JP5784074B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Description

  The present invention relates to an electrophotographic photosensitive member, a process cartridge having an electrophotographic photosensitive member, and an electrophotographic apparatus.

  At present, electrophotographic photoreceptors containing organic photoconductive substances are mainly used as electrophotographic photoreceptors used in process cartridges and electrophotographic apparatuses. An electrophotographic photoreceptor generally has a support and a photosensitive layer formed on the support.

  An undercoat layer may be provided between the support and the photosensitive layer for the purpose of suppressing charge injection from the support side to the photosensitive layer side and suppressing the occurrence of image defects such as black spots. Many.

  In recent years, charge generation materials having higher sensitivity have been used. However, as the charge generating material becomes highly sensitive, there is a problem that the amount of generated charge increases, so that the charge tends to stay in the photosensitive layer and ghost is likely to occur. Specifically, in the output image, a phenomenon called so-called positive ghost, in which the density is increased only in a portion irradiated with light during the previous rotation, is likely to occur.

  As a technique for suppressing (reducing) such a ghost phenomenon, a technique for containing an electron transport material in an undercoat layer is known. In addition, from the viewpoint of the degree of freedom in material design of the photosensitive layer formed on the undercoat layer, the undercoat layer containing the electron transport material is made of a curable material that is hardly soluble in the solvent of the photosensitive layer coating solution. It is required to use. Therefore, Patent Document 1 discloses an undercoat layer containing a polymer of a condensation polymer (electron transport material) having an aromatic tetracarbonylbisimide skeleton and a crosslinking site, and a crosslinking agent. Patent Document 2 discloses that the undercoat layer contains a polymer of an electron transport material having a non-hydrolyzable polycondensable functional group.

Special table 2009-505156 JP 2006-178504 A

  In recent years, the demand for the quality of electrophotographic images has been increasing, and the allowable range for the above-mentioned positive ghost has become much stricter.

  As a result of the study by the present inventors, the techniques disclosed in Patent Documents 1 and 2 require further improvement with respect to the reduction of positive ghost. At the same time, if the charge tends to stay at the undercoat layer, or the interface between the undercoat layer and the photosensitive layer, the potential change after repeated use tends to occur, so the potential change needs to be reduced.

  An object of the present invention is to provide an electrophotographic photosensitive member in which positive ghosts and potential fluctuations are reduced even after repeated use over a long period of time, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

The present invention relates to an electrophotographic photoreceptor having a support, an undercoat layer formed on the support, and a photosensitive layer formed on the undercoat layer.
The electrophotographic photoreceptor, wherein the undercoat layer contains a cured product having a structure represented by the following formula (1).

In formula (1), R ¹ and R ³ each independently represents an alkylene group having 1 to 10 atoms in the substituted or unsubstituted main chain, or a substituted or unsubstituted phenylene group. R ² represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 atoms in the main chain, or a substituted or unsubstituted phenylene group. The substituent of the substituted alkylene group is an alkyl group, an aryl group, a hydroxy group, or a halogen atom. The substituent of the substituted phenylene group is a halogen atom, a nitro group, a cyano group, a hydroxy group, an alkyl group, or a halogen-substituted alkyl group. R ⁹ represents a hydrogen atom or an alkyl group. A ¹ represents any group represented by the following formulas (A-1) to (A-6). B ¹ represents a group represented by any of the following formulas (B-1) to (B-3). D ¹ is a group having 5 to 15 atoms in the main chain represented by the following formula (D). E ¹ is a group Ru indicated by any one of the following formulas (E-1) ~ (E -8).

R ¹⁰ represents a hydrogen atom or an alkyl group.

In formulas (B-1) to (B-3), R ² represents a single bond, an alkylene group having 1 to 10 atoms in the substituted or unsubstituted main chain, or a substituted or unsubstituted phenylene group. R ⁶ and R ⁷ are each independently an alkylene group having 1 to 5 atoms in the main chain, an alkylene group having 1 to 5 atoms in the main chain substituted with an alkyl group having 1 to 5 carbon atoms, Number of main chain atoms substituted with a benzyl group substituted alkylene group with 1 to 5 atoms, a main chain substituted alkylene group with 1 to 5 atoms, or a phenyl group Represents an alkylene group of 1 to 5; One of the carbon atoms in the main chain of the alkylene group may be replaced by O, S, NH or NR ¹⁵ . R ¹⁵ is an alkyl group. Ar ² represents a substituted or unsubstituted phenylene group. The substituent of the substituted phenylene group is a halogen atom, a nitro group, a hydroxy group, a cyano group, an alkyl group, or a halogenated alkyl group. R ¹² represents a hydrogen atom or an alkyl group. A ¹ and A ² represent any group represented by the formulas (A-1) to (A-6). o, p, and q are each independently 0 or 1, and the sum of o, p, and q is 1 or more and 3 or less. * Represents the side bonded to R ³ in the above formula (1).

In formula (D), R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a main chain substituted with an alkylene group having 1 to 5 atoms in the main chain and an alkyl group having 1 to 5 carbon atoms. An alkylene group having 1 to 5 chain atoms, an alkylene group having 1 to 5 main chain atoms substituted with a benzyl group, an alkylene group having 1 to 5 main chain atoms substituted with an alkoxycarbonyl group, Or an alkylene group having 1 to 5 atoms in the main chain substituted with a phenyl group; One of the carbon atoms in the main chain of the alkylene group may be replaced by O, S, NH or NR ¹⁵ . R ¹⁵ is an alkyl group. Ar ¹ and Ar ² each independently represent a substituted or unsubstituted phenylene group. The substituent of the substituted phenylene group is a halogen atom, a nitro group, a hydroxy group, a cyano group, an alkyl group, or a halogenated alkyl group. A ² represents a group represented by any one of the formulas (A-1) to (A-6). l, m, n, o, p and q are each independently 0 or 1, and the sum of l, m and n and the sum of o, p and q are 1 or more and 3 or less.

Wherein (E-1) ~ (E -8), X 11 ~X 16, X 21 ~X 29, X 31 ~X 36, X 41 ~X 48, X 51 ~X 58, X 61 ~X 66, X ^{71 to} X ⁷⁸ and X ^{81 to} X ⁸⁸ each independently represent a single bond , a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a carboxyl group, a cyano group, a dialkylamino group, a hydroxy group, a heterocyclic group, or a nitro group. Represents a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkyl group.
At least one of X ¹¹ to X ^16, at least one of X 21 ^{to X 29,} at least one of X 31 ^{to X 36,} at least one of X 41 ^{to X 48,} at least one of X 51 ^{to X 58,} at least one of X ⁶¹ to X ^66, at least one of X 71 ^{to X 78,} at least one of and ^X 81 ^{to X 88} is a single bond.
Z ^{51 to} Z ⁵² , Z ^{61 to} Z ⁶² , and Z ⁸¹ each independently represent an oxygen atom, a C (CN) ₂ group, or N—R ¹¹ . R ¹¹ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group.

  Further, the present invention integrally supports the electrophotographic photosensitive member and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means, and is detachable from the main body of the electrophotographic apparatus. The present invention relates to a process cartridge.

  The present invention also relates to an electrophotographic apparatus comprising the electrophotographic photosensitive member, a charging unit, a developing unit, an exposure unit, and a transfer unit.

  According to the present invention, it is possible to provide an electrophotographic photosensitive member in which positive ghosts and potential fluctuations are reduced even after repeated use over a long period of time, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

1 is a diagram illustrating a schematic configuration of an electrophotographic apparatus having a process cartridge including the electrophotographic photosensitive member of the present invention. It is a figure explaining the printing for ghost evaluation used in the case of ghost image evaluation. It is a figure explaining a 1 dot Keima pattern image. It is a figure which shows an example of the layer structure of an electrophotographic photoreceptor.

  The electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having a support, an undercoat layer formed on the support, and a photosensitive layer formed on the undercoat layer. The photosensitive layer is preferably a stacked type (functional separation type) photosensitive layer separated into a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material. Furthermore, from the viewpoint of electrophotographic characteristics, the multilayer photosensitive layer is preferably a normal photosensitive layer in which a charge generation layer and a charge transport layer are laminated in this order from the support side.

  FIGS. 4A and 4B are views showing an example of the layer structure of the electrophotographic photosensitive member of the present invention. In FIGS. 1A and 1B, 101 is a support, 102 is an undercoat layer, 103 is a photosensitive layer, 104 is a charge generation layer, and 105 is a charge transport layer.

  The undercoat layer is a layer (cured layer) having a structure represented by the following formula (1). In other words, the undercoat layer contains a cured product (polymer) having a structure represented by the following formula (1). The undercoat layer of the present invention may be a single layer or two or more layers. When there are two or more undercoat layers, at least one of them has a structure represented by the following formula (1).

In formula (1), R ¹ and R ³ each independently represent a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenylene group. R ² represents a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenylene group. R ⁹ represents a hydrogen atom or an alkyl group. A ¹ represents any group represented by the following formulas (A-1) to (A-6). B ¹ represents a group represented by any of the following formulas (B-1) to (B-3). D ¹ is a group having 5 to 15 atoms in the main chain represented by the following formula (D). E ¹ is a group Ru indicated by any one of the following formulas (E-1) ~ (E -8).

