JP6674270B2 - Electrophotographic photosensitive member, manufacturing method thereof, process cartridge and electrophotographic apparatus - Google Patents

Description

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

For the purpose of improving the electrical characteristics, durability, and image quality of an electrophotographic photosensitive member containing an organic photoconductive substance, techniques for improving the material and physical properties of the surface of the electrophotographic photosensitive member have been studied.
Patent Literature 1 discloses an electrophotographic photoreceptor in which the infrared absorption spectrum peak intensity in a surface layer composed of a cured product of a charge transport material having a polymerizable functional group and a polycarbonate is specified to suppress a decrease in image quality after repeated use. Are listed.
Patent Document 2 describes an electrophotographic photosensitive member in which the peak area of an infrared spectral reflection spectrum in a surface layer is specified to improve electrical characteristics and scratch resistance.

JP 2011-164400 A JP 2014-191118 A

  2. Description of the Related Art In recent years, electrophotographic apparatuses have been required to improve the abrasion resistance of electrophotographic photoreceptors and achieve higher image quality. In particular, in a color electrophotographic apparatus, as a result of repeated use of the electrophotographic photosensitive member, the surface layer of the electrophotographic photosensitive member deteriorates. As a result, the lubricity decreases due to adsorption of discharge products and moisture on the electrophotographic photosensitive member surface in a high humidity environment. Sometimes. As a result, there is a problem that the state of the cleaning blade becomes unstable and a streak-like image defect occurs. Another problem is the occurrence of image defects due to scratches on the electrophotographic photosensitive member caused by repeated use. As a result of the study by the present inventors, the electrophotographic photoreceptor described in Patent Document 1 or 2 may have the above-described image defect, and has room for improvement.

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

The present invention includes a support, a photosensitive layer and a protective layer is a surface layer comprising an electrophotographic photosensitive member having in this order, the surface layer,
(Α) a hole-transporting compound having two or more acryloyloxy groups or methacryloyloxy groups and not containing a fluorine atom and a silicon atom,
(Β) a compound having 2 to 4 acryloyloxy groups or methacryloyloxy groups, not containing a fluorine atom and a silicon atom, and not having a hole transporting skeleton;
(Γ) a bisphenol Z-type or A-type or C-type polycarbonate resin; and (δ) a siloxane-modified acrylic compound having a weight average molecular weight of 300 to 10,000 and having an acryloyloxy group and no hole transporting skeleton. Stuff
Contains a cured product of a composition comprising, in said composition, (gamma) of the content of, (alpha) and the ratio of pairs total content of (beta) is 1 mass% or more 4% by weight less and, in said composition, the proportion is 60 mass% or more to the total amount of (alpha) and (beta) the total content of the material of the surface layer of the composition The present invention relates to a characteristic electrophotographic photosensitive member.

Further, the present invention is a method for producing an electrophotographic photosensitive member having a support, a photosensitive layer, and a protective layer as a surface layer in this order,
(I) forming a coating film of a coating solution for a surface layer on the photosensitive layer, and
(Ii) forming a surface layer by curing the coating film,
Coating liquid, (alpha) has two or more acryloyloxy group or methacryloyloxy group and a hole transporting compound containing no fluorine atom and a silicon atom,
(Β) a compound having 2 to 4 acryloyloxy groups or methacryloyloxy groups, not containing a fluorine atom and a silicon atom, and not having a hole transporting skeleton;
(Γ) bisphenol Z type or A type or C type polycarbonate resin,
(Δ) a siloxane-modified acrylic compound having an acryloyloxy group and having no hole-transporting skeleton having a weight average molecular weight of 300 to 10,000 , and (ε) a solvent
And have you in the coating solution, (gamma) of the content of, (alpha) and the ratio of pairs to the total amount of the total amount of (beta), it is 4 mass% 1 mass% or more, contact to the coating solution There are, (alpha) and the total content of (beta), a percentage of the total content of the material of the surface layer of the coating solution is, electrophotographic, wherein the der benzalkonium least 60 wt% The present invention relates to a method for manufacturing a photoconductor.

  Further, the present invention integrally supports the electrophotographic photosensitive member and at least one unit selected from the group consisting of a charging unit, a developing unit, a transfer unit and a cleaning unit, and is detachably attached to an electrophotographic apparatus main body. The present invention relates to a process cartridge characterized by the following.

  The present invention also relates to an electrophotographic photoreceptor and an electrophotographic apparatus having a charging unit, an exposing unit, a developing unit, and a transferring unit.

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

FIG. 2 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having an electrophotographic photosensitive member. FIG. 3 is a diagram illustrating a layer configuration of an electrophotographic photosensitive member. FIG. 3 is a diagram illustrating an example of a press-contact shape transfer processing apparatus for forming a concave portion on the surface of an electrophotographic photosensitive member. It is a top view and a sectional view showing a mold used in an example and a comparative example.

