JP2017142336A - Electrophotographic photoreceptor, method for producing the same, process cartridge, and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress an image failure caused by the surface degradation of an electrophotographic photoreceptor or scratches occurring thereon.SOLUTION: A surface layer of an electrophotographic photoreceptor has a cured product of a composition comprising a specific hole transporting compound, a compound that does not have a hole transport property, a polycarbonate resin, and a specific silicone compound or fluorine compound.SELECTED DRAWING: None

Description

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

In order to improve the electrical characteristics, durability, and image quality of an electrophotographic photosensitive member containing an organic photoconductive substance, techniques for improving the surface material and physical properties of the electrophotographic photosensitive member have been studied.
Patent Document 1 discloses an electrophotographic photosensitive member that defines an infrared absorption spectrum peak intensity in a surface layer composed of a charge transport material having a polymerizable functional group and a cured product of polycarbonate, and suppresses deterioration in image quality after repeated use. Have been described.
Patent Document 2 describes an electrophotographic photoreceptor in which the peak area of the infrared spectral reflection spectrum in the surface layer is defined and the electrical characteristics and scratch resistance are improved.

JP 2011-164400 A JP 2014-191118 A

  In recent years, an electrophotographic apparatus is required to improve the wear resistance of an electrophotographic photosensitive member and to improve the image quality. Especially in color electrophotographic devices, the surface layer of the electrophotographic photosensitive member deteriorates as a result of repeated use. As a result, the lubricity decreases due to the discharge products and moisture adsorbed on the surface of the electrophotographic photosensitive member in a high humidity environment. Sometimes. As a result, there is a problem that the state of the cleaning blade becomes unstable and streaky image defects occur. Another problem is the occurrence of image defects due to scratches generated on the electrophotographic photosensitive member due to repeated use. As a result of the study by the present inventors, the electrophotographic photosensitive member described in Patent Document 1 or 2 may cause the above-described image defect and has room for improvement.

  An object of the present invention is to provide an electrophotographic photosensitive member that suppresses the above-mentioned image defects and a method for manufacturing the same. Furthermore, another object is to provide an electrophotographic apparatus and a process cartridge having an electrophotographic photosensitive member.

The present invention is an electrophotographic photoreceptor having a support and a photosensitive layer in this order, and the surface layer of the electrophotographic photoreceptor is
(Α) a hole transporting compound having an acryloyloxy group or a methacryloyloxy group and containing no fluorine atom or silicon atom,
(Β) a compound having 2 or more and 4 or less acryloyloxy group or methacryloyloxy group and not containing a fluorine atom and a silicon atom and having no hole transporting skeleton,
(Γ) a bisphenol Z-type or A-type or C-type polycarbonate resin; and And a cured product of a composition containing a fluorine compound having no hole transporting skeleton, and the content of (γ) in the composition is (α) and (β) in the composition 1% by mass to 4% by mass with respect to the total amount, and the total content of (α) and (β) in the composition is 60% by mass or more. About.

Further, the present invention is a method for producing an electrophotographic photosensitive member having a support and a surface layer in this order, the production method comprising:
(Α) a hole transporting compound having an acryloyloxy group or a methacryloyloxy group and containing no fluorine atom or silicon atom,
(Β) a compound having 2 or more and 4 or less acryloyloxy group or methacryloyloxy group and not containing a fluorine atom and a silicon atom and having no hole transporting skeleton,
(Γ) Bisphenol Z type or A type or C type polycarbonate resin,
(Δ) a silicone compound having an acryloyloxy group or a methacryloyloxy group and not having a hole transporting skeleton, or a fluorine compound having an acryloyloxy group or a methacryloyloxy group and not having a hole transporting skeleton, and ε) The content of (γ) with respect to the total solid content in the coating liquid containing the solvent is 1% by mass to 4% by mass with respect to the total amount of (α) and (β) with respect to the total solid content in the coating liquid. And a step of preparing a coating solution for the surface layer in which the total content of (α) and (β) with respect to the total solid content in the coating solution is 60% by mass or more, and the coating solution for the surface layer The present invention relates to a method for producing an electrophotographic photoreceptor, comprising a step of forming a coating film and forming a surface layer by curing the coating film.

  Further, the present invention integrally supports the electrophotographic photosensitive member and at least one means selected from the group consisting of a charging means, a developing means, a transfer means, and a cleaning means, and is detachable from the main body of the electrophotographic apparatus. The present invention relates to a process cartridge.

  The present invention also relates to the electrophotographic photosensitive member, and an electrophotographic apparatus having a charging unit, an exposing unit, a developing unit, and a transfer unit.

According to the present invention, it is possible to provide an electrophotographic photosensitive member that has high scratch resistance and high durability, and suppresses image defects due to insufficient lubricity of the surface of the electrophotographic photosensitive member due to deterioration of the surface layer.
Further, according to the present invention, an electrophotographic apparatus and a process cartridge having the electrophotographic photosensitive member can be provided.

1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having an electrophotographic photosensitive member. It is a figure for demonstrating the layer structure of an electrophotographic photoreceptor. It is a figure which shows the example of the press-contact shape transfer processing apparatus for forming a concave shape part in the surface of an electrophotographic photoreceptor. It is the top view and sectional drawing which show the mold used by the Example and the comparative example.

The electrophotographic photoreceptor of the present invention has a support and a photosensitive layer. This electrophotographic photoreceptor is
(Α) a hole transporting compound having an acryloyloxy group or a methacryloyloxy group and containing no fluorine atom or silicon atom,
(Β) a compound having 2 or more and 4 or less acryloyloxy group or methacryloyloxy group and not containing a fluorine atom and a silicon atom and having no hole transporting skeleton,
(Γ) a bisphenol Z-type or A-type or C-type polycarbonate resin, and (δ) a silicone compound having an acryloyloxy group or a methacryloyloxy group and not having a hole transporting skeleton, or an acryloyloxy group or a methacryloyloxy group And a cured product of a composition containing a fluorine compound having no hole transporting skeleton, and the content of (γ) in the composition is (α) and (β) in the composition It is characterized by having a surface layer that is 1% by mass or more and 4% by mass or less with respect to the total amount, and that the total content of (α) and (β) in the composition is 60% by mass or more. .

The present inventors speculate about the mechanism of action that can suppress image defects due to insufficient lubricity due to deterioration of the surface of the electrophotographic photosensitive member by having the above-described characteristics, and having high scratch resistance and high durability as follows. doing.
A surface layer containing a cured product of a hole transport material having a chain polymerizable functional group has high wear resistance, but due to its high wear resistance, streak-like image defects are likely to occur during repeated use. . The occurrence of streak-like image defects is caused by the electrophotographic process in which the surface of the electrophotographic photosensitive member is chemically deteriorated to form a hydrophilic group, and the discharge product and moisture are adsorbed there, thereby causing the surface of the photosensitive member to be lubricated. It is speculated that the lowering causes the cleaning blade to become unstable.

