JP2014041271A - Electrophotographic photoreceptor, method of producing electrophotographic photoreceptor, process cartridge and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor capable of preventing slipping through of toner while inhibiting potential variation of the electrophotographic photoreceptor due to repeat use.SOLUTION: An electrophotographic photoreceptor includes a support, and a photosensitive layer provided on the support. The electrophotographic photoreceptor includes a surface layer containing an ester group containing polymer and a polyolefin resin with a specific structure.

Description

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

The electrophotographic photosensitive member takes a process of repeated charging, exposure, development, transfer, and cleaning in the image forming process. In particular, the cleaning process for removing the residual toner on the electrophotographic photosensitive member after the transfer process is an important process for obtaining a clear image. As a cleaning method, first, a rubber-like plate-shaped member called a cleaning blade is pressed against the electrophotographic photosensitive member to eliminate a gap between the electrophotographic photosensitive member and the cleaning blade, thereby suppressing toner slippage. Then, there is a method of scraping the remaining toner.
Secondly, a method is also used in which a fur brush roller is rotated so as to be in contact with the electrophotographic photosensitive member to wipe off or knock off residual toner. Among these cleaning methods, a rubber cleaning blade is advantageous in terms of cost and ease of design, and cleaning using a cleaning blade is currently the mainstream. In particular, when full-color development is performed, a desired color is produced by superimposing a plurality of colors such as magenta, cyan, yellow, and black, so that the amount of toner used is much larger than that of single-color development. Therefore, a cleaning method in which a rubber cleaning blade is pressed against the electrophotographic photosensitive member is optimal.

  However, the cleaning blade exhibiting excellent cleaning properties has a problem that the cleaning blade is likely to be reversed because the frictional force with the electrophotographic photosensitive member is large. The reversal of the cleaning blade is a phenomenon in which the blade warps in the moving direction of the electrophotographic photosensitive member (hereinafter referred to as “mekure”).

There are a method of changing the material of the cleaning blade and a method of lowering the pressing pressure in order to suppress the above-mentioned peeling. However, it is difficult to remove the residual toner on the electrophotographic photosensitive member, which is the original purpose, and the toner slips easily.
As a method for solving these problems related to the cleaning process, poor cleaning is achieved by using an electrophotographic photoreceptor containing a charge transporting polymer having a specific structure and organic fine particles composed of a crosslinked polymer having a specific average particle diameter. And suppressing abnormal noise (Patent Document 1).

JP 2002-40696 A

However, when the powder is added to the electrophotographic photosensitive member, there are few materials suitable for the electrophotographic photosensitive member in terms of the material and dispersibility of the powder, and there is room for improving the slipping of the toner. As a result, it became clear.
In addition, depending on the amount added, characteristics of the electrophotographic photosensitive member, particularly potential fluctuations due to repeated use of the electrophotographic photosensitive member and sharpness reduction in an image may easily occur.
SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic photosensitive member, a manufacturing method thereof, a process cartridge, and an electrophotographic apparatus that suppress toner slipping while suppressing potential fluctuation due to repeated use of the electrophotographic photosensitive member.

According to the present invention, an electrophotographic photosensitive member having a support and a photosensitive layer provided on the support,
The electrophotographic photosensitive member has a surface layer containing an ester group-containing polymer containing an ester group represented by Chemical Formula 1 and a polyolefin resin.
The polyolefin resin is
(A1) a repeating structural unit represented by the following formula (11):
(A2) at least one structural unit selected from the group consisting of a repeating structural unit represented by the following formula (21) and a repeating structural unit represented by the following formula (22); and (a3) in the following formula (31) At least one selected from the group consisting of the repeating structural unit shown, the repeating structural unit represented by the following formula (32), the repeating structural unit represented by the following formula (33), and the repeating structural unit represented by the following formula (34). Has a structural unit of species,
The mass ratio (%) of (a1) is (A1), the mass ratio (%) of (a2) is (A2), and the mass ratio (%) of (a3) is (A3). ), And (A2) and (A3) relate to an electrophotographic photosensitive member that satisfies the following formulas (I) and (II).
Formula (I) 55 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 ≦ 93
Formula (II) 0.01 ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 10

(In formula (11), R ^{11 to} R ¹⁴ each independently represents a hydrogen atom or an alkyl group.)

