









Example 64
An electrophotographic photosensitive member was produced in the same manner as in Example 23 except that the thickness of the undercoat layer of Example 23 was changed from 1.50 μm to 2.50 μm and the thickness of the hole transporting layer was changed from 7 μm to 3 μm.
The sensitivity of the electrophotographic photosensitive member was evaluated in the same manner as in Example 23 except that the light E was changed from 0.40 μJ/cm2 to 0.62 μJ/cm2 to measure the light portion potential (Vl). The results are shown in Table 20.
Comparative Example 8
An electrophotographic photosensitive member was produced in the same manner as in Example 64 except that the electron transport material of Example 64 was changed to the electron transport material represented by the formula (15) used in Comparative Example 1 and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 20.
Example 65
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the thickness of the hole transporting layer of Example 1 was changed from 7 μm to 5 μm.
The sensitivity of the electrophotographic photosensitive member was evaluated in the same manner as in Example 1 except that the light E was changed from 0.40 μJ/cm2 to 0.50 μJ/cm2 to measure the light portion potential (Vl) in order to be matched with the Vl potential of Example 1. The results are shown in Table 20.
Comparative Example 9
An electrophotographic photosensitive member was produced in the same manner as in Example 65 except that the electron transport material of Example 65 was changed to the electron transport material represented by the formula (15) used in Comparative Example 1 and the electrophotographic photosensitive member was evaluated similarly. The results are shown in Table 20.
Example 66
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the thickness of the hole transporting layer of Example 1 was changed from 7 μm to 10 μm.
The sensitivity of the electrophotographic photosensitive member was evaluated in the same manner as in Example 1 except that the light E was changed from 0.40 μJ/cm2 to 0.34 μJ/cm2 to measure the light portion potential (Vl) in order to be matched with the Vl potential of Example 1. The results are shown in Table 20.
Example 67
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the thickness of the hole transporting layer of Example 1 was changed from 7 μm to 15 μm.
The sensitivity of the electrophotographic photosensitive member was evaluated in the same manner as in Example 1 except that the light E was changed from 0.40 μJ/cm2 to 0.20 μJ/cm2 to measure the light portion potential (Vl) in order to be matched with the Vl potential of Example 23. The results are shown in Table 20.



















TABLE 20










Ratio of










Electron
Cross-

electron
UC
CT



transport
linking

transport
thickness
thickness
Expression
Expression


Black



material
agent
Resin
material
(μm)
(μm)
(2)
(3)
Vd (−V)
Vl (−V)
dot



























Example 64
(1-1)-4
C1-3
D1
68%
2.50
3
0.4
2.5
675
180
Absent


Comparative
Formula
↑
↑
↑
2.50
3
1.5
25
665
360
↑


Example 8
(15)


Example 65
(1-1)-1
B1:H1
D1
52%
1.25
5
0.6
5.8
670
180
↑


Comparative
Formula
↑
↑
↑
1.25
5
1.8
16
670
300
↑


Example 9
(15)


Example 66
(1-1)-1
↑
↑
↑
1.25
10
0.6
5.8
673
180
↑


Example 67
(1-1)-1
↑
↑
↑
1.25
15
0.6
5.8
677
180
↑









Examples 68 and 69
Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that the electron transport material (1-1)-1 of Example 1 was changed to an electron transport material shown in Table 21 and the electrophotographic photosensitive members were evaluated similarly. The results are shown in Table 21.
Examples 70 and 71
Electrophotographic photosensitive members were each produced in the same manner as in Example 23 except that the electron transport material (1-1)-4 of Example 23 was changed to an electron transport material shown in Table 21 and the electrophotographic photosensitive members were evaluated similarly. The results are shown in Table 21.



















