JP2018054904A - Electrophotographic photoreceptor, process cartridge, and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor that prevents potential fluctuations, has improved wear resistance, and prevents cleaning failures, and a process cartridge and an electrophotographic device having the electrophotographic photoreceptor.SOLUTION: An electrophotographic photoreceptor has an undercoat layer containing a polymer of a specific composition, and also has a surface layer containing a resin obtained by irradiating and curing a hole transporting compound having an acryloyloxy group or a methacryloyloxy group. On the surface of the electrophotographic photoreceptor, formed is a specific shape.SELECTED DRAWING: None

Description

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

  Since the electrophotographic photosensitive member is subjected to electrical and / or mechanical external forces such as charging, exposure, development, transfer, and cleaning, many problems are caused by these external forces.

  Specific examples of problems include changes in image density due to potential fluctuations, deterioration of durability performance due to surface layer scratches and wear, and image defects due to poor cleaning.

  As a technique for suppressing potential fluctuation, Patent Document 1 discloses a technique in which an undercoat layer is provided between a support and a photosensitive layer, and an electron transport material is contained in the undercoat layer.

  As a technique for improving the scratch resistance and wear resistance of the peripheral surface of the electrophotographic photosensitive member, Patent Document 2 discloses a technique in which the surface layer of the electrophotographic photosensitive member is a cured layer.

  As techniques for suppressing image defects due to poor cleaning, Patent Documents 3 to 5 disclose techniques for roughening the surface of an electrophotographic photoreceptor (providing irregularities on the surface).

JP 2014-0294979 A JP 1999-265085 A JP 2007-233355 A JP 2009-014979 A WO2011 / 067853 Publication

  In recent years, since it is desired to extend the life of an electrophotographic photosensitive member, it is necessary to maintain the performance (endurance performance) against the external force of the electrophotographic photosensitive member.

  As a result of the study by the present inventors, it has been confirmed that, when the techniques disclosed in Patent Documents 1 to 5 are combined, suppression of potential fluctuation, improvement of wear resistance, and suppression of defective cleaning are sufficiently achieved.

  An object of the present invention is to provide an electrophotographic photosensitive member in which fluctuations in potential are suppressed, wear resistance is improved, and cleaning failure is suppressed, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member. is there.

The present invention relates to an electrophotographic photosensitive member having a support, an undercoat layer formed on the support, and a photosensitive layer formed on the undercoat layer.
The undercoat layer contains a polymer of a composition containing a compound represented by the following formula (1),

(In formula (1), R ^{101 to} R ¹⁰⁶ are each independently a monovalent group represented by the following formula (A), a hydrogen atom, a cyano group, a nitro group, a halogen atom, an alkoxycarbonyl group, substituted or unsubstituted A substituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, wherein one of the carbon atoms in the main chain of the alkyl group is an oxygen atom, a sulfur atom, or- The divalent group represented by (N—R ²⁰¹ ) — may be substituted, R ²⁰¹ represents a hydrogen atom or an alkyl group, and at least one of R ^{101 to} R ¹⁰⁶ is represented by the following formula (A ) Is a monovalent group.
The substituent of the substituted alkyl group is a group selected from the group consisting of an alkyl group, an aryl group, an alkoxycarbonyl group, and a halogen atom.
The substituent of the substituted aryl group is a group selected from the group consisting of a halogen atom, a nitro group, a cyano group, an alkyl group, and a halogenated alkyl group. )

(In the formula (A), at least one of α, β and γ is a group having a substituent, and the substituent is at least selected from the group consisting of a hydroxy group, a thiol group, an amino group and a carboxy group. One kind of group.
l and m are each independently 0 or 1.

α is an alkylene group having 1 to 6 atoms in the main chain, an alkylene group having 1 to 6 carbon atoms substituted with an alkyl group having 1 to 6 carbon atoms, and a benzyl group. Of the main chain substituted with an alkylene group having 1 to 6 atoms in the main chain, an alkylene group having 1 to 6 atoms in the main chain substituted with an alkoxycarbonyl group, or a phenyl group An alkylene group having a number of 1 or more and 6 or less is shown. These groups may have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxy group as a substituent. One of the carbon atoms in the main chain of the alkylene group may be replaced with an oxygen atom, a sulfur atom, or a divalent group represented by — (N—R ³⁰¹ ) —. R ³⁰¹ represents a hydrogen atom or an alkyl group.

  β represents a phenylene group, an alkyl-substituted phenylene group having 1 to 6 carbon atoms, a nitro-substituted phenylene group, a halogenated phenylene group, or an alkoxy-substituted phenylene group. These groups may have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxy group as a substituent.

γ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in the main chain substituted with an alkyl group having 1 to 6 carbon atoms. . These groups may have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxy group as a substituent. One of the carbon atoms in the main chain of the alkyl group may be replaced with a divalent group represented by-(N-R ⁴⁰¹ )-. R ⁴⁰¹ represents an alkyl group. )
The surface layer of the electrophotographic photoreceptor contains a resin obtained by curing by irradiating a hole transporting compound having an acryloyloxy group or a methacryloyloxy group with radiation,
The surface of the electrophotographic photoreceptor satisfies any of the following:
(I) A plurality of recesses and portions other than the recesses are formed on the surface of the electrophotographic photosensitive member.
(Ii) A plurality of convex portions and portions other than the convex portions are formed on the surface of the electrophotographic photosensitive member.
(Iii) A plurality of flat portions and groove portions are alternately formed on the surface of the electrophotographic photosensitive member.
An electrophotographic photosensitive member characterized by the above.

  In addition, the present invention integrally supports the electrophotographic photosensitive member and at least one means selected from the group consisting of a charging means, an exposure means, a developing means, and a cleaning means, and is detachable from the main body of the electrophotographic apparatus. This is a process cartridge.

  The present invention also provides an electrophotographic apparatus having the electrophotographic photosensitive member, and a charging unit, an exposure unit, a developing unit, and a transfer unit.

  According to the present invention, it is possible to provide an electrophotographic photosensitive member in which potential fluctuation is suppressed, wear resistance is improved, and cleaning failure is suppressed, and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member. it can.

1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having the electrophotographic photosensitive member of the present invention. It is a figure which shows the example of the specific shape of the opening of each recessed part currently formed in the surface of the electrophotographic photoreceptor of this invention. It is a figure which shows the example of the cross-sectional shape of each recessed part currently formed in the surface of the electrophotographic photoreceptor of this invention. (A) is a figure which shows the example (partial enlarged view) of the arrangement pattern of the mask of this invention. (B) is a figure which shows the outline of the example of the laser processing apparatus of this invention. (C) is a figure which shows the example (partial enlarged view) of the arrangement pattern of the mask of this invention. (D) is a figure which shows the outline of the example of the press-contact shape transfer processing apparatus by the mold of this invention. (E) is a figure which shows the outline of another example of the press-contact shape transfer processing apparatus by the mold of this invention. (A) is a figure which shows an example of the mold shape of this invention. (B) is a figure which shows an example of the mold shape of this invention. It is a figure which shows the example of the shape of the opening of the convex part of the surface of the electrophotographic photoreceptor of this invention. It is a figure which shows the example of the shape of the cross section of the convex part of the surface of the electrophotographic photoreceptor of this invention. It is a figure which shows the example which looked at the flat part-groove part shape formed in the surrounding surface of the electrophotographic photoreceptor of this invention from the surface and the cross section. (A) is a figure which shows the example of the press-contact shape transfer processing apparatus by the mold of this invention. (B) is a figure which shows the example of the press-contact shape transfer processing apparatus by the mold of this invention. It is a figure which concerns on an Example or a comparative example. It is a figure which concerns on an Example or a comparative example. It is a figure which concerns on an Example or a comparative example. It is a figure which concerns on an Example or a comparative example. It is a figure which concerns on an Example or a comparative example. It is a figure which concerns on an Example or a comparative example.

  The electrophotographic photoreceptor of the present invention has a support, an undercoat layer formed on the support, and a photosensitive layer formed on the undercoat layer. In general, a cylindrical electrophotographic photosensitive member in which an undercoat layer or a photosensitive layer is formed on a cylindrical support is widely used as the electrophotographic photosensitive member, but a belt-like or sheet-like shape is used. It is also possible to make it.

  The photosensitive layer is preferably a laminated photosensitive layer from the viewpoint of electrophotographic characteristics. The laminated photosensitive layer may be a normal layer type photosensitive layer laminated in the order of the charge generation layer and the charge transport layer from the support side, or a reverse layer type photosensitive layer laminated in the order of the charge transport layer and the charge generation layer from the support side. It may be a layer. Further, the charge generation layer may have a stacked structure, and the charge transport layer may have a stacked structure.

[Support]
As a material for the support, one showing conductivity (conductive support) is preferable. For example, a support made of a metal (made of an alloy) such as iron, copper, gold, silver, aluminum, zinc, titanium, lead, nickel, tin, antimony, indium, chromium, an aluminum alloy, and stainless steel can be given. Alternatively, a metal (alloy) support or a resin support having a layer formed by vacuum deposition of aluminum, an aluminum alloy, or an indium oxide-tin oxide alloy can be used. In addition, a support obtained by impregnating resin or paper with conductive particles such as carbon black, tin oxide particles, titanium oxide particles, and silver particles, or a support made of conductive resin can also be used.

  The surface of the support may be subjected to cutting treatment, surface roughening treatment, and alumite treatment for the purpose of suppressing interference fringes due to scattering of laser light.

[Conductive layer]
A conductive layer may be provided between the support and the undercoat layer for the purpose of suppressing interference fringes due to laser light scattering and covering the support.

  The conductive layer can be formed using a coating liquid for a conductive layer prepared by dispersing and / or dissolving carbon black, a conductive pigment, and a resistance adjusting pigment in a binder resin. The conductive layer coating liquid may contain a compound that undergoes curing polymerization upon heating or radiation irradiation. The surface of a conductive layer containing a conductive pigment or a resistance adjusting pigment tends to be roughened.

  The thickness of the conductive layer is preferably 0.2 μm or more and 45 μm or less, more preferably 1 μm or more and 40 μm or less, and more preferably 5 μm or more and 35 μm or less.

  Examples of the binder resin used for the conductive layer include polymers / copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, trifluoroethylene, and polyvinyl alcohol. , Polyvinyl acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, epoxy resin and the like.

  Examples of the conductive pigment and the resistance adjusting pigment include particles of metals (alloys) such as aluminum, zinc, copper, chromium, nickel, silver, and stainless steel, and those obtained by vapor deposition on the surfaces of plastic particles. Alternatively, particles of metal oxide such as zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, and antimony, tantalum-doped tin oxide may be used. These may be used alone or in combination of two or more. When two or more types are used in combination, they may be simply mixed, or may be in the form of a solid solution or fusion.

[Underlayer]
An undercoat layer is provided between the support or conductive layer and the photosensitive layer. The undercoat layer contains a polymer of a composition containing a compound represented by the following formula (1).

In the formula (1), R ^{101 to} R ¹⁰⁶ are each independently a hydrogen atom, a cyano group, a nitro group, a halogen atom, an alkoxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, Alternatively, it represents a substituted or unsubstituted heterocyclic group. Or the monovalent group shown by following formula (A) is shown. One of the carbon atoms in the main chain of the alkyl group may be replaced with an oxygen atom, a sulfur atom, or a divalent group represented by — (N—R ²⁰¹ ) —. R ²⁰¹ represents a hydrogen atom or an alkyl group. At least one of R ^{101 to} R ¹⁰⁶ is a monovalent group represented by the following formula (A). The substituent of the substituted alkyl group is a group selected from the group consisting of an alkyl group, an aryl group, an alkoxycarbonyl group, and a halogen atom.
The substituent of the substituted aryl group is a group selected from the group consisting of a halogen atom, a nitro group, a cyano group, an alkyl group, and a halogenated alkyl group.

In the above formula (A), at least one of α, β and γ is a group having a substituent, and the substituent is at least selected from the group consisting of a hydroxy group, a thiol group, an amino group and a carboxy group. One kind of group.
l and m are each independently 0 or 1.

α is
An alkylene group having 1 to 6 atoms in the main chain;
An alkylene group having 1 to 6 atoms in the main chain substituted with an alkyl group having 1 to 6 carbon atoms,
An alkylene group having 1 to 6 atoms in the main chain substituted with a benzyl group, an alkylene group having 1 to 6 atoms in the main chain substituted with an alkoxycarbonyl group, or
An alkylene group having 1 to 6 atoms in the main chain substituted with a phenyl group is shown. These groups may have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxy group as a substituent. One of the carbon atoms in the main chain of the alkylene group may be replaced with an oxygen atom, a sulfur atom, or a divalent group represented by — (N—R ³⁰¹ ) —. R ³⁰¹ represents a hydrogen atom or an alkyl group.

Examples of the divalent group represented by-(N-R ³⁰¹ )-are given below.

  β represents a phenylene group, an alkyl-substituted phenylene group having 1 to 6 carbon atoms, a nitro-substituted phenylene group, a halogenated phenylene group, or an alkoxy-substituted phenylene group. These groups may have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxy group as a substituent.

γ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in the main chain substituted with an alkyl group having 1 to 6 carbon atoms. . These groups may have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxy group as a substituent. One of the carbon atoms in the main chain of the alkyl group may be replaced with a divalent group represented by-(N- (R ⁴⁰¹ )-, where R ⁴⁰¹ represents an alkyl group.

Examples of the divalent group represented by — (N—R ⁴⁰¹ ) — include the same groups as the examples of the divalent group represented by — (N—R ³⁰¹ ) —.

At least one of R ¹⁰⁵ and R ^{106 in} the above formula (1) is preferably a monovalent group represented by the above formula (A) from the viewpoint of suppressing potential fluctuation.

  In the above formula (A), at least one of α, β and γ is a group having a substituent, and from the viewpoint of suppressing potential fluctuation, the substituent is preferably a hydroxy group.

  Two or more compounds represented by the above formula (1) may be used.

  Examples of the compound represented by the above formula (1) are given below.

  The compound represented by the above formula (1) can be synthesized using, for example, the synthesis methods described in US Pat. No. 4,442,193, US Pat. No. 4,992,349, and US Pat. No. 5,468,583. In addition, Chemistry of materials, Vol. 19, no. It is also possible to synthesize using the synthesis method described in 11, 2703-2705 (2007).

  Moreover, it can synthesize | combine by reaction with the naphthalene tetracarboxylic dianhydride and monoamine derivative which can be purchased from Tokyo Chemical Industry Co., Ltd., Sigma-Aldrich Japan Co., Ltd., and Johnson Matthey Japan Incorporated.

