WO2023190690A1 - 電子写真感光体、電子写真感光体カートリッジ及び画像形成装置、化合物 - Google Patents

電子写真感光体、電子写真感光体カートリッジ及び画像形成装置、化合物 Download PDF

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WO2023190690A1
WO2023190690A1 PCT/JP2023/012826 JP2023012826W WO2023190690A1 WO 2023190690 A1 WO2023190690 A1 WO 2023190690A1 JP 2023012826 W JP2023012826 W JP 2023012826W WO 2023190690 A1 WO2023190690 A1 WO 2023190690A1
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group
substituent
optionally substituted
formula
compound
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French (fr)
Japanese (ja)
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司 長谷川
ラミレス マヌエル エミリオ オテロ
明 安藤
英貴 五郎丸
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to JP2024512679A priority Critical patent/JPWO2023190690A1/ja
Priority to CN202380030964.8A priority patent/CN118974665A/zh
Publication of WO2023190690A1 publication Critical patent/WO2023190690A1/ja
Priority to US18/901,884 priority patent/US20250036036A1/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14708—Cover layers comprising organic material
    • G03G5/14713—Macromolecular material
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0592—Macromolecular compounds characterised by their structure or by their chemical properties, e.g. block polymers, reticulated polymers, molecular weight, acidity
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
    • G03G5/07—Polymeric photoconductive materials
    • G03G5/071—Polymeric photoconductive materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14708—Cover layers comprising organic material
    • G03G5/14713—Macromolecular material
    • G03G5/14791—Macromolecular compounds characterised by their structure, e.g. block polymers, reticulated polymers, or by their chemical properties, e.g. by molecular weight or acidity
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G2215/00—Apparatus for electrophotographic processes
    • G03G2215/00953—Electrographic recording members
    • G03G2215/00957—Compositions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G2215/00—Apparatus for electrophotographic processes
    • G03G2215/00953—Electrographic recording members
    • G03G2215/00962—Electrographic apparatus defined by the electrographic recording member

Definitions

  • the present invention relates to compounds having electron transporting properties, such as compounds useful as electron transporting compounds used as raw materials for electrophotographic photoreceptors used in copiers, printers, etc., and electrophotographic photoreceptors used in copiers, printers, etc. , relates to an electrophotographic photoreceptor cartridge and an image forming apparatus using the same.
  • This type of organic photoreceptor has a wide range of materials to choose from, and the characteristics of the photoreceptor can be easily controlled. Therefore, a "functionally separated photoreceptor" in which the functions of charge generation and transfer are assigned to separate compounds is used. It is becoming mainstream.
  • a single-layer electrophotographic photoreceptor (hereinafter referred to as a single-layer photoreceptor) having a charge-generating material (CGM) and a charge-transporting material (CTM) in the same layer;
  • CGM charge-generating material
  • CTM charge-transporting material
  • a laminated electrophotographic photoreceptor hereinafter referred to as a laminated photoreceptor
  • a laminated photoreceptor which is formed by laminating a charge generation layer and a charge transport layer containing a charge transport material (CTM).
  • the charging method for the photoreceptor there can be mentioned a negative charging method in which the surface of the photoreceptor is charged with a negative charge, and a positive charging method in which the surface of the photoreceptor is charged with a positive charge.
  • a negative charging method in which the surface of the photoreceptor is charged with a negative charge
  • a positive charging method in which the surface of the photoreceptor is charged with a positive charge.
  • a “negatively charged multilayer photoreceptor” is a conductive substrate such as an aluminum tube, on which an undercoat layer (UCL) made of resin or the like is provided, and on top of that is a charge generation layer made of charge generation material (CGM) and resin. It is common to have a structure in which a charge transport layer (CTL) made of a hole transport material (HTM), a resin, etc. is provided on top of the charge transport layer (CGL).
  • CTL charge transport layer
  • HTM hole transport material
  • CGL charge transport layer
  • a "positively charged single-layer photoconductor” has an undercoat layer (UCL) made of resin or the like on a conductive substrate such as an aluminum tube, and a charge generating material (CGM), a hole transporting material, etc. It is common to have a structure in which a single photosensitive layer is formed of a material (HTM), an electron transport material (ETM), and a resin (see, for example, Patent Document 1).
  • the surface of the photoreceptor is charged using a corona discharge method or a contact method, and then the photoreceptor is exposed to light to neutralize the surface charge, forming an electrostatic latent image due to the potential difference with the surrounding surface. do. Thereafter, toner is brought into contact with the surface of the photoreceptor to form a toner image corresponding to the electrostatic latent image, and this is transferred to paper or the like and heated and fused to complete the print.
  • electrophotographic photoreceptors basically have a photosensitive layer formed on a conductive support, but a protective layer may also be provided on the photosensitive layer for the purpose of improving wear resistance. It is being said.
  • a technique for improving the mechanical strength or abrasion resistance of the surface of a photoreceptor is to form a layer containing a compound having a chain-polymerizable functional group as a binder resin on the outermost layer of the photoreceptor, and then apply heat, light, or radiation to this layer.
  • a photoreceptor is disclosed in which a cured resin layer is formed by polymerization by applying energy such as (for example, see Patent Documents 1 and 2).
  • a protective layer is provided.
  • a protective layer using a curable compound has particularly excellent mechanical strength.
  • Such a protective layer is required to have electron transport properties from the viewpoint of improving the electrical properties of the photoreceptor.
  • it is thought to be effective to include a compound having electron transporting properties in the protective layer using a curable compound.
  • the method involves dissolving a curable composition containing a compound with electron transport properties in an organic solvent to prepare a coating solution for forming a protective layer, and applying the coating solution for forming a protective layer onto the surface of a photoreceptor.
  • it can be formed by
  • some compounds with electron transport properties have insufficient solubility in organic solvents, and when included in the protective layer, electrical properties, especially residual potential properties, may become insufficient. It has become clear that there is.
  • an object of the present invention is to provide a compound having electron transporting properties and having sufficient solubility in an organic solvent, and to provide a compound having a photosensitive layer and a protective layer sequentially on a conductive support.
  • An electrophotographic photoreceptor having at least a photosensitive layer and a protective layer sequentially on a conductive support, the protective layer comprising a polymer of an electron transporting compound represented by the following formula (1).
  • X represents an electron transporting skeleton.
  • A is represented by the following formula (2)
  • B is represented by the following formula (3), and A and B are different from each other.
  • R 1 and R 2 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group , an optionally substituted heteroaryloxy group, an optionally substituted alkoxycarbonyl group, an optionally substituted dialkylamino group, an optionally substituted dialkylamino group Diarylamino group, arylalkylamino group which may have a substituent, acyl group which may have a substituent, haloalkyl group which may have a substituent, even if it has a substituent Good alkylthio group, optionally substituted arylthio group, optionally substituted silyl group, optionally substituted siloxy group, optionally substituted aromatic represents a group hydrocarbon group or an aromatic heterocyclic group which may have a substituent.