TABLE 21










Ratio of










Electron
Cross-

electron
UC
CT



transport
linking

transport
thickness
thickness
Expression
Expression


Black



material
agent
Resin
material
(μm)
(μm)
(2)
(3)
Vd (−V)
Vl (−V)
dot



























Example 68
(1-10)-2
B1:H1
D1
52%
 1.25
7
0.8
8.0
678
178
Absent


Example 69
(1-1)-11
B1:H1
↑
52%
↑
↑
0.9
9.5
670
182
↑


Example 70
(1-10)-3
C1-3
↑
68%
1.5
↑
0.7
7.3
675
170
↑


Example 71
(1-1)-12
C1-3
↑
68%
↑
↑
1.0
2.5
673
161
↑









As described above, it is understood from the results of Examples 1 to 71 and Comparative Examples 1 to 9 that, when the electrophotographic photosensitive member including the undercoat layer of the present invention was used, the occurrence of a black dot was suppressed and the sensitivity increased even when the hole transporting layer was thinned.
Example 72
An aluminum cylinder having a length of 260.5 mm and a diameter of 30 mm (JIS-A3003, aluminum alloy) was used as a support (conductive support).
Then, 50 parts of titanium oxide particles (powder resistivity: 120 Ω·cm, coverage ratio of tin oxide: 40%) each covered with oxygen-deficient tin oxide, 40 parts of a phenol resin (Plyophen J-325, manufactured by DIC Corporation, resin solid content: 60%), and 55 parts of methoxypropanol were loaded into a sand mill using glass beads each having a diameter of 1 mm and subjected to dispersion treatment for 3 hours to prepare an application liquid for an electroconductive layer.
The average particle diameter of the titanium oxide particles each covered with oxygen-deficient tin oxide in the application liquid for an electroconductive layer was measured by a centrifugal sedimentation method at a number of revolutions of 5,000 rpm using tetrahydrofuran as a dispersion medium with a particle size distribution analyzer (trade name: CAPA 700, manufactured by Horiba, Ltd.). As a result, the average particle diameter was 0.30 μm.
The application liquid for an electroconductive layer was applied onto the support by immersion to form a coating film. The coating film thus obtained was dried and thermally cured at 160° C. for 30 minutes to form an electroconductive layer having a thickness of 18 μm.
Next, 4 parts of Exemplified Compound (E101) serving as the compound represented by the formula (11), 1.5 parts of a polyvinyl butyral resin (BX-1, manufactured by Sekisui Chemical Co., Ltd.), and 0.0005 part of dioctyltin laurate serving as a catalyst were dissolved in a mixed solvent of 100 parts of dimethylacetamide and 100 parts of tetrahydrofuran. To this solution, a blocked isocyanate resin (BL3175, manufactured by Sumika Bayer Urethane Co., Ltd.) corresponding to 8 parts of a solid content was added to prepare an application liquid for an undercoat layer.
The application liquid for an undercoat layer was applied onto the electroconductive layer by immersion to obtain a coating film. The coating film thus obtained was heated at 160° C. for 40 minutes to be cured, to thereby form an undercoat layer having a thickness of 2.0 μm.
Next, a hydroxygallium phthalocyanine crystal (charge generating material) of a crystal form having peaks at Bragg angles)(2θ±0.2° in CuKα characteristic X-ray diffraction of 7.5°, 9.9°, 12.5°, 16.3°, 18.6°, 25.1°, and 28.3° was prepared. 10 Parts of the hydroxygallium phthalocyanine crystal, 5 parts of a polyvinyl butyral resin (trade name: S-LEC BX-1, manufactured by Sekisui Chemical Co., Ltd.), and 250 parts of cyclohexanone were loaded into a sand mill using glass beads each having a diameter of 1 mm, and the mixture was subjected to dispersion treatment for 2 hours. Next, 250 parts of ethyl acetate was added to the resultant to prepare an application liquid for a charge generating layer.
The application liquid for a charge generating layer was applied onto the undercoat layer by immersion to form a coating film, and the resultant coating film was dried at 95° C. for 10 minutes to form a charge generating layer having a thickness of 0.15 μm.
Next, 8 parts of a compound (hole transporting material) represented by the following formula (12-1) and parts of polyarylate having a structural unit represented by the following formula (16) and having a weight-average molecular weight (Mw) of 100,000 were dissolved in a mixed solvent of 40 parts of dimethoxymethane and 60 parts of chlorobenzene to prepare an application liquid for a hole transporting layer.
The application liquid for a hole transporting layer was applied onto the charge generating layer by immersion to form a coating film, and the resultant coating film was dried at 120° C. for 40 minutes to form a hole transporting layer having a thickness of 15 μm.