The compound represented by the above formula (1) has a monovalent group (hydroxy group, thiol group, amino group, carboxy group) represented by the above formula (A) as a polymerizable functional group. As a method of introducing these substituents, a method of directly introducing a polymerizable functional group into a precursor before introducing a polymerizable functional group of the compound represented by the above formula (1), a polymerizable functional group or There is a method of introducing a structure having a functional group that can be a precursor of a polymerizable functional group. As a method to be described later, for example, there is a method of introducing a functional group-containing aryl group using a cross-coupling reaction using a palladium catalyst and a base based on a halide of a naphthylimide derivative. For example, there is a method of introducing a functional group-containing alkyl group using a cross-coupling reaction using a FeCl ₃ catalyst and a base based on a halide of a naphthylimide derivative. In addition, there is a method of introducing a hydroxyalkyl group or a carboxy group based on a halide of a naphthylimide derivative by allowing an epoxy compound or CO ₂ to act after lithiation. As a raw material for synthesizing a naphthylimide derivative, there is a method using a naphthalenetetracarboxylic dianhydride derivative or a monoamine derivative having a polymerizable functional group or a functional group that can be a precursor of the polymerizable functional group. As a raw material for synthesizing a naphthylimide derivative, there is a method using a naphthalenetetracarboxylic dianhydride derivative or a monoamine derivative having a polymerizable functional group or a functional group that can be a precursor of the polymerizable functional group.

  When the undercoat layer contains a polymer of a composition containing the compound represented by the above formula (1), the composition preferably further contains a crosslinking agent and a resin.

  As the crosslinking agent, an electron transport material having a polymerizable functional group, and a compound that polymerizes or crosslinks with a thermoplastic resin having a polymerizable functional group can be used. Specifically, compounds described in Shinzo Yamashita and Tosuke Kaneko “Crosslinking Agent Handbook” published by Taiseisha (1981) and the like can be used.

  Examples of the functional group in the crosslinking agent include -NCO group (hereinafter also referred to as isocyanate group), -NOR group, -SiOR group, acrylic group and the like. Among these, an isocyanate group is preferable from the viewpoint of suppressing potential fluctuation.

An isocyanate compound having 2 or more and 6 or less isocyanate groups (—NCO groups) or blocked isocyanate groups (—NHCOX ¹ group, X ¹ is a protecting group) is preferable. X ¹ may be any protecting group that can be introduced into an isocyanate group, but is preferably a group represented by any of the following formulas (X ¹ ) to (X ⁷ ).

  Specific examples include triisocyanate benzene, triphenylmethane triisocyanate, lysine triisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 2,2,4-trimethyl. Examples include modified isocyanurate modified products of diisocyanates such as hexamethylene diisocyanate, methyl-2,6-diisocyanate hexanoate, norbornane diisocyanate, modified biuret, modified allophanate, and adducts with trimethylolpropane.

  The isocyanate compound preferably has a cyclic structure. More preferred is an isocyanurate structure, which is a structure represented by the following formula.

  Examples of commercially available isocyanate compounds include Sumika Bayer Urethane Co., Ltd., BL3175, BL3475, BL3575, Asahi Kasei Chemicals Corporation, TPA-B80E, TPA-B80X, SBN-70D, SBN-70M, and the like. .

  As the resin, a thermoplastic resin having a polymerizable functional group is preferable. Examples of the thermoplastic wire resin include a resin (thermoplastic resin) having a structural unit represented by the following formula (B).

In the above formula (B), R ¹¹ represents a hydrogen atom or an alkyl group. Y represents a single bond or a phenylene group. W1 represents a hydroxy group, a thiol group, an amino group, or a carboxy group.

  Examples of the thermoplastic resin having the structural unit represented by the above formula (B) include acetal resins, polyolefins, polyesters, polyethers, and polyamides.

  The structural unit represented by the above formula (B) may be included in the following characteristic structure, or may be included other than the characteristic structure. Characteristic structures are shown in the following (B-1) to (B-5). (B-1) is a structural unit of an acetal resin. (B-2) is a structural unit of polyolefin. (B-3) is a structural unit of polyester. (B-4) is a structural unit of polyether. (B-5) is a structural unit of polyamide.

In the formulas (B-1) to (B-5), R ^{501 to} R ⁵¹⁰ each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

Among the thermoplastic resins having the structural unit represented by the above formula (B), examples of commercially available resins include the following.
Polyether polyol resins such as AQD-457 and AQD-473 manufactured by Nippon Polyurethane Industry Co., Ltd., Sannics GP-400 and GP-700 manufactured by Sanyo Chemical Industries, Ltd.
Polyester polyol resins such as Hitachi Chemical Co., Ltd., Phthalkid W2343, DIC Corporation, Watersol S-118, CD-520, Harima Chemicals Co., Ltd., Haridip WH-1188,
Polyacryl polyol resins such as Burnock WE-300 and WE-304 manufactured by DIC Corporation,
Polyvinyl alcohol resins such as Kuraray Kuraray Poval PVA-203,
Polyvinyl acetal resins such as Sekisui Chemical Co., Ltd. KW-1 and KW-3, BX-1, BM-1, KS-1, KS-3, KS-5Z,
Polyamide compound resins such as Nagase ChemteX Corporation's Toresin FS-350,
Carboxy group-containing resins such as Nippon Shokubai Co., Ltd. Aquaric, Lead City Co., Ltd. Finelex SG2000,
Polyamines such as DIC's racamide;
Polythiol such as QE-340M manufactured by Toray Industries, Inc.

  The composition for the undercoat layer may contain a catalyst for the purpose of promoting polymerization. Examples of the catalyst include dibutyltin dilaurate, amine catalyst, and metal soap.

  Examples of the solvent used in the coating solution for the undercoat layer include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

  As a form of polymerization, for example, a compound represented by the above formula (1), a crosslinking agent, and a resin having a structural unit represented by the above formula (B) react to form a polymer (cured product).

  The undercoat layer can be formed by forming a coating film of the coating solution for the undercoat layer containing the compound represented by the above formula (1) and drying the coating film by heating. After the coating film is formed, these compounds are polymerized (cured) by a chemical reaction. By heating at that time, the chemical reaction is promoted and the polymerization is promoted.

  The content of the polymer in the undercoat layer is preferably 50% by mass or more and 100% by mass or less, and preferably 80% by mass or more and 100% by mass with respect to the total mass of the undercoat layer, from the viewpoint of suppressing potential fluctuation. % Or less is more preferable.

  In addition to the polymer, the undercoat layer may contain organic fine particles, inorganic fine particles, a leveling agent, and the like in order to improve the film formability and electrical characteristics of the undercoat layer. However, their content in the undercoat layer is preferably less than 50% by mass and more preferably less than 20% by mass with respect to the total mass of the undercoat layer.

  In addition, another layer such as a second undercoat layer not containing the polymer according to the present invention may be provided between the support and the undercoat layer or between the undercoat layer and the photosensitive layer. .

  The compound according to the present invention was confirmed by the following method.

Mass spectrometry Mass spectrometry (MALDI-TOFMS: Bruker Daltonics Co., ultraflex) using an acceleration voltage: 20 kV, mode: Reflector, molecular weight standard product: the conditions of fullerene _{C 60,} to measure the molecular weight. It confirmed with the obtained peak top value.

・ NMR analysis ¹ H-NMR, ¹³ C-NMR analysis (FT-NMR: manufactured by JEOL Ltd.) in 1,1,2,2-tetrachloroethane (d2) or dimethyl sulfoxide (d6) at 120 ° C. The structure was confirmed by JNM-EX400 type).

-GPC analysis It measured with the gel permeation chromatography "HLC-8120" by Tosoh Corporation, and computed in polystyrene conversion.

  In addition, an undercoat layer obtained by forming a coating film of an undercoat layer coating solution containing an isocyanate compound, a resin, and an electron transport material, and heating and drying the coating film is immersed in cyclohexanone, before and after the immersion. The weight of the undercoat layer was confirmed. It was confirmed that the components of the undercoat layer were not dissolved by immersion, and were cured (polymerized).

-Surface roughness Rzjis (X) was confirmed using the contact-type surface roughness meter (Brand name: Surfcorder SE3500, Kosaka Laboratory (made)) as a measuring device. Measurement length: 2.5 mm, measurement speed: 0.1 mm / second, the measurement location is the average of 12 points in the longitudinal direction, 3 points each of 30 mm, 185 mm, and 340 mm from the upper end of the coating, 4 points in the circumferential direction The value was taken as data.

[Photosensitive layer]
A photosensitive layer is provided on the undercoat layer.

  Examples of the charge generating material used in the photosensitive layer include azo pigments such as monoazo, disazo, and trisazo, perylene pigments, anthraquinone derivatives, anthanthrone derivatives, dibenzpyrenequinone derivatives, pyranthrone derivatives, violanthrone derivatives, and isoviolanthrone derivatives. , Indigo derivatives, thioindigo derivatives, phthalocyanine pigments having various central metals and various crystal systems (α, β, γ, ε, X type, etc.), bisbenzimidazole derivatives, quinacridone pigments, asymmetric quinocyanine pigments, quinocyanine pigments, Examples include pyrylium, thiapyrylium dyes, and amorphous silicon. Among these, azo pigments or phthalocyanine pigments are preferable. Among the phthalocyanine pigments, oxytitanium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine are preferable. These charge generation materials may be used alone or in combination of two or more.

  Examples of the charge transport material used in the photosensitive layer include pyrene compounds, N-alkylcarbazole compounds, hydrazone compounds, N, N-dialkylaniline compounds, diphenylamine compounds, triphenylamine compounds, triphenylmethane compounds, pyrazoline compounds, styryl. Compounds and stilbene compounds. Also included are polymers having groups derived from these compounds in the main chain or side chain. These charge transport materials may be used alone or in combination of two or more.

  Examples of the binder resin used in the electrophotographic photosensitive member of the present invention include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylic ester, methacrylic ester, vinylidene fluoride, and trifluoroethylene. , Polyvinyl alcohol, polyvinyl acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, epoxy resin and the like.

  When the photosensitive layer is a laminated photosensitive layer, the binder resin used for the charge generation layer is preferably polyester, polycarbonate, or polyvinyl acetal, and more preferably polyvinyl acetal.

  When the photosensitive layer is a laminated photosensitive layer, the binder resin used for the charge transport layer (hole transport layer) is preferably polycarbonate or polyarylate. Moreover, it is preferable that these weight average molecular weights (Mw) are the ranges of 10,000 or more and 300,000 or less.

  When the photosensitive layer is a laminated photosensitive layer, the mass ratio of the charge generation material to the binder resin (charge generation material / binder resin) in the charge generation layer is in the range of 10/1 to 1/10. Is preferable, and the range of 5/1 to 1/5 is more preferable. The thickness of the charge generation layer is preferably 0.05 μm or more and 5 μm or less.

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

  The charge generation layer can be formed by the following method.

  First, the charge generation material is dispersed together with a binder resin and a solvent in an amount of 0.3 to 4 times (mass ratio). Examples of the dispersion treatment method include a method using a homogenizer, ultrasonic dispersion, ball mill, vibration ball mill, sand mill, attritor, and roll mill. The charge generation layer coating solution obtained by the dispersion treatment is applied to form a coating film. The charge generation layer can be formed by drying this coating film. The charge generation layer may be a vapor generation film of a charge generation material.

  When the photosensitive layer is a laminated photosensitive layer, the mass ratio of the charge transport material to the binder resin (charge transport material / binder resin) in the charge transport layer is in the range of 10/5 to 5/10. Is preferable, and the range of 10/8 to 6/10 is more preferable. The thickness of the charge transport layer is preferably 5 μm or more and 40 μm or less.

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

  The charge transport layer can be formed by the following method.

  First, a charge transport layer coating solution is obtained by dissolving a charge transport material and a binder resin in a solvent. The obtained charge transport layer coating solution is applied to form a coating film. The charge transport layer can be formed by drying this coating film. In addition, when a charge transport material having film-forming properties alone is used, a charge transport layer can be formed by forming a film with the charge transport material alone without using a binder resin.

[Surface layer]
In the present invention, the surface layer of the electrophotographic photosensitive member is a layer located on the most surface side among the layers of the electrophotographic photosensitive member, and is a layer that is most separated from the support.

The acryloyloxy group and methacryloyloxy group of the hole transporting compound used in the surface layer are each a monovalent group represented by CH ₂ ═CHCOO— and CH ₂ ═C (CH ₃ ) COO—, respectively. Is a valent group.

  The hole transporting compound used for the surface layer in the present invention has at least one of an acryloyloxy group and a methacryloyloxy group. In addition, when irradiated with radiation, these groups undergo a polymerization reaction and cure to become a resin.

  Compounds having an acryloyloxy group or a methacryloyloxy group are roughly classified into monomers and oligomers depending on the presence or absence of repeating structural units in the structure. The monomer has an acryloyloxy group or a methacryloyloxy group, has no repeating structural units, and has a relatively small molecular weight. The oligomer is a polymer having an acryloyloxy group or a methacryloyloxy group and having about 2 to 20 repeating structural units. Moreover, the macromonomer which has an acryloyloxy group or a methacryloyloxy group only at the terminal of a polymer or an oligomer can also be used as a compound for surface layers in this invention.

  In the present invention, it is preferable to use a monomer from the viewpoint of achieving both durability and electrical characteristics. Also when using a polymer, an oligomer, and a macromonomer, it is preferable to mix and use with a monomer.

Monomers are classified according to the structure of the portion other than the acryloyloxy group or methacryloyloxy group. For example,
Alkyl types such as 1,4-butadiol diacrylate and neopentyl glycol diacrylate, alkylene glycol types such as diethylene glycol diacrylate,
Trimethylolpropane type, such as trimethylolpropane triacrylate,
Pentaerystol type such as pentaerythritol triacrylate,
Isocyanurate types such as tris (acryloxyethyl) isocyanurate,
Examples thereof include alicyclic types such as dicyclopentanyl diacrylate and ethoxylated hydrogenated bisphenol A dimethacrylate.

  In the present invention, from the viewpoint of the balance between the hardness and the characteristics of the electrophotographic photosensitive member, among these, a trimethylolpropane type, a pentaerythritol type, an isocyanurate type, and an alicyclic type are preferable.

  Examples of the oligomer include epoxy acrylate (methacrylate), urethane acrylate (methacrylate), polyester acrylate (methacrylate), polyether acrylate (methacrylate), and silicon acrylate (methacrylate).

  In the present invention, the oligomer is preferably used by mixing with a monomer.