(In formulas (21) and (22), R ^{21 to} R ²⁴ each independently represents a hydrogen atom, an alkyl group, a phenyl group, or Y ²¹ COOH (Y ²¹ represents a single bond, an alkylene group, or an arylene group). R ²⁵ and R ²⁶ each independently represents a hydrogen atom, an alkyl group or a phenyl group, and X ²¹ represents —Y ²² COOCOY ²³ — (Y ²² and Y ²³ represent Each independently represents a single bond, an alkylene group or an arylene group.) However, at least one of R ^{21 to} R ²⁴ is a monovalent group represented by —Y ²¹ COOH. Group.)

(In formulas (31) to (34), R ^{31 to} R ³⁵ each independently represent a hydrogen atom or a methyl group, and R ^{41 to} R ⁴³ each independently represents an alkyl group having 1 to 10 carbon atoms. R ^{51 to} R ⁵³ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
Moreover, according to this invention, the manufacturing method of said electrophotographic photoreceptor is provided. Furthermore, according to the present invention, a cartridge and an electrophotographic apparatus having the above electrophotographic photosensitive member are provided.

  According to the present invention, it is possible to obtain an electrophotographic photosensitive member, a manufacturing method thereof, a process cartridge, and an electrophotographic apparatus that suppress toner slipping while suppressing potential fluctuation due to repeated use of the photosensitive member.

It is a figure which shows the layer structure of the cross section of the electrophotographic photoreceptor which concerns on this invention. 1 is a diagram illustrating a schematic configuration of an electrophotographic apparatus having a process cartridge including the electrophotographic photosensitive member of the present invention.

<Electrophotographic photoreceptor>
FIG. 1 is a schematic view showing an example of a cross section of an electrophotographic photosensitive member. The layer structure of the electrophotographic photosensitive member has one of the following structures as shown in FIGS.
FIG. 1A shows a function-separated configuration in which a charge generation layer 2 is formed on a conductive support 1 and a charge transport layer 3 is formed on the charge generation layer 2.
FIG. 1B shows a structure in which a single photosensitive layer 4 in which a charge generation material and a charge transport material are dispersed is formed on a conductive support 1.
FIG. 1C shows a configuration in which a protective layer 5 is provided on the charge transport layer 3 in FIG. 1A or the single photosensitive layer 4 in FIG. 1B (FIG. 1C-1) and FIG. c-2)).
In the present invention, the surface layer means a charge transport layer in FIG. 1 (a), a single photosensitive layer in FIG. 1 (b), and in FIG. 1 (c-1) and FIG. 1 (c-2). Refers to the protective layer.

<Ester group-containing polymer>
The ester group-containing polymer contained in the surface layer is a polymer having a structure represented by the following chemical formula 1 as a part thereof, or a crosslinked polymer in which an acryloyloxy group or a methacryloyloxy group is polymerized.

  Examples of the polymer include polyester resin, polycarbonate resin, polymethacrylate resin, polyarylate resin, and the like, and polycarbonate resin and polyarylate resin are particularly preferable. These may be used alone or in combination as a mixture or copolymer.

The crosslinked polymer obtained by polymerizing acryloyloxy groups or methacryloyloxy groups may be a polymer having one or more acryloyloxy groups or methacryloyloxy groups. In particular, a hole transporting compound having two or more acryloyloxy groups or methacryloyloxy groups in the same molecule is preferable.
The hole transporting compound having two or more acryloyloxy groups or methacryloyloxy groups is preferably represented by the following formula (1).