  As a result of the study by the present inventors, by containing the compound of (β) (γ) in the above optimal range, a surface layer having a high structural strength against structural deterioration is obtained, and a photoreceptor upon repeated use. It is presumed that the deterioration of surface lubricity and the occurrence of scratches are suppressed, and as a result, image defects are also suppressed.

  Furthermore, the presence of the compound (δ) improves the affinity of the compounds (α) (β) and (γ), and the (α) (β) (γ) exists uniformly within the film. And it is estimated that the image defect can be suppressed.

When the content of (γ) is less than 1% by mass with respect to the total amount of (α) and (β) in the composition, the surface of the photoreceptor is deteriorated by an electrophotographic process, and the streak image is generated. End up.
Further, if the content of (γ) exceeds 4% by mass with respect to the total amount of (α) and (β) in the composition, scratches occur on the surface of the photoconductor during repeated use and image defects occur. . Similarly, when the total content of (α) and (β) is less than 60% by mass, image defects due to scratches on the surface of the photoreceptor during repeated use occur.

  In the present invention, the content of (δ) in the composition is preferably 1% by mass or more and 5% by mass or less. Within this range, the affinity of each of the compounds (α), (β), and (γ) is improved, and the polycarbonate of (γ) can be uniformly present in the surface layer. Effectively, the streak-like image defects are further suppressed.

  The weight average molecular weight of (δ) is preferably 300 or more and 10,000 or less. Within this range, (δ) is stably present on the surface of the electrophotographic photosensitive member, and the image defect suppression effect is further sustained.

  Furthermore, when the number of functional groups of (α) is F1 and the molecular weight is M1, F1 / M1 is 0.002 to 0.006, the number of functional groups of (β) is F2, and the molecular weight is M2. F2 / M2 is preferably 0.004 to 0.010. As a result, durability is ensured and the optimum number of functional groups in one molecule is determined, so that both high durability and image defect suppression can be achieved.

  The silicone compound is preferably a siloxane-modified acrylic compound. Thereby, the lubricity and maintainability of the surface of the electrophotographic photosensitive member are further improved, and streaky image defects are suppressed.

（Ｒ^１は、水素原子またはメチル基である。Ｒ^２は、炭素数が７以上の直鎖あるいは分岐した無置換のアルキル基である。）
このことにより、更に電子写真感光体表面の潤滑性とその維持性が向上し、スジ状の画像不良が抑制される。 The surface layer preferably further contains a cured product of a composition containing a compound represented by the formula (I).

(R ¹ is a hydrogen atom or a methyl group. R ² is a linear or branched unsubstituted alkyl group having 7 or more carbon atoms.)
This further improves the lubricity and maintainability of the electrophotographic photosensitive member surface and suppresses streak-like image defects.

（式（II）中、Ｐ^１は、下記式（III）または（IV）で示される基である。Ａ、Ｐ^１ともに、フッ素原子およびケイ素原子を含まない。
ａは１以上４以下の整数であり、ａ個のＰ^１は同一であっても異なっていてもよい。Ａは正孔輸送性基を示し、該ＡのＰ^１との結合部位を水素原子に置き換えた水素付加物は、下記式（Ｖ）、または下記式（VI）で示される化合物である。

（式（Ｖ）中、Ｒ^１１、Ｒ^１２及びＲ^１３は、フェニル基、または置換基として炭素数１以上６以下のアルキル基を有するフェニル基を示す。また、Ｒ^１１、Ｒ^１２及びＲ^１３はそれぞれ同一であっても異なっていてもよい。）

（式（VI）中、Ｒ^２１、Ｒ^２２、Ｒ^２３及びＲ^２４は、フェニル基、または置換基として炭素数１以上６以下のアルキル基を有するフェニル基を示す。また、Ｒ^２１、Ｒ^２２、Ｒ^２３及びＲ^２４はそれぞれ同一であっても異なっていてもよい。） The hole transporting compound represented by the above (α) is preferably a compound represented by the following formula (II).

(In Formula (II), P ¹ is a group represented by the following Formula (III) or (IV). Both A and P ¹ do not contain a fluorine atom or a silicon atom.
a is an integer of 1 or more and 4 or less, and a P ¹ may be the same or different. A represents a hole transporting group, and the hydrogen adduct obtained by replacing the bonding site of P with P ¹ with a hydrogen atom is a compound represented by the following formula (V) or the following formula (VI).

(In the formula (V), R ¹¹ , R ¹² and R ¹³ represent a phenyl group or a phenyl group having an alkyl group having 1 to 6 carbon atoms as a substituent. R ¹¹ , R ¹² and R ¹³ May be the same or different.)

(In formula (VI), R ²¹ , R ²² , R ²³ and R ²⁴ represent a phenyl group or a phenyl group having an alkyl group having 1 to 6 carbon atoms as a substituent. Also, R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different.)

Specific examples (exemplary compounds) of the hole transporting compound represented by (α) are shown below.

  Examples of the compound represented by (β) include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, and trimethylolpropane. Examples include acrylate, trimethylolpropane methacrylate, and ditrimethylolpropane tetraacrylate.

  The polycarbonate resin represented by (γ) is a polycarbonate resin obtained from a bisphenol Z-type, A-type or C-type structure.

  Examples of the compound represented by (δ) include a compound having an acrylic main chain or a methacryl main chain and having a siloxane structure or an alkyl fluoride structure in the side chain.

The surface layer in the electrophotographic photoreceptor is
(Α) a hole transporting compound having an acryloyloxy group or a methacryloyloxy group and containing no fluorine atom or silicon atom,
(Β) a compound having 2 or more and 4 or less acryloyloxy group or methacryloyloxy group and not containing a fluorine atom and a silicon atom and having no hole transporting skeleton,
(Γ) Bisphenol Z type or A type or C type polycarbonate resin,
(Δ) a silicone compound having an acryloyloxy group or a methacryloyloxy group and not having a hole transporting skeleton, or a fluorine compound having an acryloyloxy group or a methacryloyloxy group and not having a hole transporting skeleton, and (ε ) It can be formed by preparing a coating solution for the surface layer containing a solvent, forming a coating film of the coating solution for the surface layer, and curing the coating film.

  Here, the content of (γ) with respect to the total solid content in the coating solution is 1% by mass or more and 4% by mass or less with respect to the total amount of (α) and (β) with respect to the total solid content in the coating solution. In addition, the total content of (α) and (β) with respect to the total solid content in the coating solution is preferably 60% by mass or more.

  Furthermore, the content of (δ) with respect to the total solid content in the coating solution is preferably 1% by mass or more and 5% by mass or less. Within this range, the affinity of each of the compounds (α), (β), and (γ) is improved, and the polycarbonate of (γ) can be uniformly present in the surface layer. Effectively, the streak-like image defects are further suppressed. When the surface layer contains a cured product of a composition containing a siloxane-modified acrylic compound or a compound of formula (I), a coating solution for forming a surface layer containing a siloxane-modified acrylic compound or a compound of formula (I) is used. Good. Moreover, the coating liquid for surface layer formation may contain various additives. Among these, it is preferable to add a urea compound for the purpose of preventing deterioration due to an oxidizing gas.

