RU2567286C2 - Electrophotographic light-sensitive element, working cartridge and electrophotographic device - Google Patents

Abstract

FIELD: electricity.

SUBSTANCE: invention relates to an electrophotographic light-sensitive element used in working cartridges and electrophotographic devices. The electrophotographic light-sensitive element represents a laminated body that includes a conducting substrate, an electron transfer layer, a charge generation layer and a hole transfer layer. The above laminated body meets the following expression (1): R_opt/R_dark≤0.95(1), where R_opt is impedance of the laminated body at light irradiation, R_dark is impedance without any irradiation. Impedance is measured by formation by means of sputtering on the surface of the charge generation layer of a golden electrode of a round shape with thickness of 300 nm and diameter of 10 mm and application between it and the conducting substrate of a 100 mV and 0.1 Hz alternating electric field. With that, the surface of the charge generation layer is irradiated by light with intensity of 30 mcJ/cm²·s. Besides, the working cartridge and the electrophotographic device are described, which have the above electrophotographic light-sensitive element.

EFFECT: proposed electrophotographic light-sensitive element provides reduction of a positive repetitive image at an early stage and after long-term multiple use.

8 cl, 6 dwg, 14 tbl, 119 ex

Description

BACKGROUND OF THE INVENTION

Field of Invention

[0001] The present invention relates to an electrophotographic photosensitive member, as well as a working cartridge and an electrophotographic device having an electrophotographic photosensitive member.

Description of the Related Art

[0002] As electrophotographic photosensitive elements used for working cartridges and electrophotographic devices, currently mainly electrophotographic photosensitive elements containing organic photoconductive material predominate. The electrophotographic photosensitive member typically has a substrate and a photosensitive layer formed on the substrate. Then, a coating sublayer is provided between the substrate and the photosensitive layer in order to suppress the injection of charge from the side of the substrate towards the photosensitive layer (charge generation layer) and to suppress the generation of image defects such as tarnishing.

[0003] Recently, charge-generating substances having a higher sensitivity have been used. However, such a problem arises that the charge tends to be held in the photosensitive layer due to the fact that the amount of charge generated becomes larger as the sensitivity of the charge-generating substance increases, and a tendency for a repeated image (“shadow”) to appear. Specifically, in a printed image, a phenomenon of the so-called positive repeated image tends to occur, in which only the parts irradiated with light in the previous rotation time become high.

[0004] A technique is described for reducing such a re-image phenomenon in which a coating sublayer is made into a layer (hereinafter also referred to as an electron transfer layer) having electron transfer ability by introducing an electron-transporting substance into the coating sublayer. National Publication of International Patent Application No. 2009-505156 describes a condensed polymer (electron transferring substance) having an aromatic tetracarbonylbisimide skeleton and an active crosslinking center, and an electron transfer layer containing a polymer with a crosslinking agent. Japanese Patent Application Laid-Open No. 2003-330209 describes that a polymer of an electron-transporting substance having a non-hydrolyzable polymerizable functional group is introduced into the sublayer of the coating. Japanese Patent Application Laid-Open No. 2005-189764 describes a technology for imparting an electron mobility of 10 ^-7 cm ² / V · s or more to the sublayer to improve electron transportability.

[0005] The quality requirements for electrophotographic images have been steadily increasing in recent years, and the acceptable limits for positive early stage re-imaging and long-term positive re-image after repeated use have become noticeably more stringent. As a result of comprehensive studies by the authors of the present invention, it was found that, with regard to reducing positive re-image, the technologies described in Japanese Patent Application Publication No. 2009-505156 and Japanese Patent Application Laid-Open No. 2003-330209 and 2005-189764 still remain have room for improvement.

SUMMARY OF THE INVENTION

[0006] An object of the present invention is to provide an electrophotographic photosensitive member with reduced positive re-image at an early stage and after long-term reuse, as well as a working cartridge and an electrophotographic device having such an electrophotographic photosensitive member.

[0007] The present invention relates to an electrophotographic photosensitive member comprising a laminated body and a hole transport layer formed on the laminated body, wherein the laminated body has a conductive substrate, an electron transfer layer formed on the conductive substrate, and a charge generation layer formed on the electron transfer layer ; and the laminated body satisfies the following expression (1):

(1),R_opt / R_dark≤0.95 $$$$

(one),

where in the above expression (1), R_opt is the impedance of the laminated body, measured using the steps of: forming on the surface of the charge generation layer a circular circular gold electrode having a thickness of 300 nm and a diameter of 10 mm, sputtering and applications between the conductive substrate and the gold electrode a circular shape of an alternating electric field having a voltage of 100 mV and a frequency of 0.1 Hz, while irradiating the surface of the charge generation layer with light having an intensity of 30 μJ / cm ² · s, and measuring impedance, and R_dark pred is the impedance of a laminated body, measured using the steps of: forming on the surface of a charge generation layer a circular circular gold electrode having a thickness of 300 nm and a diameter of 10 mm, sputtering and applying an alternating electric field having a voltage of 100 mV between the conductive substrate and the circular circular gold electrode and a frequency of 0.1 Hz, without irradiating the surface of the charge generation layer with light, and measuring impedance.

[0008] The present invention also relates to a working cartridge removably attached to the main body of an electrophotographic device, the working cartridge fully supporting: an electrophotographic photosensitive member and at least one assembly selected from the group consisting of a charging unit, a developing unit, a transfer unit, and node cleaning.

[0009] The present invention also relates to an electrophotographic device having an electrophotographic photosensitive member and a charging unit, a light irradiation unit, a developing unit and a transfer unit.

[0010] The present invention can provide an electrophotographic photosensitive member with positive re-image reduction at an early stage and after long-term reuse, as well as a working cartridge and an electrophotographic device having such an electrophotographic photosensitive member.

[0011] Other features of the present invention will become apparent from the following description of exemplary embodiments with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

[0012] FIG. 1 is a diagram illustrating one example of the basic structure of a determination device for implementing the determination method in accordance with the present invention.

[0013] FIG. 2 is a graph illustrating typical examples of R_dark and R_opt when the determination method of the present invention is carried out.

[0014] FIG. 3 is a diagram illustrating a schematic structure of an electrophotographic device having a working cartridge with an electrophotographic photosensitive member.

[0015] FIG. 4 is a diagram for describing an image for evaluating a repeated image used in evaluating a repeated image.

[0016] FIG. 5 is a diagram for describing an image of a one-point Keima structure (similar to a horse move).

[0017] FIG. 5B is a diagram for describing an image of a single point structure used after long-term reuse.

[0018] FIG. 6 is a diagram illustrating one example of the structure of layers of an electrophotographic photosensitive member.

DESCRIPTION OF EMBODIMENTS

[0019] Preferred embodiments of the present invention will now be described in detail in accordance with the accompanying drawings.

[0020] First, a determination method (hereinafter, referred to as a "determination method in accordance with the present invention") will be described to determine whether the electrophotographic photosensitive member satisfies the ratio of the above expression (1) of the present invention. The temperature and humidity conditions in the implementation of the determination method in accordance with the present invention may correspond to the environment of use of an electrophotographic device having an electrophotographic photosensitive element. Conditions may correspond to a medium of normal temperature and normal humidity (23 ° C ± 3 ° C, 50% ± 2% RH (relative humidity)). The above measurement method involves using a laminated body having a conductive substrate, an electron transfer layer and a charge generation layer in this order.

[0021] In this case, the hole transport layer is peeled off from the electrophotographic photosensitive member having a laminated body and a hole transport layer formed on the laminated body, thereby obtaining a laminated body (also referred to as “electrophotographic photosensitive member for determination”), which can be used in as an object of definition. A method for exfoliating a hole transfer layer includes a method in which an electrophotographic photosensitive member is immersed in a solvent that dissolves the hole transfer layer well and poorly dissolves the electron transfer layer and the charge generation layer, and a method in which the hole transfer layer is ground.

[0022] As a solvent that dissolves the hole transport layer well and poorly dissolves the electron transfer layer and the charge generation layer, a solvent used as a liquid for applying the hole transport layer can be used. The types of solvent will be described later. The electrophotographic photosensitive member is immersed in a solvent so that the hole transport layer dissolves in the solvent, and then dried, thereby obtaining an electrophotographic photosensitive member for determination. The fact that the hole transfer layer is peeling off can be confirmed, for example, by the fact that no resin components of the hole transfer layer can be detected using the ATR method (total internal reflection method) in the FTIR measurement method (Fourier transform infrared spectrometry).

[0023] A method for grinding a hole transfer layer includes, for example, using a drum and tape grinding device manufactured by Canon Inc. and using a lapping tape (C2000 manufactured by Fujifilm Corp.). In this case, it is possible to measure while the entire hole transport layer is removed, although the thickness of the hole transfer layer is subsequently measured so that there is no grinding to the charge generation layer due to excessive grinding of the hole transfer layer, and the surface of the electrophotographic photosensitive member is observed. The case where the thickness of the charge generation layer remains of 0.10 μm or more after grinding to the charge generation layer turned out to give approximately the same value with the above determination method, as in the case when grinding is not carried out before the charge generation layer. Therefore, the above determination method can be used even if not only the hole transport layer is polished, but also the charge generation layer, in the case where the thickness of the charge generation layer is 0.10 μm or more.

[0024] FIG. 1 illustrates one example of the basic structure of a determination device for implementing the determination method in accordance with the present invention. 1, reference numeral 101 denotes a portion of an electrophotographic photosensitive member (laminated body) for detecting obtained by cutting out a 2 centimeter electrophotographic photosensitive member (peripheral direction) × 4 cm (long axis direction). Reference numeral 102 denotes a circular circular gold electrode having a diameter of 10 mm and a thickness of 300 nm, formed on the surface of the charge generation layer of the above laminated body by sputtering. The method for spraying a gold electrode is not particularly limited, but you can use Quick Auto Coater (SC-707AT) manufactured by SANYU Electronic Co., Ltd., or the like. The deposition is carried out until the thickness of the gold electrode becomes equal to 300 nm, while maintaining a discharge current of 20 mA, with the structure in which the gold target is placed above the surface of the charge generation layer, thereby producing a gold electrode. Reference number 103 denotes an impedance measuring device, and it is illustrated that a wire 105 is connected to a gold electrode on the charge generation layer and the conductive substrate. Reference number 104 denotes a device for emitting laser light (a device for irradiating light), and reference number 106 denotes an irradiating shine. As an impedance measuring device, for example, a measuring module is used, which is a combination of the SI-1287 electrochemical interface, SI-1260 amplitude-phase impedance analyzer and 1296 dielectric interface manufactured by Toyo Corp. The impedance (R_dark) under the conditions without light exposure of the present invention is measured by covering the entire device of Figure 1 with a light-shielding film to shield the room light without irradiation with the light of the device 104 for emitting laser light. An alternating electric field of 100 mV is then applied between the conductive substrate of the laminated body and the gold electrode, and the impedance is measured by sweeping the frequency from a high frequency of 1 MHz to a low frequency of 0.1 Hz, thereby obtaining an impedance (R_dark) at 0.1 Hz. That is, this impedance refers to the impedance measured by applying an alternating electric field of 100 mV and 0.1 Hz between the conductive substrate of the laminated body and the gold electrode, provided that there is no irradiation of the surface of the charge generation layer with light.

[0025] Then, the impedance (R_opt) is measured under the condition of irradiation with light, as in the above case without irradiation with the exception of the continuous emission of the irradiating light 106 from the laser light emitting device 104 to the electrophotographic photosensitive element 101 for detecting. As for the irradiating light when measuring R_opt, then use light with a wavelength corresponding to the light absorption properties of the charge generation layer, and irradiate with light having a sufficient intensity for yscheniya layer generating charge carriers excited by light generated from the charge generating substance. Specifically, by irradiation with light having a wavelength of 400 nm to 800 nm and an irradiation intensity of 30 μJ / cm ² · s or more, carriers excited by light can be saturated to a sufficient degree. In the examples of the present invention, such an irradiation intensity was used that the impedance (R_opt) saturates at the lowest value when exposed to light. Specifically, laser irradiation was carried out having a wavelength of 680 nm and an irradiation intensity of 30 μJ / cm ² · s. With regard to the time of exposure to light, exposure to light at the above irradiation intensity, carried out over a period of 1 s or more, can provide sufficient saturation of carriers excited by light, but the measurement of impedance takes several minutes. The impedance is measured when light is irradiated at the above irradiation intensity, with the result that the carriers excited by the light are saturated enough. That is, this impedance refers to the impedance measured by applying an alternating electric field of 100 mV and 0.1 Hz between the conductive substrate and the gold electrode, provided that the surface of the charge generation layer is irradiated with light having an irradiation intensity of 30 μJ / cm ² · s. Whether the electrophotographic photosensitive element satisfies the ratio of the above expression (1) or not can be determined by calculating the ratio of the measured R_dark and R_opt.

[0026] Figure 2 illustrates representative examples of R_dark and R_opt. Figure 2 illustrates the frequency dependence of the impedances (R_dark and R_opt) measured by the above method. In particular, on the low-frequency side, the change in impedance becomes large depending on the presence and absence of light exposure. That is, the ratio R_opt / R_dark at 0.1 Hz indicates 0.95 or less.

[0027] In the present invention, to reduce positive re-image at an early stage and after repeated use, the ratio R_opt / R_dark is 0.95 or less. The authors of the present invention consider the reason that compliance with the ratio of the above expression (1) can reduce the positive re-image at an early stage and after repeated use, the following.

[0028] Namely, in the case of an electrophotographic photosensitive member provided with an electron transfer layer (a coating sublayer), a charge generation layer and a hole transfer layer on the substrate in this order, on which parts of the irradiating light (light for irradiating the image) incident from charges ( holes and electrons) generated in the charge generation layer, holes are injected into the hole transfer layer, and electrons are injected into the electron transfer layer and transferred to the substrate. However, if the electrons generated in the charge generation layer under the action of light excitation do not completely transfer to the electron transfer layer before the next charge, the charge is held (stored) in the charge generation layer, still causing the movement of electrons even during the next charge. Slowly moving electrons tend to cause a local decrease in the ability to charge light-irradiated parts after the next charge. These phenomena also occur with repeated use of the electrophotographic photosensitive element, and the charge held in the charge generation layer tends to gradually increase. The charge held in the charge generation layer is the reason for generating positive re-image at an early stage and after repeated use.

