ELECTROPHOTOGRAPHIC PHOTORECEPTOR, PROCESS CARTRIDGE, AND IMAGE FORMING APPARATUS

Information

  • Patent Application
  • 20240036488
  • Publication Number
    20240036488
  • Date Filed
    April 21, 2023
    a year ago
  • Date Published
    February 01, 2024
    3 months ago
Abstract
An electrophotographic photoreceptor includes a conductive substrate, and a lamination type photosensitive layer disposed on the conductive substrate and including a charge generation layer and a charge transport layer, in which the charge transport layer contains a charge transport material, a polyester resin, and a polycarbonate resin, and the polyester resin includes the following polyester resin (1), polyester resin (1): a polyester resin having at least one selected from the group including a diol unit (B3) represented by Formula (B3), a diol unit (B5) represented by Formula (B5), a diol unit (B6) represented by Formula (B6), a diol unit (B7) represented by Formula (B7), a diol unit (B8) represented by Formula (B8), a diol unit (B9) represented by Formula (B9), a diol unit (B10) represented by Formula (B10), and a diol unit (B11) represented by Formula (B11),
Description
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is based on and claims priority under 35 USC 119 from Japanese Patent Application No. 2022-114268 filed Jul. 15, 2022.


BACKGROUND
(i) Technical Field

The present invention relates to an electrophotographic photoreceptor, a process cartridge, and an image forming apparatus.


(ii) Related Art

WO2012/124713A discloses an electrophotographic photoreceptor containing a polycarbonate resin (A) having a specific structure and at least one of a polycarbonate resin (B) having a specific structure or a polyester resin (B′) having a specific structure, in which the proportion of the polycarbonate resin (A) in the total amount of the polycarbonate resin (A) and the polycarbonate resin (B) or the polyester resin (B′) is 0.5 or greater and 0.99 or less.


JP2017-211448A discloses an electrophotographic photoreceptor including a photosensitive layer that contains a polyarylate resin having a specific structure and a polycarbonate resin having a specific structure, in which the proportion of the polyarylate resin having a specific structure in the total amount of the polyarylate resin and the polycarbonate resin is 0.10 or greater and 0.90 or less.


JP2008-203802A discloses an electrophotographic photoreceptor including a photosensitive layer that contains a polyester resin (first resin) having a specific structure and at least one (second resin) of a polyester resin having a specific structure or a polycarbonate resin, in which the proportion of the second resin in the total amount of the first resin and the second resin is 1% by weight or greater and 70% by weight or less.


SUMMARY

Aspects of non-limiting embodiments of the present disclosure relate to an electrophotographic photoreceptor that includes a lamination type photosensitive layer, in which a charge transport layer contains a polyester resin and a polycarbonate resin, and spot-like image defects are unlikely to occur as compared with a case where the charge transport layer does not contain a polyester resin (1).


Aspects of non-limiting embodiments of the present disclosure relate to an electrophotographic photoreceptor that includes a single layer type photosensitive layer, in which the single layer type photosensitive layer contains a polyester resin and a polycarbonate resin, and spot-like image defects are unlikely to occur as compared with a case where the single layer type photosensitive layer does not contain a polyester resin (1).


Aspects of certain non-limiting embodiments of the present disclosure address the above advantages and/or other advantages not described above. However, aspects of the non-limiting embodiments are not required to address the advantages described above, and aspects of the non-limiting embodiments of the present disclosure may not address advantages described above.


Specific means for achieving the above-described object includes the following aspect.


According to an aspect of the present disclosure, there is provided an electrophotographic photoreceptor including: a conductive substrate; and a lamination type photosensitive layer disposed on the conductive substrate and including a charge generation layer and a charge transport layer, in which the charge transport layer contains a charge transport material, a polyester resin, and a polycarbonate resin, and the polyester resin includes the following polyester resin (1),

    • polyester resin (1): a polyester resin having at least one selected from the group consisting of a diol unit (B3) represented by Formula (B3), a diol unit (B5) represented by Formula (B5), a diol unit (B6) represented by Formula (B6), a diol unit (B7) represented by Formula (B7), a diol unit (B8) represented by Formula (B8), a diol unit (B9) represented by Formula (B9), a diol unit (B10) represented by Formula (B10), and a diol unit (B11) represented by Formula (B11).





BRIEF DESCRIPTION OF THE DRAWINGS

Exemplary embodiment(s) of the present invention will be described in detail based on the following figures, wherein:



FIG. 1 is a partial cross-sectional view showing an example of a layer configuration of an electrophotographic photoreceptor according to a first exemplary embodiment;



FIG. 2 is a partial cross-sectional view showing an example of a layer configuration of an electrophotographic photoreceptor according to a second exemplary embodiment;



FIG. 3 is a schematic configuration view showing an example of an image forming apparatus according to the present exemplary embodiment; and



FIG. 4 is a schematic configuration view showing another example of an image forming apparatus according to the present exemplary embodiment.





DETAILED DESCRIPTION

Hereinafter, exemplary embodiments of the present disclosure will be described. The following descriptions and examples merely illustrate the exemplary embodiments, and do not limit the scope of the exemplary embodiments.


In the present disclosure, a numerical range shown using “to” indicates a range including numerical values described before and after “to” as a minimum value and a maximum value.


In a numerical range described in a stepwise manner in the present disclosure, an upper limit value or a lower limit value described in a certain numerical range may be replaced with an upper limit value or a lower limit value in another numerical range described in a stepwise manner. Further, in a numerical range described in the present disclosure, an upper limit value or a lower limit value described in the numerical range may be replaced with a value shown in Examples.


In the present disclosure, the meaning of the term “step” includes not only an independent step but also a step whose intended purpose is achieved even in a case where the step is not clearly distinguished from other steps.


In the present disclosure, in a case where an exemplary embodiment is described with reference to drawings, the configuration of the exemplary embodiment is not limited to the configuration shown in the drawings. In addition, the sizes of members in each drawing are conceptual and the relative relation in the sizes between the members is not limited thereto.


In the present disclosure, each component may include a plurality of kinds of substances corresponding to each component. In the present disclosure, in a case where a plurality of kinds of substances corresponding to each component in a composition are present, the amount of each component in the composition indicates the total amount of the plurality of kinds of substances present in the composition unless otherwise specified.


In the present disclosure, each component may include a plurality of kinds of particles corresponding to each component. In a case where a plurality of kinds of particles corresponding to each component are present in a composition, the particle diameter of each component indicates the value of a mixture of the plurality of kinds of particles present in the composition, unless otherwise specified.


In the present disclosure, an alkyl group is any of linear, branched, or cyclic unless otherwise specified.


In the present disclosure, a hydrogen atom in an organic group, an aromatic ring, a linking group, an alkyl group, an alkylene group, an aryl group, an aralkyl group, an alkoxy group, or an aryloxy group may be substituted with a halogen atom.


Electrophotographic Photoreceptor


The present disclosure provides a first exemplary embodiment and a second exemplary embodiment of an electrophotographic photoreceptor (hereinafter, also referred to as “photoreceptor”).


The photoreceptor according to the first exemplary embodiment includes a conductive substrate, and a lamination type photosensitive layer disposed on the conductive substrate and including a charge generation layer and a charge transport layer. The charge transport layer of the photoreceptor according to the first exemplary embodiment contains a charge transport material, a polyester resin, and a polycarbonate resin, and the polyester resin includes the polyester resin (1).


The photoreceptor according to the first exemplary embodiment may further include other layers (for example, an undercoat layer and an interlayer) in addition to the lamination type photosensitive layer. In the photoreceptor according to the first exemplary embodiment, for example, it is preferable that the charge transport layer is a surface layer.


The photoreceptor according to the second exemplary embodiment includes a conductive substrate, and a single layer type photosensitive layer disposed on the conductive substrate. The single layer type photosensitive layer of the photoreceptor according to the second exemplary embodiment contains a charge transport material, a polyester resin, and a polycarbonate resin, and the polyester resin includes the polyester resin (1).


The photoreceptor according to the second exemplary embodiment may further include other layers (for example, an undercoat layer and an interlayer) in addition to the single layer type photosensitive layer. In the photoreceptor according to the second exemplary embodiment, for example, it is preferable that the single layer type photosensitive layer is a surface layer.



FIG. 1 is a partial cross-sectional view schematically showing an example of the layer configuration of the photoreceptor according to the first exemplary embodiment. A photoreceptor 10A shown in FIG. 1 includes a lamination type photosensitive layer. The photoreceptor 10A has a structure in which an undercoat layer 2, a charge generation layer 3, and a charge transport layer 4 are laminated in this order on a conductive substrate 1, and the charge generation layer 3 and the charge transport layer 4 constitute a photosensitive layer 5 (so-called function separation type photosensitive layer). The photoreceptor 10A may include an interlayer (not shown) between the undercoat layer 2 and the charge generation layer 3.



FIG. 2 is a partial cross-sectional view schematically showing an example of the layer configuration of the photoreceptor according to the second exemplary embodiment. A photoreceptor 10B shown in FIG. 2 includes a single layer type photosensitive layer. The photoreceptor 10B has a structure in which the undercoat layer 2 and the photosensitive layer 5 are laminated in this order on the conductive substrate 1. The photoreceptor 10B may include an interlayer (not shown) between the undercoat layer 2 and the photosensitive layer 5.


Hereinafter, in a case of description common to the first exemplary embodiment and the second exemplary embodiment, both exemplary embodiments are collectively referred to as the present exemplary embodiment.


In the photoreceptor according to the present exemplary embodiment, the charge transport layer of the lamination type photosensitive layer or the single layer type photosensitive layer (hereinafter, referred to as “photosensitive layer” in the present description) contains a polyester resin and a polycarbonate resin. In this manner, the advantages of both resins (for example, abrasion resistance, toughness, and flexibility of the polyester resin, and impact resistance, weather fastness, and heat resistance of the polycarbonate resin) can be imparted to the photosensitive layer.


Black spots are generated by a local decrease in potential or leakage caused by sticking of foreign matter with high hardness and low resistance. The diameter of the foreign matter and the depth to which the foreign matter is stuck are indicators of the presence or absence of black spots, and local fogging is likely to occur as the diameter of the foreign matter increases. Further, in a case where foreign matter is stuck deep, dielectric breakdown (leakage) occurs in a site where the foreign matter is stuck. Further, it is considered that occurrence of cracks in the periphery of the site and floating of the interface between the charge transport layer and the charge generation layer lead to inhibition of charge transport, and thus black spots are generated.


The details of the mechanism by which the photoreceptor according to the present exemplary embodiment suppresses the generation of black spots are not clear, but the following can be considered. In a case where the resin including the polyester resin of the present exemplary embodiment is blended, the flexibility is obtained, and deep sticking of foreign matter, occurrence of cracks in the periphery, and floating of the interface with an internal base layer are unlikely to occur. Further, in a case where the resin including the polycarbonate resin of the present exemplary embodiment is blended, the electrical properties are likely to be stabilized, the decrease in potential in the periphery of the foreign matter is suppressed, and dielectric breakdown is unlikely to occur. An effect of suppressing black spots is obtained by appropriately blending the two kinds of resins.


In the first exemplary embodiment, the mass proportion of the polyester resin (1) in the total amount of the polyester resin and the polycarbonate resin contained in the charge transport layer is, for example, preferably 5% by mass or greater and 95% by mass or less. In a case where the mass proportion of the polyester resin (1) in the total amount of both resins is 5% by mass or greater and 95% by mass or less, foreign matter is unlikely to be stuck into the charge transport layer, and deep cracks are unlikely to occur even in a case where foreign matter is stuck into the charge transport layer. As a result, pinhole leak is unlikely to occur, and spot-like image defects are suppressed. From this viewpoint, the mass proportion of the polyester resin (1) in the total amount of both resins is, for example, more preferably 20% by mass or greater and 80% by mass or less, still more preferably 30% by mass or greater and 70% by mass or less, and still more preferably 40% by mass or greater and 60% by mass or less.


In the photoreceptor according to the first exemplary embodiment, an aspect in which the charge transport layer contains a charge transport material, a polyester resin, and a polycarbonate resin, the polyester resin contains the polyester resin (1), and the polycarbonate resin contains the polycarbonate resin (1), and in the charge transport layer, for example, the mass proportion of the polyester resin (1) in the total amount of the polyester resin and the polycarbonate resin is 5% by mass or greater and 95% by mass or less is preferable.


In the above-described aspect, in the charge transport layer, the mass proportion of the polyester resin (1) in the total amount of the polyester resin and the polycarbonate resin is, for example, more preferably 20% by mass or greater and 80% by mass or less, still more preferably 30% by mass or greater and 70% by mass or less, and still more preferably 40% by mass or greater and 60% by mass or less.


In the second exemplary embodiment, the mass proportion of the polyester resin (1) in the total amount of the polyester resin and the polycarbonate resin in the single layer type photosensitive layer is, for example, preferably 5% by mass or greater and 95% by mass or less. In a case where the mass proportion of the polyester resin (1) in the total amount of both resins is 5% by mass or greater and 95% by mass or less, foreign matter is unlikely to be stuck into the single layer type photosensitive layer, and deep cracks are unlikely to occur even in a case where foreign matter is stuck into the single layer type photosensitive layer. As a result, pinhole leak is unlikely to occur, and spot-like image defects are suppressed. From this viewpoint, the mass proportion of the polyester resin (1) in the total amount of both resins is, for example, more preferably 20% by mass or greater and 80% by mass or less, still more preferably 30% by mass or greater and 70% by mass or less, and still more preferably 40% by mass or greater and 60% by mass or less.


In the photoreceptor according to the second exemplary embodiment, an aspect in which the single layer type photosensitive layer contains a charge transport material, a polyester resin, and a polycarbonate resin, the polyester resin contains the polyester resin (1), and the polycarbonate resin contains the polycarbonate resin (1), and in the single layer type photosensitive layer, for example, the mass proportion of the polyester resin (1) in the total amount of the polyester resin and the polycarbonate resin is 5% by mass or greater and 95% by mass or less is preferable.


In the above-described aspect, in the single layer type photosensitive layer, the mass proportion of the polyester resin (1) in the total amount of the polyester resin and the polycarbonate resin is, for example, more preferably 20% by mass or greater and 80% by mass or less, still more preferably 30% by mass or greater and 70% by mass or less, and still more preferably 40% by mass or greater and 60% by mass or less.


Hereinafter, the polyester resin and the polycarbonate resin contained in the photosensitive layer and each layer of the photoreceptor will be described in detail.


Polyester Resin


The charge transport layer of the lamination type photosensitive layer or the single layer type photosensitive layer contains at least the polyester resin (1) as the polyester resin. The mass proportion of the polyester resin (1) in the entire polyester resin contained in the charge transport layer of the lamination type photosensitive layer or the single layer type photosensitive layer is, for example, preferably 80% by mass or greater, more preferably 90% by mass or greater, still more preferably 95% by mass or greater, and particularly preferably 100% by mass.


The polyester resin (1) is a polyester resin having at least one selected from the group consisting of a diol unit (B3) represented by Formula (B3), a diol unit (B5) represented by Formula (B5), a diol unit (B6) represented by Formula (B6), a diol unit (B7) represented by Formula (B7), a diol unit (B8) represented by Formula (B8), a diol unit (B9) represented by Formula (B9), a diol unit (B10) represented by Formula (B10), and a diol unit (B11) represented by Formula (B11).


The polyester resin (1) has, for example, preferably at least one selected from the group consisting of a diol unit (B5), a diol unit (B6), a diol unit (B9), and a diol unit (B10), more preferably at least one selected from the group consisting of a diol unit (B6), a diol unit (B9), and a diol unit (B10), and still more preferably at least one selected from the group consisting of a diol unit (B9) and a diol unit (B10).


Each diol unit will be described in detail below.




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In Formula (B3), Rb113 and Rb213 each independently represent a hydrogen atom, a linear alkyl group having 1 or more and 3 or less carbon atoms, an alkoxy group having 1 or more and 4 or less carbon atoms, or a halogen atom, d represents an integer of 7 or greater and 15 or less, and Rb403, Rb503, Rb803, and Rb903 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.