  P1 and P2 represent an acryloyloxy group or a methacryloyloxy group, and P1 and P2 may be the same or different. Y represents a hydrogen atom. a, b and d represent 0 or an integer of 1 or more. However, when a = 0, b + d is an integer of 3 or more, when b or d is 0, a is an integer of 2 or more, and in other cases, a + b + d is an integer of 3 or more. Further, when a is 2 or more, the plurality of P1s may be the same or different, respectively, when d is 2 or more, the plurality of P2s may be the same or different, and when b is 2 or more, Z may be the same or different.

  A in the above formula (1) represents a hole transporting group and may be any one as long as it exhibits hole transporting properties, and a hydrogenation compound (hole transporting compound in which P1 or Z is replaced with a hydrogen atom). ), For example, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triarylamine derivatives such as triphenylamine, 9- (p-diethylaminostyryl) anthracene, 1,1-bis- (4-dibenzylaminophenyl) ) Propane, styrylanthracene, styrylpyrazoline, phenylhydrazones, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, thiophene derivatives and N-phenylcarbazole derivatives.

Z in the formula (1) is an alkylene group which may have a substituent, an arylene group which may have a substituent, CR1 = CR2 (R1 and R2 are an alkyl group, an aryl group and a hydrogen atom) R1 and R2 may be the same or different.), C = O, S═O, SO ₂ , one selected from an oxygen atom and a sulfur atom, or an organic residue obtained by arbitrarily combining these. Among these, what is shown by following formula (2) is preferable, and what is shown by following formula (3) is especially preferable.

In formula ^(2), X 1 ~X ³ substituent methylene group which may have a ethylene group and an alkylene group having 1 to 20 carbon atoms such as _{^{propylene, (CR 1 = CR 2)}} m1, A carbonyl group, S═O, SO ₂ , an oxygen atom and a sulfur atom are shown. Ar ¹ and Ar ² are substituted or unsubstituted arylene groups (from benzene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, etc. A group in which two hydrogen atoms are taken, for example, a phenylene group).

R ¹ and R ² each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a hydrogen atom. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and a thiophenyl group. m1 represents an integer of 1 to 5, and p to t represent an integer of 0 to 10 (provided that p to t are not 0 at the same time).

In the general formula (3), X ⁴ and X ⁵ each independently represent (CH 2) _{m 2} , ( _CH═CR ³ ) _{n 2} , C═O or an oxygen atom. Ar ³ is a substituted or unsubstituted arylene group (two hydrogen atoms such as benzene, naphthalene, anthracene, phenanthrene, pyrene, benzothiophene, pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, and dibenzothiophene. An atomic group, for example, a phenylene group).

R ³ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a hydrogen atom. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and a thiophenyl group. m2 is an integer of 1 to 10, n2 is an integer of 1 to 5, u to w are integers of 0 to 10 (u to w are particularly preferably integers of 0 to 5. However, u to w are It is never 0 at the same time.)

  Furthermore, among the above-described hole transporting compounds, those represented by the following formula (4) are preferable.

In formula (4), R ⁴ , R ⁵ and R ⁶ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted aryl. Indicates a group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group, and a thienyl group. Aryl groups are phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, thiophenyl, furyl, pyridyl, quinolyl, benzoquinolyl, galazolyl, phenothiazinyl, benzofuryl, benzothiophenyl, dibenzo A furyl group, a dibenzothiophenyl group, etc. are mentioned.

However, at least two of R ⁴ , R ⁵ and R ⁶ represent an aryl group. Furthermore, among them, those in which all of R ⁴ , R ⁵ and R ⁶ are aryl groups are particularly preferable. Further, any two of R ⁴ , R ⁵ and R ^{6 in} the above formula (4) may be bonded directly or via a bonding group, and as the bonding group, a methyl group, an ethyl group and Examples include an alkylene group such as a propylene group, a hetero atom such as an oxygen atom and a sulfur atom, and a CH═CH group.