The electrophotographic photoreceptor of the present invention has a support and a photosensitive layer. This electrophotographic photoreceptor
(Α) a hole-transporting compound having an acryloyloxy group or a methacryloyloxy group and not containing a fluorine atom and a silicon atom,
(Β) a compound having 2 to 4 acryloyloxy groups or methacryloyloxy groups, not containing a fluorine atom and a silicon atom, and not having a hole transporting skeleton;
(Γ) 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 having no hole-transporting skeleton, or an acryloyloxy group or a methacryloyloxy group Containing a cured product of a composition containing a fluorine compound having no hole transporting skeleton, and wherein the content of (γ) in the composition is (α) and (β) in the composition. 1% by mass or more and 4% by mass or less with respect to the total amount of, and the surface layer has a total content of (α) and (β) in the composition of 60% by mass or more. .

The present inventors presume the following as to the mechanism of action that has the above-mentioned features, has high scratch resistance, is highly durable, and can suppress image defects due to insufficient lubricity due to deterioration of the electrophotographic photosensitive member surface, as follows. doing.
The surface layer containing a cured product of a hole transporting substance having a chain-polymerizable functional group has high abrasion resistance, but due to its high abrasion resistance, streak-like image defects are likely to occur when repeatedly used. . The occurrence of streak-like image defects is caused by the electrophotographic process in which the surface of the electrophotographic photoreceptor is chemically degraded and hydrophilic groups are generated, and the discharge products and moisture are adsorbed on the surface to reduce the lubricity of the photoreceptor surface. It is presumed that the decrease causes the behavior of the cleaning blade to become unstable.

  As a result of the study by the present inventors, the inclusion of the compound of the above (β) and (γ) in the above-mentioned optimum range results in a surface layer that is structurally resistant to deterioration and has high film strength, and is a photoreceptor that is repeatedly used. It is presumed that deterioration of the surface lubricity and generation of scratches are suppressed, and as a result, image defects are also suppressed.

  Further, the presence of the compound (δ) improves the affinity between the compounds (α), (β) and (γ), and the (α), (β), and (γ) are uniformly present inside the film. It is presumed that the image defect can be suppressed.

When the content of (γ) is less than 1% by mass relative to the total amount of (α) and (β) in the composition, the surface of the photoconductor is deteriorated by the electrophotographic process, and the streak image is generated. I will.
If the content of (γ) exceeds 4% by mass based on the total amount of (α) and (β) in the composition, the surface of the photoreceptor will be scratched during repeated use, resulting in poor image quality. . Similarly, if the total content of (α) and (β) is less than 60% by mass, image defects due to scratches on the photoreceptor surface during repeated use will 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. It is effectively exhibited, and 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 photoreceptor, and the effect of suppressing image defects is further maintained.

  Further, when the number of functional groups of (α) is F1 and the molecular weight is M1, F1 / M1 is 0.002 to 0.006, and when the number of functional groups of (β) is F2 and the molecular weight is M2, It is preferable that F2 / M2 is 0.004 to 0.010. As a result, the durability is secured and the optimal number of functional groups in one molecule is determined, so that both high durability and suppression of image defects can be achieved.

  The silicone compound is preferably a siloxane-modified acrylic compound. Thereby, the lubricity of the electrophotographic photoreceptor surface and its maintainability are further improved, and streak-like 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 the 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 of the electrophotographic photoreceptor surface and its maintainability, 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 the 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 and a silicon atom.
a is an integer of 1 or more and 4 or less, and a P's ¹ may be the same or different. A represents a positive hole transporting group, a hydrogen adduct of the binding site was replaced by a hydrogen atom and P ¹ of the A is a compound represented by the following formula (V), or the following formula (VI).

(In 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. In addition, R ¹¹ , R ^12, and R ¹³ May be the same or different.)

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

Hereinafter, specific examples (exemplary compounds) of the hole transporting compound represented by (α) will be shown.

  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 compounds having an acrylic main chain or a methacryl main chain and having a siloxane structure or an alkyl fluoride structure in a side chain.

The surface layer of the electrophotographic photoreceptor
(Α) a hole-transporting compound having an acryloyloxy group or a methacryloyloxy group and not containing a fluorine atom and a silicon atom,
(Β) a compound having 2 to 4 acryloyloxy groups or methacryloyloxy groups, not containing a fluorine atom and a silicon atom, and not having a 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 having no hole-transporting skeleton or a fluorine compound having an acryloyloxy group or a methacryloyloxy group and having no hole-transporting skeleton; ) It can be formed by preparing a coating solution for a surface layer containing a solvent, forming a coating film of the coating solution for a surface layer, and curing the coating film.

  Here, the content of (γ) based on the total solids 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) based on the total solids in the coating solution. Preferably, the total content of (α) and (β) with respect to the total solids in the coating solution is 60% by mass or more.

