WO2013018450A1 - Method for producing electrophotographic photosensitive member - Google Patents

Method for producing electrophotographic photosensitive member Download PDF

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Publication number
WO2013018450A1
WO2013018450A1 PCT/JP2012/065673 JP2012065673W WO2013018450A1 WO 2013018450 A1 WO2013018450 A1 WO 2013018450A1 JP 2012065673 W JP2012065673 W JP 2012065673W WO 2013018450 A1 WO2013018450 A1 WO 2013018450A1
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WO
WIPO (PCT)
Prior art keywords
group
resin
photosensitive member
electrophotographic photosensitive
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/065673
Other languages
French (fr)
Inventor
Kazumichi SUGIYAMA
Daisuke Tanaka
Tsutomu Nishida
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Canon Inc
Original Assignee
Canon Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Canon Inc filed Critical Canon Inc
Priority to RU2014107675/05A priority Critical patent/RU2573488C2/en
Priority to KR1020147004329A priority patent/KR101521399B1/en
Priority to EP12819536.9A priority patent/EP2737369B1/en
Priority to CN201280037688.XA priority patent/CN103718114B/en
Publication of WO2013018450A1 publication Critical patent/WO2013018450A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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 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
    • G03G5/0503—Inert supplements
    • G03G5/051—Organic non-macromolecular compounds
    • G03G5/0514—Organic non-macromolecular compounds not comprising cyclic groups
    • 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
    • G03G5/0503—Inert supplements
    • G03G5/051—Organic non-macromolecular compounds
    • G03G5/0517—Organic non-macromolecular compounds comprising one or more cyclic groups consisting of carbon-atoms only
    • 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
    • G03G5/0525—Coating methods
    • 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
    • G03G5/0557—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 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
    • G03G5/0557—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 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
    • G03G5/0557—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 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
    • G03G5/0589—Macromolecular compounds characterised by specific side-chain substituents or end groups
    • 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
    • G03G5/07—Polymeric photoconductive materials
    • G03G5/078—Polymeric photoconductive materials comprising silicon atoms
    • 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
    • G03G5/14747—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 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
    • G03G5/14786—Macromolecular compounds characterised by specific side-chain substituents or end groups
    • 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

Definitions

  • the present invention relates to a method for
  • an electrophotographic photosensitive member As an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus, an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus, an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus, an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus, an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus, an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus, an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus, an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus, an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus, an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus, an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus, an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus, an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus, an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus, an electrophotographic photosensitive member
  • electrophotographic photosensitive member containing an organic photoconductive substance charge generation substance
  • a cleaning step of removing a post-transfer residual toner by using a cleaning blade is demanded to reduce a contact stress (friction coefficient) between the cleaning blade and the electrophotographic photosensitive member, in order to suppress phenomena such as squeal of the cleaning blade and rubbing of the cleaning blade.
  • a technique has been proposed in which a siloxane-modified resin having a siloxane structure in the molecular chain is allowed to be contained in the surface layer of the electrophotographic photosensitive member, the surface layer being brought into contact with a contact member (such as cleaning blade) .
  • Japanese Patent Application Laid-open No. 2009-037229 has disclosed a technique in which a resin having a siloxane structure incorporated into a polycarbonate resin is allowed to be contained in the surface layer, thereby reducing the contact stress (friction coefficient) between the electrophotographic photosensitive member and the cleaning blade.
  • photosensitive member is formed by applying a surface-layer coating solution, that is obtained by dissolving or
  • Japanese Patent Application Laid-Open No. 2001-343767 has proposed a method for producing an electrophotographic photosensitive member that is not whitened at the time of coating and that has electrophotographic characteristics equal to or more excellent than the case of using a
  • the solvent to be used for the surface-layer coating solution contains a halogenated solvent such as monochlorobenzene from the viewpoint of solubility of the resin having a siloxane structure and other materials when the electrophotographic photosensitive member containing the resin having a siloxane structure in the surface layer is produced.
  • a halogenated solvent such as monochlorobenzene from the viewpoint of solubility of the resin having a siloxane structure and other materials when the electrophotographic photosensitive member containing the resin having a siloxane structure in the surface layer is produced.
  • the halogenated solvent has been progressively substituted with a nonhalogen solvent.
  • the halogenated solvent must be separately recovered from the nonhalogenated solvent during the recovery of waste liquids to thereby easily deteriorate the productivity, there has been a demand for substituting the halogenated solvent with the nonhalogen solvent.
  • photosensitive member includes xylene and toluene.
  • An object of the present invention is to provide a method for producing an electrophotographic photosensitive member, including the step of forming a surface layer by applying a surface-layer coating solution containing a resin having a siloxane structure and at least one of toluene and xylene, the method producing an
  • electrophotographic photosensitive member that reduces the initial friction coefficient on the surface thereof.
  • the present invention relates to a method for
  • an electrophotographic photosensitive member including a surface layer
  • the method including the steps of: forming a coat for the surface layer by using a
  • the surface-layer coating solution includes:
  • R 10 represents a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group, or a benzyl group,
  • R 11 represents a methylene group, an ethylene group, or a propylene group
  • R 12 represents a methyl group, an ethyl group, an acetyl group, a propionyl group, or a benzoyl group,
  • a method for producing an electrophotographic photosensitive member including the steps of forming a coat by applying a surface-layer coating solution containing a particular binder resin having a siloxane structure and at least one of toluene and xylene; and forming the surface layer by drying the coat, the method producing an
  • electrophotographic photosensitive member that reduces the initial friction coefficient on the surface thereof, can be provided .
  • Figure 1 is a view illustrating one example of a schematic structure of an electrophotographic apparatus provided with a process cartridge including an
  • the surface-layer coating solution includes as constituent elements, the above ( a ) (constituent element ( a ) ) , the above ( ⁇ )
  • the present inventors presume that the reason why the surface-layer coating solution of the present invention contains the compound ⁇ to thereby enable reducing the initial friction coefficient on the surface of the present invention
  • electrophotographic photosensitive member is as follows.
  • electrophotographic photosensitive member having a low initial friction coefficient is obtained as follows: the resin having a siloxane structure of the resin ⁇ migrates to the surface of the electrophotographic photosensitive member (surface migration) and the siloxane structure is distributed on the surface of the electrophotographic photosensitive member.
  • Such surface migration of the resin ⁇ is performed during the step of drying the coat formed by applying the surface-layer coating solution.
  • the resin ⁇ migrates to the surface of -the photosensitive member, it is necessary that the resin a be in the state where the resin a is easily separated from the resin ⁇ during the drying step.
  • the repeating structural unit of the resin having a siloxane structure of the resin ⁇ be selected so that the repeating structural unit is easily compatible with the resin a. If dimethylsilicone oil is used in place of the resin ⁇ of the present
  • the dimethylsilicone oil is hardly compatible with the resin a and easily migrates to the surface of the electrophotographic photosensitive member.
  • compatibility of the dimethylsilicone oil with the resin a is so low that the dimethylsilicone oil is scattered on the surface of the electrophotographic photosensitive member, an electrophotographic photosensitive member having an evenly low friction coefficient on the surface is not obtained.
  • the dimethylsilicone oil is separated and becomes cloudy, and the stability of the solution is not sufficiently obtained.
  • the surface-layer coating solution includes the compound ⁇ in order to create the state where the resin a is easily separated from the resin ⁇ during the drying step while maintaining the stability of the coating solution and the uniformity of the coat.
  • the present inventors presume that the reason why the compound ⁇ having a boiling point at one atmosphere higher than that of the solvent ⁇ , the compound having the structure represented by the above formula (1), is
  • a polar group (COO bond) in the repeating structural unit contained in the resin of the resin a and the resin ⁇ is highly compatible with a polar group (RO bond) of the compound ⁇ . It is considered that the presence of the compound ⁇ allows the repeating structural unit of the resin a and ' the repeating structural unit of the resin ⁇ to be tangled with difficulty to thereby lead to the state where the resin a is easily separated from the resin ⁇ .
  • the compound ⁇ has a boiling point higher than the boiling point of xylene of the solvent ⁇ to thereby enable maintaining the state where the resin a is easily separated from the resin ⁇ until the end of the drying step. Because the compound ⁇ has a boiling point higher than the boiling point of the solvent ⁇ , the solvent ⁇ is more previously volatilized than the compound ⁇ in the drying step and thus the ratio of the compound ⁇ is higher.
  • the compound ⁇ of the present invention is a compound having a boiling point in one atmosphere higher than that of the above ( ⁇ ) , the compound being represented by the following formula (1).
  • the boiling point of xylene is 138 to 144°C.
  • R represents a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group, or a benzyl group.
  • R 11 represents a methylene group, an ethylene group, or a propylene group.
  • R 12 represents a methyl group, an ethyl group, an acetyl group, a propionyl group, or a benzoyl group.
  • E represents a single bond or a carbonyl group.
  • q is an integer of 0 to 2. If q is 0, E and R 12 are directly bound to each other.
  • The. compound having a boiling point at one atmosphere higher than that of the above ( ⁇ ) refers to as a compound having a boiling point at one atmosphere higher than that of toluene in the case where only toluene is used as the solvent ⁇ , a compound having a boiling point at one
  • the compound represented by the above formula (1) corresponding to any of the following cases is eliminated because the compound is a compound having a boiling point at one atmosphere lower than that of the above ( ⁇ ) .
  • the specific cases include the case where q is 0, E represents a single bond, R 10 represents a methyl group, and R 12
  • R 12 represents a methyl group; the case where q is 1, E represents a single bond, R 10
  • R 11 represents an ethylene group
  • R 12 represents a methyl group
  • E represents a single bond
  • R represents a methyl group
  • R 11 represents a propylene group
  • R 12 represents a methyl group
  • the specific compound of the compound ⁇ includes methyl benzoate (boiling point: 200°C) , ethyl benzoate (boiling point: 213°C) , propyl benzoate (boiling point: 229°C) , ethylcyclohexyl ether (boiling point: 150°C) , cyclohexyl acetate (boiling point: 172°C) , cyclohexyl benzoate (boiling point: 285°C) , anisole (boiling point: 154°C) , phenetole (boiling point: 172°C) , phenyl acetate
  • boiling point 175°C
  • boiling point in the parentheses denotes the boiling point at one atmosphere.
  • the compound ⁇ can be methyl benzoate, ethyl benzoate, benzyl acetate, ethyl 3-ethoxypropionate, or diethylene glycol ethyl methyl ether.
  • the content of the compound ⁇ in the surface-layer coating solution can be not less than 3% by mass and not more than 300% by mass relative to the total mass of the resin a and the resin ⁇ .
  • the content of not less than 3% by mass and not more than 300% by mass is preferable from the viewpoints of the excellent action of separating the resin a from the resin ⁇ and the effect of reducing the initial friction coefficient on the surface of the
  • the content of not less than 5% by mass and not more than 80% by mass is also preferable from the viewpoint of solution stability of the surface-layer coating solution.
  • the content of the compound ⁇ in the surface-layer coating solution can be not less than 0.5% by mass and not more than 150% by mass relative to the total mass of the solvent ⁇ .
  • the content of not less than 0.5% by mass and not more than 150% by mass is preferable from the
  • the content is preferably not less than 0.5% by mass and not more than 40% by mass, and still preferably not less than 5% by mass and not more than 40% by mass.
  • the resin a represents at least one resin of a polycarbonate resin not having a siloxane structure at the end and a polyester resin not having a siloxane structure at the end.
  • the polycarbonate resin not having a siloxane structure at the end more specifically means a polycarbonate resin not having a siloxane structure at the both ends.
  • the polyester resin not having a siloxane structure at the end more specifically means a polyester resin not having a siloxane structure at the both ends.
  • the polycarbonate resin not having a siloxane structure at the end can be a
  • polycarbonate resin A having a repeating structural unit represented by the following formula (A) .
  • the polyester resin not having a siloxane structure at the end can be a polyester resin B having a repeating structure represented by the following formula (B) .
  • R to R each independently represents a hydrogen atom or a methyl group.
  • R to R each independently represents a hydrogen atom or a methyl group.
  • Y 1 represents a m-phenylene group, a p-phenylene group, or a divalent group having two p- phenylene groups bounded with an oxygen atom.
  • R and R each independently represents a hydrogen atom, a methyl group or a phenyl group.
  • repeating structural units represented by the formulas (A-l), (A-2) and (A-4) are preferable.
  • the polycarbonate resin A can be synthesized by, for example, a conventional phosgene method, and can also be synthesized by an interesterification method.