Examples of the substituents that R ^{1 to} R ⁶ , Ar ^{1 to} Ar ³ , X ^{1 to} X ^5, and Z in the above formulas (1) to (4) may have include fluorine, chlorine, bromine, and iodine. Alkyl groups such as halogen atoms, nitro groups, cyano groups, hydroxyl groups, alkyl groups such as methyl groups, ethyl groups, propyl groups and butyl groups, alkoxy groups such as methoxy groups, ethoxy groups and propoxy groups, and aryloxy groups such as phenoxy groups and naphthoxy groups Aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, furfuryl group and thienyl group, aryl groups such as phenyl group, naphthyl group, anthryl group and pyrenyl group, dimethylamino group, diethylamino group, dibenzylamino group, diphenyl Substituted amino groups such as amino groups and di (p-tolyl) amino groups, and aryls such as styryl groups and naphthyl vinyl groups Group and the like.

<Polyolefin resin>
The polyolefin resin contained in the surface layer of the electrophotographic photosensitive member is represented by (a1) a repeating structural unit represented by the following formula (11), (a2) a repeating structural unit represented by the following formula (21), and formula (22). At least one structural unit selected from the group consisting of repeating structural units, (a3) a repeating structural unit represented by a repeating structural unit represented by the following formula (31), and a repeating structure represented by formula (32) And at least one structural unit selected from the group consisting of a unit, a repeating structural unit represented by formula (33), and a repeating structural unit represented by formula (34). The polyolefin resin is a copolymer, and refers to a resin synthesized by using monomers having carbon-carbon double bonds as raw materials and copolymerizing them.
As specific examples of the formula (11), the formula (21), the formula (22), and the formulas (31) to (34), the names of monomers before copolymerization (ethylene, isobutylene, 1-butene, etc.) are used. However, a polyolefin resin is a copolymer of these monomers.

(In formula (11), R ^{11 to} R ¹⁴ each independently represent a hydrogen atom or an alkyl group.)
Examples of the repeating structural unit represented by the formula (11) include alkenes having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene and 1-hexene. These can be used alone or as a mixture.
Among these, alkylene having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene is more preferable, and ethylene is particularly preferable.
When the mass ratio (%) of (a1) is (A1), the mass ratio (%) of (a2) is (A2), and the mass ratio (%) of (a3) is (A3), (A1) is an equation. (I) It is necessary for the amount to satisfy 55 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 ≦ 93. Preferably 60 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 ≦ 93, more preferably 70 ≦ (A1) / {(A1) + (A2) + (A3)}. X100≤93.

<Repeating structural unit represented by formula (21) or formula (22)>

(In the formulas (21) and (22), R ^{21 to} R ²⁴ each independently represents a hydrogen atom, an alkyl group, a phenyl group or —Y ²¹ COOH (Y ²¹ represents a single bond, an alkylene group or an arylene group). R ²⁵ and R ²⁶ each independently represents a hydrogen atom, an alkyl group or a phenyl group, and X ²¹ represents —Y ²² COOCOY ²³ — (Y ²² and Y ^23. Each independently represents a single bond, an alkylene group or an arylene group.), Wherein at least one of R ^{21 to} R ²⁴ is a monovalent group represented by —Y ²¹ COOH. The base of

  The repeating structural unit represented by the formula (21) or the formula (22) is preferably a structural unit derived from an unsaturated carboxylic acid or an anhydride thereof. Specific examples include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid and the like, as well as unsaturated dicarboxylic acid half esters and half amides. Among these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable.

Moreover, the form of the said copolymer is not specifically limited, A random copolymer, a block copolymer, a graft copolymer, etc. are mentioned.
The unsaturated carboxylic acid anhydride such as maleic anhydride forms a carboxylic acid anhydride structure in which adjacent carboxyl groups are dehydrated and cyclized in the dry state of the resin. However, for example, in an aqueous medium containing a basic compound, part or all of the ring is opened, and the structure of a carboxylic acid or a salt thereof is easily formed.
Moreover, in this invention, when prescribing | regulating the quantity of a compound on the basis of the amount of carboxyl groups of resin, it calculates, assuming that all the carboxylic acid anhydrides have ring-opened and have formed the carboxyl group.