  Further, 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. It is effectively exhibited, and 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 the formula (I), a coating solution for forming a surface layer that also contains a siloxane-modified acrylic compound or a compound of the formula (I) is used. Good. Further, the coating solution for forming a surface layer may contain various additives. Among them, it is preferable to add a urea compound for the purpose of preventing deterioration due to oxidizing gas.

  When the surface layer is a protective layer, its thickness is preferably from 0.1 μm to 15 μm. More preferably, it is 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.

  Means for curing the coating film of the surface layer coating liquid includes a method of curing with heat, ultraviolet light, or electron beam. In order to maintain the strength of the surface layer and the durability of the electrophotographic photoreceptor, it is preferable to cure using an ultraviolet ray or an electron beam.

  When the compound represented by the above (α) and (β) is polymerized using an electron beam, a very dense (high-density) cured product (three-dimensional crosslinked structure) is obtained, and a surface layer having higher durability is obtained. It is preferable because it can be obtained. When irradiating with 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 that deterioration of material properties due to the electron beam can be suppressed without impairing polymerization efficiency. The electron beam absorption dose on the surface of the coating film of the coating solution for a surface layer is preferably 5 kGy or more and 50 kGy or less, more preferably 1 kGy or more and 10 kGy or less.

  When the composition is cured (polymerized) using an electron beam, the composition may be irradiated with an electron beam in an inert gas atmosphere and then heated in an inert gas atmosphere for the purpose of suppressing the polymerization inhibition effect of oxygen. preferable. Examples of the inert gas include nitrogen, argon, and helium.

  Further, 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.

  For the purpose of further stabilizing the behavior of the cleaning blade contacting the electrophotographic photosensitive member, it is more preferable to provide a concave portion or a convex portion on the surface layer of the electrophotographic photosensitive member.

  The concave portion or the convex portion may be formed over 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 photoreceptor, it is preferable that the concave portion or the convex portion is formed at least over the entire contact region with the cleaning blade. .

  When forming a concave portion, a mold having a convex portion corresponding to the concave portion is pressed against the surface of the electrophotographic photosensitive member, and the shape is transferred to form the concave portion on the surface of the electrophotographic photosensitive member. Can be.

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

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

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

  In addition, it is preferable to heat the mold 52 and the electrophotographic photosensitive member 51 from the viewpoint of efficiently transferring the shape.

  The mold 52 may be, for example, a metal or resin film having a fine surface processed, a pattern obtained by patterning a surface of a silicon wafer or the like with a resist, a resin film in which fine particles are dispersed, or a resin film having a fine surface shape. Coated ones may be mentioned.

  Further, from the viewpoint of making the pressure applied to the electrophotographic photosensitive member 51 uniform, it is preferable to provide an elastic body between the mold 52 and the pressing member 53.

Next, the overall configuration of the electrophotographic photosensitive member of the present invention will be described.
[Electrophotographic photoreceptor]
The electrophotographic photoreceptor of the present invention has a support and a photosensitive layer formed on the support. As the photosensitive layer, a single layer type photosensitive layer containing both a charge generating substance and a charge transporting substance, a laminated type photosensitive layer separated into a charge generating layer containing a charge generating substance and a charge transporting layer containing a charge transporting substance are provided. No. In the invention, a laminated photosensitive layer is preferred.

  FIG. 2 is a diagram illustrating an example of a layer configuration of the electrophotographic photosensitive member. 2, the electrophotographic photoreceptor has 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. When no protective layer is provided, the charge transport layer 24 is a surface layer. In the present invention, it is preferable that the protective layer provided on the charge transport layer be a surface layer.

And the surface layer, as described above,
(Α) a hole-transporting compound having an acryloyloxy group or a methacryloyloxy group and not containing a fluorine atom and a silicon atom,
(Β) a compound having 2 to 4 acryloyloxy groups or methacryloyloxy groups, not containing a fluorine atom and a silicon atom, and not having a hole transporting skeleton;
(Γ) 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 having no 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 photosensitive member of the present invention will be further described.
(Support)
As the support used for the electrophotographic photoreceptor, those having conductivity (conductive support) are preferable. For example, a support made of a metal or alloy such as iron, copper, gold, silver, aluminum, zinc, titanium, lead, nickel, tin, antimony, indium, chromium, an aluminum alloy, and stainless steel can be used. Alternatively, a metal support or a resin support having a coating formed by vacuum deposition of aluminum, an aluminum alloy, an indium oxide-tin oxide alloy, or the like can be used. In addition, a support formed by impregnating a resin with conductive particles such as carbon black, tin oxide particles, titanium oxide particles, and silver particles, and 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, the cylindrical shape is preferable.
The surface of the support may be subjected to a cutting treatment, a roughening treatment, an alumite treatment, or the like 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 undercoating layer for the purpose of suppressing interference fringes due to scattering of a laser or the like and covering a damage of the support.
The conductive layer is formed by applying a conductive layer coating solution obtained by dispersing conductive particles together with a binder resin and a solvent to form a coating film, and drying and / or curing the obtained coating film. can do.