  When the surface layer is a protective layer, the film thickness is preferably 0.1 μm or more and 15 μm or less. Further, it is more preferably 0.5 μm or more and 10 μm or less.

  Examples of the solvent used for preparing the coating solution for the surface layer include alcohol solvents such as methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, and 1-methoxy-2-propanol.

  Examples of means for curing the coating film of the surface layer coating solution include a method of curing with heat, ultraviolet rays, or an electron beam. In order to maintain the strength of the surface layer and the durability of the electrophotographic photosensitive member, it is preferably cured using ultraviolet rays or an electron beam.

  When the compound represented by (α) (β) is polymerized using an electron beam, a very dense (high density) cured product (three-dimensional cross-linked structure) is obtained, and a surface layer having higher durability is obtained. Since it is obtained, it is preferable. 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.

  When an electron beam is used, the acceleration voltage of the electron beam is preferably 120 kV or less from the viewpoint of suppressing material property deterioration due to the electron beam without impairing the polymerization efficiency. Further, the electron beam absorbed dose on the surface of the coating film of the surface layer coating solution is preferably 5 kGy or more and 50 kGy or less, and more preferably 1 kGy or more and 10 kGy or less.

  In addition, when the above composition is cured (polymerized) using an electron beam, it may be heated in an inert gas atmosphere after being irradiated with an electron beam in an inert gas atmosphere for the purpose of suppressing the polymerization inhibitory action by oxygen. preferable. Examples of the inert gas include nitrogen, argon, and helium.

  In addition, it is preferable to heat the electrophotographic photoreceptor to 140 ° C. or more and 170 ° C. or less after irradiation with ultraviolet rays or electron beams. By doing so, a surface layer having higher durability and suppressing image defects can be obtained.

  In order to further stabilize the behavior of the cleaning blade brought into contact with the electrophotographic photosensitive member, it is more preferable to provide a concave or convex portion on the surface layer of the electrophotographic photosensitive member.

  The concave portion or the convex portion may be formed on the entire surface of the electrophotographic photosensitive member, or may be formed on a part of the surface of the electrophotographic photosensitive member. When the concave portion or the convex portion is formed on a part of the surface of the electrophotographic photosensitive member, it is preferable that the concave portion or the convex portion is formed at least over the entire contact area with the cleaning blade. .

  When forming a concave-shaped portion, a concave-shaped portion is formed on the surface of the electrophotographic photosensitive member by pressing a mold having a convex portion corresponding to the concave portion to the surface of the electrophotographic photosensitive member and performing shape transfer. Can do.

FIG. 3 shows an example of a pressure contact shape transfer processing apparatus for forming a concave portion on the surface of the electrophotographic photosensitive member.
According to the press-contact shape transfer processing apparatus shown in FIG. 3, while rotating the electrophotographic photosensitive member 51, which is a workpiece, the mold 52 is continuously brought into contact with the surface (circumferential surface) and pressurized, A concave portion or a flat portion can be formed on the surface of the photoconductor 51.

  Examples of the material of the pressing member 53 include metals, metal oxides, plastics, and glass. Among these, stainless steel (SUS) is preferable from the viewpoint of mechanical strength, dimensional accuracy, and durability. The pressure member 53 is provided with a mold 52 on its upper surface. Further, the mold 52 is brought into contact with the surface of the electrophotographic photosensitive member 51 supported by the support member 54 with a predetermined pressure by a support member (not shown) and a pressure system (not shown) installed on the lower surface side. Can do. Further, the support member 54 may be pressed against the pressure member 53 with a predetermined pressure, or the support member 54 and the pressure member 53 may be pressed against each other.

  In the example shown in FIG. 3, the surface of the electrophotographic photosensitive member 51 is continuously processed while being driven or driven and rotated by moving the pressing member 53 in a direction perpendicular to the axial direction of the electrophotographic photosensitive member 51. This is an example. Further, by fixing the pressure member 53 and moving the support member 54 in a direction perpendicular to the axial direction of the electrophotographic photosensitive member 51, or by moving both the support member 54 and the pressure member 53, The surface of the electrophotographic photoreceptor 51 can also be processed continuously.

  Note that it is preferable to heat the mold 52 and the electrophotographic photosensitive member 51 from the viewpoint of efficiently performing shape transfer.

  As the mold 52, for example, a metal or resin film having a fine surface processed, a silicon wafer or the like patterned with a resist, a resin film in which fine particles are dispersed, or a resin film having a fine surface shape is made of metal. The thing which gave coating etc. is mentioned.

  From the viewpoint of making the pressure pressed against the electrophotographic photoreceptor 51 uniform, it is preferable to install an elastic body between the mold 52 and the pressure member 53.

Next, the overall configuration of the electrophotographic photoreceptor of the present invention will be described.
[Electrophotographic photoreceptor]
The electrophotographic photosensitive member of the present invention has a support and a photosensitive layer formed on the support. The photosensitive layer includes a single-layer type photosensitive layer containing both a charge generating substance and a charge transporting substance, and a laminated photosensitive layer separated into a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance. Can be mentioned. In the present invention, a laminated photosensitive layer is preferred.

  FIG. 2 is a diagram showing an example of the layer structure of the electrophotographic photosensitive member. In FIG. 2, the electrophotographic photosensitive member includes a support 21, an undercoat layer 22, a charge generation layer 23, a charge transport layer 24, and a protective layer 25. In this case, the charge generation layer 23 and the charge transport layer 24 constitute a photosensitive layer, and the protective layer 25 is a surface layer. Further, when no protective layer is provided, the charge transport layer 24 is a surface layer. In the present invention, the protective layer provided on the charge transport layer is preferably a surface layer.

And as mentioned above, the surface layer is
(Α) a hole transporting compound having an acryloyloxy group or a methacryloyloxy group and containing no fluorine atom or silicon atom,
(Β) a compound having 2 or more and 4 or less acryloyloxy group or methacryloyloxy group and not containing a fluorine atom and a silicon atom and having no hole transporting skeleton,
(Γ) a bisphenol Z-type or A-type or C-type polycarbonate resin, and (δ) a silicone compound having an acryloyloxy group or a methacryloyloxy group and not having a hole transporting skeleton, or an acryloyloxy group or a methacryloyloxy group And a cured product of a composition containing a fluorine compound having no hole transporting skeleton.

The electrophotographic photoreceptor of the present invention will be further described.
[Support]
As the support used in the electrophotographic photosensitive member, a conductive one (conductive support) is preferable. For example, a support made of metal or alloy such as iron, copper, gold, silver, aluminum, zinc, titanium, lead, nickel, tin, antimony, indium, chromium, aluminum alloy, stainless steel, and the like can be given. In addition, a metal support or a resin support having a film formed by vacuum deposition of aluminum, an aluminum alloy, an indium oxide-tin oxide alloy, or the like can also be used. Further, a support formed by impregnating a resin with conductive particles such as carbon black, tin oxide particles, titanium oxide particles, and silver particles, or a support containing a conductive resin can also be used. Examples of the shape of the support include a cylindrical shape, a belt shape, a sheet shape, and a plate shape. In the present invention, a cylindrical shape is preferable.
The surface of the support may be subjected to cutting treatment, roughening treatment, alumite treatment, etc. 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 photosensitive layer or the undercoat layer for the purpose of suppressing interference fringes due to scattering of a laser or the like and covering the scratch on the support.
The conductive layer is formed by coating a conductive layer coating solution obtained by dispersing conductive particles together with a binder resin and a solvent to form a coating film, and then drying and / or curing the obtained coating film. can do.