  The substituent of the substituted alkylene group is an alkyl group, an aryl group, a hydroxy group, or a halogen atom. Examples of the substituent of the substituted phenylene group include a halogen atom, a nitro group, a cyano group, a hydroxy group, an alkyl group, and a halogen-substituted alkyl group.

R ¹⁰ represents a hydrogen atom or an alkyl group.

In formulas (B-1) to (B-3), R ² represents a single bond, an alkylene group having 1 to 10 atoms in the substituted or unsubstituted main chain, or a substituted or unsubstituted phenylene group. R ⁶ and R ⁷ are each independently an alkylene group having 1 to 5 main chain atoms, an alkylene group having 1 to 5 main chain atoms substituted with an alkyl group having 1 to 5 carbon atoms, benzyl An alkylene group having 1 to 5 atoms in the main chain substituted with a group, an alkylene group having 1 to 5 atoms in the main chain substituted with an alkoxycarbonyl group, or an atom number in the main chain substituted with a phenyl group. 1 to 5 alkylene groups are shown. One of the carbon atoms in the main chain of the alkylene group may be replaced by O, S, NH or NR ¹⁵ . R ¹⁵ is an alkyl group. Ar ² represents a substituted or unsubstituted phenylene group. R ¹² represents a hydrogen atom or an alkyl group. A ¹ and A ² represent any group represented by the formulas (A-1) to (A-6). o, p and q are each independently an integer of 0 or 1, and the sum of o, p and q is 1 or more and 3 or less. The substituent of the substituted alkylene group is an alkyl group, an aryl group, or a halogen atom. Examples of the substituent of the substituted phenylene group include a halogen atom, a nitro group, a cyano group, a hydroxy group, an alkyl group, and a halogenated alkyl group. * Represents the side bonded to R ³ in the above formula (1).

In formula (D), R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a main chain substituted with an alkylene group having 1 to 5 atoms in the main chain and an alkyl group having 1 to 5 carbon atoms. An alkylene group having 1 to 5 atoms, an alkylene group having 1 to 5 atoms in the main chain substituted with a benzyl group, an alkylene group having 1 to 5 atoms in the main chain substituted with an alkoxycarbonyl group, or An alkylene group having 1 to 5 atoms in the main chain substituted with a phenyl group is shown. One of the carbon atoms in the main chain of the alkylene group may be replaced by O, S, NH or NR ¹⁵ . R ¹⁵ is an alkyl group. Ar ¹ and Ar ² represent a substituted or unsubstituted phenylene group. The substituent of the substituted alkylene group is an alkyl group, an aryl group, and a halogen atom. The substituent of the substituted phenylene group is a halogen atom, a nitro group, a hydroxy group, a cyano group, an alkyl group, or a halogenated alkyl group. A ² represents a group represented by any one of the formulas (A-1) to (A-6). l, m, n, o, p and q are each independently 0 or 1, and the sum of l, m and n and the sum of o, p and q are 1 or more and 3 or less.

R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an alkylene group having 1 to 5 main chain atoms substituted with a methyl group or an ethyl group, or an alkylene group having 1 to 5 main chain atoms It is more preferable that More preferably, Ar ¹ and Ar ² are phenylene groups.

  Further, from the viewpoint of suppressing positive ghosts, more preferably a group having 10 to 15 atoms in the main chain represented by the formula (D).

Wherein (E-1) ~ (E -8), X 11 ~X 16, X 21 ~X 29, X 31 ~X 36, X 41 ~X 48, X 51 ~X 58, X 61 ~X 66, X ^{71 to} X ⁷⁸ and X ^{81 to} X ⁸⁸ each independently represent a single bond , a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a carboxyl group, a cyano group, a dialkylamino group, a hydroxy group, a heterocyclic group, or a nitro group. Represents a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkyl group. The substituent of the substituted alkoxy group includes a carboxyl group, a cyano group, a dialkylamino group, a hydroxy group, an alkyl group, an alkoxy-substituted alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxy-substituted alkoxy group, a halogen-substituted alkoxy group, and a nitro group. Or a halogen atom. The substituent of the substituted alkyl group includes a carboxyl group, a cyano group, a dialkylamino group, a hydroxy group, an alkyl group, an alkoxy-substituted alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxy-substituted alkoxy group, a halogen-substituted alkoxy group, and a nitro group. Or a halogen atom.
At least one of X ¹¹ to X ^16, at least one of X 21 ^{to X 29,} at least one of X 31 ^{to X 36,} at least one of X 41 ^{to X 48,} at least one of X 51 ^{to X 58,} at least one of X ⁶¹ to X ^66, at least one of X 71 ^{to X 78,} at least one of and ^X 81 ^{to X 88} is a single bond.
Z ^{51 to} Z ⁵² , Z ^{61 to} Z ⁶² , and Z ⁸¹ each independently represent an oxygen atom, a C (CN) ₂ group, or N—R ¹¹ . R ¹¹ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group. The substituent of the substituted aryl group includes a carboxyl group, a cyano group, a dialkylamino group, a hydroxy group, an alkyl group, an alkoxy-substituted alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxy-substituted alkoxy group, a halogen-substituted alkoxy group, a nitro group A group, or a halogen atom. The substituent of the substituted alkyl group includes a carboxyl group, a cyano group, a dialkylamino group, a hydroxy group, an alkyl group, an alkoxy-substituted alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxy-substituted alkoxy group, a halogen-substituted alkoxy group, a nitro group A group, or a halogen atom.

In the structure represented by the formula (1) of the present invention, R ² in the formula (1) is bonded to the structure X surrounded by a broken line represented by the following formula (1-A). This structure X is considered to be a portion corresponding to a resin chain.

In D ^1, and the number of atoms of the main chain, is that the shortest number of atoms in linkage of right and left ends of the above formula (D). For example, the p-phenylene group has 4 main chain atoms. The m-phenylene group has 3 main chain atoms. The o-phenylene group has 2 main chain atoms.

  The present inventors consider the reason why the positive ghost is reduced even when used repeatedly for a long time because the undercoat layer has the structure represented by the above formula (1) as follows. .

  In the polymer of Patent Document 1, since the distance (intermolecular distance) between the electron transporting compound and the crosslinking agent is long, it is considered that the polymer easily becomes an electron trap. When an electron trap is formed in the undercoat layer, the electron transport property is likely to be lowered, and residual charges are likely to be generated. As a result, it is considered that the occurrence of positive ghost occurs because residual charges are likely to accumulate during repeated use over a long period of time.

The inventors of the present invention have a structure in which the number of atoms in the main chain is 5 between the electron transporting structure (E ¹ ) and the isocyanurate structure (the part surrounded by the broken line shown in the following formula (1-A)). It is considered that the positive ghost of the present application is reduced by bonding with 15 (5 or more and 15 or less) groups. Both the electron transporting structure (E ¹ ) and the isocyanurate structure have electron transporting properties, and by combining these two structures, a conduction level that is considered to be a factor of electron transporting properties is formed. And it is thought that a uniform conduction level is formed by the group having 5 to 15 atoms in the main chain represented by the formula (D) between the electron transporting structure and the isocyanurate structure. As a result, it is considered that charges are not easily trapped, residual charges in the undercoat layer are suppressed, and positive ghosts during long-term repeated use are reduced. D atoms of the main chain in ¹ 5 less, larger than D atoms in the main chain in ¹ 15, residual charge accumulated in the undercoat layer during long-term repeated use, prone to positive ghost .

When the number of atoms of the main chain in D ¹ is less than 5, an isocyanurate structure or an electron transport structure is bonded directly to the urethane bond portion (—NHCO—). In this case, it is considered that the urethane bond portion is easily hydrolyzed and the urethane bond is easily cleaved. Then, it is considered that a charge trap occurs due to a change in the local conduction level in the undercoat layer, and the residual charge in the undercoat layer is likely to accumulate during repeated use over a long period of time. When the number of atoms of the main chain in D ¹ is greater than 15, the electron transporting structure and the isocyanurate structure are unlikely to interact with each other, the electron transporting structures are localized, and the isocyanurate structures are easily localized. For this reason, conduction levels are formed between the electron transporting structures and the isocyanurate structures, so that it is considered that the conduction levels are not uniform in the undercoat layer. When the conduction level becomes non-uniform, charge traps are generated, and it is considered that residual charges in the undercoat layer are likely to accumulate during repeated use over a long period of time.

  As described above, when the electron transporting structure and the isocyanurate structure are bonded with a group having 5 to 15 atoms in the main chain represented by the formula (D) as in the present invention, it can be used repeatedly for a long time. It is thought that the positive ghost reduction with time is achieved.

  The undercoat layer preferably contains the structure represented by the above formula (1) in an amount of 30% by mass to 70% by mass with respect to the total mass of the undercoat layer.