  • repeating structural unit of the polyester resin B represented by the formula (B) are illustrated below.
  • the repeating structure represented by the formulas (B-l), (B-2), (B-3), (B-6) , (B-7) and (B-8) are preferable.
  • the polycarbonate resin A and the polyester resin B can be synthesized by any known method, and can be any known method, and can be any known method.
  • One or two or more of the polycarbonate resin A and the polyester resin B can be used alone, can be mixed, or can be used as a copolymer.
  • the copolymerization forms of the polycarbonate resin A and the polyester resin B may be any of block copolymerization, random copolymerization, alternating copolymerization and the like.
  • the weight average molecular weight of each of the polycarbonate resin A and the polyester resin B is the weight average molecular weight of each of the polycarbonate resin A and the polyester resin B.
  • the weight average molecular weight of the resin means a weight average molecular weight in terms of polystyrene measured by the method described in Japanese Patent Application Laid-Open No. 2007-79555 according to the common method.
  • the polycarbonate resin A and the polyester resin B as the resin a may be a copolymer having a repeating
  • the polycarbonate resin A and the polyester resin B may further have a repeating structural unit represented by the following formula (H-3) .
  • terephthalic acid backbone isophthalic acid backbone
  • the resin ⁇ has at least one resin selected from the group consisting of a polycarbonate resin having a siloxane structure at the end, a polyester resin having a siloxane structure at the end, and an acrylic resin having a
  • the polycarbonate resin having a siloxane structure at the end includes a
  • polycarbonate resin having a siloxane structure at the end of only one side and a polycarbonate resin having a
  • the polyester resin having a siloxane structure at the end includes a polyester resin having a siloxane structure at the end of only one side and a polyester resin having a siloxane structure at the both ends.
  • the structure at the end includes an acrylic resin having a siloxane structure at the end of only one side and an acrylic resin having a siloxane structure at the both ends.
  • the resin having a siloxane structure at the end is used to thereby have high
  • a resin having a siloxane structure at the end in the resin ⁇ includes a polycarbonate resin, a polyester resin, and an acrylic resin from the viewpoints of the
  • the polycarbonate resin having a siloxane structure at the end can be a
  • polycarbonate resin D having a repeating structural unit represented by the following formula (A 1 ) and an end structure represented by the following formula (D).
  • the polyester resin having a siloxane structure at the end can also be a polyester resin E having a repeating structural unit represented by the following formula ( ⁇ ') and an end structure represented by the following formula
  • R to R each independently represents a hydrogen atom or a methyl group.
  • R to R each independently represents a hydrogen atom or a methyl group.
  • Y 2 represents a m-phenylene group, a p-phenylene group, or a divalent group having two p- phenylene groups bounded with an oxygen atom.
  • R and R each independently represents a hydrogen atom, a methyl group or a phenyl group .
  • a and b represent the number of the repetition of the structure within the bracket.
  • the average value of a is not less than 20 and not more than 100, and the average value of b is not less than 1 and not more than 10, in the polycarbonate resin D or the polyester resin E. More preferably, the average value of a is not less than 30 and not more than 60, and the average value of b is not less than 3 and not more than 10.
  • the polycarbonate resin D and the polyester resin E have the end structure
  • the resin D and the resin E have the end structure represented by the formula (D) at one end or both ends of the resin.
  • a molecular weight regulator end terminator
  • the molecular weight regulator includes phenol, p- cumylphenol, p-tert-butylphenol and benzoic acid.
  • the molecular weight regulator can be phenol or p-tert-butylphenol.
  • the structure at the other one end is a structure represented below.
  • One or two or more of the polycarbonate resin D and the polyester resin E can be used alone, can be mixed, or can be used as a copolymer.
  • the copolymerization forms of the polycarbonate resin D and the polyester resin E may be any of block copolymerization, random copolymerization, alternating copolymerization and the like.
  • polycarbonate resin D and the polyester resin E may also have the repeating structural unit having a siloxane structure in the main chain, and may also be, for example, a copolymer having a repeating structural unit represented by the following formula (H) .
  • f and g represent the number of the repetition of the structure within the bracket.
  • the average value of f can be not less than 20 and not more than 100, and the average value of g can be not less than 1 and not more than 10, in the polycarbonate resin D or the polyester resin E.
  • Specific repeating structural units as the repeating structural unit represented by the formula (H) include the formulas (H-l) and (H-2) .
  • repeating structural unit represented by the formula ( ⁇ ') include the repeating structural units represented by the formulas (A-l) to (A-8).
  • the repeating structural unit represented by the formulas (A-l), (A-2) and (A-4) are preferable.
  • specific examples of the repeating structural unit represented by the formula ( ⁇ ') include the repeating structural units represented by the formulas (B-l) to (B-9) .
  • (B-8) are preferable.
  • the repeating structural units represented by the formulas (A-4), (B-l) and (B-3) are particularly preferable.
  • the siloxane moiety in the polycarbonate resin D and the polyester resin E refers to a moiety in a dotted flame of an end structure represented by the following formula (D-S) .
  • polycarbonate resin D and the polyester resin E have the repeating structural unit represented by the formula (H) , a structure in a dotted flame of a repeating structure represented by the following formula (H-S) is also included in the siloxane moiety.
  • the polycarbonate resin D and the polyester resin E can be synthesized by any known method, and can be synthesized by the method described in, for example, Japanese Patent Application Laid-open No.
  • polycarbonate resin D and the polyester resin E were used, thereby synthesizing the polycarbonate resin D and the polyester resin E shown in Synthesis Examples in Table 2.
  • the polycarbonate resin D and the polyester resin E were purified as follows: the resin D and the resin E were fractioned and separated from each other by using size exclusion chromatography, and then each fractioned
  • the acrylic resin having a siloxane structure at the end can be an acrylic resin F having a repeating structural unit represented by the following formula (F-l) and a repeating structural unit represented by the following formula (F-2), or a repeating structural unit represented by the following formula (F-l) and a repeating structural unit represented by the
  • R 51 represents hydrogen or a methyl group.
  • R 52 to R 54 each independently represents a structure represented by the following formula (F-l-2), a methyl group, a methoxy group or a phenyl group. At least one of R 52 to R 54 has a structure represented by the following structure (F-l-2).
  • d represents the number of the repetition of the structure within the bracket, and the average value of d is not less than 10 and not more than 50, in the acrylic resin F.
  • R 55 represents a hydroxyl group or a methyl group.
  • R represents hydrogen, a methyl group or a phenyl group.
  • e represents 0 or 1.
  • the siloxane moiety in the acrylic resin F refers to a moiety in a dotted flame of a structure represented by the following formula (F-S) or formula (F-T) .
  • acrylic resins F represented by the above Table 3 resins represented by Compound Examples (F-B) and (F-D) are preferable.
  • acrylic resins can be synthesized by any known method.
  • acrylic resins can be synthesized by the method described in, for example, Japanese Patent
  • the content of the resin ⁇ in the surface-layer coating solution can be not less than 0.1% by mass and not more than 50% by mass relative to the content of the resin a .
  • the content of not less than 0.1% by mass and not more than 50% by mass allows the effect of reducing the initial friction coefficient to be sufficiently exerted.
  • the solvent ⁇ is at least one selected from the group consisting of toluene and xylene.
  • the solvent ⁇ includes 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) .
  • the solvent ⁇ can be o-xylene.
  • electrophotographic photosensitive member of the present invention includes at least one of toluene and xylene, and may further include other solvent in order to form a
  • Such other solvent can include a chain ether or a cyclic ether having a low boiling point.
  • the chain ether having a low boiling point includes dimethoxymethane
  • the cyclic ether having a low boiling point include tetrahydrofuran (THF) .
  • THF tetrahydrofuran
  • the content of the solvent ⁇ can be not less than 15% by mass and not more than 99% by mass
  • the content of the compound ⁇ can be not less than 0.5% by mass and not more than 35% by mass
  • the content of the above ( ⁇ ) can be not less than 0.1% by mass and not more than 65% by mass, relative to the total mass of the
  • the electrophotographic photosensitive member The electrophotographic photosensitive member
  • the present invention includes a support and a photosensitive layer formed on the support.
  • photosensitive layer includes a one-layer type
  • the charge generation layer may have a laminated structure, and the charge transport layer may have a laminated
  • a protective layer may be formed on the photosensitive layer.
  • the charge transport layer when the charge transport layer is the topmost surface, the charge transport layer is the surface layer, and on the other hand, when the protective layer is provided on the charge transport layer, the protective layer is the surface layer.
  • the support means a support having conductivity
  • the support includes supports made of metals such as aluminum, stainless, copper, nickel and zinc or alloys of such metals.
  • the support is made of aluminum or an aluminum alloy, an ED pipe, an EI pipe, or a pipe obtained by subjecting these pipes to cutting, electrolytic composite polishing (electrolysis with an electrode having electrolytic action and an electrolytic solution and polishing with a grinding stone having polishing action) , and a wet-process or dry- process honing treatment can also be used.
  • the support also includes a support made of metal and a support where a conductive material such as aluminum, an aluminum alloy or an indium oxide-tin oxide alloy is formed on a resin
  • a support where conductive particles such as carbon black, tin oxide particles, titanium oxide particles or silver particles are impregnated with a resin or the like, and a plastic having a conductive binder resin can also be used .
  • surface of the conductive support may be subjected to a cutting, surface roughening or alumite treatment.
  • a conductive layer having conductive particles and a resin may be provided on the support.
  • the conductive layer is a layer obtained 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 powders of metals such as aluminum, nickel, iron, nichrome, copper, zinc and silver, and powders of metal oxides such as conductive tin oxide and ITO.
  • the binder resin to be used for the conductive layer includes a polyester resin, a polycarbonate resin,
  • polyvinylbutyral an acrylic resin, a silicone resin, an epoxy resin, a me1amine resin, a urethane resin, a phenol resin and an alkyd resin.
  • the solvent for the conductive-layer coating solution includes an ether-type solvent, an alcohol-type solvent, a ketone-type solvent and an aromatic hydrocarbon solvent.
  • the film thickness of the conductive layer is preferably not less than 0.2 ⁇ and 40 ⁇ or less, more preferably not less than 1 ⁇ and not more than 35 ⁇ , and still more preferably not less than 5 ⁇ and not more than 30 ⁇ .
  • An intermediate layer may be provided between the conductive support or the conductive layer and the
  • the intermediate layer is formed for improving the adhesion properties of the photosensitive layer, coating properties, and charge injection properties from the conductive support, and protecting the
  • the intermediate layer can be formed by applying an intermediate-layer coating solution containing a binder resin on the conductive support or the conductive layer, and drying or curing the resultant.
  • the binder resin of the intermediate layer includes 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 for the intermediate layer can be a thermoplastic resin, and can be specifically a thermoplastic polyamide resin.
  • the polyamide resin can be a low crystalline or non-crystalline copolymerized nylon so as to be applied in the state of a solution .
  • the film thickness of the intermediate layer is preferably not less than 0.05 ⁇ and not more than 40 ⁇ , and more preferably not less than 0.1 ⁇ and not more than 30 ⁇ .
  • the intermediate layer may contain semi-conductive particles or an electron transport substance, or an
  • the photosensitive layer (charge generation layer, charge transport layer) is formed on the conductive support, the conductive layer or the intermediate layer.
  • the charge generation substance to be used for the electrophotographic photosensitive member according to the present invention includes an azo pigment, a phthalocyanine pigment, an indigo pigment and a perylene pigment.
  • a phthalocyanine pigment e.g., a phthalocyanine pigment
  • an indigo pigment e.g., a perylene pigment
  • a perylene pigment e.g., a perylene pigment
  • charge generation substance to be used for the electrophotographic photosensitive member according to the present invention includes an azo pigment, a phthalocyanine pigment, an indigo pigment and a perylene pigment.
  • charge generation substances may be used. Among them, oxytitanium phthalocyanine,
  • phthalocyanine are particularly preferable because of a high sensitivity.
  • the binder resin to be used for the charge generation layer includes a polycarbonate resin, a polyester resin, a butyral resin, a polyvinylacetal resin, an acrylic resin, a vinyl acetate resin and a urea resin.
  • a butyral resin is particularly preferable.
  • One or two or more of the above resins can be used alone, can be mixed, or can be used as a copolymer.
  • the charge generation layer can be formed by applying an charge generation-layer coating solution obtained by dispersing a charge generation substance along with a binder resin and a solvent and drying the resultant.
  • the charge generation layer may be a film formed by vapor depositing the charge generation substance.
  • Examples of a dispersing method includes a method using a homogenizer, an ultrasonic wave, a ball mill, a sand mill, an attritor or a roll mill.