The number of carbon atoms of the linear alkyl group having 1 or more and 3 or less carbon atoms as Rb113 and Rb213 is, for example, preferably 1 or 2 and more preferably 1. Specific examples of such a group include a methyl group, an ethyl group, and an n-propyl group.


The alkyl group in the alkoxy group having 1 or more and 4 or less carbon atoms as Rb113 and Rb213 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the alkoxy group having 1 or more and 4 or less carbon atoms is, for example, preferably 1 or more and 3 or less, more preferably 1 or 2, and still more preferably 1. Specific examples of such a group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a cyclopropoxy group, and a cyclobutoxy group.


Examples of the halogen atom as Rb113 and Rb213 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.




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In Formula (B5), Ar105 represents an aryl group having 6 or more and 12 or less carbon atoms or an aralkyl group having 7 or more and 20 or less carbon atoms, Rb205 represents a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms, and Rb405, Rb505, Rb805, and Rb905 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.


The aryl group having 6 or more and 12 or less carbon atoms as Ar105 may be any of a monocycle or a polycycle. The number of carbon atoms of the aryl group is, for example, preferably 6 or more and 10 or less and more preferably 6.


The alkyl group in the aralkyl group having 7 or more and 20 or less carbon atoms as Ar105 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the aralkyl group having 7 or more and 20 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2. The aryl group in the aralkyl group having 7 or more and 20 or less carbon atoms as Ar105 may be any of a monocycle or a polycycle. The number of carbon atoms of the aryl group is, for example, preferably 6 or more and 10 or less and more preferably 6. Examples of the aralkyl group having 7 or more and 20 or less carbon atoms include a benzyl group, a phenylethyl group, a phenylpropyl group, a 4-phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a phenylheptyl group, a phenyloctyl group, a phenylnonyl group, a naphthylmethyl group, a naphthylethyl group, an anthracenylmethyl group, and a phenyl-cyclopentylmethyl group.


The alkyl group having 1 or more and 3 or less carbon atoms as Rb205 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or 2 and more preferably 1.


The alkyl group having 1 or more and 3 or less carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a cyclopropyl group.




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In Formula (B6), Rb116 and Rb216 each independently represent a hydrogen atom, a linear alkyl group having 1 or more and 3 or less carbon atoms, an alkoxy group having 1 or more and 4 or less carbon atoms, or a halogen atom, e represents an integer of 4 or greater and 6 or less, and Rb406, Rb506, Rb806, and Rb906 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.


The number of carbon atoms of the linear alkyl group having 1 or more and 3 or less carbon atoms as Rb116 and Rb216 is, for example, preferably 1 or 2 and more preferably 1. Specific examples of such a group include a methyl group, an ethyl group, and an n-propyl group.


The alkyl group in the alkoxy group having 1 or more and 4 or less carbon atoms as Rb116 and Rb216 may be linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the alkoxy group having 1 or more and 4 or less carbon atoms is, for example, preferably 1 or more and 3 or less, more preferably 1 or 2, and still more preferably 1. Specific examples of such a group include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a cyclopropoxy group, and a cyclobutoxy group.


Examples of the halogen atom as Rb116 and Rb216 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.




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In Formula (B7), Rb407, Rb507, Rb807, and Rb907 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.




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In Formula (B8), Rb408, Rb508, Rb808, and Rb908 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.




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In Formula (B9), Rb109 represents an alkyl group having 1 or more and 8 or less carbon atoms, Rb209 represents an alkyl group having 1 or more and 3 or less carbon atoms, and Rb409, Rb509, Rb809, and Rb909 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.


The alkyl group having 1 or more and 8 or less carbon atoms as Rb109 may be linear, branched, or cyclic and is, for example, preferably linear or branched. The number of carbon atoms of the alkyl group is, for example, preferably 1 or more and 6 or less and more preferably 1 or more and 4 or less.


Specific examples of Rb109 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, a cyclohexyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an isooctyl group, a sec-octyl group, and a tert-octyl group.


The alkyl group having 1 or more and 3 or less carbon atoms as Rb209 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or 2 and more preferably 1.


The alkyl group having 1 or more and 3 or less carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a cyclopropyl group.




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In Formula (B10), Rb110 represents an alkyl group having 9 or more and 20 or less carbon atoms, Rb210 represents a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms, and Rb41, Rb51, Rb810, and Rb910 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.


The alkyl group having 9 or more and 20 or less carbon atoms as Rb11 may be linear, branched, or cyclic, and is, for example, preferably linear or branched. The number of carbon atoms of the alkyl group is, for example, preferably 9 or more and 18 or less, more preferably 9 or more and 16 or less, and still more preferably 9 or more and 12 or less.


Specific examples of Rb11 include an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, a tert-decyl group, an n-undecyl group, an n-dodecyl group, an isododecyl group, a sec-dodecyl group, a tert-dodecyl group, a tridecyl group, an n-tetradecyl group, a tert-tetradecyl group, an n-pentadecyl group, a tert-pentadecyl group, an n-heptadecyl group, an n-octadecyl group, a tert-octadecyl group, an n-nonadecyl group, an n-icosyl group, and an isoicosyl group.


The alkyl group having 1 or more and 3 or less carbon atoms as Rb210 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or 2 and more preferably 1.


The alkyl group having 1 or more and 3 or less carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a cyclopropyl group.




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In Formula (B11), Rb411, Rb511, Rb811, and Rb911 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.


The specific forms and the preferable forms of Rb403 in Formula (B3), Rb405 in Formula (B5), Rb406 in Formula (B6), Rb407 in Formula (B7), Rb408 in Formula (B8), Rb409 in Formula (B9), Rb410 in Formula (B10), and Rb411 in Formula (B11) are the same as each other, and hereinafter, Rb403, Rb405, Rb406, Rb407, Rb408, Rb409, Rb410, and Rb411 will be collectively referred to as “Rb400”.


The alkyl group having 1 or more and 4 or less carbon atoms as Rb400 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or more and 3 or less, more preferably 1 or 2, and still more preferably 1.


Examples of the linear alkyl group having 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.


Examples of the branched alkyl group having 3 or 4 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.


Examples of the cyclic alkyl group having 3 or 4 carbon atoms include a cyclopropyl group and a cyclobutyl group.


The alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms as Rb400 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2.


Examples of the linear alkoxy group having 1 or more and 6 or less carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, and an n-hexyloxy group.


Examples of the branched alkoxy group having 3 or more and 6 or less carbon atoms include an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an isopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, an isohexyloxy group, a sec-hexyloxy group, and a tert-hexyloxy group.


Examples of the cyclic alkoxy group having 3 or more and 6 or less carbon atoms include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.


Examples of the halogen atom as Rb400 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.


The specific forms and the preferable forms of Rb503 in Formula (B3), Rb505 in Formula (B5), Rb506 in Formula (B6), Rb507 in Formula (B7), Rb508 in Formula (B8), Rb509 in Formula (B9), Rb510 in Formula (B10), and Rb511 in Formula (B11) are the same as each other, and hereinafter, Rb503, Rb505, Rb506, Rb507, Rb508, Rb509, Rb510, and Rb511 will be collectively referred to as “Rb500”.


The alkyl group having 1 or more and 4 or less carbon atoms as Rb500 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or more and 3 or less, more preferably 1 or 2, and still more preferably 1.


Examples of the linear alkyl group having 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.


Examples of the branched alkyl group having 3 or 4 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.


Examples of the cyclic alkyl group having 3 or 4 carbon atoms include a cyclopropyl group and a cyclobutyl group.


The alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms as Rb500 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2.


Examples of the linear alkoxy group having 1 or more and 6 or less carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, and an n-hexyloxy group.


Examples of the branched alkoxy group having 3 or more and 6 or less carbon atoms include an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an isopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, an isohexyloxy group, a sec-hexyloxy group, and a tert-hexyloxy group.


Examples of the cyclic alkoxy group having 3 or more and 6 or less carbon atoms include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.


Examples of the halogen atom as Rb500 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.


The specific forms and the preferable forms of Rb803 in Formula (B3), Rb805 in Formula (B5), Rb806 in Formula (B6), Rb807 in Formula (B7), Rb808 in Formula (B8), Rb809 in Formula (B9), Rb810 in Formula (B10), and Rb811 in Formula (B11) are the same as each other, and hereinafter, Rb803, Rb805, Rb806, Rb807, Rb808, Rb809, Rb810, and Rb811 will be collectively referred to as “Rb800”.


The alkyl group having 1 or more and 4 or less carbon atoms as Rb800 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or more and 3 or less, more preferably 1 or 2, and still more preferably 1.


Examples of the linear alkyl group having 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.


Examples of the branched alkyl group having 3 or 4 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.


Examples of the cyclic alkyl group having 3 or 4 carbon atoms include a cyclopropyl group and a cyclobutyl group.


The alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms as Rb800 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2.


Examples of the linear alkoxy group having 1 or more and 6 or less carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, and an n-hexyloxy group.


Examples of the branched alkoxy group having 3 or more and 6 or less carbon atoms include an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an isopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, an isohexyloxy group, a sec-hexyloxy group, and a tert-hexyloxy group.


Examples of the cyclic alkoxy group having 3 or more and 6 or less carbon atoms include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.


Examples of the halogen atom as Rb800 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.


The specific forms and the preferable forms of Rb903 in Formula (B3), Rb905 in Formula (B5), Rb906 in Formula (B6), Rb907 in Formula (B7), Rb908 in Formula (B8), Rb909 in Formula (B9), Rb910 in Formula (B10), and Rb911 in Formula (B11) are the same as each other, and hereinafter, Rb903, Rb905, Rb906, Rb907, Rb908, Rb909, Rb910, and Rb911 will be collectively referred to as “Rb900”.


The alkyl group having 1 or more and 4 or less carbon atoms as Rb900 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or more and 3 or less, more preferably 1 or 2, and still more preferably 1.


Examples of the linear alkyl group having 1 or more and 4 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.


Examples of the branched alkyl group having 3 or 4 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.


Examples of the cyclic alkyl group having 3 or 4 carbon atoms include a cyclopropyl group and a cyclobutyl group.


The alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms as Rb900 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2.


Examples of the linear alkoxy group having 1 or more and 6 or less carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, and an n-hexyloxy group.


Examples of the branched alkoxy group having 3 or more and 6 or less carbon atoms include an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an isopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, an isohexyloxy group, a sec-hexyloxy group, and a tert-hexyloxy group.


Examples of the cyclic alkoxy group having 3 or more and 6 or less carbon atoms include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.


Examples of the halogen atom as Rb900 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.


Hereinafter, diol units (B3-1) to (B3-4) are shown as specific examples of the diol unit (B3). The diol unit (B3) is not limited thereto.




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Hereinafter, diol units (B5-1) to (B5-6) are shown as specific examples of the diol unit (B5). The diol unit (B5) is not limited thereto.




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Hereinafter, diol units (B6-1) to (B6-4) are shown as specific examples of the diol unit (B6). The diol unit (B6) is not limited thereto.




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Hereinafter, diol units (B7-1) to (B7-3) are shown as specific examples of the diol unit (B7). The diol unit (B7) is not limited thereto.




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Hereinafter, diol units (B8-1) to (B8-3) are shown as specific examples of the diol unit (B8). The diol unit (B8) is not limited thereto.




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Hereinafter, diol units (B9-1) to (B9-10) are shown as specific examples of the diol unit (B9). The diol unit (B9) is not limited thereto.




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Hereinafter, diol units (B10-1) to (B10-10) are shown as specific examples of the diol unit (B10). The diol unit (B10) is not limited thereto.




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Hereinafter, diol units (B11-1) to (B11-3) are shown as specific examples of the diol unit (B11). The diol unit (B11) is not limited thereto.




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The diol unit (B) contained in the polyester resin (1) may be used alone or in combination of two or more kinds thereof.


The mass proportion of the diol unit (B) in the polyester resin (1) is, for example, preferably 25% by mass or greater and 80% by mass or less.


In a case where the mass proportion of the diol unit (B) is 25% by mass or greater, peeling of the photosensitive layer can be further suppressed. From this viewpoint, the mass proportion of the diol unit (B) is, for example, more preferably 30% by mass or greater and still more preferably 35% by mass or greater.


In a case where the mass proportion of the diol unit (B) is 80% by mass or less, the solubility in a coating solution for forming the photosensitive layer is maintained, and thus the abrasion resistance can be improved. From this viewpoint, the mass proportion of the diol unit (B) is, for example, more preferably 75% by mass or less and still more preferably 70% by mass or less.


Examples of other diol units in addition to the diol unit (B) include aliphatic diol (such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, and neopentyl glycol) units and alicyclic diol (such as cyclohexanediol, cyclohexane dimethanol, and hydrogenated bisphenol A) units. These diol units contained in the polyester resin (1) may be used alone or in combination of two or more kinds thereof.


It is preferable that the polyester resin (1) has, for example, a dicarboxylic acid unit (A). The dicarboxylic acid unit (A) is a constitutional unit represented by Formula (A).




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In Formula (A), ArA1 and ArA2 each independently represent an aromatic ring that may have a substituent, LA represents a single bond or a divalent linking group, and nA1 represents 0, 1, or 2.


The aromatic ring as ArA1 may be any of a monocycle or a polycycle. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Among these, for example, a benzene ring and a naphthalene ring are preferable.


The hydrogen atom on the aromatic ring as ArA1 may be substituted with an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, or the like. As the substituent in a case where the aromatic ring as ArA1 is substituted, for example, an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, and an alkoxy group having 1 or more and 6 or less carbon atoms are preferable.


The aromatic ring of ArA2 may be any of a monocycle or a polycycle. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Among these, for example, a benzene ring and a naphthalene ring are preferable.


The hydrogen atom on the aromatic ring as ArA2 may be substituted with an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, or the like. As the substituent in a case where the aromatic ring as ArA2 is substituted, for example, an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, and an alkoxy group having 1 or more and 6 or less carbon atoms are preferable.


In a case where LA represents a divalent linking group, examples of the divalent linking group include an oxygen atom, a sulfur atom, and —C(Ra1)(Ra2)—. Here, Ra1 and Ra2 each independently represent a hydrogen atom, an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, or an aralkyl group having 7 or more and 20 or less carbon atoms, and Ra1 and Ra2 may be bonded to each other to form a cyclic alkyl group.


The alkyl group having 1 or more and 10 or less carbon atoms as Ra1 and Ra2 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, and still more preferably 1 or 2.


The aryl group having 6 or more and 12 or less carbon atoms as Ra1 and Ra2 may be any of a monocycle or a polycycle. The number of carbon atoms of the aryl group is, for example, preferably 6 or more and 10 or less and more preferably 6.


The alkyl group in the aralkyl group having 7 or more and 20 or less carbon atoms as Ra1 and Ra2 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the aralkyl group having 7 or more and 20 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2.


The aryl group in the aralkyl group having 7 or more and 20 or less carbon atoms as Ra1 and Ra2 may be any of a monocycle or a polycycle. The number of carbon atoms of the aryl group is, for example, preferably 6 or more and 10 or less and more preferably 6.


It is preferable that the dicarboxylic acid unit (A) includes, for example, at least one selected from the group consisting of a dicarboxylic acid unit (A1) represented by Formula (A1), a dicarboxylic acid unit (A2) represented by Formula (A2), a dicarboxylic acid unit (A3) represented by Formula (A3), and a dicarboxylic acid unit (A4) represented Formula (A4).




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In Formula (A1), n101 represents an integer of 0 or greater and 4 or less, and n101 number of Ra101's each independently represent an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, or an alkoxy group having 1 or more and 6 or less carbon atoms.


n101 represents, for example, preferably 0, 1, or 2, more preferably 0 or 1, and still more preferably 0.




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In Formula (A2), n201 and n202 each independently represent an integer of 0 or greater and 4 or less, and n201 number of Ra201's and n202 number of Ra202's each independently represent an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, or an alkoxy group having 1 or more and 6 or less carbon atoms.


n201 represents, for example, preferably 0, 1, or 2, more preferably 0 or 1, and still more preferably 0.


n202 represents, for example, preferably 0, 1, or 2, more preferably 0 or 1, and still more preferably 0.