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

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

  Examples of the binder resin used for the conductive layer include polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylates, methacrylates, vinylidene fluoride, and trifluoroethylene, and polyvinyl alcohol. Resin, 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 liquid for an undercoat layer obtained by dissolving a 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 Examples include a nylon resin, a copolymerized nylon resin, a phenol resin, a polyurethane resin, an epoxy resin, an acrylic resin, a melamine resin, and a polyester resin.

  The undercoat layer may further contain metal oxide particles. For example, particles containing titanium oxide, zinc oxide, tin oxide, zirconium oxide, and aluminum oxide can be used. Further, the metal oxide particles may be metal oxide particles whose surfaces are treated with a surface treatment agent such as a silane coupling agent.

  Examples of the solvent used in the undercoat layer coating liquid include organic solvents such as alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aliphatic halogenated hydrocarbon solvents, and aromatic compounds. No. The thickness of the undercoat layer is preferably 0.05 μm or more and 30 μm or less, 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 substance and a binder resin with a solvent, applying a coating liquid for a charge generation layer obtained by dispersion treatment, and forming a coating film. It can be formed by drying a coating film. Further, the charge generation layer may be a deposited film of a charge generation substance.

  As the charge generating substance used in the charge generating layer, for example, azo pigments, phthalocyanine pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, squarylium dyes, pyrylium salts, thiapyrylium salts, triphenylmethane dyes, quinacridone pigments, azulhenium salts Pigment, cyanine dye, anthantrone pigment, pyranthrone pigment, xanthene dye, quinone imine dye, styryl dye and the like. Only one kind of charge generating substance may be used, or two or more kinds may be used. Among the charge generation substances, phthalocyanine pigments and azo pigments are preferable from the viewpoint of sensitivity, and phthalocyanine pigments are particularly preferable.

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

  As the binder resin used for the charge generation layer, for example, styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinylidene fluoride, a polymer of a vinyl compound such as trifluoroethylene, polyvinyl alcohol resin, polyvinyl 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 generating substance to the binder resin (charge generating substance: 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, a ball mill, a vibration ball mill, a sand mill, an attritor, and a roll mill.

Examples of the solvent used in the coating solution for the charge generation layer 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. Further, if necessary, various sensitizers, antioxidants, ultraviolet absorbers, and plasticizers can be added to the charge generation layer.

(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 drying the obtained coating film. Can be.

  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. . Preferably, it is a polycarbonate resin.

  Examples of the charge transport material used for the charge transport layer include a triarylamine compound, a hydrazone compound, a stilbene compound, a pyrazoline compound, an oxazole compound, a triarylmethane compound, and a thiazole compound. The charge transport material may be used alone or in combination of two or more.

  The ratio of the charge transport material to the binder resin in the charge transport layer is preferably from 0.3 parts by mass to 10 parts by mass per 1 part by mass of the binder resin.

  From the viewpoint of suppressing cracks in the charge transport layer, the drying temperature is preferably from 60 ° C to 150 ° C, more preferably from 80 ° C to 120 ° C. The drying time is preferably from 10 minutes to 60 minutes.

  Examples of the solvent used in the coating solution for the charge transport layer 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 from 5 μm to 40 μm, and more preferably from 10 μm to 35 μm.

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

[Surface layer (protective layer)]
And the protective layer which is a surface layer, as described above,
(Α) a hole-transporting compound having an acryloyloxy group or a methacryloyloxy group and not containing a fluorine atom and a silicon atom,
(Β) a compound having 2 to 4 acryloyloxy groups or methacryloyloxy groups, 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 having no hole transporting skeleton, or a fluorine compound having an acryloyloxy group or a methacryloyloxy group and having no hole transporting skeleton; and ε) A coating solution for a surface layer containing a solvent is prepared, a coating film of the coating solution for a surface layer is formed on the charge transport layer, and the coating film is cured.

  When applying the coating liquid for each of the above layers, for example, an application 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, and 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 driven to rotate around an axis 2 at a predetermined peripheral speed in a direction indicated by an arrow. The surface (peripheral surface) of the electrophotographic photoreceptor 1 is positively or negatively charged by a charging unit (primary charging unit) 3 during the rotation process. Next, the surface of the electrophotographic photosensitive member 1 is irradiated with exposure light (image exposure light) 4 output from an exposure unit (image exposure unit) (not shown). The exposure light 4 is intensity-modulated according to a time-series electric digital image signal of target image information. Examples of the 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 photosensitive member 1.

  Next, the electrostatic latent image formed on the surface of the electrophotographic photoreceptor 1 is developed (regular development or reversal development) with the toner contained in the developing means 5 to form a toner image. The toner image formed on the surface of the electrophotographic photosensitive member 1 is transferred to a transfer material 7 by a transfer unit 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 that of the retained charge of the toner is applied to the transfer unit 6 from a bias power supply (not shown). Further, the transfer unit may be an intermediate transfer type transfer unit 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 photoreceptor 1, conveyed to a fixing unit 8, and subjected to a fixing process of the toner image, so that the image forming material (print, copy) is processed electronically. Printed out of the photo device.