Thus, an electrophotographic photosensitive member including, on the support, the electroconductive layer, the undercoat layer, the charge generating layer, and the hole transporting layer was produced.
The electrophotographic photosensitive member thus produced was mounted onto a reconstructed machine (primary charging: roller contact DC charging, process speed: 120 mm/sec, laser exposure) of a laser beam printer (trade name: LBP-2510, manufactured by Canon Inc.) under an environment having a temperature of 23° C. and a humidity of 50% RH. Then, the initial potential of a surface and the potential of a surface after output of 15,000 sheets of images, and the output images were evaluated. Details about the foregoing are as described below.
(Measurement of Potential of Surface)
The process cartridge for a cyan color of the laser beam printer was reconstructed and a potential probe (model 6000B-8: manufactured by TREK JAPAN) was mounted at a development position. Then, a potential at the central portion of the electrophotographic photosensitive member was measured with a surface potentiometer (model 344: manufactured by TREK JAPAN). During the measurement of the potential of a surface of the photosensitive drum, the light amount of image exposure was set so that an initial dark portion potential (Vd) became −600 V and an initial light portion potential (Vl) became −150 V.
Subsequently, the electrophotographic photosensitive member produced in each of Examples was mounted onto the process cartridge for a cyan color of the laser beam printer, and the process cartridge was mounted onto a cyan process cartridge station, followed by the output of an image. First, one solid white image, five images for ghost evaluation, one solid black image, and five images for ghost evaluation were continuously output in the stated order.
Each image for ghost evaluation is obtained by: outputting a quadrangular solid image (22) in a white image (21) at the leading end of an image as illustrated in FIG. 9; and then producing a “halftone image of a one-dot knight-jump pattern” illustrated in FIG. 10. It should be noted that a ghost portion (23) in FIG. 9 is a portion where a ghost (24) resulting from the solid image (22) may appear.
Evaluation for a positive ghost was performed by measuring a difference between the image density of the halftone image of a one-dot knight-jump pattern and the image density of the ghost portion. The density difference was measured at ten sites in one image for ghost evaluation with a spectral densitometer (trade name: X-Rite 504/508, manufactured by X-Rite). The operation was performed for all of the ten images for ghost evaluation, and the average of a total of 100 measured values was calculated. The result is shown in Table 22. As the density difference (Macbeth density difference) enlarges, the positive ghost occurs more strongly. The fact that the density difference (Macbeth density difference) reduces means that the positive ghost is suppressed.
Example 73
An electrophotographic photosensitive member was produced in the same manner as in Example 72 except that 2 parts of Exemplified Compound (E101) and 2 parts of Exemplified Compound (E106) were used as the compound represented by the formula (11) and the electrophotographic photosensitive member was evaluated for a ghost similarly. The results are shown in Table 22.
Examples 74 to 121
Electrophotographic photosensitive members were each produced in the same manner as in Example 72 except that the kinds and the numbers of parts by mass of the compound represented by the formula (11), the cross-linking agent, and the resin were changed as shown in Table 22 and the electrophotographic photosensitive members were evaluated for a ghost similarly. The results are shown in Table 22.
Examples 122 to 125
Application liquids for an undercoat layer were each prepared in the same manner as in Example 72 except that: the compound represented by the formula (11) was changed as shown in Table 22; an acrylic cross-linking agent (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) represented by the formula (17) were used in place of the isocyanate compound without using a resin; and azoisobutyronitrile (AIBN) was used in place of dioctyltin laurate serving as a catalyst. Then, electrophotographic photosensitive members were produced in the same manner as in Example 72 except that coating films of the application liquids for an undercoat layer were formed, and the coating films were heated under a nitrogen stream, and the electrophotographic photosensitive members were evaluated for a ghost similarly. The results are shown in Table 22.




Example 126
An electrophotographic photosensitive member was produced in the same manner as in Example 72 except that the compound represented by the formula (12-1) was changed to a compound represented by the formula (12-4) and the electrophotographic photosensitive member was evaluated for a ghost similarly. The results are shown in Table 22.




Example 127
An electrophotographic photosensitive member was produced in the same manner as in Example 72 except that the amine compound represented by the formula (12-1) was changed to a compound represented by the formula (12-2) and the electrophotographic photosensitive member was evaluated for a ghost similarly. The results are shown in Table 22.




Example 128
An electrophotographic photosensitive member was produced in the same manner as in Example 72 except that a support was obtained by subjecting an aluminum cylinder to liquid honing treatment under the following conditions without forming the electroconductive layer. The results are shown in Table 22.
<Liquid Honing Conditions>
Abrasive grains=zirconia beads each having a particle diameter of from 70 μm to 125 μm (trade name: Zirblast B120, manufactured by Materials Science, Inc.)
Suspending medium=water
Abrasive/suspending medium=1/9 (volume ratio)
The surface roughness of the cylinder after the honing was measured through use of a surface roughness measuring instrument (Surfcorder SE3500, manufactured by Kosaka Laboratory Ltd.) according to JIS B 0601 (1994). As a result, the maximum height (RmaxD) was 2.09 μm, the ten-point average roughness (Rz) was 1.48 μm, and the arithmetic average roughness (Ra) was 0.21 μm.
Examples 129 to 134
Electrophotographic photosensitive members were each produced in the same manner as in Example 72, 76, 78, 87, 90, or 95 except that the thickness of the hole transporting layer of Example 72, 76, 78, 87, 90, or 95 was changed from 15 μm to 20 μm and the electrophotographic photosensitive members were evaluated for a ghost similarly. The results are shown in Table 22.
Comparative Example 11
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the application liquid for an undercoat layer described below was used and the electrophotographic photosensitive member was evaluated for a ghost similarly. An application liquid for an undercoat layer was prepared through use of 4 parts by mass of the following compound (18) disclosed in Japanese Patent Application Laid-Open No. 2010-145506, 4.8 parts by mass of a polycarbonate Z-type resin (Iupilon 2400, Z-type polycarbonate, manufactured by Mitsubishi Gas Chemical Company Inc.), 100 parts by mass of dimethylacetamide, and 100 parts by mass of tetrahydrofuran. The results are shown in Table 22.




