EP2757419B1 - Procédé de production d'élément photosensible électro-photographique - Google Patents

Procédé de production d'élément photosensible électro-photographique Download PDF

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Publication number
EP2757419B1
EP2757419B1 EP14000183.5A EP14000183A EP2757419B1 EP 2757419 B1 EP2757419 B1 EP 2757419B1 EP 14000183 A EP14000183 A EP 14000183A EP 2757419 B1 EP2757419 B1 EP 2757419B1
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Prior art keywords
resin
ctm
xylene
mass
dimethoxymethane
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EP14000183.5A
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German (de)
English (en)
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EP2757419A1 (fr
EP2757419A8 (fr
Inventor
Kazumichi SUGIYAMA
Daisuke Tanaka
Tsutomu Nishida
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Canon Inc
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Canon Inc
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Priority claimed from JP2013007477A external-priority patent/JP6059025B2/ja
Application filed by Canon Inc filed Critical Canon Inc
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Publication of EP2757419A8 publication Critical patent/EP2757419A8/fr
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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, 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
    • G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0546—Polymers comprising at least one carboxyl radical, e.g. polyacrylic acid, polycrotonic acid, polymaleic acid; Derivatives thereof, e.g. their esters, salts, anhydrides, nitriles, amides
    • 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, 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
    • G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/056—Polyesters
    • 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, 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
    • G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0564—Polycarbonates
    • 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, 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
    • G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0578—Polycondensates comprising silicon atoms in the main chain
    • 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, 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
    • G03G5/14717—Macromolecular material obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/14734—Polymers comprising at least one carboxyl radical, e.g. polyacrylic acid, polycrotonic acid, polymaleic acid; Derivatives thereof, e.g. their esters, salts, anhydrides, nitriles, amides
    • 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, 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
    • G03G5/14747—Macromolecular material obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/14752—Polyesters
    • 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, 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
    • G03G5/14747—Macromolecular material obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/14756—Polycarbonates
    • 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, 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
    • G03G5/14747—Macromolecular material obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/14773—Polycondensates comprising silicon atoms in the main chain

Definitions

  • the present invention relates to a method of producing an electrophotographic photosensitive member, a process cartridge, and an electrophotographic apparatus.
  • An electrophotographic photosensitive member containing an organic photoconductive substance (charge-generating substance) has been frequently used as an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus.
  • a cleaning step of removing transfer residual toner with a cleaning blade has been required to reduce a contact stress (coefficient of friction) between the cleaning blade and the electrophotographic photosensitive member in order that the occurrence of a phenomenon such as the squeaking of the cleaning blade or the turn-up of the cleaning blade may be suppressed.
  • Japanese Patent Application Laid-Open No. 2009-037229 discloses a technology involving incorporating a resin obtained by building a siloxane structure in a polycarbonate resin into the surface layer to reduce the contact stress (coefficient of friction) between the electrophotographic photosensitive member and the cleaning blade.
  • the surface layer of the electrophotographic photosensitive member is formed by: applying, onto a support or the like, a surface-layer coating solution obtained by dissolving or dispersing a binder resin or the like in a solvent to form a coat; and drying the coat.
  • the solvent is selected in consideration of the solubility of the binder resin or the like, the absence of influences on electrophotographic characteristics, and the absence of the whitening, sagging, or the like of the coat at the time of its coating.
  • various investigations have been conducted on the solvent to be used as the solvent of the coating solution.
  • 2001-343767 proposes a method of producing an electrophotographic photosensitive member free of whitening at the time of coating and having electrophotographic characteristics comparable to or better than those in the case where a halogen-based solvent is used, the method involving using an aromatic hydrocarbon and ethylene glycol dimethyl ether as solvents of a charge-transporting-layer coating solution.
  • Japanese Patent Application Laid-Open No. H06-123987 proposes that a drying temperature at the time of the production of an electrophotographic photosensitive member and the boiling point of a solvent to be used in a photosensitive-layer coating solution be regulated for suppressing the defects of a coat.
  • a solvent to be used in a surface-layer coating solution contains a halogen-based solvent such as monochlorobenzene from the viewpoints of the solubilities of the resin having a siloxane structure and any other material.
  • a halogen-based solvent such as monochlorobenzene
  • the relevance of a chemical substance to an environment has been attracting attention, and the management of the chemical substance and the regulation of its amount of emission have been enhanced.
  • the replacement of the halogen-based solvent with a non-halogen-based solvent has been progressing.
  • the halogen-based solvent must be recovered separately from the non-halogen-based solvent upon waste liquid recovery and hence productivity is liable to reduce. In view of the foregoing, its replacement with the non-halogen-based solvent has been demanded.
  • the non-halogen-based solvent suitable for use in the surface-layer coating solution for the electrophotographic photosensitive member include xylene and toluene.
  • the present invention is directed to providing a method of producing an electrophotographic photosensitive member, the method including the step of applying a surface-layer coating solution containing a resin having a siloxane moiety, and at least one of toluene and xylene to form a surface layer, in which an initial coefficient of friction in the surface of the electrophotographic photosensitive member is reduced. Further, the present invention is directed to providing an electrophotographic photosensitive member produced by the method of producing an electrophotographic photosensitive member, and a process cartridge and an electrophotographic apparatus each including the electrophotographic photosensitive member.
  • a process cartridge detachably mountable to a main body of an electrophotographic apparatus, in which the process cartridge integrally supports: an electrophotographic photosensitive member produced by the above-described method of producing an electrophotographic photosensitive member; and at least one device selected from the group consisting of a charging device, a developing device, a transferring device, and a cleaning device.
  • an electrophotographic apparatus including: an electrophotographic photosensitive member produced by the above-described method of producing an electrophotographic photosensitive member; a charging device; an exposing device; a developing device; and a transferring device.
  • the method of producing an electrophotographic photosensitive member including the steps of applying a surface-layer coating solution containing a resin having a siloxane moiety, and at least one of toluene and xylene to form a coat, and then drying the coat to form a surface layer, in which an initial coefficient of friction in the surface of the electrophotographic photosensitive member is reduced.
  • FIG. 1 is a view illustrating an example of the schematic construction of an electrophotographic apparatus including a process cartridge having an electrophotographic photosensitive member of the present invention.
  • a method of producing an electrophotographic photosensitive member of the present invention includes the following steps of: forming a coat of a surface-layer coating solution; and drying the coat to form the surface layer, in which the surface-layer coating solution includes as constituents thereof: ( ⁇ ) at least one resin selected from the group consisting of a polycarbonate resin not having a siloxane moiety at an end thereof, and a polyester resin not having a siloxane moiety at an end thereof (constituent ( ⁇ )); ( ⁇ ) at least one resin selected from the group consisting of a polycarbonate resin having a siloxane moiety at an end thereof, a polyester resin having a siloxane moiety at an end thereof, and a polyacrylate resin having a siloxane moiety at an end thereof (constituent ( ⁇ )); and ( ⁇ ) at least one solvent selected from the group consisting of toluene and xylene (constituent ( ⁇ )); and further, ( ⁇ ) a compound having a boiling point
  • R represents an alkylene group having 1 to 5 carbon atoms
  • n represents 0 or 1.