[0029] Then, if the laminated body satisfies the relation of the above expression (1), the reception and delivery of slowly moving electrons (electrons obtained due to light excitation and held in the charge generation layer) at the interface between the electron transfer layer and the charge generation layer noticeably easier. That is, in the determination method in accordance with the present invention, if the resistance between the conductive substrate and the gold electrode does not change depending on the presence and absence of light irradiation in a state where the charge generating layer of the laminated body is saturated with the charge obtained due to light excitation, it is obvious that the injection of electrons from the charge generation layer into the electron transfer layer is insufficient, and slowly moving electrons are more likely to be held in the generation layer behind poison. Then, it can be assumed that this trend corresponds to the case where R_opt / R_dark is 0.96 or more. In contrast, if the resistance between the conductive substrate and the gold electrode decreases when light is irradiated in a state where the charge generation layer is saturated with slowly moving electrons (the charge obtained due to light excitation), it can be assumed that the injection of electrons from the charge generation layer into the layer The electron transfer is carried out sufficiently, and the retention of slowly moving electrons in the charge generation layer can be reduced.

[0030] The state of confinement of slowly moving electrons can be clarified by paying attention to impedance at low frequencies. Although the evaluation method in accordance with the present invention gives 0.1 Hz as a low frequency, it can be assumed that any frequency can express the impedance of slowly moving electrons, provided that this frequency is a low frequency of less than 0.1 Hz In the present invention, the impedance of slowly moving electrons is observed using an impedance of 0.1 Hz. The frequency of 0.1 Hz corresponds to a period of about 10 s, and the state is clearly expressed when the electrons that respond to the electric field with a period of 10 s are held in the charge generation layer during repeated use, and there is a tendency to a positive re-image.

[0031] It can be assumed that if the ratio of expression (1) is satisfied, then a good injectability state is demonstrated that the retention of slowly moving electrons decreases and when reused, the retention of electrons at an early stage and after repeated use in the charging process under light irradiation decreases thereby making it possible to reduce the positive repeat image. As shown in the Comparative Examples described below, although electrophotographic photosensitive elements according to the national publication of International Patent Application No. 2009-505156 and the like have sufficient conductivity of electron transfer layers, since slowly moving electrons tend to be retained in charge generation layers, R_opt / R_dark becomes large than 0.95, and in some cases there is a tendency to a positive re-image after repeated use.

[0032] It can also be assumed that the technology of Japanese Patent Application Laid-Open No. 2005-189764, in which the electron mobility in the coating sublayer (electron transfer layer) is made equal to 10 ^-7 cm ² / V · s or more, is an object for improvement the movement of electrons with obtaining a faster movement, and it cannot eliminate the cause of the appearance of a positive repeated image due to the retention of slowly moving electrons. Japanese Patent Application Laid-Open No. 2010-145506 describes that charge mobility in the hole transfer layer and electron transfer layer (coating sublayer) is made to be within specific ranges, but it does not eliminate the cause of the positive re-image, like Japanese Patent Application Laid-Open No. 2005-189764. In addition, in this patent literature, electron mobility in the electron transfer layer is measured using a structure in which an electron transfer layer is formed on the charge generation layer, and this structure is inverse to the layer structure used in the electrophotographic photosensitive member. However, one cannot say about such a measurement that it is capable of sufficiently estimating the motion of electrons in the electron transfer layer of an electrophotographic photosensitive element.

[0033] For example, in the case where an electron transfer layer is made by introducing an electron-transporting substance into the sublayer, when liquids for applying a charge generation layer and a hole transfer layer as upper layers are applied to form a charge generation layer and a hole transfer layer, the electron-transporting substance in some cases elutes. In this case, it can be assumed that even if the electron mobility is measured by making the electron transfer layer and the charge generation layer in reverse layers, as described above, since the electron-transporting substance in the electrophotographic photosensitive element is eluted, the movement of electrons in the electron transfer layer of the electrophotographic photosensitive element cannot be appreciated sufficiently. Therefore, it is believed that the determination should be made using an electron transfer layer from which the hole transfer layer and the charge generation layer are peeled off after the charge generation layer and the hole transfer layer are formed on the electron transfer layer.

[0034] An electrophotographic photosensitive member in accordance with the present invention has a laminated body and a hole transport layer formed on the laminated body, and the laminated body has a conductive substrate, an electron transfer layer formed on the conductive substrate, and a charge generation layer formed on the electron transfer layer. 6 is a diagram illustrating one example of the structure of layers of an electrophotographic photosensitive member. 6, reference numeral 21 denotes a conductive substrate; reference numeral 22 denotes an electron transfer layer; reference numeral 23 denotes a charge generation layer; and reference numeral 24 denotes a hole transport layer.

[0035] As a conventional electrophotographic photosensitive member, a cylindrical electrophotographic photosensitive member is widely used, in which a photosensitive layer (a charge generation layer, a hole transfer layer) is formed on the cylindrical substrate, but an element of a different shape, for example, in the form of a tape or in the form, can be used sheet.

[0036] Electron Transfer Layer

[0037] The thickness of the electron transfer layer may be 0.1 μm or more and 1.5 μm or less, and more preferably 0.2 μm or more and 0.7 μm or less.

[0038] If the aforementioned laminated body satisfies the ratio of the following expression (2), then a greater effect of reducing a positive repeated image is obtained. Since a lower R_opt / R_dark value has a larger positive re-image reduction effect, this value is satisfactory if the value is greater than 0.

(2),0 <R_opt / R_dark≤0.85 $$$$

(2)

More preferably, this value satisfies the following expression (3).

(3)0.60≤R_opt / R_dark≤0.85 $$$$

(3)

[0039] In the above expressions (2) and (3), R_opt is the impedance measured by forming a gold circular electrode having a thickness of 300 nm and a diameter of 10 mm, on the surface of the laminated body charge generation layer by sputtering, by applying an alternating electric field 100 mV and 0.1 Hz between the conductive substrate and the gold electrode, provided that the surface of the charge generation layer is irradiated with light having an irradiation intensity of 30 μJ / cm ² · s and the impedance is measured. R_dark is the impedance measured by forming a gold circular electrode having a thickness of 300 nm and a diameter of 10 mm, on the surface of the layer of charge generation of the laminated body by sputtering, applying an alternating electric field of 100 mV and 0.1 Hz between the conductive substrate and the gold electrode provided the absence of light irradiation on the surface of the charge generation layer, and the measurement of impedance.

[0040] Next, the structure of the electron transfer layer will be described. The electron transfer layer may contain an electron-transporting substance or a polymer of an electron-transporting substance. The electron transfer layer may further comprise a polymer obtained by polymerizing a composition containing an electron-transporting substance having polymerizable functional groups, a thermoplastic resin having polymerizable functional groups, and a crosslinking agent.

[0041] Electron Carrier

[0042] Examples of electron-transporting substances include quinone compounds, imide compounds, benzimidazole compounds, and cyclopentadienylidene compounds. The electron transporting substance may be an electron transporting substance having polymerizable functional groups. The polymerizable functional group includes a hydroxyl group, a thiol group, an amino group, a carboxyl group, and a methoxy group.

[0043] The following are specific examples of an electron-transporting substance. The electron transporting substance includes compounds represented by one of the following formulas (A1) to (A9).

[0044] In the formulas (A1) to (A9), R ¹⁰¹ -R ¹⁰⁶ , R ²⁰¹ -R ²¹⁰ , R ³⁰¹ -R ³⁰⁸ , R ⁴⁰¹ -R ⁴⁰⁸ , R ⁵⁰¹ -R ⁵¹⁰ , R ⁶⁰¹ -R ⁶⁰⁶ , R ^701- R ⁷⁰⁸ , R ⁸⁰¹ -R ⁸¹⁰ and R ⁹⁰¹ -R ⁹⁰⁸ each independently represent a monovalent group represented by the following formula (A), hydrogen atom, cyano group, nitro group, halogen atom, alkoxycarbonyl group, substituted or unsubstituted alkyl a group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. One of the carbon atoms in the main chain of the alkyl group can be replaced by O, S, NH or NR ¹⁰⁰¹ (R ¹⁰⁰¹ represents an alkyl group). A substituent of a substituted alkyl group includes an alkyl group, an aryl group, an alkoxycarbonyl group and a halogen atom. The substituent of the substituted aryl group and the substituent of the substituted heterocyclic group include a halogen atom, a nitro group, a cyano group, an alkyl group and an alkyl halide group. Z ²⁰¹ , Z ³⁰¹ , Z ⁴⁰¹ and Z ⁵⁰¹ each independently represent a carbon atom, a nitrogen atom or an oxygen atom. In the case when Z ²⁰¹ represents an oxygen atom, R ²⁰⁹ and R ^{210 are} not present, and in the case when Z ²⁰¹ represents a nitrogen atom, R ^{210 is} not present. In the case when Z ³⁰¹ represents an oxygen atom, R ³⁰⁷ and R ^{308 are} not present, and in the case when Z ³⁰¹ represents a nitrogen atom, R ^{308 is} not present. In the case when Z ⁴⁰¹ represents an oxygen atom, R ⁴⁰⁷ and R ^{408 are} not present, and in the case when Z ⁴⁰¹ represents a nitrogen atom, R ^{408 is} not present. In the case when Z ⁵⁰¹ represents an oxygen atom, R ⁵⁰⁹ and R ^{510 are} not present, and in the case when Z ⁵⁰¹ represents a nitrogen atom, R ^{510 is} not present.

[0045] In formula (A), at least one of α, β, and γ is a group having a substituent, and this substituent is at least one group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, carboxyl group and methoxy group. l and m, each independently, are 0 or 1, and the sum of l and m is from 0 to 2.

[0046] α is an alkylene group having 1-6 atoms in the main chain, an alkylene group having 1-6 atoms in the main chain and substituted by an alkyl group having 1-6 carbon atoms, an alkylene group having 1-6 atoms in the main chain and substituted by a benzyl group, an alkylene group having 1-6 atoms in the main chain and substituted by an alkoxycarbonyl group, or an alkylene group having 1-6 atoms in the main chain and substituted by a phenyl group, and these groups may have at least one substituent selected from the group, consisting s from a hydroxyl group, a thiol group, an amino group and a carboxyl group. One of the carbon atoms in the backbone of the alkylene group can be replaced by O, S, NH or NR ¹⁰⁰² (R ¹⁰⁰² represents an alkyl group).

[0047] β is a phenylene group, a phenylene group substituted by an alkyl group having 1-6 carbon atoms, a nitro group substituted by a nitro group, a halogen substituted phenylene group or an alkoxy group phenylene group, and these groups may have at least one substituent, selected from the group consisting of a hydroxyl group, a thiol group, an amino group and a carboxyl group.

[0048] γ represents a hydrogen atom, an alkyl group having 1-6 atoms in the main chain, or an alkyl group having 1-6 atoms in the main chain and substituted by an alkyl group having 1-6 carbon atoms, and these groups may have at least one substituent selected from the group consisting of a hydroxyl group, a thiol group, an amino group and a carboxyl group. One of the carbon atoms in the main chain of the alkyl group can be replaced by O, S, NH or NR ¹⁰⁰³ (R ¹⁰⁰³ represents an alkyl group).

[0049] Among the electron transporting substances represented by one of the above formulas (A-1) to (A-9), more preferred are electron-transporting substances that have a polymerizable functional group representing a monovalent group represented by the above formula (A ), at least one of R ¹⁰¹ -R ¹⁰⁶ , at least one of R ²⁰¹ -R ²¹⁰ , at least one of R ³⁰¹ -R ³⁰⁸ , at least one of R ⁴⁰¹ -R ⁴⁰⁸ , at least one of R ⁵⁰¹ -R ⁵¹⁰ , at least one of R ⁶⁰¹ -R ⁶⁰⁶ , at least one of R ⁷⁰¹ -R ⁷⁰⁸ , at least about dyne of R ⁸⁰¹ -R ⁸¹⁰ and at least one of R ⁹⁰¹ -R ⁹⁰⁸ .

[0050] A polymer can be formed which is obtained by polymerizing a composition containing an electron-transporting substance having polymerizable functional groups, a thermoplastic resin having polymerizable functional groups, and a crosslinking agent. A method of forming an electron transfer layer includes forming a coating film from a liquid for applying an electron transfer layer containing a composition comprising an electron-transporting substance having polymerizable functional groups, a thermoplastic resin having polymerizable functional groups, and a crosslinking agent, and drying the coating film by heating for polymerization composition, thereby forming an electron transport layer. Specific examples of electron-transporting substances having polymerizable functional groups will be described below. The heating temperature, when the coating film of the liquid for applying the electron transfer layer is dried by heating, can be from 100 to 200 ° C.

[0051] In the Tables, the symbol A 'is represented by the same structure as the symbol A, specific examples of the monovalent group are shown in columns A and A'.

[0052] Specific examples of an electron-transporting substance having polymerizable functional groups will be described below. Specific examples of the compounds represented by the above formula (A1) are shown in Table 1-1, Table 1-2, Table 1-3, Table 1-4, Table 1-5, and Table 1-6. In these Tables, the case where γ is indicated as “-” indicates a hydrogen atom, and this hydrogen atom as γ is introduced into the structure shown in the column α or β.

[0053] Table 1-1

[0054] Table 1-2

[0055] Table 1-3

[0056] Table 1-4

[0057] Table 1-5

[0058] Table 1-6

[0059] Specific examples of the compounds represented by the above formula (A2) are shown in Table 2-1, Table 2-2, and Table 2-3. In these Tables, the case where γ is indicated as “-” indicates a hydrogen atom, and this hydrogen atom as γ is introduced into the structure shown in the column α or β.

[0060] Table 2-1

[0061] Table 2-2

[0062] Table 2-3

[0063] Specific examples of the compounds represented by the above formula (A3) are shown in Table 3-1, Table 3-2, and Table 3-3. In these Tables, the case where γ is indicated as “-” indicates a hydrogen atom, and this hydrogen atom as γ is introduced into the structure shown in the column α or β.

[0064] Table 3-1

[0065] Table 3-2

[0066] Table 3-3

[0067] Specific examples of the compounds represented by the above formula (A4) are shown in Table 4-1 and Table 4-2. In these Tables, the case where γ is indicated as “-” indicates a hydrogen atom, and this hydrogen atom as γ is introduced into the structure shown in the column α or β.

[0068] Table 4-1

[0069] Table 4-2

[0070] Specific examples of the compounds represented by the above formula (A5) are shown in Table 5-1 and Table 5-2. In these Tables, the case where γ is indicated as “-” indicates a hydrogen atom, and this hydrogen atom as γ is introduced into the structure shown in the column α or β.

[0071] Table 5-1

[0072] Table 5-2

[0073] Specific examples of the compounds represented by the above formula (A6) are shown in Table 6. In this Table, the case when γ is indicated as “-” indicates a hydrogen atom, and this hydrogen atom as γ is introduced into the structure shown in column α or β.