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In Formula (A3), n301 and n302 each independently represent an integer of 0 or greater and 4 or less, and n301 number of Ra301's and n302 number of Ra302's each independently represent an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, or an alkoxy group having 1 or more and 6 or less carbon atoms.


n301 represents, for example, preferably 0, 1, or 2, more preferably 0 or 1, and still more preferably 0.


n302 represents, for example, preferably 0, 1, or 2, more preferably 0 or 1, and still more preferably 0.




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In Formula (A4), n401 represents an integer of 0 or greater and 6 or less, and n401 number of Ra401's each independently represent an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, or an alkoxy group having 1 or more and 6 or less carbon atoms.


n401 represents, for example, preferably an integer of 0 or greater and 4 or less, more preferably 0, 1, or 2, and still more preferably 0.


The specific forms and the preferable forms of Ra101 in Formula (A1), Ra201 and Ra202 in Formula (A2), Ra301 and Ra302 in Formula (A3), and Ra401 in Formula (A4) are the same as each other, and hereinafter, Ra101, Ra201, Ra202, Ra301, Ra302, and Ra401 will be collectively referred to as “Ra”.


The alkyl group having 1 or more and 10 or less carbon atoms as Ra may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or more and 6 or less, more preferably 1 or more and 4 or less, and still more preferably 1 or 2.


Examples of the linear alkyl group having 1 or more and 10 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decyl group.


Examples of the branched alkyl group having 3 or more and 10 or less carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an isodecyl group, a sec-decyl group, and a tert-decyl group.


Examples of the cyclic alkyl group having 3 or more and 10 or less carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and polycyclic (for example, bicyclic, tricyclic, or spirocyclic) alkyl groups to which these monocyclic alkyl groups are linked.


The aryl group having 6 or more and 12 or less carbon atoms as Ra may be any of a monocycle or a polycycle. The number of carbon atoms of the aryl group is, for example, preferably 6 or more and 10 or less and more preferably 6.


Examples of the aryl group having 6 or more and 12 or less carbon atoms include a phenyl group, a biphenyl group, a 1-naphthyl group, and a 2-naphthyl group.


The alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms as Ra may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the alkoxy group having 1 or more and 6 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2.


Examples of the linear alkoxy group having 1 or more and 6 or less carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, and an n-hexyloxy group.


Examples of the branched alkoxy group having 3 or more and 6 or less carbon atoms include an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an isopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, an isohexyloxy group, a sec-hexyloxy group, and a tert-hexyloxy group.


Examples of the cyclic alkoxy group having 3 or more and 6 or less carbon atoms include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.


Hereinafter, dicarboxylic acid units (A1-1) to (A1-9) are shown as specific examples of the dicarboxylic acid unit (A1). The dicarboxylic acid unit (A1) is not limited thereto.




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Hereinafter, dicarboxylic acid units (A2-1) to (A2-3) are shown as specific examples of the dicarboxylic acid unit (A2). The dicarboxylic acid unit (A2) is not limited thereto.




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Hereinafter, dicarboxylic acid units (A3-1) and (A3-2) are shown as specific examples of the dicarboxylic acid unit (A3). The dicarboxylic acid unit (A3) is not limited thereto.




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Hereinafter, dicarboxylic acid units (A4-1) to (A4-3) are shown as specific examples of the dicarboxylic acid unit (A4). The dicarboxylic acid unit (A4) is not limited thereto.




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As the dicarboxylic acid unit (A), for example, (A1-1), (A1-7), (A2-3), (A3-2), and (A4-3) in the specific examples shown above are preferable, and (A2-3) is most preferable.


The total mass proportion of the dicarboxylic acid units (A1) to (A4) in the polyester resin (1) is, for example, preferably 15% by mass or greater and 60% by mass or less.


In a case where the total mass proportion of the dicarboxylic acid units (A1) to (A4) is 15% by mass or greater, the abrasion resistance of the photosensitive layer is enhanced. From this viewpoint, the total mass proportion of the dicarboxylic acid units (A1) to (A4) is, for example, more preferably 20% by mass or greater and still more preferably 25% by mass or greater.


In a case where the total mass proportion of the dicarboxylic acid units (A1) to (A4) is 60% by mass or less, peeling of the photosensitive layer can be suppressed. From this viewpoint, the total mass proportion of the dicarboxylic acid units (A1) to (A4) is, for example, more preferably 55% by mass or less and still more preferably 50% by mass or less.


The dicarboxylic acid units (A1) to (A4) contained in the polyester resin (1) may be used alone or in combination of two or more kinds thereof.


Examples of other dicarboxylic acid units (A) in addition to the dicarboxylic acid units (A1) to (A4) include aliphatic dicarboxylic acid (such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, alkenyl succinic acid, adipic acid, and sebacic acid) units, alicyclic dicarboxylic acid (such as cyclohexanedicarboxylic acid) units, and lower (for example, having 1 or more and 5 or less carbon atoms) alkyl ester units thereof. These dicarboxylic acid units contained in the polyester resin (1) may be used alone or in combination of two or more kinds thereof.


The dicarboxylic acid unit (A) contained in the polyester resin (1) may be used alone or in combination of two or more kinds thereof.


Terminals of the polyester resin and the polyester resin (1) may be sealed or modified with a terminal-sealing agent, a molecular weight modifier, or the like used during the production. Examples of the terminal-sealing agent or the molecular weight modifier include monohydric phenol, monovalent acid chloride, monohydric alcohol, and monovalent carboxylic acid.


Examples of the monohydric phenol include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-propylphenol, m-propylphenol, p-propylphenol, o-tert-butylphenol, m-tert-butylphenol, p-tert-butylphenol, pentylphenol, hexylphenol, octylphenol, nonylphenol, a 2,6-dimethylphenol derivative, a 2-methylphenol derivative, o-phenylphenol, m-phenylphenol, p-phenylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2-phenyl-2-(4-hydroxyphenyl)propane, 2-phenyl-2-(2-hydroxyphenyl)propane, and 2-phenyl-2-(3-hydroxyphenyl)propane.


Examples of the monovalent acid chloride include monofunctional acid halides such as benzoyl chloride, benzoic acid chloride, methanesulfonyl chloride, phenylchloroformate, acetic acid chloride, butyric acid chloride, octyl acid chloride, benzenesulfonyl chloride, benzenesulfinyl chloride, sulfinyl chloride, benzene phosphonyl chloride, and substituents thereof.


Examples of the monohydric alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, and phenethyl alcohol.


Examples of the monovalent carboxylic acid include acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, phenylacetic acid, p-tert-butylbenzoic acid, and p-methoxyphenylacetic acid.


The weight-average molecular weight of the polyester resin and the polyester resin (1) is, for example, preferably 30,000 or greater and 300,000 or less, more preferably 40,000 or greater and 250,000 or less, and still more preferably 50,000 or greater and 200,000 or less. The molecular weight of the polyester resin is a molecular weight measured by gel permeation chromatography (GPC) in terms of polystyrene. The GPC is carried out by using tetrahydrofuran as an eluent.


Examples of the method of producing the polyester resin and the polyester resin (1) include an interfacial polymerization method, a solution polymerization method, and a melt polymerization method.


Polycarbonate Resin


The kind of the polycarbonate resin is not limited, but the polycarbonate resin (1) having a constitutional unit (C) is preferable. The mass proportion of the polycarbonate resin (1) in the entire polycarbonate resin contained in the charge transport layer of the lamination type photosensitive layer or the single layer type photosensitive layer is, for example, preferably 80% by mass or greater, more preferably 90% by mass or greater, still more preferably 95% by mass or greater, and particularly preferably 100% by mass.


The constitutional unit (C) is a constitutional unit represented by Formula (C).




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In Formula (C), ArC1 and ArC2 each independently represent an aromatic ring that may have a substituent, LC represents a single bond or a divalent linking group, and nC1 represents 0, 1, or 2.


The aromatic ring as ArC1 may be any of a monocycle or a polycycle. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Among these, for example, a benzene ring and a naphthalene ring are preferable.


The hydrogen atom on the aromatic ring as ArC1 may be substituted with an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, or the like. As the substituent in a case where the aromatic ring as ArC1 is substituted, for example, an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, and an alkoxy group having 1 or more and 6 or less carbon atoms are preferable.


The aromatic ring as ArC2 may be any of a monocycle or a polycycle. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Among these, for example, a benzene ring and a naphthalene ring are preferable.


The hydrogen atom on the aromatic ring as ArC2 may be substituted with an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, or the like. As the substituent in a case where the aromatic ring as ArC2 is substituted, for example, an alkyl group having 1 or more and 10 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, and an alkoxy group having 1 or more and 6 or less carbon atoms are preferable.


In a case where LC represents a divalent linking group, examples of the divalent linking group include an oxygen atom, a sulfur atom, and —C(Rc1)(Rc2)—. Here, Rc1 and Rc2 each independently represent a hydrogen atom, an alkyl group having 1 or more and 20 or less carbon atoms, an aryl group having 6 or more and 12 or less carbon atoms, or an aralkyl group having 7 or more and 20 or less carbon atoms, and Rc1 and Rc2 may be bonded to each other to form a cyclic alkyl group.


The alkyl group having 1 or more and 20 or less carbon atoms as Rc1 and Rc2 may be linear, branched, or cyclic. The number of carbon atoms of the alkyl group is, for example, preferably 1 or more and 18 or less, more preferably 1 or more and 14 or less, and still more preferably 1 or more and 10 or less.


The aryl group having 6 or more and 12 or less carbon atoms as Rc1 and Rc2 may be any of a monocycle or a polycycle. The number of carbon atoms of the aryl group is, for example, preferably 6 or more and 10 or less and more preferably 6.


The alkyl group in the aralkyl group having 7 or more and 20 or less carbon atoms as Rc1 and Rc2 may be any of linear, branched, or cyclic. The number of carbon atoms of the alkyl group in the aralkyl group having 7 or more and 20 or less carbon atoms is, for example, preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or 2.


The aryl group in the aralkyl group having 7 or more and 20 or less carbon atoms as Rc1 and Rc2 may be any of a monocycle or a polycycle. The number of carbon atoms of the aryl group is, for example, preferably 6 or more and 10 or less and more preferably 6.


It is preferable that the constitutional unit (C) includes, for example, at least one selected from the group consisting of a constitutional unit (Cb1) represented by Formula (Cb1), a constitutional unit (Cb2) represented by Formula (Cb2), a constitutional unit (Cb3) represented by Formula (Cb3), a constitutional unit (Cb4) represented by Formula (Cb4), a constitutional unit (Cb5) represented by Formula (Cb5), a constitutional unit (Cb6) represented by Formula (Cb6), a constitutional unit (Cb7) represented by Formula (Cb7), and a constitutional unit (Cb8) represented by Formula (Cb8).


The polycarbonate resin (1) has, for example, preferably at least one selected from the group consisting of a constitutional unit (Cb3), a constitutional unit (Cb4), a constitutional unit (Cb5), a constitutional unit (Cb6), and a constitutional unit (Cb7), more preferably at least one selected from the group consisting of a constitutional unit (Cb4), a constitutional unit (Cb6), and a constitutional unit (Cb7), and still more preferably at least one selected from the group consisting of a constitutional unit (Cb6) and a constitutional unit (Cb7).


Hereinafter, each constitutional unit will be described in detail.




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In Formula (Cb1), Rb101 represents a branched alkyl group having 4 or more and 20 or less carbon atoms, Rb201 represents a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms, and Rb401, Rb501, Rb801, and Rb901 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.


Rb101, Rb201, Rb401, Rb501, Rb801, and Rb901 in Formula (Cb1) each have the same definition as that for Rb101, Rb201, Rb401, Rb501, Rb801, and Rb901 in Formula (B1), and the specific forms thereof are also the same as each other.




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In Formula (Cb2), Rb102 represents a linear alkyl group having 4 or more and 20 or less carbon atoms, Rb202 represents a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms, and Rb402, Rb502, Rb802, and Rb902 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.


Rb102, Rb202, Rb402, Rb502, Rb802, and Rb902 in Formula (Cb2) each have the same definition as that for Rb102, Rb202, Rb402, Rb502, Rb802, and Rb902 in Formula (B2), and the specific forms thereof are also the same as each other.




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In Formula (Cb3), Rb113 and Rb213 each independently represent a hydrogen atom, a linear alkyl group having 1 or more and 3 or less carbon atoms, an alkoxy group having 1 or more and 4 or less carbon atoms, or a halogen atom, d represents an integer of 7 or greater and 15 or less, and Rb403, Rb53, Rb803, and Rb903 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.


Rb113, Rb213, d, Rb403, Rb503, Rb803, and Rb903 in Formula (Cb3) each have the same definition as that for Rb113, Rb213, d, Rb403, Rb503, Rb803, and Rb903 in Formula (B3), and the specific forms thereof are also the same as each other.




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In Formula (Cb4), Rb104 and Rb204 each independently represent a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms, and Rb404, Rb504, Rb804, and Rb904 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.


Rb104, Rb204, Rb404, Rb504, Rb804, and Rb904 in Formula (Cb4) each have the same definition as that for Rb104, Rb204, Rb404, Rb504, Rb804 and Rb904 in Formula (B4), and the specific forms thereof are also the same as each other.




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In Formula (Cb5), Ar105 represents an aryl group having 6 or more and 12 or less carbon atoms or an aralkyl group having 7 or more and 20 or less carbon atoms, Rb205 represents a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms, and Rb405, Rb505, Rb805, and Rb905 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.


Ar105, Rb205, Rb405, Rb505, Rb805, and Rb905 in Formula (Cb5) each have the same definition as that for Ar105, Rb205, Rb405, Rb505, Rb805, and Rb905 in Formula (B5), and the specific forms thereof are also the same as each other.




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In Formula (Cb6), Rb116 and Rb216 each independently represent a hydrogen atom, a linear alkyl group having 1 or more and 3 or less carbon atoms, an alkoxy group having 1 or more and 4 or less carbon atoms, or a halogen atom, e represents an integer of 4 or greater and 6 or less, and Rb406, Rb506, Rb806, and Rb906 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.


Rb116, Rb216, e, Rb406, Rb506, Rb806, and Rb906 in Formula (Cb6) each have the same definition as that for Rb116, Rb216, e, Rb406, Rb506, Rb806, and Rb906 in Formula (B6), and the specific forms thereof are also the same as each other.




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In Formula (Cb7), Rb407, Rb507, Rb807, and Rb907 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.


Rb407, Rb507, Rb807, and Rb907 in Formula (Cb7) each have the same definition as that for Rb407, Rb507, Rb807, and Rb907 in Formula (B7), and the specific forms thereof are also the same as each other.




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In Formula (Cb8), Rb408, Rb508, Rb808, and Rb908 each independently represent a hydrogen atom, an alkyl group having 1 or more and 4 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, or a halogen atom.


Rb408, Rb508, Rb808, and Rb908 in Formula (Cb8) each have the same definition as that for Rb408, Rb508, Rb808, and Rb908 in Formula (B8), and the specific forms thereof are also the same as each other.


Hereinafter, constitutional units (Cb1-1) to (Cb1-6) are shown as specific examples of the constitutional unit (Cb1). The constitutional unit (Cb1) is not limited thereto.




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Hereinafter, constitutional units (Cb2-1) to (Cb2-11) are shown as specific examples of the constitutional unit (Cb2). The constitutional unit (Cb2) is not limited thereto.




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Hereinafter, constitutional units (Cb3-1) to (Cb3-4) are shown as specific examples of the constitutional unit (Cb3). The constitutional unit (Cb3) is not limited thereto.




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Hereinafter, constitutional units (Cb4-1) to (Cb4-7) are shown as specific examples of the constitutional unit (Cb4). The constitutional unit (Cb4) is not limited thereto.




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Hereinafter, constitutional units (Cb5-1) to (Cb5-6) are shown as specific examples of the constitutional unit (Cb5). The constitutional unit (Cb5) is not limited thereto.