  • the ( ⁇ ) is sometimes referred to as "resin ⁇ "
  • the ( ⁇ ) is sometimes referred to as "resin ⁇ ”
  • the ( ⁇ ) is sometimes referred to as “solvent ⁇ ”
  • the ( ⁇ ) is sometimes referred to as “compound ⁇ ”.
  • the inventors of the present invention assume the reason why an initial coefficient of friction in the surface of the electrophotographic photosensitive member can be reduced by incorporating the compound ⁇ into the surface-layer coating solution in the present invention to be as described below.
  • the surface of the electrophotographic photosensitive member having a low initial coefficient of friction is obtained through the following: the resin ⁇ having a siloxane moiety migrates to the surface of the electrophotographic photosensitive member (surface migration) and the siloxane moiety is distributed in the surface of the electrophotographic photosensitive member.
  • the surface migration of the resin ⁇ is performed in the step of drying the coat formed by applying the surface-layer coating solution.
  • the resin ⁇ and the resin ⁇ need to be in a state of easily separating from each other in the drying step in order that the resin ⁇ may migrate to the surface of the photosensitive member.
  • the resin ⁇ and the resin ⁇ need to be compatible with each other to some extent from the viewpoints of the stability of the coating solution (surface-layer coating solution) and the uniformity of the coat. Therefore, the repeating structural unit of the resin ⁇ having a siloxane moiety needs to be selected so as to be easily compatible with the resin ⁇ .
  • the dimethyl silicone oil is hardly compatible with the resin ⁇ and easily migrates to the surface of the electrophotographic photosensitive member.
  • compatibility between the dimethyl silicone oil and the resin ⁇ is so low that the dimethyl silicone oil is scattered in the surface of the electrophotographic photosensitive member and an electrophotographic photosensitive member whose surface has a uniformly low coefficient of friction is not obtained.
  • the dimethyl silicone oil separates and becomes opaque, and hence the stability of the solution is not sufficiently obtained.
  • the resin ⁇ and the resin ⁇ are easily compatible with each other, and the resin ⁇ and the resin ⁇ hardly separate from each other in the drying step, and hence the resin ⁇ hardly migrates to the surface and a sufficient initial coefficient of friction is not obtained.
  • the compound ⁇ is incorporated into the surface-layer coating solution for establishing a state where the resin ⁇ and the resin ⁇ easily separate from each other in the drying step while maintaining the stability of the coating solution and the uniformity of the coat.
  • the inventors of the present invention assume the reason why the incorporation of the compound 5 having a boiling point in one atmosphere higher than that of the solvent ⁇ out of the compounds each having a structure represented by the formula (1) facilitates the separation of the resin ⁇ and the resin ⁇ to be as described below.
  • the compound ⁇ in the present invention is a compound having a boiling point in one atmosphere higher than that of the ( ⁇ ) out of the compounds each represented by the following formula (1).
  • the boiling point of xylene is 138 to 144°C.
  • the boiling point of toluene is 111°C.
  • R represents an alkylene group having 1 to 5 carbon atoms
  • n represents 0 or 1.
  • the compound having a boiling point in one atmosphere higher than that of the ( ⁇ ) is a compound having a boiling point in one atmosphere higher than that of toluene when the solvent ⁇ is toluene alone.
  • the compound is a compound having a boiling point in one atmosphere higher than that of xylene.
  • the solvent ⁇ is xylene alone, the compound is a compound having a boiling point in one atmosphere higher than that of xylene.
  • propylene carbonate 240°C
  • ⁇ -butyrolactone 204°C
  • ⁇ -valerolactone 230°C
  • ⁇ -caprolactone 253°C
  • propylene carbonate ⁇ -butyrolactone
  • 5-valerolactone are preferred.
  • the content of the compound ⁇ in the surface-layer coating solution is preferably 3 mass% or more and 300 mass% or less with respect to the total mass of the resin ⁇ and the resin ⁇ .
  • a content of 3 mass% or more and 300 mass% or less is preferred from the viewpoint of a reducing effect on the initial coefficient of friction in the surface of the photosensitive member because an excellent separating action on the resin ⁇ and the resin ⁇ is obtained.
  • the content of the compound ⁇ in the surface-layer coating solution is preferably 5 mass% or more and 80 mass% or less with respect to the total mass of the resin ⁇ and the resin ⁇ .
  • the content of the compound ⁇ in the surface-layer coating solution is preferably 0.5 mass% or more and 150 mass% or less with respect to the total content of the solvent ⁇ .
  • a content of 0.5 mass% or more and 150 mass% or less is preferred from the viewpoints of the reducing effect on the initial coefficient of friction in the surface of the photosensitive member and the effect of the stability of the coating solution.
  • the content of the compound ⁇ in the surface-layer coating solution is preferably 0.5 mass% or more and 40 mass% or less, more preferably 5 mass% or more and 40 mass% or less with respect to the total content of the solvent ⁇ .
  • the resin ⁇ is at least one resin selected from the group consisting of a polycarbonate resin not having a siloxane moiety at an end thereof, and a polyester resin not having a siloxane moiety at an end thereof.
  • the polycarbonate resin not having a siloxane moiety at an end thereof be a polycarbonate resin A having a structural unit represented by the following formula (A). It is preferred that the polyester resin not having a siloxane moiety at an end thereof be a polyester resin B having a structural unit represented by the following formula (B).
  • R 21 to R 24 each independently represent a hydrogen atom or a methyl group
  • X 1 represents a single bond, a cyclohexylidene group, or a divalent group having a structure represented by the following formula (C).
  • R 31 to R 34 each independently represent a hydrogen atom or a methyl group
  • X 2 represents a single bond, a cyclohexylidene group, or a divalent group having a structure represented by the following formula (C)
  • Y 1 represents an m-phenylene group, a p-phenylene group, or a divalent group in which two p-phenylene groups are bonded through an oxygen atom.
  • R 41 and R 42 each independently represent a hydrogen atom, a methyl group, or a phenyl group.
  • repeating structural unit of the polycarbonate resin A represented by the formula (A) are shown below.
  • the polycarbonate resin A can be synthesized by, for example, a conventional phosgene method.
  • the resin can also be synthesized by an ester exchange method.
  • those polycarbonate resins A and polyester resins B can be synthesized by a known method.
  • those resins can be synthesized by a method disclosed in Japanese Patent Application Laid-Open No. 2007-047655 or Japanese Patent Application Laid-Open No. 2007-072277 .
  • One kind of the polycarbonate resin A and the polyester resin B can be used alone, or two or more kinds thereof can be used as a mixture or a copolymer.
  • Their copolymerization form may be any one of the forms such as block copolymerization, random copolymerization, and alternating copolymerization.
  • the weight-average molecular weight of each of the polycarbonate resin A and the polyester resin B is preferably 20,000 or more and 300,000 or less, more preferably 50,000 or more and 200,000 or less.