  Examples of the macro part of the macromonomer include ethylene, styrene, and acrylic.

  In the present invention, the macromonomer is preferably used as a mixture with the monomer.

  In addition, compounds having an acryloyloxy group or a methacryloyloxy group can be classified by the number of functional groups in one molecule (the number of acryloyloxy groups and methacryloyloxy groups). Those having one functional group in one molecule are called monofunctional compounds, and those having two or more functional groups are called polyfunctional compounds.

  In the present invention, it is preferable to use a polyfunctional compound from the viewpoint of durability, and it is preferable to use a polyfunctional compound having three or more acryloyloxy groups or methacryloyloxy groups in one molecule. .

  In the present invention, the compounds having an acryloyloxy group or a methacryloyloxy group may be used alone or in combination of two or more.

  In the present invention, when forming the surface layer, the hole transporting compound having an acryloyloxy group or a methacryloyloxy group is cured by irradiation with radiation. The radiation is preferably an electron beam or gamma ray. In the present invention, it is preferable to use an electron beam from the viewpoints of absorption rate and working efficiency. When irradiating an electron beam, examples of the accelerator include a scanning type, an electro curtain type, a broad beam type, a pulse type, and a laminar type accelerator. When the electron beam is irradiated, the electron beam irradiation conditions are important in order to develop the excellent electrical characteristics and durability performance of the electrophotographic photosensitive member. In the present invention, the acceleration voltage is preferably 250 kV or less, and more preferably 200 kV or less. The irradiation dose is preferably in the range of 0.5 Mrad to 100 Mrad, and more preferably in the range of 0.5 Mrad to 10 Mrad. If the acceleration voltage is 250 kV or less, and if the irradiation dose is 100 Mrad or less, damage due to electron beam irradiation on the characteristics of the electrophotographic photosensitive member can be suppressed. Moreover, if the irradiation dose is 0.5 Mrad or more, the hole transporting compound can be sufficiently cured.

  In the present invention, the surface layer includes a pyrene compound, an N-alkylcarbazole compound, a hydrazone compound, an N, N-dialkylaniline compound, a diphenylamine compound, a triphenylamine compound, a triphenylmethane compound, a pyrazoline compound, and a styryl compound. In addition, a charge transport material such as a stilbene compound may be contained together. In addition, charge transport materials such as polymers having groups derived from these compounds in the main chain or side chain, styrene, vinyl acetate, vinyl chloride, acrylate esters, methacrylate esters, vinylidene fluoride, trifluoroethylene, etc. Polymers and copolymers of vinyl compounds, polyvinyl alcohol, polyvinyl acetal, polycarbonate, polyester, polysulfone, polyphenylene oxide, polyurethane, cellulose resin, phenol resin, melamine resin, silicon resin, epoxy resin, etc. are combined in the surface layer. May be included.

  The film thickness of the surface layer is preferably 0.1 μm or more and 20 μm or less, and more preferably 1 μm or more and 10 μm or less.

  The electrophotographic photosensitive member having the above surface layer is less likely to be worn on the surface. As a result, the charged product adhering to the surface of the electrophotographic photosensitive member tends to accumulate, friction with the cleaning blade increases, chattering or turning occurs, and image flow occurs when the electrophotographic apparatus is in a high humidity atmosphere. There is a case to do.

Therefore, the electrophotographic photosensitive member of the present invention preferably has a surface elastic deformation rate of 45% or more and 65% or less, and more preferably 50% or more. The universal hardness value (HU) of the surface of the electrophotographic photosensitive member is preferably 150 N / mm ² or more and 220 N / mm ² or less.

  If the universal hardness value (HU) is too large or the elastic deformation rate is too small, the elastic force on the surface of the electrophotographic photosensitive member may be insufficient. If the elastic force is insufficient, paper dust or toner sandwiched between the surface of the electrophotographic photosensitive member and the cleaning blade rubs the surface of the electrophotographic photosensitive member, resulting in scratches on the surface of the electrophotographic photosensitive member. It becomes easy. As a result, the surface of the electrophotographic photosensitive member is also easily worn.

  If the universal hardness value (HU) is too large, the amount of elastic deformation is small even if the elastic deformation rate is high. As a result, a large pressure is applied to the local area of the surface of the electrophotographic photosensitive member, and the electronic Deep scratches are likely to occur on the surface of the photoconductor. Further, even if the universal hardness value (HU) is in the above range, if the elastic deformation rate is too small, the amount of plastic deformation becomes relatively large, so that fine scratches are likely to occur on the surface of the electrophotographic photosensitive member. And wear tends to occur. This is particularly noticeable not only when the elastic deformation rate is too small but also when the universal hardness value (HU) is too small.

  As described above, when the universal hardness value (HU) and the elastic deformation rate are in the above ranges, the surface of the electrophotographic photosensitive member is less likely to be worn and scratches are less likely to occur. Therefore, since the surface shape of the electrophotographic photosensitive member changes very little from the beginning to after repeated use or does not change, the initial performance can be maintained well even when used repeatedly for a long time.

  Each layer of the electrophotographic photosensitive member of the present invention can contain various additives. Examples of additives include deterioration inhibitors such as antioxidants and ultraviolet absorbers, organic fine particles such as fluorine-containing resin particles and acrylic resin particles, inorganic fine particles such as silica, titanium oxide, and alumina, and carbon fluoride. Examples include lubricants.

[Surface shape]
The surface of the electrophotographic photoreceptor of the present invention satisfies any of the following.

(I) A plurality of recesses and portions other than the recesses are formed on the surface of the electrophotographic photosensitive member.
(Ii) A plurality of convex portions and portions other than the convex portions are formed on the surface of the electrophotographic photosensitive member.
(Iii) A plurality of flat portions and groove portions are alternately formed on the surface of the electrophotographic photosensitive member.

  The fact that a plurality of recesses and portions other than the recesses are formed on the surface of the electrophotographic photosensitive member (i) will be described.

  The concave portion in the present invention refers to a concave portion in which each concave portion is clearly separated from other concave portions.

  2A to 2G show examples of specific shapes of the openings of the respective recesses formed on the surface of the electrophotographic photosensitive member. 3A to 3F show examples of cross-sectional shapes of the respective recesses.

  2 and 3, D represents the major axis diameter of the recess, and H represents the depth of the recess. Examples of the shape of the opening of each concave portion include various shapes such as a circle, an ellipse, a square, a rectangle, a triangle, a quadrangle, and a hexagon as shown in FIGS. . Moreover, as a shape of the cross section of a recessed part, what has edges, such as a triangle, a tetragon | quadrangle, and a polygon as shown to (A)-(F) of FIG. 3, is mentioned, for example. In addition, a waveform having a continuous curve, a triangle, a quadrangle, a polygon having a part or all of its edges deformed into a curve, and the like are also included.

  The plurality of recesses formed on the surface of the electrophotographic photosensitive member may all have the same shape, size, and depth, or may have different shapes, sizes, and depths. .

  As shown in FIG. 2, the major axis diameter of the opening of each recess is defined as the length of the maximum straight line among the straight lines crossing the opening of each recess. For example, the diameter is used as the major axis diameter in the case of a circle, the major axis in the case of an ellipse, and the diagonal in the case of a quadrangle. In the measurement of the major axis diameter, for example, when the boundary between the recess and the non-recess is not clear as shown in FIG. The maximum length obtained in the same manner as described above is defined as the major axis diameter. Furthermore, when a flat part is unclear as shown in FIG. 3F, a center line m is provided in a cross-sectional view of adjacent recesses to define a major axis diameter.

  The region where the concave portion is formed on the surface of the electrophotographic photosensitive member may be formed on the entire surface of the electrophotographic photosensitive member, or may be formed on a part of the surface. In order to exhibit good performance, it is preferably formed at least at a site in contact with the cleaning blade.

  In the present invention, the number of the recesses is preferably 76 or more and 1000 or less per 100 μm square, and more preferably 100 or more and 500 or less. Moreover, it is preferable that an average major axis diameter is larger than 3.0 micrometers, and is 14.0 micrometers or less, and it is more preferable that they are 5 micrometers or more and 10 micrometers or less. Even when the average major axis diameter is larger than 3.0 μm, if the number of recesses per 100 μm square is less than 76, the effect of reducing the frictional force between the surface of the electrophotographic photosensitive member and the cleaning blade is sufficient. Since it cannot be obtained, the effect of the present invention tends to be difficult to obtain. In addition, when the average major axis diameter is less than 3.0 μm, even if the number of concave portions per 100 μm square is 76 or more, the toner is likely to be fused to the surface of the electrophotographic photosensitive member. There is a tendency. In particular, this phenomenon is prominent in a high temperature and high humidity environment.

  In the present invention, the 100 μm square area is obtained by dividing the surface of the electrophotographic photosensitive member into four equal parts in the rotation direction of the electrophotographic photosensitive member and dividing it into 25 equal parts in a direction perpendicular to the rotation direction of the electrophotographic photosensitive member. 100 areas are obtained. And it sets by providing the square area | region of 100 micrometers in one side in each of the area | region of a total of 100 places obtained. The average major axis diameter in the present invention is defined as an average value obtained by statistically processing the major axis diameter of each concave portion per 100 μm square according to the above definition.

  Furthermore, in the present invention, in the statistical processing, it is preferable that there are few concave portions having a major axis diameter of 3.0 μm or less, and it is more preferable that they do not exist. Even when the average major axis diameter per unit area is larger than 3.0 μm, as the number of recesses having a major axis diameter of 3.0 μm or less increases, the toner tends to be fused to the surface of the electrophotographic photosensitive member. is there. Specifically, the number of recesses having a major axis diameter of 3.0 μm or less is preferably 50% by number or less, and more preferably 10% by number or less.

  The depth of the concave portion in the present invention is defined as the maximum distance between the major axis diameter and the bottom surface of the concave portion in the cross section of the concave portion with respect to the major axis diameter, as shown in FIGS. . In the depth measurement, similarly to the measurement of the average major axis diameter, the surface of the electrophotographic photosensitive member is divided into four equal parts in the rotation direction of the electrophotographic photosensitive member, and is orthogonal to the rotation direction of the electrophotographic photosensitive member. Divide into 25 equal directions to obtain a total of 100 regions. Then, a square region having a side of 100 μm is provided in each of the obtained 100 regions, and the concave portion included therein is performed. The average depth is defined as an average value obtained by statistically processing the depth of each recess per 100 μm square according to the above definition.

  In the present invention, the depth of the recess is preferably 0.1 μm or more, and more preferably 0.5 μm or more. When the depth is smaller than 0.1 μm, the effects of the present invention tend not to be obtained.

In the present invention, the area ratio of the opening of the recess is preferably 40% or more and 99% or less, and more preferably 60% or more and 80% or less. When the area ratio of the opening of the recess is too small, the effect of the present invention is hardly obtained. In addition, this "area ratio of the opening of a recessed part" means the ratio for which the total area of the opening of a recessed part calculated | required by the following formula in the said 100 micrometer square area | region.
{Total area of recess openings / (Total area of recess openings + Total area of non-recesses)} × 100

  In the present invention, the arrangement of the concave portions is arbitrary and can be optimized.

  In the present invention, the shape of the recesses on the surface of the electrophotographic photosensitive member can be measured using, for example, a commercially available laser microscope, white interference microscope, optical microscope, electron microscope, or atomic force microscope.

As the laser microscope, for example, the following devices can be used.
Shape analysis laser microscope VK-X150 / 160, VK-X250 / 260 (manufactured by Keyence Corporation)
3D measurement laser microscope OLS4100 (manufactured by Olympus Corporation)
Laser microscope opretex hybrid (Lasertec Corporation)
As the white interference microscope, for example, the following devices can be used.
Surface shape measurement system Surface Explorer SX-520DR (manufactured by Ryoka System Co., Ltd.)
Scanning white interference microscope VS-1000 series (manufactured by Hitachi High-Tech Science Co., Ltd.)
White interference microscope system BW-S500 series, BW-D500 series (Nikon Corporation)
3D Optical Profiler Zigo New View Series (Canon Co., Ltd.)

As the optical microscope, for example, the following devices can be used.
Digital microscope VHX-5000, one-shot 3D measurement macroscope VR3000 series (manufactured by Keyence Corporation)
Digital Microscope Leica DVM6 (manufactured by Leica Microsystems)
As the electron microscope, for example, the following devices can be used.
3D Real Surface View Microscope VE-9800, 8800 (manufactured by Keyence Corporation)
Scanning electron microscope SU3000, S-3400N (manufactured by Hitachi High-Technologies Corporation)
Scanning electron microscope JSM-IT300, JSM-6510 series (manufactured by JEOL Ltd.)
Scanning electron microscope Quanta series (manufactured by Shimadzu Corporation)

As the atomic force microscope, for example, the following devices can be used.
Scanning probe microscope probe station AFM5000II, AFM5000, general-purpose small unit AFM5100N (manufactured by Hitachi High-Tech Science Co., Ltd.)
Scanning probe microscope SPM-9700 (manufactured by Shimadzu Corporation)
AFM system multi-mode 8AFM (manufactured by Bruker AXS Co., Ltd.)

  Using the microscope, the number of recesses, the major axis diameter, and the depth in the measurement visual field can be measured with a predetermined magnification. Furthermore, the average major axis diameter, average depth, and area ratio of the openings per unit area can be obtained by calculation.

  As an example, a measurement example using an analysis program by the Surface Explorer SX-520DR type machine will be described.

The electrophotographic photosensitive member to be measured is placed on the work table, and the tilt is adjusted to adjust the horizontal, and the three-dimensional shape data of the peripheral surface of the electrophotographic photosensitive member is captured in the wave mode. At that time, the magnification of the objective lens may be 50 times, and the field of view may be 100 μm × 100 μm (10000 μm ² ). By this method, the surface of the electrophotographic photosensitive member to be measured is divided into four equal parts in the rotation direction of the electrophotographic photosensitive member, and divided into 25 equal parts in a direction perpendicular to the rotational direction of the electrophotographic photosensitive member, for a total of 100 points. In each of the regions, a square region having a side of 100 μm is provided for measurement.

  Next, the contour line data of the surface of the electrophotographic photosensitive member is displayed using a particle analysis program in the data analysis software.

The hole analysis parameters of the recess, such as the shape of the recess, the major axis diameter, the depth, and the opening area, can be optimized depending on the formed recess. For example, when observing and measuring a concave portion having a major axis diameter of about 10 μm, the major axis diameter upper limit may be 15 μm, the major axis diameter lower limit may be 1 μm, the depth lower limit may be 0.1 μm, and the volume lower limit may be 1 μm ³ or more. Then, the number of recesses that can be identified as recesses on the analysis screen is counted, and this is used as the number of recesses.