  • the proportion of the charge generation substance is preferably within a range of not less than 0.1 parts by mass and not more than 10 parts by mass, and more preferably not less than 1 part by mass and not more than 3 parts by mass, relative to 1 part by mass of the resin.
  • the solvent to be used for the charge generation-layer coating solution includes an alcohol-type solvent, a sulfoxide-type solvent, a ketone-type solvent, an ether- type solvent, an ester-type solvent or an aromatic
  • the film thickness of the charge generation layer is preferably not less than 0.01 ⁇ and not more than 5 ⁇ , and more preferably not less than 0.1 ⁇ and not more than 2 ⁇ .
  • the charge generation layer may contain the electron transport substance and the electron-accepting substance .
  • the charge transport layer is provided on the charge generation layer.
  • the charge transport substance to be used in the present invention includes a triarylamine compound, a hydrazone compound, a styryl compound and a stilbene compound.
  • the charge transport substance can be any of compounds represented by the following structural formulas (CTM-1) to (CTM-7) .
  • the charge transport layer can be formed by applying the charge transport-layer coating solution obtained by dissolving the charge transport substance and the binder resin in the solvent, and drying the resultant.
  • the binder resin containing the resin a and the resin ⁇ is used, and may be used while being further mixed with other resin.
  • Such other resin to be mixed that may be used is described above.
  • electrophotographic photosensitive member of the present invention is a charge transport layer
  • a charge transport- layer coating solution (surface-layer coating solution) includes the solvent ⁇ and the compound ⁇ , and may further include other solvent as described above.
  • the proportion of the charge transport substance to the binder resin is preferably not less than 0.3 parts by mass and not more than 2 parts by mass, and more
  • the film thickness of the charge transport layer is not less than 5 ⁇ and not more than 50 ⁇ , and more
  • a variety of additives may be added to the respective layers of the electrophotographic photosensitive member according to the present invention. Examples of the
  • additives include degradation inhibitors such as an
  • antioxidant an ultraviolet absorber and a light stabilizer
  • fine particles such as organic fine particles and inorganic fine particles.
  • the degradation inhibitors include hindered phenol- type antioxidants, hindered amine-type light stabilizers, sulfur atom-containing antioxidants and phosphorus atom- containing antioxidants.
  • the organic fine particles include fluorine atom- containing resin particles, and polymer resin particles such as polystyrene fine particles and polyethylene resin particles.
  • Examples of the inorganic fine particles include metal oxides such as silica and alumina.
  • any coating method such as a dip coating method, a spray coating method, a spinner coating method, a roller coating method, a Meyer bar coating method and a blade coating method can be used.
  • a dip coating method can be used.
  • the drying temperature for drying the above respective layer coating solutions to form the respective coats can be 60°C or higher and 160°C or lower. Among them, the drying temperature for drying the charge transport-layer coating solution (surface-layer coating solution) can be
  • Figure 1 illustrates one example of a schematic structure of an electrophotographic apparatus provided with a process cartridge having the electrophotographic
  • reference number 1 denotes a cylindrical electrophotographic photosensitive member, which is
  • the surface of the electrophotographic photosensitive member 1 to be rotatably driven is uniformly charged to a
  • a charging device primary charging device: charging roller or the like 3 in the course of rotation. Then, the charged
  • electrophotographic photosensitive member is subjected to exposure light (image exposure light) 4 which is emitted from an exposure device (not illustrated) such as a slit exposure device or a laser beam scanning exposure device and whose intensity has been modulated according to the time-series electric digital image signal of the intended image information.
  • exposure light image exposure light
  • an exposure device not illustrated
  • an electrostatic latent image according to the intended image is sequentially formed on the surface of the electrophotographic
  • the electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1 is developed with a toner contained in a developer of a developing device 5 by reverse developing to be formed into a toner image. Then, the toner image formed and supported on the surface of the electrophotographic photosensitive member 1 is sequentially transferred to a transfer material (paper or the like) P with a transfer bias from a
  • the transfer material P is taken out from a
  • a bias voltage having a polarity opposite to the polarity of the charge possessed by the toner is applied to the transferring device 6 from a bias supply (not illustrated) .
  • the transfer material P to which the toner image is transferred is separated from the surface of the transfer material
  • electrophotographic photosensitive member 1 and conveyed to a fixing device 8, and is subjected to a treatment of fixing the toner image and conveyed outside the apparatus as an image-formed material (printed or copied material) .
  • the surface of the electrophotographic photosensitive member 1, on which the toner image is transferred, is cleaned by a cleaning device (cleaning blade or the like) 7 so that a transfer residual developer (post-transfer
  • the charging device 3 is a contact charging device using a charging roller or the like as illustrated in
  • cleaning device 7 and the like may be accommodated in a container to be integrally supported as a process cartridge.
  • a process cartridge may be detachably attachable to the main body of the electrophotographic apparatus such as a copier or a laser beam printer.
  • electrophotographic photosensitive member 1, the charging device 3, the developing device 5 and the cleaning device 7 are integrally supported to be formed into a cartridge, and thus set up to a process cartridge 9 detachably attachable to the main body of the electrophotographic apparatus by using a guiding device 10 such as a rail provided in the main body of the electrophotographic apparatus.
  • An aluminum cylinder of 30 mm in diameter and 260.5 mm in length was used as a support (conductive support) .
  • conductive particles 3 parts of titanium oxide (pigment for resistance modification) , 6 parts of a phenol resin (binder resin), 0.001 parts of silicone oil (leveling agent) and a mixed solvent of 4 parts of methanol and 16 parts of methoxypropanol were used to prepare a conductive- layer coating solution.
  • the conductive-layer coating solution was applied onto the support by dip coating and cured (heat cured) at 140°C for 30 minutes to thereby form a conductive layer having a film thickness of 25 urn.
  • 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 film thickness of 0.7 ⁇ .
  • the charge generation-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 generation layer having a film thickness of 0.22 ⁇ . Then, 5.6 parts of a compound represented by. the formula (CTM-1) (charge transport substance), 2.4 parts of a compound represented by the formula (CTM-2) (charge transport substance) , and 10 parts of a polycarbonate resin A(l) (resin (Al)) and 0.36 parts of a polycarbonate resin D(l) (resin (Dl)) were dissolved in a mixed solvent of 30 parts of o-xylene, 20 parts of dimethoxymethane and 2.5 parts of methyl benzoate, to thereby prepare a charge transport-layer coating solution.
  • CTM-1 charge transport substance
  • CTM-2 charge transport substance
  • CTM-2 charge transport substance
  • the charge transport-layer coating solution was applied onto the charge generation layer by dip coating to form a coat and the coat was dried at 125°C for 30 minutes to thereby form a charge transport layer having a film thickness of 15 ⁇ to produce an electrophotographic photosensitive member.
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the drying temperature in forming the charge transport layer was changed to 115°C and 135°C, respectively, in Example 1. [Examples 4 and 5]
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the film thickness of the charge transport layer was changed to 10 ⁇ and 30 ⁇ , respectively, in Example 1.
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the solvent ⁇ was changed to each solvent shown in Table 4, in Example 1.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 6 except that dimethoxymethane was changed to tetrahydrofuran (THF) in Example 6.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that dimethoxymethane was not used and the content of o-xylene was changed to 50 parts in Example 1 as shown in Table 4. [Example 13]
  • An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the content of o-xylene was changed to 20 parts and the content of dimethoxymethane was changed to 30 parts in Example 1 as shown in Table 4.
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the compound ⁇ was changed as shown in Table 4, respectively, in Example 1.
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the content of the resin (Dl) was changed as shown in Table 4, respectively, in Example 1.
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the content of methyl benzoate was changed as shown in Table 4, respectively, in Example 1.
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the content of the resin (Dl) and the content of methyl
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the types and contents of the resin a, the resin ⁇ , the solvent ⁇ , the compound ⁇ , the charge transport substance and other solvent 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 the film thickness of the charge transport layer and the drying temperature during the formation of charge transport layer were changed to 10 ⁇ and 115°C in Example 31.
  • Example 87 and 88 Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 0.8 parts of a compound represented by the following formula (AD-1) and 0.2 parts of a compound represented by the following formula (AD-2) were contained as additives, and the types and contents of the resin a, the resin ⁇ , the solvent ⁇ , the compound ⁇ and the charge transport
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the types and contents of the resin a, the resin ⁇ , the solvent ⁇ , the compound ⁇ , the charge transport substance and other solvent were changed as shown in Table 6, respectively, in Example 1.
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the compound ⁇ was not contained or was changed to monoglyme, diisobutylketone or n-pentyl acetate, and the types and contents of the resin ⁇ , the solvent ⁇ and other solvent were changed as shown in Table 7, respectively, in Example 1.
  • monoglyme, diisobutylketone and n-pentyl acetate are comparative compounds of the compound ⁇ .
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the types and contents of the resin a , the resin ⁇ , the solvent ⁇ , the compound ⁇ and the charge transport substance were changed as shown in Table 7, respectively, in Example 1.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 87 except that the compound ⁇ was not contained in Example 87 as shown in
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that, in
  • Example 1 the resin ⁇ was changed to dimethylsilicone oil (KF-96-lOOcs , produced by Shin-Etsu Chemical Co., Ltd.) as shown in Table 7, the compound ⁇ was not contained in
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the types and contents of the resin a, the resin ⁇ , the solvent ⁇ , the compound ⁇ , the charge transport substance and the other solvent were changed as shown in Tables 8-10, respectively, in Example 1.
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 88 except that the types and contents of the resin ⁇ and the charge transport substance were changed as shown in Table 10, respectively, in Example 88.
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the types and contents of the resin a, the resin ⁇ , the solvent ⁇ , the compound ⁇ , the charge transport substance and other solvent were changed as shown in Table 10, respectively, in Example 1.
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 89 except that the compound ⁇ was not contained or was changed to
  • monoglyme, diisobutylketone or n-pentyl acetate as shown in Table 11, respectively, in Example 89.
  • monoglyme, diisobutylketone and n-pentyl acetate are Comparative Compounds of the compound ⁇ .
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the types and contents of the resin a, the resin ⁇ , the solvent ⁇ , the compound ⁇ and the charge transport substance were changed as shown in Table 11, respectively, in Example 89.
  • the types and contents of the resin a, the resin ⁇ , the solvent ⁇ , the compound ⁇ and the charge transport substance were changed as shown in Table 11, respectively, in Example 89.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 169 except that the compound ⁇ was not contained in Example 169 as shown in Table 11.
  • Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the compound ⁇ was not contained and the types and contents of the resin a and the resin ⁇ were changed as shown in Table 11, respectively, in Example 1.
  • the measurement of the coefficient of kinetic friction was performed by using HEIDON-14 manufactured by SHINTO Scientific Co., Ltd. under a normal temperature and normal humidity environment (23°C/50% RH) .
  • a blade (urethane rubber blade) to which a constant load was applied (50 g/cm 2 ) was placed in contact with the electrophotographic photosensitive member.
  • a frictional force exerted between the electrophotographic photosensitive member and the urethane rubber blade was measured when the
  • electrophotographic photosensitive member was parallel translated at a process speed of 50 mm/min.
  • the frictional force was measured as the amount of strain of a strain gauge attached at the side of the urethane rubber blade and converted into a tensile load (force to be applied to the photosensitive member) .
  • the urethane rubber blade used was a urethane blade (rubber hardness: 67°) manufactured by Hokushin
  • the abundance of silicon elements in the surface of the electrophotographic photosensitive member was measured by using X-ray photoelectron spectroscopy (ESCA) .
  • ESCA X-ray photoelectron spectroscopy
  • the element distribution in the topmost surface of the substance was determined.
  • the obtained coefficient of kinetic friction and the abundance of silicon elements are shown in Tables 12 to 13.
  • the coefficient of kinetic friction in each Examples 1 to 88, in which the polycarbonate resin or the polyester resin was used as the resin ⁇ was determined as the relative value when the coefficient of kinetic friction in
  • Example 54 in which the resin ⁇ was the acrylic resin, was assumed to be 1. Similarly, the coefficient of kinetic friction in each of Comparative Examples 32 to 62 was also determined as the relative value. Table 12
  • Table 12 shows the "coefficient of kinetic friction" in each of Examples and Comparative Examples as the
  • the numerical value in the parentheses is a value obtained by measuring the coefficient of kinetic friction.