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Hereinafter, constitutional units (Cb6-1) to (Cb6-4) are shown as specific examples of the constitutional unit (Cb6). The constitutional unit (Cb6) is not limited thereto.




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Hereinafter, constitutional units (Cb7-1) to (Cb7-3) are shown as specific examples of the constitutional unit (Cb7). The constitutional unit (Cb7) is not limited thereto.




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Hereinafter, constitutional units (Cb8-1) to (Cb8-3) are shown as specific examples of the constitutional unit (Cb8). The constitutional unit (Cb8) is not limited thereto.




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The constitutional unit (C) of the polycarbonate resin (1) may be used alone or two or more kinds thereof.


The polycarbonate resin (1) may have other constitutional units in addition to the constitutional unit (C). Examples of other constitutional units include a constitutional unit derived from an aliphatic diol (such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, or neopentyl glycol) and phosgene, and a constitutional unit derived from an alicyclic diol (such as cyclohexanediol, cyclohexane dimethanol, or hydrogenated bisphenol A) and phosgene. These constitutional units of the polycarbonate resin (1) may be used alone or two or more kinds thereof.


The mass proportion of the constitutional unit (C) in the mass of the polycarbonate resin (1) is, for example, preferably 80% by mass or greater and 100% by mass or less, more preferably 90% by mass or greater and 100% by mass or less, and still more preferably 95% by mass or greater and 100% by mass or less.


The weight-average molecular weight of the polycarbonate resin and the polycarbonate resin (1) is, for example, preferably 35,000 or greater and 300,000 or less, more preferably 40,000 or greater and 250,000 or less, and still more preferably 50,000 or greater and 200,000 or less. The molecular weight of the polycarbonate resin is a molecular weight measured by gel permeation chromatography (GPC) in terms of polystyrene. The GPC is carried out by using tetrahydrofuran as an eluent.


Examples of the method of producing the polycarbonate resin and the polycarbonate resin (1) include an interfacial polymerization method, a solution polymerization method, and a melt polymerization method.


Conductive Substrate


Examples of the conductive substrate include metal plates containing metals (such as aluminum, copper, zinc, chromium, nickel, molybdenum, vanadium, indium, gold, and platinum) or alloys (such as stainless steel), metal drums, metal belts, and the like. Further, examples of the conductive substrate include paper, a resin film, a belt, and the like obtained by being coated, vapor-deposited or laminated with a conductive compound (such as a conductive polymer or indium oxide), a metal (such as aluminum, palladium, or gold) or an alloy. Here, the term “conductive” denotes that the volume resistivity is less than 1×1013 Ωcm.


In a case where the electrophotographic photoreceptor is used in a laser printer, for example, it is preferable that the surface of the conductive substrate is roughened such that a centerline average roughness Ra thereof is 0.04 μm or greater and 0.5 μm or less for the purpose of suppressing interference fringes from occurring in a case of irradiation with laser beams. In a case where incoherent light is used as a light source, roughening of the surface to prevent interference fringes is not particularly necessary, and the roughening is appropriate for longer life because occurrence of defects due to the unevenness of the surface of the conductive substrate is suppressed.


Examples of the roughening method include wet honing performed by suspending an abrasive in water and spraying the suspension to the conductive substrate, centerless grinding performed by pressure-welding the conductive substrate against a rotating grindstone and continuously grinding the conductive substrate, and an anodizing treatment.


Examples of the roughening method also include a method of dispersing conductive or semi-conductive powder in a resin without roughening the surface of the conductive substrate to form a layer on the surface of the conductive substrate, and performing roughening using the particles dispersed in the layer.


The roughening treatment performed by anodization is a treatment of forming an oxide film on the surface of the conductive substrate by carrying out anodization in an electrolytic solution using a conductive substrate made of a metal (for example, aluminum) as an anode. Examples of the electrolytic solution include a sulfuric acid solution and an oxalic acid solution. However, a porous anodized film formed by anodization is chemically active in a natural state, is easily contaminated, and has a large resistance fluctuation depending on the environment. Therefore, for example, it is preferable that a sealing treatment is performed on the porous anodized film so that the micropores of the oxide film are closed by volume expansion due to a hydration reaction in pressurized steam or boiling water (a metal salt such as nickel may be added thereto) for a change into a more stable a hydrous oxide.


The film thickness of the anodized film is, for example, preferably 0.3 μm or greater and 15 μm or less. In a case where the film thickness is in the above-described range, the barrier properties against injection tend to be exhibited, and an increase in the residual potential due to repeated use tends to be suppressed.


The conductive substrate may be subjected to a treatment with an acidic treatment liquid or a boehmite treatment.


The treatment with an acidic treatment liquid is carried out, for example, as follows. First, an acidic treatment liquid containing phosphoric acid, chromic acid, and hydrofluoric acid is prepared. In the blending ratio of phosphoric acid, chromic acid, and hydrofluoric acid to the acidic treatment liquid, for example, the concentration of the phosphoric acid is 10% by mass or greater and 11% by mass or less, the concentration of the chromic acid is 3% by mass or greater and 5% by mass or less, and the concentration of the hydrofluoric acid is 0.5% by mass or greater and 2% by mass or less, and the concentration of all these acids may be 13.5% by mass or greater and 18% by mass or less. The treatment temperature is, for example, preferably 42° C. or higher and 48° C. or lower. The film thickness of the coating film is, for example, preferably 0.3 μm or greater and 15 μm or less.


The boehmite treatment is carried out, for example, by immersing the conductive substrate in pure water at 90° C. or higher and 100° C. or lower for 5 minutes to 60 minutes or by bringing the conductive substrate into contact with heated steam at 90° C. or higher and 120° C. or lower for 5 minutes to 60 minutes. The film thickness of the coating film is, for example, preferably 0.1 μm or greater and 5 μm or less. This coating film may be further subjected to the anodizing treatment using an electrolytic solution having low film solubility, such as adipic acid, boric acid, a borate, a phosphate, a phthalate, a maleate, a benzoate, a tartrate, or a citrate.


Undercoat Layer


The undercoat layer is, for example, a layer containing inorganic particles and a binder resin.


Examples of the inorganic particles include inorganic particles having a powder resistance (volume resistivity) of 1×102 Ωcm or greater and 1×1011 Ωcm or less.


Among these, as the inorganic particles having the above-described resistance value, for example, metal oxide particles such as tin oxide particles, titanium oxide particles, zinc oxide particles, and zirconium oxide particles may be used, and zinc oxide particles are particularly preferable.


The specific surface area of the inorganic particles measured by the BET method may be, for example, 10 m2/g or greater.


The volume average particle diameter of the inorganic particles may be, for example, 50 nm or greater and 2,000 nm or less (for example, preferably 60 nm or greater and 1,000 nm or less).


The content of the inorganic particles is, for example, preferably 10% by mass or greater and 80% by mass or less and more preferably 40% by mass or greater and 80% by mass or less with respect to the amount of the binder resin.


The inorganic particles may be subjected to a surface treatment. As the inorganic particles, inorganic particles subjected to different surface treatments or inorganic particles having different particle diameters may be used in the form of a mixture of two or more kinds thereof.


Examples of the surface treatment agent include a silane coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, and a surfactant. In particular, for example, a silane coupling agent is preferable, and a silane coupling agent containing an amino group is more preferable.


Examples of the silane coupling agent containing an amino group include 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and N,N-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, but are not limited thereto.


The silane coupling agent may be used in the form of a mixture of two or more kinds thereof. For example, a silane coupling agent containing an amino group and another silane coupling agent may be used in combination. Examples of other silane coupling agents include vinyltrimethoxysilane, 3-methacryloxypropyl-tris(2-methoxyethoxy)silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N,N-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, and 3-chloropropyltrimethoxysilane, but are not limited thereto.


The surface treatment method using a surface treatment agent may be any method as long as the method is a known method, and any of a dry method or a wet method may be used.


The treatment amount of the surface treatment agent is, for example, preferably 0.5% by mass or greater and 10% by mass or less with respect to the amount of the inorganic particles.


Here, the undercoat layer may contain, for example, an electron-accepting compound (acceptor compound) together with the inorganic particles from the viewpoint of enhancing the long-term stability of the electrical properties and the carrier blocking properties.


Examples of the electron-accepting compound include electron-transporting substances, for example, a quinone-based compound such as chloranil or bromanil; a tetracyanoquinodimethane-based compound; a fluorenone compound such as 2,4,7-trinitrofluorenone or 2,4,5,7-tetranitro-9-fluorenone; an oxadiazole-based compound such as 2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole, 2,5-bis(4-naphthyl)-1,3,4-oxadiazole, or 2,5-bis(4-diethylaminophenyl)-1,3,4-oxadiazole; a xanthone-based compound; a thiophene compound; a diphenoquinone compound such as 3,3′,5,5′-tetra-t-butyldiphenoquinone; and a benzophenone compound.


In particular, as the electron-accepting compound, for example, a compound having an anthraquinone structure is preferable. As the compound having an anthraquinone structure, for example, a hydroxyanthraquinone compound, an aminoanthraquinone compound, or an aminohydroxyanthraquinone compound is preferable, and specifically, for example, anthraquinone, alizarin, quinizarin, anthrarufin, or purpurin is preferable.


The electron-accepting compound may be contained in the undercoat layer in a state of being dispersed with inorganic particles or in a state of being attached to the surface of each inorganic particle.


Examples of the method of attaching the electron-accepting compound to the surface of the inorganic particle include a dry method and a wet method.


The dry method is, for example, a method of attaching the electron-accepting compound to the surface of each inorganic particle by adding the electron-accepting compound dropwise to inorganic particles directly or by dissolving the electron-accepting compound in an organic solvent while stirring the inorganic particles with a mixer having a large shearing force and spraying the mixture together with dry air or nitrogen gas. The electron-accepting compound may be added dropwise or sprayed, for example, at a temperature lower than or equal to the boiling point of the solvent. After the dropwise addition or the spraying of the electron-accepting compound, the compound may be further baked at 100° C. or higher. The baking is not particularly limited as long as the temperature and the time are adjusted such that the electrophotographic characteristics can be obtained.


The wet method is, for example, a method of attaching the electron-accepting compound to the surface of each inorganic particle by adding the electron-accepting compound to inorganic particles while dispersing the inorganic particles in a solvent using a stirrer, ultrasonic waves, a sand mill, an attritor, or a ball mill, stirring or dispersing the mixture, and removing the solvent. The solvent removing method is carried out by, for example, filtration or distillation so that the solvent is distilled off. After removal of the solvent, the mixture may be further baked at 100° C. or higher. The baking is not particularly limited as long as the temperature and the time are adjusted such that the electrophotographic characteristics can be obtained. In the wet method, the moisture contained in the inorganic particles may be removed before the electron-accepting compound is added, and examples thereof include a method of removing the moisture while stirring and heating the moisture in a solvent and a method of removing the moisture by azeotropically boiling the moisture with a solvent.


The electron-accepting compound may be attached to the surface before or after the inorganic particles are subjected to a surface treatment with a surface treatment agent or simultaneously with the surface treatment performed on the inorganic particles with a surface treatment agent.


The content of the electron-accepting compound may be, for example, 0.01% by mass or greater and 20% by mass or less and preferably 0.01% by mass or greater and 10% by mass or less with respect to the amount of the inorganic particles.


Examples of the binder resin used for the undercoat layer include known polymer compounds such as an acetal resin (such as polyvinyl butyral), a polyvinyl alcohol resin, a polyvinyl acetal resin, a casein resin, a polyamide resin, a cellulose resin, gelatin, a polyurethane resin, a polyester resin, an unsaturated polyester resin, a methacrylic resin, an acrylic resin, a polyvinyl chloride resin, a polyvinyl acetate resin, a vinyl chloride-vinyl acetate-maleic acid anhydride resin, a silicone resin, a silicone-alkyd resin, a urea resin, a phenol resin, a phenol-formaldehyde resin, a melamine resin, a urethane resin, an alkyd resin, and an epoxy resin, a zirconium chelate compound, a titanium chelate compound, an aluminum chelate compound, a titanium alkoxide compound, an organic titanium compound, and known materials such as a silane coupling agent.


Examples of the binder resin used for the undercoat layer include a charge-transporting resin containing a charge-transporting group, and a conductive resin (such as polyaniline).


Among these, as the binder resin used for the undercoat layer, for example, a resin insoluble in a coating solvent of the upper layer is preferable, and a resin obtained by reaction between a curing agent and at least one resin selected from the group consisting of a thermosetting resin such as a urea resin, a phenol resin, a phenol-formaldehyde resin, a melamine resin, a urethane resin, an unsaturated polyester resin, an alkyd resin, or an epoxy resin; a polyamide resin, a polyester resin, a polyether resin, a methacrylic resin, an acrylic resin, a polyvinyl alcohol resin, and a polyvinyl acetal resin is particularly preferable.


In a case where these binder resins are used in combination of two or more kinds thereof, the mixing ratio thereof is set as necessary.


The undercoat layer may contain various additives for improving the electrical properties, the environmental stability, and the image quality.


Examples of the additives include known materials, for example, an electron-transporting pigment such as a polycyclic condensed pigment or an azo-based pigment, a zirconium chelate compound, a titanium chelate compound, an aluminum chelate compound, a titanium alkoxide compound, an organic titanium compound, and a silane coupling agent. The silane coupling agent is used for a surface treatment of the inorganic particles as described above, but may be further added to the undercoat layer as an additive.


Examples of the silane coupling agent serving as an additive include vinyltrimethoxysilane, 3-methacryloxypropyl-tris(2-methoxyethoxy)silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N,N-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, and 3-chloropropyltrimethoxysilane.


Examples of the zirconium chelate compound include zirconium butoxide, ethyl zirconium acetoacetate, zirconium triethanolamine, acetylacetonate zirconium butoxide, ethyl zirconium butoxide acetoacetate, zirconium acetate, zirconium oxalate, zirconium lactate, zirconium phosphonate, zirconium octanoate, zirconium naphthenate, zirconium laurate, zirconium stearate, zirconium isostearate, zirconium butoxide methacrylate, stearate zirconium butoxide, and isostearate zirconium butoxide.


Examples of the titanium chelate compound include tetraisopropyl titanate, tetranormal butyl titanate, a butyl titanate dimer, tetra(2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate ammonium salt, titanium lactate, titanium lactate ethyl ester, titanium triethanol aminate, and polyhydroxy titanium stearate.


Examples of the aluminum chelate compound include aluminum isopropylate, monobutoxyaluminum diisopropylate, aluminum butyrate, diethylacetoacetate aluminum diisopropylate, and aluminum tris(ethylacetoacetate).


These additives may be used alone or in the form of a mixture or a polycondensate of a plurality of compounds.


The undercoat layer may have, for example, a Vickers hardness of 35 or greater.


The surface roughness (ten-point average roughness) of the undercoat layer may be adjusted, for example, to ½ from 1/(4n) (n represents a refractive index of an upper layer) of a laser wavelength λ for exposure to be used to suppress moire fringes.


Resin particles or the like may be added to the undercoat layer to adjust the surface roughness. Examples of the resin particles include silicone resin particles and crosslinked polymethyl methacrylate resin particles. Further, the surface of the undercoat layer may be polished to adjust the surface roughness. Examples of the polishing method include buff polishing, a sandblast treatment, wet honing, and a grinding treatment.


The formation of the undercoat layer is not particularly limited, and a known forming method is used. For example, a coating film of a coating solution for forming an undercoat layer in which the above-described components are added to a solvent is formed, and the coating film is dried and, as necessary, heated.


Examples of the solvent for preparing the coating solution for forming an undercoat layer include known organic solvents such as an alcohol-based solvent, an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, a ketone-based solvent, a ketone alcohol-based solvent, an ether-based solvent, and an ester-based solvent.


Specific examples of these solvents include typical organic solvents such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, ethyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene.


Examples of the method of dispersing the inorganic particles in a case of preparing the coating solution for forming an undercoat layer include known methods such as a roll mill, a ball mill, a vibration ball mill, an attritor, a sand mill, a colloid mill, and a paint shaker.


Examples of the method of coating the conductive substrate with the coating solution for forming an undercoat layer include typical coating methods such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method.