  • L 1 represents a divalent group.
  • Z 1 is an acryloyl group that may have a substituent, a methacryloyl group that may have a substituent, an acrylamide group that may have a substituent, or an acrylamide group that may have a substituent Represents methacrylamide group.
  • a1 is an integer of 1 or more, and when a1 is an integer of 2 or more, each of R 1 , R 2 , L 1 , and Z 1 may be the same or different from each other.
  • R 3 and R 4 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group , an optionally substituted heteroaryloxy group, an optionally substituted alkoxycarbonyl group, an optionally substituted dialkylamino group, an optionally substituted dialkylamino group Diarylamino group, arylalkylamino group which may have a substituent, acyl group which may have a substituent, haloalkyl group which may have a substituent, even if it has a substituent Good alkylthio group, optionally substituted arylthio group, optionally substituted silyl group, optionally substituted siloxy group, optionally substituted aromatic represents a group hydrocarbon group or an aromatic heterocyclic group which may have a substituent.
  • L 2 represents a divalent group.
  • Z 2 represents a hydrogen atom, an alkoxy group, or an amide group.
  • b1 is an integer of 1 or more, and when b1 is an integer of 2 or more, each of R 3 , R 4 , L 2 , and Z 2 may be the same or different from each other. )
  • R A11 to R A262 may be different from each other.
  • L 1 and L 2 each independently represent an alkylene group, a divalent group having a ketone group, a divalent group having an ether bond, or an ester bond.
  • An electrophotographic photoreceptor cartridge comprising the electrophotographic photoreceptor according to any one of [1] to [5].
  • An image forming apparatus comprising the electrophotographic photoreceptor according to any one of [1] to [5].
  • X represents an electron transporting skeleton.
  • A is represented by the following formula (2)
  • B is represented by the following formula (3), and A and B are different from each other.
  • R 1 and R 2 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group , an optionally substituted heteroaryloxy group, an optionally substituted alkoxycarbonyl group, an optionally substituted dialkylamino group, an optionally substituted dialkylamino group Diarylamino group, arylalkylamino group which may have a substituent, acyl group which may have a substituent, haloalkyl group which may have a substituent, even if it has a substituent Good alkylthio group, optionally substituted arylthio group, optionally substituted silyl group, optionally substituted siloxy group, optionally substituted aromatic represents a group hydrocarbon group or an aromatic heterocyclic group which may have a substituent.
  • L 1 represents a divalent group.
  • Z 1 is an acryloyl group that may have a substituent, a methacryloyl group that may have a substituent, an acrylamide group that may have a substituent, or an acrylamide group that may have a substituent Represents methacrylamide group.
  • a1 is an integer of 1 or more, and when a1 is an integer of 2 or more, each of R 1 , R 2 , L 1 , and Z 1 may be the same or different from each other.
  • R 3 and R 4 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group , an optionally substituted heteroaryloxy group, an optionally substituted alkoxycarbonyl group, an optionally substituted dialkylamino group, an optionally substituted dialkylamino group Diarylamino group, arylalkylamino group which may have a substituent, acyl group which may have a substituent, haloalkyl group which may have a substituent, even if it has a substituent Good alkylthio group, optionally substituted arylthio group, optionally substituted silyl group, optionally substituted siloxy group, optionally substituted aromatic represents a group hydrocarbon group or an aromatic heterocyclic group which may have a substituent.
  • L 2 represents a divalent group.
  • Z 2 represents a hydrogen atom, an alkoxy group, or an amide group.
  • b1 is an integer of 1 or more, and when b1 is an integer of 2 or more, each of R 3 , R 4 , L 2 , and Z 2 may be the same or different from each other.
  • R A11 to R A262 may be different from each other.
  • L 1 and L 2 each independently represent an alkylene group, a divalent group having a ketone group, a divalent group having an ether bond, or an ester bond.
  • the compound proposed by the present invention has an electron-transporting skeleton at its center, and has a side chain having a polymerizable functional group on one of the left and right sides, and a side chain without a polymerizable functional group on the other side. Since it has an asymmetric structure, it has electron transport properties and has sufficient solubility in organic solvents. Therefore, it is useful, for example, as an electron transporting compound used as a raw material for electrophotographic photoreceptors used in copying machines, printers, and the like.
  • the electrophotographic photoreceptor proposed by the present invention has an electron-transporting skeleton at its center, and has side chains having a polymerizable functional group on one of the left and right sides, and side chains that do not have a polymerizable functional group on the other side.
  • the protective layer contains a polymer of an electron-transporting compound with an asymmetric structure, which improves the electron-transporting properties in the protective layer and improves electrical properties, especially residual potential properties. It can be done.
  • FIG. 1 is a diagram schematically showing a configuration example of an image forming apparatus that can be configured using an electrophotographic photoreceptor according to an example of the present invention.
  • An electrophotographic photoreceptor according to an example of an embodiment of the present invention (also referred to as “the present electrophotographic photoreceptor”) is an electrophotographic photoreceptor that includes at least a photosensitive layer and a protective layer in this order on a conductive support. .
  • the present electrophotographic photoreceptor may optionally have layers other than the photosensitive layer and the protective layer.
  • the charging method of the present electrophotographic photoreceptor may be either a negative charging method in which the surface of the photoreceptor is charged with a negative charge or a positive charging method in which the surface of the photoreceptor is charged with a positive charge.
  • the positive charging method is preferable because it is thought that the effects of the present invention can be enjoyed even more with the positive charging method.
  • the side opposite to the conductive support is the upper side or front side, and the side of the conductive support is the lower side or back side.
  • This protective layer is preferably a layer containing an electron transporting compound.
  • the protective layer is preferably a layer containing a polymer of the electron-transporting compound. . That is, the layer preferably contains a cured product obtained by curing an electron transporting compound.
  • the protective layer preferably contains a cured product obtained by further curing a curable compound. That is, a layer containing a polymer of an electron transporting compound and a curable compound, in other words, a layer containing a cured product obtained by curing an electron transporting compound and a curable compound is preferable.
  • the term "electron-transporting compound” refers to a compound having electron-transporting properties, in other words, a compound having an electron-transporting skeleton.
  • This protective layer can be formed from a composition containing, for example, an electron-transporting compound and, if necessary, a curable compound, a polymerization initiator, inorganic particles, and other materials.
  • the present protective layer is not limited to one formed from such a composition.
  • the present protective layer is preferably the outermost layer, that is, the outermost layer located on the opposite side to the conductive support, from the viewpoint of obtaining more effects of the present invention.