  • Comparative Examples 4 to 6 reveals that the proportion of silicon elements in the surface cannot be made higher and the coefficient of kinetic friction is not lowered even in the case of not having the structure represented by the formula (1) but containing a solvent having the higher boiling point than xylene or toluene (diisobutylketone, n- pentyl acetate) .
  • the comparison also reveals that the proportion of silicon elements in the surface cannot be made higher and the coefficient of kinetic friction is not lowered even in the case of a solvent having the structure represented by the formula (1) as long as the solvent is a solvent having the lower boiling point than xylene or toluene (monoglyme) .
  • Such an effect is exerted even if the types of the resin a, the resin ⁇ , the solvent ⁇ and the like are changed.

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Abstract

The present invention provides a method for producing an electrophotographic photosensitive member, wherein a surface-layer coating solution includes (α) a polycarbonate or polyester resin not having a siloxane moiety at the end, (β) a polycarbonate or polyester or acrylate resin having a siloxane moiety at the end,(γ) toluene or xylene as a solvent, and (δ) a compound, for example, a methyl benzoate, an ethyl benzoate, a benzyl acetate, ethyl 3-ethoxypropionate or a diethylene glycol ethyl methyl ether.

Description

DESCRIPTION
Title of Invention
METHOD FOR PRODUCING ELECTROPHOTOGRAPHIC PHOTOSENSITIVE
MEMBER
Technical Field
The present invention relates to a method for
producing an electrophotographic photosensitive member.
Background Art
As an electrophotographic photosensitive member to be mounted on an electrophotographic apparatus, an
electrophotographic photosensitive member containing an organic photoconductive substance (charge generation substance) is commonly used. In an electrophotographic process, a cleaning step of removing a post-transfer residual toner by using a cleaning blade is demanded to reduce a contact stress (friction coefficient) between the cleaning blade and the electrophotographic photosensitive member, in order to suppress phenomena such as squeal of the cleaning blade and rubbing of the cleaning blade.
In order to reduce the contact stress of the
electrophotographic photosensitive member, a technique has been proposed in which a siloxane-modified resin having a siloxane structure in the molecular chain is allowed to be contained in the surface layer of the electrophotographic photosensitive member, the surface layer being brought into contact with a contact member (such as cleaning blade) . Japanese Patent Application Laid-open No. 2009-037229 has disclosed a technique in which a resin having a siloxane structure incorporated into a polycarbonate resin is allowed to be contained in the surface layer, thereby reducing the contact stress (friction coefficient) between the electrophotographic photosensitive member and the cleaning blade.
The surface layer of the electrophotographic
photosensitive member is formed by applying a surface-layer coating solution, that is obtained by dissolving or
dispersing a binder resin or the like in a solvent, onto a support or the like to form a coat, and drying this coat. The solvent is selected with taking into consideration the solubility of the binder resin or the like, the absence of impact on electrophotographic characteristics, and the absence of whitening, drips and the like of the coat at the time of coating. Thus, various studies have been performed for the solvent to be used as the solvent of the coating solution from the viewpoint of simultaneously satisfying electrophotographic characteristics and coating properties. Japanese Patent Application Laid-Open No. 2001-343767 has proposed a method for producing an electrophotographic photosensitive member that is not whitened at the time of coating and that has electrophotographic characteristics equal to or more excellent than the case of using a
halogenated solvent by using an aromatic hydrocarbon and ethylene glycol dimethyl ether as a solvent of a charge transport-layer coating solution. Japanese Patent
Application Laid-Open No. H06-123987 has proposed that in order to suppress defects of the coat, the drying
temperature at the time of producing an electrophotographic photosensitive member and the boiling point of a solvent to be used for a photosensitive-layer coating solution be adj usted .
Citation List
Patent Literature
PTL 1: Japanese Patent Application No. 2009 -37229
PTL 2: Japanese Patent Application No. 2001 -343767
PTL 3: Japanese Patent Application No. H06- 123987
PTL 4: Japanese Patent Application No. 2007 -47655
PTL 5: Japanese Patent Application No. 2007 -72277
PTL 6: Japanese Patent Application No. 2007 -79555
PTL 7: Japanese Patent Application No. 2007 -199688
PTL 8: Japanese Patent Application No. S58- 167606
PTL 9: Japanese Patent Application No. S62- 75462
Summary of Invention
Technical Problem
As disclosed in Japanese Patent Application Laid-Open No. 2009-037229 and the like, the solvent to be used for the surface-layer coating solution contains a halogenated solvent such as monochlorobenzene from the viewpoint of solubility of the resin having a siloxane structure and other materials when the electrophotographic photosensitive member containing the resin having a siloxane structure in the surface layer is produced. However, the relationship between chemical substances and the environment has been recently focused, and the management of the chemical substances and the regulation of the amounts of the
chemical substances discharged are tightened. As part of such circumstances, the halogenated solvent has been progressively substituted with a nonhalogen solvent. In addition, since the halogenated solvent must be separately recovered from the nonhalogenated solvent during the recovery of waste liquids to thereby easily deteriorate the productivity, there has been a demand for substituting the halogenated solvent with the nonhalogen solvent. The nonhalogenated solvent suitable for using for the surface- layer coating solution of the electrophotographic
photosensitive member includes xylene and toluene.
However,, if toluene or xylene is used for the solvent of the surface-layer coating solution containing the resin having a siloxane structure in order to reduce the contact stress of the surface layer, the effect of reducing the initial friction coefficient cannot be sufficiently
achieved as compared with the case where monochlorobenzene is used. Therefore, there is a need for reducing the initial friction coefficient.
Solution to Problem
An object of the present invention is to provide a method for producing an electrophotographic photosensitive member, including the step of forming a surface layer by applying a surface-layer coating solution containing a resin having a siloxane structure and at least one of toluene and xylene, the method producing an
electrophotographic photosensitive member that reduces the initial friction coefficient on the surface thereof.
The above objects are achieved according to the following present invention.
The present invention relates to a method for
producing an electrophotographic photosensitive member including a surface layer, the method including the steps of: forming a coat for the surface layer by using a
surface-layer coating solution and forming the surface layer by drying the coat, wherein the surface-layer coating solution includes:
( a ) at least one resin selected from the group
consisting of a polycarbonate resin not having a siloxane moiety at the end, and a polyester resin not having a siloxane moiety at the end,
( β ) at least one resin selected from the group
consisting of a polycarbonate resin having a siloxane moiety at the end, a polyester resin having a siloxane moiety at the end, and an acrylic resin having a siloxane moiety at the end,
(γ) at least one solvent selected from the group consisting of toluene and xylene, and
(δ) a compound having the boiling point in one atmosphere higher than that of the (γ) , the compound being represented by the following formula (1), and
Figure imgf000008_0001
in the formula (1),
R10 represents a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group, or a benzyl group,
R11 represents a methylene group, an ethylene group, or a propylene group,
R12 represents a methyl group, an ethyl group, an acetyl group, a propionyl group, or a benzoyl group,
E represents a single bond or a carbonyl group, q represents an integer number selected from 0■ to 2. Advantageous Effects of Invention
According to the present invention, a method for producing an electrophotographic photosensitive member including the steps of forming a coat by applying a surface-layer coating solution containing a particular binder resin having a siloxane structure and at least one of toluene and xylene; and forming the surface layer by drying the coat, the method producing an
electrophotographic photosensitive member that reduces the initial friction coefficient on the surface thereof, can be provided .
Further features of the present invention will become apparent from the following description of exemplary embodiments with reference to the attached drawings.
Brief Description of Drawing
Figure 1 is a view illustrating one example of a schematic structure of an electrophotographic apparatus provided with a process cartridge including an
electrophotographic photosensitive member according to the present invention.
Description of Embodiments
Preferred embodiments of the present invention will now be described in detail in accordance with the
accompanying drawings .
The production method of the present invention
includes the steps of forming a coat for the surface layer by using a surface-layer coating solution and forming the surface layer by drying the coat, wherein the surface-layer coating solution includes as constituent elements, the above ( a ) (constituent element ( a ) ) , the above ( β )
(constituent element ( β ) ) and the above (γ) (constituent element (γ) ) , and also the above ( δ ) (constituent element ( δ ) ) . Hereinafter, the above ( a ) is also referred to as
"resin a" , the above ( β ) is also referred to as "resin ,β " , the above (γ) is also referred to as "solvent γ", and the above ( δ ) is also referred to as "compound δ " .
The present inventors presume that the reason why the surface-layer coating solution of the present invention contains the compound δ to thereby enable reducing the initial friction coefficient on the surface of the
electrophotographic photosensitive member is as follows.
In the present invention, the surface of an
electrophotographic photosensitive member having a low initial friction coefficient is obtained as follows: the resin having a siloxane structure of the resin β migrates to the surface of the electrophotographic photosensitive member (surface migration) and the siloxane structure is distributed on the surface of the electrophotographic photosensitive member. Such surface migration of the resin β is performed during the step of drying the coat formed by applying the surface-layer coating solution. In order that the resin β migrates to the surface of -the photosensitive member, it is necessary that the resin a be in the state where the resin a is easily separated from the resin β during the drying step.
However, it is necessary that the resin a be
compatible with the resin β to a certain extent from the viewpoints of stability of the coating solution (surface- layer coating solution) and uniformity of the coat.
Therefore, it is necessary that the repeating structural unit of the resin having a siloxane structure of the resin β be selected so that the repeating structural unit is easily compatible with the resin a. If dimethylsilicone oil is used in place of the resin β of the present
invention, the dimethylsilicone oil is hardly compatible with the resin a and easily migrates to the surface of the electrophotographic photosensitive member. However, since compatibility of the dimethylsilicone oil with the resin a is so low that the dimethylsilicone oil is scattered on the surface of the electrophotographic photosensitive member, an electrophotographic photosensitive member having an evenly low friction coefficient on the surface is not obtained. Also in the state of the coating solution, the dimethylsilicone oil is separated and becomes cloudy, and the stability of the solution is not sufficiently obtained.
On the other hand, if xylene or toluene is used as the solvent of the surface-layer coating solution, the resin a is easily compatible with the resin β and the resin a is hardly separated from the resin β in the drying step, and thus the resin β hardly migrates to the surface and a sufficient initial friction coefficient is not obtained. Therefore, in the present invention, the surface-layer coating solution includes the compound δ in order to create the state where the resin a is easily separated from the resin β during the drying step while maintaining the stability of the coating solution and the uniformity of the coat. The present inventors presume that the reason why the compound δ having a boiling point at one atmosphere higher than that of the solvent γ, the compound having the structure represented by the above formula (1), is
contained so that the resin a is easily separated from the resin β is as follows. A polar group (COO bond) in the repeating structural unit contained in the resin of the resin a and the resin β is highly compatible with a polar group (RO bond) of the compound δ . It is considered that the presence of the compound δ allows the repeating structural unit of the resin a and ' the repeating structural unit of the resin β to be tangled with difficulty to thereby lead to the state where the resin a is easily separated from the resin β . In addition, the compound δ has a boiling point higher than the boiling point of xylene of the solvent γ to thereby enable maintaining the state where the resin a is easily separated from the resin β until the end of the drying step. Because the compound δ has a boiling point higher than the boiling point of the solvent γ, the solvent γ is more previously volatilized than the compound δ in the drying step and thus the ratio of the compound δ is higher.
Therefore, it is considered that while the content of the compound δ is lower than the content of the solvent γ in the surface-layer coating solution and thus the coating solution is stable, the content of the compound δ is higher in the coat in the course of drying to thereby lead to the state where the resin a is easily separated from the resin β .
Actually,, with respect to the surface-layer coating solution including the resin a and the resin β , when the case where only the solvent γ is used as the solvent is compared with the case where the compound δ is further added besides the solvent γ, whitening possibly derived from the state where the resin a is separated from the resin β is observed in the surface-layer coating solution in the latter case.
<Regarding Compound δ>
The compound δ of the present invention is a compound having a boiling point in one atmosphere higher than that of the above (γ) , the compound being represented by the following formula (1). The boiling point of xylene is 138 to 144°C.
Figure imgf000013_0001
In the formula (1), R represents a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group, or a benzyl group. R11 represents a methylene group, an ethylene group, or a propylene group. R12 represents a methyl group, an ethyl group, an acetyl group, a propionyl group, or a benzoyl group. E represents a single bond or a carbonyl group. q is an integer of 0 to 2. If q is 0, E and R12 are directly bound to each other.
The. compound having a boiling point at one atmosphere higher than that of the above (γ) refers to as a compound having a boiling point at one atmosphere higher than that of toluene in the case where only toluene is used as the solvent γ, a compound having a boiling point at one
atmosphere higher than that of xylene in the case where xylene and toluene are used as the solvent γ, or a compound having a boiling point at one atmosphere higher than that of xylene in the case where only xylene is used as the solvent γ.