The average thickness of the undercoat layer is, for example, preferably 15 μm or greater and more preferably 20 μm or greater and 50 μm or less.


Interlayer


An interlayer may be further provided between the undercoat layer and the photosensitive layer.


The interlayer is, for example, a layer containing a resin. Examples of the resin used for the interlayer include a polymer compound, for example, an acetal resin (such as polyvinyl butyral), a polyvinyl alcohol resin, a polyvinyl acetal resin, a casein resin, a polyamide resin, a cellulose resin, gelatin, a polyurethane resin, a polyester resin, a methacrylic resin, an acrylic resin, a polyvinyl chloride resin, a polyvinyl acetate resin, a vinyl chloride-vinyl acetate-maleic acid anhydride resin, a silicone resin, a silicone-alkyd resin, a phenol-formaldehyde resin, or a melamine resin.


The interlayer may be a layer containing an organometallic compound. Examples of the organometallic compound used for the interlayer include an organometallic compound containing metal atoms such as zirconium, titanium, aluminum, manganese, and silicon.


The compounds used for the interlayer may be used alone or in the form of a mixture or a polycondensate of a plurality of compounds.


Among these, it is preferable that the interlayer is, for example, a layer containing an organometallic compound having a zirconium atom or a silicon atom.


The formation of the interlayer is not particularly limited, and a known forming method is used. For example, a coating film of a coating solution for forming an interlayer in which the above-described components are added to a solvent is formed, and the coating film is dried and, as necessary, heated.


Examples of the coating method of forming the interlayer include typical coating methods such as a dip coating method, a push-up coating method, a wire bar coating method, a spray coating method, a blade coating method, an air knife coating method, and a curtain coating method.


The average thickness of the interlayer is, for example, preferably 0.1 μm or greater and 3 μm or less. The interlayer may be used as the undercoat layer.


Charge Generation Layer


The charge generation layer is, for example, a layer containing a charge generation material and a binder resin. Further, the charge generation layer may be a deposition layer of the charge generation material. The deposition layer of the charge generation material is, for example, appropriate in a case where an incoherent light source such as a light emitting diode (LED) or an organic electroluminescence (EL) image array is used.


Examples of the charge generation material include an azo pigment such as bisazo or trisazo; a fused ring aromatic pigment such as dibromoanthanthrone; a perylene pigment; a pyrrolopyrrole pigment; a phthalocyanine pigment; zinc oxide; and trigonal selenium.


Among these, for example, a metal phthalocyanine pigment or a metal-free phthalocyanine pigment is preferably used as the charge generation material in order to deal with laser exposure in a near infrared region. Specifically, for example, hydroxygallium phthalocyanine, chlorogallium phthalocyanine, dichloro-tin phthalocyanine, and titanyl phthalocyanine are more preferable.


On the other hand, for example, a fused ring aromatic pigment such as dibromoanthanthrone, a thioindigo-based pigment, a porphyrazine compound, zinc oxide, trigonal selenium, or a bisazo pigment is preferable as the charge generation material in order to deal with laser exposure in a near ultraviolet region.


The above-described charge generation material may also be used even in a case where an incoherent light source such as an LED or an organic EL image array having a center wavelength of light emission at 450 nm or greater and 780 nm or less is used, but from the viewpoint of the resolution, the field intensity in the photosensitive layer is increased, and a decrease in charge due to injection of a charge from the substrate, that is, image defects referred to as so-called black spots are likely to occur in a case where a thin film having a thickness of m or less is used as the photosensitive layer. The above-described tendency is evident in a case where a p-type semiconductor such as trigonal selenium or a phthalocyanine pigment is used as the charge generation material that is likely to generate a dark current.


On the other hand, in a case where an n-type semiconductor such as a fused ring aromatic pigment, a perylene pigment, or an azo pigment is used as the charge generation material, a dark current is unlikely to be generated, and image defects referred to as black spots can be suppressed even in a case where a thin film is used as the photosensitive layer. The n-type is determined by the polarity of the flowing photocurrent using a typically used time-of-flight method, and a material in which electrons more easily flow as carriers than positive holes is determined as the n-type.


The binder resin used for the charge generation layer is selected from a wide range of insulating resins, and the binder resin may be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene, polyvinylpyrene, and polysilane.


Examples of the binder resin include a polyvinyl butyral resin, a polyarylate resin (a polycondensate of bisphenols and aromatic divalent carboxylic acid), a polycarbonate resin, a polyester resin, a phenoxy resin, a vinyl chloride-vinyl acetate copolymer, a polyamide resin, an acrylic resin, a polyacrylamide resin, a polyvinylpyridine resin, a cellulose resin, a urethane resin, an epoxy resin, casein, a polyvinyl alcohol resin, and a polyvinylpyrrolidone resin. Here, the term “insulating” denotes that the volume resistivity is 1×1013 Ωcm or greater.


These binder resins may be used alone or in the form of a mixture of two or more kinds thereof.


The blending ratio between the charge generation material and the binder resin is, for example, preferably in a range of 10:1 to 1:10 in terms of the mass ratio.


The charge generation layer may also contain other known additives.


The formation of the charge generation layer is not particularly limited, and a known forming method is used. For example, a coating film of a coating solution for forming a charge generation layer in which the above-described components are added to a solvent is formed, and the coating film is dried and, as necessary, heated. The charge generation layer may be formed by vapor deposition of the charge generation material. The formation of the charge generation layer by vapor deposition is, for example, particularly appropriate in a case where a fused ring aromatic pigment or a perylene pigment is used as the charge generation material.


Examples of the solvent for preparing the coating solution for forming a charge generation layer include methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene. These solvents are used alone or in the form of a mixture of two or more kinds thereof.


As a method of dispersing particles (for example, the charge generation material) in the coating solution for forming a charge generation layer, for example, a media disperser such as a ball mill, a vibration ball mill, an attritor, a sand mill, or a horizontal sand mill, or a medialess disperser such as a stirrer, an ultrasonic disperser, a roll mill, or a high-pressure homogenizer is used. Examples of the high-pressure homogenizer include a collision type homogenizer in which a dispersion liquid is dispersed by a liquid-liquid collision or a liquid-wall collision in a high-pressure state, and a penetration type homogenizer in which a dispersion liquid is dispersed by penetrating the liquid through a micro-flow path in a high-pressure state.


During the dispersion, it is effective to set the average particle diameter of the charge generation material in the coating solution for forming a charge generation layer to 0.5 μm or less, for example, preferably 0.3 μm or less, and more preferably 0.15 μm or less.


Examples of the method of coating the undercoat layer (or the interlayer) with the coating solution for forming a charge generation layer include typical methods such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method.


The average thickness of the charge generation layer is, for example, preferably 0.1 μm or greater and 5.0 μm or less and more preferably 0.2 μm or greater and 2.0 μm or less.


Charge Transport Layer


The charge transport layer is, for example, a layer containing a charge transport material and a binder resin. The charge transport layer may be a layer containing a polymer charge transport material.


Examples of the charge transport material include a quinone-based compound such as p-benzoquinone, chloranil, bromanil, or anthraquinone; a tetracyanoquinodimethane-based compound; a fluorenone compound such as 2,4,7-trinitrofluorenone; a xanthone compound; a benzophenone-based compound; a cyanovinyl-based compound; and an electron-transporting compound such as an ethylene-based compound. Examples of the charge transport material include a positive hole-transporting compound such as a triarylamine-based compound, a benzidine-based compound, an arylalkane-based compound, an aryl-substituted ethylene-based compound, a stilbene-based compound, an anthracene-based compound, or a hydrazone-based compound. These charge transport materials may be used alone or in combination of two or more kinds thereof, but are not limited thereto.


Examples of the polymer charge transport material include known compounds having charge transport properties, such as poly-N-vinylcarbazole and polysilane. For example, a polyester-based polymer charge transport material is preferable. The polymer charge transport material may be used alone or in combination with a binder resin.


Examples of the charge transport material or the polymer charge transport material include a polycyclic aromatic compound, an aromatic nitro compound, an aromatic amine compound, a heterocyclic compound, a hydrazone compound, a styryl compound, an enamine compound, a benzidine compound, a triarylamine compound (particularly, a triphenylamine compound), a diamine compound, an oxadiazole compound, a carbazole compound, an organic polysilane compound, a pyrazoline compound, an indole compound, an oxazole compound, an isoxazole compound, a thiazole compound, a thiadiazole compound, an imidazole compound, a pyrazole compound, a triazole compound, a cyano compound, a benzofuran compound, an aniline compound, a butadiene compound, and a resin containing a group derived from any of these substances. Specific examples thereof include compounds described in paragraphs 0078 to 0080 of JP2021-117377A, paragraphs 0046 to 0048 of JP2019-035900A, paragraphs 0052 and 0053 of JP2019-012141A, paragraphs 0122 to 0134 of JP2021-071565A, paragraphs 0101 to 0110 of JP2021-015223A, paragraph 0116 of JP2013-097300A, paragraphs 0309 to 0316 of WO2019/070003A, paragraphs 0103 to 0107 of JP2018-159087A, and paragraphs 0102 to 0113 of JP2021-148818A.


From the viewpoint of the charge mobility, it is preferable that the charge transport material contains, for example, at least one selected from the group consisting of a compound (D1) represented by Formula (D1), a compound (D2) represented by Formula (D2), a compound (D3) represented by Formula (D3), and a compound (D4) represented by Formula (D4).




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In Formula (D1), ArT1, ArT2, and ArT3 each independently represent an aryl group, —C6H4—C(RT4)═C(RT5)(RT6) or —C6H4—CH═CH—CH═C(RT7)(RT8). RT4, RT5, RT6, RT7, and RT8 each independently represent a hydrogen atom, an alkyl group, or an aryl group. In a case where RT5 and RT6 represent an aryl group, the aryl groups may be linked via a divalent group of —C(R51)(R52)— and/or —C(R61)═C(R62)—. R51, R52, R61, and R62 each independently represent a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms.


The group in Formula (D1) may be substituted with a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group having 1 or more and 5 or less carbon atoms, or a substituted amino group substituted with an alkyl group having 1 or more and 3 or less carbon atoms.


From the viewpoint of the charge mobility, as the compound (D1), for example, a compound containing at least one of an aryl group or —C6H4—CH═CH—CH═C(RT7)(RT8) is preferable, and a compound (D′1) represented by Formula (D′1) is more preferable.




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In Formula (D′1), RT111, RT112, RT121, RT122, RT131, and RT132 each independently represent a hydrogen atom, a halogen atom, an alkyl group (for example, preferably an alkyl group having 1 or more and 3 or less carbon atoms), an alkoxy group (for example, preferably an alkoxy group having 1 or more and 3 or less carbon atoms), a phenyl group, or a phenoxy group. Tj1, Tj2, Tj3, Tk1, Tk2, and Tk3 each independently represent 0, 1, or 2.




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In Formula (D2), RT201, RT202, RT211, and RT212 each independently represent a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group having 1 or more and 5 or less carbon atoms, an amino group substituted with an alkyl group having 1 or 2 carbon atoms, an aryl group, —C(RT21)═C(RT22)(RT23), or —CH═CH—CH═C(RT24)(RT25). RT21, RT22, RT23, RT24, and RT25 each independently represent a hydrogen atom, an alkyl group, or an aryl group. RT221 and RT222 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, or an alkoxy group having 1 or more and 5 or less carbon atoms. Tm1, Tm2, Tn1, and Tn2 each independently represent 0, 1, or 2.


The group in Formula (D2) may be substituted with a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group having 1 or more and 5 or less carbon atoms, or a substituted amino group substituted with an alkyl group having 1 or more and 3 or less carbon atoms.


From the viewpoint of the charge mobility, as the compound (D2), for example, a compound containing at least one of an alkyl group, an aryl group, or —CH═CH—CH═C(RT24)(RT25) is preferable, and a compound containing two of an alkyl group, an aryl group, or —CH═CH—CH═C(RT24)(RT25) is more preferable.




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In Formula (D3), RT301, RT302, RT311, and RT312 each independently represent a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group having 1 or more and 5 or less carbon atoms, an amino group substituted with an alkyl group having 1 or 2 carbon atoms, an aryl group, —C(RT31)═C(RT32)(RT33), or —CH═CH—CH═C(RT34)(RT35). RT31, RT32, RT33, RT34, and RT35 each independently represent a hydrogen atom, an alkyl group, or an aryl group. RT321, RT322, and RT331 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, or an alkoxy group having 1 or more and 5 or less carbon atoms. To1, To2, Tp1, Tp2, Tq1, Tq2, and Tr each independently represent 0, 1, or 2.


The group in Formula (D3) may be substituted with a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group having 1 or more and 5 or less carbon atoms, or a substituted amino group substituted with an alkyl group having 1 or more and 3 or less carbon atoms.




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In Formula (D4), RT401, RT402, RT411, and RT412 each independently represent a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group having 1 or more and 5 or less carbon atoms, an amino group substituted with an alkyl group having 1 or 2 carbon atoms, an aryl group, —C(RT41)═C(RT42)(RT43), or —CH═CH—CH═C(RT44)(RT45). RT41, RT42, RT43, RT44, and RT45 each independently represent a hydrogen atom, an alkyl group, or an aryl group. RT421, RT422, and RT431 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, or an alkoxy group having 1 or more and 5 or less carbon atoms. Ts1, Ts2, Tt1, Tt2, Tu1, Tu2, and Tv1 each independently represent 0, 1, or 2.


The group in Formula (D4) may be substituted with a halogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, an alkoxy group having 1 or more and 5 or less carbon atoms, or a substituted amino group substituted with an alkyl group having 1 or more and 3 or less carbon atoms.


The content of the charge transport material contained in the charge transport layer is, for example, preferably 20% by mass or greater and 70% by mass or less with respect to the total mass of the charge transport layer.


The charge transport layer contains a polyester resin and a polycarbonate resin as binder resins. The proportion of the total amount of the polyester resin and the polycarbonate resin in the entire binder resins contained in the charge transport layer is, for example, preferably 80% by mass or greater, more preferably 90% by mass or greater, still more preferably 95% by mass or greater, and particularly preferably 100% by mass.


The charge transport layer may contain other binder resins in addition to the polyester resin and the polycarbonate resin. Examples of other binder resins include a methacrylic resin, an acrylic resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polystyrene resin, a polyvinyl acetate resin, a styrene-butadiene copolymer, a vinylidene chloride-acrylonitrile copolymer, a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-vinyl acetate-maleic acid anhydride copolymer, a silicone resin, a silicone alkyd resin, a phenol-formaldehyde resin, a styrene-alkyd resin, poly-N-vinylcarbazole, and polysilane. These binder resins may be used alone or in combination of two or more kinds thereof.


The charge transport layer may also contain other known additives. Examples of the additives include an antioxidant, a leveling agent, an antifoaming agent, a filler, and a viscosity adjuster.


The formation of the charge transport layer is not particularly limited, and a known forming method is used. For example, a coating film of a coating solution for forming a charge transport layer in which the above-described components are added to a solvent is formed, and the coating film is dried and, as necessary, heated.


Examples of the solvent for preparing the coating solution for forming a charge transport layer include typical organic solvents, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; ketones such as acetone and 2-butanone; halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, and ethylene chloride; and cyclic or linear ethers such as tetrahydrofuran and ethyl ether. These solvents are used alone or in the form of a mixture of two or more kinds thereof.


Examples of the coating method of coating the charge generation layer with the coating solution for forming a charge transport layer include typical methods such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, and a curtain coating method.


The average thickness of the charge transport layer is, for example, preferably 5 μm or greater and 50 μm or less, more preferably 10 μm or greater and 40 μm or less, and still more preferably 15 μm or greater and 30 μm or less.


Single Layer Type Photosensitive Layer


The single layer type photosensitive layer (charge generation/charge transport layer) is a layer containing a charge generation material, a charge transport material, a binder resin, and as necessary, other additives. These materials are the same as the materials described in the sections of the charge generation layer and the charge transport layer.