Also, with the same visual field and analysis conditions as described above, the total opening area of the recesses is calculated from the sum of the opening areas of the respective recesses determined using the particle analysis program, and the area ratio of the opening of the recesses (hereinafter referred to as the following) Or simply referred to as “area ratio”).
{Total opening area of recess / (Total opening area of recess + Total area of non-recessed portion)} × 100

<Method for Forming Recesses on Surface of Electrophotographic Photoreceptor According to the Present Invention>
The method for forming the recess is not particularly limited as long as the method can satisfy the requirements related to the recess. For example, a method for forming a surface shape of an electrophotographic photosensitive member by laser light irradiation having an output characteristic with a pulse width of 100 ns (nanoseconds) or less, or a mold having a predetermined shape is pressed against the surface of the electrophotographic photosensitive member, There is a method of performing shape transfer.

  A method of forming a recess by laser light irradiation having an output characteristic with a pulse width of 100 ns (nanoseconds) or less will be described. As a laser used in this method, for example, an excimer laser using a gas such as ArF, KrF, XeF, or XeCl (particularly KrF or ArF is preferable) or a femtosecond laser using titanium sapphire as a medium. Can be mentioned. In the laser irradiation, the wavelength of the laser beam is preferably 1,000 nm or less. The excimer laser is laser light emitted in the following steps. First, high energy such as discharge, electron beam, and X-ray is applied to a mixed gas of a rare gas such as Ar, Kr, or Xe and a halogen gas such as F or Cl to excite and bond the above elements. Let Thereafter, excimer laser light is emitted when dissociating by falling to the ground state.

As a method for forming the concave portion, for example, a mask in which a laser light blocking portion a and a laser light transmitting portion b are appropriately arranged as shown in FIG. Only laser light that has passed through the mask is condensed by the lens and irradiated onto the workpiece, so that a recess having a desired shape and arrangement can be formed. Since a large number of recesses within a certain area can be simultaneously processed regardless of the shape and area, the process can be performed in a short time. Laser irradiation using a mask processes several mm ² to several cm ² per irradiation. In laser processing, as shown in FIG. 4B, first, the electrophotographic photosensitive member is rotated by a workpiece rotating motor d. While rotating, the laser irradiation position is shifted in the axial direction of the electrophotographic photosensitive member by the work moving device e, so that the concave portion can be efficiently formed on the entire surface of the electrophotographic photosensitive member. The depth of the concave portion can be adjusted within a desired range depending on the irradiation time and the number of irradiation times of the laser beam. According to the present invention, it is possible to realize rough surface processing with high controllability of the size, shape, and arrangement of the recesses, and high accuracy and high flexibility.

  Further, in the method for forming a recess on the surface of the electrophotographic photosensitive member by laser irradiation, the above-described method for forming a recess may be applied to a plurality of parts or the entire surface of the electrophotographic photosensitive member using the same mask pattern. Good. By this method, the concave portions can be uniformly formed on the entire surface of the electrophotographic photosensitive member. As a result, the mechanical load applied to the cleaning blade when used in the electrophotographic apparatus becomes uniform. In addition, as shown in FIG. 4C, cleaning is performed by forming a mask pattern on an arbitrary circumferential line of the electrophotographic photosensitive member so as to form an array in which both concave portions h and non-concave portions g are present. The uneven distribution of the mechanical load on the blade can be further suppressed.

  Next, a description will be given of a method for forming a concave portion in which a mold having a predetermined shape is pressed against the surface of the electrophotographic photosensitive member to transfer the shape.

  FIG. 4D is a diagram showing an example of a schematic diagram of a pressure contact shape transfer processing apparatus using a mold according to the present invention. After the predetermined mold B is attached to the pressure device A that can repeatedly press and release, the mold B is brought into contact with the electrophotographic photosensitive member C at a predetermined pressure to transfer the shape. Thereafter, the pressure is once released and the electrophotographic photosensitive member C is rotated, and then the pressure is again applied to perform the shape transfer process. By repeating this process, it is possible to form a predetermined concave shape over the entire circumference of the electrophotographic photosensitive member.

  Further, as shown in FIG. 4E, first, a mold B longer than the entire circumference of the electrophotographic photosensitive member C is attached to the pressure device A. Thereafter, a predetermined dimple shape can be formed over the entire circumference of the electrophotographic photosensitive member by rotating and moving the electrophotographic photosensitive member while applying a predetermined pressure to the electrophotographic photosensitive member C.

  As another example, a sheet-shaped mold can be sandwiched between a roll-shaped pressurizing device and an electrophotographic photosensitive member, and surface processing can be performed while feeding the mold sheet.

  The mold or the electrophotographic photosensitive member may be heated for the purpose of efficiently transferring the shape.

  The material, size, and shape of the mold itself can be selected as appropriate. Materials include metal and resin film with fine surface processing, silicon wafers and other surfaces patterned with resist, resin film with fine particles dispersed, and resin film with a predetermined fine surface shape. The ones that have been An example of the mold shape is shown in FIG. 5A and 5B, 9A-1 and 9B-1 are views of the mold as viewed from above, and 9A-2 and 9B-2 are views of the mold as viewed from the side.

  Further, it is possible to install an elastic body between the mold and the pressure device for the purpose of uniformly applying pressure to the electrophotographic photosensitive member.

  The fact that a plurality of convex portions and portions other than the convex portions are formed on the surface of the electrophotographic photosensitive member (ii) will be described.

The electrophotographic photosensitive member of the present invention has a plurality of convex portions and portions other than the convex portions on the surface, and the convex portion area ratio Smr is expressed by the following formula (2).
Smr = Scut / Sk (2)
(Sk indicates a reference area, and Scut indicates a three-dimensional surface shape curved surface obtained with the reference area at an average height plane (a plane constituted by the average height of all measurement data). Shows the cross-sectional area obtained by
The convex area ratio Smr is defined by the following formula (3).
Smr ≦ 0.40 (3)
It is preferable to satisfy.

  Here, Scut in the present invention is a value obtained by extending the load length Rmr (50%) of the roughness curve defined in JIS B0601-2001 in the surface direction.

  The measurement parameters were determined as follows.

Reference area (Sk) = 100 μm ²
Cut-off value (λs) = 0.25 μm
Cut-off value (λc) = 0.08mm

  The measurement is carried out by dividing the surface of the electrophotographic photosensitive member into four equal parts in the rotation direction of the electrophotographic photosensitive member and dividing it into 25 equal parts in the direction perpendicular to the rotation direction of the electrophotographic photosensitive member. On the other hand, according to the above parameters. Then, the Scut value obtained for each measurement point is arithmetically averaged, and the value obtained by dividing by the reference area is defined as Smr in the present invention.

Next, in the electrophotographic photosensitive member of the present invention, the standard deviation Tσ of the convex shape interval with respect to the longitudinal direction of the electrophotographic photosensitive member is expressed by the following formula (4).
Tσ ≦ Lpc (4)
(Lpc preferably represents the average diameter of each convex shape obtained from the cross-sectional area obtained by cutting the surface shape curved surface with the average height surface).

  In the present invention, the standard deviation Tσ is determined by the following procedure.

First, the surface shape data of 100 μm ² used for the calculation of Scut is divided into 10 in the direction orthogonal to the rotation direction of the electrophotographic photosensitive member, and contour curve data with respect to the height direction at the dividing line position is extracted. Next, the obtained contour curve is cut at a cutting level of 50%, and the load length of each convex element is obtained. Here, the distance between the midpoints of the adjacent convex element load length line segments is defined as T (i), and the standard deviation for the entire T (i) obtained is defined as Tσ.

  The shape of the convex portion on the surface of the electrophotographic photosensitive member can be measured using the commercially available laser microscope, white interference microscope, optical microscope, electron microscope, and atomic force microscope described in the above measurement of the concave portion.

  6A to 6G show examples of specific Scut measurement surface shapes of the respective convex portions. The average diameter of each convex shape obtained from the cross-sectional area of the Scut measurement surface is defined as Lpc.

  7A to 7F show examples of specific shapes of cross sections in the normal direction of the electrophotographic photosensitive member of the respective convex portions. Examples of the Scut measurement surface shape include various shapes such as a circle, an ellipse, a square, a rectangle, a triangle, and a hexagon as shown in FIGS. Moreover, as a cross-sectional shape to a normal line direction, what has edges, such as a triangle, a square, and a polygon as shown to (A)-(F) of FIG. 7, is mentioned, for example. In addition, a waveform having a continuous curve, a triangle, a quadrangle, a polygon having a part or all of its edges deformed into a curve, and the like are also included.

  The plurality of convex portions formed on the surface of the electrophotographic photosensitive member may all have the same shape, size, and depth, or may have a mixture of different shapes and sizes.

  Here, as shown in FIGS. 6A to 6G, the length of the straight line that is the maximum of each convex portion is defined as the major axis diameter Rpc. For example, the diameter is adopted as the minor axis diameter in the case of a circle, the minor axis in the case of an ellipse, and the shorter one of the sides in the case of a rectangle. In addition, for example, the diameter is defined as the major axis diameter Rpc in the case of a circle, the longer diameter in the case of an ellipse, and the diagonal line in the case of a quadrangle.

<Method for Forming Protrusions on Surface of Electrophotographic Photoreceptor According to the Present Invention>
The method for forming the convex portion is not particularly limited as long as the method can satisfy the requirements related to the convex portion. For example, a method for forming the surface shape of the electrophotographic photosensitive member by laser light irradiation having an output characteristic having a pulse width of 100 ns (nanoseconds) or less, similar to the method for forming the concave shape described above, can be mentioned. Another example is a method of transferring a shape by pressing a mold having a predetermined shape against the surface of the electrophotographic photosensitive member.

  The fact that a plurality of flat portions and groove portions are alternately formed on the surface (circumferential surface) of the electrophotographic photosensitive member (iii) will be described.

  The surface of the electrophotographic photosensitive member is a shape composed of a flat portion and a groove portion (hereinafter also referred to as “flat portion-groove portion shape”), and the flat portion-groove portion shape is highly uniform. Specifically, a flat portion having a width e (μm) of 0.1 ≦ e ≦ 25 and a width w (μm) of 0.1 ≦ w ≦ 25 and deep on the peripheral surface of the electrophotographic photosensitive member. It is preferable that a plurality of grooves having a length d (μm) of 0.1 ≦ d ≦ 3.0 are alternately formed. It is preferable that a plurality of the flat portions and the groove portions are alternately formed so as to form an angle θ (°) of 80 ≦ θ ≦ 100 with respect to the axial direction of the electrophotographic photosensitive member. The total value eSum (μm) of the width e of the flat portion per 100 μm axial width of the peripheral surface of the electrophotographic photosensitive member is preferably 5 ≦ eSum ≦ 75. Further, when the average value of the width e of the flat portion is eAv (μm) and the standard deviation is eσ, it is preferable that eσ / eAv is eσ / eAv ≦ 0.46.

  FIG. 8 shows an example in which the flat portion-groove portion shape formed on the peripheral surface of the electrophotographic photosensitive member according to the present invention is viewed from the surface and the cross section. In FIG. 8, a plurality of flat portions having a width e (μm) and groove portions having a width w (μm) and a depth d (μm) are alternately formed on the peripheral surface of the electrophotographic photosensitive member.

  The width e (μm) of the flat portion is preferably in the range of 0.1 ≦ e ≦ 25. When the width e (μm) of the flat portion exceeds 25 μm, the contact portion between the cleaning blade and the peripheral surface of the electrophotographic photosensitive member increases in the axial direction of the electrophotographic photosensitive member, and the effect of reducing the frictional force tends to decrease. It is in. On the other hand, when the width e (μm) of the flat portion is smaller than 0.1 μm, the contact portion becomes small, and the behavior of the cleaning blade tends to become unstable. Further, when the width e of the flat portion is smaller than 0.1 μm, the dot reproducibility tends to be lowered when the toner image formed on the peripheral surface of the electrophotographic photosensitive member is transferred to the transfer material. The flat portion having a width e (μm) smaller than 0.1 μm is preferably not formed on the peripheral surface of the electrophotographic photosensitive member. Further, it is preferable that a flat portion having a width e (μm) larger than 25 μm is not formed on the peripheral surface of the electrophotographic photosensitive member.

  The width w (μm) of the groove is preferably in the range of 0.1 ≦ w ≦ 25. When the width w (μm) of the groove exceeds 25 μm, it becomes close to the exposure spot diameter of a laser generally used for image exposure during image formation, so it is formed on the peripheral surface of the electrophotographic photosensitive member due to scattering. The transferability of the toner image thus formed tends to be non-uniform. On the other hand, when the width w (μm) of the groove is smaller than 0.1 μm, the contact portion between the cleaning blade and the peripheral surface of the electrophotographic photosensitive member is increased, and the effect of reducing the frictional force is reduced. Tend to be unstable. It is preferable that the groove portion having a width w (μm) smaller than 0.1 μm is not formed on the peripheral surface of the electrophotographic photosensitive member. Further, it is preferable that the groove portion having a width w (μm) larger than 25 μm is not formed on the peripheral surface of the electrophotographic photosensitive member.

  The depth d (μm) of the groove is preferably in the range of 0.1 ≦ d ≦ 3.0. When the depth d (μm) of the groove exceeds 3.0 μm, the groove tends to appear as an image defect. On the other hand, when the depth d (μm) of the groove is smaller than 0.1 μm, the frictional force reducing effect tends to be small. It is preferable that the groove portion having a depth d (μm) smaller than 0.1 μm is not formed on the peripheral surface of the electrophotographic photosensitive member. Further, it is preferable that the groove portion having a depth d (μm) larger than 3.0 μm is not formed on the peripheral surface of the electrophotographic photosensitive member.

  In the present invention, the groove is formed on the peripheral surface of the electrophotographic photosensitive member together with the flat portion at an angle of 90 ° ± 10 ° which is substantially perpendicular to the axial direction of the electrophotographic photosensitive member. That is, in the present invention, the groove portion has a circumferential surface of the electrophotographic photosensitive member so as to form an angle θ (°) of 80 ≦ θ ≦ 100 (for example, θ in FIG. 8) with respect to the axial direction of the electrophotographic photosensitive member. It is preferable that a plurality are formed. When the angle θ (°) deviates from the range of 80 ≦ θ ≦ 100, the flat portion-groove portion shape tends to disappear due to repeated use, and the effects of the present invention tend not to be obtained.