[0074] Table 6

[0075] Specific examples of the compounds represented by the above formula (A7) are shown in Table 7-1, Table 7-2, and Table 7-3. In these Tables, the case where γ is indicated as “-” indicates a hydrogen atom, and this hydrogen atom as γ is introduced into the structure shown in the column α or β.

[0076] Table 7-1

[0077] Table 7-2

[0078] Table 7-3

[0079] Specific examples of the compounds represented by the above formula (A8) are shown in Table 8-1, Table 8-2, and Table 8-3. In these Tables, the case where γ is indicated as “-” indicates a hydrogen atom, and this hydrogen atom as γ is introduced into the structure shown in the column α or β.

[0080] Table 8-1

[0081] Table 8-2

[0082] Table 8-3

[0083] Specific examples of the compounds represented by the above formula (A9) are shown in Table 9-1 and Table 9-2. In these Tables, the case where γ is indicated as “-” indicates a hydrogen atom, and this hydrogen atom as γ is introduced into the structure shown in the column α or β.

[0084] Table 9-1

[0085] Table 9-2

[0086] A derivative (derivative of an electron-transporting substance) having structure (A1) can be synthesized using a well-known synthesis method described, for example, in US Pat. Nos. 4,442,193, 4,992,349 and 5,468,583, and Chemistry of Materials, Vol.19 No.11, 2703-2705 (2007). The derivative can also be synthesized by the reaction of naphthalene tetracarboxylic dianhydride and monoamine derivative, which are commercially available from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Co., Ltd. and Johnson Matthey Japan Inc.

[0087] The compound represented by (A1) has polymerizable functional groups (hydroxyl group, thiol group, amino group, carboxyl group, and methoxy group) polymerizable by a crosslinking agent. A method for introducing these polymerizable functional groups into a derivative having a structure (A1) includes a method for directly introducing polymerizable functional groups into a derivative having a structure (A1), and a method for introducing structures having polymerizable functional groups or functional groups that can become precursors of polymerizable functional groups into a derivative having the structure (A1). Examples of the latter method include, based on the naphthylimide derivative halide, a method for introducing a functional group-containing aryl group, for example using a cross-coupling reaction using a palladium catalyst and a base, a method for introducing a functional group-containing alkyl group using a cross-coupling reaction using a catalyst FeCl ₃ and the base and method of introducing a hydroxyalkyl group and a carboxyl group, causing the epoxy compound or CO _{2 to} act on after lithiation. There is a method of using a naphthalene tetracarboxylic dianhydride derivative or a monoamine derivative having polymerizable functional groups or functional groups that can become precursors of polymerizable functional groups as starting materials for the synthesis of a naphthylimide derivative.

[0088] Derivatives having structure (A2) are commercially available, for example, from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Co., Ltd. and Johnson Matthey Japan Inc. Derivatives can also be synthesized based on the phenanthrene derivative or phenanthroline derivative using the synthesis methods described in Chem. Educator No.6, 227-234 (2001), Journal of Synthetic Organic Chemistry, Japan, vol. 15, 29-32 (1957) and Journal of Synthetic Organic Chemistry, Japan, vol. 15, 32-34 (1957). The dicyanomethylene group may also be introduced by reaction with malononitrile.

[0089] The compound represented by (A2) has polymerizable functional groups (hydroxyl group, thiol group, amino group, carboxyl group and methoxy group) polymerizable by a crosslinking agent. A method for introducing these polymerizable functional groups into a derivative having a structure (A2) includes a method for directly introducing polymerizable functional groups into a derivative having a structure (A2), and a method for introducing a structure having polymerizable functional groups or functional groups that can become precursors of polymerizable functional groups into a derivative having structure (A2). Examples of the latter method include, based on phenatrenquinone halide, a method for introducing a functional group-containing aryl group using a cross-coupling reaction using a palladium catalyst and a base, a method for introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl ₃ catalyst and a base and route of administration hydroxyalkyl group and a carboxyl group, forcing epoxy compound or CO ₂ to act after itiirovaniya.

[0090] Derivatives having structure (A3) are commercially available from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Co., Ltd. and Johnson Matthey Japan Inc. Derivatives can also be synthesized based on the phenanthrene derivative or phenanthroline derivative using the synthesis method described in Bull. Chem. Soc., Jpn., Vol. 65, 1006-1011 (1992). The dicyanomethylene group may also be introduced by reaction with malononitrile.

[0091] A compound represented by (A3) has polymerizable functional groups (hydroxyl group, thiol group, amino group, carboxyl group, and methoxy group) polymerizable by a crosslinking agent. A method for introducing these polymerizable functional groups into a derivative having a structure of the above formula (A3) includes a method for directly introducing polymerizable functional groups into a derivative having a structure of formula (A3), and a method for introducing a structure having polymerizable functional groups or functional groups that can become precursors of polymerizable functional groups, in a derivative having the structure of formula (A3). Examples of the latter method include, based on the phenatrolinquinone halide, a method for introducing a functional group-containing aryl group using a cross-coupling reaction using a palladium catalyst and a base, a method for introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl ₃ catalyst and a base and a method for introducing a hydroxyalkyl group and a carboxyl group, causing the epoxy compound or CO _{2 to} act after e lithiation.

[0092] Derivatives having structure (A4) are commercially available, for example, from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Co., Ltd. and Johnson Matthey Japan Inc. Derivatives can also be synthesized based on the acenaphtenequinone derivative using the synthesis methods described in Tetrahedron Letters, 43 (16), 2991-2994 (2002) and Tetrahedron Letters, 44 (10), 2087-2091 (2003). The dicyanomethylene group may also be introduced by reaction with malononitrile.

[0093] The compound represented by formula (A4) has polymerizable functional groups (hydroxyl group, thiol group, amino group, carboxyl group, and methoxy group) polymerizable by a crosslinking agent. A method for introducing these polymerizable functional groups into a derivative having a structure (A4) includes a method for directly introducing polymerizable functional groups into a derivative having a structure (A4), and a method for introducing a structure having polymerizable functional groups or functional groups that can become precursors of polymerizable functional groups, in a derivative having the structure (A4). Examples of the latter method include, based on phenatrolinquinone halide, a method for introducing a functional group containing an aryl group, for example, using a cross-coupling reaction using a palladium catalyst and a base, a method for introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl catalyst ₃ and the base and method of introducing a hydroxyalkyl group and a carboxyl group, causing the epoxy compound or CO _{2 to} act After lithiation.

[0094] Derivatives having structure (A5) are commercially available, for example, from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Co., Ltd. and Johnson Matthey Japan Inc. Derivatives can also be synthesized using the fluorenone derivative and malononitrile using the synthesis method described in US patent No. 4562132. Derivatives can also be synthesized using the fluorenone derivative and aniline derivative using the synthesis methods described in Japanese Patent Application Laid-Open No. H05 -279582 and H07-70038.

[0095] The compound represented by formula (A5) has polymerizable functional groups (hydroxyl group, thiol group, amino group, carboxyl group, and methoxy group) polymerizable by a crosslinking agent. A method for introducing these polymerizable functional groups into a derivative having a structure (A5) includes a method for directly introducing polymerizable functional groups into a derivative having a structure (A5), and a method for introducing a structure having polymerizable functional groups or functional groups that can become precursors of polymerizable functional groups into a derivative having the structure (A5). Examples of the latter method include, based on fluorenone halide, a method for introducing a functional group-containing aryl group, for example, using a cross-coupling reaction using a palladium catalyst and a base, a method for introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl catalyst ₃ and a base and the method of administration hydroxyalkyl group and a carboxyl group, forcing epoxy compound or CO ₂ to act After lithiation.

[0096] Derivatives having structure (A6) can be synthesized using synthesis methods described, for example, in Chemistry Letters, 37 (3), 360-361 (2008) and Japanese Patent Application Laid-Open No. H09-151157. Derivatives are commercially available from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Co., Ltd. and Johnson Matthey Japan Inc.

[0097] The compound represented by formula (A6) has polymerizable functional groups (hydroxyl group, thiol group, amino group, carboxyl group, and methoxy group) polymerizable by a crosslinking agent. A method for introducing these polymerizable functional groups into a derivative having a structure (A6) includes a method for directly introducing polymerizable functional groups into a naphthoquinone derivative and a method for introducing a structure having polymerizable functional groups or functional groups that can become precursors of polymerizable functional groups into a naphthoquinone derivative. Examples of the latter method include, based on the naphthoquinone halide, a method for introducing a functional group-containing aryl group, for example, using a cross-coupling reaction using a palladium catalyst and a base, a method for introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl catalyst ₃ and the base and method of introducing a hydroxyalkyl group and a carboxyl group, causing the epoxy compound or CO _{2 to} act after lithiation.

[0098] Derivatives having structure (A7) can be synthesized using the synthesis methods described in Japanese Patent Application Laid-Open No. H01-206349 and Proceedings of PPCI / Japan Hard Copy '98, Proceedings, p.207 (1998). Derivatives can be synthesized, for example, using phenolic derivatives commercially available from Tokyo Chemical Industry Co., Ltd., or Sigma-Aldrich Japan Co., Ltd., as starting materials.

[0099] The compound represented by (A7) has polymerizable functional groups (hydroxyl group, thiol group, amino group, carboxyl group, and methoxy group) polymerizable by a crosslinking agent. A method for introducing these polymerizable functional groups into a derivative having a structure (A7) includes a method for introducing a structure having polymerizable functional groups or functional groups that can become precursors of polymerizable functional groups. Examples of the method include, based on the diphenoquinone halide, a method for introducing a functional group containing an aryl group, for example, using a cross-coupling reaction using a palladium catalyst and a base, a method for introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl ₃ catalyst and a base and the method of administration hydroxyalkyl group and a carboxyl group, forcing epoxy compound or CO ₂ to act after lit. ation.

[00100] Derivatives having structure (A8) can be synthesized using a well-known synthesis method described, for example, in Journal of American Chemical Society, Vol.129, No.49, 15259-78 (2007). Derivatives can also be synthesized by the reaction of perylene tetracarbonate dianhydride and a monoamine derivative commercially available from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Co., Ltd. and Johnson Matthey Japan Inc.

[00101] The compound represented by formula (A8) has polymerizable functional groups (hydroxyl group, thiol group, amino group, carboxyl group, and methoxy group) polymerizable by a crosslinking agent. A method for introducing these polymerizable functional groups into a derivative having a structure (A8) includes a method for directly introducing polymerizable functional groups into a derivative having a structure (A8), and a method for introducing a structure having polymerizable functional groups or functional groups that can become precursors of polymerizable functional groups into a derivative having the structure (A8). Examples of the latter method include, based on the peryleneimide derivative halide, a method for using a cross coupling reaction using a palladium catalyst and a base, and a method for using a cross coupling reaction using a FeCl ₃ catalyst and a base. There is a method of using a perylenetetracarboxylic dianhydride derivative or monoamine derivative having polymerizable functional groups or functional groups that can become precursors of polymerizable functional groups as starting materials for synthesizing the perylene imide derivative.

[00102] Derivatives having structure (A9) are commercially available, for example, from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Co., Ltd. and Johnson Matthey Japan Inc.

[00103] The compound represented by formula (A9) has polymerizable functional groups (hydroxyl group, thiol group, amino group, carboxyl group, and methoxy group) polymerizable by a crosslinking agent. A method for introducing these polymerizable functional groups into a derivative having a structure (A9) includes a method for introducing a structure having polymerizable functional groups or functional groups that can become precursors of polymerizable functional groups into a commercially available anthraquinone derivative. Examples of the method include, based on the anthraquinone halide, a method for introducing a functional group-containing aryl group, for example, using a cross-coupling reaction using a palladium catalyst and a base, a method for introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl ₃ catalyst and a base and the method of administration hydroxyalkyl group and a carboxyl group, forcing epoxy compound or CO ₂ to act after lithium tion.

[00104] Crosslinking agent

[00105] A crosslinking agent will then be described. As a crosslinking agent, a compound that polymerizes or crosslinks with an electron-transporting substance having polymerizable functional groups and a thermoplastic resin having polymerizable functional groups can be used. Specifically, the connections described in the Crosslinking Agent Handbook, ed. Shinzo Yamashita, Tosuke Kaneko, published by Taiseisha Ltd. (1981) (in Japanese), and the like.

[00106] The crosslinking agents used for the electron transfer layer may be isocyanate compounds and amine compounds. Crosslinking agents are more preferably crosslinking agents (isocyanate compounds, amine compounds) having 3-6 groups from an isocyanate group, a blocked isocyanate group or a monovalent group represented by —CH ₂ —OR ¹ , from the point of view of obtaining a uniform polymer layer .

[00107] An isocyanate compound having a molecular weight in the range of 200-1300 can be used as the isocyanate compound. You can also use an isocyanate compound having 3-6 isocyanate groups or blocked isocyanate groups. Examples of isocyanate compounds include isocyanurate modified, biuret modified, allophanate modified and modifications trimethylolpropane or pentaerythritol adducts triisocyanatobenzene, triizotsianatometilbenzola, triphenylmethane triisocyanate, lizintriizotsianata and, further, diisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 2,2 , 4-trimethylhexamethylene diisocyanate, me yl-2,6-diizotsianatgeksanoat and norbornane. First of all, modified isocyanurate and modified adducts are more preferred.

[00108] A blocked isocyanate group is a group having the structure —NHCOX ¹ (X ¹ is a blocking group). X ¹ may be any blocking group, provided that X ¹ can be introduced into the isocyanate group, but a group represented by one of the following formulas (H1) to (H7) is more preferred.

[00109]

[00110] Specific examples of isocyanate compounds will be described below.

[00111]

[00112]

[00113] The amine compound may be at least one compound selected from the group consisting of a compound represented by the following formula (C1), oligomers of the compounds represented by the following formula (C1), compounds represented by the following formula (C2) oligomers of compounds represented by the following formula (C2), compounds represented by the following formula (C3), oligomers of compounds represented by the following formula (C3), compounds represented by the following formula (C4), compounds of the oligomers represented by the following formula (C4), compounds represented by the following formula (C5), oligomers and the compounds represented by the following formula (C5).