  • the protective layer does not necessarily have to be the outermost layer to enjoy the effects of the present invention. For example, the effect can be obtained even if the protective layer is not the outermost layer, such as when some kind of segregation layer is present on the outermost layer of the photoreceptor.
  • electron transport compound As the electron transporting compound used in this protective layer, it is preferable to use a compound proposed by the present invention. That is, a compound represented by the following formula (1) is preferable. Such compounds have an asymmetrical structure with an electron-transporting skeleton at the center, a side chain having a polymerizable functional group on one side of the electron-transporting skeleton, and a side chain having no polymerizable functional group on the other side. It is an electron-transporting compound. By containing such an electron-transporting compound in the protective layer, the electron-transporting property in the protective layer becomes good, and the electrical properties of the photoreceptor become good.
  • X represents an electron transporting skeleton. This X will be explained in detail later.
  • A preferably has a structure represented by the following formula (2), and B preferably has a structure represented by the following formula (3).
  • the electron transporting compound represented by formula (1) preferably has at least two or more polymerizable functional groups from the viewpoint of curability, and preferably has eight or less polymerizable functional groups from the viewpoint of stability. , more preferably 6 or less, and even more preferably 4 or less.
  • formula (2) shows an example of a preferable structure of A in formula (1).
  • Formula (2) represents a side chain having a polymerizable functional group, and * represents a bond with formula (1).
  • R 1 and R 2 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group , an optionally substituted heteroaryloxy group, an optionally substituted alkoxycarbonyl group, an optionally substituted dialkylamino group, an optionally substituted dialkylamino group Diarylamino group, arylalkylamino group which may have a substituent, acyl group which may have a substituent, haloalkyl group which may have a substituent, even if it has a substituent Good alkylthio group, optionally substituted arylthio group, optionally substituted silyl group, optionally substituted siloxy group, optionally substituted aromatic It is preferably a group hydrocarbon group or an aromatic heterocyclic group which may have a substituent.
  • substituents such as an alkyl group which may have a substituent include an alkyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkoxycarbonyl group, a dialkylamino group, and a diarylamino group.
  • the substituent is preferably an alkyl group, and more preferably has no substituent.
  • L 1 may be a divalent group.
  • examples include an alkylene group, a divalent group having a ketone group, a divalent group having an ether bond, a divalent group having an ester bond, or a group in which these are linked. However, it is not limited to these.
  • the divalent group having an ester bond a group represented by the following formula (E-1) or formula (E-2) is preferable.
  • Z 1 is an acryloyl group that may have a substituent, a methacryloyl group that may have a substituent, an acrylamide group that may have a substituent, or a substituent
  • it is a methacrylamide group which may have
  • the acryloyl group that may have a substituent or the methacryloyl group that may have a substituent may be a group represented by the following formulas (P-1) to (P-5). .
  • a1 is an integer of 1 or more, preferably 4 or less, especially 3 or less, and even more preferably 2 or less.
  • each of R 1 , R 2 , L 1 , and Z 1 may be the same or different from each other.
  • formula (3) shows an example of a preferable structure of B in formula (1).
  • Formula (3) shows a side chain that does not have a polymerizable functional group, and * represents a bond with formula (1).
  • R 3 and R 4 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group , an optionally substituted heteroaryloxy group, an optionally substituted alkoxycarbonyl group, an optionally substituted dialkylamino group, an optionally substituted dialkylamino group Diarylamino group, arylalkylamino group which may have a substituent, acyl group which may have a substituent, haloalkyl group which may have a substituent, even if it has a substituent Good alkylthio group, optionally substituted arylthio group, optionally substituted silyl group, optionally substituted siloxy group, optionally substituted aromatic It is preferably a group hydrocarbon group or an aromatic heterocyclic group which may have a substituent. Note that
  • L 2 may be any divalent group. Examples include an alkylene group, a divalent group having a ketone group, a divalent group having an ether bond, a divalent group having an ester bond, or a group in which these are linked. However, it is not limited to these.
  • the divalent group having an ester bond is preferably a group represented by the following formula (E-1) or formula (E-2).
  • Z 2 is preferably a hydrogen atom, an alkoxy group which may have a substituent, or an amide group which may have a substituent.
  • b1 is an integer of 1 or more, preferably 4 or less, especially 3 or less, and even more preferably 2 or less.
  • b1 is an integer of 2 or more, each of R 3 , R 4 , L 2 , and Z 2 may be the same or different from each other.
  • the side chain having no polymerizable functional group represented by formula (3) has a branched structure. It is presumed that the branching causes more pronounced steric hindrance and lowers crystallinity, resulting in better solubility in solvents, especially alcohols.
  • X in the formula (1) that is, the electron transporting skeleton
  • the electron transporting skeleton there can be mentioned, for example, at least one skeleton selected from the group consisting of the following formulas (A-1) to (A-27).
  • an aralkyl group that may have a substituent an aromatic group that may have a substituent, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent , an acyl group that may have a substituent, an ester group that may have a substituent, a cyano group that may have a substituent, a nitro group that may have a substituent, a substituted
  • m11, m21, m31, m41, m51, m61, m62, m71, m72, m81, m82, m91, m92, m101, m111, m121, m131, m141, m151, m161, m171, m181, m182, m191, m192, m201, m202, m211, m212, m221, m222, m231, m232, m241, m242, m251, m252, m261, m262 are each independently 0 or more Any integer may be used, and from the viewpoint of stability, it is preferably 3 or less, especially 2 or less, and even more preferably 1 or less.
  • R A11 to R A262 may be different from each other.
  • formula (A-1), formula (A-10), and formula (A-11) are preferable from the viewpoint of electron transport properties and stability; -11) is more preferable.
  • the content of the electron transporting compound in the present protective layer is preferably 40 parts by mass or more, more preferably 60 parts by mass or more, and 80 parts by mass based on 100 parts by mass of the total mass of the present protective layer.
  • the electron transporting compound in the present protective layer may contain another electron transporting compound different from the compound represented by formula (1).
  • the compound represented by formula (1) in the present protective layer is preferably 40 parts by mass or more, and 50 parts by mass or more based on 100 parts by mass of the total mass of the electron transporting compound in the present protective layer. is more preferable, and even more preferably 60 parts by mass or more.
  • the curable compound may be any compound having a chain polymerizable functional group. Among these, monomers, oligomers, or polymers having radically polymerizable functional groups are preferred. Among these, curable compounds having crosslinking properties, particularly photocurable compounds, are preferred. For example, a curable compound having two or more radically polymerizable functional groups can be mentioned. A compound having one radically polymerizable functional group can also be used in combination. Examples of the radically polymerizable functional group include acryloyl groups (including acryloyloxy groups) and methacryloyl groups (including methacryloyloxy groups), or both of these groups.
  • Preferred compounds as the curable compound having a radically polymerizable functional group are illustrated below.