  The content of the structure represented by the above formula (1) in the undercoat layer can be analyzed by a general analysis method. Examples of analysis methods are shown below. For the content of the structure represented by the above formula (1) in the undercoat layer, FT-IR is used and the KBr-tab method is used. By creating a calibration curve based on the absorption derived from the isocyanurate structure in the sample in which the amount of tris (2-hydroxyethyl) isocyanurate added to the KBr powder is changed, the equation (1) in the undercoat layer shows The content of the structure to be obtained can be calculated.

Furthermore, the structure represented by the formula (1) has a solid ¹³ C-NMR measurement, mass spectrometry measurement, MS spectrum measurement by pyrolysis GC-MS analysis, characteristic absorption measurement by infrared spectroscopy, etc. This can be confirmed by the measurement method. For example, solid ¹³ C-NMR measurement is performed using CMX-300 Infinity manufactured by Chemenetics, using observation nucleus ¹³ C, reference material polydimethylsiloxane, integration number 8192 times, pulse sequence CP / MAS, DD / MAS, pulse width 2.1 μsec. (DD / MAS) Measurement was performed under the conditions of 4.2 μsec (CP / MAS), contact time 2.0 msec, and sample rotation speed 10 kHz. Mass spectrometry Mass spectrometry: using (MALDI-TOF MS Bruker Daltonics Co. ultraflex), accelerating voltage: 20 kV, mode: Reflector, molecular weight standard product: the conditions of fullerene _{C 60,} to measure the molecular weight. It confirmed with the obtained peak top value.

  In addition to the structure represented by the above formula (1), the undercoat layer contains various resins, cross-linking agents, leveling agents, metal oxide particles and the like in order to improve film forming properties and electrophotographic characteristics. May be. However, the content thereof is preferably less than 50% by mass and more preferably less than 20% by mass with respect to the total mass of the undercoat layer. The thickness of the undercoat layer is preferably 0.1 μm or more and 5.0 μm or less.

  Although the specific example of the structure shown by Formula (1) below is shown, this invention is not limited to these.

Here, the right side of E ¹ in Formula (1) represents a hydrogen atom, a substituted or unsubstituted aryl group, an alkyl group, or a bonding site. One of the carbon atoms in the main chain of the substituted or unsubstituted alkyl group may be replaced with O, S, NH, or NR ¹⁶ . R ¹⁶ is an alkyl group. Examples of the substituent of the substituted aryl group include an alkyl group, a halogen atom, a nitro group, and a cyano group. Examples of the substituent of the substituted alkyl group include an alkyl group, an aryl group, a halogen atom, a nitro group, and a cyano group. In the case of a binding site, it indicates that it is bonded to D ¹ by removing E ¹ from the structure represented by formula (1) via a substituted or unsubstituted arylene group or an alkylene group. Examples of the substituent of the substituted arylene group include an alkyl group, a halogen atom, and a nitro group. L, m, n, o, p and q are 0 or 1.

B ¹ in the table represents a group represented by any of the following formulas (B-1) to (B-3). Here, the right side of E ¹ in (B-2) represents a hydrogen atom, a substituted or unsubstituted aryl group, an alkyl group, a heterocyclic group, or a bonding site. Examples of the substituent for the substituted aryl group include an alkyl group, a halogen atom, and a nitro group. In the case of a binding site, E ¹ is excluded from the structure represented by the above formula (1) via a substituted or unsubstituted arylene group or an alkylene group, and the bond is bonded to D ¹ in the above formula (1). Indicates that In formula (B-3), the lower side of R ² indicates that it is bonded to the side chain of the resin present in the undercoat layer.

In Tables 1 to 9 below, the binding sites are indicated by broken lines. In the case of a single bond, “single” is indicated. Moreover, the left-right direction of Formula (1) and the left-right direction of each structure in Table 1 to Table 9 are the same. Moreover, in the exemplary compounds in Table 1 to Table 9, all of R ⁹ in Formula (1) are hydrogen atoms.

  The undercoat layer having the structure represented by the formula (1) of the present invention can be formed as follows. First, an isocyanate compound (crosslinking agent), a resin having a polymerizable functional group capable of reacting with an isocyanate group of the isocyanate compound, and an electron transporting material having a polymerizable functional group capable of reacting with the isocyanate group of the isocyanate compound are dissolved in a solvent. . Thereby, the coating liquid for undercoat layers is prepared, the coating film of the coating liquid for undercoat layers is formed, and it obtains by thermosetting a coating film. Thermal curing is preferable because the reaction can be performed uniformly during drying of the coating film.

  The isocyanate compound has an isocyanurate structure. The isocyanate group of the isocyanate compound is preferably an isocyanate compound (blocked isocyanate compound) protected with a blocking agent such as oxime. When the blocked isocyanate compound is heated together with the resin and the electron transport material, the addition reaction is started, and the blocking agent is removed and the crosslinking reaction proceeds. And the hardened | cured material which has a structure shown by Formula (1) in an undercoat layer is obtained.

  Examples of the blocking agent include active methylene compounds such as ethyl acetate and acetylacetone, mercaptan compounds such as butyl mercaptan and dodecyl mercaptan, acid amide compounds such as acetanilide and acetic acid amide, ε-caprolactam, δ-valerolactam, γ- Lactam compounds such as butyrolactam, acid imide compounds such as succinimide and maleic imide, imidazole compounds such as imidazole and 2-methylimidazole, urea compounds such as urea, thiourea and ethyleneurea, formamide oxime, Oxime compounds such as acetoaldoxime, acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, diphenylaniline, aniline, carbazole, ethylene Min, include amine compounds such as polyethyleneimine, these blocking agents can be used alone or in combination of two or more kinds of them.

  Among these blocking agents, oxime compounds such as methyl ethyl ketoxime, lactam compounds such as ε-caprolactam, and imidazole compounds such as 2-methylimidazole from the viewpoints of versatility, ease of production, workability, and thermosetting temperature. Compounds are preferred.

  Next, the example of the said isocyanate compound is given below.

  The isocyanate group of the isocyanate compound (number of moles = I) is 0.5 or more with respect to the sum of the polymerizable functional group of the resin and the polymerizable functional group of the electron transport material (number of moles = H). It is preferably present at a molar ratio (I / H) of 2.5 or less. It is preferable for this molar ratio (I / H) to be 0.5 or more and 2.5 or less because the reaction efficiency between the isocyanate group and the polymerizable functional group is good and the crosslinking density is increased.

  The polymerizable functional group of the resin is preferably a hydroxy group, a carboxyl group, an amino group, or a thiol group. Furthermore, it is preferable that it is a hydroxyl group or an amino group with high reaction efficiency with an isocyanate group. That is, the resin is preferably a polyol resin, polyvinyl phenol resin, polyvinyl phenol resin or polyamide resin having two or more hydroxy groups or amide groups. The molecular weight of the resin used in the present invention is preferably in the range of weight average molecular weight (Mw) = 5000 to 1500,000.

  The cured product having the structure represented by the above formula (1) preferably further has a structure represented by the following formula (2). That is, the resin preferably has a structure represented by the following formula (2). With the structure represented by the formula (2), the adhesion of the undercoat layer to the lower layer and the upper layer and the film thickness uniformity of the undercoat layer are improved, and the positive ghost and potential fluctuation during repeated use for a longer period are reduced. Is done.

In the formula (2), R ⁸ represents a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms. The substituent of the substituted alkyl group is an alkyl group, an aryl group or a halogen atom.

R ⁴ , R ⁵ , R ⁶ and R ^{7 in} D ¹ are each independently an alkylene group having a methyl or ethyl group-substituted main chain having 1 to 5 atoms or a main chain having 1 to 5 atoms. 5 is preferable from the viewpoint of reducing the initial positive ghost.

In the polymer having the structure represented by the above formula (1), Ar ¹ and Ar ² in D ¹ are preferably each independently an unsubstituted phenylene group from the viewpoint of reducing initial positive ghost.

  Next, examples of the electron transport material having the polymerizable functional group are listed below.

  Among these electron transport materials, the compounds exemplified in the exemplified compounds (E-1-1) to (E-1-34) are more preferred. In addition, an electron transport material having two or more polymerizable functional groups is preferable because it tends to increase the polymerization (crosslinking) density.

  Derivatives having a structure of (E-1) (electron transport material derivatives) are disclosed in, for example, US Pat. No. 4,442,193, US Pat. No. 4,992,349, US Pat. No. 5,468,583, Chemistry of materials, Vol. 19, no. It is possible to synthesize using a known synthesis method described in 11, 2703-2705 (2007). Moreover, it can synthesize | combine by reaction with the naphthalene tetracarboxylic dianhydride and monoamine derivative which can be purchased from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Co., Ltd., and Johnson Matthey Japan Incorporated.