  Examples of the conductive particles used in the conductive layer include carbon particles such as carbon black, acetylene black, aluminum, nickel, iron, nichrome, copper, zinc, silver, zinc oxide, titanium oxide, tin oxide, and antimony oxide. And particles of metal oxides such as indium oxide, bismuth oxide, and ITO. Alternatively, indium oxide doped with tin, tin oxide doped with antimony or tantalum may be used.

  Examples of the solvent for the conductive layer coating solution include ether solvents, alcohol solvents, ketone solvents, and aromatic hydrocarbon solvents. The film thickness of the conductive layer is preferably from 0.1 μm to 50 μm, more preferably from 0.5 μm to 40 μm, and even more preferably from 1 μm to 30 μm.

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

[Undercoat layer (intermediate layer)]
An undercoat layer (intermediate layer) may be provided between the support or the conductive layer and the charge generation layer.
The undercoat layer can be formed by applying a coating solution for the undercoat layer obtained by dissolving the binder resin in a solvent to form a coating film, and drying the obtained coating film.

  Examples of the binder resin used for the undercoat layer include polyvinyl alcohol resin, poly-N-vinylimidazole, polyethylene oxide resin, ethyl cellulose, ethylene-acrylic acid copolymer, casein, polyamide resin, and N-methoxymethylated 6 Nylon resin, copolymer nylon resin, phenol resin, polyurethane resin, epoxy resin, acrylic resin, melamine resin, and polyester resin can be mentioned.

  The undercoat layer may further contain metal oxide particles. Examples thereof include particles containing titanium oxide, zinc oxide, tin oxide, zirconium oxide, and aluminum oxide. The metal oxide particles may be metal oxide particles in which the surface of the metal oxide particles is treated with a surface treatment agent such as a silane coupling agent.

  Examples of the solvent used for the coating solution for the undercoat layer include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aliphatic halogenated hydrocarbon solvents, and organic solvents such as aromatic compounds. Can be mentioned. The thickness of the undercoat layer is preferably 0.05 μm or more and 30 μm or less, and more preferably 1 μm or more and 25 μm or less. The undercoat layer may further contain organic resin fine particles and a leveling agent.

(Charge generation layer)
In the case of a laminated photosensitive layer, the charge generation layer is formed by mixing a charge generation material and a binder resin with a solvent and applying a coating solution for charge generation layer obtained by dispersion treatment to form a coating film. It can be formed by drying the coating film. The charge generation layer may be a vapor generation film of a charge generation material.

  Examples of the charge generation material used in the charge generation layer include azo pigments, phthalocyanine pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, squarylium dyes, pyrylium salts, thiapyrylium salts, triphenylmethane dyes, quinacridone pigments, and azurenium salts. Examples thereof include pigments, cyanine dyes, anthanthrone pigments, pyranthrone pigments, xanthene dyes, quinoneimine dyes, and styryl dyes. Only one kind of charge generation substance may be used, or two or more kinds may be used. Among charge generation materials, phthalocyanine pigments and azo pigments are preferable from the viewpoint of sensitivity, and phthalocyanine pigments are more preferable.

  Among phthalocyanine pigments, oxytitanium phthalocyanine, chlorogallium phthalocyanine, and hydroxygallium phthalocyanine exhibit excellent charge generation efficiency. Further, among the hydroxygallium phthalocyanines, from the viewpoint of sensitivity, the crystalline form having strong peaks at 7.4 ° ± 0.3 ° and 28.2 ° ± 0.3 ° of the Bragg angle 2θ in CuKα characteristic X-ray diffraction. A hydroxygallium phthalocyanine crystal is more preferable.

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

  The mass ratio of the charge generation material to the binder resin (charge generation material: binder resin) is preferably in the range of 1: 0.3 to 1: 4.

  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.

Examples of the solvent used in the charge generation layer coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aliphatic halogenated hydrocarbon solvents, and aromatic compounds.
The thickness of the charge generation layer is preferably from 0.01 μm to 5 μm, and more preferably from 0.1 μm to 1 μm. In addition, various sensitizers, antioxidants, ultraviolet absorbers, and plasticizers can be added to the charge generation layer as necessary.

(Charge transport layer)
Next, the charge transport layer will be described. The charge transport layer is formed on the charge generation layer. The charge transport layer is formed by applying a charge transport layer coating solution obtained by dissolving a charge transport material and a binder resin in a solvent to form a coating film, and then drying the obtained coating film. Can do.

  Examples of the binder resin used for the charge transport layer include polyvinyl butyral, polycarbonate resin, polyester resin, phenoxy resin, polyvinyl acetate, acrylic resin, polyacrylamide, polyamide, polyvinyl pyridine, cellulose resin, urethane resin, and epoxy resin. . Polycarbonate resin is preferable.

  Examples of the charge transport material used for the charge transport layer include triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, triarylmethane compounds, and thiazole compounds. Only one type of charge transport material may be used, or two or more types may be used.

  The ratio of the charge transport material and the binder resin in the charge transport layer is preferably 0.3 parts by mass or more and 10 parts by mass or less of the charge transport material with respect to 1 part by mass of the binder resin.

  Further, from the viewpoint of suppressing cracks in the charge transport layer, the drying temperature is preferably 60 ° C. or higher and 150 ° C. or lower, and more preferably 80 ° C. or higher and 120 ° C. or lower. The drying time is preferably 10 minutes or more and 60 minutes 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, aliphatic halogenated hydrocarbon solvents, and aromatic hydrocarbon solvents. The thickness of the charge transport layer is preferably 5 μm to 40 μm, and more preferably 10 μm to 35 μm.

  In addition, an antioxidant, an ultraviolet absorber, a plasticizer, metal oxide particles, and inorganic particles can be added to the charge transport layer as necessary. Further, fluorine atom-containing resin particles or silicone-containing resin particles may be contained.

[Surface layer (protective layer)]
And the protective layer which is a surface layer is as described above,
(Α) a hole transporting compound having an acryloyloxy group or a methacryloyloxy group and containing no fluorine atom or silicon atom,
(Β) a compound having 2 or more and 4 or less acryloyloxy group or methacryloyloxy group and not containing a fluorine atom and a silicon atom and having no hole transporting skeleton,
(Γ) Bisphenol Z type or A type or C type polycarbonate resin,
(Δ) a silicone compound having an acryloyloxy group or a methacryloyloxy group and not having a hole transporting skeleton, or a fluorine compound having an acryloyloxy group or a methacryloyloxy group and not having a hole transporting skeleton, and It can be formed by preparing a coating solution for the surface layer containing ε) a solvent, forming a coating film of the coating solution for the surface layer on the charge transport layer, and curing the coating film.