Comparative Example 12
An electrophotographic photosensitive member was produced in the same manner as in Example 72 except that the compound (18) described in Comparative Example 11 was used in place of the compound represented by the formula (11) and the electrophotographic photosensitive member was evaluated for a ghost similarly. The results are shown in Table 22.
Comparative Example 13
An electrophotographic photosensitive member was produced in the same manner as in Example 72 except that the following application liquid for an undercoat layer was used and the electrophotographic photosensitive member was evaluated for a ghost similarly. The results are shown in Table 22.
10 Parts of a compound represented by the formula (19) and 5 parts of a phenol resin (PL-4804, manufactured by Gun Ei Chemical Industry Co., Ltd.) were dissolved in a mixed solvent of 200 parts of dimethylformamide and 150 parts of benzyl alcohol to prepare an application liquid for an undercoat layer.




Comparative Example 14
A photosensitive member was produced in the same manner as in Example 122 except that a compound (20) disclosed in Japanese Patent Application Laid-Open No. 2003-330209 was used in place of the compound represented by the formula (11) and the photosensitive member was evaluated for a ghost similarly. The results are shown in Table 22.




















TABLE 22










Number of

Parts by

Parts by






Parts
polymerizable

mass

mass
Macbeth
Macbeth


Example
Compound
by
functional groups

(solid

(solid
density
density

















No
No
mass
R7, R8
Y
Cross-linking agent
content)
Resin
content)
(initial)
(difference)




