Moreover, in order to have a functional group (hydroxy group, thiol group, amino group, and carboxyl group) polymerizable with the crosslinking agent, the following method may be mentioned. For example, a method of directly introducing a polymerizable functional group into a derivative having the structure (E-1). There is a method of introducing a structure having a polymerizable functional group or a functional group that can be a precursor of the polymerizable functional group. As a method described later, for example, a functional group-containing aryl group is introduced using a cross-coupling reaction using a palladium catalyst and a base based on a halide of a naphthylimide derivative. A method for introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl ₃ catalyst and a base based on a halide of a naphthylimide derivative. Based on the halide of the naphthylimide derivative, a method of introducing a hydroxyalkyl group or a carboxyl group by allowing an epoxy compound or CO ₂ to act after lithiation is used. As a raw material when synthesizing a naphthylimide derivative, there is a method of using the polymerizable functional group or a naphthalene tetracarboxylic dianhydride derivative or a monoamine derivative having a functional group that can be a precursor of the polymerizable functional group.

  The derivative having the structure of (E-2) or (E-8) can be purchased from, for example, Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Johnson Matthey Japan Inc. Further, it can be synthesized using a fluorenone derivative and malononitrile by the synthesis method described in US Pat. No. 4,562,132. Moreover, it can also synthesize | combine using the synthesis method as described in Unexamined-Japanese-Patent No. 5-279582 and Unexamined-Japanese-Patent No. 7-70038 using a fluorenone derivative and an aniline derivative.

Moreover, in order to have a functional group (hydroxy group, thiol group, amino group, and carboxyl group) polymerizable with the crosslinking agent, the following method may be mentioned. For example, a method of introducing a polymerizable functional group into a derivative having the structure (E-2) or (E-8). There is a method of introducing a structure having a polymerizable functional group or a functional group that becomes a precursor of the polymerizable functional group. As a method described later, for example, a functional group-containing aryl group is introduced using a cross-coupling reaction using a palladium catalyst and a base based on a halide of fluorenone. A method of introducing a functional group-containing alkyl group using a cross coupling reaction using a FeCl ₃ catalyst and a base based on a halide of fluorenone. There is a method of introducing a hydroxyalkyl group or a carboxyl group based on a halide of fluorenone by allowing an epoxy compound or CO ₂ to act after lithiation.

  The derivative having the structure of (E-3) can be synthesized by using a synthesis method described in, for example, Chemistry Letters, 37 (3), 360-361 (2008), and JP-A-9-151157. Moreover, it can be purchased from, for example, Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Johnson Matthey Japan Inc.

In addition, in order to have a functional group (hydroxy group, thiol group, amino group, and carboxyl group) that can be polymerized with a crosslinking agent, a functional group that becomes a polymerizable functional group or a precursor of a polymerizable functional group is added to a naphthoquinone derivative. There is a method for introducing a structure having the same. As this method, for example, based on a naphthoquinone halide, a functional group-containing aryl group is introduced using a cross-coupling reaction using a palladium catalyst and a base. A method of introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl ₃ catalyst and a base based on a naphthoquinone halide. Based on the naphthoquinone halide, there is a method of introducing a hydroxyalkyl group or a carboxyl group by allowing an epoxy compound or CO ₂ to act after lithiation.

  Derivatives having the structure of (E-4) are disclosed in, for example, JP-A-1-206349, PPCI / Japan Hard Copy '98 Preliminary Collection p. 207 (1998). For example, a phenol derivative that can be purchased from Tokyo Chemical Industry Co., Ltd. or Sigma Aldrich Japan Co., Ltd. can be used as a raw material.

Moreover, in order to have a functional group (hydroxy group, thiol group, amino group, and carboxyl group) that can be polymerized with a crosslinking agent, a structure having a functional group that becomes a polymerizable functional group or a precursor of a polymerizable functional group is used. There is a way to introduce. As this method, for example, based on a halide of diphenoquinone, a functional group-containing aryl group is introduced using a cross-coupling reaction using a palladium catalyst and a base. A method of introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl ₃ catalyst and a base based on a diphenoquinone halide. Based on the diphenoquinone halide, there is a method of introducing a hydroxyalkyl group or a carboxyl group by allowing an epoxy compound or CO ₂ to act after lithiation.

  The derivative having the structure of (E-5) can be purchased from, for example, Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Co., Ltd., or Johnson Matthey Japan Inc. Further, based on phenanthrene derivatives or phenanthroline derivatives, Chem. Educator No. 6, 227-234 (2001), Journal of Synthetic Organic Chemistry, vol. 15, 29-32 (1957), Journal of Synthetic Organic Chemistry, vol. 15, 32-34 (1957). A dicyanomethylene group can also be introduced by reaction with malononitrile.

Moreover, in order to have a functional group (hydroxy group, thiol group, amino group, and carboxyl group) polymerizable with the crosslinking agent, the following method may be mentioned. For example, after synthesizing a derivative having the structure of the above formula (E-5), a method of directly introducing a polymerizable functional group, a structure having a functional group that becomes a polymerizable functional group or a precursor of a polymerizable functional group is introduced. There is a way to do it. As a method described later, for example, a functional group-containing aryl group is introduced using a cross-coupling reaction using a palladium catalyst and a base based on a halide of phenanthrenequinone. A method of introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl ₃ catalyst and a base based on a halide of phenanthrenequinone. Based on the halide of phenanthrenequinone, there is a method of introducing a hydroxyalkyl group or a carboxyl group by allowing an epoxy compound or CO ₂ to act after lithiation.

  The derivative having the structure of (E-6) can be purchased from, for example, Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Johnson Matthey Japan Inc. Also, based on phenanthrene derivatives or phenanthroline derivatives, Bull. Chem. Soc. Jpn. , Vol. 65, 1006-1011 (1992). A dicyanomethylene group can also be introduced by reaction with malononitrile.

Moreover, in order to have a functional group (hydroxy group, thiol group, amino group, and carboxyl group) polymerizable with the crosslinking agent, the following method may be mentioned. For example, after synthesizing a derivative having the structure of the above formula (E-6), a method for directly introducing a polymerizable functional group, a structure having a functional group that becomes a polymerizable functional group or a precursor of a polymerizable functional group is introduced. There is a way to do it. As a method described later, for example, a functional group-containing aryl group is introduced using a cross-coupling reaction using a palladium catalyst and a base based on a halide of phenanthroline quinone. A method of introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl ₃ catalyst and a base based on a halide of phenanthroline quinone. Based on the halide of phenanthroline quinone, there is a method of introducing a hydroxyalkyl group or a carboxyl group by allowing an epoxy compound or CO ₂ to act after lithiation.

  The derivative having the structure of (E-7) can be purchased from, for example, Tokyo Chemical Industry Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Johnson Matthey Japan Incorporated.

Moreover, in order to have a functional group (hydroxy group, thiol group, amino group, and carboxyl group) that can be polymerized with a crosslinking agent, it becomes a polymerizable functional group or a precursor of a polymerizable functional group to a commercially available anthraquinone derivative. There is a method of introducing a structure having a functional group. As this method, for example, based on an anthraquinone halide, a functional group-containing aryl group is introduced using, for example, a cross-coupling reaction using a palladium catalyst and a base. A method of introducing a functional group-containing alkyl group using a cross-coupling reaction using an FeCl ₃ catalyst and a base based on an anthraquinone halide. Based on the anthraquinone halide, there is a method of introducing a hydroxyalkyl group or a carboxyl group by allowing an epoxy compound or CO ₂ to act after lithiation.

  Examples of the solvent used in the coating solution for the undercoat layer include alcohol solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ketone solvents, ketone alcohol solvents, ether solvents, ester solvents, and the like. It is done. More specifically, methanol, ethanol, n-propanol, iso-propanol, n-butanol, benzyl alcohol, methyselsolve, ethylcellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene Examples include chloride, chloroform, chlorobenzene, and toluene. These solvents can be used alone or in admixture of two or more. In the case of using a mixture of two or more kinds, there is no particular limitation as long as it is a solvent that can dissolve the isocyanate compound, the resin, and the electron transport material as a mixed solvent.

  The electrophotographic photosensitive member of the present invention is generally a cylindrical electrophotographic photosensitive member in which a photosensitive layer (a charge generation layer, a charge transport layer) is formed on a cylindrical support. It is also possible to have a shape such as a shape or a sheet shape.

  As the support, those having conductivity (conductive support) are preferable, and for example, a support made of a metal such as aluminum, nickel, copper, gold, iron, or an alloy can be used. A support in which a thin film of metal such as aluminum, silver, or gold is formed on an insulating support such as polyester resin, polycarbonate resin, polyimide resin, or glass, or a thin film of conductive material such as indium oxide or tin oxide is formed. A support is mentioned.

  The surface of the support may be subjected to electrochemical treatment such as anodic oxidation, wet honing treatment, blast treatment, cutting treatment, etc. in order to improve electrical characteristics and suppress interference fringes.

  A conductive layer may be provided between the support and the undercoat layer described above. The conductive layer is obtained by forming a coating film of a coating solution for conductive layer in which conductive particles are dispersed in a resin on a support and drying the coating film. Examples of the conductive particles include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc, and silver, and metal oxide powder such as conductive tin oxide and ITO. Can be mentioned.

  Examples of the resin include polyester resin, polycarbonate resin, polyvinyl butyral resin, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol resin, and alkyd resin.