[00114]

[00115] In the formulas (C1) to (C5), R ¹¹ -R ¹⁶ , R ²² -R ²⁵ , R ³¹ -R ³⁴ , R ⁴¹ -R ⁴⁴ and R ⁵¹ -R ⁵⁴ each independently represent a hydrogen atom a hydroxyl group, an acyl group or a monovalent group represented by —CH ₂ —OR ¹ ; at least one of R ¹¹ -R ¹⁶ , at least one of R ²² -R ²⁵ , at least one of R ³¹ -R ³⁴ , at least one of R ⁴¹ -R ^44, and at least one of R ⁵¹ —R ⁵⁴ are a monovalent group represented by —CH ₂ —OR ¹ ; R ¹ represents a hydrogen atom or an alkyl group having 1-10 carbon atoms; the alkyl group may be a methyl group, an ethyl group, a propyl group (n-propyl group, iso-propyl group) or a butyl group (n-butyl group, iso-butyl group, tert-butyl group), from the point of view of polymerizability; R ²¹ represents an aryl group, an alkyl group substituted by an aryl group, a cycloalkyl group or a cycloalkyl group substituted by an alkyl group.

[00116] Specific examples of the compounds represented by one of formulas (C1) to (C5) will be described below. Oligomers (multimers) of the compounds represented by one of the formulas (C1) to (C5) may be contained. Compounds (monomers) represented by one of formulas (C1) to (C5) may be contained in an amount of 10% by mass or more in the total mass of amine compounds from the point of view of obtaining a uniform polymer layer. The degree of polymerization of the above multimer may be 2 or more and 100 or less. The above multimer and monomer can be used as a mixture of two or more.

[00117] Examples of compounds represented by the above formula (C1), which are usually commercially available, include Supermelami No. 90 (manufactured by NOF Corp.), Superbekamine (R) TD-139-60, L-105-60, L127-60, L110-60, J-820-60 and G-821-60 (manufactured by DIC Corporation), Yuban 2020 (manufactured by Mitsui Chemicals Inc.), Sumitex Resin M-3 (manufactured by Sumitomo Chemical Co., Ltd.) and Nikalac MW-30, MW-390 and MX-750LM (Nihon Carbide Industries, Co., Inc.). Examples of compounds represented by the above formula (C2), which are usually commercially available, include Superbekamine (R) L-148-55, 13-535, L-145-60, and TD-126 (manufactured by Dainippon Ink and Chemicals, Inc. ) and Nikalac BL-60 and BX-4000 (Nihon Carbide Industries, Co., Inc.). Examples of compounds represented by the above formula (C3), which are usually commercially available, include Nikalac MX-280 (Nihon Carbide Industries, Co., Inc.). Examples of compounds represented by the above formula (C4), which are usually commercially available, include Nikalac MX-270 (Nihon Carbide Industries, Co., Inc.). Examples of compounds represented by the above formula (C5), which are usually commercially available, include Nikalac MX-290 (Nihon Carbide Industries, Co., Inc.).

[00118] Specific examples of compounds of formula (C1) will be described below.

[00119]

[00120]

[00121] Specific examples of compounds of formula (C2) will be described below.

[00122]

[00123] Specific examples of compounds of formula (C3) will be described below.

[00124]

[00125] Specific examples of compounds of formula (C4) will be described below.

[00126]

[00127] Specific examples of compounds of formula (C5) will be described below.

[00128]

[00129] Resin

[00130] A thermoplastic resin having polymerizable functional groups will then be described. A thermoplastic resin having polymerizable functional groups can be a thermoplastic resin having a structural unit represented by the following formula (D).

[00131]

[00132] In the formula (D), R ⁶¹ represents a hydrogen atom or an alkyl group; Y ¹ represents a single bond, an alkylene group or a phenylene group; and W ¹ represents a hydroxyl group, a thiol group, an amino group, a carboxyl group, or a methoxy group.

[00133] A resin (also referred to as resin D below) having a structural unit represented by formula (D) can be prepared by polymerizing, for example, a monomer commercially available from Sigma-Aldrich Japan Co., Ltd. and Tokyo Chemical Industry Co., Ltd. and having a polymerizable functional group (hydroxyl group, thiol group, amino group, carboxyl group and methoxy group).

[00134] Resins are usually commercially available. Examples of resins that are commercially available include polyol ether resins such as AQD-457 and AQD-473, Nippon Polyurethane Industry Co., Ltd., and Sunnix GP-400, GP-700, and the like, Sanyo Chemical Industries, Ltd. polyester-based polyol resins such as Phthalkid W2343, manufactured by Hitachi Chemical Co., Ltd., Watersol S-118 and CD-520 and Beckolite M-6402-50 and M-6201-40IM manufactured by DIC Corporation, Haridip WH-1188, manufactured by Harima Chemicals Group, Inc. and ES3604, ES6538, and the like, manufactured by Japan UPICA Co., Ltd., polyacryl polyol resins such as Burnock WE-300 and WE-304, DIC Corporation products, polyvinyl alcohol resins such as Kuraray Poval PVA- 203, manufactured by Kuraray Co., Ltd., polyvinyl acetal-based resins such as BX-1, BM-1, KS-1 and KS-5, Sekisui Chemical Co., Ltd. products, polyamide-based resins such as Toresin FS-350, manufactured by Nagase ChemteX Corp., resins containing carboxyl groups such as Aqualic, manufactured by Nippon Shokubai Co., Ltd. and Finelex SG2000, manufactured by Namariichi Co., Ltd., polyamine resins, such as Rackamide, manufactured by DIC Corporation, and polythiol resins, such as QE-340M, manufactured by Toray Industries, Inc. First of all, resins based on polyvinyl acetal, resins based on polyester polyols and the like are more preferable from the point of view of polymerizability and uniformity of the electron transfer layer.

[00135] The weight average molecular weight (Mw) of resin D may be in the range of 5000-400000, and more preferably in the range of 5000-300000. Examples of a method for the quantitative determination of polymerizable functional groups in a resin include titration of carboxyl groups using potassium hydroxide, titration of amino groups using sodium nitrite, titration of hydroxyl groups using acetic anhydride and potassium hydroxide, titration of thiol groups using 5.5'-dithiobis (2- nitrobenzoic acid) and a calibration curve method using IR spectra of samples in which the ratio of the introduction of polymerizable functional groups changes.

[00136] In Table 10 below, specific examples of resin D will be described.

[00137]

Table 10 Structure The number of moles per 1 g of functional groups Another active center Molecular mass R ⁶¹ Y W D1 H single bond OH 3.3 mmol butyral 1 × 10 ⁵ D2 H single bond OH 3.3 mmol butyral 4 × 10 ⁴ D3 H single bond OH 3.3 mmol butyral 2 × 10 ⁴ D4 H single bond OH 1.0 mmol polyolefin 1 × 10 ⁵ D5 H single bond OH 3.0 mmol ester 8 × 10 ⁴ D6 H single bond OH 2.5 mmol polyester 5 × 10 ⁴ D7 H single bond OH 2.8 mmol cellulose 3 × 10 ⁴ D8 H single bond Cool 3.5 mmol polyolefin 6 × 10 ⁴ D9 H single bond NH ₂ 1.2 mmol polyamide 2 × 10 ⁵ D10 H single bond SH 1.3 mmol polyolefin 9 × 10 ³ D11 H phenylene OH 2.8 mmol polyolefin 4 × 10 ³ D12 H single bond OH 3.0 mmol butyral 7 × 10 ⁴ D13 H single bond OH 2.9 mmol polyester 2 × 10 ⁴ D14 H single bond OH 2.5 mmol polyester 6 × 10 ³ D15 H single bond OH 2.7 mmol polyester 8 × 10 ⁴ D16 H single bond Cool 1.4 mmol polyolefin 2 × 10 ⁵ D17 H single bond Cool 2.2 mmol polyester 9 × 10 ³ D18 H single bond Cool 2.8 mmol polyester 8 × 10 ² D19 CH ₃ alkylene OH 1.5 mmol polyester 2 × 10 ⁴ D20 C ₂ H ₅ alkylene OH 2.1 mmol polyester 1 × 10 ⁴ D21 C ₂ H ₅ alkylene OH 3.0 mmol polyolefin 5 × 10 ⁴ D22 H single bond Och ₃ 2.8 mmol polyester 7 × 10 ³ D23 H single bond OH 3.3 mmol butyral 2.7 × 10 ⁵ D24 H single bond OH 3.3 mmol butyral 4 × 10 ⁵ D25 H single bond OH 2.5 mmol acetal 4 × 10 ⁵

[00138] An electron transferring material having polymerizable functional groups can be 30% by mass or more and 70% by mass or less relative to the total weight of a composition comprising an electron transferring material having polymerizable functional groups, a crosslinking agent, and a resin having polymerizable functional groups.

[00139] Conductive substrate

[00140] As the conductive substrate (also referred to as the substrate), for example, substrates made of a metal or an alloy of aluminum, nickel, copper, gold, iron or the like can be used. The substrate includes substrates in which a thin film of metallic aluminum, silver, gold or the like is formed on an insulating substrate of polyester resin, polycarbonate resin, polyimide resin, glass or the like, and substrates in which a thin film of conductive material is formed from indium oxide, tin oxide or the like.

[00141] The surface of the substrate may be subjected to a treatment, such as an electrochemical treatment, such as anodic oxidation, wet honing, inkjet and cutting, to improve electrical properties and suppress harmful inhomogeneities.

[00142] A conductive layer may be provided between the substrate and the coating sublayer described below. A conductive layer is obtained by forming a coating film on a substrate from a liquid for applying a conductive layer in which the conductive particles are dispersed in the resin, and drying the coating film. Examples of conductive particles include carbon black, acetylene black, metal powders such as aluminum, nickel, iron, nichrome, copper, zinc and silver, and metal oxide powders such as conductive tin oxide and ITO (indium tin oxide).

[00143] Examples of the resin include polyester resins, polycarbonate resins, polyvinyl butyral resins, acrylic resins, silicone resins, epoxies, melamine resins, urethane resins, phenolic resins and alkyd resins.

[00144] Examples of a solvent for applying a conductive layer include ether solvents, alcohol solvents, ketone solvents, and aromatic hydrocarbon solvents. The thickness of the conductive layer may be 0.2 μm or more and 40 μm or less, more preferably 1 μm or more and 35 μm or less, and even more preferably 5 μm or more and 30 μm or less.

[00145] a charge generation layer

[00146] A charge generation layer is provided on the coating sublayer (electron transfer layer).

[00147] The charge generating substance includes azo pigments, perylene pigments, anthraquinone derivatives, anthanthron derivatives, dibenzopyrenquinone derivatives, virantantrone derivatives, isoviolantrone derivatives, indigo derivatives, thioindigo derivatives, phthalo cyano, phthalo cyano, . First of all, at least one of the azo pigments and phthalocyanine pigments can be used. Among the phthalocyanine pigments, oxytitanium phthalocyanine, chlorogallium phthalocyanine and hydroxygallium phthalocyanine can be used.

[00148] Examples of a binder resin used for the charge generation layer include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic ester, methacrylic ester, vinylidene fluoride and trifluoroethylene, polyvinyl alcohol based resins, polyvinyl acetal resins, polycarbonate resins, polyester resins, polysulfone resins, polyphenylene oxide resins, polyurethane resins, cellulose resins, phenolic resins, melamine resins, silicone resins and epoxies. First of all, polyester resins, polycarbonate resins and polyvinyl acetal resins can be used, and polyvinyl acetal is more preferred.

[00149] In the charge generation layer, the ratio of the charge generating substance to the binder resin (charge generating substance / binder resin) may be in the range of 10/1 to 1/10, and more preferably it is in the range of 5/1 to 1 / 5. The solvent used as the liquid for applying the charge generation layer includes alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents. The thickness of the charge generation layer may be 0.05 μm or more and 5 μm or less.

[00150] Hole Transfer Layer

[00151] A hole transport layer is provided on the charge generation layer. Examples of a hole transporting substance include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, benzidine compounds and triarylamine compounds, triphenylamine and polymers having a group derived from these compounds in the main chain or side chain. First of all, triarylamine compounds, benzidine compounds and styryl compounds can be used.

[00152] Examples of a binder resin used for the hole transfer layer include polyester resins, polycarbonate resins, polymethacrylate ester resins, polyarylate resins, polysulfone resins and polystyrene resins. First of all, polycarbonate resins and polyarylate resins can be used. Regarding their molecular weight, the weight average molecular weight (Mw) may be in the range of 10,000-300,000.

[00153] In the hole transfer layer, the ratio of the hole transporting substance to the binder resin (hole transporting substance / binder resin) can be from 10/5 to 5/10, and more preferably it is from 10/8 to 6/10. The thickness of the hole transport layer may be 3 μm or more and 40 μm or less. More preferably, the thickness is 5 μm or more and 16 μm or less in terms of the thickness of the electron transfer layer. The solvent used for the liquid for applying the hole transfer layer includes alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

[00154] Another layer, such as a second coating sublayer that does not contain a polymer in accordance with the present invention, may be provided between the substrate and the electron transfer layer and between the electron transfer layer and the charge generation layer.

[00155] A surface protecting layer may be provided on the hole transfer layer. The surface protecting layer contains conductive particles or a charge transfer agent and a binder resin. The surface protecting layer may further comprise additives, such as a lubricant. The binder resin of the protective layer itself may have electrical conductivity and charge transfer ability; in this case, the protective layer should not contain conductive particles and a charge transfer substance other than a binder resin. The binder resin of the protective layer may be a thermoplastic resin, or it may be a curable resin, which may polymerize under the influence of heat, light, radiation (electron beams) or the like.

[00156] A method for forming each layer, such as an electron transfer layer, a charge generation layer and a hole transfer layer constituting the electrophotographic photosensitive member, may be a method in which a coating liquid is obtained by dissolving and / or dispersing a material constituting each layer, in a solvent, and the resulting coating film are dried and / or cured. Examples of a method for applying a coating liquid include a dip coating method, a spray coating method, a bulk coating method, and a centrifugal coating method. First of all, you can use the method of coating by immersion in terms of efficiency and productivity.

[00157] Work cartridge and electrophotographic device

[00158] Fig. 3 illustrates the basic structure of an electrophotographic device having a working cartridge with an electrophotographic photosensitive member.

[00159] In FIG. 3, reference numeral 1 denotes a cylindrical electrophotographic photosensitive member that is rotationally driven at a predetermined peripheral speed in the direction of the arrow around shaft 2 as a center. The surface (peripheral surface) of the rotationally moving electrophotographic photosensitive member 1 is uniformly charged at a given positive or negative potential using the charging unit 3 (primary charging unit: charging roller or the like). Then, the surface is exposed to irradiating light (light for exposing the image) 4 from the light irradiation unit (exposure unit, not illustrated), such as irradiating light through a slit or irradiating light with a scanning laser beam. Thus, electrostatic latent images corresponding to the target images are successively formed on the surface of the electrophotographic photosensitive member 1.