The single layer type photosensitive layer contains a polyester resin and a polycarbonate resin as a binder resin. The proportion of the total proportion of the polyester resin and the polycarbonate resin in the entire binder resin contained in the single layer type photosensitive layer is, for example, preferably 80% by mass or greater, more preferably 90% by mass or greater, still more preferably 95% by mass or greater, and particularly preferably 100% by mass or greater.


The content of the charge generation material in the single layer type photosensitive layer may be, for example, 0.1% by mass or greater and 10% by mass or less and preferably 0.8% by mass or greater and 5% by mass or less with respect to the total solid content.


The content of the charge transport material contained in the single layer type photosensitive layer may be, for example, 40% by mass or greater and 60% by mass or less with respect to the total solid content.


The method of forming the single layer type photosensitive layer is the same as the method of forming the charge generation layer or the charge transport layer.


The average thickness of the single layer type photosensitive layer is, for example, preferably 5 μm or greater and 50 μm or less, more preferably 10 μm or greater and 40 μm or less, and still more preferably 15 μm or greater and 30 μm or less.


Protective Layer


A protective layer is provided on the photosensitive layer as necessary. The protective layer is provided, for example, for the purpose of preventing a chemical change in the photosensitive layer during charging and further improving the mechanical strength of the photosensitive layer.


Therefore, for example, a layer formed of a cured film (crosslinked film) may be applied to the protective layer. Examples of these layers include the layers described in the items 1) and 2) below.

    • 1) A layer formed of a cured film of a composition containing a reactive group-containing charge transport material having a reactive group and a charge-transporting skeleton in an identical molecule (that is, a layer containing a polymer or a crosslinked body of the reactive group-containing charge transport material)
    • 2) A layer formed of a cured film of a composition containing a non-reactive charge transport material and a reactive group-containing non-charge transport material containing a reactive group without having a charge-transporting skeleton (that is, a layer containing the non-reactive charge transport material and a polymer or crosslinked body of the reactive group-containing non-charge transport material)


Examples of the reactive group of the reactive group-containing charge transport material include known reactive groups such as a chain polymerizable group, an epoxy group, —OH, —OR [here, R represents an alkyl group], —NH2, —SH, —COOH, and —SiRQ13-Qn(ORQ2)Qn[here, RQ1 represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group, RQ1 represents a hydrogen atom, an alkyl group, or a trialkylsilyl group, and Qn represents an integer of 1 to 3].


The chain polymerizable group is not particularly limited as long as the group is a functional group capable of radical polymerization and is, for example, a functional group containing a group having at least a carbon double bond. Specific examples thereof include a vinyl group, a vinyl ether group, a vinyl thioether group, a phenyl vinyl group, a vinyl phenyl group, an acryloyl group, a methacryloyl group, and a group containing at least one selected from derivatives thereof. Among these, from the viewpoint that the reactivity is excellent, for example, a vinyl group, a phenylvinyl group, a vinylphenyl group, an acryloyl group, a methacryloyl group, and a group containing at least one selected from derivatives thereof are preferable as the chain polymerizable group.


The charge-transporting skeleton of the reactive group-containing charge transport material is not particularly limited as long as the skeleton is a known structure in the electrophotographic photoreceptor, and examples thereof include a structure conjugated with a nitrogen atom, which is a skeleton derived from a nitrogen-containing positive hole-transporting compound such as a triarylamine-based compound, a benzidine-based compound, or a hydrazone-based compound. Among these, for example, a triarylamine skeleton is preferable.


The reactive group-containing charge transport material having the reactive group and the charge-transporting skeleton, the non-reactive charge transport material, and the reactive group-containing non-charge transport material may be selected from known materials.


The protective layer may also contain other known additives.


The formation of the protective layer is not particularly limited, and a known forming method is used. For example, a coating film of a coating solution for forming a protective layer in which the above-described components are added to a solvent is formed, and the coating film is dried and, as necessary, subjected to a curing treatment such as heating.


Examples of the solvent for preparing the coating solution for forming a protective layer include an aromatic solvent such as toluene or xylene; a ketone-based solvent such as methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone; an ester-based solvent such as ethyl acetate or butyl acetate; an ether-based solvent such as tetrahydrofuran or dioxane; a cellosolve-based solvent such as ethylene glycol monomethyl ether; and an alcohol-based solvent such as isopropyl alcohol or butanol. These solvents are used alone or in the form of a mixture of two or more kinds thereof.


The coating solution for forming a protective layer may be a solvent-less coating solution.


Examples of the method of coating the photosensitive layer (such as the charge transport layer) with the coating solution for forming a protective layer include typical coating methods such as a dip coating method, a push-up coating method, a wire bar coating method, a spray coating method, a blade coating method, an air knife coating method, and a curtain coating method.


The average thickness of the protective layer is, for example, preferably 1 μm or greater and 20 μm or less and more preferably 2 μm or greater and 10 μm or less.


Image Forming Apparatus and Process Cartridge


An image forming apparatus according to the present exemplary embodiment includes the electrophotographic photoreceptor, a charging device that charges a surface of the electrophotographic photoreceptor, an electrostatic latent image forming device that forms an electrostatic latent image on the charged surface of the electrophotographic photoreceptor, a developing device that develops the electrostatic latent image formed on the surface of the electrophotographic photoreceptor with a developer containing a toner to form a toner image, and a transfer device that transfers the toner image to a surface of a recording medium. Further, the electrophotographic photoreceptor according to the present exemplary embodiment is employed as the electrophotographic photoreceptor.


As the image forming apparatus according to the present exemplary embodiment, known image forming apparatuses such as an apparatus including a fixing device that fixes a toner image transferred to the surface of a recording medium; a direct transfer type apparatus that transfers a toner image formed on the surface of an electrophotographic photoreceptor directly to a recording medium; an intermediate transfer type apparatus that primarily transfers a toner image formed on the surface of an electrophotographic photoreceptor to the surface of an intermediate transfer member and secondarily transfers the toner image transferred to the surface of the intermediate transfer member to the surface of a recording medium; an apparatus including a cleaning device that cleans the surface of an electrophotographic photoreceptor after the transfer of a toner image and before the charging; an apparatus including a destaticizing device that destaticizes the surface of an electrophotographic photoreceptor by irradiating the surface with destaticizing light after the transfer of a toner image and before the charging; and an apparatus including an electrophotographic photoreceptor heating member for increasing the temperature of an electrophotographic photoreceptor and decreasing the relative temperature are employed.


In a case of the intermediate transfer type apparatus, the transfer device is, for example, configured to include an intermediate transfer member having a surface onto which the toner image is transferred, a primary transfer device primarily transferring the toner image formed on the surface of the electrophotographic photoreceptor to the surface of the intermediate transfer member, and a secondary transfer device secondarily transferring the toner image transferred to the surface of the intermediate transfer member to the surface of the recording medium.


The image forming apparatus according to the present exemplary embodiment may be any of a dry development type image forming apparatus or a wet development type (development type using a liquid developer) image forming apparatus.


In the image forming apparatus according to the present exemplary embodiment, for example, the portion including the electrophotographic photoreceptor may have a cartridge structure (process cartridge) that is attachable to and detachable from the image forming apparatus. As the process cartridge, for example, a process cartridge including the electrophotographic photoreceptor according to the present exemplary embodiment is preferably used. Further, the process cartridge may include, for example, at least one selected from the group consisting of a charging device, an electrostatic latent image forming device, a developing device, and a transfer device in addition to the electrophotographic photoreceptor.


Hereinafter, an example of the image forming apparatus according to the present exemplary embodiment will be described, but the present exemplary embodiment is not limited thereto. Further, main parts shown in the figures will be described, but description of other parts will not be provided.



FIG. 3 is a schematic configuration view showing an example of an image forming apparatus according to the present exemplary embodiment.


As shown in FIG. 3, an image forming apparatus 100 according to the present exemplary embodiment includes a process cartridge 300 including an electrophotographic photoreceptor 7, an exposure device 9 (an example of an electrostatic latent image forming device), a transfer device 40 (primary transfer device), and an intermediate transfer member 50. In the image forming apparatus 100, the exposure device 9 is disposed at a position that can be exposed to the electrophotographic photoreceptor 7 from an opening portion of the process cartridge 300, the transfer device 40 is disposed at a position that faces the electrophotographic photoreceptor 7 via the intermediate transfer member 50, and the intermediate transfer member 50 is disposed such that a part of the intermediate transfer member 50 is in contact with the electrophotographic photoreceptor 7. Although not shown, the image forming apparatus also includes a secondary transfer device that transfers the toner image transferred to the intermediate transfer member 50 to a recording medium (for example, paper). Further, the intermediate transfer member 50, the transfer device 40 (primary transfer device), and the secondary transfer device (not shown) correspond to an example of the transfer device.


The process cartridge 300 in FIG. 3 integrally supports the electrophotographic photoreceptor 7, a charging device 8 (an example of the charging device), a developing device 11 (an example of the developing device), and a cleaning device 13 (an example of the cleaning device) in a housing. The cleaning device 13 has a cleaning blade (an example of the cleaning member) 131, and the cleaning blade 131 is disposed to come into contact with the surface of the electrophotographic photoreceptor 7. The cleaning member may be a conductive or insulating fibrous member instead of the aspect of the cleaning blade 131, and may be used alone or in combination with the cleaning blade 131.



FIG. 3 shows an example of an image forming apparatus including a fibrous member 132 (roll shape) that supplies a lubricant 14 to the surface of the electrophotographic photoreceptor 7 and a fibrous member 133 (flat brush shape) that assists cleaning, but these are disposed as necessary.


Hereinafter, each configuration of the image forming apparatus according to the present exemplary embodiment will be described.


Charging Device


As the charging device 8, for example, a contact-type charger formed of a conductive or semi-conductive charging roller, a charging brush, a charging film, a charging rubber blade, a charging tube, or the like is used. Further, a known charger such as a non-contact type roller charger, or a scorotron charger or a corotron charger using corona discharge is also used.


Exposure Device


Examples of the exposure device 9 include an optical system device that exposes the surface of the electrophotographic photoreceptor 7 to light such as a semiconductor laser beam, LED light, and liquid crystal shutter light in a predetermined image pattern. The wavelength of the light source is within the spectral sensitivity region of the electrophotographic photoreceptor. As the wavelength of a semiconductor laser, near infrared, which has an oscillation wavelength in the vicinity of 780 nm, is mostly used. However, the wavelength is not limited thereto, and a laser having an oscillation wavelength at a level of 600 nm or a laser having an oscillation wavelength of 400 nm or greater and 450 nm or less as a blue laser may also be used. Further, a surface emission type laser light source capable of outputting a multi-beam is also effective for forming a color image.


Developing Device


Examples of the developing device 11 include a typical developing device that performs development in contact or non-contact with the developer. The developing device 11 is not particularly limited as long as the developing device has the above-described functions, and is selected depending on the purpose thereof. Examples of the developing device include known developing machines having a function of attaching a one-component developer or a two-component developer to the electrophotographic photoreceptor 7 using a brush, a roller, or the like. Among these, for example, a developing device formed of a developing roller having a surface on which a developer is held is preferably used.


The developer used in the developing device 11 may be a one-component developer containing only a toner or a two-component developer containing a toner and a carrier. Further, the developer may be magnetic or non-magnetic. Known developers are employed as these developers.


Cleaning Device


As the cleaning device 13, a cleaning blade type device including the cleaning blade 131 is used. In addition to the cleaning blade type device, a fur brush cleaning type device or a simultaneous development cleaning type device may be employed.


Transfer Device


Examples of the transfer device 40 include a known transfer charger such as a contact-type transfer charger using a belt, a roller, a film, a rubber blade, or the like, or a scorotron transfer charger or a corotron transfer charger using corona discharge.


Intermediate Transfer Member


As the intermediate transfer member 50, a belt-like intermediate transfer member (intermediate transfer belt) containing semi-conductive polyimide, polyamide-imide, polycarbonate, polyarylate, polyester, rubber, or the like is used. Further, as the form of the intermediate transfer member, a drum-like intermediate transfer member may be used in addition to the belt-like intermediate transfer member.



FIG. 4 is a schematic configuration view showing an example of an image forming apparatus according to the present exemplary embodiment.


An image forming apparatus 120 shown in FIG. 4 is a tandem type multicolor image forming apparatus on which four process cartridges 300 are mounted. The image forming apparatus 120 is formed such that four process cartridges 300 are arranged in parallel on the intermediate transfer member 50, and one electrophotographic photoreceptor is used for each color. The image forming apparatus 120 has the same configuration as the image forming apparatus 100 except that the image forming apparatus 120 is of a tandem type.


Examples

Hereinafter, exemplary embodiments of the invention will be described in detail based on examples, but the exemplary embodiments of the invention are not limited to the examples.


In the following description, “parts” and “%” are on a mass basis unless otherwise specified.


In the following description, the synthesis, the treatment, the production, and the like are carried out at room temperature (25° C.±3° C.) unless otherwise specified.


Preparation of Resin in Photosensitive Layer


Polyester Resin


Polyester resins (PE1) to (PE6), which are polyester resins (1), are prepared. Table 1 shows units, compositions, and weight-average molecular weights (Mw) of the polyester resins.


Table 1 shows “constitutional unit:compositional ratio” (for example, A2-3:50). The compositional ratio is in units of % by mole of each of the dicarboxylic acid unit and the diol unit.


A2-3 and the like listed in Table 1 are specific examples of the dicarboxylic acid unit (A) described above.


B9-5 and the like listed in Table 1 are specific examples of the diol unit (B) described above.









TABLE 1







Polyester resin













Mw


Resin No.
Dicarboxylic acid unit
Diol unit
[×10,000]















PE1
A2-3:50

B9-5:50

11


PE2
A2-3:50

B10-1:50

12


PE3
A2-3:50

B9-7:50

10


PE4
A3-2:50

B6-4:25
B10-1:25
11


PE5
A3-2:50

B3-4:25
B7-1:25
12


PE6
A3-2:25
A4-3:25
B11-3:50

13









A polyester resin (PEc1) other than the polyester resin (1) is prepared as a comparative polyester resin. The units constituting the polyester resin (PEc1) are as follows. The compositional ratio of the dicarboxylic acid unit to the diol unit is 50:50 in units of % by mole. The weight-average molecular weight of the polyester resin (PEc1) is 100,000.




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Polycarbonate Resin


Polycarbonate resins (PC1) to (PC4), which are polycarbonate resins (1), are prepared. Table 2 shows constitutional units, compositional ratios, and weight-average molecular weights (Mw) of the polycarbonate resins.


Table 2 shows “constitutional unit:compositional ratio” (for example, Cb6-3:50). The compositional ratio of each constitutional unit is in units of % by mole.


Cb6-3 and the like listed in Table 2 are specific examples of the constitutional unit (C) described above.









TABLE 2







Polycarbonate resin












Resin No.
Constitutional unit

Mw [×10,000]
















PC1
Cb6-3:50
Cb7-1:50
17



PC2
Cb6-3:100

19



PC3
Cb4-3:100

15



PC4
Cb4-1:100

14










Production of Photoreceptor Including Lamination Type Photosensitive Layer


Example S1

Formation of Undercoat Layer


An aluminum cylindrical tube having an outer diameter of 30 mm, a length of 250 mm, and a thickness of 1 mm is prepared as a conductive substrate.


0 parts of zinc oxide (average particle diameter of 70 nm, specific surface area of 15 m2/g, manufactured by Tayca Corporation) is stirred and mixed with 500 parts of toluene, 1.3 parts of a silane coupling agent (trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd., N-2-(aminoethyl)-3-aminopropyltrimethoxysilane) is added thereto, and the mixture is stirred for 2 hours. Thereafter, toluene is distilled off under reduced pressure and baked at 120° C. for 3 hours to obtain zinc oxide subjected to a surface treatment with a silane coupling agent.


110 parts of the surface-treated zinc oxide is stirred and mixed with 500 parts of tetrahydrofuran, a solution obtained by dissolving 0.6 part of alizarin in 50 parts of tetrahydrofuran is added thereto, and the mixture is stirred at 50° C. for 5 hours. Thereafter, the solid content is separated by filtration by carrying out filtration under reduced pressure and dried at 60° C. under reduced pressure, thereby obtaining zinc oxide with alizarin.