  Examples of the solvent for the conductive layer coating solution include ether solvents, alcohol solvents, ketone solvents, and aromatic hydrocarbon solvents. The thickness of the conductive layer is preferably 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.

  The undercoat layer described above is provided between the support or the conductive layer and the photosensitive layer.

  Next, a photosensitive layer is provided on the undercoat layer.

  Examples of charge generating materials include azo pigments, perylene pigments, anthraquinone derivatives, anthanthrone derivatives, dibenzpyrenequinone derivatives, pyranthrone derivatives, violanthrone derivatives, isoviolanthrone conductors, indigo derivatives, thioindigo derivatives, metal phthalocyanines, metal-free Examples thereof include phthalocyanine pigments such as phthalocyanine and bisbenzimidazole derivatives. Among these, azo pigments or phthalocyanine pigments are preferable. Among the phthalocyanine pigments, oxytitanium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine are preferable.

  When the photosensitive layer is a laminated photosensitive layer, the binder resin used for the charge generation layer includes vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, and trifluoroethylene. Polymers and copolymers, polyvinyl alcohol resin, polyvinyl acetal resin, polycarbonate resin, polyester resin, polysulfone resin, polyphenylene oxide resin, polyurethane resin, cellulose resin, phenol resin, melamine resin, silicon resin, epoxy resin, etc. It is done. Among these, polyester, polycarbonate, and polyvinyl acetal are preferable, and among these, a polyvinyl acetal resin is more preferable.

  In the charge generation layer, the ratio of the charge generation material to the binder resin (charge generation material / binder resin) is preferably in the range of 10/1 to 1/10, and in the range of 5/1 to 1/5. It is more preferable that The thickness of the charge generation layer is preferably 0.05 μm or more and 5 μm or less. Examples of the solvent used in the charge generation layer coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

  Examples of the hole transport material include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, benzidine compounds, triarylamine compounds, and triphenylamine compounds. Also included are polymers having groups derived from these compounds in the main chain or side chain.

  When the photosensitive layer is a laminated photosensitive layer, the binder resin used for the charge transport layer (hole transport layer) is a polyester resin, polycarbonate resin, polymethacrylate resin, polyarylate resin, polysulfone resin, polystyrene resin. Etc. Among these, polycarbonate resin and polyarylate resin are preferable. The weight average molecular weight (Mw) of these resins is preferably in the range of 10,000 to 300,000.

  In the charge transport layer, the ratio of the hole transport material to the binder resin (hole transport material / binder resin) is preferably in the range of 10/5 to 5/10, and 10/8 to 6/10. More preferably, it is the range. The thickness of the hole transport layer is preferably 5 μm or more and 40 μm or less.

  Examples of the solvent used in the charge transport layer coating liquid include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

  In addition, a protective layer (surface protective layer) containing conductive particles or a hole transport material and a binder resin may be formed on the photosensitive layer (charge transport layer). The protective layer may further contain an additive such as a lubricant. Further, the binder resin itself of the protective layer may have conductivity and hole transportability. In that case, the protective layer may not contain conductive particles or a hole transport material other than the resin. The binder resin for the protective layer may be a thermoplastic resin, or a curable resin that is cured (polymerized) by heat, light, radiation (electron beam or the like), and the like.

  As a method for forming each layer constituting the electrophotographic photosensitive member such as an undercoat layer, a charge generation layer, and a charge transport layer, a coating solution obtained by dissolving or dispersing materials constituting each layer in a solvent is applied, The method of forming by drying and / or polymerizing the obtained coating film is preferable. Examples of the method for applying the coating liquid include a dip coating method (dip coating method), a spray coating method, a curtain coating method, and a spin coating method. Among these, the dip coating method is preferable from the viewpoints of efficiency and productivity.

  FIG. 1 shows a schematic configuration of an electrophotographic apparatus having a process cartridge provided with the electrophotographic photosensitive member of the present invention.

  In FIG. 1, reference numeral 1 denotes a cylindrical electrophotographic photosensitive member, which is rotationally driven in a direction of an arrow about a shaft 2 at a predetermined peripheral speed. The surface (circumferential surface) of the electrophotographic photosensitive member 1 that is rotationally driven is uniformly charged to a predetermined positive or negative potential by a charging unit 3 (primary charging unit: charging roller or the like). Next, it receives exposure light (image exposure light) 4 from exposure means (not shown) such as slit exposure or laser beam scanning exposure. In this way, electrostatic latent images corresponding to the target image are sequentially formed on the surface of the electrophotographic photosensitive member 1.

  The electrostatic latent image formed on the surface of the electrophotographic photoreceptor 1 is then developed with toner contained in the developer of the developing means 5 to become a toner image. Next, the toner image formed and supported on the surface of the electrophotographic photosensitive member 1 is sequentially transferred onto a transfer material (such as paper) P by a transfer bias from a transfer unit (such as a transfer roller) 6. The transfer material P is taken out from the transfer material supply means (not shown) between the electrophotographic photoreceptor 1 and the transfer means 6 (contact portion) in synchronization with the rotation of the electrophotographic photoreceptor 1 and fed. Is done.

  The transfer material P that has received the transfer of the toner image is separated from the surface of the electrophotographic photosensitive member 1 and introduced into the fixing means 8 to receive the image fixing, and is printed out as an image formed product (print, copy). Is done.

  The surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by receiving a developer (toner) remaining after transfer by a cleaning means (cleaning blade or the like) 7. Next, after being subjected to charge removal processing by pre-exposure light (not shown) from pre-exposure means (not shown), it is repeatedly used for image formation. As shown in FIG. 2, when the charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not necessarily required.

  A plurality of components such as the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, the transfer unit 6 and the cleaning unit 7 described above are selected and placed in a container, and integrally combined as a process cartridge. May be. The process cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. In FIG. 1, an electrophotographic photosensitive member 1, a charging unit 3, a developing unit 5 and a cleaning unit 7 are integrally supported to form a cartridge, and an electrophotographic apparatus is provided using a guide unit 10 such as a rail of the electrophotographic apparatus main body. The process cartridge 9 is detachable from the main body.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. In the examples, “part” means “part by mass”.

Example 1
Two electrophotographic photoreceptors prepared as follows were prepared. One was used for structural analysis of the undercoat layer, and the other was used for evaluation of positive ghost.

  An aluminum cylinder (JIS-A3003, aluminum alloy) having a length of 260.5 mm and a diameter of 30 mm was used as a support (conductive support).

Next, titanium oxide particles coated with oxygen-deficient tin oxide (powder resistivity: 120 Ω · cm, SnO ₂ coverage (mass ratio): 40%), 50 parts of phenol resin (Pryofen J- 325, manufactured by Dainippon Ink & Chemicals, Inc., resin solid content: 60%.) 40 parts and 40 parts of methoxypropanol were dispersed for 3 hours in a sand mill using glass beads having a diameter of 1 mm to apply for a conductive layer. A liquid (dispersion) was prepared. The conductive layer coating solution was dip-coated on a support, and the resulting coating film was dried and thermally cured at 145 ° C. for 30 minutes to form a conductive layer having a thickness of 16 μm.

  The average particle diameter of the titanium oxide particles coated with oxygen-deficient tin oxide in the coating liquid for the conductive layer was measured using a particle size distribution meter (trade name: CAPA700) manufactured by Horiba, Ltd., and tetrahydrofuran as a dispersion medium. , And measured by centrifugal sedimentation at a rotational speed of 5000 rpm. As a result, the average particle size was 0.33 μm.

  Next, 3.6 parts of exemplary compound (E-1-1) as an electron transport substance, 6.2 parts of exemplary compound (I-8) as an isocyanate compound, and butyral resin (trade name: BM-1, Sekisui as resin) 1.29 parts of Chemical Industry Co., Ltd. was dissolved in a mixed solution of 50 parts of methyl ethyl ketone and 50 parts of dimethylacetamide. 0.031 parts of dioctyltin diurarate as a catalyst was added to the obtained solution to prepare a coating solution for an undercoat layer. The undercoat layer coating solution is dip-coated on the conductive layer, and the resulting coating film is heated for 30 minutes at 160 ° C. and polymerized (cured), whereby the undercoat layer has a thickness of 0.5 μm. Formed.

  Next, hydroxygallium phthalocyanine crystal (charge generation material, BraK angle (2θ ± 0.2 °) of CuKα characteristic X-ray diffraction of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18 10 parts, butyral resin (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 260 parts of cyclohexanone having a diameter of 6 parts, 6 parts, 25.1 degrees and 28.3 degrees. The mixture was placed in a sand mill using 1 mm glass beads and dispersed for 1.5 hours. Next, 240 parts of ethyl acetate was added thereto to prepare a charge generation layer coating solution. This charge generation layer coating solution was dip-coated on the undercoat layer, and the resulting coating film was dried at 95 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.18 μm.