The compound represented by the above formula (1) corresponding to any of the following cases is eliminated because the compound is a compound having a boiling point at one atmosphere lower than that of the above (γ) . The specific cases include the case where q is 0, E represents a single bond, R10 represents a methyl group, and R12
represents a methyl group; the case where q is 0, E
represents a single bond, R10 represents a methyl group, and R12 represents an ethyl group; the case where q is 0, E represents a single bond, R10 represents a methyl group, and R12 represents an acetyl group; the case where q is 0, E represents a single bond, R10 represents an ethyl group, and R12 represents a methyl group; the case where q is 0, E represents a single bond, R10 represents an ethyl group, and R12 represents an ethyl group; the case where q is 0, E represents a single bond, R10 represents an ethyl group, and R12 represents an acetyl group; the case where q is 0, R represents a cyclohexyl group, and R represents a methyl group; the case where q is 1, E represents a single bond, R10 represents a methyl group, R11 represents a
methylene group, and R12 represents a methyl group; the case where q is 1, E represents a single bond, R10
represents a methyl group, R11 represents an ethylene group, and R12 represents a methyl group; and the case where q is 1, E represents a single bond, R represents a methyl group, R11 represents a propylene group, and R12 represents a methyl group.
The specific compound of the compound δ includes methyl benzoate (boiling point: 200°C) , ethyl benzoate (boiling point: 213°C) , propyl benzoate (boiling point: 229°C) , ethylcyclohexyl ether (boiling point: 150°C) , cyclohexyl acetate (boiling point: 172°C) , cyclohexyl benzoate (boiling point: 285°C) , anisole (boiling point: 154°C) , phenetole (boiling point: 172°C) , phenyl acetate
(boiling point: 195°C) , benzylmethyl ether (boiling point: 174°C), benzylethyl ether (boiling point: 189°C) , benzyl acetate (boiling point: 212°C) , benzyl benzoate (boiling point: 324°C) , ethyl 3-ethoxypropionate (boiling point: 166°C) , diethylene glycol ethyl methyl ether (boiling point: 176°C) , diethylene glycol dimethyl ether (boiling point: 162°C) , diethylene glycol diethyl ether (boiling point: 189°C), and dipropylene glycol dimethyl ether
(boiling point: 175°C) . Herein, the boiling point in the parentheses denotes the boiling point at one atmosphere.
Among them, the compound δ can be methyl benzoate, ethyl benzoate, benzyl acetate, ethyl 3-ethoxypropionate, or diethylene glycol ethyl methyl ether.
The content of the compound δ in the surface-layer coating solution can be not less than 3% by mass and not more than 300% by mass relative to the total mass of the resin a and the resin β. The content of not less than 3% by mass and not more than 300% by mass is preferable from the viewpoints of the excellent action of separating the resin a from the resin β and the effect of reducing the initial friction coefficient on the surface of the
photosensitive member. The content of not less than 5% by mass and not more than 80% by mass is also preferable from the viewpoint of solution stability of the surface-layer coating solution.
The content of the compound δ in the surface-layer coating solution can be not less than 0.5% by mass and not more than 150% by mass relative to the total mass of the solvent γ. The content of not less than 0.5% by mass and not more than 150% by mass is preferable from the
viewpoints of the effect of reducing the initial friction coefficient on the surface of the photosensitive member and the effect of stability of the coating solution. In addition, from the viewpoint of solution stability of the surface-layer coating solution, the content is preferably not less than 0.5% by mass and not more than 40% by mass, and still preferably not less than 5% by mass and not more than 40% by mass.
<Regarding Resin a>
The resin a represents at least one resin of a polycarbonate resin not having a siloxane structure at the end and a polyester resin not having a siloxane structure at the end. The polycarbonate resin not having a siloxane structure at the end more specifically means a polycarbonate resin not having a siloxane structure at the both ends. The polyester resin not having a siloxane structure at the end more specifically means a polyester resin not having a siloxane structure at the both ends.
In the present invention, the polycarbonate resin not having a siloxane structure at the end can be a
polycarbonate resin A having a repeating structural unit represented by the following formula (A) . The polyester resin not having a siloxane structure at the end can be a polyester resin B having a repeating structure represented by the following formula (B) .
Figure imgf000017_0001
In the formula (A) , R to R each independently represents a hydrogen atom or a methyl group. X1
represents a single bond, a cyclohexylidene group, or a divalent group having a structure represented by the following formula (C) .
Figure imgf000017_0002
In the formula (B) , R to R each independently represents a hydrogen atom or a methyl group. X2
represents a single bond, a cyclohexylidene group, or a divalent group having a structure represented by the following formula (C) . Y1 represents a m-phenylene group, a p-phenylene group, or a divalent group having two p- phenylene groups bounded with an oxygen atom.
Figure imgf000018_0001
In the formula (C) , R and R each independently represents a hydrogen atom, a methyl group or a phenyl group.
Specific examples of the repeating structural unit the polycarbonate resin A represented by the formula (A) are illustrated below.
(A-1 )
Figure imgf000018_0002
Figure imgf000019_0001
Among them, the repeating structural units represented by the formulas (A-l), (A-2) and (A-4) are preferable.
The polycarbonate resin A can be synthesized by, for example, a conventional phosgene method, and can also be synthesized by an interesterification method.
Specific examples of the repeating structural unit of the polyester resin B represented by the formula (B) are illustrated below.
Figure imgf000019_0002

Figure imgf000020_0001
Among them, the repeating structure represented by the formulas (B-l), (B-2), (B-3), (B-6) , (B-7) and (B-8) are preferable.
The polycarbonate resin A and the polyester resin B can be synthesized by any known method, and can be
synthesized by the method described in, for example,
Japanese Patent Application Laid-Open No. 2007-047655 or Japanese Patent Application Laid-Open No. 2007-072277.
One or two or more of the polycarbonate resin A and the polyester resin B can be used alone, can be mixed, or can be used as a copolymer. The copolymerization forms of the polycarbonate resin A and the polyester resin B may be any of block copolymerization, random copolymerization, alternating copolymerization and the like.
The weight average molecular weight of each of the polycarbonate resin A and the polyester resin B is
preferably not less than 20,000 and not more than 300,000, and more preferably not less than 50,000 and not more than 200,000.
In the present invention, the weight average molecular weight of the resin means a weight average molecular weight in terms of polystyrene measured by the method described in Japanese Patent Application Laid-Open No. 2007-79555 according to the common method.
The polycarbonate resin A and the polyester resin B as the resin a may be a copolymer having a repeating
structural unit containing a siloxane structure besides the structural unit represented by the formula (A) or the formula (B) . Specific examples include repeating
structural units represented by the following formulas (H- 1) and (H-2). The polycarbonate resin A and the polyester resin B may further have a repeating structural unit represented by the following formula (H-3) .
Figure imgf000022_0001
Specific resins to be used as the resin a are shown below .
Table 1
Figure imgf000023_0001
In Table 1, with respect to the repeating structural units represented by the formulas (B-l) and (B-6) in the resin B(l) and the resin B(2), the molar ratio of a terephthalic acid structure to an isophthalic acid
structure (terephthalic acid backbone : isophthalic acid backbone) is 5/5.
<Regarding Resin β>
The resin β has at least one resin selected from the group consisting of a polycarbonate resin having a siloxane structure at the end, a polyester resin having a siloxane structure at the end, and an acrylic resin having a
siloxane structure at the end. The polycarbonate resin having a siloxane structure at the end includes a
polycarbonate resin having a siloxane structure at the end of only one side and a polycarbonate resin having a
siloxane structure at the both ends. The polyester resin having a siloxane structure at the end includes a polyester resin having a siloxane structure at the end of only one side and a polyester resin having a siloxane structure at the both ends. The acrylic resin having a siloxane
structure at the end includes an acrylic resin having a siloxane structure at the end of only one side and an acrylic resin having a siloxane structure at the both ends.
In the present invention, the resin having a siloxane structure at the end is used to thereby have high
lubricating properties on the surface of the photosensitive member and reducing the initial friction coefficient. The reason for this is considered to be due to the following that the incorporation of a dimethylpolysiloxane moiety at the end allows such a siloxane portion to have a high degree of freedom and high surface migration properties.
A resin having a siloxane structure at the end in the resin β includes a polycarbonate resin, a polyester resin, and an acrylic resin from the viewpoints of the
compatibility with the resin a, the stability of the coating solution, and coating property.
In the present invention, the polycarbonate resin having a siloxane structure at the end can be a
polycarbonate resin D having a repeating structural unit represented by the following formula (A1 ) and an end structure represented by the following formula (D). The polyester resin having a siloxane structure at the end can also be a polyester resin E having a repeating structural unit represented by the following formula (Β') and an end structure represented by the following formula
Figure imgf000025_0001
In the formula (A' ) , R to R each independently represents a hydrogen atom or a methyl group. X3
represents a single bond, a cyclohexylidene group, or a divalent group having a structure represented by the following formula (C).
Figure imgf000025_0002
In the formula (Β'), R to R each independently represents a hydrogen atom or a methyl group. X4
represents a single bond, a cyclohexylidene group, or a divalent group having a structure represented by the following formula (C)- Y2 represents a m-phenylene group, a p-phenylene group, or a divalent group having two p- phenylene groups bounded with an oxygen atom.
Figure imgf000026_0001
In the formula (C) R and R each independently represents a hydrogen atom, a methyl group or a phenyl group .
Figure imgf000026_0002
In the formula (D) , a and b represent the number of the repetition of the structure within the bracket. The average value of a is not less than 20 and not more than 100, and the average value of b is not less than 1 and not more than 10, in the polycarbonate resin D or the polyester resin E. More preferably, the average value of a is not less than 30 and not more than 60, and the average value of b is not less than 3 and not more than 10.
In the present invention, the polycarbonate resin D and the polyester resin E have the end structure
represented by the formula (D) at one end or both ends of the resin. In the case where the resin D and the resin E have the end structure represented by the formula (D) at one end, a molecular weight regulator (end terminator) is used. The molecular weight regulator includes phenol, p- cumylphenol, p-tert-butylphenol and benzoic acid. In the present invention, the molecular weight regulator can be phenol or p-tert-butylphenol. In the case where the resin D and the resin E have the end structure represented by the formula (D) at one end, the structure at the other one end (other end structure) is a structure represented below.
OH (G-1)
Figure imgf000027_0001
Specific examples of the end structure represented by the formula (D) are illustrated below.
Figure imgf000027_0002
One or two or more of the polycarbonate resin D and the polyester resin E can be used alone, can be mixed, or can be used as a copolymer. The copolymerization forms of the polycarbonate resin D and the polyester resin E may be any of block copolymerization, random copolymerization, alternating copolymerization and the like. The
polycarbonate resin D and the polyester resin E may also have the repeating structural unit having a siloxane structure in the main chain, and may also be, for example, a copolymer having a repeating structural unit represented by the following formula (H) .
Figure imgf000028_0001
In the formula (H) , f and g represent the number of the repetition of the structure within the bracket. The average value of f can be not less than 20 and not more than 100, and the average value of g can be not less than 1 and not more than 10, in the polycarbonate resin D or the polyester resin E. Specific repeating structural units as the repeating structural unit represented by the formula (H) include the formulas (H-l) and (H-2) .
In the polycarbonate resin D, specific examples of the repeating structural unit represented by the formula (Α') include the repeating structural units represented by the formulas (A-l) to (A-8). The repeating structural unit represented by the formulas (A-l), (A-2) and (A-4) are preferable. In the polyester resin E, specific examples of the repeating structural unit represented by the formula (Β') include the repeating structural units represented by the formulas (B-l) to (B-9) . The repeating structural unit represented by the formulas (B-l), (B-3), (B-6) , (B-7) and
(B-8) are preferable. Among them, the repeating structural units represented by the formulas (A-4), (B-l) and (B-3) are particularly preferable.
In the present invention, the siloxane moiety in the polycarbonate resin D and the polyester resin E refers to a moiety in a dotted flame of an end structure represented by the following formula (D-S) . In the case where the
polycarbonate resin D and the polyester resin E have the repeating structural unit represented by the formula (H) , a structure in a dotted flame of a repeating structure represented by the following formula (H-S) is also included in the siloxane moiety.
Figure imgf000029_0001
In the present invention, the polycarbonate resin D and the polyester resin E can be synthesized by any known method, and can be synthesized by the method described in, for example, Japanese Patent Application Laid-open No.