100 parts of a solution obtained by dissolving 60 parts of the zinc oxide with alizarin, 13.5 parts of a curing agent (blocked isocyanate, trade name: SUMIDUR 3175, manufactured by Sumitomo Bayer Urethane Co., Ltd.), and 15 parts of a butyral resin (trade name: S-LEC BM-1, manufactured by Sekisui Chemical Co., Ltd.) in 68 parts of methyl ethyl ketone is mixed with 5 parts of methyl ethyl ketone, and the solution is dispersed in a sand mill for 2 hours using glass beads with a diameter of 1 mmφ, thereby obtaining a dispersion liquid. 0.005 part of dioctyltin dilaurate as a catalyst and 4 parts of silicone resin particles (trade name: TOSPEARL 145, manufactured by Momentive Performance Materials Inc.) are added to the dispersion liquid, thereby obtaining a coating solution for forming an undercoat layer. The outer peripheral surface of the conductive substrate is coated with the coating solution for forming an undercoat layer by a dip coating method, and dried and cured at 170° C. for 40 minutes to form an undercoat layer. The average thickness of the undercoat layer is 25 μm.


Formation of Charge Generation Layer


A mixture of 15 parts of hydroxygallium phthalocyanine as a charge generation material (Bragg angle (2θ±0.2°) of the X-ray diffraction spectrum using Cukα characteristic X-ray has diffraction peaks at positions at least of 7.5°, 9.9°, 12.5, 16.3°, 18.6°, 25.1°, and 28.3°), 10 parts of a vinyl chloride-vinyl acetate copolymer resin (trade name: VMCH, Nippon Unicar Company Limited) as a binder resin, and 200 parts of n-butyl acetate is dispersed in a sand mill for 4 hours using glass beads having a diameter of 1 mm. 175 parts of n-butyl acetate and 180 parts of methyl ethyl ketone are added to the dispersion liquid, and the mixture is stirred, thereby obtaining a coating solution for forming a charge generation layer. The undercoat layer is immersed in and coated with the coating solution for forming a charge generation layer, and dried at room temperature (25° C.±3° C.) to form a charge generation layer having an average thickness of 0.18 μm.


Formation of Charge Transport Layer


30 parts of the polyester resin (PE1), 30 parts of the polycarbonate resin (PC1), and 40 parts of the charge transport material CTM-1 are dissolved in 270 parts of tetrahydrofuran and 30 parts of toluene, thereby obtaining a coating solution for forming a charge transport layer. The charge generation layer is immersed in and coated with the coating solution for forming a charge transport layer, and dried at 145° C. for 30 minutes to form ae charge transport layer. The average thickness of the charge transport layer is 30 μm.




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Examples S2 to S144 and Comparative Examples SC1 to SC2

Each photoreceptor is prepared in the same manner as in Example S1 except that the kind and the content proportion of the charge transport layer are changed to the specification listed in Tables 3-1 to 3-6.


Production of Photoreceptor Including Single Layer Type Photosensitive Layer


Example T1

Formation of Undercoat Layer


An aluminum cylindrical tube having an outer diameter of 30 mm, a length of 250 mm, and a thickness of 1 mm is prepared as a conductive substrate.


100 parts of zinc oxide (average particle diameter of 70 nm, specific surface area of 15 m2/g, manufactured by Tayca Corporation) is stirred and mixed with 500 parts of toluene, 1.3 parts of a silane coupling agent (trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd., N-2-(aminoethyl)-3-aminopropyltrimethoxysilane) is added thereto, and the mixture is stirred for 2 hours. Thereafter, toluene is distilled off under reduced pressure and baked at 120° C. for 3 hours to obtain zinc oxide subjected to a surface treatment with a silane coupling agent.


110 parts of the surface-treated zinc oxide is stirred and mixed with 500 parts of tetrahydrofuran, a solution obtained by dissolving 0.6 part of alizarin in 50 parts of tetrahydrofuran is added thereto, and the mixture is stirred at 50° C. for 5 hours. Thereafter, the solid content is separated by filtration by carrying out filtration under reduced pressure and dried at 60° C. under reduced pressure, thereby obtaining zinc oxide with alizarin.


100 parts of a solution obtained by dissolving 60 parts of the zinc oxide with alizarin, 13.5 parts of a curing agent (blocked isocyanate, trade name: SUMIDUR 3175, manufactured by Sumitomo Bayer Urethane Co., Ltd.), and 15 parts of a butyral resin (trade name: S-LEC BM-1, manufactured by Sekisui Chemical Co., Ltd.) in 68 parts of methyl ethyl ketone is mixed with 5 parts of methyl ethyl ketone, and the solution is dispersed in a sand mill for 2 hours using glass beads with a diameter of 1 mmφ, thereby obtaining a dispersion liquid. 0.005 part of dioctyltin dilaurate as a catalyst and 4 parts of silicone resin particles (trade name: TOSPEARL 145, manufactured by Momentive Performance Materials Inc.) are added to the dispersion liquid, thereby obtaining a coating solution for forming an undercoat layer. The outer peripheral surface of the conductive substrate is coated with the coating solution for forming an undercoat layer by a dip coating method, and dried and cured at 170° C. for 40 minutes to form an undercoat layer. The average thickness of the undercoat layer is 25 μm.


Formation of Single Layer Type Photosensitive Layer


22.88 parts of the polyester resin (PE1), 22.88 parts of the polycarbonate resin (PC1), 1.25 parts of V-type hydroxygallium phthalocyanine as a charge generation material (Bragg angle (2θ±0.2°) of the X-ray diffraction spectrum using Cukα characteristic X-ray has diffraction peaks at positions of at least 7.3°, 16.0°, 24.9°, and 28.0°), 9 parts of ETM-1 as an electron transport material, 44 parts of CTM-1 as a charge transport material, and 175 parts of tetrahydrofuran and 75 parts of toluene as solvents are mixed, and the mixture is subjected to a dispersion treatment in a sand mill for 4 hours using glass beads having a diameter of 1 mm, thereby obtaining a coating solution for forming a photosensitive layer. The undercoat layer is immersed in and coated with the coating solution for forming a photosensitive layer and dried and cured at a temperature of 110° C. for 40 minutes, thereby forming a single layer type photosensitive layer. The average thickness of the single layer type photosensitive layer is 30 μm.




embedded image


Examples T2 to T24 and Comparative Examples TC1 to TC2

Each photoreceptor is prepared in the same manner as in Example T1 except that the kind and the content proportion of the single layer type photosensitive layer are changed to the specification listed in Table 4.


Performance Evaluation of Photoreceptor


Each photoreceptor of the examples and the comparative examples is mounted on an image forming apparatus DocuCentre Color 500 (manufactured by FUJIFILM Business Innovation Corporation). Columnar carbon fibers (average diameter of 10 μm, average length of 70 μm) are mixed into a black toner cartridge.


A black image with an image density of 10% is continuously output onto one entire surface of each of 1,000 sheets of A4 paper in a high-temperature and high-humidity environment of a temperature of 30° C. and a relative humidity of 85%. The last 10 sheets are visually observed, and the number of black spots is counted. Further, the surface of the photoreceptor is analyzed with a laser microscope (manufactured by Lasertec Corporation), the depths of cracks (m) from the unevenness profile in a site where foreign matter is stuck within 10 visual fields are measured at a magnification of 20 times, and the average value thereof is calculated. The results are listed in Tables 3-1 to 3-6 and Table 4.











TABLE 3-1









Performance evaluation











Charge transport layer
Generation of














Polyester resin (1) or
Polycarbonate
Proportion of polyester resin (1)
black spots
Depth of



comparative resin
resin
or comparative resin in resins
Number of
cracks



Resin No.
Resin No.
mass %
black spots
μm
















Comparative
PEc1
PC1
50
10360
5.2


Example SC1


Comparative
PEc1
PC2
50
10600
5.3


Example SC2


Example S1
PE1
PC1
50
1355
0.4


Example S2
PE1
PC1
5
2606
1.3


Example S3
PE1
PC1
20
1322
0.6


Example S4
PE1
PC1
30
1333
0.5


Example S5
PE1
PC1
40
1344
0.5


Example S6
PE1
PC1
60
1366
0.4


Example S7
PE1
PC1
70
1377
0.3


Example S8
PE1
PC1
80
1388
0.3


Example S9
PE1
PC1
95
2705
0.8


Example S10
PE1
PC2
50
1505
0.5


Example S11
PE1
PC2
5
2906
1.4


Example S12
PE1
PC2
20
1472
0.6


Example S13
PE1
PC2
30
1483
0.6


Example S14
PE1
PC2
40
1494
0.5


Example S15
PE1
PC2
60
1516
0.4


Example S16
PE1
PC2
70
1527
0.4


Example S17
PE1
PC2
80
1538
0.3


Example S18
PE1
PC2
95
3005
1.0


Example S19
PE1
PC3
50
1398
0.6


Example S20
PE1
PC3
5
2610
1.3


Example S21
PE1
PC3
20
1339
0.6


Example S22
PE1
PC3
80
1456
0.5


Example S23
PE1
PC3
95
2785
1.1


Example S24
PE1
PC4
50
1461
0.5


Example S25
PE1
PC4
5
2730
1.3


Example S26
PE1
PC4
20
1400
0.6


Example S27
PE1
PC4
80
1519
0.4


Example S28
PE1
PC4
95
2909
1.1


















TABLE 3-2









Performance evaluation











Charge transport layer
Generation of














Polyester resin (1) or

Proportion of polyester resin (1)
black spots
Depth of



comparative resin
Polycarbonate resin
or comparative resin in resins
Number of
cracks



Resin No.
Resin No.
mass %
black spots
μm
















Example S29
PE2
PC1
50
1953
0.7


Example S30
PE2
PC1
5
3805
1.9


Example S31
PE2
PC1
20
1921
0.9


Example S32
PE2
PC1
30
1932
0.8


Example S33
PE2
PC1
40
1942
0.8


Example S34
PE2
PC1
60
1963
0.7


Example S35
PE2
PC1
70
1974
0.6


Example S36
PE2
PC1
80
1984
0.6


Example S37
PE2
PC1
95
3900
1.4


Example S38
PE2
PC2
50
2103
0.8


Example S39
PE2
PC2
5
4105
2.0


Example S40
PE2
PC2
20
2071
0.9


Example S41
PE2
PC2
30
2082
0.9


Example S42
PE2
PC2
40
2092
0.8


Example S43
PE2
PC2
60
2113
0.7


Example S44
PE2
PC2
70
2124
0.7


Example S45
PE2
PC2
80
2134
0.6


Example S46
PE2
PC2
95
4200
1.6


Example S47
PE2
PC3
50
2104
0.8


Example S48
PE2
PC3
5
4010
2.0


Example S49
PE2
PC3
20
2042
0.9


Example S50
PE2
PC3
80
2166
0.6


Example S51
PE2
PC3
95
4198
1.5


Example S52
PE2
PC4
50
2163
0.7


Example S53
PE2
PC4
5
4130
2.0


Example S54
PE2
PC4
20
2101
0.9


Example S55
PE2
PC4
80
2225
0.6


Example S56
PE2
PC4
95
4316
1.5


















TABLE 3-3









Performance evaluation











Charge transport layer
Generation of














Polyester resin (1) or

Proportion of polyester resin (1)
black spots
Depth of



comparative resin
Polycarbonate resin
or comparative resin in resins
Number of
cracks



Resin No.
Resin No.
mass %
black spots
μm
















Example S57
PE3
PC1
50
2758
1.1


Example S58
PE3
PC1
5
5406
2.7


Example S59
PE3
PC1
20
2723
1.3


Example S60
PE3
PC1
30
2735
1.2


Example S61
PE3
PC1
40
2746
1.2


Example S62
PE3
PC1
60
2769
1.1


Example S63
PE3
PCI
70
2781
1.0


Example S64
PE3
PC1
80
2792
1.0


Example S65
PE3
PC1
95
5509
2.2


Example S66
PE3
PC2
50
2908
1.2


Example S67
PE3
PC2
5
5706
2.8


Example S68
PE3
PC2
20
2873
1.3


Example S69
PE3
PC2
30
2885
1.3


Example S70
PE3
PC2
40
2896
1.2


Example S71
PE3
PC2
60
2919
1.1


Example S72
PE3
PC2
70
2931
1.1


Example S73
PE3
PC2
80
2942
1.0


Example S74
PE3
PC2
95
5809
2.4


Example S75
PE3
PC3
50
2803
1.1


Example S76
PE3
PC3
5
5410
2.7


Example S77
PE3
PC3
20
2741
1.3


Example S78
PE3
PC3
80
2865
1.0


Example S79
PE3
PC3
95
5596
2.2


Example S80
PE3
PC4
50
2862
1.1


Example S81
PE3
PC4
5
5530
2.7


Example S82
PE3
PC4
20
2801
1.3


Example S83
PE3
PC4
80
2923
0.9


Example S84
PE3
PC4
95
5714
2.2


















TABLE 3-4









Performance evaluation











Charge transport layer
Generation of














Polyester resin (1) or

Proportion of polyester resin (1)
black spots
Depth of



comparative resin
Polycarbonate resin
or comparative resin in resins
Number of
cracks



Resin No.
Resin No.
mass %
black spots
μm
















Example S85
PE4
PC1
50
3558
1.5


Example S86
PE4
PC1
5
7006
3.5


Example S87
PE4
PC1
20
3523
1.7


Example S88
PE4
PC1
80
3592
1.4


Example S89
PE4
PC1
95
7109
3.0


Example S90
PE4
PC2
50
3708
1.6


Example S91
PE4
PC2
5
7306
3.6


Example S92
PE4
PC2
20
3673
1.7


Example S93
PE4
PC2
80
3742
1.4


Example S94
PE4
PC2
95
7409
3.2


Example S95
PE4
PC3
50
1398
0.6


Example S96
PE4
PC3
5
2610
1.3


Example S97
PE4
PC3
20
1339
0.6


Example S98
PE4
PC3
80
1456
0.5


Example S99
PE4
PC3
95
2785
1.1


Example S100
PE4
PC4
50
1461
0.5


Example S101
PE4
PC4
5
2730
1.3


Example S102
PE4
PC4
20
1400
0.6


Example S103
PE4
PC4
80
1519
0.4


Example S104
PE4
PC4
95
2909
1.1


















TABLE 3-5









Performance evaluation











Charge transport layer
Generation of














Polyester resin (1) or

Proportion of polyester resin (1)
black spots
Depth of



comparative resin
Polycarbonate resin
or comparative resin in resins
Number of
cracks



Resin No.
Resin No.
mass %
black spots
μm
















Example S105
PE5
PC1
50
4352
1.9


Example S106
PE5
PC1
5
8605
4.3


Example S107
PE5
PC1
20
4321
2.1


Example S108
PE5
PC1
80
4382
1.8


Example S109
PE5
PC1
95
8698
3.8


Example S110
PE5
PC2
50
4502
2.0


Example S111
PE5
PC2
5
8905
4.4


Example S112
PE5
PC2
20
4471
2.1


Example S113
PE5
PC2
80
4532
1.8


Example S114
PE5
PC2
95
8998
4.0


Example S115
PE5
PC3
50
4204
1.8


Example S116
PE5
PC3
5
8210
4.1


Example S117
PE5
PC3
20
4142
2.0


Example S118
PE5
PC3
80
4266
1.7


Example S119
PE5
PC3
95
8398
3.6


Example S120
PE5
PC4
50
4263
1.8


Example S121
PE5
PC4
5
8330
4.1


Example S122
PE5
PC4
20
4201
2.0


Example S123
PE5
PC4
80
4325
1.6


Example S124
PE5
PC4
95
8516
3.6


















TABLE 3-6









Performance evaluation











Charge transport layer
Generation of














Polyester resin (1) or

Proportion of polyester resin (1)
black spots
Depth of



comparative resin
Polycarbonate resin
or comparative resin in resins
Number of
cracks