  Next, a polyarylate resin (having a repeating structural unit represented by the following formula (16-1) and a repeating structural unit represented by the following formula (16-2) at a ratio of 5/5, and having a weight average molecular weight (Mw ) Is 100,000.) By dissolving 10 parts and 7 parts of an amine compound (hole transport material) represented by the following formula (15) in a mixed solvent of 30 parts of dimethoxymethane and 70 parts of chlorobenzene, A coating solution for charge transport layer was prepared. The charge transport layer coating solution was dip coated on the charge generation layer, and the resulting coating film was dried at 120 ° C. for 40 minutes to form a charge transport layer having a thickness of 18 μm.

  Thus, an electrophotographic photosensitive member having a conductive layer, an undercoat layer, a charge generation layer, and a charge transport layer on a support was produced.

The structure of the undercoat layer was analyzed as follows. The electrophotographic photoreceptor for structural analysis of the undercoat layer was immersed in a mixed solvent of 40 parts of dimethoxymethane and 60 parts of chlorobenzene for 5 minutes, and ultrasonic waves were applied to peel off the hole transport layer. Next, the charge generation layer was polished using a wrapping tape (C2000: manufactured by Fuji Photo Film Co., Ltd.) and then dried at 100 ° C. for 10 minutes to obtain an electrophotographic photoreceptor for structural analysis of the undercoat layer. . In addition, it was confirmed that the components of the charge transport layer and the charge generation layer did not remain on the surface of the undercoat layer using the FTIR-ATR method. The photoconductor was allowed to stand in a 25 ° C./50% RH environment for 24 hours, and then the central portion (130 mm position from the end) of the electrophotographic photoconductor was cut into a 1 cm square to obtain a sample for structural analysis of the undercoat layer. The structure represented by the formula (1) and the structure of D ¹ confirmed by the above-mentioned solid ¹³ C-NMR measurement, mass spectrometry measurement, MS spectrum measurement by pyrolysis GC-MS analysis, and characteristic absorption measurement by infrared spectroscopy analysis The number of atoms in the main chain is shown in Tables 15-17.

  The following evaluation was performed using another electrophotographic photosensitive member. The manufactured electrophotographic photosensitive member was mounted on a modified laser beam printer (trade name: LBP-2510) manufactured by Canon Inc. in an environment of a temperature of 23 degrees and a humidity of 50% RH. Thereafter, measurement of the surface potential was performed, evaluation of bright part potential fluctuation (potential fluctuation) when 5000 sheets were repeatedly used, and ghost evaluation when 5000 sheets were repeatedly used. Details are as follows.

  Attach the manufactured electrophotographic photosensitive member to the cyan process cartridge of the laser beam printer modified so that the pre-exposure does not emit light, attach the process cartridge to the cyan process cartridge station, and output the image did. First, image output was successively performed in the order of one solid white image, five ghost evaluation images, one solid black image, and five ghost evaluation images. Next, 5000 test charts (character images with a printing rate of 5%) are output on A4 size plain paper, and then 1 solid white image, 5 ghost evaluation images, 1 solid black image, Images were output continuously in the order of five ghost evaluation images.

  As shown in FIG. 2, the ghost evaluation image is obtained by outputting a square “solid image” in the “white image” at the head of the image and then displaying the “halftone image of the 1-dot Keima pattern” shown in FIG. It was created. In FIG. 2, the “ghost” portion is a portion where a ghost attributed to the “solid image” may appear.

  The evaluation of the positive ghost image was performed by measuring the density difference (Macbeth density difference) between the image density of the 1-dot Keima pattern image and the image density of the ghost part. A spectral densitometer (trade name: X-Rite 504/508, manufactured by X-Rite Co., Ltd.) was used to measure 10 density differences in one ghost evaluation image. This operation was performed on all 10 images for ghost evaluation, the average of 100 points was calculated, and the Macbeth density difference after initial use and after 5000 repeated use was evaluated. An image having a higher ghost density is a positive ghost image. This density difference means that the smaller the value, the more positive ghost is suppressed. Further, the smaller the difference between the Macbeth density difference after outputting 5000 sheets and the Macbeth density difference when outputting the initial image, the greater the positive ghost fluctuation suppressing effect. The results are shown in Tables 15 to 17.

  The potential fluctuation (bright part potential fluctuation amount) was evaluated as follows.

The exposure amount (image exposure amount) of the 780 nm laser light source of the evaluation apparatus was set so that the light amount on the surface of the electrophotographic photosensitive member was 0.3 μJ / cm ² . To measure the surface potential (dark part potential and bright part potential) of the electrophotographic photosensitive member, replace the jig and the developing device fixed so that the potential measuring probe is positioned 130 mm from the end of the electrophotographic photosensitive member. Then, it was carried out at the developing unit position. The applied bias was set so that the dark portion potential of the non-exposed portion of the electrophotographic photosensitive member was −450 V, and the light portion potential was attenuated from the dark portion potential by laser irradiation. In addition, using A4 size plain paper, image output is continuously performed for 5000 sheets, and the subsequent bright part potential (bright part potential after repeated use) is measured. The initial bright part potential and the bright part potential after repeated use are measured. (Light portion potential fluctuation amount) was calculated. A test chart having a printing ratio of 5% was used. The results are shown as potential fluctuations in Tables 15-17.

(Examples 2 to 10)
In Example 1, an electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the electron transport material, isocyanate compound (crosslinking agent), and resin were changed as shown in Table 15. The results are shown in Table 15.

(Example 11)
In Example 1, the electron transport material and the isocyanate compound were changed as shown in Table 15, and Example 1 was changed except that the resin was changed to 1.29 parts of butyral resin (trade name: BX-1, manufactured by Sekisui Chemical Co., Ltd.). In the same manner as above, an electrophotographic photoreceptor was produced and evaluated. The results are shown in Table 15.

(Example 12)
In Example 1, the electron transport material and the isocyanate compound were changed as shown in Table 15, and Example 1 was changed except that the resin was changed to 1.29 parts of polyvinyl alcohol resin (trade name: PVA117, manufactured by Kuraray Co., Ltd.). Similarly, an electrophotographic photoreceptor was produced and evaluated. The results are shown in Table 15.

(Example 13)
In Example 1, 1.29 parts of a vinyl chloride / vinyl acetate resin (trade name: VAGH, manufactured by Dow Chemical Co., Ltd.) obtained by changing the electron transport material and the isocyanate compound as shown in Table 15 and partially hydrolyzing the resin. An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the above was changed. The results are shown in Table 15.

(Example 14)
In Example 1, the electron transport material and the isocyanate compound were changed as shown in Table 15, and the resin was changed to 1.29 parts of poly (p-hydroxystyrene) (trade name: Marcalinker, manufactured by Maruzen Petrochemical Co., Ltd.). Except that, an electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1. The results are shown in Table 15.

(Examples 15 to 90)
In Example 1, an electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the electron transport material, the isocyanate compound, and the resin were changed as shown in Tables 15 to 17. The results are shown in Tables 15-17.

(Example 91)
In Example 1, an electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the adjustment of the conductive layer coating solution, the undercoat layer coating solution, and the charge transport layer coating solution was changed as follows. Similarly, positive ghost was evaluated. The results are shown in Table 17.

The preparation of the coating solution for the conductive layer was changed as follows. 214 parts of titanium oxide (TiO ₂ ) particles coated with oxygen-deficient tin oxide (SnO ₂ ) as metal oxide particles, phenol resin as a binder resin (trade name: Priorofen J-325, Dainippon Ink Chemical Co., Ltd., resin solid content: 60% by mass.) 132 parts and 98 parts of 1-methoxy-2-propanol as a solvent were put in a sand mill using 450 parts of glass beads with a diameter of 0.8 mm. Then, dispersion treatment (dispersion conditions, rotation speed: 2000 rpm, dispersion treatment time: 4.5 hours, set temperature of cooling water: 18 ° C.) was performed to obtain a dispersion. Glass beads were removed from this dispersion with a mesh (aperture: 150 μm).

  Silicone resin particles as a surface-roughening agent were added to the dispersion so as to be 10% by mass with respect to the total mass of the metal oxide particles and the binder resin in the dispersion after removing the glass beads. The silicone resin particles are Tospearl 120 (trade name) manufactured by Momentive Performance Materials Co., Ltd., and the average particle size is 2 μm. In addition, silicone oil as a leveling agent (trade name: SH28PA, manufactured by Toray Dow Corning Co., Ltd.) so that the total mass of the metal oxide particles and the binder resin in the dispersion is 0.01% by mass. .) Was added to the dispersion and stirred to prepare a coating solution for a conductive layer. The conductive layer coating solution was dip-coated on a support, and the resulting coating film was dried and thermally cured at 150 ° C. for 30 minutes to form a conductive layer having a thickness of 30 μm.

  Next, the electron transport material and isocyanate compound were changed as shown in Table 17, acetal resin (trade name: KS-5, manufactured by Sekisui Chemical Co., Ltd.) as the resin, and 0.031 part of zinc octylate (II) as the catalyst. A coating solution for the undercoat layer was prepared as in Example 1 except for the addition. The undercoat layer coating solution is dip-coated on the conductive layer to form a coating film, and the resulting coating film is heated at 160 ° C. for 30 minutes to be polymerized (cured), whereby the film thickness is reduced to 0. A subbing layer of 5 μm was formed.