  (A1), (A2), and (A3) must satisfy the formula (II) 0.01 ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 10. It is. Preferably, it is an amount satisfying the formula (II-2) 0.01 ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 5, more preferably the formula (II-3) 3. ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 5.

<Repeating structural unit represented by formula (31), (32), (33) or (34)>

(In formulas (31) to (34), R ^{31 to} R ³⁵ each independently represent a hydrogen atom or a methyl group, and R ^{41 to} R ⁴³ each independently represents an alkyl group having 1 to 10 carbon atoms. R ^{51 to} R ⁵³ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
Examples of the repeating structural units represented by the formulas (31) to (34) include structural units derived from the following compounds.
In the formula (31), (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate may be mentioned.
In the formula (32), maleate esters such as dimethyl maleate, diethyl maleate, dibutyl maleate and the like can be mentioned.
In formula (33), (meth) acrylic acid amides may be mentioned.
Formula (34) includes alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, and vinyl alcohol obtained by saponifying vinyl esters with a basic compound or the like.

In addition, these compounds can also be used individually or as a mixture.
In this, the (meth) acrylic acid ester shown by Formula (31) is preferable, and methyl acrylate or ethyl acrylate is more preferable.
(A3) is preferably an amount satisfying the formula (III) 55/42 ≦ (A1) / (A3) ≦ 99/1.
The mass ratio (%) of (A3) alone with respect to the total mass of the polyolefin resin is preferably 1% by mass or more and 20% by mass or less, more preferably 10% by mass or more and less than 20% by mass. (A3) When the single mass ratio (%) is 1% by mass or more and 20% by mass or less, characteristic stability due to environmental fluctuations is also maintained.
(A3) The single mass ratio (%) is calculated by the following equation.
(A3) / {(A1) + (A2) + (A3)} × 100

The polyolefin resin used in the present invention particularly preferably contains a terpolymer comprising ethylene, methyl (meth) acrylate or ethyl (meth) acrylate, and maleic anhydride.
Specific examples of the terpolymer include ethylene-maleic anhydride-acrylic acid ester ternary copolymer or ethylene-maleic anhydride-methacrylic acid ester ternary copolymer.

  The polyolefin resin used in the present invention may contain components other than those described above as components of the copolymer to the extent that the effects of the present invention are not impaired. Specific examples of other monomers include dienes, (meth) acrylonitrile, vinyl halides, halogenated vinylidenes, carbon monoxide, sulfur disulfide and the like. In addition, it is preferable that the mass ratio (%) of the total amount of (A1), (A2), and (A3) in the polyolefin resin is 90% to 100%.

  The weight average molecular weight of the polyolefin resin used in the present invention is not particularly limited, but is preferably 20,000 or more in order to suppress toner slip-through. Also, the synthesis method is not particularly limited, and the polyolefin resin can be obtained, for example, by high-pressure radical copolymerization of a monomer constituting the polyolefin resin in the presence of a radical generator. As specific methods for synthesizing polyolefin resins, chapters 1 to 4 (Kyoritsu Shuppan Co., Ltd.) of “New Polymer Experiments 2 Polymer Synthesis and Reaction (1)”, Japanese Patent Application Laid-Open No. 2003-105145. It is possible to use a known method described in JP-A-2003-147028.

In the present invention, the characteristics of the resin were measured or evaluated by the following method.
(1) Content of unsaturated carboxylic acid component (a2) in olefin The acid value of olefin was measured in accordance with JIS K5407, and the content (graft ratio) of unsaturated carboxylic acid was determined from the value from the following formula. .
Unsaturated carboxylic acid component content (mass%) = (mass of grafted unsaturated carboxylic acid) / (mass of raw material olefin resin) × 100

(2) Content of component other than unsaturated carboxylic acid component (a2) in olefin ¹ H-NMR, ¹³ C-NMR analysis at 120 ° C. in orthodichlorobenzene (d4) (Varian Technologies Japan (Limited, 300 MHz). ^{In 13} C-NMR analysis, measurement was performed using a gated decoupling method in consideration of quantitativeness.
The mass ratio of the polyolefin resin in the surface layer is preferably 1% or more and 40% or less, and more preferably 3 or more and 30% or less.