  When applying the coating liquid for each of the above layers, for example, a coating method such as a dip coating method, a spray coating method, a ring coating method, a spin coating method, a roller coating method, a Meyer bar coating method, or a blade coating method can be used.

Next, FIG. 1 shows an example of a schematic configuration of an electrophotographic apparatus provided with a process cartridge having an electrophotographic photosensitive member.
In FIG. 1, a cylindrical electrophotographic photosensitive member 1 is rotationally driven around a shaft 2 in the direction of an arrow with a predetermined peripheral speed. The surface (circumferential surface) of the electrophotographic photosensitive member 1 is positively or negatively charged by a charging unit (primary charging unit) 3 during the rotation process. Next, the surface of the electrophotographic photoreceptor 1 is irradiated with exposure light (image exposure light) 4 output from an exposure means (image exposure means) (not shown). The exposure light 4 is intensity-modulated corresponding to the time-series electric digital image signal of the target image information. Examples of exposure means include slit exposure and laser beam scanning exposure. Thus, an electrostatic latent image corresponding to the target image information is formed on the surface of the electrophotographic photoreceptor 1.

  The electrostatic latent image formed on the surface of the electrophotographic photoreceptor 1 is then developed (regular development or reversal development) with toner stored in the developing means 5 to form a toner image. The toner image formed on the surface of the electrophotographic photoreceptor 1 is transferred to the transfer material 7 by the transfer means 6. Here, when the transfer material 7 is paper, it is taken out from a paper feeding unit (not shown) in synchronization with the rotation of the electrophotographic photosensitive member 1 and fed between the electrophotographic photosensitive member 1 and the transfer means 6. Is done. Further, a bias voltage having a polarity opposite to the charge held in the toner is applied to the transfer means 6 from a bias power source (not shown). The transfer means may be an intermediate transfer type transfer means having a primary transfer member, an intermediate transfer member, and a secondary transfer member.

  The transfer material 7 onto which the toner image has been transferred is separated from the surface of the electrophotographic photosensitive member 1, transported to a fixing unit 8, and subjected to a fixing process of the toner image, whereby an electronic image forming product (print, copy) is obtained. Printed out of the photographic device.

  The surface of the electrophotographic photoreceptor 1 after the transfer of the toner image is cleaned by a cleaning unit 9 to remove deposits such as transfer residual toner. The transfer residual toner can also be collected by a developing means or the like. Further, if necessary, the surface of the electrophotographic photosensitive member 1 is subjected to charge removal treatment by irradiation with pre-exposure light 10 from a pre-exposure unit (not shown), and then repeatedly used for image formation. When the charging unit 3 is a contact charging unit using a charging roller or the like, the pre-exposure unit is not always necessary.

  Among the components such as the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, the transfer unit 6, and the cleaning unit 9, a plurality of components are selected and placed in a container and integrally supported as a process cartridge. To do. The process cartridge may be configured to be detachable from an electrophotographic apparatus main body 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 9 are integrally supported to form a cartridge. The process cartridge 11 is detachably attached to the main body of the electrophotographic apparatus using guide means 12 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 specific examples. In the examples, “part” means “part by mass”.

Example 1
An aluminum cylinder having a diameter of 30 mm, a length of 357.5 mm, and a wall thickness of 1 mm was used as a support (conductive support).

Next, 100 parts of zinc oxide particles (specific surface area: 19 m ² / g, powder resistance: 4.7 × 10 ⁶ Ω · cm) are stirred and mixed with 500 parts of toluene, and 0.8 part of a silane coupling agent is added thereto. Was added and stirred for 6 hours. Thereafter, toluene was distilled off under reduced pressure, followed by heating and drying at 130 ° C. for 6 hours to obtain surface-treated zinc oxide particles. As the silane coupling agent, KBM602 (compound name: N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. was used.
Next, 15 parts of polyvinyl butyral resin (weight average molecular weight: 40000, trade name: BM-1, manufactured by Sekisui Chemical Co., Ltd.) and blocked isocyanate (trade name: Sumidur 3175, Sumika Bayer Urethane ( 15 parts) was dissolved in a mixed solution of 73.5 parts of methyl ethyl ketone and 73.5 parts of 1-butanol. 80.8 parts of the surface-treated zinc oxide particles and 0.8 part of 2,3,4-trihydroxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to this solution, and this was added to a glass having a diameter of 0.8 mm. Dispersion was performed in a sand mill apparatus using beads in an atmosphere of 23 ± 3 ° C. for 3 hours. After dispersion, 0.01 parts of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Co., Ltd.) and crosslinked polymethyl methacrylate (PMMA) particles (trade name: TECHPOLYMER SSX-103, Sekisui Plastics Co., Ltd.) 5.6 parts of an average primary particle size of 3 μm) was added and stirred to prepare an undercoat layer coating solution.
This undercoat layer coating solution was dip-coated on the aluminum cylinder to form a coating film, and the resulting coating film was dried at 160 ° C. for 40 minutes to form an undercoat layer having a thickness of 18 μm.

Next, crystalline hydroxygallium phthalocyanine crystals having strong peaks at 7.4 ° and 28.2 ° with a Bragg angle 2θ ± 0.2 ° of CuKα characteristic X-ray diffraction were prepared. 20 parts of this hydroxygallium phthalocyanine crystal, 0.2 part of a compound represented by the following formula (2), 10 parts of polyvinyl butyral resin (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 600 parts of cyclohexanone The dispersion was carried out for 4 hours by a sand mill using glass beads having a diameter of 1 mm. Thereafter, 700 parts of ethyl acetate was added to prepare a coating solution for charge generation layer. This coating solution for charge generation layer is dip-coated on the undercoat layer to form a coating film, and the resulting coating film is heated and dried in an oven at a temperature of 80 ° C. for 15 minutes, whereby the film thickness is 0.17 μm A charge generation layer was formed.

Next, 30 parts of the compound represented by the following formula (3) (charge transporting substance), 60 parts of the compound represented by the following formula (4) (charge transporting substance), 10 parts of the compound represented by the following formula (5), polycarbonate 100 parts of resin (trade name: Iupilon Z400, manufactured by Mitsubishi Engineering Plastics Co., Ltd., bisphenol Z type), a structural unit represented by the following formula (6-1) and a structural unit represented by the following formula (6-2) A charge transport layer coating solution was prepared by dissolving 0.02 part of polycarbonate (viscosity average molecular weight Mv: 20000) in a solvent of 600 parts of mixed xylene and 200 parts of dimethoxymethane. The charge transport layer coating solution was dip coated on the charge generation layer to form a coating film, and the resulting coating film was dried at 100 ° C. for 30 minutes to form a charge transport layer having a thickness of 18 μm.