2007-199688. Also in the present invention, the same method was used and raw materials according to the
polycarbonate resin D and the polyester resin E were used, thereby synthesizing the polycarbonate resin D and the polyester resin E shown in Synthesis Examples in Table 2. Herein, the polycarbonate resin D and the polyester resin E were purified as follows: the resin D and the resin E were fractioned and separated from each other by using size exclusion chromatography, and then each fractioned
component was measured by means of XH-NMR to determine a composition of each resin by the relative ratio of the siloxane moiety in each resin. The weight average
molecular weights and the contents of the siloxane moieties in the synthesized polycarbonate resin D and the polyester resin E are shown in Table 2.
Specific examples of the polycarbonate resin D and the polyester resin E are shown below.
Table 2
Figure imgf000030_0001
In Table 2, the mass ratio of each repeating structural unit in the main chain in the resin D(3) satisfies (A-4): (H-2) = 9:1.
In the present invention, the acrylic resin having a siloxane structure at the end can be an acrylic resin F having a repeating structural unit represented by the following formula (F-l) and a repeating structural unit represented by the following formula (F-2), or a repeating structural unit represented by the following formula (F-l) and a repeating structural unit represented by the
following formula (F-3) .
Figure imgf000031_0001
R51 represents hydrogen or a methyl group. c
represents the number of the repetition of the structure within the bracket, and the average value of c is not less than 0 and not more than 5, in the acrylic resin F. R52 to R54 each independently represents a structure represented by the following formula (F-l-2), a methyl group, a methoxy group or a phenyl group. At least one of R52 to R54 has a structure represented by the following structure (F-l-2).
Figure imgf000031_0002
In the formula (F-l-2), d represents the number of the repetition of the structure within the bracket, and the average value of d is not less than 10 and not more than 50, in the acrylic resin F. R55 represents a hydroxyl group or a methyl group.
Figure imgf000032_0001
In the formula (F-3), R represents hydrogen, a methyl group or a phenyl group. e represents 0 or 1.
In the present invention, the siloxane moiety in the acrylic resin F refers to a moiety in a dotted flame of a structure represented by the following formula (F-S) or formula (F-T) .
Figure imgf000032_0002
Specific examples of the repeating structural unit in the acrylic resin F are shown in Table 3 below.
Figure imgf000033_0001
Among the acrylic resins F represented by the above Table 3, resins represented by Compound Examples (F-B) and (F-D) are preferable.
Such acrylic resins can be synthesized by any known method. Such acrylic resins can be synthesized by the method described in, for example, Japanese Patent
Application Laid-Open No. S58-167606 or Japanese Patent Application Laid-Open No. S62-75462.
The content of the resin β in the surface-layer coating solution can be not less than 0.1% by mass and not more than 50% by mass relative to the content of the resin a . The content of not less than 0.1% by mass and not more than 50% by mass allows the effect of reducing the initial friction coefficient to be sufficiently exerted.
<Regarding Solvent γ>
In the surface-layer coating solution of the present invention, the solvent γ is at least one selected from the group consisting of toluene and xylene. Specifically, the solvent γ includes 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) . The solvent γ can be o-xylene.
These solvents may be used alone or two or more thereof may be mixed for use. Herein, the boiling point in the
parentheses denotes the boiling point at one atmosphere.
The surface-layer coating solution of the
electrophotographic photosensitive member of the present invention includes at least one of toluene and xylene, and may further include other solvent in order to form a
surface layer having a uniform film thickness. Such other solvent can include a chain ether or a cyclic ether having a low boiling point. The chain ether having a low boiling point includes dimethoxymethane, and the cyclic ether having a low boiling point include tetrahydrofuran (THF) . At least one of dimethoxymethane and tetrahydrofuran
(hereinafter, also referred to as the above (ε) ) can be used. In this case, the content of the solvent γ can be not less than 15% by mass and not more than 99% by mass, the content of the compound δ can be not less than 0.5% by mass and not more than 35% by mass, and the content of the above (ε) can be not less than 0.1% by mass and not more than 65% by mass, relative to the total mass of the
solution of the solvent γ, the compound δ and the above (ε) .
Then, the configuration of the electrophotographic photosensitive member according to the present invention will be described.
The electrophotographic photosensitive member
according to the present invention includes a support and a photosensitive layer formed on the support. The
photosensitive layer includes a one-layer type
photosensitive layer containing a charge transport
substance and a charge generation substance in one layer; and a laminate type (functional separation type)
photosensitive layer in which a charge generation layer containing a charge generation substance and a charge transport layer containing a charge transport substance are separated from each other. The laminate type
photosensitive layer can be used in the present invention. The charge generation layer may have a laminated structure, and the charge transport layer may have a laminated
configuration. For the purpose of enhancing durability of the electrophotographic photosensitive member, a protective layer may be formed on the photosensitive layer.
With respect to the surface layer of the
electrophotographic photosensitive member according to the present invention, when the charge transport layer is the topmost surface, the charge transport layer is the surface layer, and on the other hand, when the protective layer is provided on the charge transport layer, the protective layer is the surface layer.
<Support>
The support means a support having conductivity
(conductive support) . Examples of the support include supports made of metals such as aluminum, stainless, copper, nickel and zinc or alloys of such metals. In the case where the support is made of aluminum or an aluminum alloy, an ED pipe, an EI pipe, or a pipe obtained by subjecting these pipes to cutting, electrolytic composite polishing (electrolysis with an electrode having electrolytic action and an electrolytic solution and polishing with a grinding stone having polishing action) , and a wet-process or dry- process honing treatment can also be used. The support also includes a support made of metal and a support where a conductive material such as aluminum, an aluminum alloy or an indium oxide-tin oxide alloy is formed on a resin
support in the form of a thin film.
A support where conductive particles such as carbon black, tin oxide particles, titanium oxide particles or silver particles are impregnated with a resin or the like, and a plastic having a conductive binder resin can also be used .
For the purpose of preventing interference fringes caused by scattering of laser light or the like, the
surface of the conductive support may be subjected to a cutting, surface roughening or alumite treatment.
In the electrophotographic photosensitive member according to the present invention, a conductive layer having conductive particles and a resin may be provided on the support. The conductive layer is a layer obtained 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, powders of metals such as aluminum, nickel, iron, nichrome, copper, zinc and silver, and powders of metal oxides such as conductive tin oxide and ITO.
The binder resin to be used for the conductive layer includes a polyester resin, a polycarbonate resin,
polyvinylbutyral , an acrylic resin, a silicone resin, an epoxy resin, a me1amine resin, a urethane resin, a phenol resin and an alkyd resin.
The solvent for the conductive-layer coating solution includes an ether-type solvent, an alcohol-type solvent, a ketone-type solvent and an aromatic hydrocarbon solvent. The film thickness of the conductive layer is preferably not less than 0.2 μπι and 40 μιη or less, more preferably not less than 1 μπι and not more than 35 μπι, and still more preferably not less than 5 μηι and not more than 30 μηι.
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 adhesion properties of the photosensitive layer, coating properties, and charge injection properties from the conductive support, and protecting the
photosensitive layer against electric fracture.
The intermediate layer can be formed by applying an intermediate-layer coating solution containing a binder resin on the conductive support or the conductive layer, and drying or curing the resultant.
The binder resin of the intermediate layer includes 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 for the intermediate layer can be a thermoplastic resin, and can be specifically a thermoplastic polyamide resin. The polyamide resin can be a low crystalline or non-crystalline copolymerized nylon so as to be applied in the state of a solution .
The solvent for the intermediate-layer coating
solution includes an ether-type solvent, an alcohol-type solvent, a ketone-type solvent and an aromatic hydrocarbon solvent. The film thickness of the intermediate layer is preferably not less than 0.05 μιη and not more than 40 μιτι, and more preferably not less than 0.1 μπι and not more than 30 μπι. The intermediate layer may contain semi-conductive particles or an electron transport substance, or an
electron-accepting substance.
<Photosensitive Layer>
The photosensitive layer (charge generation layer, charge transport layer) is formed on the conductive support, the conductive layer or the intermediate layer.
The charge generation substance to be used for the electrophotographic photosensitive member according to the present invention includes an azo pigment, a phthalocyanine pigment, an indigo pigment and a perylene pigment. One or two or more of such charge generation substances may be used. Among them, oxytitanium phthalocyanine,
hydroxygallium phthalocyanine and chlorogallium .
phthalocyanine are particularly preferable because of a high sensitivity.
The binder resin to be used for the charge generation layer includes a polycarbonate resin, a polyester resin, a butyral resin, a polyvinylacetal resin, an acrylic resin, a vinyl acetate resin and a urea resin. Among them, a butyral resin is particularly preferable. One or two or more of the above resins can be used alone, can be mixed, or can be used as a copolymer.
The charge generation layer can be formed by applying an charge generation-layer coating solution obtained by dispersing a charge generation substance along with a binder resin and a solvent and drying the resultant. The charge generation layer may be a film formed by vapor depositing the charge generation substance.
Examples of a dispersing method includes a method using a homogenizer, an ultrasonic wave, a ball mill, a sand mill, an attritor or a roll mill.
With respect to the proportion of the charge
generation substance to the binder resin, the proportion of the charge generation substance is preferably within a range of not less than 0.1 parts by mass and not more than 10 parts by mass, and more preferably not less than 1 part by mass and not more than 3 parts by mass, relative to 1 part by mass of the resin.
The solvent to be used for the charge generation-layer coating solution includes an alcohol-type solvent, a sulfoxide-type solvent, a ketone-type solvent, an ether- type solvent, an ester-type solvent or an aromatic
hydrocarbon solvent.
The film thickness of the charge generation layer is preferably not less than 0.01 μπι and not more than 5 μπ\, and more preferably not less than 0.1 μιη and not more than 2 μπι.
A variety of sensitizers, antioxidants, ultraviolet absorbers plasticizers and the like can also be added to the charge generation layer where necessary. In order not to interrupt the flow of a charge (carrier) in the charge generation layer, the charge generation layer may contain the electron transport substance and the electron-accepting substance .
In the electrophotographic photosensitive member including the laminate type photosensitive layer, the charge transport layer is provided on the charge generation layer.
The charge transport substance to be used in the present invention includes a triarylamine compound, a hydrazone compound, a styryl compound and a stilbene compound. The charge transport substance can be any of compounds represented by the following structural formulas (CTM-1) to (CTM-7) .
Figure imgf000041_0001
Figure imgf000042_0001
The charge transport layer can be formed by applying the charge transport-layer coating solution obtained by dissolving the charge transport substance and the binder resin in the solvent, and drying the resultant.
In the present invention, when the charge transport layer is the surface layer, the binder resin containing the resin a and the resin β is used, and may be used while being further mixed with other resin. Such other resin to be mixed that may be used is described above.
In the case where the surface layer of the
electrophotographic photosensitive member of the present invention is a charge transport layer, a charge transport- layer coating solution (surface-layer coating solution) includes the solvent γ and the compound δ, and may further include other solvent as described above.
With respect to the proportion of the charge transport substance to the binder resin, the proportion of the charge transport substance is preferably not less than 0.3 parts by mass and not more than 2 parts by mass, and more
preferably not less than 0.5 parts by mass and not more than 1.5 parts by mass, per part by mass of the binder resin .
The film thickness of the charge transport layer is not less than 5 μπι and not more than 50 μηι, and more
preferably not less than 10 μπι and not more than 35 μπι.
A variety of additives may be added to the respective layers of the electrophotographic photosensitive member according to the present invention. Examples of the
additives include degradation inhibitors such as an
antioxidant, an ultraviolet absorber and a light stabilizer, and fine particles such as organic fine particles and inorganic fine particles.
The degradation inhibitors include hindered phenol- type antioxidants, hindered amine-type light stabilizers, sulfur atom-containing antioxidants and phosphorus atom- containing antioxidants.
The organic fine particles include fluorine atom- containing resin particles, and polymer resin particles such as polystyrene fine particles and polyethylene resin particles. Examples of the inorganic fine particles include metal oxides such as silica and alumina.
When the above respective layer coating solutions are applied, any coating method such as a dip coating method, a spray coating method, a spinner coating method, a roller coating method, a Meyer bar coating method and a blade coating method can be used. Among the methods, a dip coating method can be used.
The drying temperature for drying the above respective layer coating solutions to form the respective coats can be 60°C or higher and 160°C or lower. Among them, the drying temperature for drying the charge transport-layer coating solution (surface-layer coating solution) can be
particularly not lower than 110°C and not higher than 140°C [Electrophotographic Apparatus]
Figure 1 illustrates one example of a schematic structure of an electrophotographic apparatus provided with a process cartridge having the electrophotographic
photosensitive member according to the present invention.