<Method for producing electrophotographic photoreceptor>
Below, the manufacturing method of an electrophotographic photoreceptor is demonstrated.
The support used in the present invention is preferably a conductive support, and a metal support such as aluminum, nickel, copper, gold, or iron can be used. In addition, an insulating support such as an alloy, polyester, polycarbonate, polyimide, glass, etc., on which a thin film of a metal such as aluminum, silver or gold or a conductive material such as indium oxide or tin oxide is formed, carbon or conductive filler It is also possible to use a material that is dispersed in a resin to impart conductivity.

Further, the shape of the support is not particularly limited, and a plate, drum or belt may be used as necessary.
These support surfaces may be subjected to an electrochemical treatment such as anodization in order to improve electrical characteristics or adhesion. Also, chemical treatment using a solution obtained by dissolving a metal salt compound or a fluorine compound metal salt in an alkaline aqueous solution or an acidic aqueous solution mainly composed of phosphoric acid or tannic acid may be performed. good.

Further, when the electrophotographic photosensitive member of the present invention is used in a printer using a single wavelength laser beam or the like, it is preferable that the surface of the support is moderately roughened in order to suppress interference fringes.
That is, the support is preferably a support whose surface is treated by honing, blasting, cutting, electropolishing, or the like. Alternatively, it is preferable to have a conductive film (hereinafter referred to as a conductive layer) made of a conductive metal oxide and a binder resin on an aluminum or aluminum alloy support.

As the honing treatment, there are dry and wet treatment methods, and any of them may be used. The wet honing process is a method in which a powdered abrasive is suspended in a liquid such as water and sprayed onto the surface of the support at a high speed to roughen the surface. The surface roughness is the spray pressure, speed, and amount of abrasive. It can be controlled by the type, shape, size, hardness, specific gravity, suspension temperature and the like.
On the other hand, the dry honing treatment is a method in which an abrasive is sprayed onto the support surface at a high speed with air to roughen the surface, and the surface roughness can be controlled by the same method as the wet honing treatment. Examples of the abrasive used for the wet or dry honing treatment include particles such as silicon carbide, alumina, iron, and glass beads.

In the method of applying the conductive layer made of the conductive metal oxide and the binder resin on the support of aluminum or aluminum alloy, the conductive layer preferably contains a powder made of conductive fine particles as a filler. .
This method has the effect of dispersing the conductive fine particles in the conductive layer to diffusely reflect the laser light to prevent interference fringes and to cover the scratches and protrusions of the support before coating.

Examples of the conductive fine particles include zinc oxide, titanium oxide, and barium sulfate. Further, if necessary, it is possible to provide an appropriate specific resistance as a filler by providing a conductive coating layer with tin oxide or the like on the conductive fine particles.
The specific resistance of the conductive fine particles is preferably from 0.1 Ωcm to 1000 Ωcm, more preferably from 1 Ωcm to 1000 Ωcm.
In the present invention, the specific resistance of the conductive fine particles was measured using a resistance measuring apparatus Loresta AP (Loresta Ap) manufactured by Mitsubishi Chemical Corporation. The conductive fine particles to be measured were hardened at a pressure of 500 kg / cm ² and attached to the measuring device as a coin-like sample.