[00160] Electrostatic latent images formed on the surface of the electrophotographic photosensitive member 1 are developed using toner contained in the developer of the developing unit 5, thereby obtaining toner images. Then, the toner images formed and located on the surface of the electrophotographic photosensitive member 1 are sequentially transferred to the material to be transferred (paper or the like) P by a transfer bias voltage from the transfer unit 6 (transfer roller or the like). The material P intended for transfer is supplied from the supply unit of the material intended for transfer (not illustrated) and is supplied between the electrophotographic photosensitive member 1 and the transfer unit 6 (into the contacting part) in synchronization with the rotation of the electrophotographic photosensitive member 1.

[00161] The transfer material P with the transferred toner images is separated from the surface of the electrophotographic photosensitive member 1, inserted into the fixing unit 8 to undergo the fixing of the image, and printed as material with the generated image (print, copy) outside the device.

[00162] After the transfer of the toner image, the surface of the electrophotographic photosensitive member 1 is subjected to removal of the un transferred developer (toner) by the cleaning unit 7 (a cleaning blade or the like) for cleaning in this way. Then, the surface is subjected to a charge neutralizing treatment using irradiating light (not illustrated) from the light irradiation unit (exposure unit, not illustrated), and then it is used repeatedly for imaging. As illustrated in FIG. 3, in the case where the charging unit 3 is a contact charging unit using a charging roller or the like, light irradiation is not necessary.

[00163] Many of the constituent elements of the constituent elements, including the above-described electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, the transfer unit 6, and the cleaning unit 7, can be selected and suitably located in the container and generally comprise a working cartridge; and the working cartridge can be made detachable from the body of the electrophotographic device of a copy machine, laser printer, or the like. In Fig. 3, the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5 and the cleaning unit 7 are fully supported and are configured as a cartridge, thereby obtaining a working cartridge 9 connected to and disconnected from the body of the electrophotographic device using the guide unit 10, such as guide rails of the body of an electrophotographic device.

[00164] Examples

[00165] Next, the manufacture and evaluation of electrophotographic photosensitive elements will be described. "Parts" in the Examples means "parts by mass".

[00166] (Example 1)

[00167] An aluminum cylinder (JIS-A3003, aluminum alloy) with a length of 260.5 mm and a diameter of 30 mm was made as a substrate (conductive substrate).

[00168] Then, 50 parts of oxygen deficient tin oxide particles coated with powder (specific resistivity of powder: 120 Ohm · cm, tin oxide coating ratio: 40%), 40 parts of phenolic resin (Plyophen J-325 manufactured by DIC Corporation, content solid resin components: 60%) and 50 parts of methoxypropanol as a solvent (dispersion solvent) were placed in a sand mill using glass beads with a diameter of 0.8 mm and subjected to dispersion treatment for 3 hours, thereby obtaining a liquid dispersion. After dispersion, 0.01 parts of SH28PA silicone oil (manufactured by Dow Corning Toray Co., Ltd.) and silicone microparticles (Tospearl 120CA) as organic resin particles were added to the liquid dispersion and mixed to thereby provide a conductive layer liquid. The content of silicone microparticles was the sum of the content of solid components in it and amounted to 5% by weight of the total mass of particles of titanium oxide and phenolic resin. The liquid for applying the conductive layer was applied by immersion on a substrate, and the resulting coating film was dried and thermally polymerized for 30 min at 150 ° C, thereby forming a conductive layer having a thickness of 16 μm.

[00169] The average particle diameter of oxygen deficient tin oxide coated titanium oxide particles in the conductive layer deposition liquid was measured using a centrifugal precipitation method using tetrahydrofuran as a dispersion medium at a speed of 5000 rpm using a particle size distribution analyzer (trade name: CAPA700) manufactured by HORIBA Ltd. As a result, the average particle diameter was 0.31 μm.

[00170] Then, 4 parts of an electron transporting substance (A101), 7.3 parts of a crosslinking agent (B1: blocking group (H1) = 5.1: 2.2 (mass ratio)), 0.9 parts of a resin (D1) and 0.05 parts of dioctyltin laurate as a catalyst was dissolved in a mixed solvent of 100 parts of dimethylacetoamide and 100 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer. The liquid for applying the electron transfer layer was applied by immersion on the conductive layer, and the resulting coating film was heated for 40 minutes at 160 ° C for polymerization, thereby forming an electron transfer layer (coating sublayer) having a thickness of 0.53 μm.

[00171] The content of the electron transporting substance with respect to the total mass of the electron transporting substance, a crosslinking agent and a resin was 33% by weight.

[00172] Then, 10 parts of crystalline hydroxyl gallium phthalocyanine (a charge generating substance) having a crystalline form exhibiting strong peaks at Bragg angles (2θ ± 0.2 °) 7.5 °, 9.9 °, 12.5 °, 16, 3 °, 18.6 °, 25.1 ° and 28.3 ° for X-ray diffractometry using CuKα characteristic radiation, 0.1 parts of the compound represented by the following formula (17), 5 parts of polyvinyl butyral resin (trade name: Eslec BX- 1 manufactured by Sekisui Chemical Co., Ltd.) and 250 parts of cyclohexanone were placed in a sand mill using glass beads for ametrom 0.8 mm and subjected to a dispersion treatment for 1.5 hours. Then, thereto was added 250 parts of ethyl acetate to thereby obtain a coating liquid for the charge generating layer.

[00173]

[00174] The liquid for applying the charge generation layer was immersed on an electron transfer layer, and the resulting coating film was dried for 10 minutes at 100 ° C., thereby forming a charge generation layer having a thickness of 0.15 μm. Thus, a laminated body was formed having a conductive substrate, a conductive layer, an electron transfer layer and a charge generation layer.

[00175] Then, 4 parts of each of the triarylamine compound represented by the following formula (9-1) and a benzidine compound represented by the following formula (9-2) and 10 parts of a polyarylate resin having a repeating structural unit represented by the following formula ( 10-1), and a repeating structural unit represented by the following formula (10-2), in a 5/5 ratio, and having a weight average molecular weight (Mw) of 100,000, was dissolved in a mixed solvent of 40 parts of dimethoxymethane and 60 parts of chlorobenzene to give by thereby creating a liquid for applying a hole transport layer. The liquid for applying the hole transport layer was applied by immersion on the charge generation layer, and the resulting coating film was dried for 40 minutes at 120 ° C., thereby forming a hole transfer layer having a thickness of 15 μm.

[00176]

[00177]

[00178] Thus, an electrophotographic photosensitive member having a laminated body and a hole transport layer was manufactured to evaluate a positive re-image. In addition, as above, another electrophotographic photosensitive member was made and made for determination by an electrophotographic photosensitive member.

[00179] (Study to determine)

[00180] The electrophotographic photosensitive member described above was immersed for 5 minutes by applying an ultrasonic wave to a mixed solvent of 40 parts of dimethoxymethane and 60 parts of chlorobenzene to peel the hole transfer layer, and then the resulting product was dried for 10 minutes at 100 ° C, thereby obtaining a laminated body having a substrate, an electron transfer layer and a charge generation layer, and this laminated body was made to be determined by electrophotographic a light-sensitive element. Using the FTIR-ATR method, it was confirmed that its surface had no hole transport layer components.

[00181] Then, a measurement portion with a size of 2 cm (the peripheral direction of the electrophotographic photosensitive member) × 4 cm (the direction of its long axis) was cut from the electrophotographic photosensitive member to be determined, and a circular circular gold electrode having a thickness of 300 nm was applied to the charge generation layer and a diameter of 10 mm using the above spraying.

[00182] Then, the electrophotographic photosensitive member to be determined was allowed to stand for 24 hours in an environment with a temperature of 25 ° C and a humidity of 50% RH, and then a sample was obtained which consisted of a substrate, a conductive layer, an electron transfer layer, a generation layer charge and gold electrode, with the above method of determination. First, the entire sample was covered with a light-protective film and the impedance (R_dark) was measured when an alternating electric field of 100 mV and 0.1 Hz was applied between the conductive substrate and the gold electrode, with a frequency sweeping from 1 MHz to 0.1 Hz and provided that there was no radiation light of the surface of the charge generation layer. Next, the impedance (R_opt) was measured when an alternating electric field of 100 mV and 0.1 Hz was applied between the conductive substrate and the gold electrode, provided that the surface of the charge generation layer was irradiated with light having an irradiation intensity of 30 μJ / cm ² · s, in a state when a laser light having a wavelength of 680 nm was emitted, and the charge generation layer and the side of the sample with a gold electrode were irradiated with light so that the irradiation intensity became equal to 30 μJ / cm ² · s. From the obtained R_dark and R_opt values, R_opt / R_dark was calculated. The measurement results are shown in Table 11.

[00183] (Positive Repeat Image Evaluation)

[00184] The manufactured electrophotographic photosensitive member for evaluating a positive repeat image was mounted on an upgraded laser printer (primary charging: direct contact charging method with a charging roller, process speed: 120 mm / s, irradiation with laser light), in which the power supply unit was disconnected pre-irradiation with light (trade name: LBP-2510) manufactured by Canon Corp., and evaluated the printed image at an early stage (repeated image at an early step) and re-positive images during repeated use. Details are as follows.

[00185] 1. An early re-image

[00186] Upgraded the cyan working cartridge from the laser printer and installed a potential sensor (model: 6000B-8, manufactured by Trek Japan KK) in the developing position; and the fabricated electrophotographic photosensitive member was installed, and the potential of the central portion of the electrophotographic photosensitive member was measured in a medium with a temperature of 23 ° C. and a humidity of 50% RH using a surface electrometer (model: 344, manufactured by Trek Japan KK). The charging voltage and the intensity of the irradiating light were regulated so that the potential of the dark region (Vd) of the surface potential of the electrophotographic photosensitive element became -600 V, and the potential of its bright region (Vl) became -200 V.

[00187] Then, the electrophotographic photosensitive member was mounted on a blue print cartridge for a laser printer, and this print cartridge was installed on a blue print cartridge station and images were printed. The images were printed continuously in this order: one sheet of a solid white image, 5 sheets of an image for evaluating a repeated image, one sheet of a solid black image and 5 sheets of an image for evaluating a repeated image.

[00188] The image for evaluating the repeated image, as illustrated in FIG. 4, had a “white image” printed in its main part, in which square “solid images” were printed, and had a “halftone image of a Keima single-dot structure” illustrated in FIG. .5A received after the main part. In Fig. 4, the parts with “repeated image” were those parts where repeated images (“shadows”) caused by “solid images” could appear.

[00189] A positive re-image was evaluated by measuring the density difference between the image density of the halftone image of the Keima single-point structure described above and the image density of the re-image part. 10 density difference points were measured on a single image sheet to evaluate duplicate images using a spectrodensitometer (trade name: X-Rite 504/508, manufactured by X-Rite Inc.). This operation was carried out for all 10 sheets of image to evaluate repeated images and calculated the average value for 100 points in total. The results are shown in Table 11. It was found that a higher density of the repeated image part caused a stronger positive repeated image. This means that the smaller the density difference on the Macbeth scale, the stronger the positive repeat image is suppressed. The image density difference for the repeated image (the density difference on the Macbeth scale) of 0.05 or more gave its level having a visually obvious difference, and the image density difference for the repeated image less than 0.05 gave its level that did not have a visually obvious difference.

[00190] 2. Long-term re-image

[00191] 1000-sheet continuous printing of the image was carried out using halftone images of a single-dot structure illustrated in Fig. 5B described above, with a controlled charging voltage and a controlled irradiation light intensity, fixed at the values determined in the evaluation in the above-described section "1. Repeated image at an early stage. " Within 2 minutes after printing the image of the 1000th sheet, images were printed, as illustrated in FIG. 4, as in the case of the repeated image at an early stage, and a positive repeated image was evaluated (image density using a spectrodensitometer) after 1000-sheet printing images. The results are shown in Table 11.

[00192] (Examples 2-5)

[00193] Electrophotographic photosensitive elements were made and evaluated as in Example 1, except for changing the thickness of the electron transfer layer from 0.53 μm to 0.38 μm (Example 2), 0.25 μm (Example 3), 0.20 μm ( Example 4) and 0.15 μm (Example 5), as shown in Table 11. The results are shown in Table 11.

[00194] (Example 6)

[00195] An electrophotographic photosensitive member was fabricated and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 11.

[00196] 4 parts of an electron-transporting substance (A101), 5.5 parts of an isocyanate compound (B1: blocking group (H1) = 5.1: 2.2 (mass ratio)), 0.3 parts of resin (D1) and 0 , 05 parts of dioctyltin laurate as a catalyst was dissolved in a mixed solvent of 100 parts of dimethylacetoamide and 100 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer. Liquid for applying an electron transfer layer was applied by immersion on a conductive layer, and the resulting coating film was heated for 40 minutes at 160 ° C. for polymerization, thereby forming an electron transfer layer having a thickness of 0.61 μm.

[00197] (Examples 7-12)

[00198] Electrophotographic photosensitive elements were manufactured and evaluated as in Example 6, except for changing the thickness of the electron transfer layer from 0.61 μm to the values shown in Table 11. The results are shown in Table 11.

[00199] (Example 13)

[00200] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 11.

[00201] 5 parts of an electron-transporting substance (A-101), 2.3 parts of an amine compound (C1-3), 3.3 parts of a resin (D1) and 0.1 parts of dodecylbenzenesulfonic acid were dissolved as a catalyst in a mixed solvent of 100 parts of dimethylacetoamide and 100 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer. Liquid for applying an electron transfer layer was applied by immersion on a conductive layer, and the resulting coating film was heated for 40 minutes at 160 ° C. for polymerization, thereby forming an electron transfer layer having a thickness of 0.51 μm.

[00202] (Examples 14-17)

[00203] Electrophotographic photosensitive elements were manufactured and evaluated as in Example 13, except for changing the thickness of the electron transfer layer from 0.51 μm to the values shown in Table 11. The results are shown in Table 11.

[00204] (Example 18)

[00205] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 11.

[00206] 5 parts of an electron-transporting substance (A-101), 1.75 parts of an amine compound (C1-3), 2 parts of a resin (D1) and 0.1 part of dodecylbenzenesulfonic acid as a catalyst were dissolved in a mixed solvent of 100 parts of dimethylacetoamide and 100 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer. The liquid for applying the electron transfer layer was applied by immersion on the conductive layer, and the resulting coating film was heated for 40 minutes at 160 ° C for polymerization, thereby forming an electron transfer layer having a thickness of 0.70 μm.

[00207] (Examples 19-24)

[00208] Electrophotographic photosensitive elements were manufactured and evaluated as in Example 18, except for changing the thickness of the electron transfer layer from 0.70 μm to the values shown in Table 11. The results are shown in Table 11.