In Figure 1, reference number 1 denotes a cylindrical electrophotographic photosensitive member, which is
rotatably driven at a predetermined circumferential speed around an axis 2 in the direction shown by an arrow. The surface of the electrophotographic photosensitive member 1 to be rotatably driven is uniformly charged to a
predetermined negative potential by a charging device (primary charging device: charging roller or the like) 3 in the course of rotation. Then, the charged
electrophotographic photosensitive member is subjected to exposure light (image exposure light) 4 which is emitted from an exposure device (not illustrated) such as a slit exposure device or a laser beam scanning exposure device and whose intensity has been modulated according to the time-series electric digital image signal of the intended image information. In this way, an electrostatic latent image according to the intended image is sequentially formed on the surface of the electrophotographic
photosensitive member 1.
The electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1 is developed with a toner contained in a developer of a developing device 5 by reverse developing to be formed into a toner image. Then, the toner image formed and supported on the surface of the electrophotographic photosensitive member 1 is sequentially transferred to a transfer material (paper or the like) P with a transfer bias from a
transferring device (transfer roller or the like) 6.
Herein, the transfer material P is taken out from a
transfer material feed device (not illustrated) in
synchronous with the rotation of the electrophotographic photosensitive member 1, and fed to a portion (abutting portion) between the electrophotographic photosensitive member 1 and the transferring device 6. A bias voltage having a polarity opposite to the polarity of the charge possessed by the toner is applied to the transferring device 6 from a bias supply (not illustrated) .
The transfer material P to which the toner image is transferred is separated from the surface of the
electrophotographic photosensitive member 1 and conveyed to a fixing device 8, and is subjected to a treatment of fixing the toner image and conveyed outside the apparatus as an image-formed material (printed or copied material) .
The surface of the electrophotographic photosensitive member 1, on which the toner image is transferred, is cleaned by a cleaning device (cleaning blade or the like) 7 so that a transfer residual developer (post-transfer
residual toner) is removed. Then, the surface is subjected to a neutralization treatment with pre-exposure light (not illustrated) from a pre-exposure device (not illustrated) , and thereafter repeatedly used for image forming. Herein, when the charging device 3 is a contact charging device using a charging roller or the like as illustrated in
Figure 1, such pre-exposing is not necessarily required.
In the present invention, a plurality of constituent elements selected from the electrophotographic
photosensitive member 1, the charging device 3, the
developing device 5, the transferring device 6, the
cleaning device 7 and the like may be accommodated in a container to be integrally supported as a process cartridge. Such a process cartridge may be detachably attachable to the main body of the electrophotographic apparatus such as a copier or a laser beam printer. In Figure 1, the
electrophotographic photosensitive member 1, the charging device 3, the developing device 5 and the cleaning device 7 are integrally supported to be formed into a cartridge, and thus set up to a process cartridge 9 detachably attachable to the main body of the electrophotographic apparatus by using a guiding device 10 such as a rail provided in the main body of the electrophotographic apparatus.
[Example]
Hereinafter, the present invention will be described in more detail with reference to specific Examples. It is to be noted that the present invention is not limited to the Examples. Herein, "part(s)" in Examples is meant to be "part(s) by mass".
[Example 1]
An aluminum cylinder of 30 mm in diameter and 260.5 mm in length was used as a support (conductive support) .
Then, 12 parts of Sn02-coated barium sulfate
(conductive particles ) , 3 parts of titanium oxide (pigment for resistance modification) , 6 parts of a phenol resin (binder resin), 0.001 parts of silicone oil (leveling agent) and a mixed solvent of 4 parts of methanol and 16 parts of methoxypropanol were used to prepare a conductive- layer coating solution.
The conductive-layer coating solution was applied onto the support by dip coating and cured (heat cured) at 140°C for 30 minutes to thereby form a conductive layer having a film thickness of 25 urn.
Then, 3 parts of N-methoxymethylated nylon and 3 parts of copolymerized nylon were dissolved in a mixed solvent of 65 parts of methanol and 30 parts of n-butanol to thereby prepare an intermediate-layer coating solution.
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 film thickness of 0.7 μπι.
Then, 10 parts of hydroxygallium phthalocyanine crystal (charge generation substance) of a crystal form having strong peaks at 7.5°, 9.9°, 16.3°, 18.6°, 25.1° and 28.3° of Bragg angles 2Θ ± 0.2° in CuKa characteristic X- ray diffraction was added to a solution obtained by
dissolving 5 parts of a polyvinylbutyral resin (trade name: S-LEC BX-1, produced by Sekisui Chemical Co., Ltd., binder resin) in 250 parts of cyclohexanone . This was dispersed in the solution by means of a sand mill apparatus using glass beads of 1 mm in diameter under an atmosphere of 23 ± 3°C for 1 hour. After such dispersion, 250 parts of ethyl acetate was added thereto to thereby prepare a charge generation-layer coating solution.
The charge generation-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 generation layer having a film thickness of 0.22 μπι. Then, 5.6 parts of a compound represented by. the formula (CTM-1) (charge transport substance), 2.4 parts of a compound represented by the formula (CTM-2) (charge transport substance) , and 10 parts of a polycarbonate resin A(l) (resin (Al)) and 0.36 parts of a polycarbonate resin D(l) (resin (Dl)) were dissolved in a mixed solvent of 30 parts of o-xylene, 20 parts of dimethoxymethane and 2.5 parts of methyl benzoate, to thereby prepare a charge transport-layer coating solution.
The charge transport-layer coating solution was applied onto the charge generation layer by dip coating to form a coat and the coat was dried at 125°C for 30 minutes to thereby form a charge transport layer having a film thickness of 15 μιτι to produce an electrophotographic photosensitive member.
[Examples 2 and 3]
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the drying temperature in forming the charge transport layer was changed to 115°C and 135°C, respectively, in Example 1. [Examples 4 and 5]
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the film thickness of the charge transport layer was changed to 10 μιη and 30 μπι, respectively, in Example 1.
[Examples 6 to 10]
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the solvent γ was changed to each solvent shown in Table 4, in Example 1.
[Example 11]
An electrophotographic photosensitive member was produced in the same manner as in Example 6 except that dimethoxymethane was changed to tetrahydrofuran (THF) in Example 6.
[Example 12]
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that dimethoxymethane was not used and the content of o-xylene was changed to 50 parts in Example 1 as shown in Table 4. [Example 13]
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the content of o-xylene was changed to 20 parts and the content of dimethoxymethane was changed to 30 parts in Example 1 as shown in Table 4.
[Examples 14 to 20]
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the compound δ was changed as shown in Table 4, respectively, in Example 1.
[Examples 21 and 22]
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the content of the resin (Dl) was changed as shown in Table 4, respectively, in Example 1.
[Examples 23 and 24]
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the content of methyl benzoate was changed as shown in Table 4, respectively, in Example 1.
[Examples 25 and 26]
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the content of the resin (Dl) and the content of methyl
benzoate were changed as shown in Table 4, respectively, in Example 1.
[Examples 27 to 31 and 33 to 86]
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the types and contents of the resin a, the resin β , the solvent γ, the compound δ, the charge transport substance and other solvent were changed as shown in Tables 4 to 6, ■
respectively, in Example 1.
[Example 32]
An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the film thickness of the charge transport layer and the drying temperature during the formation of charge transport layer were changed to 10 μη and 115°C in Example 31.
[Examples 87 and 88] Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that 0.8 parts of a compound represented by the following formula (AD-1) and 0.2 parts of a compound represented by the following formula (AD-2) were contained as additives, and the types and contents of the resin a, the resin β, the solvent γ, the compound δ and the charge transport
substance were changed as shown in Table 6, respectively, in Example 1.
Figure imgf000052_0001
[Examples 200 to 203]
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the types and contents of the resin a, the resin β, the solvent γ, the compound δ, the charge transport substance and other solvent were changed as shown in Table 6, respectively, in Example 1.
[Comparative Examples 1 to 8]
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the compound δ was not contained or was changed to monoglyme, diisobutylketone or n-pentyl acetate, and the types and contents of the resin β , the solvent γ and other solvent were changed as shown in Table 7, respectively, in Example 1. Herein, monoglyme, diisobutylketone and n-pentyl acetate are comparative compounds of the compound δ .
[Comparative Examples 9 to 27]
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the types and contents of the resin a , the resin β , the solvent γ, the compound δ and the charge transport substance were changed as shown in Table 7, respectively, in Example 1.
[Comparative Example 28]
An electrophotographic photosensitive member was produced in the same manner as in Example 87 except that the compound δ was not contained in Example 87 as shown in
Table 7.
[Comparative Examples 29 to 31]
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that, in
Example 1, the resin β was changed to dimethylsilicone oil (KF-96-lOOcs , produced by Shin-Etsu Chemical Co., Ltd.) as shown in Table 7, the compound δ was not contained in
Comparative Example 29, and the solvent γ was changed to chlorobenzene (monochlorobenzene ) and the compound δ was not contained in Comparative Example 30. Table 4
Figure imgf000054_0001
Table 4 (Continued)
Figure imgf000055_0001
Table 4 (Continued)
Figure imgf000056_0001
Table 5
Figure imgf000057_0001
Table 5 (Continued)
Figure imgf000058_0001
Table 5 (Continued)
Figure imgf000059_0001
Table 6
Figure imgf000060_0001
Table 6 (Continued)
Figure imgf000061_0001
Table 7
Figure imgf000062_0001
Table 7 (Continued)
Figure imgf000063_0001
Table 7 (Continued)
Figure imgf000064_0001
[Examples 89 to 168] .
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the types and contents of the resin a, the resin β , the solvent γ, the compound δ, the charge transport substance and the other solvent were changed as shown in Tables 8-10, respectively, in Example 1.
[Examples 169 to 170]
Each electrophotographic photosensitive member was produced in the same manner as in Example 88 except that the types and contents of the resin β and the charge transport substance were changed as shown in Table 10, respectively, in Example 88.
[Examples 204 to 207]
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the types and contents of the resin a, the resin β , the solvent γ , the compound δ , the charge transport substance and other solvent were changed as shown in Table 10, respectively, in Example 1.
[Comparative Examples 32 to 35]
Each electrophotographic photosensitive member was produced in the same manner as in Example 89 except that the compound δ was not contained or was changed to
monoglyme, diisobutylketone or n-pentyl acetate. as shown in Table 11, respectively, in Example 89. Herein, monoglyme, diisobutylketone and n-pentyl acetate are Comparative Compounds of the compound δ .
[Comparative Examples 36 to 55]
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the types and contents of the resin a, the resin β , the solvent γ, the compound δ and the charge transport substance were changed as shown in Table 11, respectively, in Example 89. [Comparative Example 56]
An electrophotographic photosensitive member was produced in the same manner as in Example 169 except that the compound δ was not contained in Example 169 as shown in Table 11.
[Comparative Examples 57 to 62]
Each electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the compound δ was not contained and the types and contents of the resin a and the resin β were changed as shown in Table 11, respectively, in Example 1.
Table 8
Figure imgf000067_0001
Table 8 (Continued)
Figure imgf000068_0001
Table 8 (Continued)
Figure imgf000069_0001
Table 9
Figure imgf000070_0001
Table 9 (Continued)
Figure imgf000071_0001
Table 9 (Continued)
Figure imgf000072_0001
Table 10
Figure imgf000073_0001
Table 10 (Continued)
Figure imgf000074_0001
Table 11
Figure imgf000075_0001
Table 11 (Continued)
Figure imgf000076_0001
Table 11 (Continued)
Figure imgf000077_0001
Hereinafter, evaluations will be described. The coefficient of kinetic friction of the electrophotographic photosensitive member produced in each of Examples and Comparative Examples was measured by the method described below.
The measurement of the coefficient of kinetic friction was performed by using HEIDON-14 manufactured by SHINTO Scientific Co., Ltd. under a normal temperature and normal humidity environment (23°C/50% RH) . A blade (urethane rubber blade) to which a constant load was applied (50 g/cm2) was placed in contact with the electrophotographic photosensitive member. A frictional force exerted between the electrophotographic photosensitive member and the urethane rubber blade was measured when the
electrophotographic photosensitive member was parallel translated at a process speed of 50 mm/min. The frictional force was measured as the amount of strain of a strain gauge attached at the side of the urethane rubber blade and converted into a tensile load (force to be applied to the photosensitive member) . The coefficient of kinetic
friction was obtained from [force to be applied to
photosensitive member (frictional force) (gf)]/[load applied to blade (gf) ] when the urethane rubber blade was operated. The urethane rubber blade used was a urethane blade (rubber hardness: 67°) manufactured by Hokushin
Industry Inc., which was cut into a piece measuring 5 mm x 30 mm x 2 mm, and the friction coefficient was measured under a load of 50 g/cm2 at an angle of 27° to the with direction of the electrophotographic photosensitive member.