The average particle size of the conductive fine particles is preferably 0.05 μm or more and 1.0 μm or less, and more preferably 0.07 μm or more and 0.7 μm or less. The average particle diameter of the conductive fine particles is a value measured by a centrifugal sedimentation method.
Furthermore, the content of the conductive fine particles as a filler is preferably 1.0% by mass or more and 90% by mass or less, and more preferably 5.0% by mass or more and 80% by mass or less with respect to the conductive layer. preferable. The conductive layer may contain fluorine or antimony as necessary.

  Examples of the binder resin used for the conductive layer include phenol resin, polyurethane, polyamide, polyimide, polyamideimide, polyamic acid, polyvinyl acetal, epoxy resin, acrylic resin, melamine resin, and polyester. These resins may be used alone or in combination of two or more. When these resins are used, the adhesiveness of the conductive layer to the support is good, the dispersibility of the conductive fine particles is improved, and the solvent resistance after film formation is preferable. Among the above resins, phenol resin, polyurethane and polyamic acid are particularly preferable.

The conductive layer can be formed by, for example, immersion or solvent application using a Meyer bar or the like. The thickness of the conductive layer is preferably from 0.1 μm to 30 μm, and more preferably from 0.5 μm to 20 μm. The volume resistivity of the conductive layer, it is preferably, 1.0 × 10 ⁵ Ωcm or more 1.0 × ^{10 12} Ωcm or less is 1.0 × 10 ⁵ Ωcm or more 1.0 × ^{10 13} Ωcm or less It is more preferable.
In the present invention, the volume resistivity is obtained by applying a conductive layer to be measured on an aluminum plate, further forming a gold thin film on the conductive layer, and calculating a current value flowing between both electrodes of the aluminum plate and the gold thin film. , Measured using a pA meter. Furthermore, a leveling agent may be added to the conductive layer in order to improve surface properties.

<Intermediate layer>
An intermediate layer having an adhesion function and a barrier function can be provided on the support or the conductive layer as necessary. Materials for the intermediate layer include polyamide, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, casein, polyurethane, polyether urethane, and other thermoplastic resins, melamine resins, phenol resins, alkyd resins, epoxy resins, silane coupling agents, organometallic complexes And other thermosetting materials. These are dissolved in a suitable solvent and applied. The film thickness of the intermediate layer is preferably 0.05 μm or more and 5 μm or less, and particularly preferably 0.3 μm or more and 3 μm or less.

<Charge generation layer>
A charge generation layer is formed on the support, the conductive layer or the intermediate layer. The charge generation layer is preferably formed containing a charge generation material and other components such as a binder resin. For example, the charge generation layer may be obtained by dissolving a binder resin in a solvent, adding a charge generation material thereto, and dispersing the charge generation material to obtain a charge generation layer coating solution obtained by dispersing the charge generation layer coating solution. It can form by apply | coating on a layer, forming a coating film, and drying the obtained coating film. When dispersing the charge generating material, a media type disperser such as a sand mill or a ball mill, or a disperser such as a liquid collision type disperser can be used.

Examples of the charge generating substance include pyrylium dyes, thiopyrylium dyes, phthalocyanine pigments, anthanthrone pigments, dibenzpyrenequinone pigments, pyratron pigments, azo pigments, indigo pigments, quinacridone pigments, and quinocyanine dyes. Can be mentioned.
Examples of the phthalocyanine pigment include metal-free phthalocyanine, oxytitanium phthalocyanine, hydroxyphthalocyanine, and gallium halide phthalocyanine such as chlorogallium. These charge generation materials can be used alone or as a mixture.

  In the charge generation layer, when a charge generation material other than the phthalocyanine pigment and the phthalocyanine pigment is mixed and used, the charge generation material other than the phthalocyanine pigment may be contained up to 50% by mass with respect to the total charge generation material. Is possible. In this case, as a charge generating substance other than the phthalocyanine pigment, for example, selenium-tellurium, pyrylium, thiapyrylium dye, anthanthrone, dibenzpyrenequinone, trisazo, cyanine, disazo, monoazo, indigo, quinacridone, and asymmetric quinocyanine And pigments.