ポリカーボネート樹脂（商品名：ユーピロンＺ４００、三菱エンジニアリングプラスチックス（株）製、ビスフェノールＺ型）１部、下記式（８）で示され、重量平均分子量が５０００のシロキサン変性アクリル化合物１部、

下記式（９）で示されるビニルエステル化合物１０部（東京化成工業（株）製）、

１−プロパノール２００部、１，１，２，２，３，３，４−ヘプタフルオロシクロペンタン（商品名：ゼオローラＨ、日本ゼオン（株）製）１００部を混合し、撹拌した。その後ポリフロンフィルター（商品名：ＰＦ−０２０、アドバンテック東洋（株）製）でこの溶液を濾過することによって、表面層用塗布液（保護層用塗布液）を調製した。 Next, 80 parts of the exemplified compound (1-1), 20 parts of a compound having no hole transporting skeleton represented by the following formula (7),

1 part of a polycarbonate resin (trade name: Iupilon Z400, manufactured by Mitsubishi Engineering Plastics Co., Ltd., bisphenol Z type), 1 part of a siloxane-modified acrylic compound represented by the following formula (8) and having a weight average molecular weight of 5000,

10 parts of vinyl ester compound represented by the following formula (9) (manufactured by Tokyo Chemical Industry Co., Ltd.),

200 parts of 1-propanol and 100 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.) were mixed and stirred. Thereafter, this solution was filtered through a polyflon filter (trade name: PF-020, manufactured by Advantech Toyo Co., Ltd.) to prepare a surface layer coating solution (protective layer coating solution).

This surface layer coating solution is dip-coated on the charge transport layer to form a coating film, and then the support (irradiated body) is 200 rpm under a nitrogen atmosphere under conditions of an acceleration voltage of 70 kV and a beam current of 5.0 mA. The coating film was irradiated with an electron beam for 1.6 seconds while rotating at a speed of. In addition, when the absorbed dose of the electron beam at this time was measured, it was 15 kGy. Then, it heated up over 15 seconds until the temperature of the coating film became 25 degreeC from 150 degreeC in nitrogen atmosphere, and the coating film was heated. The oxygen concentration from the electron beam irradiation to the subsequent heat treatment was 15 ppm or less. Next, in the atmosphere, the coating film is naturally cooled until the temperature of the coating film reaches 25 ° C., and heat treatment is performed for 30 minutes under the condition that the temperature of the coating film becomes 105 ° C., thereby forming a protective layer (surface layer) having a thickness of 5 μm Formed.
In this manner, an electrophotographic photosensitive member having a protective layer before forming a recess was produced.

Next, a mold member (mold) was installed in the pressure-contact shape transfer processing apparatus, and surface processing was performed on the produced electrophotographic photosensitive member before forming the concave portion.
Specifically, the mold shown in FIG. 4 was installed in the press-fitting shape transfer processing apparatus having a configuration shown in FIG. 3 and surface processing was performed on the electrophotographic photosensitive member formed before forming the concave shape portion. FIG. 4 is a view showing a mold used in Examples and Comparative Examples, and FIG. 4A is a top view showing an outline of the mold. FIG. 4B is a schematic cross-sectional view in the axial direction of the electrophotographic photosensitive member of the mold convex part (cross-sectional view in the SS ′ cross section of FIG. 4A), and FIG. 4C is the mold convex part. FIG. 6 is a cross-sectional view in the circumferential direction of the electrophotographic photosensitive member (cross-sectional view taken along the line TT ′ in FIG. 4A). The mold shown in FIG. 4 has a maximum width (the maximum width in the axial direction of the electrophotographic photosensitive member when the convex portion on the mold is viewed from above) X: 50 μm, the maximum length (the convex portion on the mold is The maximum length in the circumferential direction of the electrophotographic photosensitive member when viewed from above) Y: 75 μm, area ratio 56%, height H: 4 μm. In addition, an area ratio is a ratio of the area of the convex part which occupies for the whole surface when a mold is seen from the top. During processing, the temperature of the electrophotographic photosensitive member and the mold is controlled so that the surface temperature of the electrophotographic photosensitive member becomes 120 ° C., and the electrophotographic photosensitive member and the pressure member are pressed against the mold at a pressure of 7.0 MPa. The electrophotographic photosensitive member was rotated in the circumferential direction to form a concave portion on the entire surface layer (circumferential surface) of the electrophotographic photosensitive member. Thus, an electrophotographic photosensitive member having a concave portion on the surface was produced.

  The surface of the obtained electrophotographic photosensitive member was magnified and observed with a 50 × lens with a laser microscope (manufactured by Keyence Co., Ltd., trade name: X-100), and a concave portion provided on the surface of the electrophotographic photosensitive member was observed. Observations were made. At the time of observation, adjustment was performed so that there is no inclination in the longitudinal direction of the electrophotographic photosensitive member, and the circumferential direction was focused on the apex of the arc of the electrophotographic photosensitive member. The images subjected to magnified observation were connected by an image connection application to obtain a square region having a side of 500 μm. And about the obtained result, image processing height data was selected with attached image analysis software, and the filter process was performed by the filter type median.

As a result of the above observation, the depth of the concave portion was 2 μm, the axial width of the opening was 50 μm, the circumferential length of the opening was 75 μm, and the area was 140000 μm ² . The area is the area of the concave portion when the surface of the electrophotographic photosensitive member is viewed from above, and means the area of the opening of the concave portion.

  The obtained electrophotographic photosensitive member is mounted on a cyan station of a modified machine of an electrophotographic apparatus (copier) (trade name: iR-ADV C5051) manufactured by Canon Inc., which is an evaluation apparatus. Image evaluation at% RH was performed.

In the image evaluation, the presence or absence of a streak image due to the deterioration of the surface of the electrophotographic photosensitive member was examined. As a method, the total discharge current amount in the charging process was set to 120 μA, and the cassette heater (drum heater) in the apparatus was turned off. Thereafter, an image of 17 gradations with an A4 horizontal and an output resolution of 600 dpi was formed, and the obtained initial images of the entire A4 surface were evaluated as follows.
A: There is no vertical stripe or image flow, and the image reproducibility is good.
B: Slight vertical stripes or image flow can be seen, but the image reproducibility is good for other portions.
C: Some defects are observed when magnified, but the image reproducibility is good.
D: A clear vertical streak or image flow occurs, and the image reproducibility is low.

  Subsequently, 50,000 continuous images were formed using a test chart with an image ratio of 5%. After completion of the image formation, it was left for 3 days, and thereafter, in the same manner as described above, image formation of 17 gradations with A4 horizontal and output resolution of 600 dpi was performed, and the obtained image of the entire A4 surface was evaluated.

Also, the surface of the electrophotographic photosensitive member after forming 50,000 continuous images using a surface surfcoder SE3500 manufactured by Kosaka Laboratory under the conditions of a cutoff of 0.8 mm, a measurement length of 8 mm, and a measurement speed of 0.5 mm / s. The roughness (maximum height Rmax) was determined, and this Rmax value was defined as “scratch depth”.
The results are shown in Table 1.