  • the weight-average molecular weight of each of the resins is a weight-average molecular weight in terms of polystyrene measured according to a conventional method by a method described in Japanese Patent Application Laid-Open No. 2007-079555 .
  • the polycarbonate resin A and the polyester resin B each serving as the resin ⁇ may each be a copolymer having a structural unit including a siloxane moiety in addition to the structural unit represented by the formula (A) or the formula (B). Specific examples thereof include structural units represented by the following formulae (H-1) and (H-2).
  • the copolymer may further have a structural unit represented by the following formula (H-3).
  • the resin ⁇ is at least one resin defined in claim 1, selected from the group consisting of a polycarbonate resin having a siloxane moiety at an end thereof, a polyester resin having a siloxane moiety at an end thereof, and a polyacrylate resin having a siloxane moiety at an end thereof.
  • the surface of the photosensitive member has high lubricity and hence its initial coefficient of friction can be reduced. This is probably because the presence of a dimethylpolysiloxane moiety at an end increases the degree of freedom of a siloxane moiety and hence improves the surface migration property of the resin.
  • the resins each having a siloxane moiety at an end thereof in the resin ⁇ are a polycarbonate resin, a polyester resin, and a polyacrylate resin from the viewpoints of compatibility with the resin ⁇ , and the stability and coatability of the coating solution.
  • the polycarbonate resin having a siloxane moiety at an end thereof is a polycarbonate resin D having a structural unit represented by the following formula (A') and an end structure represented by the following formula (D).
  • the polyester resin having a siloxane moiety at an end thereof is a polyester resin E having a structural unit represented by the following formula (B') and an end structure represented by the following formula (D).
  • R 25 to R 28 each independently represent a hydrogen atom or a methyl group
  • X 3 represents a single bond, a cyclohexylidene group, or a divalent group having a structure represented by the following formula (C').
  • R 35 to R 38 each independently represent a hydrogen atom or a methyl group
  • X 4 represents a single bond, a cyclohexylidene group, or a divalent group having a structure represented by the following formula (C')
  • Y 2 represents an m-phenylene group, a p-phenylene group, or a divalent group in which two p-phenylene groups are bonded through an oxygen atom.
  • R 43 and R 44 each independently represent a hydrogen atom, a methyl group, or a phenyl group.
  • a and b each independently represent the repetition number of a structure in respective parentheses, and the average value of a for the polycarbonate resin D or the polyester resin E is 20 or more and 100 or less, and the average value of b therefor is 1 or more and 10 or less. It is more preferred that the average value of a be 30 or more and 60 or less, and the average value of b be 3 or more and 10 or less.
  • the polycarbonate resin D and the polyester resin E each have the end structure represented by the formula (D) at one end, or each of both ends, of the resin.
  • a molecular weight modifier an end stopping agent
  • the molecular weight modifier include phenol, p-cumylphenol, p-tert-butylphenol, and benzoic acid. In the present invention, phenol or p-tert-butylphenol is preferred.
  • One kind of the polycarbonate resin D and the polyester resin E can be used alone, or two or more kinds thereof can be used as a mixture or a copolymer.
  • Their copolymerization form may be any one of the forms such as block copolymerization, random copolymerization, and alternating copolymerization.
  • a structural unit having a siloxane moiety may be present in the main chain of each of the polycarbonate resin D and the polyester resin E.
  • a copolymer having a structural unit represented by the following formula (H) is permitted.
  • f and g each represent the repetition number of a structure in parentheses, and the average value of f for the polycarbonate resin D and the polyester resin E is 20 or more and 100 or less, and the average value of g therefor is 1 or more and 10 or less.
  • Specific examples of the structural unit represented by the formula (H) include the structural units represented by the formulae (H-1) and (H-2).
  • the structural unit represented by the formula (A') in the polycarbonate resin D include the structural units represented by the formulae (A-1) to (A-8). Of those, the structural units represented by the formulae (A-1), (A-2), and (A-4) are preferred.
  • Specific examples of the structural unit represented by the formula (B') in the polyester resin E include the structural units represented by the formulae (B-1) to (B-9). Of those, the structural units represented by the formulae (B-1), (B-3), (B-6), (B-7), and (B-8) are preferred. Of those, the structural units represented by the formulae (A-4), (B-1), and (B-3) are particularly preferred.
  • the siloxane moiety of each of the polycarbonate resin D and the polyester resin E refers to a structure in a frame indicated by a dotted line in an end structure represented by the following formula (D-S). Further, when the polycarbonate resin D and the polyester resin E each have the structural unit represented by the formula (H), a structure in a frame indicated by a dotted line in a structural unit represented by the following formula (H-S) is also included in the category of the siloxane moiety.
  • the polycarbonate resin D and the polyester resin E can be synthesized by a known method.
  • the resins can be synthesized by a method described in Japanese Patent Application Laid-Open No. 2007-199688 .
  • the polycarbonate resin D and the polyester resin E shown in the synthesis examples of Table 2 were synthesized by employing the same synthesis method with raw materials corresponding to the polycarbonate resin D and the polyester resin E. It should be noted that the purification of each of the polycarbonate resin D and the polyester resin E was performed as described below.
  • each fractionated component was subjected to 1 H-NMR measurement and then resin composition was determined from the relative ratio of the siloxane moiety in the resin.
  • Table 2 shows the weight-average molecular weights of the synthesized polycarbonate resin D and polyester resin E, and the contents of their siloxane moieties.
  • the polyacrylate resin having a siloxane moiety at an end thereof is preferably a polyacrylate resin F having an end structure represented by the following formula (F-1) and a structural unit represented by the following formula (F-2), or having an end structure represented by the following formula (F-1) and a structural unit represented by the following formula (F-3) .
  • R 51 represents a hydrogen atom or a methyl group
  • c represents the repetition number of a structure in a parenthesis
  • the average value of c for the polyacrylate resin F is 0 or more and 5 or less
  • R 52 to R 54 each independently represent a structure represented by the following formula (F-1-2), a methyl group, a methoxy group, or a phenyl group, and at least one of R 52 to R 54 has a structure represented by the following formula (F-1-2).
  • d represents the repetition number of a structure in a parenthesis, and the average value of d for the polyacrylate resin F is 10 or more and 50 or less, and R 55 represents a hydroxy group or a methyl group.
  • R 56 represents a hydrogen atom, a methyl group, or a phenyl group, and e represents 0 or 1.
  • the siloxane moiety of the polyacrylate resin F refers to a structure in a frame indicated by a dotted line in a structure represented by the following formula (F-S) or the following formula (F-T).
  • Table 3 below shows specific examples of the structural units of the polyacrylate resin F.
  • Table 3 Compound Example (F-1) (F-2) or (F-3) Weight ratio between structural units Weight-average molecular weight Mw F-A 2/8 105,000 F-B 2/8 100,000 F-C 1/9 100,000 F-D 1/9 105,000 F-E 2/8 110,000 F-F 1.5/8.5 100,000 F-G 1/9 110,000
  • polyacrylate resins F shown in Table 3 resins represented by Compound Examples (F-B) and (F-D) are preferred.