  The charge generation layer was formed in the same manner as in Example 1.

  Next, the preparation of the charge transport layer coating solution was changed as follows. Polyester resin F (having a repeating structure represented by the following formula (24), a repeating structure represented by the formula (26) and a repeating structure represented by the formula (25) in a ratio of 7: 3, and a weight average molecular weight of 90, 3 parts, polyester resin H (containing a repeating structure represented by the following formula (27) and a repeating structure represented by the following formula (28) in a ratio of 5: 5, and a weight average molecular weight of 120,000. 7 parts, 9 parts of the charge transport material represented by the above formula (15) and 1 part of the charge transport material represented by the following formula (18) in a mixed solvent of 30 parts of dimethoxymethane and 50 parts of orthoxylene. By dissolving, a coating solution for a charge transport layer was prepared. In addition, the content of the repeating structural unit represented by the following formula (24) in the polyester resin F is 10% by mass, and the content of the repeating structural unit represented by the following formulas (25) and (26) is 90% by mass. %Met.

  The charge transport layer coating solution was dip coated on the charge generation layer and dried at 120 ° C. for 1 hour to form a charge transport layer having a thickness of 16 μm. It was confirmed that the formed charge transport layer contained a domain structure containing the polyester resin F in a matrix containing the charge transport material and the polyester resin H.

(Examples 92 to 111)
In Example 91, an electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 91 except that the electron transport material, the isocyanate compound, and the resin were changed as shown in Table 17. The results are shown in Table 16.

(Example 112)
In Example 93, an electrophotographic photosensitive member was produced in the same manner as in Example 93 except that the preparation of the coating solution for the charge transport layer was changed as follows, and evaluation was performed in the same manner. The results are shown in Table 17.

  The preparation of the coating solution for the charge transport layer was changed as follows. 10 parts of polycarbonate resin I (having a repeating structure represented by the following formula (29) and a weight average molecular weight of 70,000), polycarbonate resin J (a repeating structure represented by the following formula (29), 30) and at least one of the terminals has a structure represented by the following formula (31) and a weight average molecular weight of 40,000.) 0.3 part, the above formula (15) A charge transport layer coating solution was prepared by dissolving in 9 parts of the charge transport material represented by formula (1) and 1 part of the charge transport material represented by the formula (18), 30 parts of dimethoxymethane and 50 parts of orthoxylene. . In addition, the total mass of the repeating structural units represented by the following formulas (30) and (31) in the polycarbonate resin J was 30% by mass.

  The charge transport layer coating solution was dip coated on the charge generation layer and dried at 120 ° C. for 1 hour to form a charge transport layer having a thickness of 16 μm.

(Example 113)
An electrophotographic process similar to that of Example 112, except that the charge transport layer coating solution of Example 112 was changed from polycarbonate resin I (weight average molecular weight 70,000) to 10 parts of polyester resin H (weight average molecular weight 120,000). Photoconductors were manufactured and evaluated in the same manner. The results are shown in Table 17.

(Example 114)
In Example 93, an electrophotographic photosensitive member was produced in the same manner as in Example 93 except that the preparation of the conductive layer coating solution was changed as follows, and the same evaluation was performed. The results are shown in Table 17.

The preparation of the coating solution for the conductive layer was changed as follows. 207 parts of titanium oxide (TiO ₂ ) particles coated with tin oxide (SnO ₂ ) doped with phosphorus (P) as metal oxide particles, phenol resin as a binder resin (trade name: Pryofen J -325) 144 parts and 98 parts of 1-methoxy-2-propanol as a solvent are put in a sand mill using 450 parts of glass beads having a diameter of 0.8 mm, the rotation speed is 2000 rpm, and the dispersion treatment time is 4.5. Dispersion treatment was performed under the conditions of time and cooling water set temperature: 18 ° C. to obtain a dispersion. Glass beads were removed from this dispersion with a mesh (aperture: 150 μm).

  Silicone resin particles as a surface roughening agent (trade name: Tospearl 120) so as to be 15% by mass with respect to the total mass of the metal oxide particles and the binder resin in the dispersion after removing the glass beads Was added to the dispersion. Further, a silicone oil (trade name: SH28PA) as a leveling agent is added to the dispersion so as to be 0.01% by mass with respect to the total mass of the metal oxide particles and the binder resin in the dispersion, followed by stirring. By doing this, the coating liquid for conductive layers was prepared. The conductive layer coating solution was dip-coated on a support, and the resulting coating film was dried and thermally cured at 150 ° C. for 30 minutes to form a conductive layer having a thickness of 30 μm.

(Example 115)
In Example 112, an electrophotographic photosensitive member was produced in the same manner as in Example 112 except that the adjustment of the coating liquid for the conductive layer was changed as follows, and the same evaluation was performed. The results are shown in Table 17.

The adjustment of the coating liquid for the conductive layer was changed as follows. 207 parts of titanium oxide (TiO ₂ ) particles coated with tin oxide (SnO ₂ ) doped with phosphorus (P) as metal oxide particles, phenol resin as binder (monomers / oligomers of phenol resin) ) (Product name: Priorofen J-325) 144 parts and 98 parts of 1-methoxy-2-propanol as a solvent were put in a sand mill using 450 parts of glass beads having a diameter of 0.8 mm, and the rotational speed was 2000 rpm. The dispersion treatment was performed under the conditions of dispersion treatment time: 4.5 hours and cooling water set temperature: 18 ° C. to obtain a dispersion.

  Glass beads were removed from this dispersion with a mesh (aperture: 150 μm).

  Silicone resin particles as a surface-roughening agent (trade name: Tospearl 120) so as to be 15% by mass with respect to the total mass of the metal oxide particles and the binder material in the dispersion after removing the glass beads Was added to the dispersion. Further, a silicone oil (trade name: SH28PA) as a leveling agent is added to the dispersion so as to be 0.01% by mass with respect to the total mass of the metal oxide particles and the binder material in the dispersion, followed by stirring. By doing this, the coating liquid for conductive layers was prepared. The conductive layer coating solution was dip-coated on a support, and the resulting coating film was dried and thermally cured at 150 ° C. for 30 minutes to form a conductive layer having a thickness of 30 μm.

(Example 116)
In Example 113, an electrophotographic photosensitive member was produced in the same manner as in Example 113 except that the preparation of the conductive layer coating solution was changed as follows, and the same evaluation was performed. The results are shown in Table 17.

The preparation of the coating solution for the conductive layer was changed as follows. 207 parts of titanium oxide (TiO ₂ ) particles coated with tin oxide (SnO ₂ ) doped with phosphorus (P) as metal oxide particles, 144 parts of phenol resin (trade name: Priorofen J-325) In addition, 98 parts of 1-methoxy-2-propanol was put into a sand mill using 450 parts of glass beads having a diameter of 0.8 mm, the rotational speed: 2000 rpm, the dispersion treatment time: 4.5 hours, and the set temperature of the cooling water: Dispersion treatment was performed at 18 ° C. to obtain a dispersion. Glass beads were removed from this dispersion with a mesh (aperture: 150 μm).

  Silicone resin particles (trade name: Tospearl 120) were added to the dispersion so that the total mass of the metal oxide particles and the phenol resin in the dispersion after removing the glass beads was 15% by mass. In addition, silicone oil (trade name: SH28PA) is added to the dispersion so as to be 0.01% by mass with respect to the total mass of the metal oxide particles and the phenol resin in the dispersion, and the conductive is obtained. A layer coating solution was prepared. The conductive layer coating solution was dip-coated on a support, and the resulting coating film was dried and thermally cured at 150 ° C. for 30 minutes to form a conductive layer having a thickness of 30 μm.

(Comparative Example 1)
In Example 1, an electrophotographic photosensitive member was used in the same manner as in Example 1 except that the compound represented by the following formula (C-1) was used as the electron transport material and (I-1) was used as the isocyanate compound (crosslinking agent). Were manufactured and evaluated. The results are shown in Table 18. The number of atoms in the main chain of the structure corresponding to D ¹ in the structure represented by the formula (1) was 4.

(Comparative Example 2)
In Example 1, an electrophotographic photosensitive member was used in the same manner as in Example 1 except that the compound represented by the following formula (C-2) was used as the electron transporting material and (I-1) was used as the isocyanate compound (crosslinking agent). Were manufactured and evaluated. The results are shown in Table 18. The number of atoms in the main chain of the structure corresponding to D ¹ in the structure represented by the formula (1) was 4.

(Comparative Example 3)
In Example 1, the present invention was carried out except that an undercoat layer was formed using a block copolymer having a structure represented by the following formula described in JP-T-2009-505156 as an electron transport material. An electrophotographic photosensitive member was produced in the same manner as in Example 1 and evaluated. The results are shown in Table 18. The number of atoms in the main chain of the structure corresponding to D ¹ in the structure represented by the formula (1) was 25.

(Comparative Example 4)
A photoconductor was produced in the same manner as in Example 1 except that an undercoat layer was prepared using hexamethylene diisocyanate and the following compound (11) (configuration of Example 1 of JP-A-2007-148293). Evaluation was performed. The results are shown in Table 18.