を、ｎ−プロパノール２００部および１，１，２，２，３，３，４−ヘプタフルオロシクロペンタン（商品名：ゼオローラＨ、日本ゼオン（株）製）１００部の混合溶剤に加え、これを超高圧分散機で分散処理することによって得られた保護層用塗布液に変更した以外は、実施例１と同様にして電子写真感光体を製造し、評価を行った。 (Example 2)
65 parts of exemplary compound (1-1), 15 parts of compound having no hole transporting skeleton represented by formula (7), 0.8 part of polycarbonate resin, siloxane-modified acrylic represented by formula (8) 1 part of a compound, 10 parts of a vinyl ester compound represented by the above formula (9), 40 parts of polytetrafluoroethylene particles (trade name: Lubron L2, manufactured by Daikin Corporation), and a repetition represented by the following formula (A1) Resin having a structural unit and a repeating structural unit represented by the following formula (A2) (weight average molecular weight: 130,000, copolymerization ratio (A1) / (A2) = 1/1 (molar ratio)) 2 parts

Is added to a mixed solvent of 200 parts of n-propanol and 100 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.). An electrophotographic photoreceptor was produced and evaluated in the same manner as in Example 1 except that the coating solution for the protective layer obtained by carrying out dispersion treatment with an ultrahigh pressure disperser was used.

(Example 3)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the addition amount of the polycarbonate resin was changed to 4 parts by mass.

Example 4
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound having the hole transporting skeleton represented by the formula (7) was changed to trimethylolpropane triacrylate (TMPTA). It was.

(Example 5)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound having no hole transporting skeleton represented by formula (7) was changed to trimethylolpropane trimethacrylate (TMPTM). It was.

(Example 6)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound having no hole transporting skeleton represented by formula (7) was changed to ditrimethylolpropane tetraacrylate (DTMPA). It was.

(Example 7)
An electrophotographic photoreceptor was produced and evaluated in the same manner as in Example 1 except that the exemplified compound (1-1) was changed to the exemplified compound (1-2).

(Example 8)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the vinyl ester compound represented by the formula (9) was not added.

Example 9
An electrophotographic photoreceptor was produced and evaluated in the same manner as in Example 1 except that the siloxane-modified acrylic compound represented by the formula (8) was changed to 2- (perfluorobutyl) ethyl acrylate.

(Example 10)
An electrophotographic photoreceptor was produced and evaluated in the same manner as in Example 9 except that the exemplified compound (1-1) was changed to the exemplified compound (1-7).

(Example 11)
An electrophotographic photoreceptor was produced and evaluated in the same manner as in Example 9 except that the exemplified compound (1-1) was changed to the exemplified compound (1-8).

(Example 12)
Except having changed the compound which does not have the positive hole transport skeleton shown by Formula (7) into polyethyleneglycol # 400 diacrylate (A-400, Shin-Nakamura Chemical Co., Ltd. product), it carried out similarly to Example 9, and changed it. An electrophotographic photoreceptor was manufactured and evaluated.

(Example 13)
An electrophotographic photoreceptor was produced and evaluated in the same manner as in Example 9 except that the exemplified compound (1-1) was changed to the exemplified compound (1-9).

(Example 14)
An electrophotographic photoreceptor was produced and evaluated in the same manner as in Example 9 except that the exemplified compound (1-1) was changed to the exemplified compound (1-10).

(Example 15)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 9 except that the compound having no hole transporting skeleton represented by formula (7) was changed to tetramethylolmethane tetraacrylate (TMMTA). It was.

(Example 16)
Except having changed the compound which does not have the hole transportable skeleton shown by Formula (7) into ethoxylated bisphenol A diacrylate (ABPE-10, Shin-Nakamura Chemical Co., Ltd.), it carried out similarly to Example 9, and changed it. An electrophotographic photoreceptor was manufactured and evaluated.

(Example 17)
An electrophotographic photoreceptor was produced and evaluated in the same manner as in Example 9 except that 2- (perfluorobutyl) ethyl acrylate was changed to 2,2,3,3,3-pentafluoropropyl acrylate.

(Example 18)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 9 except that 2- (perfluorobutyl) ethyl acrylate was changed to a siloxane-modified acrylic compound represented by the following formula (10) and having a weight average molecular weight of 12000. Went.

(Example 19)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 9 except that the addition amount of the siloxane-modified acrylic compound was 6 parts.

(Example 20)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 9 except that the addition amount of the siloxane-modified acrylic compound was 0.5 part.

(Example 21)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 9 except that the addition amount of the siloxane-modified acrylic compound was 7 parts.

ポリカーボネート樹脂（商品名：ユーピロンＺ４００、三菱エンジニアリングプラスチックス（株）製、ビスフェノールＺ型）１部、下記式（８）で示され、重量平均分子量が５０００のシロキサン変性アクリル化合物１部、

下記式（９）で示されるビニルエステル化合物１０部（東京化成工業（株）製）、

１−プロパノール２００部、１，１，２，２，３，３，４−ヘプタフルオロシクロペンタン（商品名：ゼオローラＨ、日本ゼオン（株）製）１００部を混合し、撹拌した。その後ポリフロンフィルター（商品名：ＰＦ−０２０、アドバンテック東洋（株）製）でこの溶液を濾過することによって、表面層用塗布液（保護層用塗布液）を調製した。 (Example 22)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the surface layer was formed as follows.
80 parts of the exemplary compound (1-1), 20 parts of a compound having no hole transporting skeleton represented by the following formula (7),

1 part of a polycarbonate resin (trade name: Iupilon Z400, manufactured by Mitsubishi Engineering Plastics Co., Ltd., bisphenol Z type), 1 part of a siloxane-modified acrylic compound represented by the following formula (8) and having a weight average molecular weight of 5000,

10 parts of vinyl ester compound represented by the following formula (9) (manufactured by Tokyo Chemical Industry Co., Ltd.),

200 parts of 1-propanol and 100 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.) were mixed and stirred. Thereafter, this solution was filtered through a polyflon filter (trade name: PF-020, manufactured by Advantech Toyo Co., Ltd.) to prepare a surface layer coating solution (protective layer coating solution).

Next, the coating solution for the surface layer is dip-coated on the charge transport layer to form a coating film, and ultraviolet rays are applied to the coating film for 30 seconds with a light intensity of 1.20 × 10 ⁻⁵ W / m ² using a metal halide lamp. Irradiated to perform photocuring. Then, this coating film was dried by heating at 120 ° C. for 1 hour and 40 minutes to form a surface layer having a thickness of 5 μm.

(Example 23)
After irradiating the electron beam to the coating film, the temperature of the coating film was increased over 30 seconds in a nitrogen atmosphere until the coating film temperature was changed from 25 ° C. to 170 ° C., and the coating film was heated. Similarly, an electrophotographic photosensitive member was produced and evaluated.

(Example 24)
After irradiating the coating with an electron beam, in Example 1 except that the coating was heated in a nitrogen atmosphere over 30 seconds until the coating temperature changed from 25 ° C. to 140 ° C., and the coating was heated. Similarly, an electrophotographic photosensitive member was produced and evaluated.

(Example 25)
After irradiating the coating with an electron beam, in Example 1 except that the coating was heated in a nitrogen atmosphere over 30 seconds until the coating reached 25 ° C. to 180 ° C., and the coating was heated. Similarly, an electrophotographic photosensitive member was produced and evaluated.