  • Those polyacrylate resins can be synthesized by a known method.
  • the resins can be synthesized by a method described in Japanese Patent Application Laid-Open No. S58-167606 or Japanese Patent Application Laid-Open No. S62-075462 .
  • the content of the resin ⁇ in the surface-layer coating solution is preferably 0.1 mass% or more and 50 mass% or less with respect to the content of the resin ⁇ .
  • the content is 0.1 mass% or more and 50 mass% or less, the reducing effect on the initial coefficient of friction is sufficiently exerted.
  • the solvent ⁇ is at least one solvent selected from the group consisting of toluene and xylene. Specific examples thereof include toluene (boiling point: 111°C), o-xylene (boiling point: 144°C), m-xylene (boiling point: 139°C), p-xylene (boiling point: 138°C), and mixed xylene (boiling point: 138 to 144°C). Of those, o-xylene is preferred. One of those solvents may be used alone, or two or more thereof may be used as a mixture. It should be noted that a numerical value in parentheses represents a boiling point in one atmosphere.
  • the surface-layer coating solution for an electrophotographic photosensitive member in the present invention may further contain any other solvent for forming a surface layer having a uniform thickness.
  • the coating solution preferably contains a chain ether or cyclic ether having a low boiling point as the other solvent.
  • the chain ether having a low boiling point is, for example, dimethoxymethane
  • the cyclic ether having a low boiling point is, for example, tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • At least one of dimethoxymethane and tetrahydrofuran (hereinafter sometimes referred to as "( ⁇ )" is preferably used.
  • the content of the solvent ⁇ be 15 mass% or more and 99 mass% or less, the content of the compound ⁇ be 0.5 mass% or more and 35 mass% or less, and the content of the ( ⁇ ) be 0.1 mass% or more and 65 mass% or less.
  • the electrophotographic photosensitive member of the present invention includes a support and a photosensitive layer formed on the support.
  • the photosensitive layer include such a single layer type photosensitive layer that a charge-transporting substance and a charge-generating substance are incorporated into the same layer, and a laminated type (separated-function type) photosensitive layer separated into a charge-generating layer containing the charge-generating substance and a charge-transporting layer containing the charge-transporting substance.
  • the laminated type photosensitive layer is preferred.
  • the charge-generating layer may be of a laminated structure, or the charge-transporting layer may be of a laminated structure.
  • a protective layer may be formed on the photosensitive layer for the purpose of improving the durability of the electrophotographic photosensitive member.
  • the charge-transporting layer when the charge-transporting layer is the outermost surface, the charge-transporting layer is the surface layer, and when the protective layer is provided on the charge-transporting layer, the protective layer is the surface layer.
  • the support is one having conductivity (conductive support).
  • the support is one made of a metal such as aluminum, an aluminum alloy, stainless steel, copper, nickel, or zinc, or an alloy thereof.
  • the support to be used may be an ED tube or an EI tube or one obtained by subjecting the tube to cutting, electrolytic compound polishing (electrolysis with an electrolyte solution and electrodes having an electrolytic action, and polishing with a grinding stone having a polishing action), or a wet- or dry-honing process.
  • Further examples thereof include a support made of a metal or a resin having formed thereon a thin film of a conductive material such as aluminum, an aluminum alloy, or an indium oxide-tin oxide alloy.
  • a support obtained by impregnating conductive particles such as carbon black, tin oxide particles, titanium oxide particles, or silver particles in a resin or the like, or a plastic containing a conductive binder resin may be used.
  • the surface of the conductive support may be subjected to, for example, cutting treatment, roughening treatment, or alumite treatment.
  • a conductive layer containing conductive particles and a resin may be provided on the support.
  • the conductive layer is a layer formed by using a conductive-layer coating solution in which conductive particles are dispersed in a binder resin.
  • the conductive particles include carbon black, acetylene black, metal powders made of, for example, aluminum, nickel, iron, nichrome, copper, zinc, and silver, and metal oxide powders made of, for example, conductive tin oxide and ITO.
  • binder resin to be used in the conductive layer examples include a polyester resin, a polycarbonate resin, a polyvinyl butyral resin, a polyacrylate resin, a silicone resin, an epoxy resin, a melamine resin, a urethane resin, a phenol resin, and an alkyd resin.
  • a solvent for the conductive-layer coating solution for example, there are given an ether-based solvent, an alcohol-based solvent, a ketone-based solvent, and an aromatic hydrocarbon solvent.
  • the thickness of the conductive layer is preferably 0.2 ⁇ m or more and 40 ⁇ m or less, more preferably 1 ⁇ m or more and 35 ⁇ m or less, still more preferably 5 ⁇ m or more and 30 ⁇ m or less.
  • An intermediate layer may be provided between the conductive support or the conductive layer and the photosensitive layer.
  • the intermediate layer is formed for improving the adhesiveness of the photosensitive layer, improving the coatability, improving the property relative to charge injection from the conductive support, and protecting the photosensitive layer from an electrical breakdown.
  • the intermediate layer can be formed by applying an intermediate-layer coating solution containing a binder resin onto the conductive support or the conductive layer, and then drying or curing the coating solution.
  • binder resin of the intermediate layer examples include polyacrylic acids, methylcellulose, ethylcellulose, a polyamide resin, a polyimide resin, a polyamideimide resin, a polyamide acid resin, a melamine resin, an epoxy resin, and a polyurethane resin.
  • the binder resin to be used in the intermediate layer is preferably a thermoplastic resin, and specifically, a thermoplastic polyamide resin is preferred.
  • the polyamide resin is preferably copolymer nylon with low crystallinity or amorphous which can be applied in a solution state.
  • the intermediate-layer coating solution As a solvent for the intermediate-layer coating solution, there are given an ether-based solvent, an alcohol-based solvent, a ketone-based solvent, and an aromatic hydrocarbon solvent.
  • the thickness of the intermediate layer is preferably 0.05 ⁇ m or more and 40 ⁇ m or less, more preferably 0.1 ⁇ m or more and 30 ⁇ m or less.
  • the intermediate layer may further contain semiconductive particles, an electron-transporting substance, or an electron-accepting substance.
  • the photosensitive layer (charge-generating layer, charge-transporting layer) is formed on the conductive support, conductive layer, or intermediate layer.
  • Examples of the charge-generating substance to be used in the electrophotographic photosensitive member of the present invention include azo pigments, phthalocyanine pigments, indigo pigments, and perylene pigments. Only one of those charge-generating substances may be used, or two or more thereof may be used. Of those, oxytitanium phthalocyanine, hydroxygallium phthalocyanine, chlorogallium phthalocyanine, and the like are particularly preferred because of their high sensitivity.
  • binder resin to be used in the charge-generating layer examples include a polycarbonate resin, a polyester resin, a butyral resin, a polyvinyl acetal resin, a polyacrylate resin, a vinyl acetate resin, and a urea resin.