[00209] (Examples 25-45)

[00210] Electrophotographic photosensitive elements were manufactured and evaluated as in Example 6, except for replacing the electron-transporting substance from Example 6 s (A-101) with electron-transporting substances shown in Table 11, and changing the thickness of the electron transfer layer to the values shown in Table 11. The results are shown in Table 11.

[00211] (Examples 46-66)

[00212] Electrophotographic photosensitive elements were fabricated and evaluated as in Example 18, except for replacing the electron-transporting substance from Example 18 s (A-101) with electron-transporting substances shown in Table 11, and changing the thickness of the electron transfer layer to the values shown in Table 11. The results are shown in Table 11.

[00213] (Examples 67-72)

[00214] Electrophotographic photosensitive elements were manufactured and evaluated as in Example 8, except for the replacement of a crosslinking agent (B1: blocking group (H1) = 5.1: 2.2 (mass ratio)) from Example 8 with crosslinking agents shown in Table 11. The results are shown in Tables 11 and 12.

[00215] (Examples 73 and 74)

[00216] Electrophotographic photosensitive elements were made and evaluated as in Example 21, except for the replacement of the crosslinking agent (C1-3) from Example 21 with crosslinking agents shown in Table 11. The results are shown in Table 12.

[00217] (Example 75)

[00218] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 12.

[00219] 4 parts of an electron-transporting substance (A-101), 4 parts of an amine compound (C1-9), 1.5 parts of a resin (D1) and 0.2 parts of dodecylbenzenesulfonic acid as a catalyst were dissolved in a mixed solvent of 100 parts of dimethylacetoamide and 100 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer. Liquid for applying the electron transfer layer was applied by immersion on the conductive layer, and the resulting coating film was heated for 40 minutes at 160 ° C. for polymerization, thereby forming an electron transfer layer having a thickness of 0.35 μm.

[00220] (Examples 76 and 77)

[00221] Electrophotographic photosensitive elements were made and evaluated as in Example 75, with the exception of replacing the crosslinking agent (C1-9) from Example 75 with crosslinking agents shown in Table 12. The results are shown in Table 12.

[00222] (Examples 78-81)

[00223] Electrophotographic photosensitive elements were made and evaluated as in Example 9, except for replacing the resin (D1) from Example 9 with the resins shown in Table 12. The results are shown in Table 12.

[00224] (Example 82)

[00225] An electrophotographic photosensitive member was fabricated and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 12.

[00226] 6 parts of the electron-transporting substance (A-124), 2.1 parts of the amine compound (C1-3), 1.2 parts of the resin (D1) and 0.1 parts of dodecylbenzenesulfonic acid were dissolved as a catalyst in a mixed solvent of 100 parts of dimethylacetoamide and 100 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer. The liquid for applying the electron transfer layer was applied by immersion on the conductive layer, and the resulting coating film was heated for 40 minutes at 160 ° C. for polymerization, thereby forming an electron transfer layer having a thickness of 0.45 μm.

[00227] (Examples 83 and 84)

[00228] Electrophotographic photosensitive elements were fabricated and evaluated as in Example 82, except for replacing the electron-transporting substance from Example 82 s (A-124) with the electron-transporting substances shown in Table 12. The results are shown in Table 12.

[00229] (Example 85)

[00230] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 12.

[00231] 6 parts of an electron-transporting substance (A-125), 2.1 parts of an amine compound (C1-3), 0.5 parts of a resin (D1) and 0.1 parts of dodecylbenzenesulfonic acid were dissolved as a catalyst in a mixed solvent of 100 parts of dimethylacetoamide and 100 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer. The liquid for applying the electron transfer layer was applied by immersion on the conductive layer, and the resulting coating film was heated for 40 minutes at 160 ° C., thereby forming an electron transfer layer having a thickness of 0.49 μm.

[00232] (Example 86)

[00233] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 12.

[00234] 6.5 parts of an electron-transporting substance (A-125), 2.1 parts of an amine compound (C1-3), 0.4 parts of a resin (D1) and 0.1 parts of dodecylbenzenesulfonic acid were dissolved as a catalyst in a mixed solvent from 100 parts of dimethylacetoamide and 100 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer. The liquid for applying the electron transfer layer was applied by immersion on the conductive layer, and the resulting coating film was heated for 160 minutes at 160 ° C for polymerization, thereby forming an electron transfer layer having a thickness of 0.49 μm.

[00235] (Example 87-89)

[00236] An electrophotographic photosensitive member was manufactured and evaluated as in Example 85, except for changing the thickness of the electron transfer layer from 0.49 μm to the values shown in Table 12. The results are shown in Table 12.

[00237] (Example 90)

[00238] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 12.

[00239] 3.6 parts of an electron-transporting substance (A101), 7 parts of an isocyanate compound (B1: blocking group (H1) = 5.1: 2.2 (mass ratio)), 1.3 parts of a resin (D1) and 0 , 05 parts of dioctyltin laurate as a catalyst was dissolved in a mixed solvent of 100 parts of dimethylacetoamide and 100 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer. Liquid for applying an electron transfer layer was applied by immersion on a conductive layer, and the resulting coating film was heated for 40 minutes at 160 ° C. for polymerization, thereby forming an electron transfer layer having a thickness of 0.53 μm.

[00240] (Example 91)

[00241] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for changing the thickness of the charge generation layer from 0.53 μm to 0.15 μm. The results are shown in Table 12.

[00242] (Example 92)

[00243] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of a charge generation layer by the method described below. The results are shown in Table 12.

[00244] Used 10 parts of phthalocyanine oxytitanium, showing strong peaks at Bragg angles (2θ ± 0.2 °) of 9.0 °, 14.2 °, 23.9 ° and 27.1 ° when x-ray diffractometry using CuKα radiation, and 166 parts of a solution were prepared in which the polyvinyl butyral resin (trade name: Eslec BX-1, manufactured by Sekisui Chemical Co., Ltd.) was dissolved in a mixed solvent of cyclohexanone: water = 97: 3 to obtain a 5% by weight solution. The solution and 150 parts of a mixed solvent of cyclohexanone: water = 97: 3 were dispersed together for 4 hours in a sand mill using 400 parts of a glass ball with a diameter of 1 mm, and then 210 parts of a mixed solvent of cyclohexanone: water = 97: 3 were added to them. and 260 parts of cyclohexanone, thereby obtaining a liquid for applying a charge generation layer. The liquid for applying the charge generation layer was applied by immersion on an electron transfer layer, and the resulting coating film was dried for 10 minutes at 80 ° C., thereby forming a charge generation layer having a thickness of 0.20 μm.

[00245] (Example 93)

[00246] An electrophotographic photosensitive member was fabricated and evaluated as in Example 1, except for the formation of a charge generation layer by the method described below. The results are shown in Table 12.

[00247] 20 parts of a bisazopigment represented by the following structural formula (11) and 10 parts of a polyvinyl butyral resin (trade name: Eslec BX-1, manufactured by Sekisui Chemical Co., Ltd.) were mixed and dispersed in 150 parts of tetrahydrofuran, thereby liquids for applying a charge generation layer. Then, this deposition liquid was immersed on an electron transfer layer, and the obtained coating film was dried at 110 ° C. for 30 minutes, thereby forming a charge generation layer having a thickness of 0.30 μm.

[00248]

[00249] (Example 94)

[00250] An electrophotographic photosensitive member was fabricated and evaluated as in Example 1, except for replacing the benzidine compound represented by the above formula (9-2) from Example 1 with a styryl compound (hole transporting substance) represented by the following formula (9-3 ) The results are shown in Table 13.

[00251]

[00252] (Examples 95 and 96)

[00253] Electrophotographic photosensitive elements were manufactured and evaluated as in Example 1, except for changing the thickness of the hole transport layer from 15 μm to 10 μm (Example 95) and 25 μm (Example 96). The results are shown in Table 13.

[00254] (Example 97)

[00255] An aluminum cylinder (JIS-A3003, aluminum alloy) with a length of 260.5 mm and a diameter of 30 mm was made as a substrate (conductive substrate).

[00256] Then 214 parts of oxygen deficient tin oxide particles (TiO ₂ ) coated as metal oxide particles, 132 parts of phenolic resin (trade name: Plyophen J-325) as a binder resin and 98 parts of 1-methoxy -2-propanol as a solvent was placed in a sand mill using 450 parts of glass beads with a diameter of 0.8 mm and subjected to dispersion treatment under conditions of a speed of 2000 rpm, a dispersion treatment time of 4.5 hours and a predetermined cooling water temperature of 18 ° C thereby obtaining Coy dispersion. Glass beads were removed from the liquid dispersion with a sieve (sieve mesh opening: 150 μm). After removing the glass beads, silicone resin particles (trade name: Tospearl 120, manufactured by Momentive Performance Materials Inc., average particle diameter: 2 μm) were added to the liquid dispersion as a surface roughness material so that they were 10% by weight with respect to the total mass of particles of metal oxide and a binder resin in a liquid dispersion; and silicone oil (trade name: SH28PA, manufactured by Dow Corning Toray Co., Ltd.) was added to the liquid dispersion as a leveling agent so that it was 0.01% by weight relative to the total weight of the metal oxide particles and the binder resin in liquid dispersion; and the resulting mixture was mixed, thereby obtaining a liquid for applying a conductive layer. A liquid for applying a conductive layer was applied by immersion on a substrate, and the resulting coating film was dried and thermally cured for 30 minutes at 150 ° C., thereby forming a conductive layer having a thickness of 30 μm.

[00257] Then, 6.2 parts of an electron-transporting substance (A157), 8.0 parts of a crosslinking agent (B1: blocking group (H5) = 5.1: 2.9 (mass ratio)), 1.1 parts of a resin (D25 ) and 0.05 parts of zinc (II) hexanoate as a catalyst were dissolved in a mixed solvent of 100 parts of dimethylacetoamide and 100 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer. The liquid for applying the electron transfer layer was applied by immersion on the conductive layer, and the resulting coating film was heated for 40 minutes at 160 ° C for polymerization, thereby forming an electron transfer layer (coating sublayer) having a thickness of 0.53 μm. The content of the electron-transporting substance with respect to the total mass of the electron-transporting substance, crosslinking agent and resin was 34% by weight.

[00258] Then formed a charge generation layer having a thickness of 0.15 μm, as in Example 1.

[00259] 9 parts of a triarylamine compound represented by the above structural formula (9-1), 1 part of a benzidine compound (hole transporting substance) represented by the following structural formula (18), 3 parts of a polyester resin E (weight average molecular weight: 90,000) having a repeating structural unit represented by the following formula (24) and a repeating structural unit represented by the following formula (26) and a repeating structural unit represented by the following formula (25) in in a ratio of 7: 3 and 7 parts of a polyester resin F (weight average molecular weight: 120,000) having a repeating structural unit represented by the following formula (27) and a repeating structural unit represented by the following formula (28) in a 5: 5 ratio , was dissolved in a mixed solvent of 30 parts of dimethoxymethane and 50 parts of orthoxylene, thereby obtaining a liquid for applying a hole transport layer. The content of the repeating structural units represented by the following formula (24) in the polyester resin E was 10% by mass, and the content of the repeating structural units represented by the following formulas (25) and (26) was 90% by mass .

[00260]

[00261]

[00262] The liquid for applying the hole transport layer was immersed on the charge generation layer and dried for 1 h at 120 ° C., thereby forming a hole transfer layer having a thickness of 16 μm. It was confirmed that the formed hole transfer layer had a domain structure in which the matrix containing the hole transporting substance and the polyester resin F contained the polyester resin E.

[00263] The evaluation was carried out as in Example 1. The results are shown in Table 13.

[00264] (Example 98)

[00265] An electrophotographic photosensitive member was made as in Example 1, except for forming a hole transport layer by the method described below. The results are shown in Table 13.

[00266] 9 parts of a triarylamine compound represented by the above structural formula (9-1), 1 part of a benzidine compound represented by the above structural formula (18), 10 parts of a polycarbonate resin G (weight average molecular weight: 70,000) having a repeating structural unit represented by the following formula (29) and 0.3 parts of a polycarbonate resin H (weight average molecular weight: 40,000) having a repeating structural unit represented by the following formula (29), repeating structural unit nitsu represented by the following formula (30), and structure the at least one terminal group represented by the following formula (31) was dissolved in a mixed solvent of 30 parts of dimethoxymethane and 50 parts of o-xylene to thereby obtain a liquid for application of the hole transport layer. Moreover, the total mass of the structures represented by the following formulas (30) and (31) in the polycarbonate resin H was 30% by weight. The liquid for applying the hole transport layer was applied by immersion on the charge generation layer and dried for 1 h at 120 ° C, thereby forming a hole transport layer having a thickness of 16 μm.

[00267]

[00268] (Example 99)

[00269] An electrophotographic photosensitive member was manufactured and evaluated as in Example 98, except for replacing 10 parts of polycarbonate resin G (weight average molecular weight: 70,000) in a liquid for applying a hole transfer layer from Example 98 to 10 parts of polyester resin F (weight average molecular weight: 120,000). The results are shown in Table 13.

[00270] (Example 100)

[00271] An electrophotographic photosensitive member was manufactured and evaluated as in Example 97, except for the formation of a conductive layer as follows. The results are shown in Table 13.

[00272] 207 parts of particles of titanium oxide (TiO ₂ ) coated with tin oxide (SnO ₂ ) doped with phosphorus (P) as metal oxide particles, 144 parts of phenolic resin (trade name: Plyophen J-325) as a binder resin and 98 parts of 1-methoxy-2-propanol as a solvent were placed in a sand mill using 450 parts of glass beads with a diameter of 0.8 mm and subjected to dispersion treatment under conditions of a speed of 2000 rpm, a dispersion treatment time of 4.5 hours and a predetermined cooling water temperature of 18 ° C, thereby obtaining idkoy dispersion. Glass beads were removed from the liquid dispersion with a sieve (sieve mesh opening: 150 μm).

[00273] After removing the glass beads, silicone resin particles (trade name: Tospearl 120) were added to the liquid dispersion as a surface roughness material so that they were 15% by weight relative to the total mass of the metal oxide and binder resin in the liquid dispersion ; and silicone oil (trade name: SH28PA) was added to the liquid dispersion as a leveling agent so that it was 0.01% by weight relative to the total mass of the metal oxide particles and the binder resin in the liquid dispersion; and the resulting mixture was mixed, thereby obtaining a liquid for applying a conductive layer. A liquid for applying a conductive layer was applied by immersion on a substrate, and the resulting coating film was dried and thermally cured for 30 minutes at 150 ° C., thereby forming a conductive layer having a thickness of 30 μm.