  • monomers having an acryloyl group or a methacryloyl group include trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerol triacrylate, and tris(acryloxyethyl) isocyanurate.
  • examples of oligomers and polymers having acryloyl or methacryloyl groups include urethane acrylate, ester acrylate, acryl acrylate, and epoxy acrylate. Among these, urethane acrylate and ester acrylate are preferred, and among these, ester acrylate is more preferred.
  • the above curable compounds can be used alone or in combination of two or more.
  • the content ratio (mass ratio) of the curable compound to the electron transport compound in this protective layer is preferably 1.0 or less, more preferably 0.5 or less, and even more preferably 0.1 or less. preferable.
  • polymerization initiator examples include thermal polymerization initiators, photopolymerization initiators, and the like.
  • thermal polymerization initiator include peroxide compounds such as 2,5-dimethylhexane-2,5-dihydroperoxide, and azo compounds such as 2,2'-azobis(isobutyronitrile). be able to.
  • Photopolymerization initiators can be classified into direct cleavage type and hydrogen abstraction type, depending on the radical generation mechanism.
  • direct cleavage type photopolymerization initiator absorbs light energy, some of the covalent bonds within the molecule are cleaved to generate radicals.
  • hydrogen abstraction type photopolymerization initiator molecules that become excited by absorbing light energy generate radicals by abstracting hydrogen from a hydrogen donor.
  • Direct cleavage type photopolymerization initiators include, for example, acetophenone, 2-benzoyl-2-propanol, 1-benzoylcyclohexanol, 2,2-diethoxyacetophenone, benzyl dimethyl ketal, 2-methyl-4'-(methylthio )-2-morpholinopropiophenone, acetophenone or ketal compounds, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, O-tosylbenzoin, etc., benzoin ether compounds, diphenyl ( Acyl phosphines such as 2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, lithium phenyl(2,4,6-trimethylbenzoyl)phosphonate, etc. Examples include oxide compounds.
  • hydrogen abstraction type photopolymerization initiators examples include benzophenone, 4-benzoylbenzoic acid, 2-benzoylbenzoic acid, methyl 2-benzoylbenzoate, methyl benzoylformate, benzyl, p-anisyl, 2-benzoylnaphthalene, Benzophenone compounds such as 4,4'-bis(dimethylamino)benzophenone, 4,4'-dichlorobenzophenone, 1,4-dibenzoylbenzene, 2-ethylanthraquinone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2 Examples include anthraquinone-based or thioxanthone-based compounds such as , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone.
  • photopolymerization initiators examples include camphorquinone, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, acridine compounds, triazine compounds, and imidazole compounds. I can do it.
  • the photopolymerization initiator preferably has an absorption wavelength in the wavelength range of the light source used for light irradiation.
  • an acylphosphine oxide compound and a hydrogen abstraction type initiator together.
  • the content ratio of the hydrogen abstraction type initiator to the acylphosphine oxide compound is not particularly limited. From the viewpoint of supplementing surface curability, it is preferably 0.1 parts by mass or more per 1 part by mass of the acylphosphine oxide compound, and from the viewpoint of maintaining internal curability, it is preferably 5 parts by mass or less.
  • those having a photopolymerization promoting effect can be used alone or in combination with the above photopolymerization initiators.
  • examples of those having a photopolymerization promoting effect include triethanolamine, methyldiethanolamine, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino)ethyl benzoate, and 4,4'- Examples include dimethylaminobenzophenone.
  • the polymerization initiators may be used alone or in combination of two or more.
  • the content of the polymerization initiator is preferably 0.5 to 40 parts by mass, based on 100 parts by mass of the total content having radical polymerizability, and more preferably 1 part by mass or more or 20 parts by mass or less. preferable.
  • the total content having radical polymerizability includes the electron transporting compound represented by the formula (1) and the curable compound.
  • This protective layer may contain inorganic particles from the viewpoint of improving strong exposure characteristics and mechanical strength, or from the viewpoint of imparting charge transport ability. However, it is not necessary to contain inorganic particles.
  • One of the features of the present invention is that by containing a specific electron-transporting compound in the protective layer, it is not necessary to contain inorganic particles.
  • the inorganic particles include metal powders, metal oxides, metal fluorides, potassium titanate, boron nitride, and any inorganic particles that can be used in electrophotographic photoreceptors.
  • the inorganic particles only one type of particles may be used, or a plurality of types of particles may be mixed and used.
  • This protective layer may contain other materials as necessary.
  • other materials include stabilizers (thermal stabilizers, ultraviolet absorbers, light stabilizers, antioxidants, etc.), dispersants, antistatic agents, colorants, lubricants, and the like. These may be used alone or in combination of two or more in any ratio.
  • This protective layer may be made of, for example, a coating solution or dispersion of a curable composition containing an electron transporting compound and, if necessary, a curable compound, a polymerization initiator, inorganic particles, and other materials, dissolved in a solvent.
  • the main protective layer can be formed by applying a coating liquid dispersed in a medium (referred to as "coating liquid for forming the main protective layer") onto the main photosensitive layer and curing it.
  • coating liquid for forming the main protective layer a medium
  • the method is not limited to this method.
  • the electron transporting compound is an electron transporting compound represented by the above formula (1), it has a chain polymerizable functional group such as an acrylamide group, a methacrylamide group, an acryloyl group, or a methacryloyl group.
  • a curable compound can also serve as a curable compound.
  • the electron transporting compound used in the coating solution for forming a protective layer is preferably a compound represented by the formula (1).
  • Preferred embodiments of the curable compound, polymerization initiator, inorganic particles, and other materials used in the coating liquid for forming the protective layer are the same as those for each material used in the protective layer.
  • the content ratio of the curable compound to the electron transporting compound (curable compound/electron transporting compound) in the coating solution for forming the protective layer is the content ratio of the curable compound to the electron transporting compound in the protective layer described above (curable compound/electron transporting compound). This is the same as the chemical compound/electron-transporting compound).
  • the content of the electron transporting compound in the present coating solution for forming a protective layer is preferably 4 parts by mass or more, more preferably 6 parts by mass or more, and more preferably 8 parts by mass or more based on 100 parts by mass of the solvent. Parts by mass or more are more preferable.
  • the amount is preferably 14 parts by mass or less, more preferably 12 parts by mass or less, and even more preferably 10 parts by mass or less based on 100 parts by mass of the solvent.
  • the content of the curable compound in the coating solution for forming a protective layer is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 0 parts by mass. preferable.
  • an organic solvent can be used as the solvent used in the coating liquid for forming the protective layer.
  • the organic solvent include alcohols such as methanol, ethanol, propanol, and 2-methoxyethanol; ethers such as tetrahydrofuran, 1,4-dioxane, and dimethoxyethane; esters such as methyl formate and ethyl acetate; acetone and methyl ethyl ketone.