72
E101
4
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.020
0.004


73
E101/E106
2/2
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.023
0.005


74
E106
4
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.024
0.006


75
E108
4
0
2
Cross-linking agent 1
10
Resin 2
1.5
0.022
0.004


76
E109
4
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.025
0.003


77
E111
4
0
2
Cross-linking agent 2
6
Resin 2
1.5
0.026
0.006


78
E117
4
0
2
Cross-linking agent 1
8
Resin 3
1.5
0.027
0.008


79
E127
4
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.027
0.009


80
E134
4
0
2
Cross-linking agent 1
10
Resin 1
1.5
0.028
0.009


81
E139
4
0
2
Cross-linking agent 2
6
Resin 1
1.5
0.032
0.011


82
E144
4
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.028
0.009


83
E145
4
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.030
0.011


84
E146
4
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.031
0.011


85
E147
4
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.021
0.007


86
E201
4
2
2
Cross-linking agent 1
16
Resin 1
1.5
0.034
0.012


87
E206
4
2
2
Cross-linking agent 2
12
Resin 1
1.5
0.038
0.016


88
E211
4
4
2
Cross-linking agent 1
30
Resin 1
1.5
0.039
0.016


89
E301
4
2
1
Cross-linking agent 1
12
Resin 1
1.5
0.040
0.017


90
E307
4
2
1
Cross-linking agent 2
18
Resin 1
1.5
0.044
0.018


91
E312
4
2
1
Cross-linking agent 2
9
Resin 1
1.5
0.048
0.023


92
E313
4
2
1
Cross-linking agent 1
15
Resin 1
1.5
0.046
0.022


93
E402
4
0
1
Cross-linking agent 1
4
Resin 1
1.5
0.049
0.024


94
E403
4
0
1
Cross-linking agent 1
6
Resin 2
1.5
0.052
0.026


95
E409
4
0
1
Cross-linking agent 1
4
Resin 1
1.5
0.049
0.024


96
E104
4
0
2
Cross-linking agent 3
8
Resin 1
1.5
0.023
0.005


97
E105
4
0
2
Cross-linking agent 3
8
Resin 3
1.5
0.021
0.003


98
E110
4
0
2
Cross-linking agent 3
10
Resin 1
1.5
0.026
0.007


99
E113
4
0
2
Cross-linking agent 4
6
Resin 3
1.5
0.025
0.007


100
E131
4
0
2
Cross-linking agent 3
8
Resin 1
1.5
0.032
0.011


101
E135
4
0
2
Cross-linking agent 3
8
Resin 2
1.5
0.030
0.009


102
E203
4
2
2
Cross-linking agent 3
16
Resin 1
1.5
0.036
0.013


103
E212
4
2
2
Cross-linking agent 3
20
Resin 1
1.5
0.035
0.016


104
E305
4
4
1
Cross-linking agent 3
25
Resin 1
1.5
0.041
0.018


105
E308
4
2
1
Cross-linking agent 3
12
Resin 1
1.5
0.045
0.019


106
E311
4
2
1
Cross-linking agent 3
9
Resin 1
1.5
0.047
0.020


107
E314
4
2
1
Cross-linking agent 3
12
Resin 1
1.5
0.046
0.020


108
E320
4
2
1
Cross-linking agent 3
15
Resin 1
1.5
0.048
0.021


109
E401
4
0
1
Cross-linking agent 3
4
Resin 1
1.5
0.049
0.026


110
E404
4
0
1
Cross-linking agent 3
4
Resin 3
1.5
0.050
0.025


111
E405
4
0
1
Cross-linking agent 3
4
Resin 1
1.5
0.051
0.025


112
E407
4
0
1
Cross-linking agent 3
6
Resin 1
1.5
0.050
0.024


113
E412
4
0
1
Cross-linking agent 3
4
Resin 2
1.5
0.052
0.026


114
E415
4
0
1
Cross-linking agent 3
4
Resin 1
1.5
0.052
0.026


115
E417
4
0
1
Cross-linking agent 3
2
Resin 1
1.5
0.052
0.025


116
E420
4
0
1
Cross-linking agent 3
4
Resin 1
1.5
0.051
0.024


117
E102
4
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.023
0.005


118
E315
4
2
1
Cross-linking agent 3
12
Resin 1
1.5
0.042
0.018


119
E103
4
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.028
0.010


120
E316
4
2
1
Cross-linking agent 3
12
Resin 1
1.5
0.046
0.022


121
E317
4
2
1
Cross-linking agent 1
12
Resin 1
1.5
0.048
0.020


122
E114
4
0
2
Cross-linking agent 5
2
—
—
0.022
0.011


123
E115
4
0
2
Cross-linking agent 5
3
—
—
0.029
0.006


124
E116
4
0
2
Cross-linking agent 5
3
—
—
0.028
0.005


125
E136
4
0
2
Cross-linking agent 5
2
—
—
0.025
0.003


126
E101
4
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.022
0.006


127
E101
4
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.026
0.003


128
E101
4
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.022
0.005


129
E101
4
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.021
0.005


130
E109
4
0
2
Cross-linking agent 1
8
Resin 1
1.5
0.025
0.005


131
E117
4
0
2
Cross-linking agent 1
8
Resin 3
1.5
0.027
0.010


132
E206
4
2
2
Cross-linking agent 2
12
Resin 1
1.5
0.04
0.017


133
E307
4
2
1
Cross-linking agent 2
18
Resin 1
1.5
0.044
0.022


134
E409
4
0
1
Cross-linking agent 1
4
Resin 1
1.5
0.051
0.025


Comparative
Compound
4
—
—
—
—
Z400
4.8
0.140
0.121


Example 11
(18)


Comparative
Compound
4
—
—
Cross-linking agent 1
8
Resin 1
1.5
0.116
0.090


Example 12
(18)


Comparative
Compound
10 
—
—
—
—
PL-4804
5.0
0.063
0.058


Example 13
(19)


Comparative
Compound
4
—
—
Cross-linking agent 5
2
—
—
0.081
0.076


Example 14
(20)









In Table 22, the cross-linking agent 1 is an isocyanate-based cross-linking agent (trade name: DESMODUR BL3575, manufactured by Sumika Bayer (solid content: 75%)), the cross-linking agent 2 is an isocyanate-based cross-linking agent (trade name: DESMODUR BL3175, manufactured by Sumika Bayer (solid content: 75%)), the cross-linking agent 3 is a butylated melamine-based cross-linking agent (trade name: SUPER BECKAMINE J821-60, manufactured by DIC Corporation (solid content: 60%)), the cross-linking agent is a butylated urea-based cross-linking agent (trade name: BECKAMINE P138, manufactured by DIC Corporation (solid content: 60%)), and the cross-linking agent 5 is an acrylic cross-linking agent (A-TMPT: manufactured by Shin-Nakamura Chemical Co., Ltd.).
In Table 22, the resin 1 (resin having a polymerizable functional group) is a polyvinyl acetal resin having a number of moles of a hydroxyl group per 1 g of 3.3 mmol and a molecular weight of 1×105, the resin 2 is a polyvinyl acetal resin having a number of moles of a hydroxyl group per 1 g of 3.3 mmol and a molecular weight of 2×104, and the resin 3 is a polyvinyl acetal resin having a number of moles of a hydroxyl group per 1 g of 2.5 mmol and a molecular weight of 3.4×105.
As described above, it is understood from the results of Examples 72 to 134 and Comparative Examples 11 to 14 that a positive ghost was able to be suppressed by using the electrophotographic photosensitive member including the undercoat layer of the present invention.
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.
This application claims the benefit of Japanese Patent Application No. 2014-217358, filed Oct. 24, 2014, Japanese Patent Application No. 2015-069755, filed Mar. 30, 2015, and Japanese Patent Application No. 2015-200570, filed Oct. 8, 2015, which are hereby incorporated by references herein in their entirety.