  The surface of the electrophotographic photoreceptor 1 after the transfer of the toner image is cleaned by a cleaning unit 9 to remove extraneous matters such as untransferred toner. The transfer residual toner can also be collected by a developing unit or the like. Further, if necessary, the surface of the electrophotographic photoreceptor 1 is subjected to static elimination by irradiation with pre-exposure light 10 from a pre-exposure unit (not shown), and then used repeatedly 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 necessarily required.

  A plurality of components, such as the electrophotographic photoreceptor 1, the charging unit 3, the developing unit 5, the transfer unit 6, and the cleaning unit 9, are selected and stored in a container, and are integrally supported as a process cartridge. I do. The process cartridge may be configured to be detachable from a 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 means 3, the developing means 5, and the cleaning means 9 are integrally supported to form a cartridge. The process cartridge 11 is detachable from the main body of the electrophotographic apparatus by 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, “parts” means “parts by mass”. Examples 9 to 21 which are (δ) and do not contain a siloxane-modified acrylic compound having an acryloyl group and having no hole-transporting skeleton having a weight average molecular weight of 300 or more and 10,000 or less are reference examples. .

(Example 1)
An aluminum cylinder having a diameter of 30 mm, a length of 357.5 mm, and a 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) were stirred and mixed with 500 parts of toluene, and 0.8 part of a silane coupling agent was added thereto. Was added and stirred for 6 hours. Thereafter, toluene was distilled off under reduced pressure, and the residue was dried by heating at 130 ° C. for 6 hours to obtain surface-treated zinc oxide particles. As a silane coupling agent, KBM602 (compound name: N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. was used.
Next, as a polyol resin, 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. To this solution, 80.8 parts of the surface-treated zinc oxide particles and 0.8 parts of 2,3,4-trihydroxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was added to a glass having a diameter of 0.8 mm. The particles were dispersed in a sand mill using beads at 23 ± 3 ° C. for 3 hours. After dispersion, 0.01 part of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Co., Ltd.) and cross-linked polymethyl methacrylate (PMMA) particles (trade name: TECHPOLYMER SSX-103, Sekisui Plastics Co., Ltd.) (Average primary particle size: 3 μm) was added and stirred to prepare an undercoat layer coating solution.
The undercoat layer coating solution was applied onto the aluminum cylinder by dip coating to form a coating film, and the obtained coating film was dried at 160 ° C. for 40 minutes to form an undercoat layer having a thickness of 18 μm.

Next, a hydroxygallium phthalocyanine crystal having a strong peak at 7.4 ° and 28.2 ° at a Bragg angle of 2θ ± 0.2 ° in CuKα characteristic X-ray diffraction was prepared. 20 parts of this hydroxygallium phthalocyanine crystal, 0.2 part of a compound represented by the following formula (2), 10 parts of a polyvinyl butyral resin (trade name: Eslek BX-1, manufactured by Sekisui Chemical Co., Ltd.) and 600 parts of cyclohexanone The mixture was dispersed 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 charge generating layer coating solution. This coating solution for a charge generation layer was applied onto the undercoat layer by dip coating to form a coating film, and the obtained coating film was heated and dried in an oven at a temperature of 80 ° C. for 15 minutes to form a film having a thickness of 0.17 μm. A charge generation layer was formed.

Next, 30 parts of a compound (charge transport material) represented by the following formula (3), 60 parts of a compound (charge transport material) represented by the following formula (4), 10 parts of a compound represented by the following formula (5), polycarbonate 100 parts of resin (trade name: Iupilon Z400, manufactured by Mitsubishi Engineering-Plastics Corporation, 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 coating liquid for a charge transport layer was prepared by dissolving 0.02 part of a polycarbonate (viscosity average molecular weight Mv: 20,000) in a solvent of 600 parts of mixed xylene and 200 parts of dimethoxymethane. This coating solution for a charge transport layer was applied onto the charge generation layer by dip coating to form a coating film, and the obtained 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 above 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 a 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: Zeolara H, manufactured by Zeon Corporation) 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 coating solution for a surface layer (a coating solution for a protective layer).

This coating solution for the surface layer is applied onto the charge transport layer by dip coating to form a coating film. Thereafter, under nitrogen atmosphere, the support (irradiation target) is rotated at 200 rpm under the conditions of an acceleration voltage of 70 kV and a beam current of 5.0 mA. The coating was irradiated with an electron beam for 1.6 seconds while rotating at a speed of. When the absorbed dose of the electron beam at this time was measured, it was 15 kGy. Thereafter, under a nitrogen atmosphere, the temperature of the coating was raised from 25 ° C. to 150 ° C. over 15 seconds, and the coating was heated. The oxygen concentration from 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 becomes 25 ° C., and is subjected to a heat treatment for 30 minutes under the condition that the temperature of the coating film becomes 105 ° C. to form a protective layer (surface layer) having a thickness of 5 μm. Formed.
Thus, an electrophotographic photoreceptor having a protective layer before the formation of the concave portion was manufactured.