  • benzene toluene, xylene, anisole, and other aromatic hydrocarbons; dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, tetrachloroethane , 1,2-dichloropropane, trichloroethylene, and other chlorinated hydrocarbons; n-butylamine, isopropanolamine, diethylamine, triethanolamine, ethylenediamine, triethylenediamine, and other nitrogen-containing compounds; acetonitrile, N-methylpyrrolidone, N, Examples include aprotic polar solvents such as N-dimethylformamide and dimethyl sulfoxide.
  • a mixed solvent in any combination and in any ratio from among these.
  • alcohols, ethers, aromatic hydrocarbons, and aprotic polar solvents are preferred, alcohols, ethers, and aromatic hydrocarbons are more preferred, and alcohols , ethers are more preferred, and alcohols are most preferred.
  • an organic solvent does not dissolve the electron transporting compound used in the protective layer of the present electrophotographic photoreceptor alone, it may be used if it can be dissolved, for example, by forming a mixed solvent with the above-mentioned organic solvent. be able to.
  • using a mixed solvent can reduce coating unevenness.
  • the ratio of the solvent and solid content used in this coating solution for forming a protective layer varies depending on the coating method of the coating solution for forming a protective layer, and should be changed as appropriate to form a uniform coating film depending on the coating method used. Just use it.
  • the method of applying the coating liquid for forming the present protective layer is not particularly limited, and examples thereof include spray coating, spiral coating, ring coating, dip coating, and the like.
  • the coating film After forming a coating film by the above coating method, the coating film is dried. At this time, the drying temperature and time are not limited as long as necessary and sufficient drying can be achieved. However, when the protective layer is applied only by air drying after application of the photosensitive layer, it is preferable to perform sufficient drying by the method described in the method for forming a photosensitive layer described below.
  • the protective layer can be formed by applying the coating liquid for forming the protective layer and then curing it by applying energy from the outside. External energy used at this time may include heat, light, and radiation.
  • Examples of methods for adding thermal energy include heating methods using air, gas such as nitrogen, steam, various heat media, infrared rays, and electromagnetic waves. Further, the heating can be performed from the coated surface side or the support side.
  • the heating temperature is preferably 100°C or more and 170°C or less.
  • UV irradiation light sources such as high-pressure mercury lamps, metal halide lamps, electrodeless lamp bulbs, and light emitting diodes, which mainly emit light at ultraviolet (UV) wavelengths, can be used. Further, it is also possible to select a visible light source according to the absorption wavelength of the chain polymerizable compound and the photopolymerization initiator. From the viewpoint of curability, the amount of light irradiation is preferably 10 J/cm 2 or more, more preferably 30 J/cm 2 or more, and particularly preferably 100 J/cm 2 or more.
  • examples of radiation energy include those using electron beams (EB).
  • a heating step may be added from the viewpoint of alleviating residual stress, alleviating residual radicals, and improving electrical properties.
  • the heating temperature is preferably 60°C or higher, more preferably 100°C or higher, and preferably 200°C or lower, more preferably 150°C or lower.
  • the thickness of the protective layer is preferably 0.5 ⁇ m or more, and more preferably 1 ⁇ m or more.
  • the thickness is preferably 5 ⁇ m or less, and more preferably 3 ⁇ m or less.
  • the thickness of the present protective layer is preferably 1/50 or more of the thickness of the present photosensitive layer, more preferably 1/40 or more, and even more preferably 1/40 or more of the thickness of the present photosensitive layer. More preferably, it is 30 or more. On the other hand, it is preferably 1/5 or less, more preferably 1/10 or less, and even more preferably 1/20 or less.
  • the photosensitive layer (also referred to as "main photosensitive layer") in the present electrophotographic photoreceptor may be a layer containing at least a charge generating material (CGM) and a charge transporting material.
  • CGM charge generating material
  • This photosensitive layer may be a single-layer type photosensitive layer containing both a charge-generating substance and a charge-transporting substance in the same layer, or a laminated type photosensitive layer in which a charge-generating layer and a charge-transporting layer are separated. It may be a layer.
  • ⁇ Single layer type photosensitive layer> When the present photosensitive layer is a single-layer type photosensitive layer, it is preferable that at least a charge generating material (CGM), a hole transporting material (HTM), an electron transporting material (ETM), and a binder resin are contained in the same layer. .
  • CGM charge generating material
  • HTM hole transporting material
  • ETM electron transporting material
  • charge generating substance As the charge generating substance used in the photosensitive layer, various photoconductive materials such as inorganic photoconductive materials and organic pigments can be used. Among these, organic pigments are particularly preferred, and phthalocyanine pigments and azo pigments are more preferred.
  • metal-free phthalocyanine when using a phthalocyanine pigment as a charge generating substance, specifically, metal-free phthalocyanine, metals such as copper, indium, gallium, tin, titanium, zinc, vanadium, silicon, germanium, or their oxides, halides, etc. Coordinated phthalocyanines are used. Among these, X-type, ⁇ -type metal-free phthalocyanine, A-type, B-type, D-type titanyl phthalocyanine, vanadyl phthalocyanine, chloroindium phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, etc., which have particularly high sensitivity, are preferable.
  • one type of charge generating substance may be used alone, or two or more types may be used in combination in any combination and ratio.
  • the method of mixing the charge-generating substances to be used together may be to mix each charge-generating substance afterwards, or to use synthesis, pigmentation, crystallization, etc. They may be mixed and used in the production and treatment process of the charge generating substance.
  • the particle size of the charge generating substance is small.
  • the particle size of the charge generating substance is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less.
  • the lower limit is 0.01 ⁇ m or more.
  • the particle size of the charge-generating substance means the particle size when it is contained in the photosensitive layer.
  • the amount of the charge generating substance in the single-layer type photosensitive layer is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. Further, from the viewpoint of sensitivity and chargeability, the amount is preferably 50% by mass or less, and more preferably 20% by mass or less.
  • Charge transport materials are classified into hole transport materials that mainly have a hole transport ability and electron transport materials that mainly have an electron transport ability.
  • the present photosensitive layer is a single-layer type photosensitive layer, it is preferable that at least a hole transporting substance and an electron transporting substance are contained in the same layer.
  • the hole transport material can be selected from known materials.
  • heterocyclic compounds such as carbazole derivatives, indole derivatives, imidazole derivatives, oxazole derivatives, pyrazole derivatives, thiadiazole derivatives, benzofuran derivatives, aniline derivatives, hydrazone derivatives, arylamine derivatives, stilbene derivatives, butadiene derivatives and enamine derivatives, and these compounds.
  • electron-donating substances such as those in which multiple types of these compounds are bonded, and polymers having a group consisting of these compounds in the main chain or side chain.