  Further, the flat portion-groove shape formed on the peripheral surface of the electrophotographic photosensitive member of the present invention is the total value eSum (μm) of the width e of the flat portion per 100 μm in the axial direction of the peripheral surface of the electrophotographic photosensitive member. Is preferably 5 ≦ eSum ≦ 75. When the total value eSum (μm) exceeds 75 μm, the frictional force between the cleaning blade and the peripheral surface of the electrophotographic photosensitive member tends to increase, and the cleaning failure tends to occur. On the other hand, from the viewpoint of reducing the frictional force between the cleaning blade and the peripheral surface of the electrophotographic photosensitive member, the total value eSum (μm) is preferably small. However, since the effect of the present invention tends to decrease as the total value eSum (μm) falls below 5 μm and the proportion of the flat portion decreases, the total value eSum (μm) is preferably 5 μm or more. More preferably, 10 ≦ eSum ≦ 50.

  Further, the flat part-groove part shape formed on the peripheral surface of the electrophotographic photosensitive member of the present invention has a flat part width e (μm), a groove part width w (μm), and a groove part depth d (μm). Smaller variations are preferred. That is, the standard deviations eσ, wσ, dσ of the average values eAv (μm), wAv (μm), and dAv (μm) of the width e of the flat part, the width w of the groove part, and the depth d of the groove part are small. Is preferred. In particular, increasing the uniformity of the width of the flat portion in contact with the cleaning blade is important because it is particularly directly related to the effects of the present invention. Specifically, it is preferable that eσ / eAv ≦ 0.46. Preferably, eσ / eAv ≦ 0.27, and more preferably eσ / eAv ≦ 0.08. Furthermore, it is preferable that wσ / wAv ≦ 0.08 regarding the uniformity of the width of the groove portion. Moreover, it is preferable that it is d (sigma) / dAv <= 0.08 also regarding the uniformity of the depth of a groove part. The uniform width of the flat portion, the width of the groove portion, and the depth of the groove portion stabilize the contact state between the microscopic peripheral surface of the electrophotographic photosensitive member and the cleaning blade, and the effect of the present invention is remarkably obtained. It tends to be. Also, with regard to dot reproducibility and transferability, it is effective to make the width of the flat part, the width of the groove part, and the depth of the groove part uniform.

  In order to obtain the effect of the present invention remarkably, it is preferable that the flat portion-groove shape according to the present invention is formed at least in a region in contact with the cleaning blade on the peripheral surface of the electrophotographic photosensitive member.

  Next, the method for observing the flat portion-groove shape on the peripheral surface of the electrophotographic photosensitive member and the data processing method in the present invention will be described in detail.

  In the present invention, the flat part-groove part shape of the peripheral surface of the electrophotographic photosensitive member is measured using a commercially available laser microscope, white interference microscope, optical microscope, electron microscope, atomic force microscope, etc. described in the measurement of the concave part. Is possible.

  Using the microscope, the size of the flat portion and the groove portion in the measurement visual field can be measured with a predetermined magnification. Specifically, the width e of each flat part in the field of view, and the width w and depth d of the groove part can be measured. Further, the average width eAv of the flat portion per unit length in the field of view, its standard deviation eσ, the average groove width wAv of the groove portion, its standard deviation wσ, the average depth dAv, its standard deviation dσ, the width of the flat portion The total value eSum can be obtained by calculation.

The values of eAv, eσ, wAv, wσ, dAv, dσ, and eSum are obtained by dividing the circumferential surface of the electrophotographic photosensitive member to be measured into four equal parts in the rotation direction of the electrophotographic photosensitive member, and rotating the electrophotographic photosensitive member. A total of 100 regions are obtained by dividing into 25 equal parts in the direction orthogonal to the direction. Then, a square (10000 μm ² ) region having a side of 100 μm was provided in each of the obtained 100 regions, and each of the regions was observed, and finally an average value of 100 locations was calculated.

  In the present invention, the flat part-groove part shape of the peripheral surface of the electrophotographic photosensitive member can be measured using, for example, the above-described commercially available laser microscope, optical microscope, electron microscope, atomic force microscope, and the like.

  Using the microscope, the size of the flat portion and the groove portion in the measurement visual field can be measured with a predetermined magnification. Specifically, the width e of each flat part in the field of view, and the width w and depth d of the groove part can be measured. Further, the average width eAv of the flat portion per unit length in the field of view, its standard deviation eσ, the average groove width wAv of the groove portion, its standard deviation wσ, the average depth dAv, its standard deviation dσ, the width of the flat portion The total value eSum can be obtained by calculation.

The values of eAv, eσ, wAv, wσ, dAv, dσ, and eSum are obtained by dividing the circumferential surface of the electrophotographic photosensitive member to be measured into four equal parts in the rotation direction of the electrophotographic photosensitive member, and rotating the electrophotographic photosensitive member. A total of 100 regions are obtained by dividing into 25 equal parts in the direction orthogonal to the direction. Then, a square (10000 μm ² ) region having a side of 100 μm was provided in each of the obtained 100 regions, and each of the regions was observed, and finally an average value of 100 locations was calculated.

<Method for forming flat portion-groove shape on peripheral surface of electrophotographic photosensitive member>
In the present invention, a mold having a predetermined uneven shape is pressed against the peripheral surface of the electrophotographic photosensitive member, and the shape of the mold is transferred (shape transfer), whereby the flat surface-groove portion shape is formed on the peripheral surface. A photographic photoreceptor can be obtained.

  FIG. 9 is a diagram illustrating an example of a pressure contact shape transfer processing apparatus using a mold.

  According to these press contact shape transfer processing apparatuses, the peripheral surface is continuously brought into contact with the mold 13-2 and pressed while rotating the electrophotographic photosensitive member 13-1 to be transferred, so that the flat portion- The groove shape can be formed on the peripheral surface of the electrophotographic photosensitive member.

  In FIG. 9, the size and shape of the pressure member 13-3 are determined according to the processing pressure and the processing area. Moreover, as a material of the pressurizing member 13-3, for example, metal, metal oxide, plastic, or glass can be used. Among them, it is preferable to use stainless steel (SUS) from the viewpoint of mechanical strength, dimensional accuracy, and durability. The pressure member 13-3 has a mold on its upper surface, and a shape transfer target electrophotographic photoreceptor 13-1 supported on the support member 13-4 by a support member (not shown) on the lower surface and a pressure system. The shape transfer can be performed by contacting the peripheral surface with a predetermined pressure. Further, a method of applying pressure by pressing a supporting member holding the electrophotographic photosensitive member against the pressing member can be employed, or a method of applying pressure to both can be employed.

  In the example shown in FIG. 9B, the peripheral surface is continuously processed while the electrophotographic photosensitive member 13-1 to be shape transferred is driven or driven and rotated by the movement of the pressing member 13-3. This is an example.

  Instead of this example, the peripheral surface of the electrophotographic photoreceptor 13-1 to be shape transferred can be continuously processed by moving the support member 13-4.

  In order to efficiently transfer the shape, it is preferable to heat the mold or the electrophotographic photosensitive member.

  The material, size, and shape of the mold can be selected as appropriate. As a material of the mold, for example, a metal, a resin film, a silicon wafer, or the like that has been subjected to patterning with a resist on the surface, such as a fine surface processed. In addition, a resin film in which fine particles are dispersed, a resin film having a predetermined fine surface shape, and a metal coating are also included.

  Further, for the purpose of making the pressure on the electrophotographic photosensitive member uniform, it is also possible to install an elastic member between the mold and the pressure device.

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

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

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

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

  The surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by receiving a transfer residual developer (transfer residual toner) by a cleaning means (cleaning blade or the like) 7.

  Next, after being subjected to charge removal processing by pre-exposure light (not shown) from pre-exposure means (not shown), it is repeatedly used for image formation. As shown in FIG. 1, when the charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not necessarily required.

  Of the above-described components such as the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, the transfer unit 6 and the cleaning unit 7, a plurality of components may be housed in a container and integrally combined as a process cartridge. Good. The process cartridge may be configured to be detachable from the main body of an electrophotographic apparatus such as a copying machine or a laser beam printer.

  In FIG. 1, the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, and the cleaning unit 7 are integrally supported to form a cartridge. The process cartridge 9 is detachably attached to the main body of the electrophotographic apparatus using guide means 10 such as a rail of the main body of the electrophotographic apparatus.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “part” means “part by mass”. First, a synthesis example of the electron transport material according to the present invention is shown.

(Synthesis Example 1)
Under a nitrogen atmosphere, 5.4 parts of naphthalenetetracarboxylic dianhydride, 4 parts of 2,6-diisopropylaniline and 3 parts of 2-amino-1,3-propanediol are added to 200 parts of dimethylacetamide. Stir for hours to prepare a solution.

  After preparing the solution, the mixture was refluxed for 10 hours and separated by silica gel column chromatography (developing solvent: ethyl acetate / toluene), and then the fraction containing the desired product was concentrated. The concentrate was recrystallized with a mixed solution of ethyl acetate / toluene to obtain 1.5 parts of an imide compound represented by the above formula (12).

(Synthesis Example 2)
In a nitrogen atmosphere, 5.4 parts of naphthalenetetracarboxylic dianhydride, 4 parts of 4-heptylamine and 3 parts of 2-amino-1,3-propanediol are added to 200 parts of dimethylacetamide and stirred at room temperature for 1 hour. To prepare a solution. After preparing the solution, the mixture was heated to reflux for 8 hours, separated by silica gel column chromatography (developing solvent: ethyl acetate / toluene), and the fraction containing the desired product was concentrated. The concentrate was recrystallized with a mixed solution of ethyl acetate / toluene to obtain 2.0 parts of an imide compound represented by the above formula (14).

(Synthesis Example 3)
Under a nitrogen atmosphere, 5.4 parts of naphthalenetetracarboxylic dianhydride, 2.6 parts of leucinol and 2.7 parts of 2- (2-aminoethylthio) ethanol are added to 200 parts of dimethylacetamide at room temperature for 1 hour. After stirring, the mixture was refluxed for 7 hours. Dimethylacetamide was removed from the resulting black brown solution by distillation under reduced pressure, and then dissolved in an ethyl acetate / toluene mixed solution.

  After separation by silica gel column chromatography (developing solvent: ethyl acetate / toluene), the fraction containing the desired product was concentrated. The obtained concentrate was recrystallized with a toluene / hexane mixed solution to obtain 2.5 parts of an imide compound represented by the above formula (15).

  Next, an electrophotographic photoreceptor was produced and evaluated as follows.

[Support Example 1]
An aluminum cylinder having a diameter of 30 mm and a length of 357.5 mm was used as a support (cylindrical support).

[Conductive layer formation example 1]
214 parts of titanium oxide (TiO ₂ ) particles coated with oxygen-deficient tin oxide (SnO ₂ ) as metal oxide particles, phenol resin (monomer / oligomer of phenol resin) as a binder (trade name: ply Orphen J-325, manufactured by Dainippon Ink & Chemicals, Inc., resin solid content: 60% by mass) and 132 parts of 1-methoxy-2-propanol as a solvent were mixed with glass beads 450 having a diameter of 0.8 mm. It put into the sand mill which used the part. And the dispersion process was performed on the conditions of rotation speed: 2000rpm, dispersion processing time: 4.5 hours, and the setting temperature of cooling water: 18 degreeC, and the dispersion liquid was obtained.

  Glass beads were removed from this dispersion with a mesh (aperture: 150 μm). Silicone resin particles as a surface-roughening agent were added to the dispersion so as to be 10% by mass with respect to the total mass of the metal oxide particles and the binder material in the dispersion after removing the glass beads. The silicone resin particles are silicone resin particles (trade name: Tospearl 120, average particle size 2 μm) manufactured by Momentive Performance Materials Co., Ltd. Further, the conductive layer is prepared by adding silicone oil as a leveling agent to the dispersion and stirring so that the total mass of the metal oxide particles and the binder material in the dispersion is 0.01% by mass. A coating solution was prepared. The silicone oil is a silicone oil (trade name: SH28PA) manufactured by Toray Dow Corning. This conductive layer coating solution was dip-coated on a support, and the resulting coating film was dried and thermally cured at 150 ° C. for 30 minutes to form a conductive layer 1 having a thickness of 30 μm.

[Conductive layer formation example 2]
100 parts of zinc oxide particles (average primary particle size: 50 nm, specific surface area: 19 m ² / g, manufactured by Teika Co., Ltd.) were mixed with 500 parts of toluene while stirring. To this was added 1.25 parts of N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) as a surface treatment agent, and mixed with stirring for 2 hours. . Thereafter, toluene was distilled off under reduced pressure and dried at 120 ° C. for 3 hours to obtain zinc oxide particles surface-treated with a silane coupling agent.

  75 parts of zinc oxide particles surface-treated with a silane coupling agent, 16 parts of an isocyanate compound having a blocked isocyanate group represented by the following formula (H),

9 parts of polyvinyl butyral resin (trade name: ESREC BM-1, manufactured by Sekisui Chemical Co., Ltd.), 1 part of 2,3,4-trihydroxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.), 60 parts of methyl ethyl ketone and 1 part -A dispersion was prepared in addition to 60 parts of butanol mixed solvent.

  This dispersion was subjected to a dispersion treatment using a glass bead having an average particle size of 1.0 mm in a vertical sand mill at 23 ° C. for 3 hours at a rotation speed of 1,500 rpm. After the dispersion treatment, 5 parts of crosslinked polymethyl methacrylate particles (trade name: SSX-103, average particle size: 3 μm, manufactured by Sekisui Chemical Co., Ltd.) and silicone oil (trade name: SH28PA, An undercoat layer coating solution was prepared by adding 0.01 parts of Toray Dow Corning Co., Ltd.) and stirring. The undercoat layer coating solution was dip-coated on a support to form a coating film, and the coating film was heated and polymerized at 170 ° C. for 30 minutes to form a conductive layer 2 having a thickness of 30 μm.

[Conductive layer formation example 3]
100 parts of zinc oxide particles (average primary particle size: 50 nm, specific surface area: 19 m ² / g, manufactured by Teika Co., Ltd.) were mixed with 500 parts of toluene while stirring. To this was added 1.25 parts of N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) as a surface treatment agent, and mixed with stirring for 2 hours. . Thereafter, toluene was distilled off under reduced pressure and dried at 120 ° C. for 3 hours to obtain zinc oxide particles surface-treated with a silane coupling agent.

  50 parts of zinc oxide particles surface-treated with a silane coupling agent, 30 parts of a triazine compound having, as a polymerizable functional group, a methylol group represented by the following formula (I) that is butyl etherified,

20 parts of alkyd resin (trade name: M-6405-50, manufactured by DIC Corporation), 1 part of 2,3,4-trihydroxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.), 60 parts of methyl ethyl ketone and 1-butanol A dispersion was prepared in addition to 60 parts of the mixed solvent.