Resin No.
Resin No.
mass %
black spots
μm
















Example S125
PE6
PC1
50
4554
2.0


Example S126
PE6
PC1
5
9005
4.5


Example S127
PE6
PC1
20
4522
2.2


Example S128
PE6
PC1
80
4586
1.9


Example S129
PE6
PC1
95
9103
4.0


Example S130
PE6
PC2
50
4704
2.1


Example S131
PE6
PC2
5
9305
4.6


Example S132
PE6
PC2
20
4672
2.2


Example S133
PE6
PC2
80
4736
1.9


Example S134
PE6
PC2
95
9403
4.2


Example S135
PE6
PC3
50
4894
2.3


Example S136
PE6
PC3
5
9609
4.8


Example S137
PE6
PC3
20
4837
2.3


Example S138
PE6
PC3
80
4950
2.2


Example S139
PE6
PC3
95
9778
4.5


Example S140
PE6
PC4
50
4937
2.1


Example S141
PE6
PC4
5
9728
4.8


Example S142
PE6
PC4
20
4891
2.3


Example S143
PE6
PC4
80
4983
2.0


Example S144
PE6
PC4
95
9866
4.3


















TABLE 4









Performance evaluation











Charge transport layer
Generation of














Polyester resin (1) or

Proportion of polyester resin (1)
black spots
Depth of



comparative resin
Polycarbonate resin
or comparative resin in resins
Number of
cracks



Resin No.
Resin No.
mass %
black spots
μm
















Comparative
PEc1
PC1
50
10361
4.9


Example TC1


Comparative
PEc1
PC2
50
10660
5.1


Example TC2


Example T1
PE1
PC1
50
1352
0.4


Example T2
PE1
PC2
50
1651
0.6


Example T3
PE1
PC3
50
1852
0.6


Example T4
PE1
PC4
50
2004
0.7


Example T5
PE2
PC1
50
1953
0.7


Example T6
PE2
PC2
50
2250
0.9


Example T7
PE2
PC3
50
2453
0.9


Example T8
PE2
PC4
50
2600
1.0


Example T9
PE3
PC1
50
2751
1.1


Example T10
PE3
PC2
50
3049
1.3


Example T11
PE3
PC3
50
4051
1.7


Example T12
PE3
PC4
50
4199
1.8


Example T13
PE4
PC1
50
3549
1.5


Example T14
PE4
PC2
50
3850
1.7


Example T15
PE4
PC3
50
4049
1.7


Example T16
PE4
PC4
50
4200
1.8


Example T17
PE5
PC1
50
4352
1.9


Example T18
PE5
PC2
50
4653
2.1


Example T19
PE5
PC3
50
4852
2.1


Example T20
PE5
PC4
50
5003
2.2


Example T21
PE6
PC1
50
5150
2.3


Example T22
PE6
PC2
50
5451
2.5


Example T23
PE6
PC3
50
5654
2.5


Example T24
PE6
PC4
50
5801
2.6











    • (((1)))

    • An electrophotographic photoreceptor comprising:

    • a conductive substrate; and

    • a lamination type photosensitive layer disposed on the conductive substrate and including a charge generation layer and a charge transport layer,

    • wherein the charge transport layer contains a charge transport material, a polyester resin, and a polycarbonate resin, and

    • the polyester resin includes the following polyester resin (1),

    • polyester resin (1): a polyester resin having at least one selected from the group consisting of a diol unit (B3) represented by Formula (B3), a diol unit (B5) represented by Formula (B5), a diol unit (B6) represented by Formula (B6), a diol unit (B7) represented by Formula (B7), a diol unit (B8) represented by Formula (B8), a diol unit (B9) represented by Formula (B9), a diol unit (B10) represented by Formula (B10), and a diol unit (B11) represented by Formula (B11).

    • (((2)))

    • The electrophotographic photoreceptor according to (((1))),

    • wherein a mass proportion of the polyester resin (1) in a total amount of the polyester resin and the polycarbonate resin in the charge transport layer is 5% by mass or greater and 95% by mass or less.

    • (((3)))

    • The electrophotographic photoreceptor according to (((1))),

    • wherein a mass proportion of the polyester resin (1) in a total amount of the polyester resin and the polycarbonate resin in the charge transport layer is 20% by mass or greater and 80% by mass or less.

    • (((4)))

    • The electrophotographic photoreceptor according to any one of (((1))) to (((3))),

    • wherein the polyester resin (1) has a dicarboxylic acid unit (A) represented by Formula (A).

    • (((5)))

    • The electrophotographic photoreceptor according to (((4))),

    • wherein the dicarboxylic acid unit (A) represented by Formula (A) includes at least one selected from the group consisting of a dicarboxylic acid unit (A1) represented by Formula (A1), a dicarboxylic acid unit (A2) represented by Formula (A2), a dicarboxylic acid unit (A3) represented by Formula (A3), and a dicarboxylic acid unit (A4) represented Formula (A4).

    • (((6)))

    • The electrophotographic photoreceptor according to any one of (((1))) to (((5))),

    • wherein the polycarbonate resin includes a polycarbonate resin (1) having a constitutional unit (C) represented by Formula (C).

    • (((7)))

    • The electrophotographic photoreceptor according to (((6))),

    • wherein the constitutional unit (C) represented by Formula (C) includes at least one selected from the group consisting of a constitutional unit (Cb1) represented by Formula (Cb1), a constitutional unit (Cb2) represented by Formula (Cb2), a constitutional unit (Cb3) represented by Formula (Cb3), a constitutional unit (Cb4) represented by Formula (Cb4), a constitutional unit (Cb5) represented by Formula (Cb5), a constitutional unit (Cb6) represented by Formula (Cb6), a constitutional unit (Cb7) represented by Formula (Cb7), and a constitutional unit (Cb8) represented by Formula (Cb8).

    • (((8)))

    • An electrophotographic photoreceptor comprising:

    • a conductive substrate; and

    • a single layer type photosensitive layer disposed on the conductive substrate,

    • wherein the single layer type photosensitive layer contains a charge transport material, a polyester resin, and a polycarbonate resin, and

    • the polyester resin includes the following polyester resin (1),

    • polyester resin (1): a polyester resin having at least one selected from the group consisting of a diol unit (B3) represented by Formula (B3), a diol unit (B5) represented by Formula (B5), a diol unit (B6) represented by Formula (B6), a diol unit (B7) represented by Formula (B7), a diol unit (B8) represented by Formula (B8), a diol unit (B9) represented by Formula (B9), a diol unit (B10) represented by Formula (B10), and a diol unit (B11) represented by Formula (B11).

    • (((9)))

    • The electrophotographic photoreceptor according to (((8))),

    • wherein a mass proportion of the polyester resin (1) in a total amount of the polyester resin and the polycarbonate resin in the single layer type photosensitive layer is 5% by mass or greater and 95% by mass or less.

    • (((10)))

    • The electrophotographic photoreceptor according to (((8))),

    • wherein a mass proportion of the polyester resin (1) in a total amount of the polyester resin and the polycarbonate resin in the single layer type photosensitive layer is 20% by mass or greater and 80% by mass or less.

    • (((11)))

    • The electrophotographic photoreceptor according to any one of (((8))) to (((10))),

    • wherein the polyester resin (1) has a dicarboxylic acid unit (A) represented by Formula (A).

    • (((12)))

    • The electrophotographic photoreceptor according to (((11))),

    • wherein the dicarboxylic acid unit (A) represented by Formula (A) includes at least one selected from the group consisting of a dicarboxylic acid unit (A1) represented by Formula (A1), a dicarboxylic acid unit (A2) represented by Formula (A2), a dicarboxylic acid unit (A3) represented by Formula (A3), and a dicarboxylic acid unit (A4) represented Formula (A4).

    • (((13)))

    • The electrophotographic photoreceptor according to any one of (((8))) to (((12))),

    • wherein the polycarbonate resin includes a polycarbonate resin (1) having a constitutional unit (C) represented by Formula (C).

    • (((14)))

    • The electrophotographic photoreceptor according to (((13))),

    • wherein the constitutional unit (C) represented by Formula (C) includes at least one selected from the group consisting of a constitutional unit (Cb1) represented by Formula (Cb1), a constitutional unit (Cb2) represented by Formula (Cb2), a constitutional unit (Cb3) represented by Formula (Cb3), a constitutional unit (Cb4) represented by Formula (Cb4), a constitutional unit (Cb5) represented by Formula (Cb5), a constitutional unit (Cb6) represented by Formula (Cb6), a constitutional unit (Cb7) represented by Formula (Cb7), and a constitutional unit (Cb8) represented by Formula (Cb8).

    • (((15)))

    • A process cartridge comprising:

    • the electrophotographic photoreceptor according to any one of (((1))) to (((14))),

    • wherein the process cartridge is attachable to and detachable from an image forming apparatus.

    • (((16)))

    • An image forming apparatus comprising:

    • the electrophotographic photoreceptor according to any one of (((1))) to (((14)));

    • a charging device that charges a surface of the electrophotographic photoreceptor;

    • an electrostatic latent image forming device that forms an electrostatic latent image on the charged surface of the electrophotographic photoreceptor;

    • a developing device that develops the electrostatic latent image formed on the surface of the electrophotographic photoreceptor with a developer containing a toner to form a toner image; and

    • a transfer device that transfers the toner image to a surface of a recording medium.





The foregoing description of the exemplary embodiments of the present invention has been provided for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Obviously, many modifications and variations will be apparent to practitioners skilled in the art. The embodiments were chosen and described in order to best explain the principles of the invention and its practical applications, thereby enabling others skilled in the art to understand the invention for various embodiments and with the various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the following claims and their equivalents.

Claims
  • 1. An electrophotographic photoreceptor comprising: a conductive substrate; anda lamination type photosensitive layer disposed on the conductive substrate and including a charge generation layer and a charge transport layer,wherein the charge transport layer contains a charge transport material, a polyester resin, and a polycarbonate resin, andthe polyester resin includes the following polyester resin (1),polyester resin (1): a polyester resin having at least one selected from the group consisting of a diol unit (B3) represented by Formula (B3), a diol unit (B5) represented by Formula (B5), a diol unit (B6) represented by Formula (B6), a diol unit (B7) represented by Formula (B7), a diol unit (B8) represented by Formula (B8), a diol unit (B9) represented by Formula (B9), a diol unit (B10) represented by Formula (B10), and a diol unit (B11) represented by Formula (B11),
  • 2. The electrophotographic photoreceptor according to claim 1, wherein a mass proportion of the polyester resin (1) in a total amount of the polyester resin and the polycarbonate resin in the charge transport layer is 5% by mass or greater and 95% by mass or less.
  • 3. The electrophotographic photoreceptor according to claim 1, wherein a mass proportion of the polyester resin (1) in a total amount of the polyester resin and the polycarbonate resin in the charge transport layer is 20% by mass or greater and 80% by mass or less.
  • 4. The electrophotographic photoreceptor according to claim 1, wherein the polyester resin (1) has a dicarboxylic acid unit (A) represented by Formula (A),
  • 5. The electrophotographic photoreceptor according to claim 4, wherein the dicarboxylic acid unit (A) represented by Formula (A) includes at least one selected from the group consisting of a dicarboxylic acid unit (A1) represented by Formula (A1), a dicarboxylic acid unit (A2) represented by Formula (A2), a dicarboxylic acid unit (A3) represented by Formula (A3), and a dicarboxylic acid unit (A4) represented Formula (A4),
  • 6. The electrophotographic photoreceptor according to claim 1, wherein the polycarbonate resin includes a polycarbonate resin (1) having a constitutional unit (C) represented by Formula (C),
  • 7. The electrophotographic photoreceptor according to claim 6, wherein the constitutional unit (C) represented by Formula (C) includes at least one selected from the group consisting of a constitutional unit (Cb1) represented by Formula (Cb1), a constitutional unit (Cb2) represented by Formula (Cb2), a constitutional unit (Cb3) represented by Formula (Cb3), a constitutional unit (Cb4) represented by Formula (Cb4), a constitutional unit (Cb5) represented by Formula (Cb5), a constitutional unit (Cb6) represented by Formula (Cb6), a constitutional unit (Cb7) represented by Formula (Cb7), and a constitutional unit (Cb8) represented by Formula (Cb8),
  • 8. An electrophotographic photoreceptor comprising: a conductive substrate; anda single layer type photosensitive layer disposed on the conductive substrate,wherein the single layer type photosensitive layer contains a charge transport material, a polyester resin, and a polycarbonate resin, andthe polyester resin includes the following polyester resin (1),polyester resin (1): a polyester resin having at least one selected from the group consisting of a diol unit (B3) represented by Formula (B3), a diol unit (B5) represented by Formula (B5), a diol unit (B6) represented by Formula (B6), a diol unit (B7) represented by Formula (B7), a diol unit (B8) represented by Formula (B8), a diol unit (B9) represented by Formula (B9), a diol unit (B10) represented by Formula (B10), and a diol unit (B11) represented by Formula (B11),
  • 9. The electrophotographic photoreceptor according to claim 8, wherein a mass proportion of the polyester resin (1) in a total amount of the polyester resin and the polycarbonate resin in the single layer type photosensitive layer is 5% by mass or greater and 95% by mass or less.
  • 10. The electrophotographic photoreceptor according to claim 8, wherein a mass proportion of the polyester resin (1) in a total amount of the polyester resin and the polycarbonate resin in the single layer type photosensitive layer is 20% by mass or greater and 80% by mass or less.
  • 11. The electrophotographic photoreceptor according to claim 8, wherein the polyester resin (1) has a dicarboxylic acid unit (A) represented by Formula (A),
  • 12. The electrophotographic photoreceptor according to claim 11, wherein the dicarboxylic acid unit (A) represented by Formula (A) includes at least one selected from the group consisting of a dicarboxylic acid unit (A1) represented by Formula (A1), a dicarboxylic acid unit (A2) represented by Formula (A2), a dicarboxylic acid unit (A3) represented by Formula (A3), and a dicarboxylic acid unit (A4) represented Formula (A4),
  • 13. The electrophotographic photoreceptor according to claim 8, wherein the polycarbonate resin includes a polycarbonate resin (1) having a constitutional unit (C) represented by Formula (C),
  • 14. The electrophotographic photoreceptor according to claim 13, wherein the constitutional unit (C) represented by Formula (C) includes at least one selected from the group consisting of a constitutional unit (Cb1) represented by Formula (Cb1), a constitutional unit (Cb2) represented by Formula (Cb2), a constitutional unit (Cb3) represented by Formula (Cb3), a constitutional unit (Cb4) represented by Formula (Cb4), a constitutional unit (Cb5) represented by Formula (Cb5), a constitutional unit (Cb6) represented by Formula (Cb6), a constitutional unit (Cb7) represented by Formula (Cb7), and a constitutional unit (Cb8) represented by Formula (Cb8),
  • 15. A process cartridge comprising: the electrophotographic photoreceptor according to claim 1,wherein the process cartridge is attachable to and detachable from an image forming apparatus.
  • 16. A process cartridge comprising: the electrophotographic photoreceptor according to claim 2,wherein the process cartridge is attachable to and detachable from an image forming apparatus.
  • 17. A process cartridge comprising: the electrophotographic photoreceptor according to claim 3,wherein the process cartridge is attachable to and detachable from an image forming apparatus.
  • 18. A process cartridge comprising: the electrophotographic photoreceptor according to claim 4,wherein the process cartridge is attachable to and detachable from an image forming apparatus.
  • 19. A process cartridge comprising: the electrophotographic photoreceptor according to claim 5,wherein the process cartridge is attachable to and detachable from an image forming apparatus.
  • 20. An image forming apparatus comprising: the electrophotographic photoreceptor according to claim 1;a charging device that charges a surface of the electrophotographic photoreceptor;an electrostatic latent image forming device that forms an electrostatic latent image on the charged surface of the electrophotographic photoreceptor;a developing device that develops the electrostatic latent image formed on the surface of the electrophotographic photoreceptor with a developer containing a toner to form a toner image; anda transfer device that transfers the toner image to a surface of a recording medium.
Priority Claims (1)
Number Date Country Kind
2022-114268 Jul 2022 JP national