  • a butyral resin is particularly preferred.
  • One of those resins may be used alone, or two or more thereof may be used as a mixture or as a copolymer.
  • the charge-generating layer can be formed by applying a charge-generating-layer coating solution, which is prepared by dispersing the charge-generating substance together with the binder resin and a solvent, and then drying the coating solution. Further, the charge-generating layer may be a deposited film of a charge-generating substance.
  • An example of the dispersion method is one using a homogenizer, an ultrasonic wave, a ball mill, a sand mill, an attritor, or a roll mill.
  • a ratio between the charge-generating substance and the binder resin is preferably 0.1 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 3 parts by mass or less of the charge-generating substance with respect to 1 part by mass of the resin.
  • Examples of the solvent to be used in the charge-generating-layer coating solution include an alcohol-based solvent, a sulfoxide-based solvent, a ketone-based solvent, an ether-based solvent, an ester-based solvent, and an aromatic hydrocarbon solvent.
  • the thickness of the charge-generating layer is preferably 0.01 ⁇ m or more and 5 ⁇ m or less, more preferably 0.1 ⁇ m or more and 2 ⁇ m or less.
  • any of various sensitizers, antioxidants, UV absorbents, plasticizers, and the like may be added to the charge-generating layer, if required.
  • An electron-transporting substance or an electron-accepting substance may also be added to the charge-generating layer to prevent the flow of charge (carrier) from being disrupted in the charge-generating layer.
  • the charge-transporting layer is formed on the charge-generating layer.
  • a triarylamine compound, a hydrazone compound, a styryl compound, and a stilbene compound are given as the charge-transporting substance to be used in the present invention.
  • a compound represented by any one of the following structural formulae (CTM-1) to (CTM-7) is preferred.
  • the charge-transporting layer can be formed by applying a charge-transporting-layer coating solution obtained by dissolving the charge-transporting substance and a binder resin in a solvent, and then drying the coating solution.
  • the resin ⁇ and the resin ⁇ are contained as binder resins; any other resin may be further mixed therein before use.
  • the other resin that may be mixed before use is as described above.
  • the charge-transporting-layer coating solution (surface-layer coating solution), which contains the solvent ⁇ and the compound ⁇ , may further contain any other solvent as described above.
  • a ratio between the charge-transporting substance and the binder resins is as follows: the amount of the charge-transporting substance is preferably 0.3 part by mass or more and 2 parts by mass or less, more preferably 0.5 part by mass or more and 1.5 parts by mass or less per 1 part by mass of the binder resins.
  • the charge-transporting layer has a thickness of preferably 5 ⁇ m or more and 50 ⁇ m or less, more preferably 10 ⁇ m or more and 35 ⁇ m or less.
  • additives may be added to each layer of the electrophotographic photosensitive member of the present invention.
  • the additives include: an antidegradant such as an antioxidant, a UV absorbent, or a light stabilizer; and fine particles such as organic fine particles or inorganic fine particles.
  • antidegradant examples include a hindered phenol-based antioxidant, a hindered amine-based light stabilizer, a sulfur atom-containing antioxidant, and a phosphorus atom-containing antioxidant.
  • organic fine particles examples include polymer resin particles such as fluorine atom-containing resin particles, polystyrene fine particles, and polyethylene resin particles.
  • inorganic fine particles include metal oxides such as silica and alumina.
  • any of the application methods can be employed, such as dip coating, spraying coating, spinner coating, roller coating, Mayer bar coating, and blade coating.
  • dip coating method is preferred.
  • the drying temperature at which the coating solution for each layer is dried to form a coat is as follows: the coating solution is preferably dried at 60°C or more and 160°C or less.
  • the drying temperature for the charge-transporting-layer coating solution (surface-layer coating solution) is particularly preferably 110°C or more and 140°C or less out of such range.
  • FIG. 1 illustrates an example of the schematic construction of an electrophotographic apparatus including a process cartridge having the electrophotographic photosensitive member of the present invention.
  • a cylindrical electrophotographic photosensitive member 1 is driven to rotate around an axis 2 in the direction indicated by the arrow at a predetermined peripheral speed.
  • the surface of the electrophotographic photosensitive member 1 driven to rotate is uniformly charged to a predetermined negative potential by a charging device (primary charging device: such as a charging roller) 3 during the process of rotation.
  • a charging device primary charging device: such as a charging roller
  • the surface of the electrophotographic photosensitive member 1 receives exposure light (image exposure light) 4 which is emitted from an exposing device (not shown) such as slit exposure or laser-beam scanning exposure and is intensity-modulated according to a time-series electric digital image signal of image information of interest.
  • an exposing device not shown
  • electrostatic latent images corresponding to images of interest are sequentially formed on the surface of the electrophotographic photosensitive member 1.
  • the electrostatic latent images formed on the surface of the electrophotographic photosensitive member 1 are converted into toner images by reversal development with toner contained in a developer of a developing device 5. Subsequently, the toner images being formed and carried on the surface of the electrophotographic photosensitive member 1 are sequentially transferred to a transfer material (such as paper) P by a transfer bias from a transferring device (such as transfer roller) 6.
  • a transfer material such as paper
  • a transfer bias having a polarity reverse to that of the electric charges of the toner is applied to the transferring device 6 from a bias power source (not shown).
  • the transfer material P which has been transferred to the toner images is separated from the surface of the electrophotographic photosensitive member 1 and then introduced to a fixing device 8.
  • the transfer material P is subjected to an image fixation of the toner images and then printed as an image-formed product (print or copy) out of the apparatus.
  • the surface of the electrophotographic photosensitive member 1 after the transfer of the toner images is cleaned by removal of the residual developer after the transfer (transfer residual toner) by a cleaning device (such as cleaning blade) 7. Subsequently, the surface of the electrophotographic photosensitive member 1 is subjected to a neutralization process with pre-exposure light (not shown) from a pre-exposing device (not shown) and then repeatedly used in image formation.
  • a pre-exposure light not shown
  • the electrophotographic photosensitive member 1 and multiple components selected from, for example, the charging device 3, the developing device 5, the transferring device 6, and the cleaning device 7 may be stored in a container and integrally supported to form a process cartridge.
  • the process cartridge may be detachably mountable to the main body of an electrophotographic apparatus.
  • the process cartridge may be detachably mountable to the main body of an electrophotographic apparatus such as a copying machine or a laser beam printer.
  • the charging device 3, the developing device 5, and the cleaning device 7 are integrally supported with the electrophotographic photosensitive member 1 to form a cartridge.
  • the cartridge is used as a process cartridge 9 detachably mountable to the main body of the electrophotographic apparatus with a guiding device 10 such as a rail of the main body of the electrophotographic apparatus.
  • part(s) means “part(s) by mass” in the examples.
  • An aluminum cylinder with a diameter of 30 mm and a length of 260.5 mm was used as a support (conductive support).
  • the conductive-layer coating solution was applied onto the support by dip coating and cured (thermally cured) at 140°C for 30 minutes, to thereby form a conductive layer having a thickness of 25 ⁇ m.