Next, a mold member (mold) was set in the press-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-contact shape transfer processing apparatus having a configuration substantially as shown in FIG. 3, and the produced electrophotographic photosensitive member before forming the concave portion was subjected to surface processing. FIG. 4 is a diagram showing a mold used in the examples and comparative examples, and FIG. 4 (a) is a top view schematically showing the mold. FIG. 4B is a schematic cross-sectional view of the convex portion of the mold in the axial direction of the electrophotographic photosensitive member (cross-sectional view taken along the line SS ′ in FIG. 4A), and FIG. FIG. 5 is a cross-sectional view in the circumferential direction of the electrophotographic photosensitive member (a cross-sectional view taken along 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 and a 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. Note that the area ratio is a ratio of the area of the convex portion to the entire surface when the mold is viewed from above. During processing, the temperature of the electrophotographic photoreceptor and the mold are controlled so that the surface temperature of the electrophotographic photoreceptor becomes 120 ° C., and the electrophotographic photoreceptor and the pressing 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 (peripheral surface) of the electrophotographic photosensitive member. Thus, an electrophotographic photosensitive member having a concave portion on the surface was manufactured.

  The surface of the obtained electrophotographic photoreceptor was magnified and observed with a laser microscope (manufactured by KEYENCE CORPORATION, trade name: X-100) using a 50 × lens, and the concave portion provided on the surface of the electrophotographic photoreceptor was observed. Observations were made. At the time of observation, adjustment was performed so that there was no inclination in the longitudinal direction of the electrophotographic photosensitive member, and in the circumferential direction, the apex of the arc of the electrophotographic photosensitive member was focused. The images subjected to the magnification observation were connected by an image connection application to obtain a 500 μm-square area. Then, with respect to the obtained result, image processing height data was selected by attached image analysis software, and a filtering process was performed by a 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 140,000 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.

  Further, the obtained electrophotographic photosensitive member was mounted on a cyan station of a modified machine of an electrophotographic apparatus (copier) (trade name: iR-ADV C5051) manufactured by Canon Inc., which was an evaluation apparatus, and was heated at 30 ° C. 80 Image evaluation at% RH was performed.

In the image evaluation, the presence or absence of a streak image due to deterioration of the electrophotographic photosensitive member surface was examined. As a method, the total discharge current in the charging step was set to 120 μA, and the cassette heater (drum heater) in the apparatus was turned off. Thereafter, an image of 17 gradations of A4 width and an output resolution of 600 dpi was formed, and the obtained image of the entire A4 at an early stage of durability was evaluated as follows.
A: There are no vertical stripes or image deletion, and the image reproducibility is good.
B: Vertical stripes or image bleeding are slightly observed, but the other portions have good image reproducibility.
C: Some defects are observed when observed under magnification, but the image reproducibility is good.
D: Clear vertical streaks or image deletion occurred, and image reproducibility was low.

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

Also, using a surface surf coder SE3500 manufactured by Kosaka Laboratory, with a cutoff of 0.8 mm, a measurement length of 8 mm, and a measurement speed of 0.5 mm / s, the surface of the electrophotographic photoreceptor after forming 50,000 continuous images. (Maximum height Rmax) was obtained, and this Rmax value was defined as “scratch depth”.
Table 1 shows the results.

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 exemplified compound (1-1), 15 parts of compound having no hole-transporting skeleton represented by formula (7), 0.8 part of polycarbonate resin, and siloxane-modified acrylic represented by formula (8) 1 part of the compound, 10 parts of the vinyl ester compound represented by the formula (9), 40 parts of polytetrafluoroethylene particles (trade name: Lubron L2, manufactured by Daikin Co., Ltd.), and repetition represented by the following formula (A1) 2 parts of a 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))

Was 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: Zeorola H, manufactured by Nippon Zeon Co., Ltd.). An electrophotographic photoreceptor was manufactured and evaluated in the same manner as in Example 1, except that the coating liquid for a protective layer was obtained by performing a dispersion treatment with an ultrahigh-pressure disperser.

(Example 3)
An electrophotographic photosensitive member was manufactured 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 manufactured 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 changed to trimethylolpropane triacrylate (TMPTA). Was.

(Example 5)
An electrophotographic photoreceptor was manufactured 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 changed to trimethylolpropane trimethacrylate (TMPTM). Was.

(Example 6)
An electrophotographic photoreceptor was manufactured 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 changed to ditrimethylolpropanetetraacrylate (DTMPA). Was.