The abundance of silicon elements in the surface of the electrophotographic photosensitive member was measured by using X-ray photoelectron spectroscopy (ESCA) . In X-ray photoelectron spectroscopy, the element distribution in the topmost surface of the substance was determined. In the measurement, Quantum 2000 Scanning ESCA Microprobe
manufactured by PHI was used.
The obtained coefficient of kinetic friction and the abundance of silicon elements are shown in Tables 12 to 13. The coefficient of kinetic friction in each Examples 1 to 88, in which the polycarbonate resin or the polyester resin was used as the resin β , was determined as the relative value when the coefficient of kinetic friction in
Comparative Example 7, in which the resin β was the
polycarbonate resin or the polyester resin, was assumed to be 1. Similarly, the coefficient of kinetic friction in each of Comparative Examples 1 to 31 was also determined as the relative value. The coefficient of kinetic friction in each Examples 89 to 170, in which the acrylic resin was used as the resin β , was determined as the relative value when the coefficient of kinetic friction in Comparative
Example 54, in which the resin β was the acrylic resin, was assumed to be 1. Similarly, the coefficient of kinetic friction in each of Comparative Examples 32 to 62 was also determined as the relative value. Table 12
Figure imgf000080_0001
Table 12 (Continued)
Figure imgf000081_0001
Table 12 (Continued)
Figure imgf000082_0001
Table 13
Figure imgf000083_0001
Table 13 (Continued)
Figure imgf000084_0001
Figure imgf000084_0002
Table 13 (Continued)
Figure imgf000085_0001
Table 12 shows the "coefficient of kinetic friction" in each of Examples and Comparative Examples as the
relative value to the coefficient of kinetic friction in Comparative Example 7 (0.39). Herein, the numerical value in the parentheses is a value obtained by measuring the coefficient of kinetic friction. Table 13 shows the
"coefficient of kinetic friction" in each of Examples and Comparative Examples as the relative value to the
coefficient of kinetic friction in Comparative Example 54 (0.57). Herein, the numerical value in the parentheses is a value obtained by measuring the coefficient of kinetic friction.
The comparison of Examples with Comparative Examples 1 to 3 reveals that the case where the compound δ is not contained causes a lower proportion of silicon elements in the surface and a higher coefficient of kinetic friction as compared with Examples. Such an effect is exerted even if the types of the resin a, the resin β , the solvent γ and the like are changed.
In addition, the comparison of Examples with
Comparative Examples 4 to 6 reveals that the proportion of silicon elements in the surface cannot be made higher and the coefficient of kinetic friction is not lowered even in the case of not having the structure represented by the formula (1) but containing a solvent having the higher boiling point than xylene or toluene (diisobutylketone, n- pentyl acetate) . The comparison also reveals that the proportion of silicon elements in the surface cannot be made higher and the coefficient of kinetic friction is not lowered even in the case of a solvent having the structure represented by the formula (1) as long as the solvent is a solvent having the lower boiling point than xylene or toluene (monoglyme) . Such an effect is exerted even if the types of the resin a, the resin β , the solvent γ and the like are changed.
It is revealed from Comparative Examples 56 to 61 that in the case of not containing the resin β , the coefficient of kinetic friction is very high and the reduction in friction coefficient due to the addition of the compound δ is not observed regardless of containing the resin having a siloxane structure in the resin a .
It is revealed from Comparative Examples 29 to 31 that in the case of using a dimethylsilicone oil in place of the resin β , the effect due to containing the compound δ is not exerted and the coefficient of kinetic friction is not lowered. It is also revealed that no difference between the case of using monochlorobenzene and the case of using xylene is exhibited in terms of the coefficient of kinetic friction, and little change in initial friction coefficient due to the use of xylene is exhibited in the case of a dimethylsilicone 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. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.
This application claims the benefit of Japanese Patent
Applications No. 2011-166765, filed July 29, 2011, and No. 2012-123498, filed May 30, 2012 which are hereby
incorporated by reference herein in their entirety.

Claims

CLAIMES
[Claim 1]
A method of producing an electrophotographic
photosensitive member comprising a surface layer,
the method comprising the steps of:
forming a coat for the surface layer by using a surface-layer coating solution, and
forming the surface layer by drying the coat, wherein the surface-layer coating solution comprises: (a) at least one resin selected from the group consisting of a polycarbonate resin not having a siloxane moiety at the end, and a polyester resin not having a siloxane moiety at the end,
(β) at least one resin selected from the group consisting of a polycarbonate resin having a siloxane moiety at the end, a polyester resin having a siloxane moiety at the end, and an acrylate resin having a siloxane moiety at the end,
(γ) at least one solvent selected from the group consisting of toluene and xylene, and
(δ) a compound having the boiling point in one atmosphere higher than that of the (γ) , the compound being represented by the following formula (1), and
R10O—E-(R110)^R12 ( 1 )
wherein, in the formula (1),
R10 represents a methyl group, an ethyl group, a propyl group, a cyclohexyl group, a phenyl group, or a benzyl group,
R11 represents a methylene group, an ethylene group, or a propylene group,
R12 represents a methyl group, an ethyl group, an acetyl group, a propionyl group, or a benzoyl group,
E represents a single bond or a carbonyl group, q represents an integer number selected from 0 to 2.
[Claim 2]
The method of producing the electrophotographic photosensitive member according to claim 1,
wherein the above (δ) is at least one selected from the group consisting of a methyl benzoate, an ethyl
benzoate, a benzyl acetate, ethyl 3-Ethoxypropionate, and a diethylene glycol ethyl methyl ether.
[Claim 3]
The method of producing the electrophotographic photosensitive member according to claim 1 or 2,
wherein the content of the above (δ) in the surface- layer coating solution is not less than 3% by mass and not more than 300% by mass relative to the total mass of the above (a) and the above (β) , and
the content of the above (δ) is not less than 0.5% by mass and not more than 150% by mass relative to the total mass of the above (γ) .
[Claim 4]
The method of producing the electrophotographic photosensitive member according to claim 3,
wherein the content of the above ( δ ) in the surface- layer coating solution is not less than 5% by mass and not more than 80% by mass relative to the total mass of the above ( a ) and the above ( β ) , and
the content of the above ( δ ) is not less than 0.5% by mass and not more than 40% by mass relative to the total mass of the above (γ) .
[Claim 5]
The method of producing the electrophotographic
photosensitive member according to any one of claims 1 to 4, wherein the content of the above ( β ) in the surface- layer coating solution is not less than 0.1% by mass and not more than 50% by mass relative to the mass of the above ( a ) .
[Claim 6]
The method of producing the electrophotographic
photosensitive member according to any one of claims 1 to 5, wherein the surface-layer coating solution further comprises:
(ε) at least one of dimethoxymethane and
tetrahydrofuran .
[Claim 7]
The method of producing the electrophotographic
photosensitive member according to claim 6,
wherein the content of the above (γ) is not less than 15% by mass and not more than 99% by mass relative to the total mass of the above (γ) , the above (δ) and the above (ε) ,
the content of the above (δ) is not less than 0.5% by mass and not more than 35% by mass relative to the total mass of the above (γ) , the above (δ) and the above (ε), and the content of the above (ε) is not less than 0.1% by mass and not more than 65% by mass relative to the total mass of the above (γ) , the above (δ) a nd the above (ε) .
[Claim 8]
The method of producing the electrophotographic photosensitive member according to any one of claims 1 to 7 wherein the polycarbonate resin not having a siloxane moiety at the end is a polycarbonate resin A having a repeating structural unit represented by the following formula (A) ,
Figure imgf000092_0001
wherein, in the formula (A) ,
R21 to R24 each independently represents a hydrogen atom, or a methyl group,
X1 represents a single bond, a cyclohexylidene group, or a bivalent group having a structure represented by the following formula (C) , and
Figure imgf000093_0001
wherein, in the formula (C) ,
R41 to R42 each independently represents a hydrogen atom, a methyl group, or a phenyl group.
[Claim 9]
The method of producing the electrophotographic
photosensitive member according to any one of claims 1 to 7, wherein the polyester resin not having a siloxane moiety at the end is a polyester resin B having a repeating structural unit represented by the following formula (B) ,
Figure imgf000093_0002
wherein, in the formula (B) ,
R31 to R34 each independently represents a hydrogen atom, or a methyl group,
X2 represents a single bond, a cyclohexylidene group, or a bivalent group having a structure represented by the following formula (C).,
Y1 represents a meta-phenylene group, a para- pheneylene group, or a bivalent group having two para- phenylene groups bonded with an oxygen atom, and
Figure imgf000094_0001
wherein, in the formula (C) ,
R41 to R42 each independently represents a hydrogen atom, a methyl group, or a phenyl group.
[Claim 10]
The method of producing the electrophotographic photosensitive member according to any one of claims 1 to wherein the polycarbonate resin having a siloxane moiety at the end is a polycarbonate resin D having a repeating structural unit represented by the following formula (A' ) , and a end structure represented by the following formula (D) , .
Figure imgf000094_0002
wherein, in the formula (A' ) ,
R25 to R28 each independently represents a hydrogen atom, or a methyl group,
X3 represents a single bond, a cyclohexylidene group, or a bivalent group having a structure represented by the following formula (C ) , and
Figure imgf000095_0001
wherein, in the formula (C ) ,
R to R each independently represents a hydrogen atom, a methyl group, or a phenyl group, and
Figure imgf000095_0002
wherein, in the formula (D) ,
a and b each independently represents number of
repetitions of a structure within the bracket,
an average of a in the polycarbonate resin D ranges from 20 to 100,
an average of b in the polycarbonate resin D ranges from 1 to 10.
[Claim 11]
The method of producing the electrophotographic
photosensitive member according to any one of claims 1 to 9, wherein the polyester resin having a siloxane moiety at the end is a polyester resin E having a repeating
structural unit represented by the following formula (B' ) , and a end structure represented by the following formula
■(D) ,
Figure imgf000096_0001
wherein, in the formula (B' ) ,
R35 to R38 each independently represents a hydrogen atom, or a methyl group,
X4 represents a single bond, a cyclohexylidene group, or a bivalent group having a structure represented by the following formula (C ) ,
Y2 represents a meta-phenylene group, a para- pheneylene group, or a bivalent group having two para- phenylene groups bonded with an oxygen atom, and
Figure imgf000096_0002
wherein, in the formula (C ) ,
R43 to R44 each independently represents a hydrogen atom, a methyl group, or a phenyl group, and
Figure imgf000096_0003
wherein, in the formula (D),
a and b each independently represents number of repetitions of a structure within the bracket, an average of a in the polyester resin E ranges from 20 to 100,
an average of b in the polyester resin E ranges from 1 to 10.
[Claim 12]
The method of producing the electrophotographic
photosensitive member according to any one of claims 1 to 9, wherein the acrylate resin having a siloxane moiety at the end is
a acrylate resin F having a repeating structural unit represented by the following formula (F-l) and a repeating structural unit represented by the following formula (F-2), or
a acrylate resin F having a repeating structural unit represented by the following formula (F-l) and a repeating structural unit represented by the following formula (F-3) ,
Figure imgf000097_0001
wherein, in the formula (F-l) ,
R represents a hydrogen atom, or a methyl group, c represents number of repetitions of a structure within the bracket,
an average of c in the acrylate resin F ranges from 0 to 5 , R to R each independently represents a structure represented by the following formula (F-1-2) , a methyl roup, a methoxy group, or a phenyl group,
Figure imgf000098_0001
wherein, in the formula (F-1-2),
d represents number of repetitions of a structure within the bracket,
an average of d in the acrylate resin F ranges from to 50,
R55 represents a methyl group, or a hydroxy! group, and
Figure imgf000098_0002
wherein, in the formula (F-3) ,
R56 represents a hydrogen group, a methyl group, or a phenyl group, and
e is 0 or 1.
[Claim 13]
The method of producing the electrophotographic photosensitive member according to any one of claims 1 to
12,
wherein the above (γ) is xylene.
PCT/JP2012/065673 2011-07-29 2012-06-13 Method for producing electrophotographic photosensitive member Ceased WO2013018450A1 (en)

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