## Claims

1. An electrophotographic photosensitive member, comprising:
a laminated body and a hole transporting layer on the laminated body, the laminated body comprising:
a support;
an undercoat layer having a thickness of d1 (μm), on the support; and
a charge generating layer having a thickness of d2 (μm), on the undercoat layer, wherein
the hole transporting layer has a thickness of 15 μm or less,
the undercoat layer comprises a polymerized product of a composition including an electron transport material represented by formula (1), a cross-linking agent, and a thermoplastic resin having a polymerizable functional group:


Z1—X—Z2  (1)


in which Z1 and Z2 each represent a group having an electron transport property;
X represents a linking group, and the linking group is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted heterocyclic group, or a group derived by substituting one of methylene groups in a main chain of the substituted or unsubstituted alkylene group with R1, the R1 representing an oxygen atom, a sulfur atom, SO2, NR2, CO, or a substituted or unsubstituted arylene group, the R2 representing a hydrogen atom, an alkyl group, or an aryl group; and
at least one of Z1, Z2, and X has a polymerizable functional group, and the polymerizable functional group is a hydroxyl group, a thiol group, an amino group, a carboxyl group, or a methoxy group;
when the charge generating layer of the laminated body is charged by corona charging so that a dark potential of a surface of the charge generating layer after 1.0 second from the corona charging being defined as Vd1, Vd1 satisfies expression (4)


Vd1=−100×(d1+d2)  (4), and


a dark potential of the surface of the charge generating layer after 0.80 second from the corona charging is defined as Vd2, Vd1 and Vd2 satisfies expression (2)


0.20≦|Vd2−Vd1|≦2.0  (2), and


when the surface of the charge generating layer which has a potential of Vd1 (V) is exposed to a laser light having a wavelength of 780 nm for 1 microsecond and a light intensity so that the potential of the surface of the charge generating layer decays by 20% with respect to Vd1 (V) after 0.04 second from the exposure to the laser light, and a transit time (ms) determined based on a time change rate of the potential of the surface of the charge generating layer after the exposure to the laser light is defined as τ, τ, satisfies expression (3):


τ≦10  (3).

2. An electrophotographic photosensitive member according to claim 1, wherein the hole transporting layer has a thickness of 3 to 10 μm.

3. An electrophotographic photosensitive member according to claim 1, wherein a content of the electron transport material represented by the formula (1) is 50 to 85 mass % with respect to a total mass of the composition.

4. An electrophotographic photosensitive member according to claim 1, wherein the thickness d1 of the undercoat layer is 0.7 to 3.0 μm.

5. An electrophotographic photosensitive member according to claim 1, wherein the cross-linking agent has 2 to 6 isocyanate groups, 2 to 6 blocked isocyanate groups, or 2 to 6 groups each represented by —CH2—OR6 where R6 represents an alkyl group.

6. An electrophotographic photosensitive member according to claim 1, wherein 0.01≦τ≦2.

7. An electrophotographic photosensitive member according to claim 1, wherein the electron transport material represented by formula (1) comprises a compound represented by formula (11):



in which X1 and X2 each independently represent a residue obtained by removing four carboxyl groups from a substituted or unsubstituted aromatic tetracarboxylic acid, and when the residue has a substituent, the substituent is a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group;
Y represents a substituted or unsubstituted alkylene group having a polymerizable functional group or a substituted or unsubstituted arylene group having a polymerizable functional group;
R7 and R8 each independently represent a substituted or unsubstituted alkyl group, a group derived by substituting one of methylene groups of the substituted or unsubstituted alkyl group with an oxygen atom, a group derived by substituting one of the methylene groups of the substituted or unsubstituted alkyl group with a sulfur atom, a group derived by substituting one of the methylene groups of the substituted or unsubstituted alkyl group with NR9, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or an alkoxycarbonyl group, and R7 and R8 may each independently have a polymerizable functional group; and
the polymerizable functional group is a hydroxyl group, a thiol group, an amino group, a carboxyl group, or a methoxy group,
provided that the oxygen atom, the sulfur atom, and the NR9 are free from being directly bonded to nitrogen atoms to which R7 and R8 are bonded.

8. An electrophotographic photosensitive member according to claim 1, wherein the charge generating layer comprises at least one kind of charge generating material selected from the group consisting of a phthalocyanine pigment and an azo pigment.

9. An electrophotographic photosensitive member according to claim 1, wherein the hole transporting layer comprises at least one kind of hole transporting material selected from the group consisting of a triarylamine compound, a benzidine compound, and a styryl compound.

10. An electrophotographic photosensitive member, comprising:
a support;
an undercoat layer on the support; and
a photosensitive layer on the undercoat layer, wherein
the undercoat layer comprises a polymerized product of one of the following (i) and (ii):
(i) a polymerized product of a compound represented by formula (11); and
(ii) a polymerized product of a composition containing the compound represented by formula (11) and a cross-linking agent:




in which X1 and X2 each independently represent a residue obtained by removing four carboxyl groups from a substituted or unsubstituted aromatic tetracarboxylic acid, and when the residue has a substituent, the substituent comprises is a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group;
Y represents a substituted or unsubstituted alkylene group having a polymerizable functional group or a substituted or unsubstituted arylene group having a polymerizable functional group; and
R7 and R8 each independently represent a substituted or unsubstituted alkyl group, a group derived by substituting one of methylene groups of the substituted or unsubstituted alkyl group with an oxygen atom, a group derived by substituting one of the methylene groups of the substituted or unsubstituted alkyl group with a sulfur atom, a group derived by substituting one of the methylene groups of the substituted or unsubstituted alkyl group with NR9, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or an alkoxycarbonyl group, and R7 and R8 are free of a polymerizable functional group,
provided that the oxygen atom, the sulfur atom, and the NR9 are free from being directly bonded to nitrogen atoms to which R7 and R8 are bonded.