(Example 7)
An electrophotographic photosensitive member was manufactured 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 manufactured 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 manufactured 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 photosensitive member was manufactured 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)
Example 9 was repeated except that the compound having no hole transporting skeleton represented by the formula (7) was changed to polyethylene glycol # 400 diacrylate (A-400, manufactured by Shin-Nakamura Chemical Co., Ltd.). To produce an electrophotographic photoreceptor, and evaluated.

(Example 13)
An electrophotographic photosensitive member was manufactured 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 manufactured and evaluated in the same manner as in Example 9 except that the compound having no hole-transporting skeleton represented by the formula (7) was changed to tetramethylolmethanetetraacrylate (TMMTA). Was.

(Example 16)
Example 9 was repeated except that the compound having no hole-transporting skeleton represented by the formula (7) was changed to ethoxylated bisphenol A diacrylate (ABPE-10, manufactured by Shin-Nakamura Chemical Co., Ltd.). To produce an electrophotographic photoreceptor, and evaluated.

(Example 17)
An electrophotographic photoreceptor was manufactured 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 manufactured 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 12,000. Was done.

(Example 19)
An electrophotographic photosensitive member was manufactured and evaluated in the same manner as in Example 9 except that the amount of 2- (perfluorobutyl) ethyl acrylate was changed to 6 parts.

(Example 20)
An electrophotographic photosensitive member was manufactured and evaluated in the same manner as in Example 9 except that the amount of 2- (perfluorobutyl) ethyl acrylate was changed to 0.5 part.

(Example 21)
An electrophotographic photosensitive member was manufactured and evaluated in the same manner as in Example 9 except that the amount of 2- (perfluorobutyl) ethyl acrylate was changed to 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 manufactured and evaluated in the same manner as in Example 1 except that the surface layer was formed as described below.
80 parts of the above 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 a 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: Zeolara H, manufactured by Zeon Corporation) 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 coating solution for a surface layer (a coating solution for a protective layer).

Next, the coating solution for the surface layer was applied onto the charge transport layer by dip coating to form a coating film. The coating film was irradiated with UV light for 30 seconds at a light intensity of 1.20 × 10 ⁻⁵ W / m ² using a metal halide lamp. Irradiation and photocuring were performed. Thereafter, the 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 coating film with an electron beam, the temperature of the coating film was raised from 25 ° C. to 170 ° C. over 30 seconds in a nitrogen atmosphere, and the coating film was heated. In the same manner, an electrophotographic photosensitive member was manufactured and evaluated.

(Example 24)
After irradiating the coating film with an electron beam, the temperature of the coating film was increased from 25 ° C. to 140 ° C. over 30 seconds in a nitrogen atmosphere over 30 seconds, and the coating film was heated. In the same manner, an electrophotographic photosensitive member was manufactured and evaluated.

(Example 25)
After irradiating the coating film with an electron beam, the temperature of the coating film was raised from 25 ° C. to 180 ° C. over 30 seconds in a nitrogen atmosphere over 30 seconds, and the coating film was heated. In the same manner, an electrophotographic photosensitive member was manufactured and evaluated.

(Example 26)
After irradiating the coating film with an electron beam, the temperature of the coating film was increased from 25 ° C. to 130 ° C. over 30 seconds in a nitrogen atmosphere over 30 seconds, and the coating film was heated. In the same manner, an electrophotographic photosensitive member was manufactured and evaluated.

(Comparative Example 1)
An electrophotographic photosensitive member was manufactured and evaluated in the same manner as in Example 1 except that the addition amount of the polycarbonate resin was changed to 0.4 part.
In this case, in particular, the level of the streak image after forming 50,000 sheets of image was deteriorated as compared with Example 1.

(Comparative Example 2)
An electrophotographic photosensitive member was manufactured and evaluated in the same manner as in Example 1 except that the addition amount of the polycarbonate resin was 4.5 parts.
In this case, although a streak-like image defect due to the deterioration of the photoreceptor surface did not occur, the level of flaws generated on the surface of the electrophotographic photoreceptor after forming 50,000 sheets of images deteriorated, and the image due to the flaws was deteriorated. Bad was 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 the exemplified compound (1-1), 15 parts of the compound having no hole-transporting skeleton represented by the formula (7), 0.5 part of the polycarbonate resin, and siloxane-modified acrylic represented by the formula (8) 0.6 part of the compound, 10 parts of the vinyl ester compound represented by the above formula (9), 50 parts of polytetrafluoroethylene particles (trade name: Lubron L2, manufactured by Daikin Co., Ltd.), and the following formula (A1) Having a repeating structural unit represented by the following formula (A2) 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

Was 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: Zeorola H, manufactured by Nippon Zeon Co., Ltd.). An electrophotographic photoreceptor was manufactured in the same manner as in Example 1, except that the coating liquid for a protective layer was obtained by performing a dispersion treatment with an ultrahigh-pressure disperser.
In this case as well, no streak-like image defects caused by the deterioration of the photoconductor surface occurred, but the level of scratches generated on the surface of the electrophotographic photoconductor after forming 50,000 sheets of image deteriorated, and Image failure was observed.