<Dissolution test>
0.5 g of the coating solution for the undercoat layer prepared in Examples 1-116 was uniformly applied on the aluminum sheet by the wire bar method, and the resulting coating film was heated at 160 ° C. for 30 minutes to polymerize (cured). ) To obtain a sample. The central part of this sample was cut out in a region of 100 mm × 50 mm, and immersed in a mixed solution of anone and ethyl acetate (weight ratio = 1: 1) at a temperature of 20 degrees, respectively, for the initial weight before immersion and after immersion. The weight was measured. Furthermore, the coating film formed on the sample was scraped off, and the weight of the aluminum sheet was measured. The weight reduction rate (elution amount,%) after immersion was determined by the following formula.
Weight reduction rate after immersion (%) = ((initial weight−weight after immersion) / initial weight−aluminum sheet weight)) × 100
When the weight reduction rate (%) after immersion was 5% or less, the undercoat layer was judged to be a film that hardly dissolves. As a result, the undercoat layer formed in Examples 1 to 116 had a weight reduction rate (%) after immersion of 5% or less, and was a film that was difficult to elute.

  In Tables 15, 16, and 17, “content of electron transport material” indicates the content (parts by mass) of the electron transport material in the coating liquid for the undercoat layer. “Content of isocyanate compound” indicates the content (part by mass) of the isocyanate compound in the coating solution for the undercoat layer. “Resin part by mass” indicates the content (parts by mass) of the resin in the coating solution for the undercoat layer.

According to Example 60 and Comparative Example 1 and Comparative Example 2, when the number of atoms of the main chain of D ^{1 in} the structure represented by Formula (1) is smaller than 5, a sufficient effect of suppressing positive ghost fluctuation cannot be obtained. It is shown. This is shown by the fact that the change in Macbeth concentration at the initial stage of this evaluation method and after repeated use of 5000 sheets is larger than that of the Examples. This is thought to be because when the number of atoms in the main chain of D ¹ is less than 5, the bond distance between the urethane bond and the electron transporting structure is short, and thus the number of charge traps increases due to hydrolysis during repeated use.

Example 13 and Comparative Example 3 show that when the number of atoms of the main chain of D ^{1 in} the structure represented by the formula (1) is larger than 15, sufficient effect of suppressing positive ghost fluctuation cannot be obtained. Yes. This is shown by the fact that the change in Macbeth concentration at the initial stage of this evaluation method and after repeated use of 5000 sheets is larger than that of the Examples. This is because, when the number of atoms in the main chain of D ¹ is larger than 15, the naphthalenecarboxylic acid anhydride structure, which is an electron transporting structure of Comparative Example 3, and the isocyanurate structure portion are unlikely to interact with each other, and the conduction level is uneven. It is thought that it becomes. As a result, the electron transport structure is deteriorated and the charge traps are increased.

DESCRIPTION OF SYMBOLS 1 Electrophotographic photosensitive member 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Cleaning means 8 Fixing means 9 Process cartridge 10 Guide means P Transfer material 101 Support body 102 Undercoat layer 103 Photosensitive layer 104 Charge generation layer 105 Charge Transport layer

Claims (7)

In an electrophotographic photosensitive member having a support, an undercoat layer formed on the support, and a photosensitive layer formed on the undercoat layer,
The electrophotographic photoreceptor, wherein the undercoat layer contains a cured product having a structure represented by the following formula (1).

(In formula (1), R ¹ and R ³ each independently represents an alkylene group having 1 to 10 atoms in the substituted or unsubstituted main chain, or a substituted or unsubstituted phenylene group. R ² represents Represents a single bond, an alkylene group having 1 to 10 atoms in the substituted or unsubstituted main chain, or a substituted or unsubstituted phenylene group, which can be an alkyl group, an aryl group, a hydroxy group, The substituent of the substituted phenylene group is a halogen atom, a nitro group, a cyano group, a hydroxy group, an alkyl group, or a halogen-substituted alkyl group, and R ⁹ is a hydrogen atom or an alkyl group A ¹ represents any group represented by the following formulas (A-1) to (A-6), and B ¹ represents any of the following formulas (B-1) to (B-3). Indicated by .D ¹ showing the group, .E ¹ is a group of 15 atoms in the main chain is from 5 represented by the following formula (D) is any one of the following formulas (E-1) ~ (E -8) in a indicated Ru group.)

(R ¹⁰ represents a hydrogen atom or an alkyl group.)

(In formulas (B-1) to (B-3), R ² represents a single bond, an alkylene group having 1 to 10 atoms of a substituted or unsubstituted main chain, or a substituted or unsubstituted phenylene group. R ⁶ and R ⁷ are each independently an alkylene group having 1 to 5 atoms in the main chain, or an alkylene group having 1 to 5 atoms in the main chain substituted with an alkyl group having 1 to 5 carbon atoms. An alkylene group having 1 to 5 atoms in the main chain substituted with a benzyl group, an alkylene group having 1 to 5 atoms in the main chain substituted with an alkoxycarbonyl group, or an atom in the main chain substituted with a phenyl group Represents an alkylene group having a number of 1 to 5. One of the carbon atoms in the main chain of the alkylene group may be replaced by O, S, NH or NR ^15. R ¹⁵ is an alkyl group Ar ² Is a substituted or unsubstituted phenylene group Shown. Substituents of phenylene group as said substituent include a halogen atom, a nitro group, hydroxy group, a cyano group, an alkyl group or .R ¹² is a halogenated alkyl group, it is .A ¹ and a hydrogen atom or an alkyl group A ² represents any group represented by the formulas (A-1) to (A-6), o, p and q are each independently 0 or 1, and o, p and q The sum is from 1 to 3. * represents the side bonded to R ³ in the above formula (1).

(In formula (D), R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently substituted with an alkylene group having 1 to 5 atoms in the main chain and an alkyl group having 1 to 5 carbon atoms. An alkylene group having 1 to 5 atoms in the main chain, an alkylene group having 1 to 5 atoms in the main chain substituted with a benzyl group, and an alkylene group having 1 to 5 atoms in the main chain substituted with an alkoxycarbonyl group Or an alkylene group having 1 to 5 atoms in the main chain substituted with a phenyl group, and one of the carbon atoms in the main chain of the alkylene group may be replaced by O, S, NH or NR ¹⁵ R ¹⁵ is an alkyl group, Ar ¹ and Ar ² each independently represents a substituted or unsubstituted phenylene group, and the substituted phenylene group includes a halogen atom, a nitro group, a hydroxy group, Cyano group, alkyl A ² represents a group represented by any one of the formulas (A-1) to (A-6), and l, m, n, o, p and q are Each independently 0 or 1, and the sum of l, m and n, and the sum of o, p and q is 1 or more and 3 or less.)

(In the formula (E-1) ~ (E -8), X 11 ~X 16, X 21 ~X 29, X 31 ~X 36, X 41 ~X 48, X 51 ~X 58, X 61 ~X 66 , X ^{71 to} X ⁷⁸ , and X ^{81 to} X ⁸⁸ are each independently a single bond , a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a carboxyl group, a cyano group, a dialkylamino group, a hydroxy group, a heterocyclic group, nitro A group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkyl group;
At least one of X ¹¹ to X ^16, at least one of X 21 ^{to X 29,} at least one of X 31 ^{to X 36,} at least one of X 41 ^{to X 48,} at least one of X 51 ^{to X 58,} at least one of X ⁶¹ to X ^66, at least one of X 71 ^{to X 78,} at least one of and ^X 81 ^{to X 88} is a single bond.
Z ^{51 to} Z ⁵² , Z ^{61 to} Z ⁶² , and Z ⁸¹ each independently represent an oxygen atom, a C (CN) ₂ group, or N—R ¹¹ . R ¹¹ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group. ) The electrophotographic photosensitive member according to claim 1 , wherein the cured product further has a structure represented by the following formula (2).

(In Formula (2), R ⁸ represents a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms. The substituent of the substituted alkyl group having 1 to 5 carbon atoms is an alkyl group or an aryl group. Or a halogen atom.) Wherein in D ^1, electrophotographic photosensitive member according to claim 1 or 2 atoms of the main chain represented by the formula (D) is 10 to 15 groups. R ⁴ , R ⁵ , R ⁶ and R ⁷ in the formula (D) are each independently an alkylene group having 1 to 5 atoms in the main chain of methyl group or ethyl group substitution, or the number of atoms in the main chain The electrophotographic photoreceptor according to any one of claims 1 to 3 , wherein is an alkylene group of 1 to 5. Formula (D) is Ar ¹ and Ar ² in the electrophotographic photosensitive member according to claim 1, any one of 4 is a phenylene group. An electrophotographic photosensitive member according to any one of claims 1 to 5 , and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means, are integrally supported, and electrophotographic A process cartridge that is detachable from the main unit. The electrophotographic photosensitive member according to any one of claims 1 5, as well as, a charging means, an exposure means, the electrophotographic apparatus having the developing means and the transfer means.