  This dispersion was subjected to a dispersion treatment using a glass bead having an average particle size of 1.0 mm in a vertical sand mill at 23 ° C. for 3 hours at a rotation speed of 1,500 rpm. After the dispersion treatment, 5 parts of crosslinked polymethyl methacrylate particles (trade name: SSX-103, average particle size: 3 μm, manufactured by Sekisui Chemical Co., Ltd.) and silicone oil (trade name: SH28PA, An undercoat layer coating solution was prepared by adding 0.01 parts of Toray Dow Corning Co., Ltd.) and stirring. The undercoat layer coating solution was dip-coated on a support to form a coating film, and the coating film was heated and polymerized at 170 ° C. for 30 minutes to form a conductive layer 3 having a thickness of 30 μm.

[Undercoat layer formation example 1]
8.5 parts of the compound represented by the above formula (11), 15 parts of blocked isocyanate compound (trade name: SBN-70D, manufactured by Asahi Kasei Chemicals Corporation), polyvinyl acetal resin (trade name: KS-5Z, Sekisui Chemical) 1.97 parts of zinc hexanoate (II) (trade name: zinc hexanoate (II), manufactured by Mitsuwa Chemical Co., Ltd.) It was dissolved in a mixed solvent of 88 parts of 2-propanol and 88 parts of tetrahydrofuran to prepare an undercoat layer coating solution.

  The undercoat layer coating solution is dip-coated on the conductive layer, and the resulting coating film is heated at 170 ° C. for 20 minutes to be cured (polymerized), thereby forming the undercoat layer 1 having a thickness of 0.6 μm. Formed. Table 1 shows the thickness and composition of the undercoat layer.

[Undercoat layer formation example 2]
In the undercoat layer formation example 1, the compound represented by the formula (11) was changed to 8.0 parts of the compound represented by the formula (13). Also, the blocked isocyanate compound was changed to 15.7 parts. In other respects, the undercoat layer 2 was formed in the same manner as in the undercoat layer formation example 1. Table 1 shows the thickness and composition of the undercoat layer.

[Undercoat layer formation example 3]
In the undercoat layer formation example 2, the compound represented by the above formula (13) was changed to the compound represented by the above formula (14). Otherwise, the undercoat layer 3 was formed in the same manner as in the undercoat layer formation example 2. Table 1 shows the thickness and composition of the undercoat layer.

[Undercoat layer formation example 4]
In the undercoat layer formation example 2, the compound represented by the formula (13) was changed to the compound represented by the formula (15). Other than that, the undercoat layer 4 was formed in the same manner as in the undercoat layer formation example 2. Table 1 shows the thickness and composition of the undercoat layer.

[Undercoat layer formation example 5]
In subbing layer formation example 1, the catalyst was changed to zinc 2-ethylhexanoate (trade name: bis (2-ethylhexanoic acid) zinc / mineral spirit solution (Zn: 15%), Wako Pure Chemical Industries, Ltd.) did. Further, the compound represented by the formula (11) was changed to 8.0 parts of the compound represented by the formula (32). Also, the blocked isocyanate compound was changed to 15.7 parts. Other than that, the undercoat layer 5 was formed in the same manner as in the undercoat layer formation example 1. Table 1 shows the thickness and composition of the undercoat layer.

[Charge generation layer formation example 1]
4 parts of a crystalline form of a hydroxygallium phthalocyanine crystal (charge generation material) having strong peaks at 7.4 ° and 28.1 ° with a Bragg angle 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction, and the following formula (A 0.04 parts of the compound represented by

Was added to a solution obtained by dissolving 2 parts of polyvinyl butyral (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) in 100 parts of cyclohexanone. Thereafter, this solution is put into a sand mill using glass beads having a diameter of 1 mm, dispersed for 1 hour in an atmosphere of 23 ± 3 ° C., and after dispersion treatment, 100 parts of ethyl acetate is added, thereby applying a coating for a charge generation layer. A liquid was prepared.

  The charge generation layer coating solution was dip-coated on the undercoat layer, and the resulting coating film was dried at 90 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.21 μm.

[Charge transport layer formation example 1]
50 parts of a compound (charge transport material) represented by the following formula (B), 50 parts of a compound (charge transport material) represented by the following formula (C),

A coating solution for a charge transport layer was prepared by dissolving 100 parts of polycarbonate (trade name: Iupilon Z400, manufactured by Mitsubishi Gas Chemical Co., Ltd.) in a mixed solvent of 650 parts of chlorobenzene and 150 parts of dimethoxymethane.

  The charge transport layer coating solution was allowed to stand for 1 day after the solution became uniform, then dip coated on the charge generation layer, and the obtained coating film was dried at 110 ° C. for 60 minutes to obtain a film thickness. Formed a 18 μm charge transport layer.

[Surface layer formation example 1]
In a mixed solvent of 80 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.) / 1 80 parts of 1-propanol, the following formula (D) 100 parts of a hole transporting compound represented by the formula:

  By filtering this with a polyflon filter (trade name: PF-020, manufactured by Advantech Toyo Co., Ltd.), a surface coating solution was prepared.

  This surface layer coating solution was dip-coated on the charge transport layer, and the resulting coating film was dried at 50 ° C. for 5 minutes. After drying, the coating film was cured by irradiating the coating film with an electron beam while rotating the aluminum cylinder for 1.6 seconds under the conditions of an acceleration voltage of 70 kV and an absorbed dose of 13000 Gy in a nitrogen atmosphere. Thereafter, heat treatment was performed for 3 minutes in a nitrogen atmosphere under conditions where the coating film became 120 ° C. Note that the oxygen concentration from the electron beam irradiation to the heat treatment for 3 minutes was 20 ppm. Next, in the atmosphere, a heat treatment was performed for 30 minutes under the condition that the coating film reached 100 ° C., thereby forming a surface layer having a film thickness of 5 μm.

The obtained electrophotographic photosensitive member had an elastic deformation rate of 57% and a universal hardness (HU) value of 185 N / mm ² .

[Surface layer formation example 2]
As a dispersant, 0.5 part of a fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) is added to 1,1,2,2,3,3,4-heptafluorocyclopentane (Zeorolla H). , Manufactured by Nippon Zeon Co., Ltd.) and 20 parts of 1-propanol, and then dissolved in a mixed solvent of tetrafluoroethylene resin powder (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) A solution with 10 parts added was made. Then, the solution was subjected to four treatments at a pressure of 58.8 MPa [600 kgf / cm ² ] with a high-pressure disperser (trade name: Microfluidizer M-110EH, manufactured by Microfluidics, USA), and uniformly dispersed. This was filtered with a polyflon filter (trade name: PF-040, manufactured by Advantech Toyo Co., Ltd.) to prepare a lubricant dispersion.

  Thereafter, 90 parts of the hole transporting compound represented by the above formula (D), 70 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane and 70 parts of 1-propanol were added to the lubricant dispersion. Added to. And it filtered with the polyfluorone filter [Brand name: PF-020, Advantech Toyo Co., Ltd.], and prepared the coating liquid for surface layers.

  This surface layer coating solution was dip-coated on the charge transport layer, and the resulting coating film was dried at 50 ° C. for 5 minutes. After drying, the coating film was irradiated with an electron beam for 1.6 seconds under a nitrogen atmosphere while rotating an aluminum cylinder under the conditions of an acceleration voltage of 70 kV and an absorbed dose of 10,000 Gy to cure the coating film. Thereafter, heat treatment was performed for 3 minutes in a nitrogen atmosphere under conditions where the coating film became 120 ° C. Note that the oxygen concentration from the electron beam irradiation to the heat treatment for 3 minutes was 20 ppm. Next, in the atmosphere, a heat treatment was performed for 30 minutes under the condition that the coating film reached 100 ° C., thereby forming a surface layer having a film thickness of 5 μm.

The obtained electrophotographic photosensitive member had an elastic deformation rate of 55% and a universal hardness (HU) value of 180 N / mm ² .

[Surface Layer Formation Example 3]
As a dispersant, 1.5 parts of a fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) was added to 1,1,2,2,3,3,4-heptafluorocyclopentane (Zeorolla H). , Manufactured by Nippon Zeon Co., Ltd.) and a mixed solvent of 45 parts of 1-propanol, followed by tetrafluoroethylene resin powder as a lubricant (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) A solution with 30 parts added was made. Then, the solution was subjected to four treatments at a pressure of 58.8 MPa [600 kgf / cm ² ] with a high-pressure disperser (trade name: Microfluidizer M-110EH, manufactured by Microfluidics, USA), and uniformly dispersed. This was filtered with a polyflon filter (trade name: PF-040, manufactured by Advantech Toyo Co., Ltd.) to prepare a lubricant dispersion.

  Thereafter, 70 parts of the hole transporting compound represented by the above formula (D), 35 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane and 35 parts of 1-propanol were added to the lubricant dispersion. Added to. And it filtered with the polyfluorone filter [Brand name: PF-020, Advantech Toyo Co., Ltd.], and prepared the coating liquid for surface layers.

  This surface layer coating solution was dip-coated on the charge transport layer, and the resulting coating film was dried at 50 ° C. for 5 minutes. After drying, the coating film was irradiated with an electron beam for 1.6 seconds under a nitrogen atmosphere while rotating an aluminum cylinder under conditions of an acceleration voltage of 70 kV and an absorbed dose of 8500 Gy to cure the coating film. Thereafter, heat treatment was performed for 3 minutes in a nitrogen atmosphere under conditions where the coating film became 120 ° C. Note that the oxygen concentration from the electron beam irradiation to the heat treatment for 3 minutes was 20 ppm. Next, in the atmosphere, a heat treatment was performed for 30 minutes under the condition that the coating film reached 100 ° C., thereby forming a surface layer having a film thickness of 5 μm.

The obtained electrophotographic photosensitive member had an elastic deformation rate value of 50% and a universal hardness (HU) value of 175 N / mm ² .

[Surface Layer Formation Example 4]
The hole transporting member used in Surface Layer Formation Example 1 was a hole transporting compound represented by the following formula (E). Otherwise, the surface layer was formed in the same manner as in Surface layer formation example 1.

The obtained electrophotographic photosensitive member had an elastic deformation rate of 55% and a universal hardness (HU) value of 185 N / mm ² .

[Surface Layer Formation Example 5]
The hole transporting member used in Surface Layer Formation Example 1 was a hole transporting compound represented by the following formula (F). Otherwise, the surface layer was formed in the same manner as in Surface layer formation example 1.

The obtained electrophotographic photosensitive member had an elastic deformation rate of 51% and a universal hardness (HU) value of 195 N / mm ² .

[Surface Layer Formation Example 6]
The hole transporting member used in Surface Layer Formation Example 1 was a hole transporting compound represented by the following formula (G). Otherwise, the surface layer was formed in the same manner as in Surface layer formation example 1.

The obtained electrophotographic photosensitive member had an elastic deformation rate of 55% and a universal hardness (HU) value of 175 N / mm ² .

[Surface shape formation example 1]
<Recess formation by mold press-fit shape transfer>
In the apparatus having the configuration shown in FIG. 4E, the shape transfer mold shown in FIG. 10A (major axis diameter D: 5.0 μm, interval E: 0.5 μm, height F: 2.0 μm). The cylindrical shape was installed and surface processing was performed. In FIG. 10A, 14-1 and 14-2 show the shapes of the mold viewed from above and from the side, respectively. The shape of the electrophotographic photosensitive member was rotated in the circumferential direction while controlling the temperature of the electrophotographic photosensitive member and the mold so that the surface temperature of the electrophotographic photosensitive member during processing was 110 ° C., and the shape was transferred. .

  The mold pressurization conditions were 2.7 MPa for surface layer formation example 1 and 3.0 MPa and 5.0 MPa for surface layer formation example 2.

<Observation of formed recesses>
The surface shape of the obtained electrophotographic photosensitive member was magnified and observed with a laser microscope (trade name: VK-9500, manufactured by Keyence Corporation). As a result, as shown in FIG. 10B, it is understood that cylindrical recesses having a major axis diameter D: 5.0 μm and a depth H: 1.0 μm are formed at an interval E: 0.5 μm. It was. In FIG. 10B, 15-1 shows the arrangement of the concave portions on the surface of the electrophotographic photosensitive member, and 15-2 shows the cross-sectional shape of the surface having the concave portions of the electrophotographic photosensitive member. The average major axis diameter, average depth, number and area ratio of the concave portions per 100 μm square were as shown in Table 2.

[Surface shape formation example 2]
<Recess formation by mold press-fit shape transfer>
The mold used in the surface shape formation example 1 is a shape transfer mold (major axis diameter D: 5.0 μm, interval E: 0.5 μm, height F: 2.0 μm) shown in FIG. Changed to column shape). Others were processed in the same manner as in Surface shape formation example 1. In FIG. 10C, 16-1 and 16-2 show the shapes of the mold viewed from above and from the lateral direction, respectively.

<Observation of formed recesses>
The surface shape of the obtained electrophotographic photosensitive member was magnified and observed with a laser microscope (trade name: VK-9500, manufactured by Keyence Corporation). As a result, as shown in FIG. 10D, it is understood that hexagonal columnar concave portions having a major axis diameter D of 5.0 μm and a depth H of 1.0 μm are formed at an interval E of 0.5 μm. It was. In FIG. 10D, 17-1 shows the arrangement state of the concave portions on the surface of the electrophotographic photosensitive member, and 17-2 shows the cross-sectional shape of the surface having the concave portions of the electrophotographic photosensitive member. The average major axis diameter, average depth, number and area ratio of the recesses per 100 μm square were as shown in Table 2.

[Surface shape formation example 3]
<Recess formation by mold press-fit shape transfer>
The mold used in the surface shape formation example 1 is a mold for shape transfer shown in FIG. 10E (the skirt major axis diameter D: 7.5 μm, the interval E: 0.5 μm, the height F: 2.0 μm). Changed to Yamagata shape). Others were processed in the same manner as in Surface shape formation example 1. In FIG. 10 (F), 19-1 and 19-2 show the shapes of the mold viewed from above and from the side, respectively.

<Observation of formed recesses>
The surface shape of the obtained electrophotographic photosensitive member was magnified and observed with a laser microscope (trade name: VK-9500, manufactured by Keyence Corporation). As a result, as shown in FIG. 10 (F), it is found that the concave portions having a chevron shape having a major axis diameter D: 7.5 μm and a depth H: 1.0 μm are formed at an interval E: 0.5 μm. It was. In FIG. 10F, 19-1 shows the arrangement of the concave portions on the surface of the electrophotographic photosensitive member, and 19-2 shows the cross-sectional shape of the surface having the concave portions of the electrophotographic photosensitive member. The average major axis diameter, average depth, number and area ratio of the recesses per 100 μm square were as shown in Table 2.