  • carbazole derivatives arylamine derivatives, stilbene derivatives, butadiene derivatives, enamine derivatives, and combinations of multiple types of these compounds are preferred, and arylamine derivatives and enamine derivatives are more preferred.
  • One type of hole transport substance may be used alone, or two or more types may be used in any ratio and combination.
  • the electron transport material can be selected from known materials.
  • electron-withdrawing substances such as aromatic nitro compounds such as 2,4,7-trinitrofluorenone, cyano compounds such as tetracyanoquinodimethane, and quinone compounds such as diphenoquinone, known cyclic ketone compounds, and perylene pigments ( perylene derivatives).
  • quinone compounds and perylene pigments perylene derivatives
  • quinone compounds are more preferred.
  • diphenoquinone or dinaphthylquinone is preferred from the viewpoint of electrical properties. Among them, dinaphthylquinone is more preferred.
  • the electron transport substance only one type may be used alone, or two or more types may be used in any ratio and combination.
  • ET-2 and ET-5 are preferred from the viewpoint of electrical properties, and ET-2 is more preferred.
  • binder resin used in this photosensitive layer
  • examples of the binder resin used in the photosensitive layer include vinyl polymers such as polymethyl methacrylate, polystyrene, and polyvinyl chloride, or copolymers thereof; vinyl alcohol resins; polyvinyl butyral resins; polyvinyl formal resins; partially modified polyvinyl acetal resins; Polyarylate resins; polyamide resins; polyurethane resins; polycarbonate resins; polyester resins; polyester carbonate resins; polyimide resins; phenoxy resins; epoxy resins; silicone resins; and partially crosslinked cured products thereof.
  • the resin may be modified with a silicon reagent or the like. Further, one type of these may be used alone, or two or more types may be used in any ratio and combination.
  • the binder resin used in the present photosensitive layer preferably contains one or more types of polymers obtained by interfacial polymerization.
  • the binder resin obtained by the interfacial polymerization is preferably a polycarbonate resin or a polyester resin, and particularly a polycarbonate resin or a polyarylate resin. Moreover, it is particularly preferable to use a polymer made from an aromatic diol as a raw material.
  • this photosensitive layer contains well-known antioxidants, plasticizers, ultraviolet Additives such as an absorber, an electron-withdrawing compound, a leveling agent, and a visible light shielding agent may be included.
  • various additives such as sensitizers, dyes, pigments (excluding the above-mentioned charge-generating substances, hole-transporting substances, and electron-transporting substances), surfactants, etc. may be added to the photosensitive layer as necessary. It may also contain an agent. Examples of surfactants include silicone oil and fluorine compounds. In the present invention, these may be used alone or in any ratio and combination of two or more.
  • the photosensitive layer may contain a fluororesin, a silicone resin, etc., or may contain particles made of these resins or particles of an inorganic compound such as aluminum oxide. .
  • the thickness of the photosensitive layer is preferably 20 ⁇ m or more, more preferably 25 ⁇ m or more, from the viewpoint of dielectric breakdown resistance. On the other hand, from the viewpoint of electrical properties, the thickness is preferably 50 ⁇ m or less, and more preferably 40 ⁇ m or less.
  • a charge transport layer (CTL) containing a charge transporting substance is laminated on a charge generating layer (CGL) containing a charge generating substance (CGM).
  • CTL charge transport layer
  • CGL charge generating layer
  • CGM charge generating substance
  • the charge generation layer typically contains a charge generation material (CGM) and a binder resin.
  • the charge generating material (CGM) and binder resin are the same as those explained for the single-layer photosensitive layer above.
  • the charge generating layer may contain other components as necessary.
  • the charge generating layer may contain other components as necessary.
  • known antioxidants, plasticizers, ultraviolet absorbers, electron-withdrawing compounds, leveling agents, Additives such as visible light blocking agents and fillers may also be included.
  • the blending ratio (mass) of the binder resin and the charge generating substance is preferably 10 parts by mass or more of the charge generating substance per 100 parts by mass of the binder resin, especially 30 parts by mass. On the other hand, it is preferably contained in a proportion of 1,000 parts by mass or less, and even more preferably in a proportion of 500 parts by mass or less, and from the viewpoint of film strength, 300 parts by mass or less. The content is more preferably 200 parts by mass or less, and even more preferably 200 parts by mass or less.
  • the thickness of the charge generation layer is preferably 0.1 ⁇ m or more, and more preferably 0.15 ⁇ m or more. On the other hand, it is preferably 10 ⁇ m or less, and more preferably 0.6 ⁇ m or less.
  • a charge transport layer (CTL) typically contains a charge transport material and a binder resin.
  • the charge transport material and binder resin are the same as those explained for the single-layer photosensitive layer above.
  • the blending ratio of the binder resin and the hole transport material (HTM) is such that the hole transport material (HTM) is blended in a ratio of 20 parts by mass or more to 100 parts by mass of the binder resin.
  • HTM hole transport material
  • HTM hole transport material
  • HTM hole transport material
  • the hole transport material (HTM) From the viewpoint of compatibility with the binder resin, it is more preferable to blend in a proportion of 150 parts by mass or less, and from the viewpoint of glass transition temperature, it is particularly preferable to blend in a proportion of 120 parts by mass or less.
  • the charge transport layer can contain other components as necessary.
  • the charge transport layer can contain other components as necessary.
  • known antioxidants, plasticizers, ultraviolet absorbers, electron-withdrawing compounds, leveling agents, Additives such as visible light blocking agents and fillers may also be included.
  • the thickness of the charge transport layer is not particularly limited. From the viewpoint of electrical properties, image stability, and high resolution, it is preferably 5 ⁇ m or more and 50 ⁇ m or less, more preferably 10 ⁇ m or more or 35 ⁇ m or less, and among these, 15 ⁇ m or more or 25 ⁇ m or less. is even more preferable.
  • each of the above layers can be formed as follows.
  • a coating solution obtained by dissolving or dispersing the substance to be contained in a solvent is coated onto a conductive support layer by layer by a known method such as dip coating, spray coating, nozzle coating, bar coating, roll coating, or blade coating. It can be formed by sequentially repeating the coating and drying process.
  • the formation method is not limited to this.
  • solvent or dispersion medium used to prepare the coating liquid.
  • Specific examples include alcohols, ethers, aromatic hydrocarbons, chlorinated hydrocarbons, and the like. Further, one type of these may be used alone, or two or more types may be used in combination in any combination and type.
  • the amount of solvent or dispersion medium used is not particularly limited. It is preferable to take into account the purpose of each layer and the properties of the selected solvent/dispersion medium, and adjust the physical properties of the coating liquid, such as solid content concentration and viscosity, as appropriate so that they fall within desired ranges.