  • the intermediate-layer coating solution was applied onto the conductive layer by dip coating and dried at 100°C for 10 minutes, to thereby form an intermediate layer having a thickness of 0.7 ⁇ m.
  • a hydroxygallium phthalocyanine crystal charge-generating substance
  • 10 parts of a hydroxygallium phthalocyanine crystal (charge-generating substance) in a crystal form having strong peaks at Bragg angles (2 ⁇ 0.2°) in CuK ⁇ -characteristic X-ray diffraction of 7.5°, 9.9°, 16.3°, 18.6°, 25.1°, and 28.3° were added to a solution by dissolving 5 parts of a polyvinyl butyral resin (product name: S-LEC BX-1, manufactured by Sekisui Chemical Co., Ltd., binder resin) in 250 parts of cyclohexanone.
  • the resultant mixture was dispersed by a sand mill apparatus using glass beads each having a diameter of 1 mm under a 23 ⁇ 3°C atmosphere for 1 hour. After the dispersion, 250 parts of ethyl acetate were added thereto to prepare a charge-generating-layer coating solution.
  • the charge-generating-layer coating solution was applied onto the intermediate layer by dip coating and dried at 100°C for 10 minutes, to thereby form a charge-generating layer having a thickness of 0.22 ⁇ m.
  • the charge-transporting-layer coating solution was applied onto the charge-generating layer by dip coating to form a coat, and then the coat was dried at 125°C for 30 minutes to form a charge-transporting layer having a thickness of 15 ⁇ m. Thus, an electrophotographic photosensitive member was produced.
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that in Example 1, the drying temperature in the formation of the charge-transporting layer was changed to 115°C or 135°C.
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that in Example 1, the thickness of the charge-transporting layer was changed to 10 ⁇ m or 30 ⁇ m.
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that in Example 1, the solvent ⁇ was changed as shown in Table 4.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 6 except that in Example 6, dimethoxymethane as the ( ⁇ ) was changed to tetrahydrofuran (THF).
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that in Example 1, as shown in Table 4, dimethoxymethane was not used and the content of o-xylene was changed to 50 parts.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that in Example 1, as shown in Table 4, the content of o-xylene was changed to 20 parts and the content of dimethoxymethane was changed to 30 parts.
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that in Example 1, the compound ⁇ was changed as shown in Table 4.
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that in Example 1, the content of the resin (D1) was changed as shown in Table 4.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that in Example 1, the content of propylene carbonate was changed as shown in Table 4.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that in Example 1, as shown in Table 4, the content of o-xylene was changed to 28 parts, the content of propylene carbonate was charged to 8 parts, and the content of dimethoxymethane was changed to 18 parts.
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that in Example 1, the content of the resin (D1) and the content of propylene carbonate were changed as shown in Table 4.
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that in Example 1, the kinds and contents of the resin ⁇ , the resin ⁇ , the solvent ⁇ , the compound ⁇ , the charge-transporting substances, and the ( ⁇ ) were changed as shown in Tables 4 to 6.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that in Example 28, the thickness of the charge-transporting layer was changed to 10 ⁇ m and the drying temperature in the formation of the charge-transporting layer was changed to 115°C.
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that in Example 1, 0.8 part of a compound represented by the following formula (AD-1) and 0.2 part of a compound represented by the following formula (AD-2) were contained as additives, and the kinds and contents of the resin ⁇ , the resin ⁇ , the solvent ⁇ , the compound ⁇ , the charge-transporting substances, and the ( ⁇ ) were changed as shown in Table 6.
  • AD-1 0.8 part of a compound represented by the following formula (AD-1) and 0.2 part of a compound represented by the following formula (AD-2) were contained as additives, and the kinds and contents of the resin ⁇ , the resin ⁇ , the solvent ⁇ , the compound ⁇ , the charge-transporting substances, and the ( ⁇ ) were changed as shown in Table 6.
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that in Example 1, the kinds and contents of the resin ⁇ , the resin ⁇ , the solvent ⁇ , the compound ⁇ , the charge-transporting substances, and the ( ⁇ ) were changed as shown in Table 6.
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that in Example 1, the compound ⁇ was not contained, or was changed to diisobutyl ketone or n-pentyl acetate, and the kinds and contents of the resin ⁇ , the solvent ⁇ , and the ( ⁇ ) were changed as shown in Table 7. It should be noted that diisobutyl ketone and n-pentyl acetate are comparative compounds of the compound ⁇ .
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that in Example 1, the kinds and contents of the resin ⁇ , the resin ⁇ , the solvent ⁇ , the compound ⁇ , the charge-transporting substances, and the ( ⁇ ) were changed as shown in Table 7.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 80 except that in Example 80, the compound ⁇ was not contained as shown in Table 7.
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that the following change was performed: in Example 1, as shown in Table 7, the resin ⁇ was changed to a dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-96-100cs), and the compound ⁇ was not contained in Comparative Example 26, or the solvent ⁇ was changed to chlorobenzene (monochlorobenzene) and the compound 5 was not contained in Comparative Example 27.
  • Example 1 As shown in Table 7, the resin ⁇ was changed to a dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-96-100cs), and the compound ⁇ was not contained in Comparative Example 26, or the solvent ⁇ was changed to chlorobenzene (monochlorobenzene) and the compound 5 was not contained in Comparative Example 27.
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that in Example 1, the kinds and contents of the resin ⁇ , the resin ⁇ , the solvent ⁇ , the compound ⁇ , the charge-transporting substances, and the ( ⁇ ) were changed as shown in Tables 8 to 10.
  • Electrophotographic photosensitive members were each produced in the same manner as in Examples 80 and 81 except that in Examples 80 and 81, the kinds and contents of the resin ⁇ and the resin ⁇ were changed as shown in Table 10.
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that in Example 1, the kinds and contents of the resin ⁇ , the resin ⁇ , the solvent ⁇ , the compound ⁇ , the charge-transporting substances, and the ( ⁇ ) were changed as shown in Table 10.
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 86 except that in Example 86, the compound ⁇ was not contained, or was changed to diisobutyl ketone or n-pentyl acetate as shown in Table 11. It should be noted that diisobutyl ketone and n-pentyl acetate are comparative compounds of the compound ⁇ .
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 86 except that in Example 86, the kinds and contents of the resin ⁇ , the solvent ⁇ , the compound ⁇ , the charge-transporting substances, and the ( ⁇ ) were changed as shown in Table 11.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 158 except that in Example 158, the compound 5 was not contained as shown in Table 11.
  • Electrophotographic photosensitive members were each produced in the same manner as in Example 1 except that in Example 1, the resin ⁇ was not contained, and the kinds and contents of the resin ⁇ and the compound ⁇ were changed as shown in Table 11.