11. An electrophotographic photosensitive member according to claim 10, wherein in R7 and R8 a substituent of the substituted alkyl group is an aryl group, a carbonyl group, an alkoxycarbonyl group, or a halogen atom, and
a substituent of the substituted aryl group and a substituent of the substituted heterocyclic group are each a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxycarbonyl group, an alkoxy group, or a halogenated alkyl group.

12. An electrophotographic photosensitive member according to claim 10, wherein the polymerizable functional group is at least one kind selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a thiol group.

13. An electrophotographic photosensitive member according to claim 10, wherein the polymerizable functional group is an unsaturated hydrocarbon group.

14. An electrophotographic photosensitive member according to claim 13, wherein the unsaturated hydrocarbon group is at least one kind selected from the group consisting of an acryloyloxy group and a methacryloyloxy group.

15. An electrophotographic photosensitive member according to claim 10, wherein the compound represented by formula (11) has two or more polymerizable functional groups.

16. An electrophotographic photosensitive member according to claim 10, wherein Y of the compound represented by formula (11) has two polymerizable functional groups.

17. An electrophotographic photosensitive member according to claim 10, wherein, in Y of the compound represented by formula (11), the polymerizable functional group is a hydroxyl group.

18. An electrophotographic photosensitive member according to claim 10, wherein X1 and X2 of the compound represented by formula (11) each represent any one selected from the following group

19. An electrophotographic photosensitive member according to claim 10, wherein
the photosensitive layer comprises a charge generating layer and a hole transporting layer on the charge generating layer; and
the hole transporting layer has a thickness of more than 15 μm.

20. An electrophotographic photosensitive member according to claim 10, wherein a mass ratio between the compound represented by the formula (11) and the cross-linking agent in the composition is 100:50 to 100:500.

21. A process cartridge, comprising:
an electrophotographic photosensitive member; and
at least one unit selected from the group consisting of a charging unit, a developing unit, and a cleaning unit,
the process cartridge integrally supporting the electrophotographic photosensitive member and the at least one unit,
the process cartridge being removably mounted onto an electrophotographic apparatus, wherein
the electrophotographic photosensitive member comprises a laminated body and a hole transporting layer on the laminated body,
the laminated body comprises:
a support;
an undercoat layer having a thickness of d1 (μm), on the support; and
a charge generating layer having a thickness of d2 (μm), on the undercoat layer, wherein
the hole transporting layer has a thickness of 15 μm or less;
the undercoat layer comprises a polymerized product of a composition including an electron transport material represented by formula (1), a cross-linking agent, and a thermoplastic resin having a polymerizable functional group:


Z1—X—Z2  (1)


in which Z1 and Z2 each represent a group having an electron transport property;
X represents a linking group, and the linking group is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted heterocyclic group, or a group derived by substituting one of methylene groups in a main chain of the substituted or unsubstituted alkylene group with R1, the R1 representing an oxygen atom, a sulfur atom, SO2, NR2, CO, or a substituted or unsubstituted arylene group, the R2 representing a hydrogen atom, an alkyl group, or an aryl group; and
at least one of Z1, Z2, and X has a polymerizable functional group, and the polymerizable functional group is a hydroxyl group, a thiol group, an amino group, a carboxyl group, or a methoxy group;
when the charge generating layer of the laminated body is charged by corona charging so that a dark potential of a surface of the charge generating layer after 1.0 second from the corona charging being defined as Vd1, Vd1 satisfies expression (4)


Vd1=−100×(d1+d2)  (4), and


a dark potential of the surface of the charge generating layer after 0.80 second from the corona charging is defined as Vd2, Vd1 and Vd2 satisfies expression (2)


0.20≦|Vd2−Vd1|≦2.0  (2), and


when the surface of the charge generating layer which has a potential of Vd1 (V) is exposed to a laser light having a wavelength of 780 nm for 1 microsecond and a light intensity so that the potential of the surface of the charge generating layer decays by 20% with respect to Vd1 (V) after 0.04 second from the exposure to the laser light, and a transit time (ms) determined based on a time change rate of the potential of the surface of the charge generating layer after the exposure to the laser light is defined as τ, τ, satisfies expression (3):


τ≦10  (3).