  • the coating film is dried to the touch at room temperature, and then it is preferably dried by heating at a temperature range of 30° C. or higher and 200° C. or lower for 1 minute to 2 hours, either stationary or under ventilation. Further, the heating temperature may be constant, or heating may be performed while changing the temperature during drying.
  • the conductive support of the present electrophotographic photoreceptor (also referred to as “the present conductive support”) is not particularly limited as long as it supports a layer formed thereon and exhibits conductivity.
  • the conductive support include metal materials such as aluminum, aluminum alloy, stainless steel, copper, and nickel, and resin materials that have been made conductive by coexisting with conductive powder such as metal, carbon, and tin oxide. Resin, glass, paper, etc., on the surface of which a conductive material such as aluminum, nickel, ITO (indium oxide tin oxide alloy), etc., is vapor-deposited or coated can be mainly used.
  • the conductive support may be in the form of a drum, cylinder, sheet, belt, or the like.
  • the present conductive support may be a conductive support made of a metal material coated with a conductive material having an appropriate resistance value in order to control conductivity, surface properties, etc. or to cover defects. .
  • the metal material When using a metal material such as an aluminum alloy as the conductive support, the metal material may be coated with an anodized film.
  • the average thickness of the anodic oxide film is preferably 20 ⁇ m or less, particularly preferably 7 ⁇ m or less.
  • the sealing process can be performed by a known method.
  • the surface of the conductive support may be smooth or may be roughened by using a special cutting method or by polishing. Further, the surface may be roughened by mixing particles of an appropriate particle size into the material constituting the support. Note that an undercoat layer, which will be described below, may be provided between the conductive support and the photosensitive layer in order to improve adhesiveness, blocking properties, and the like.
  • the present electrophotographic photoreceptor may have an undercoat layer (also referred to as “this undercoat layer”) between the present photosensitive layer and the present conductive support.
  • the undercoat layer for example, a resin or a resin in which particles of organic pigments, metal oxides, etc. are dispersed can be used.
  • organic pigments used in the undercoat layer include phthalocyanine pigments, azo pigments, and perylene pigments. Among them, phthalocyanine pigments and azo pigments, specifically, phthalocyanine pigments and azo pigments when used as the charge generating substance described above, can be mentioned.
  • metal oxide particles used in the undercoat layer include metal oxide particles containing one type of metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, iron oxide, calcium titanate, Examples include metal oxide particles containing multiple metal elements such as strontium titanate and barium titanate. In the undercoat layer, only one type of particles may be used, or a plurality of types of particles may be mixed in any ratio and combination.
  • titanium oxide and aluminum oxide are preferred, and titanium oxide is particularly preferred.
  • the particle size of the metal oxide particles used in the present undercoat layer is not particularly limited. From the viewpoint of the properties of the undercoat layer and the stability of the solution for forming the undercoat layer, the average primary particle size is preferably 10 nm or more, and 100 nm or less, more preferably 50 nm or less.
  • binder resins used in the undercoat layer include polyvinyl acetal resins such as polyvinyl butyral resins; polyarylate resins, polycarbonate resins, polyester resins, phenoxy resins, acrylic resins, methacrylic resins, polyamide resins, polyurethane resins, and epoxy resins.
  • the material can be selected from insulating resins such as resins, silicone resins, polyvinyl alcohol resins, and styrene-alkyd resins. However, it is not limited to these polymers.
  • these binder resins may be used alone, or in combination of two or more types, or may be used in a cured form together with a curing agent.
  • polyvinyl acetal resins, alcohol-soluble copolyamides, modified polyamides, and the like are preferred because they exhibit good dispersibility and coating properties.
  • alcohol-soluble copolyamides are particularly preferred.
  • the mixing ratio of particles to the binder resin can be arbitrarily selected. It is preferable to use it in a range of 10% by mass to 500% by mass in terms of stability and coatability of the dispersion.
  • this undercoat layer can be arbitrarily selected. In view of the characteristics of the electrophotographic photoreceptor and the coating properties of the dispersion, the thickness is preferably 0.1 ⁇ m or more, and more preferably 20 ⁇ m or less. Further, the undercoat layer may contain a known antioxidant or the like.
  • present electrophotographic photoreceptor may have other layers as appropriate in addition to the above-described present conductive support, present photosensitive layer, present protective layer, and present subbing layer.
  • this image forming apparatus can be constructed using this electrophotographic photoreceptor.
  • the present image forming apparatus described below is an example of an image forming apparatus that can be configured using the present electrophotographic photoreceptor.
  • the image forming apparatus includes an electrophotographic photoreceptor 1, a charging device 2, an exposure device 3, and a developing device 4, and further includes a transfer device 5 and a cleaning device 6 as required. and a fixing device 7 are provided.
  • the present electrophotographic photoreceptor 1 is not particularly limited as long as it is the above-mentioned present electrophotographic photoreceptor.
  • FIG. 1 shows a drum-shaped photoreceptor in which the above-described photosensitive layer is formed on the surface of a cylindrical conductive support.
  • a charging device 2, an exposure device 3, a developing device 4, a transfer device 5, and a cleaning device 6 are arranged along the outer peripheral surface of this electrophotographic photoreceptor 1, respectively.
  • Examples of the charging device 2 include a non-contact corona charging device such as a corotron or a scorotron, or a contact-type charging device (direct-type charging device) that charges a photoreceptor surface by bringing a charging member to which a voltage is applied into contact with the surface of the photoreceptor.
  • Examples of contact charging devices include charging rollers, charging brushes, and the like. Note that FIG. 1 shows a roller-type charging device (charging roller) as an example of the charging device 2. As shown in FIG.
  • the type of exposure device 3 is not particularly limited as long as it can expose the electrophotographic photoreceptor 1 to form an electrostatic latent image on the photosensitive surface of the electrophotographic photoreceptor 1.
  • the exposure may be performed using a photoreceptor internal exposure method.
  • the light used for exposure is arbitrary.
  • the type of toner T is arbitrary, and in addition to powder toner, polymerized toner using suspension polymerization method, emulsion polymerization method, etc. can be used.
  • the configuration of the developing device 4 is also arbitrary.
  • the developing device 4 shown in FIG. 1 thins the toner T using a regulating member (developing blade) 45, frictionally charges the toner T to a predetermined polarity, carries the toner T while carrying it on a developing roller 44, and transfers the toner T to the photoreceptor 1. It has a configuration that allows it to come into contact with the surface of the However, the configuration is not limited to this.
  • the type of transfer device 5 is not particularly limited, and a device using any method such as an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method can be used. .
  • the cleaning device 6 is not particularly limited. Any cleaning device can be used, such as a brush cleaner, magnetic roller cleaner, blade cleaner, etc. If there is little or almost no toner remaining on the surface of the photoreceptor, the cleaning device 6 may be omitted.