(Comparative Example 4)
An electrophotographic photosensitive member was manufactured 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, the level of the streak image after forming 50,000 sheets of image was worse than that in Example 1.

(Comparative Example 5)
An electrophotographic photosensitive member was manufactured 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, in particular, the level of the streak image after forming 50,000 sheets of image was deteriorated as compared with Example 1.

  As a result of the evaluation, in Example, streak-like image defects in repeated use, image defects due to scratches generated on the surface of the electrophotographic photosensitive member were sufficiently suppressed, and a problem-free image was obtained. Indicates that 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 22 Subbing layer 23 Charge generation layer 24 Hole transport layer 25 Surface layer

Claims (11)

A support, and has a photosensitive layer and a protective layer is a surface layer comprising an electrophotographic photosensitive member having in this order, the surface layer is a (alpha) 2 or more acryloyloxy group or methacryloyloxy group A hole-transporting compound containing no fluorine and silicon atoms,
(Β) a compound having 2 to 4 acryloyloxy groups or methacryloyloxy groups, not containing a fluorine atom and a silicon atom, and not having a hole transporting skeleton;
(Γ) a bisphenol Z-type or A-type or C-type polycarbonate resin, and (δ) a siloxane-modified acrylic compound having a weight average molecular weight of 300 to 10,000 and having an acryloyloxy group and no hole transporting skeleton . a cured product of a composition comprising:
In the composition, (gamma) of the content of, (alpha) and the ratio of pairs to the total content of (beta), is 4 mass% 1 mass% or more,
In the composition, the ratio of the total content of (α) and (β) to the total content of the material of the surface layer in the composition is 60% by mass or more. Photoreceptor . The electrophotographic photoreceptor according to claim 1, wherein (α) has a structure represented by Formula (1-1) or Formula (1-2):

. When the number of functional groups in (α) is F1 and the molecular weight is M1, F1 / M1 is 0.002 to 0.006, and when the number of functional groups in (β) is F2 and the molecular weight is M2, F2 / M2 the electrophotographic photosensitive member according to 請 Motomeko 1 or 2 but Ru der 0.004 to 0.010. The electrophotographic photoreceptor according to any one of claims 1 to 3, wherein (δ) has a structure represented by formula (8):

(In the formula (8), n represents a number necessary to satisfy the weight average molecular weight of (δ)). Wherein the composition formula (I) compound represented by the further including請 Motomeko 1 electrophotographic photosensitive member according to any one of 4:

(R ¹ is .R ² is a hydrogen atom or a methyl group, an unsubstituted alkyl group which number is a straight-chain or branched 7 or more carbon atoms.). The electrophotographic photoreceptor according to any one of claims 1 to 5, wherein the composition further includes a compound having a structure represented by Formula (9).

. A method for producing an electrophotographic photosensitive member having a support, a photosensitive layer, and a protective layer as a surface layer in this order ,
(I) forming a coating film of a coating solution for a surface layer on the photosensitive layer, and
(Ii) forming a surface layer by curing the coating film,
The coating liquid is
(Α) a hole-transporting compound having two or more acryloyloxy groups or methacryloyloxy groups and not containing a fluorine atom and a silicon atom,
(Β) a compound having 2 to 4 acryloyloxy groups or methacryloyloxy groups, not containing a fluorine atom and a silicon atom, and not having a hole transporting skeleton;
(Γ) bisphenol Z type or A type or C type polycarbonate resin,
([Delta]) weight average molecular weight comprises 300 to 10,000, the siloxane modified acrylic compound having no hole-transport skeleton has a acryloyloxy group, your and <br/> (epsilon) solvent
And have you in the coating solution, the content of (γ), (α) and the ratio of the total content of (beta) is Ri 1 mass% or more 4% by mass or less,
In the coating solution, the total content of (alpha) and (beta), a percentage of the total content of the material of the surface layer of the coating solution is, Ru der least 60 wt%,
Process for producing an electrophotographic photoreceptor, wherein the this. Claim wherein step (ii) is, with the coating film is irradiated with an electron beam or ultraviolet light, Thereafter, the step of curing the coating film An electrophotographic photosensitive member was heated at a temperature of 170 ° C. 140 ° C. or higher 8. The method for producing an electrophotographic photosensitive member according to item 7 . 9. The method for producing an electrophotographic photoreceptor according to claim 7, wherein the paint further comprises a compound represented by the formula (9).

. A process cartridge that is detachable from an electrophotographic apparatus main body,
An electrophotographic photosensitive member according to any one of claims 1 to 6, a charging means, a developing means, that supports integrated and at least one means selected from the group consisting of transfer means and a cleaning means A process cartridge. The electrophotographic photosensitive member according to any one of claims 1 to 6, and charging means, exposure means, the electrophotographic apparatus, characterized in that it comprises a developing means and transfer means.

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