  • Table 8 ⁇ ⁇ CTM ⁇ ⁇ ⁇ Example Resin kind Part(s) by mass Resin kind Part(s) by mass Structure Part(s) by mass Kind Part(s) by mass Kind Part(s) by mass Kind Part(s) by mass 86
  • Resin A(1) 10 F-B 0.18 CTM-1/CTM-2 5.6/2.4 o-Xylene 30 Propylene carbonate 2.5 Dimethoxymethane 20
  • Propylene carbonate 2.5 Dimethoxymethane 20 Resin A(1) 10 F-B 0.18 CTM-1 /CTM-2 5.6/2.4 Toluene 30 Propylene carbonate 2.5 Dimethoxymethane 20 89 Resin A(1) 10 F-B 0.18
  • Dimethoxymethane 40 49 Resin B(3) 10 F-B 0.18 CTM-1/CTM-2 5.6/2.4 o-Xylene 60 - - Dimethoxymethane 40 50 Resin B(3)/Resin A(6) 7/3 F-B 0.18 CTM-1/CTM-2 5.6/2.4 o-Xylene 60 - - Dimethoxymethane 40 51 Resin A(1) 10 - - CTM-l/CTM-2 5.6/2.4 o-Xylene 30 - - Dimethoxymethane 20 52 Resin A(1) 10 - - CTM-1/CTM-2 5.6/2.4 o-Xylene 30 Propylene carbonate 2.5 Dimethoxymethane 20 53 Resin A(1)/Resin A(7) 9/1 - - CTM-1/CTM-2 5.6/2.4 o-Xylene 30 - - Dimethoxymethane 20 54 Resin A(1)/Resin A(7) 9/1 - - CTM-1/CTM-2 5.6/
  • the coefficients of kinetic friction were measured under a normal-temperature and normal-humidity environment (23°C/50%RH) with HEIDON-14 manufactured by Shinto Scientific Co., Ltd.
  • a blade urethane rubber blade
  • Frictional force acting between the electrophotographic photosensitive member and the urethane rubber blade when the electrophotographic photosensitive member was moved in a parallel manner at a process speed of 50 mm/min was measured.
  • the frictional force was measured as the strain amount of a strain gauge attached to the urethane rubber blade side and was converted into a tensile load (force applied to the photosensitive member).
  • the coefficient of kinetic friction is determined by dividing the "force (frictional force) (gf) applied to the photosensitive member" when the urethane rubber blade is moving by the "load (gf) applied to the blade.”
  • a urethane blade (having a rubber hardness of 67°) manufactured by Hokushin Kogyo Co., Ltd. cut into a piece measuring 5 mm by 30 mm by 2 mm was used as the urethane rubber blade, and the coefficient of friction was measured in a width direction at a load of 50 g/cm 2 and an angle of 27°.
  • the abundance ratio of a silicon element in the surface of each of the electrophotographic photosensitive members was measured by employing electron spectroscopy for chemical analysis (ESCA). Electron spectroscopy for chemical analysis reveals an element distribution on the extreme surface of a substance. Quantum 2000 Scanning ESCA Microprobe manufactured by ULVAC-PHI, Inc. was used in the measurement.
  • Tables 12 and 13 show the resultant coefficients of kinetic friction and abundance ratios of the silicon element. It should be noted that in Examples 1 to 85 in each of which a polycarbonate resin or a polyester resin was used as the resin ⁇ , the coefficients of kinetic friction of Examples 1 to 85 were determined as relative values when the coefficient of kinetic friction of Comparative Example 6 in which the resin ⁇ was a polycarbonate resin or a polyester resin was defined as 1. Relative values for coefficients of kinetic friction were similarly determined for Comparative Examples 1 to 28.
  • Comparative Examples 1 to 3 shows that when the compound ⁇ is not contained, the ratios of the silicon element in the surfaces are low and the coefficients of kinetic friction are high as compared with Examples. The same effect as the foregoing is exerted even when the kinds of the resin ⁇ , the resin ⁇ , the solvent ⁇ , and the like are changed.
  • Comparative Examples 4 and 5 show that even when the compound ⁇ having a structure represented by the formula (1) is not contained and a solvent (diisobutyl ketone or n-pentyl acetate) having a boiling point higher than that of xylene or toluene is contained, the ratios of the silicon element in the surfaces cannot be increased and the coefficients of kinetic friction are not reduced. The same effect as the foregoing is exerted even when the kinds of the resin ⁇ , the resin ⁇ , the solvent y, and the like are changed.
  • a solvent diisobutyl ketone or n-pentyl acetate
  • Comparative Examples 51 to 56 when the resin ⁇ is not contained, the coefficient of kinetic friction is extremely high irrespective of whether a resin having a siloxane moiety is contained or not as the resin ⁇ , and the reduction of the coefficient of friction by the addition of the compound ⁇ is not observed.
  • Comparative Examples 26 to 28 each show that when the dimethyl silicone oil is used instead of the resin ⁇ , an effect due to the containing the compound ⁇ is not observed and the coefficient of kinetic friction is not reduced. Further, there was no difference in coefficient of kinetic friction between the case where monochlorobenzene was used and the case where xylene was used, and a change in initial coefficient of friction by the use of xylene was substantially absent in the dimethyl silicone oil. While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments.

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Claims (11)

  1. Procédé de production d'un élément photosensible électrophotographique comprenant une couche de surface,
    le procédé comprenant les étapes suivantes de :
    formation d'une couche de solution de revêtement de couche de surface ; et
    séchage de la couche pour former la couche de surface, la solution de revêtement de couche de surface comprenant :
    (α) au moins une résine choisie dans le groupe consistant en une résine de polycarbonate ne comprenant pas de groupement siloxane à une de ses extrémités, et une résine polyester ne comprenant pas de groupement siloxane à une de ses extrémités ;
    (β) au moins une résine choisie dans le groupe consistant en une résine de polycarbonate ayant un groupement siloxane à une de ses extrémités, une résine polyester ayant un groupement siloxane à une de ses extrémités et une résine de polyacrylate ayant un groupement siloxane à une de ses extrémités ;
    (γ) au moins un solvant choisi dans le groupe consistant en le toluène et le xylène ; et
    (δ) un composé dont le point d'ébullition dans une atmosphère est supérieur à celui du solvant de (γ), et est représenté par la formule (1) suivante :
    Figure imgb0092
     où, dans la formule (1),
    R représente un groupe alkylène ayant 1 à 5 atomes de carbone, et n est égal à 0 ou 1,
    la résine de polycarbonate ayant un groupement siloxane à une de ses extrémités étant une résine de polycarbonate D comportant un motif structural représenté par la formule (A') suivante et une structure terminale représentée par la formule (D) suivante :
    Figure imgb0093
     dans la formule (A'), R25 à R28 représentent chacun indépendamment un atome d'hydrogène ou un groupe méthyle et X3 représente une liaison simple, un groupe cyclohexylidène ou un groupe divalent ayant une structure représentée par la formule (C') suivante :
    Figure imgb0094
     dans la formule (C'), R43 et R44 représentent chacun indépendamment un atome d'hydrogène, un groupe méthyle ou un groupe phényle :
    Figure imgb0095
     dans la formule (D), "a" et "b" représentent chacun indépendamment un nombre de répétitions d'une structure entre les parenthèses respectives, et une valeur moyenne de "a" pour la résine de polycarbonate D va de 20 ou plus à 100 ou moins, et une valeur moyenne de "b" pour cette résine va de 1 ou plus à 10 ou moins, et
    la résine polyester ayant un groupement siloxane à une de ses extrémités étant une résine polyester E comportant un motif structural représenté par la formule (B') suivante et une structure terminale représentée par la formule (D) suivante :
    Figure imgb0096
     dans la formule (B'), R35 à R38 représentent chacun indépendamment un atome d'hydrogène ou un groupe méthyle, X4 représente une liaison simple, un groupe cyclohexylidène ou un groupe divalent ayant une structure représentée par la formule (C') suivante et Y2 représente un groupe m-phénylène, un groupe p-phénylène ou un groupe divalent dans lequel deux groupes p-phénylène sont liés avec un atome d'oxygène :
    Figure imgb0097
     dans la formule (C'), R43 et R44 représentent chacun indépendamment un atome d'hydrogène, un groupe méthyle ou un groupe phényle :
    Figure imgb0098
     dans la formule (D), "a" et "b" représentent chacun indépendamment un nombre de répétitions d'une structure entre les parenthèses respectives, et une valeur moyenne de "a" pour la résine polyester E va de 20 ou plus à 100 ou moins, et une valeur moyenne de "b" pour cette résine va de 1 ou plus à 10 ou moins.