22. An electrophotographic apparatus, comprising:
an electrophotographic photosensitive member;
an exposing unit;
a charging unit;
a developing unit; and
a transferring unit, wherein
the electrophotographic photosensitive member comprises:
a laminated body and a hole transporting layer on the laminated body, the laminated body comprising:
a support;
an undercoat layer having a thickness of d1 (μm), on the support; and
a charge generating layer having a thickness of d2 (μm), on the undercoat layer, wherein
the hole transporting layer has a thickness of 15 μm or less;
the undercoat layer comprises a polymerized product of a composition including an electron transport material represented by formula (1), a cross-linking agent, and a thermoplastic resin having a polymerizable functional group:


Z1—X—Z2  (1)


in which Z1 and Z2 each represent a group having an electron transport property;
X represents a linking group, and the linking group is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted heterocyclic group, or a group derived by substituting one of methylene groups in a main chain of the substituted or unsubstituted alkylene group with R1, the R1 representing an oxygen atom, a sulfur atom, SO2, NR2, CO, or a substituted or unsubstituted arylene group, the R2 representing a hydrogen atom, an alkyl group, or an aryl group; and
at least one of Z1, Z2, and X has a polymerizable functional group, and the polymerizable functional group is a hydroxyl group, a thiol group, an amino group, a carboxyl group, or a methoxy group;
when the charge generating layer of the laminated body is charged by corona charging so that a dark potential of a surface of the charge generating layer after 1.0 second from the corona charging being defined as Vd1, Vd1 satisfies expression (4)


Vd1=−100×(d1+d2)  (4), and


a dark potential of the surface of the charge generating layer after 0.80 second from the corona charging is defined as Vd2, Vd1 and Vd2 satisfies expression (2)


0.20≦|Vd2−Vd1|≦2.0  (2), and


when the surface of the charge generating layer which has a potential of Vd1 (V) is exposed to a laser light having a wavelength of 780 nm for 1 microsecond and a light intensity so that the potential of the surface of the charge generating layer decays by 20% with respect to Vd1 (V) after 0.04 second from the exposure to the laser light, and a transit time (ms) determined based on a time change rate of the potential of the surface of the charge generating layer after the exposure to the laser light is defined as τ, τ, satisfies expression (3):


τ≦10  (3).

23. A process cartridge, comprising:
an electrophotographic photosensitive member; and
at least one unit selected from the group consisting of a charging unit, a developing unit, and a cleaning unit,
the process cartridge integrally supporting the electrophotographic photosensitive member and the at least one unit, and
the process cartridge being removably mounted onto an electrophotographic apparatus, wherein
the electrophotographic photosensitive member comprises:
a support;
an undercoat layer on the support; and
a photosensitive layer on the undercoat layer,
wherein the undercoat layer comprises a polymerized product of one of the following (i) and (ii):
(i) a polymerized product of a compound represented by the following formula (11); and
(ii) a polymerized product of a composition containing the compound represented by formula (11) and a cross-linking agent:




in which X1 and X2 each independently represent a residue obtained by removing four carboxyl groups from a substituted or unsubstituted aromatic tetracarboxylic acid, and when the residue has a substituent, the substituent comprises is a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group;
Y represents a substituted or unsubstituted alkylene group having a polymerizable functional group or a substituted or unsubstituted arylene group having a polymerizable functional group; and
R7 and R8 each independently represent a substituted or unsubstituted alkyl group, a group derived by substituting one of methylene groups of the substituted or unsubstituted alkyl group with an oxygen atom, a group derived by substituting one of the methylene groups of the substituted or unsubstituted alkyl group with a sulfur atom, a group derived by substituting one of the methylene groups of the substituted or unsubstituted alkyl group with NR9, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or an alkoxycarbonyl group, and R7 and R8 are free of a polymerizable functional group,
provided that the oxygen atom, the sulfur atom, and the NR9 are free from being directly bonded to nitrogen atoms to which R7 and R8 are bonded.

24. An electrophotographic apparatus, comprising:
an electrophotographic photosensitive member;
an exposing unit;
a charging unit;
a developing unit; and
a transferring unit, wherein
the electrophotographic photosensitive member comprises:
a support;
an undercoat layer on the support; and
a photosensitive layer on the undercoat layer,
the undercoat layer comprising a polymerized product of one of the following (i) and (ii):
(i) a polymerized product of a compound represented by formula (11); and
(ii) a polymerized product of a composition containing the compound represented by formula (11) and a cross-linking agent:




in which X1 and X2 each independently represent a residue obtained by removing four carboxyl groups from a substituted or unsubstituted aromatic tetracarboxylic acid, and when the residue has a substituent, the substituent comprises is a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group;
Y represents a substituted or unsubstituted alkylene group having a polymerizable functional group or a substituted or unsubstituted arylene group having a polymerizable functional group; and
R7 and R8 each independently represent a substituted or unsubstituted alkyl group, a group derived by substituting one of methylene groups of the substituted or unsubstituted alkyl group with an oxygen atom, a group derived by substituting one of the methylene groups of the substituted or unsubstituted alkyl group with a sulfur atom, a group derived by substituting one of the methylene groups of the substituted or unsubstituted alkyl group with NR9, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or an alkoxycarbonyl group, and R7 and R8 are free of polymerizable functional group,
provided that the oxygen atom, the sulfur atom, and the NR9 are free from being directly bonded to nitrogen atoms to which R7 and R8 are bonded.