[00274] (Examples 101-119)

[00275] Electrophotographic photosensitive elements were manufactured and evaluated as in Example 97, except for replacing the electron-transporting substance from Example 97 s (A157) with the electron-transporting substances shown in Table 13. The results are shown in Table 13.

[00276] (Comparative example 1)

[00277] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 12.

[00278] 2.4 parts of an electron-transporting substance (A101), 4.2 parts of an isocyanate compound (B1: blocking group (H1) = 5.1: 2.2 (mass ratio)), 5.4 parts of a resin (D1) and 0.05 parts of dioctyltin laurate as a catalyst was dissolved in a mixed solvent of 100 parts of dimethylacetoamide and 100 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer. Liquid for applying an electron transfer layer was applied by immersion on a conductive layer, and the resulting coating film was heated for 40 minutes at 160 ° C. for polymerization, thereby forming an electron transfer layer having a thickness of 0.53 μm.

[00279] (Comparative example 2)

[00280] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 12.

[00281] 3.2 parts of an electron-transporting substance (A101), 5 parts of an isocyanate compound (B1: blocking group (H1) = 5.1: 2.2 (mass ratio)), 4.2 parts of resin (D1) and 0 , 05 parts of dioctyltin laurate as a catalyst was dissolved in a mixed solvent of 100 parts of dimethylacetoamide and 100 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer. Liquid for applying an electron transfer layer was applied by immersion on a conductive layer, and the resulting coating film was heated for 40 minutes at 160 ° C. for polymerization, thereby forming an electron transfer layer having a thickness of 0.53 μm.

[00282] (Comparative Examples 3 and 4)

[00283] Electrophotographic photosensitive elements were manufactured and evaluated as in Comparative Example 2, except for changing the thickness of the electron transfer layer from 0.53 μm to 0.40 μm and 0.32 μm. The results are shown in Table 12.

[00284] (Comparative Examples 5-8)

[00285] Electrophotographic photosensitive elements were manufactured and evaluated as in Example 1, except for changing the thickness of the electron transfer layer from 0.53 μm to 0.78 μm, 1.03 μm, 1.25 μm and 1.48 μm. The results are shown in Table 12.

[00286] (Comparative example 9)

[00287] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 12.

[00288] 4 parts of an electron-transporting substance (A225), 3 parts of hexamethylene diisocyanate and 4 parts of a resin (D1) were dissolved in a mixed solvent of 100 parts of dimethylacetoamide and 100 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer. Liquid for applying an electron transfer layer was applied by immersion on a conductive layer, and the resulting coating film was heated for 160 minutes at 160 ° C. for polymerization, thereby forming an electron transfer layer having a thickness of 1.00 μm.

[00289] (Comparative example 10)

[00290] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 12.

[00291] 5 parts of an electron-transporting substance (A124), 2.5 parts of 2,4-toluene diisocyanate and 2.5 parts of poly (p-hydroxystyrene) (trade name: Malkalinker, manufactured by Maruzen Petrochemical Co., Ltd.) were dissolved in a mixed a solvent of 100 parts of dimethylacetoamide and 100 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer. The liquid for applying the electron transfer layer was applied by immersion on the conductive layer, and the resulting coating film was heated for 160 minutes at 160 ° C. for polymerization, thereby forming an electron transfer layer having a thickness of 0.40 μm.

[00292] (Comparative example 11)

[00293] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 12.

[00294] 7 parts of an electron-transporting substance (A124), 2 parts of 2,4-toluene diisocyanate and 1 part of poly (p-hydroxystyrene) were dissolved in a mixed solvent of 100 parts of dimethylacetoamide and 100 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer . The liquid for applying the electron transfer layer was applied by immersion on the conductive layer, and the resulting coating film was heated for 160 minutes at 160 ° C. for polymerization, thereby forming an electron transfer layer having a thickness of 0.40 μm.

[00295]

Table 11 Example Electron transporting substance Crosslinking agent Resin The proportion of electron-transporting substance Coating sublayer thickness R_opt /
R_dark Early reproduction Repeated image after 1000 sheets The difference between repeated images one A101 B1: H1 D1 33% 0.53 0.85 0,03 0,03 0.00 2 A101 B1: H1 D1 33% 0.38 0.85 0,03 0,03 0.00 3 A101 B1: H1 D1 33% 0.25 0.85 0,03 0,03 0.00 four A101 B1: H1 D1 33% 0.20 0.85 0,03 0,03 0.00 5 A101 B1: H1 D1 33% 0.15 0.95 0.04 0.05 0.01 6 A101 B1: H1 D1 41% 0.61 0.75 0.02 0.02 0.00 7 A101 B1: H1 D1 41% 0.52 0.75 0.02 0.02 0.00 8 A101 B1: H1 D1 41% 0.40 0.85 0,03 0,03 0.00 9 A101 B1: H1 D1 41% 0.25 0.85 0,03 0,03 0.00 10 A101 B1: H1 D1 41% 0.70 0.85 0,03 0,03 0.00 eleven A101 B1: H1 D1 41% 0.90 0.90 0.04 0.05 0.01 12 A101 B1: H1 D1 41% 1.10 0.95 0.04 0.05 0.01 13 A101 C1-3 D1 47% 0.51 0.75 0.02 0.02 0.00 fourteen A101 C1-3 D1 47% 0.45 0.75 0.01 0.01 0.00 fifteen A101 C1-3 D1 47% 0.34 0.75 0.02 0.02 0.00 16 A101 C1-3 D1 47% 0.70 0.85 0.02 0.02 0.00 17 A101 C1-3 D1 47% 0.91 0.93 0,03 0.04 0.01 eighteen A101 C1-3 D1 57% 0.70 0.85 0,03 0,03 0.00 19 A101 C1-3 D1 57% 0.58 0.75 0.02 0.02 0.00 twenty A101 C1-3 D1 57% 0.50 0.75 0.02 0.02 0.00 21 A101 C1-3 D1 57% 0.35 0.85 0,03 0,03 0.00 22 A101 C1-3 D1 57% 0.92 0.90 0,03 0.04 0.01 23 A101 C1-3 D1 57% 1,11 0.93 0,03 0.04 0.01 24 A101 C1-3 D1 57% 1.32 0.95 0.04 0.05 0.01 25 A106 B1: H1 D1 41% 0.52 0.75 0.02 0.02 0.00 25 A125 B1: H1 D1 41% 0.52 0.75 0.02 0.02 0.00 27 A125 B1: H1 D1 41% 0.20 0.75 0.02 0.02 0.00 28 A125 B1: H1 D1 41% 0.70 0.75 0.02 0.02 0.00 29th A136 B1: H1 D1 41% 0.51 0.75 0.02 0.02 0.00 thirty A136 B1: H1 D1 41% 0.21 0.75 0.02 0.02 0.00 31 A136 B1: H1 D1 41% 0.69 0.75 0.02 0.02 0.00 32 A116 B1: H1 D1 41% 0.52 0.85 0,03 0,03 0.00 33 A119 B1: H1 D1 41% 0.52 0.85 0,03 0,03 0.00 34 A120 B1: H1 D1 41% 0.52 0.85 0,03 0,03 0.00 35 A124 B1: H1 D1 41% 0.52 0.85 0,03 0,03 0.00 35 A130 B1: H1 D1 41% 0.52 0.95 0.04 0.05 0.01 37 A156 B1: H1 D1 41% 0.52 0.95 0.04 0.05 0.01 38 A214 B1: H1 D1 41% 0.52 0.95 0.04 0.05 0.01 39 A310 B1: H1 D1 41% 0.52 0.95 0.04 0.05 0.01 40 A423 B1: H1 D1 41% 0.52 0.95 0.04 0.05 0.01 41 A523 B1: H1 D1 41% 0.52 0.95 0.04 0.05 0.01 42 A618 B1: H1 D1 41% 0.52 0.95 0.04 0.05 0.01 43 A731 B1: H1 D1 41% 0.52 0.95 0.04 0.05 0.01 44 A819 B1: H1 D1 41% 0.52 0.95 0.04 0.05 0.01 45 A919 B1: H1 D1 41% 0.52 0.95 0.04 0.05 0.01 46 A106 C1-3 D1 57% 0.48 0.65 0.01 0.01 0.00 47 A113 C1-3 D1 57% 0.48 0.65 0.01 0.01 0.00 4S A116 C1-3 D1 57% 0.48 0.65 0.01 0.01 0.00 49 A120 C1-3 D1 57% 0.48 0.65 0.01 0.01 0.00 fifty A124 C1-3 D1 57% 0.48 0.65 0.01 0.01 0.00 51 A136 C1-3 D1 57% 0.48 0.65 0.01 0.01 0.00 52 A136 C1-3 D1 57% 0.15 0.85 0.02 0.02 0.00 53 A136 C1-3 D1 57% 0.65 0.60 0.01 0.01 0.00 54 A136 C1-3 D1 57% 0.75 0.65 0.01 0.01 0.00

[00296]

Table 12 Example Electron transporting substance Crosslinking agent Resin Proportion of electron-transporting substance Sublayer thickness
coverings R_opt /
R_dark Early reproduction Repeated image after 1000 sheets The difference between repeated images 55 A136 C1-3 D1 57% 0.90 0.75 0.02 0.02 0.00 56 A136 C1-3 D1 57% 1.12 0.77 0.02 0.02 0.00 57 A136 C1-3 D1 57% 1.30 0.80 0.02 0.02 0.00 58 A201 C1-3 D1 57% 1.30 0.85 0,03 0,03 0.00 59 A306 C1-3 D1 57% 1.30 0.85 0,03 0,03 0.00 60 A306 C1-3 D1 57% 1.30 0.75 0.02 0.02 0.00 61 A404 C1-3 D1 57% 1.30 0.75 0.02 0.02 0.00 62 A510 C1-3 D1 57% 1.30 0.75 0.02 0.02 0.00 63 A602 C1-3 D1 57% 1.30 0.85 0,03 0,03 0.00 64 A709 C1-3 D1 57% 1.30 0.85 0,03 0,03 0.00 65 A807 C1-3 D1 57% 1.30 0.75 0.02 0.02 0.00 66 A902 C1-3 D1 57% 1.30 0.75 0.02 0.02 0.00 67 A101 B1: H2 D1 41% 0.40 0.85 0,03 0,03 0.00 68 A101 B1: H3 D1 41% 0.40 0.85 0,03 0,03 0.00 69 A101 B4: H1 D1 41% 0.40 0.85 0,03 0,03 0.00 70 A101 B5: H1 D1 41% 0.40 0.85 0,03 0,03 0.00 71 A101 B7: H1 D1 41% 0.40 0.85 0,03 0,03 0.00 72 A101 B12: H1 D1 41% 0.40 0.85 0,03 0,03 0.00 73 A101 C1-1 D1 57% 0.35 0.75 0.02 0.02 0.00 74 A101 C1-7 D1 57% 0.35 0.75 0.02 0.02 0.00 75 A101 C1-9 D1 41% 0.35 0.75 0.02 0.02 0.00 76 A101 C2-1 D1 41% 0.35 0.75 0.02 0.02 0.00 77 A101 C3-3 D1 41% 0.35 0.75 0.02 0.02 0.00 78 A101 B1: H1 D3 41% 0.26 0.85 0,03 0,03 0.00 79 A101 B1: H1 D5 41% 0.26 0.85 0,03 0,03 0.00 80 A101 B1: H1 D19 41% 0.26 0.85 0,03 0,03 0.00 81 A101 B1: H1 D20 41% 0.26 0.85 0,03 0,03 0.00 82 A124 C1-3 D1 65% 0.45 0.65 0.01 0.01 0.00 83 A130 C1-3 D1 65% 0.45 0.65 0.01 0.01 0.00 84 A156 C1-3 D1 65% 0.45 0.65 0.01 0.01 0.00 85 A125 C1-3 D1 70% 0.49 0.65 0.01 0.01 0.00 86 A125 C1-3 D1 72% 0.49 0.75 0.02 0.02 0.00 87 A125 C1-3 D1 70% 0.70 0.75 0.02 0.02 0.00 88 A125 C1-3 D1 70% 0.95 0.75 0.02 0.02 0.00 89 A125 C1-3 D1 70% 1.24 0.80 0,03 0,03 0.00 90 A101 B1: H1 D1 thirty% 0.53 0.95 0.04 0.05 0.01 91 A101 B1: H1 D1 33% 0.15 0.85 0,03 0,03 0.00 92 A101 B1: H1 D1 33% 0.53 0.95 0.04 0.05 0.01 93 A101 B1: H1 D1 33% 0.53 0.85 0,03 0,03 0.00 Comp. example 1 A101 B1: H1 D1 twenty% 0.53 0.99 0.1 0.13 0,03 Comp. example 2 A101 B1: H1 D1 25% 0.53 0.98 0,07 0.10 0,03 Comp. example 3 A101 B1: H1 D1 25% 0.40 0.98 0,07 0.10 0,03 Comp. example 4 A101 B1: H1 D1 25% 0.32 0.97 0,07 0.09 0.02 Comp. example 5 A101 B1: H1 D1 33% 0.78 0.98 0.06 0.09 0,03 Comp. example 6 A101 B1: H1 D1 33% 1,03 0.99 0,07 0.10 0,03 Comp. example 7 A101 B1: H1 D1 33% 1.25 0.99 0.08 0.11 0,03 Comp. example 8 A101 B1: H1 D1 33% 1.48 one 0.09 0.13 0.04 Comp. example 9 A225 hexamethylene diisocyanate D1 36% 1.00 0.99 0,07 0.10 0,03 Comp. example 10 A124 2,4-toluene diisocyanate poly (p-hydroxy styrene) fifty% 0.40 0.99 0,07 0.10 0,03 Comp. example 11 A124 2,4-toluene diisocyanate poly (p-hydroxy styrene) 70% 0.40 0.98 0.06 0.09 0,03

[00297]

Table 13 Example Electron transporting substance Crosslinking agent Resin The proportion of electron-transporting substance Sublayer thickness
coverings R_opt / R_dark Early reproduction Repeated image after 1000 sheets The difference between repeated images 94 A101 B1: H1 D1 33% 0.53 0.85 0,03 0,03 0.00 95 A106 B1: H6 D14 33% 0.53 0.85 0,03 0,03 0.00 96 A107 B1: H7 D15 33% 0.53 0.85 0.04 0.04 0.00 97 A157 B1: H5 D25 41% 0.47 0.80 0,03 0,03 0.00 98 A157 B1: H5 D25 41% 0.47 0.80 0,03 0,03 0.00 99 A157 B1: H5 D25 41% 0.47 0.80 0,03 0,03 0.00 one hundred A157 B1: H5 D25 41% 0.47 0.80 0.04 0.04 0.00 101 A124 B1: H5 D25 41% 0.47 0.80 0.04 0.04 0.00 102 A125 B1: H5 D25 41% 0.47 0.70 0,03 0,03 0.00 103 A152 B1: H5 D25 41% 0.47 0.85 0.04 0.04 0.00 104 A159 B1: H5 D25 41% 0.47 0.70 0,03 0,03 0.00 105 A164 B1: H5 D25 41% 0.47 0.65 0,03 0,03 0.00 106 A166 B1: H5 D25 41% 0.47 0.85 0.04 0.04 0.00 107 A167 B1: H5 D25 41% 0.47 0.80 0.04 0.04 0.00 108 A168 B1: H5 D25 41% 0.47 0.70 0,03 0,03 0.00 109 A172 B1: H5 D25 41% 0.47 0.75 0,03 0,03 0.00 110 A177 B1: H5 D25 41% 0.47 0.65 0,03 0,03 0.00 111 A178 B1: H5 D25 41% 0.47 0.65 0,03 0,03 0.00 112 A207 B1: H5 D25 41% 0.47 0.85 0.04 0.04 0.00 113 A315 B1: H5 D25 41% 0.47 0.85 0.04 0.04 0.00 114 A402 B1: H5 D25 41% 0.47 0.70 0,03 0,03 0.00 115 A509 B1: H5 D25 41% 0.47 0.70 0,03 0,03 0.00 116 A602 B1: H5 D25 41% 0.47 0.80 0.04 0.04 0.00 117 A707 B1: H5 D25 41% 0.47 0.65 0,03 0,03 0.00 118 A819 B1: H5 D25 41% 0.47 0.65 0,03 0,03 0.00 119 A908 B1: H5 D25 41% 0.47 0.70 0,03 0,03 0.00

[00298] (Comparative example 12)

[00299] An electrophotographic photosensitive member was made and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 14.