[Surface shape formation example 4]
In the surface shape formation example 2, the mold used was changed to a mold having a hexagonal column shape with a major axis diameter of 10.0 μm, an interval of 1.0 μm, and a height of 2.0 μm. Others were processed in the same manner as in Surface shape formation example 2. The results are shown in Table 2.

[Surface shape formation example 5]
<Recess formation by mold press-fit shape transfer>
The mold used in the surface shape formation example 1 is a mold for shape transfer shown in FIG. 11A (long axis diameter D: 8.0 μm, interval E: 1.0 μm, height F: 2.0 μm). Changed to a prismatic shape. Others were processed in the same manner as in Surface shape formation example 1. In FIG. 11A, 20-1 and 20-2 show the shapes of the mold as viewed from above and from the lateral direction, respectively.

<Observation of formed recesses>
The surface shape of the obtained electrophotographic photosensitive member was magnified and observed with a laser microscope (trade name: VK-9500, manufactured by Keyence Corporation). As a result, as shown in FIG. 11B, square columnar concave portions having a major axis diameter D of 8.0 μm and a depth H of 1.0 μm are formed at intervals E of 1.0 μm. all right. In FIG. 11B, reference numeral 21-1 denotes an arrangement state of the concave portions on the surface of the electrophotographic photosensitive member, and 21-2 denotes a cross-sectional shape of the surface having the concave portions of the electrophotographic photosensitive member. The average major axis diameter, average depth, number and area ratio of the recesses per 100 μm square were as shown in Table 2.

[Surface shape formation example 6]
<Recess formation by mold press-fit shape transfer>
The mold used in the surface shape formation example 1 is the shape transfer mold shown in FIG. 11C (major axis diameter D1: 6.0 μm, minor axis diameter D2: 3.0 μm, major axis side interval E1: 1. 0.0 μm, short axis side interval E2: 0.5 μm, height F: 2.0 μm elliptical column shape). Others were processed in the same manner as in Surface shape formation example 1. In FIG. 11C, 22-1 and 22-2 show the shapes of the mold viewed from above and from the lateral direction, respectively.

<Observation of formed recesses>
The surface shape of the obtained electrophotographic photosensitive member was magnified and observed with a laser microscope (trade name: VK-9500, manufactured by Keyence Corporation). As a result, as shown in FIG. 11 (D), the long axis diameter D1: 6.0 μm / short axis diameter D2: 3, 0 μm and the depth H: 1.0 μm of the elliptical columnar recesses are spaced apart from the long axis. E1: 1.0 μm / short axis side interval E2: It was found that the gap was formed at 0.5 μm interval. In FIG. 11D, reference numeral 23-1 denotes an arrangement state of the concave portions on the surface of the electrophotographic photosensitive member, and 23-2 denotes a cross-sectional shape of the surface having the concave portions of the electrophotographic photosensitive member. The average major axis diameter, average depth, number and area ratio of the recesses per 100 μm square were as shown in Table 2.

[Surface shape formation example 7]
In the surface shape formation example 5, the mold used was changed to a mold having a quadrangular prism shape with a major axis diameter: 12.0 μm, a spacing: 2.5 μm, and a height: 2.0 μm. The other processes were performed in the same manner as in the surface shape formation example 5. The results are shown in Table 2.

[Surface shape formation example 8]
In the surface shape formation example 5, the mold used was changed to a mold having a quadrangular prism shape with a major axis diameter: 14.0 μm, a spacing: 1.0 μm, and a height: 2.0 μm. The other processes were performed in the same manner as in the surface shape formation example 5. The results are shown in Table 2.

[Surface shape formation example 9]
In the surface shape formation example 1, the mold used was changed to a mold having a cylindrical shape with a major axis diameter of 4.0 μm, an interval of 1.0 μm, and a height of 2.0 μm. Others were processed in the same manner as in Surface shape formation example 1. The results are shown in Table 2.

[Surface shape formation example 10]
In the surface shape formation example 1, the mold used was changed to a mold having a cylindrical shape with a major axis diameter: 3.0 μm, an interval: 0.5 μm, and a height: 2.0 μm. Others were processed in the same manner as in Surface shape formation example 1. The results are shown in Table 2.

[Surface shape formation example 11]
In the surface shape formation example 1, the mold used was changed to a mold having a cylindrical shape with a major axis diameter of 10.0 μm, an interval of 1.0 μm, and a height of 2.0 μm. Others were processed in the same manner as in Surface shape formation example 1. The results are shown in Table 2.

[Surface shape formation example 12]
The mold used in the surface shape formation example 1 was changed to a mold having a cylindrical shape with a major axis diameter: 5.0 μm, an interval: 2.0 μm, and a height: 2.0 μm. Others were processed in the same manner as in Surface shape formation example 1. The results are shown in Table 2.

[Surface shape formation example 13]
<Concave formation by excimer laser>
A concave portion was formed on the outermost surface layer of the obtained electrophotographic photoreceptor using a KrF excimer laser (wavelength λ = 248 nm). At this time, as shown in FIG. 12A, a quartz glass mask having a pattern in which circular laser light transmitting portions b having a diameter of 30 μm are arranged at intervals of 10 μm was used. The irradiation energy of the excimer laser was 0.9 J / cm ² and the irradiation area per irradiation was 2 mm square. As shown in FIG. 4B, the electrophotographic photosensitive member was rotated, and irradiation was performed while shifting the irradiation position in the axial direction.

<Observation of formed recesses>
The surface shape of the obtained electrophotographic photosensitive member was magnified and observed with a laser microscope (trade name: VK-9500, manufactured by Keyence Corporation). As a result, as shown in FIG. 12B, cylindrical recesses having no major edge D: 8.6 μm and depth H: 0.9 μm are formed at intervals E: 2.9 μm. I found out.

  In FIG. 12B, reference numeral 25-1 denotes an arrangement state of the concave portions on the surface of the electrophotographic photosensitive member, and reference numeral 25-2 denotes a cross-sectional shape of the surface having the concave portions of the electrophotographic photosensitive member. In addition, Table 2 shows the average major axis diameter, average depth, number and area ratio of the concave portion per 100 μm square.

[Surface shape formation example 14]
In the surface shape formation example 13, the mask shown in FIG. 12A was changed to the mask shown in FIG. Moreover, the irradiation energy of the excimer laser was set to 1.2 J / cm ² . Otherwise, the electrophotographic photosensitive member was processed in the same manner as in Surface Shape Formation Example 13. The results are shown in Table 2.

[Surface shape formation example 15]
In the surface shape formation example 1, the mold used was a shape transfer mold shown in FIG. 13A (major axis diameter D1: 7.5 μm, major axis diameter D2: 2.5 μm, interval E: 1.0 μm). , Height F: a shape in which two types of cylinders of 2.0 μm are mixed). Others were processed in the same manner as in Surface shape formation example 1. In FIG. 13A, 27-1 and 27-2 show the shapes of the mold as viewed from above and from the lateral direction, respectively.

<Observation of formed recesses>
The surface shape of the obtained electrophotographic photosensitive member was magnified and observed with a laser microscope (trade name: VK-9500, manufactured by Keyence Corporation). As a result, as shown in FIG. 13B, it is understood that cylindrical recesses having a major axis diameter D1: 7.3 μm and a depth H: 1.0 μm are formed at an interval E: 1.0 μm. It was. Moreover, it turned out that the cylindrical recessed part of major axis diameter D2: 2.2micrometer and depth H: 1.0micrometer is formed in the ratio of one per four said cylindrical recessed parts. In FIG. 13B, 28-1 shows the arrangement of the concave portions on the surface of the electrophotographic photosensitive member, and 28-2 shows the cross-sectional shape of the surface having the concave portions of the electrophotographic photosensitive member. The average major axis diameter, average depth, number and area ratio of the recesses per 100 μm square were as shown in Table 2. Moreover, the ratio of the concave-shaped part whose major axis diameter is 3.0 μm or less was 46% by number.

[Surface shape formation example 16]
In the surface shape formation example 1, the mold used was a shape transfer mold shown in FIG. 13C (major axis diameter D1: 7.5 μm, major axis diameter D2: 2.5 μm, interval E: 1.0 μm). , Height F: a shape in which two types of cylinders of 2.0 μm are mixed). Others were processed in the same manner as in Surface shape formation example 1. In FIG. 13C, reference numerals 29-1 and 29-2 indicate shapes of the mold viewed from above and from the lateral direction, respectively.

<Observation of formed recesses>
The surface shape of the obtained electrophotographic photosensitive member was magnified and observed with a laser microscope (trade name: VK-9500, manufactured by Keyence Corporation). As a result, as shown in FIG. 13D, it is understood that cylindrical concave portions having a major axis diameter D1: 7.3 μm and a depth H: 1.0 μm are formed at an interval E: 1.0 μm. It was. Moreover, it turned out that the cylindrical recessed part of major axis diameter D2: 1.5micrometer and depth H: 1.0micrometer is formed in the ratio of two per four said cylindrical recessed parts. In FIG. 13D, 30-1 shows the arrangement of the concave portions on the surface of the electrophotographic photosensitive member, and 30-2 shows the cross-sectional shape of the surface having the concave portions of the electrophotographic photosensitive member. The average major axis diameter, average depth, number and area ratio of the recesses per 100 μm square were as shown in Table 2. Further, the ratio of the concave portion having a major axis diameter of 3.0 μm or less was 63% by number.

[Surface shape formation example 17]
In the surface shape formation example 12, the mold used was changed to a mold having a cylindrical shape with a major axis diameter: 5.0 μm, an interval: 2 μm, and a height: 3.0 μm. The pressurizing conditions of the mold were 3.2 MPa for the surface layer formation example 1, 3.5 MPa for the surface layer formation example 2, and 5.6 MPa for the surface layer formation example 3. Others were processed in the same manner as in the surface shape formation example 12. The results are shown in Table 2.

[Surface shape formation example 18]
In the surface shape formation example 17, the mold used was changed to a mold having a cylindrical shape with a major axis diameter: 5.0 μm, an interval: 2 μm, and a height: 4.0 μm. The pressing conditions of the mold were set to 3.8 MPa in the case of the surface layer formation example 1, 4.3 MPa in the case of the surface layer formation example 2, and 6.0 MPa in the case of the surface layer formation example 3. Others were processed in the same manner as in Surface shape formation example 17. The results are shown in Table 2.

[Surface shape formation example 19]
In the surface shape formation example 6, the mold used was (major axis diameter: 6.0 μm, minor axis diameter: 3.0 μm, major axis side spacing: 1.0 μm, minor axis side spacing: 0.5 μm, height: (3.0 μm elliptical column shape). The pressurizing conditions of the mold were 3.2 MPa for the surface layer formation example 1, 3.5 MPa for the surface layer formation example 2, and 5.6 MPa for the surface layer formation example 3. Others were processed in the same manner as in surface shape formation example 6. The results are shown in Table 2.

[Surface shape formation example 20]
In the surface shape formation example 19, the mold used was a major axis diameter D1: 6.0 μm, minor axis diameter D2: 3.0 μm, major axis side spacing: 1.0 μm, minor axis side spacing: 0.5 μm, height : Changed to a mold having an elliptical column shape of 4.0 μm. The mold pressing conditions were set to 3.8 MPa for surface layer formation example 1, 4.3 MPa for surface layer formation example 2, and 6.0 MPa for surface layer formation example 3. Others were processed in the same manner as in surface shape formation example 6. The results are shown in Table 2.

[Surface shape formation example 21]
In surface shape formation example 11, the mold used was changed to a mold having a cylindrical shape with a major axis diameter of 10.0 μm, a spacing of 1 μm, and a height of 3.0 μm. The pressurizing conditions of the mold were 3.2 MPa for the surface layer formation example 1, 3.5 MPa for the surface layer formation example 2, and 5.6 MPa for the surface layer formation example 3. Others were processed in the same manner as in the surface shape formation example 12. The results are shown in Table 2.

[Surface shape formation example 22]
In surface shape formation example 21, the mold used was changed to a mold having a cylindrical shape with a major axis diameter of 10.0 μm, a spacing of 1 μm, and a height of 5.0 μm. The pressing conditions of the mold were set to 3.8 MPa in the case of the surface layer formation example 1, 4.3 MPa in the case of the surface layer formation example 2, and 6.0 MPa in the case of the surface layer formation example 3. Others were processed in the same manner as in the surface shape formation example 12. The results are shown in Table 2.

[Surface shape formation example 23]
In the surface shape formation example 7, the mold used was changed to a mold having a rectangular column shape with a major axis diameter of 12.0 μm, a spacing of 2.5 μm, and a height of 3.0 μm. The pressurizing conditions of the mold were 3.2 MPa for the surface layer formation example 1, 3.5 MPa for the surface layer formation example 2, and 5.6 MPa for the surface layer formation example 3. Others were processed in the same manner as in Surface shape formation example 7. The results are shown in Table 2.

[Surface shape formation example 24]
In the surface shape formation example 23, the mold used was changed to a mold having a quadrangular prism shape with a major axis diameter of 12.0 μm, an interval of 2.5 μm, and a height of 4.0 μm. The pressing conditions of the mold were set to 3.8 MPa in the case of the surface layer formation example 1, 4.3 MPa in the case of the surface layer formation example 2, and 6.0 MPa in the case of the surface layer formation example 3. Others were processed in the same manner as in Surface shape formation example 7. The results are shown in Table 2.

[Surface shape formation example 25]
In surface shape formation example 3, the mold used was changed to a mold having a chevron shape with a hem major axis diameter: 7.5 μm, a spacing: 0.5 μm, and a height: 3.0 μm. The pressurizing conditions of the mold were 3.2 MPa for the surface layer formation example 1, 3.5 MPa for the surface layer formation example 2, and 5.6 MPa for the surface layer formation example 3. Others were processed in the same manner as in the surface shape formation example 3. The results are shown in Table 2.

[Surface shape formation example 26]
In the surface shape formation example 25, the mold used was changed to a mold having a chevron shape with a hem long axis diameter: 7.5 μm, a spacing: 0.5 μm, and a height: 4.0 μm. The pressing conditions of the mold were set to 3.8 MPa in the case of the surface layer formation example 1, 4.3 MPa in the case of the surface layer formation example 2, and 6.0 MPa in the case of the surface layer formation example 3. Others were processed in the same manner as in the surface shape formation example 3. The results are shown in Table 2.