  • the structure of the fixing device 7 is also arbitrary. Note that, in addition to the above-described configuration, the image forming apparatus may have a configuration that can perform a static elimination process, for example.
  • the image forming apparatus may be configured in a further modified manner, for example, it may be configured to perform processes such as a pre-exposure process and an auxiliary charging process, it may be configured to perform offset printing, or it may be configured to perform multiple types of printing. A full color tandem system configuration using toner may also be used.
  • the present electrophotographic photoreceptor 1 is combined with one or more of the charging device 2, the exposure device 3, the developing device 4, the transfer device 5, the cleaning device 6, and the fixing device 7 to form an integrated cartridge (referred to as an "electrophotographic cartridge").
  • the present electrophotographic cartridge described below is an example of an electrophotographic cartridge that can be constructed using the present electrophotographic photoreceptor.
  • the present electrophotographic cartridge can be configured to be detachable from an electrophotographic apparatus body such as a copying machine or a laser beam printer. In that case, for example, if the present electrophotographic photoreceptor 1 or other members deteriorate, this electrophotographic photoreceptor cartridge is removed from the image forming apparatus main body, and another new electrophotographic photoreceptor cartridge is installed in the image forming apparatus main body. This facilitates maintenance and management of the image forming apparatus.
  • an electrophotographic apparatus body such as a copying machine or a laser beam printer.
  • DMF N,N-dimethylformamide
  • MEHQ 4-methoxyphenol
  • ⁇ Completely dissolved at room temperature. Good: Undissolved residue was observed at room temperature, and it was completely dissolved by stirring at room temperature for 10 minutes or more or heating at 40° C. for less than 10 minutes. ⁇ : Completely dissolved when heated at 40°C for 10 minutes or more. ⁇ : Even after heating at 40° C. for 10 minutes or more, undissolved portions were observed.
  • Examples 1 to 5 had better solubility in organic solvents than Comparative Examples 1 to 4.
  • the electron transporting compounds of Examples 1 to 5 were all compounds represented by the above-mentioned formula (1). This compound has an asymmetric structure with an electron-transporting skeleton at its center, side chains with polymerizable functional groups on either side, and side chains without polymerizable functional groups on the other side. It is an electron-transporting compound.
  • the electron-transporting skeleton is the center, and one side chain having a polymerizable functional group is provided on one of the left and right sides, and the other side chain is
  • a compound with a left-right asymmetric structure that has a side chain that does not have a polymerizable functional group has a left-right asymmetric structure, and one of the side chains does not have a polymerizable functional group, so it has crystallinity. It is presumed that the solubility in solvents, especially alcohols, is good.
  • THF tetrahydrofuran
  • TL toluene
  • a single-layer photoreceptor was produced by the following procedure.
  • Coating liquid P1 for forming an undercoat layer was applied by dip coating to an aluminum cylinder having a diameter of 30 mm and a length of 244 mm with a machined surface, so that the undercoat layer had a thickness of 0.3 ⁇ m after drying.
  • Coating liquid Q1 for forming a single-layer photosensitive layer was dip-coated on the undercoat layer and dried at 100° C. for 24 minutes to form a single-layer photosensitive layer such that the film thickness after drying was 32 ⁇ m.
  • Coating liquid S1 for forming a protective layer was ring-coated on the single-layer type photosensitive layer, and immediately after coating, while rotating the photoconductor at 60 rpm in a nitrogen atmosphere, 365 nm LED light was applied at 0.9 W/cm 2 (108 J/cm). By irradiating at the intensity of 2 ) for 2 minutes, a protective layer was provided so that the film thickness after curing would be 1.5 ⁇ m, and photoreceptor A1 was produced.
  • Photoreceptors A2 to A7 were produced in the same manner as photoreceptor A1 except that the protective layer forming coating liquid S1 was changed to the protective layer forming coating liquids S2 to S7.
  • the exposure light As the exposure light, light from a halogen lamp was converted into monochromatic light of 780 nm using an interference filter.
  • the measurement environment was a temperature of 25° C. and a relative humidity of 50% (N/N environment).
  • the residual potential (VL) is shown in Table 2. The smaller the absolute value of the residual potential (VL), the more the charge is sufficiently transported and the potential is lowered, which can be said to be a better result.
  • a case where the residual potential (VL) was 320V or less was evaluated as "passing".
  • Comparative Examples 5 and 7 the solubility of the electron transporting compound was poor and a uniform protective layer could not be formed, so the residual potential could not be measured.
  • Dark decay (DDR) represents the retention rate (%) of surface potential when a photoreceptor whose surface is charged is left for a certain period of time. A higher surface potential retention rate (%) is a better result because the potential is maintained over time and the charging property is better.
  • a case where the dark decay (DDR) was 65.0% or more was evaluated as "passing".
  • dark decay (DDR) could not be measured because the electron transporting compound had poor solubility and a uniform protective layer could not be formed.
  • the electron-transporting skeleton is the center, and one side chain having a polymerizable functional group is provided on one of the left and right sides, and the other side chain is Furthermore, electrical properties, particularly residual potential properties, can be improved by adding to the protective layer an electron-transporting compound that has a side chain that does not have a polymerizable functional group and has an asymmetric structure.
  • an electron-transporting compound that has a side chain that does not have a polymerizable functional group and has an asymmetric structure.
  • it is asymmetrical and one of the side chains does not have a polymerizable functional group, it has low crystallinity and good solubility in solvents, especially alcohol, and has good coating properties when forming a protective layer. It is presumed that this results in good electron transport properties in the protective layer and good electrical properties of the photoreceptor.
  • Photoreceptor electrophotoreceptor
  • Charging device Charging roller; charging section
  • Exposure device Exposure section
  • Exposure section Exposure section
  • Transfer device 6
  • Cleaning device 7
  • Fixing device 41
  • Developing tank Agitator
  • Supply roller 44
  • Developing roller 45
  • Regulating member 71
  • Upper fixing member pressure roller
  • Lower fixing member 72
  • Heating device T
  • Toner P Recording paper paper, medium

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  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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WO2024143485A1 (ja) * 2022-12-28 2024-07-04 三菱ケミカル株式会社 化合物、組成物及び電子写真感光体
WO2024143484A1 (ja) * 2022-12-28 2024-07-04 三菱ケミカル株式会社 化合物、組成物及び電子写真感光体
WO2024204544A1 (ja) * 2023-03-31 2024-10-03 三菱ケミカル株式会社 電子写真感光体

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WO2024143484A1 (ja) * 2022-12-28 2024-07-04 三菱ケミカル株式会社 化合物、組成物及び電子写真感光体
WO2024204544A1 (ja) * 2023-03-31 2024-10-03 三菱ケミカル株式会社 電子写真感光体

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