(Example 26)
After irradiating the electron beam to the coating film, in Example 1 except that the coating film was heated in a nitrogen atmosphere over 30 seconds until the coating film temperature was changed from 25 ° C. to 130 ° C. Similarly, an electrophotographic photosensitive member was produced and evaluated.

(Comparative Example 1)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the amount of polycarbonate resin added was 0.4 parts.
In this case, compared with Example 1, the streak image level after the formation of 50000 sheets of images was particularly deteriorated.

(Comparative Example 2)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the amount of polycarbonate resin added was 4.5 parts.
In this case, the streak-like image defect due to the deterioration of the surface of the photoconductor did not occur, but the level of scratches generated on the surface of the electrophotographic photoconductor after the image formation of 50000 sheets deteriorated, and the image due to the scratches Defects were seen.

を、ｎ−プロパノール２００部および１，１，２，２，３，３，４−ヘプタフルオロシクロペンタン（商品名：ゼオローラＨ、日本ゼオン（株）製）１００部の混合溶剤に加え、これを超高圧分散機で分散処理することによって得られた保護層用塗布液に変更した以外は、実施例１と同様にして電子写真感光体を製造した。
この場合も、前記の感光体表面の劣化に起因したスジ状の画像不良は発生しなかったが、５００００枚画像形成後の電子写真感光体の表面に発生したキズのレベルが悪化し、キズによる画像不良が見られた。 (Comparative Example 3)
60 parts of exemplary compound (1-1), 15 parts of compound having no hole transporting skeleton represented by the formula (7), 0.5 part of the polycarbonate resin, siloxane-modified acrylic represented by the formula (8) 0.6 parts of the compound, 10 parts of the vinyl ester compound represented by the formula (9), 50 parts of polytetrafluoroethylene particles (trade name: Lubron L2, manufactured by Daikin Co., Ltd.), and the following formula (A1) 2 parts of a resin having a repeating structural unit and a repeating structural unit represented by the following formula (A2) (weight average molecular weight: 130,000, copolymerization ratio (A1) / (A2) = 1/1 (molar ratio))

Is added to a mixed solvent of 200 parts of n-propanol and 100 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.). An electrophotographic photosensitive member was produced in the same manner as in Example 1, except that the coating solution for the protective layer was obtained by carrying out dispersion treatment with an ultrahigh pressure disperser.
Also in this case, the streak-like image defect due to the deterioration of the surface of the photoconductor did not occur, but the level of the scratch generated on the surface of the electrophotographic photoconductor after the image formation of 50000 sheets was deteriorated. Image defect was seen.

(Comparative Example 4)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the compound having no hole transporting skeleton represented by the formula (7) was not added.
In this case, compared with Example 1, the streak image level after forming 50,000 sheets of images was deteriorated.

(Comparative Example 5)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the siloxane-modified acrylic compound represented by the formula (8) was not added.
In this case, compared with Example 1, the streak image level after the formation of 50000 sheets of images was particularly deteriorated.

  As a result of the evaluation, in the initial examples, streaky image defects in repeated use, image defects due to scratches generated on the surface of the electrophotographic photosensitive member were sufficiently suppressed, and an image having no problem was obtained. The above-mentioned image defect occurred.

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means 21 Support body 22 Undercoat layer 23 Charge generation layer 24 Hole transport layer 25 Surface layer

Claims (11)

In the electrophotographic photosensitive member having a support and a photosensitive layer in this order, the surface layer of the electrophotographic photosensitive member includes:
(Α) a hole transporting compound having an acryloyloxy group or a methacryloyloxy group and containing no fluorine atom or silicon atom,
(Β) a compound having 2 or more and 4 or less acryloyloxy group or methacryloyloxy group and not containing a fluorine atom and a silicon atom and having no hole transporting skeleton,
(Γ) a bisphenol Z-type or A-type or C-type polycarbonate resin, and (δ) a silicone compound having an acryloyloxy group or a methacryloyloxy group and not having a hole transporting skeleton, or an acryloyloxy group or a methacryloyloxy group. A cured product of a composition containing a fluorine compound having no hole-transporting skeleton, and the content of (γ) in the composition is that of (α) and (β) in the composition An electrophotographic photoreceptor, wherein the content is 1% by mass or more and 4% by mass or less with respect to the total amount, and the total content of (α) and (β) in the composition is 60% by mass or more.   2. The electrophotographic photosensitive member according to claim 1, wherein the content of (δ) in the composition is 1% by mass or more and 5% by mass or less.   The electrophotographic photosensitive member according to claim 1, wherein the weight average molecular weight of (δ) is 300 or more and 10,000 or less.   When the number of functional groups in (α) is F1 and the molecular weight is M1, F1 / M1 is 0.002 to 0.006. When the number of functional groups in (β) is F2 and the molecular weight is M2, F2 / M2 The electrophotographic photosensitive member according to any one of claims 1 to 3, wherein is from 0.004 to 0.010.   The electrophotographic photosensitive member according to any one of claims 1 to 4, wherein the silicone compound is a siloxane-modified acrylic compound. 6. The electrophotographic photosensitive member according to claim 1, wherein the surface layer of the electrophotographic photosensitive member further contains a cured product of a composition containing a compound represented by the formula (I). body.

(R ¹ is a hydrogen atom or a methyl group. R ² is a linear or branched unsubstituted alkyl group having 7 or more carbon atoms.) A method for producing an electrophotographic photosensitive member having a support and a surface layer in this order,
The manufacturing method comprises:
(Α) a hole transporting compound having an acryloyloxy group or a methacryloyloxy group and containing no fluorine atom or silicon atom,
(Β) a compound having 2 or more and 4 or less acryloyloxy group or methacryloyloxy group and not containing a fluorine atom and a silicon atom and having no hole transporting skeleton,
(Γ) Bisphenol Z type or A type or C type polycarbonate resin,
(Δ) a silicone compound having an acryloyloxy group or a methacryloyloxy group and not having a hole transporting skeleton, or a fluorine compound having an acryloyloxy group or a methacryloyloxy group and not having a hole transporting skeleton, and (ε ) The content of (γ) with respect to the total solid content in the coating solution containing the solvent is 1% by mass or more and 4% by mass or less with respect to the total amount of (α) and (β) with respect to the total solid content in the coating solution. And a step of preparing a coating solution for the surface layer in which the total content of (α) and (β) with respect to the total solid content in the coating solution is 60% by mass or more, and application of the coating solution for the surface layer A method for producing an electrophotographic photoreceptor, comprising a step of forming a surface layer by forming a film and curing the coating film.   The method for producing an electrophotographic photosensitive member according to claim 7, wherein the content of (δ) with respect to the total solid content in the coating solution is 1% by mass or more and 5% by mass or less.   The electron of Claim 7 or 8 which has the process of irradiating an electron beam or an ultraviolet-ray to the said coating film, and also hardening a coating film by heating an electrophotographic photoreceptor at the temperature of 140 to 170 degreeC after that. A method for producing a photographic photoreceptor.   An electrophotographic photosensitive member according to any one of claims 1 to 6 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 electrophotographic A process cartridge which is detachable from the apparatus main body.   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.

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