  2. Procédé de production d'un élément photosensible électrophotographique suivant la revendication 1, dans lequel le composé de (δ) comprend au moins un composé choisi dans le groupe consistant en le carbonate de propylène, la γ-butyrolactone, la δ- valérolactone et l'ε-caprolactone.
  3. Procédé de production d'un élément photosensible électrophotographique suivant la revendication 1 ou 2, dans lequel une quantité du composé de (δ) va de 3 % en masse ou plus à 300 % en masse ou moins par rapport à une masse totale de la résine de (α) et de la résine de (β), et va de 0,5 % en masse ou plus à 150 % en masse ou moins par rapport à une quantité du solvant de (γ).
  4. Procédé de production d'un élément photosensible électrophotographique suivant l'une quelconque des revendications 1 à 3, dans lequel une quantité du composé de (δ) va de 5 % en masse ou plus à 80 % en masse ou moins, par rapport à une masse totale de la résine de (α) et de la résine de (β), et va de 0,5 % en masse ou plus à 40 % en masse ou moins par rapport à une quantité du solvant de (γ).
  5. Procédé de production d'un élément photosensible électrophotographique suivant l'une quelconque des revendications 1 à 4, dans lequel une quantité de la résine de (β) va de 0,1 % en masse ou plus à 50 % en masse ou moins, par rapport à une quantité de la résine de (α).
  6. Procédé de production d'un élément photosensible électrophotographique suivant l'une quelconque des revendications 1 à 5, dans lequel la solution de revêtement de couche de surface comprend en outre (ε) au moins du diméthoxyméthane et du tétrahydrofuranne.
  7. Procédé de production d'un élément photosensible électrophotographique suivant la revendication 6, dans lequel, par rapport à une masse totale du solvant de (γ), du composé de (δ) et de (ε), une quantité du solvant de (γ) va de 15 % en masse ou plus à 99 % en masse ou moins, une quantité du composé de (δ) va de 0,5 % en masse ou plus à 35 % en masse ou moins et une quantité de (ε) va de 0,1 % en masse ou plus à 65 % en masse ou moins.
  8. Procédé de production d'un élément photosensible électrophotographique suivant l'une quelconque des revendications 1 à 7, dans lequel la résine de polycarbonate ne comprenant pas de groupement siloxane à une de ses extrémités, comprend une résine de polycarbonate A ayant un motif structural représenté par la formule (A) suivante :
    Figure imgb0099
     dans la formule (A), R21 à R24 représentent chacun indépendamment un atome d'hydrogène ou un groupe méthyle et X1 représente une liaison simple, un groupe cyclohexylidène ou un groupe divalent ayant une structure représentée par la formule (C) suivante :
    Figure imgb0100
     dans la formule (C), R41 et R42 représentent chacun indépendamment un atome d'hydrogène, un groupe méthyle ou un groupe phényle.
  9. Procédé de production d'un élément photosensible électrophotographique suivant l'une quelconque des revendications 1 à 7, dans lequel la résine polyester ne comprenant pas de groupement siloxane à une de ses extrémités, comprend une résine polyester B ayant un motif structural représenté par la formule (B) suivante :
    Figure imgb0101
     dans la formule (B), R31 à R34 représentent chacun indépendamment un atome d'hydrogène ou un groupe méthyle, X2 représente une liaison simple, un groupe cyclohexylidène ou un groupe divalent ayant une structure représentée par la formule (C) suivante et Y1 représente un groupe m-phénylène, un groupe p-phénylène ou un groupe divalent dans lequel deux groupes p-phénylène sont liés par un atome d'oxygène :
    Figure imgb0102
     dans la formule (C), R41 et R42 représentent chacun indépendamment un atome d'hydrogène, un groupe méthyle ou un groupe phényle.
  10. Procédé de production d'un élément photosensible électrophotographique suivant l'une quelconque des revendications 1 à 7, dans lequel la résine de polyacrylate ayant un groupement siloxane à une de ses extrémités comprend l'une d'une résine de polyacrylate F ayant une structure terminale représentée par la formule (F-1) suivante et un motif structural représenté par la formule (F-2) suivante, et d'une résine de polyacrylate F ayant une structure terminale représentée par la formule (F-1) suivante et un motif structural représenté par la formule (F-3) suivante :
    Figure imgb0103
     dans la formule (F-1), R51 représente un atome d'hydrogène ou un groupe méthyle, "c" représente un nombre de répétitions d'une structure entre parenthèses, et une valeur moyenne de "c" pour la résine de polyacrylate F va de 0 ou plus à 5 ou moins, et R52 à R54 représentent chacun indépendamment une structure représentée par la formule (F-1-2) suivante, un groupe méthyle, un groupe méthoxy ou un groupe phényle ;
    Figure imgb0104
     dans la formule (F-1-2), "d" représente un nombre de répétitions d'une structure entre parenthèses, et une valeur moyenne de "d" pour la résine de polyacrylate F va de 10 ou plus à 50 ou moins, et R55 représente un groupe hydroxy ou un groupe méthyle :
    Figure imgb0105
     dans la formule (F-3), R56 représente un atome d'hydrogène, un groupe méthyle ou un groupe phényle et "e" est égal à 0 ou 1.
  11. Procédé de production d'un élément photosensible électrophotographique suivant l'une quelconque des revendications 1 à 10, dans lequel le solvant de (γ) comprend le xylène.
EP14000183.5A 2013-01-18 2014-01-17 Procédé de production d'élément photosensible électro-photographique Active EP2757419B1 (fr)

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