[00300] 5 parts of an electron-transporting substance (A922), 13.5 parts of an isocyanate compound (Sumidule 3173, manufactured by Sumitomo Bayer Urethane Co., Ltd.), 10 parts of butyral resin (BM-1, manufactured by Sekisui Chemical Co., Ltd. ) and 0.005 parts of dioctyltin laurate as a catalyst were dissolved in a solvent of 120 parts of methyl ethyl ketone, thereby obtaining a liquid for applying an electron transfer layer. The liquid for applying the electron transfer layer was applied by immersion on the conductive layer, and the resulting coating film was heated for 40 minutes at 170 ° C. for polymerization, thereby forming an electron transfer layer having a thickness of 1.00 μm.

[00301] (Comparative example 13)

[00302] An electrophotographic photosensitive member was fabricated and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 14.

[00303] 5 parts of an electron-transporting substance (A101) and 2.4 parts of a melamine resin (Yuban 20HS, manufactured by Mitsui Chemicals Inc.) were dissolved in a mixed solvent of 50 parts of tetrahydrofuran and 50 parts of methoxypropanol, thereby obtaining a liquid for applying an electron transfer layer . The liquid for applying the electron transfer layer was applied by immersion on the conductive layer, and the resulting coating film was heated for 60 minutes at 150 ° C. for polymerization, thereby forming an electron transfer layer having a thickness of 1.00 μm.

[00304] (Comparative example 14)

[00305] An electrophotographic photosensitive member was fabricated and evaluated as in Comparative Example 12, except for changing the thickness of the electron transfer layer from 1.00 μm to 0.50 μm. The results are shown in Table 14.

[00306] (Comparative example 15)

[00307] An electrophotographic photosensitive member was fabricated and evaluated as in Comparative Example 12, except for replacing the melamine resin (Yuban 20HS, manufactured by Mitsui Chemicals Inc.) with an electron transfer layer to a phenolic resin (Plyophen J-325, manufactured by DIC Corporation). The results are shown in Table 14.

[00308] (Comparative example 16)

[00309] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 14.

[00310] 10 parts of a mixture of a compound having the structure represented by the following formula (12-1) and a compound having a structure represented by the following formula (12-2) were dissolved in a mixed solvent of 30 parts of N-methyl-2- pyrrolidone and 60 parts of cyclohexanone, thereby obtaining a liquid for applying an electron transfer layer. The liquid for applying the electron transfer layer was applied by immersion on the conductive layer, and the resulting coating film was heated for 30 minutes at 150 ° C for polymerization, thereby forming an electron transfer layer having the structure represented by the following formula (12-3) and having a thickness of 0.20 microns.

[00311]

[00312] (Comparative Examples 17 and 18)

[00313] Electrophotographic photosensitive elements were made and evaluated as in Comparative Example 16, except for changing the thickness of the electron transfer layer from 0.20 μm to 0.30 μm and 0.60 μm. The results are shown in Table 14.

[00314] (Comparative example 19)

[00315] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 14.

[00316] 10 parts of an electron-transporting substance represented by the following formula (13) were dissolved in 60 parts of toluene, thereby obtaining a liquid for applying an electron transfer layer. A liquid for applying an electron transfer layer was applied by immersion on a conductive layer, and the resulting coating film was irradiated with electron beams under conditions of an accelerating voltage of 150 kV and an irradiation dose of 10 Mrad for polymerization, thereby forming an electron transfer layer having a thickness of 1.00 μm.

[00317]

[00318] (Comparative example 20)

[00319] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 14.

[00320] 5 parts of the electron-transporting substance represented by the above formula (13), 5 parts of trimethylol propane triacrylate (Kayarad TMPTA, Nippon Kayaku Co., Ltd.) and 0.1 parts of AIBN (2,2-azobisisobutyronitrile) were dissolved in 190 parts of tetrahydrofuran (THF), thereby obtaining a liquid for applying an electron transfer layer. Liquid for applying an electron transfer layer was applied by immersion on a conductive layer, and the resulting coating film was heated for 30 minutes at 150 ° C for polymerization, thereby forming an electron transfer layer having a thickness of 0.80 μm.

[00321] (Comparative example 21)

[00322] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 14.

[00323] 5 parts of the electron transporting substance represented by the above formula (13) and 5 parts of a compound represented by the following formula (14) were dissolved in 60 parts of toluene, thereby obtaining a liquid for applying an electron transfer layer. A liquid for applying an electron transfer layer was applied by immersion on a conductive layer, and the resulting coating film was irradiated with electron beams under conditions of an accelerating voltage of 150 kV and an irradiation dose of 10 Mrad for polymerization, thereby forming an electron transfer layer having a thickness of 1.00 μm.

[00324]

[00325] (Comparative example 22)

[00326] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 14.

[00327] An electron transfer layer (structure according to Example 1 from the national publication of International Patent Application No. 2009-505156) was formed using a block copolymer represented by the following structure, a blocked isocyanate and a vinyl chloride-vinyl acetate copolymer, thereby forming an electron transfer layer having a thickness of 0.32 μm.

[00328]

[00329] (Comparative example 23)

[00330] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 14.

[00331] 5 parts of an electron-transporting substance (A101) and 5 parts of a polycarbonate resin (Z200 manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in a mixed solvent of 50 parts of dimethylacetoamide and 50 parts of chlorobenzene, thereby obtaining a liquid for applying a transfer layer electrons. Liquid for applying an electron transfer layer was applied by immersion on a conductive layer, and the resulting coating film was heated for 30 minutes at 120 ° C. for polymerization, thereby forming an electron transfer layer having a thickness of 1.00 μm.

[00332] (Comparative example 24)

[00333] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 14.

[00334] 5 parts of an electron-transporting substance (pigment) represented by the following structural formula (16) was added to a liquid in which 5 parts of a resin (D1) were dissolved in 200 parts of methyl ethyl ketone and subjected to a dispersion treatment for 3 hours using a sand mills, thereby obtaining a liquid for applying an electron transfer layer. The liquid for applying the electron transfer layer was applied by immersion on the conductive layer, and the resulting coating film was heated for 10 minutes at 100 ° C., thereby forming an electron transfer layer having a thickness of 1.50 μm.

[00335]

[00336] (Comparative example 25)

[00337] An electrophotographic photosensitive member was fabricated and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 14.

[00338] An electron transfer layer was formed by using a liquid to deposit an electron transfer layer in which the polymer of the electron transfer agent described in Example 1 of Japanese Patent No. 4,594,444 was dissolved in a solvent, thereby forming an electron transfer layer having a thickness of 2.00 microns.

[00339] (Comparative example 26)

[00340] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 14.

[00341] An electron transfer layer was formed by using particles of a copolymer containing an electron transfer substance described in Example 1 of Japanese Patent No. 4,594,444, thereby forming an electron transfer layer having a thickness of 1.00 μm.

[00342] (Comparative example 27)

[00343] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 14.

[00344] An electron transfer layer (structure of Example 1 of Japanese Patent Application Laid-open No. 2006-030698) was formed by using a zinc oxide pigment that was subjected to a surface treatment with a silane coupling agent, alizarin (A922), a blocked isocyanate compound and butyral resin, with thereby forming an electron transfer layer 25 microns thick.

[00345] (Comparative example 28)

[00346] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 14.

[00347] 5 parts of a polyamide resin (N-methoxymethylated 6-nylon resin (trade name: Toresin EF-30T, manufactured by Nagase ChemteX Corp., polymerization degree: 420, methoxymethylation ratio: 36.8%)) was dissolved in 100 parts methanol and 100 parts of 1-butanol, thereby obtaining a coating liquid. The coating sublayer fluid was applied by immersion on the conductive layer, and the resulting coating film was dried at 100 ° C. for 10 minutes, thereby forming a coating sublayer.

[00348] (Comparative example 29)

[00349] An electrophotographic photosensitive member was manufactured and evaluated as in Example 1, except for the formation of an electron transfer layer by the method described below. The results are shown in Table 14.

[00350] An electron transfer layer was formed (a coating sublayer using an electron transferring pigment, polyvinyl butyral resin and a curable electron transfer substance having an alkoxysilyl group) described in Example 25 of Japanese Patent Application Laid-Open No. H11-119458.

[00351]

Table 14 Electron Transfer Layer Thickness R_opt / R_dark Early reproduction Repeated image after 1000 sheets The difference between repeated images Reference Example 12 1.00 0.99 0.10 0.13 0,03 Reference Example 13 1.00 1.00 0,07 0.10 0,03 Reference Example 14 0.50 1.00 0.06 0.10 0.04 Reference Example 15 1.00 1.01 0.08 0.12 0.04 Reference Example 16 0.20 0.99 0,07 0.10 0,03 Reference Example 17 0.30 0.99 0,07 0.10 0,03 Reference Example 18 0.60 1.00 0.08 0.11 0,03 Reference Example 19 1.00 0.99 0.09 0.12 0,03 Reference Example 20 0.80 0.99 0.09 0.13 0.04 Reference Example 21 1.00 0.99 0.10 0.13 0,03 Reference Example 22 0.32 0.99 0,07 0.10 0,03 Reference Example 23 1.00 0.99 0.09 0.13 0.04 Reference Example 24 1,50 1.00 0.10 0.13 0,03 Reference Example 25 2.00 1,02 0.10 0.14 0.04 Reference Example 26 1.00 1.10 0.11 0.14 0,03 Reference Example 27 25.00 1.05 0.11 0.15 0.04 Reference Example 28 0.80 1.10 0.05 0.12 0,07 Reference Example 29 3.00 0.99 0.06 0.09 0,03

[00352] Although the present invention has been described with reference to exemplary embodiments, it should be understood that the present invention is not limited to the described exemplary embodiments. The scope of the following claims should be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.

Claims (8)

1. Electrophotographic photosensitive element containing:
a laminated body that contains a conductive substrate, an electron transfer layer formed on the substrate, a charge generation layer formed on the electron transfer layer, and a hole transfer layer formed on the charge generation layer,
wherein the electron transfer layer is a layer containing a polymerized product of a composition containing an electron-transporting substance having a polymerizable functional group, a thermoplastic resin having a polymerizable functional group, and a crosslinking agent, wherein the electron-transporting substance having the polymerizable functional group has a content of 30% by weight or more and 70% by weight or less with respect to the total weight of the composition, and
while the laminated body satisfies the following expression (1):
R_opt / R_dark≤0.95 (1),
where R_opt represents the impedance of the laminated body, measured using stages:
forming on the surface of the charge generation layer a circular circular gold electrode having a thickness of 300 nm and a diameter of 10 mm, by sputtering, and
applications between the conductive substrate and the circular circular gold electrode of an alternating electric field having a voltage of 100 mV and a frequency of 0.1 Hz, while irradiating the surface of the charge generation layer with light having an intensity of 30 μJ / cm ² · s, and
impedance measurements, and
R_dark is the impedance of a laminated body, measured using the steps of:
forming on the surface of the charge generation layer a circular circular gold electrode having a thickness of 300 nm and a diameter of 10 mm, by sputtering, and
applying between the conductive substrate and the circular circular-shaped gold electrode an alternating electric field having a voltage of 100 mV and a frequency of 0.1 Hz without irradiating the surface of the charge generation layer with light, and
impedance measurements. 2. An electrophotographic photosensitive element according to claim 1, wherein the laminated body satisfies the following expression (2):
0 <R_opt / R_dark≤0, 85 (2). 3. An electrophotographic photosensitive member according to claim 1 or 2, wherein the electron transfer layer has a thickness of 0.2 μm or more and 0.7 μm or less. 4. The electrophotographic photosensitive element according to claim 1, wherein the crosslinking agent is a compound having 3-6 groups of an isocyanate group, a compound having 3-6 groups of a blocked isocyanate group, or a compound having 3-6 groups of an isovalent group, represented as —CH ₂ —OR ¹ where R ¹ represents an alkyl group. 5. An electrophotographic photosensitive member according to claim 1 or 2, wherein the charge generating layer comprises at least one charge generating substance selected from the group consisting of phthalocyanine pigments and azo pigments. 6. An electrophotographic photosensitive member according to claim 1 or 2, wherein the hole transport layer contains at least one hole transporting substance selected from the group consisting of triarylamino compounds, benzidine compounds and styryl compounds. 7. A working cartridge removably attached to the main body of an electrophotographic device, while the working cartridge fully supports:
an electrophotographic photosensitive member according to claim 1 and
at least one node selected from the group consisting of a charging unit, a developing unit, a transfer unit, and a cleaning unit. 8. An electrophotographic device comprising an electrophotographic photosensitive member according to claim 1 or 2 and a charging unit, a light irradiation unit, a developing unit and a transfer unit.

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