[Surface shape formation example 27]
In the surface shape formation example 2, the mold used was changed to a hexagonal column shape having a major axis diameter of 5 μm, an interval of 0.5 μm, and a height of 3.0 μm. The pressurizing conditions of the mold were 3.2 MPa for the surface layer formation example 1, 3.5 MPa for the surface layer formation example 2, and 5.6 MPa for the surface layer formation example 3. Others were processed in the same manner as in Surface shape formation example 2. The results are shown in Table 2.

[Surface shape formation example 28]
In the surface shape formation example 27, the mold used was changed to a mold having a hexagonal column shape with a major axis diameter: 5 μm, a spacing: 0.5 μm, and a height: 4.0 μm. The pressing conditions of the mold were set to 3.8 MPa in the case of the surface layer formation example 1, 4.3 MPa in the case of the surface layer formation example 2, and 6.0 MPa in the case of the surface layer formation example 3. Others were processed in the same manner as in the surface shape formation example 27. The results are shown in Table 2.

[Surface shape formation example 29]
As in surface shape formation example 13, concave portions were formed on the surface layer of the electrophotographic photosensitive member using a KrF excimer laser (wavelength λ = 248 nm). At this time, as shown in FIG. 12D, a quartz glass mask having a pattern in which circular laser light transmitting portions b having a diameter of 30 μm are arranged at intervals of 10 μm was used. The excimer laser irradiation energy was 0.9 J / cm ^2, and the irradiation area per irradiation was 1.4 mm square. As shown in FIG. 4B, the electrophotographic photosensitive member was rotated, and irradiation was performed while shifting the irradiation position in the axial direction.

<Observation of formed protrusions>
The surface shape of the electrophotographic photosensitive member was magnified and observed with a laser microscope (trade name: VK-9500, manufactured by Keyence Corporation). As shown in FIG. 14A, columnar convex portions having an average diameter Lpc of the convex portions of 5.6 μm are formed at intervals of 2.8 μm. B in FIG. 10B is a cross-sectional view taken along line 15B of A in FIG.

The average value of the height Ldv of the convex portion was 1.0 μm. Further, the average value of the convex shape intervals T was 8.0 μm, and the standard deviation Tσ was 0.4 μm. Further, the number of convex portions per 10,000 μm ² was 156, and Smr was 38%.

[Surface shape formation example 30]
As in surface shape formation example 1, in the apparatus having the configuration shown in FIG. 4E, the shape transfer molds shown in FIGS. 14A and 14B were installed to perform surface processing. 14A shows the shape of the mold viewed from above, and FIG. 14B shows the shape of the mold viewed from the lateral direction. Moreover, D, E, and F represent the longest diameter, space | interval, and height of a recessed part, respectively.

<Observation of formed protrusions>
When the surface shape of the obtained electrophotographic photosensitive member was enlarged and observed with a laser microscope (trade name: VK-9500, manufactured by Keyence Corporation), as shown in FIGS. 14C and 14D, Lpc: 1 It was found that a recess having a thickness of 0.4 μm and a depth Ldv of 1.0 μm was formed. In FIG. 14, (C) shows the arrangement state of the Scut plane. Further, (D) shows that the surface shape data of 100 μm ² used for the calculation of the Scut of the electrophotographic photosensitive member in the normal direction of the Scut plane is divided into 10 in the direction orthogonal to the rotation direction of the electrophotographic photosensitive member. The cross-sectional shape of the surface which has the contour curve data convex part with respect to the height direction in a position is shown. The results are shown in Table 3.

[Surface shape formation example 31]
In the surface shape formation example 30, the excimer laser irradiation energy was 1.8 J / cm ² . Others were processed in the same manner as in the surface shape formation example 30. The results are shown in Table 3.

[Surface shape formation example 32]
In the surface shape formation example 30, the mold was changed to the mold shown in FIGS. 14E and 14F. Otherwise, the same processing as in the surface shape formation example 30 was performed. The results are shown in Table 3.

[Surface shape formation example 33]
The electrophotographic photosensitive member was installed in the surface shape processing apparatus shown in FIG. The pressurizing member was made of stainless steel (SUS), and a heater for heating was installed inside. The mold has a shape as shown in FIG. 15A, with a convex width X: 1.0 μm, a concave width Y: 1.0 μm, and a convex height Z: 2.0 μm. A nickel mold having a thickness of 50 μm was used. Then, the mold was fixed on the pressure member so that the concave portion of the mold was at an angle of 90 ° with respect to the axial direction of the electrophotographic photosensitive member to be transferred. A cylindrical SUS holding member having a diameter substantially the same as the inner diameter of the support was inserted into the support of the electrophotographic photosensitive member to be transferred. Using the apparatus configured as described above, a flat portion-groove portion shape is formed on the peripheral surface of the electrophotographic photosensitive member to be shape-transferred under the conditions of a mold temperature of 140 ° C., a processing pressure of 10 MPa, and a processing speed of 20 mm / s. It was.

<Observation of formed flat end-groove shape>
The peripheral surface of the electrophotographic photosensitive member was enlarged and observed with a laser microscope (trade name: VK-9500, manufactured by Keyence Corporation). As a result, a flat portion-groove portion shape having a flat portion width e of 1.0 μm, a groove portion width w of 1.0 μm, and a groove portion depth d of 1.0 μm is formed on the peripheral surface of the electrophotographic photosensitive member in FIG. I found out. Further, it was found that the flat portion and the groove portion were formed so as to form an angle of 90 ° with respect to the axial direction of the electrophotographic photosensitive member. Further, the average value eAv of the flat portion, its standard deviation eσ, the average value wAv of the groove portion, its standard deviation wσ, the average value of the depth of the groove portion: dAv, its standard deviation dσ, and the electrophotographic photosensitive member The total value eSum of the width e of the flat portion per 100 μm width in the axial direction of the peripheral surface was calculated as described above. The results are shown in Table 4.

[Surface shape formation examples 34 to 41]
In the surface shape formation example 33, the mold was changed to the shape shown in Table 5. Otherwise, the surface shape formation examples 33 to 41 were produced in the same manner as the surface shape formation example 33. Table 4 shows the results of observation of the peripheral surfaces.

[Surface shape formation examples 42 to 43]
In the surface shape formation example 33, the mold during shape transfer is placed on the pressure member so that the concave portions of the mold are at angles of 80 ° and 100 ° with respect to the axial direction of the electrophotographic photosensitive member to be shape transferred. Fixed to. Otherwise, the surface shape formation examples 42 to 43 were produced in the same manner as the surface shape formation example 33. Table 4 shows the results of observation of the peripheral surfaces.

[Surface shape formation examples 44 to 46]
In the surface shape formation example 33, the mold was changed to the shape shown in FIG. Otherwise, surface shape formation examples 44 to 46 were made in the same manner as surface shape formation example 33. Table 4 shows the results of observation of the peripheral surfaces.

[Surface shape formation examples 47 to 48]
In the surface shape formation example 33, the mold was changed to the shape shown in FIG. Otherwise, surface shape formation examples 47 to 48 were produced in the same manner as surface shape formation example 33. Table 4 shows the results of observation of the peripheral surfaces.

[Surface shape formation examples 49 to 50]
In the surface shape formation example 33, the mold was changed to the shape shown in FIG. Otherwise, the surface shape formation examples 49 to 50 were produced in the same manner as the surface shape formation example 33. Table 4 shows the results of observation of the peripheral surfaces.

[Surface shape formation example 51]
In the surface shape formation example 33, the mold was changed to the shape shown in FIG. Otherwise, surface shape formation example 51 was made in the same manner as surface shape formation example 33. Table 4 shows the results of observation of the peripheral surfaces.

[Surface shape formation example 52]
In the surface shape formation example 33, the mold was changed to the shape shown in FIG. Otherwise, the surface shape formation example 52 was produced in the same manner as the surface shape formation example 33. Table 4 shows the results of observation of the peripheral surfaces.

[Electrophotographic photoconductor preparation example]
The electrophotographic photosensitive member was combined with the formation example of each layer to obtain an electrophotographic photosensitive member. Specifically, electrophotographic photoreceptors were produced according to electrophotographic photoreceptor preparation examples 1 to 60 shown in Table 6.

[Evaluation Example 1]
The electrophotographic photosensitive member produced in the above production example is mounted on a remodeling machine of a full-color copying machine (trade name: image RUNNER ADVANCE C5255, manufactured by Canon Inc.) in an environment of a temperature of 23 ° C. and a humidity of 50% RH. The surface potential was measured as follows.

  The surface potential was measured by modifying the black process cartridge of the color copying machine and removing the cleaning blade.

  The black developer was modified, and a potential probe (trade name: model6000B-8, manufactured by Trek Japan Co., Ltd.) was attached to the development position. Further, the potential of the central portion of the electrophotographic photosensitive member was measured using a surface potentiometer (model 344: manufactured by Trek Japan Co., Ltd.).

  As for the surface potential of the electrophotographic photosensitive member, the output condition of the charging means and the amount of light for image exposure were adjusted so that the initial dark portion potential (Vd) was −700 v and the initial bright portion potential (Vl) was −200 v.

  Thereafter, repeated use corresponding to 1000 sheets was carried out under the above charging conditions and exposure conditions, and the difference between the bright part potential (Vlt) after the repeated use and the initial bright part potential (Vl) was set as ΔVl and evaluated. .

ΔVl = light portion potential after repeated use (Vlt) −initial light portion potential (Vl)
The above ΔVl was also measured after outputting 300,000 images as described below.

[Evaluation Example 2]
An electrophotographic photosensitive member was mounted on the black station of the full-color copying machine (trade name: image RUNNER ADVANCE C5255, manufactured by Canon Inc.). Then, 300,000 full-color images (images with a color printing rate of 5%) were output on A4 size plain paper. Then, the streak image generated in the circumferential direction that seems to be caused by the defective cleaning was evaluated as follows.

A: No streak image is generated. B: A slight white image is generated, and a halftone image is not generated.
C: Both solid white image and halftone image are generated.

[Evaluation Example 3]
The film thickness of the surface layer of the electrophotographic photosensitive member produced in the above production example was measured with a light interference film thickness meter (trade name: MCPD-9800, manufactured by Otsuka Electronics Co., Ltd.). The film thickness of the surface layer of the electrophotographic photosensitive member after the image output in Evaluation Example 2 was measured, and the difference was taken as the amount of abrasion of the surface layer.

"Examples 1 to 62"
The electrophotographic photoreceptors produced in the electrophotographic photoreceptor preparation examples 1 to 62 were evaluated in evaluation examples 1 to 3. The results are shown in Table 7.

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Cleaning means 8 Fixing means 9 Process cartridge 10 Guide means 13-1 Electrophotographic photoreceptor 13-2 Mold 13-3 Pressure member 13- 4 Support members

Claims (3)

In an electrophotographic photosensitive member having a support, an undercoat layer formed on the support, and a photosensitive layer formed on the undercoat layer,
The undercoat layer contains a polymer of a composition containing a compound represented by the following formula (1),

(In formula (1), R ^{101 to} R ¹⁰⁶ are each independently a monovalent group represented by the following formula (A), a hydrogen atom, a cyano group, a nitro group, a halogen atom, an alkoxycarbonyl group, substituted or unsubstituted A substituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, wherein one of the carbon atoms in the main chain of the alkyl group is an oxygen atom, a sulfur atom, or- The divalent group represented by (N—R ²⁰¹ ) — may be substituted, R ²⁰¹ represents a hydrogen atom or an alkyl group, and at least one of R ^{101 to} R ¹⁰⁶ is represented by the following formula (A ) Is a monovalent group.
The substituent of the substituted alkyl group is a group selected from the group consisting of an alkyl group, an aryl group, an alkoxycarbonyl group, and a halogen atom.
The substituent of the substituted aryl group is a group selected from the group consisting of a halogen atom, a nitro group, a cyano group, an alkyl group, and a halogenated alkyl group. )

(In the formula (A), at least one of α, β and γ is a group having a substituent, and the substituent is at least selected from the group consisting of a hydroxy group, a thiol group, an amino group and a carboxy group. One kind of group.
l and m are each independently 0 or 1.
α is an alkylene group having 1 to 6 atoms in the main chain, an alkylene group having 1 to 6 carbon atoms substituted with an alkyl group having 1 to 6 carbon atoms, and a benzyl group. Of the main chain substituted with an alkylene group having 1 to 6 atoms in the main chain, an alkylene group having 1 to 6 atoms in the main chain substituted with an alkoxycarbonyl group, or a phenyl group An alkylene group having a number of 1 or more and 6 or less is shown. These groups may have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxy group as a substituent. One of the carbon atoms in the main chain of the alkylene group may be replaced with an oxygen atom, a sulfur atom, or a divalent group represented by — (N—R ³⁰¹ ) —. R ³⁰¹ represents a hydrogen atom or an alkyl group.
β represents a phenylene group, an alkyl-substituted phenylene group having 1 to 6 carbon atoms, a nitro-substituted phenylene group, a halogenated phenylene group, or an alkoxy-substituted phenylene group. These groups may have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxy group as a substituent.
γ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms in the main chain substituted with an alkyl group having 1 to 6 carbon atoms. . These groups may have at least one group selected from the group consisting of a hydroxy group, a thiol group, an amino group, and a carboxy group as a substituent. One of the carbon atoms in the main chain of the alkyl group may be replaced with a divalent group represented by-(N-R ⁴⁰¹ )-. R ⁴⁰¹ represents an alkyl group. )
The surface layer of the electrophotographic photoreceptor contains a resin obtained by curing by irradiating a hole transporting compound having an acryloyloxy group or a methacryloyloxy group with radiation,
The surface of the electrophotographic photoreceptor satisfies any of the following:
(I) A plurality of recesses and portions other than the recesses are formed on the surface of the electrophotographic photosensitive member.
(Ii) A plurality of convex portions and portions other than the convex portions are formed on the surface of the electrophotographic photosensitive member.
(Iii) A plurality of flat portions and groove portions are alternately formed on the surface of the electrophotographic photosensitive member.
An electrophotographic photosensitive member characterized by the above.   The electrophotographic photosensitive member according to claim 1 and at least one means selected from the group consisting of a charging means, a developing means, a transfer means and a cleaning means are integrally supported, and are detachable from the main body of the electrophotographic apparatus. A process cartridge.   An electrophotographic apparatus comprising: the electrophotographic photosensitive member according to claim 1; and a charging unit, an exposure unit, a developing unit, and a transfer unit.

Images