The charge generation layer comprises a homogenizer, an ultrasonic dispersion, a ball mill, a vibration ball mill, a sand mill, an attritor, a roll mill, together with a binder resin having a mass ratio of 0.3 to 4 times the binder resin and a solvent. It is formed by applying and drying a sufficiently dispersed solution using a liquid collision type high-speed disperser or the like.
Examples of the binder resin include butyral resin, polyester resin, polycarbonate resin, polyarylate resin, polystyrene resin, polyvinyl methacrylate resin, polyvinyl acrylate resin, polyvinyl acetate resin, polyvinyl chloride resin, polyamide resin, polyurethane resin, silicone resin, Examples include, but are not limited to, alkyd resins, epoxy resins, cellulose resins, and melamine resins. Of these, a butyral resin is particularly preferred.

<Charge transport layer>
A charge transport layer is formed on the charge generation layer. The charge transport layer is formed by applying a coating solution in which a charge transport material and a binder resin are mainly dissolved in a solvent to form a coating film on the charge generation layer, and drying the obtained coating film. Examples of the charge transport material include triarylamine compounds, hydrazone compounds, stilbene compounds, pyrazoline compounds, oxazole compounds, triallylmethane compounds, and thiazole compounds.

  Examples of the binder resin include a polyester resin, a polycarbonate resin, a polyarylate resin, a polystyrene resin, and a polyvinyl methacrylate resin. When the surface layer is a charge transport layer in the present invention, the binder resin is represented by the above chemical formula 1. It is necessary to be an ester group-containing polymer containing an ester group. Preferred are ester group-containing polymers such as polycarbonate resins, polyarylate resins, and polyvinyl methacrylate resins. More preferred are polycarbonate resins and polyarylate resins. Dispersion containing an ester group-containing polymer, a charge transport material, and a polyolefin resin having a repeating structural unit represented by the above formula (11), formula (21), formula (22), or formula (31) to (34) A charge transport layer is formed by performing a heat treatment after applying the liquid on the charge generation layer.

<Protective layer>
In the present invention, a protective layer may be provided on the photosensitive layer (charge transport layer) for the purpose of protecting the photosensitive layer and improving wear resistance and cleaning properties.
The protective layer can be formed by applying a protective layer coating solution obtained by dissolving a binder resin in an organic solvent to form a coating film and drying the resulting coating film. Examples of the resin used for the protective layer include polyvinyl butyral resin, polyester resin, polycarbonate resin, polyamide resin, polyimide resin, polyarylate resin, polyurethane resin, styrene-butadiene copolymer, styrene-acrylic acid copolymer, and styrene-acrylonitrile copolymer. It is done.

In order to give the protective layer a charge transporting ability, the protective layer may be formed by curing a monomer material having a charge transporting ability or a polymer type charge transporting substance using various crosslinking reactions. Preferably, a cured layer is formed by polymerizing or crosslinking a charge transporting compound having a chain polymerizable functional group. Examples of the chain polymerizable functional group include an acryl group, a methacryl group, an alkoxysilyl group, and an epoxy group. Examples of the curing reaction include radical polymerization, ionic polymerization, thermal polymerization, photopolymerization, radiation polymerization (electron beam polymerization), plasma CVD method, and photo CVD method.
The thickness of the protective layer is preferably from 0.5 μm to 10 μm, and preferably from 1 μm to 7 μm. Moreover, electroconductive particle etc. can also be added to a protective layer as needed.
In addition, the surface layer (charge transport layer or protective layer) of the electrophotographic photoreceptor has a lubricant such as silicone oil, wax, fluorine atom-containing resin particles such as polytetrafluoroethylene particles, silica particles, alumina particles, and boron nitride. May be included.
In the present invention, when a protective layer is provided on the charge transport layer, this protective layer is the surface layer described in the present application.

<Process cartridge and electrophotographic apparatus>
The process cartridge and the electrophotographic apparatus to which the cartridge is detachably mounted are not limited to a copying machine, a facsimile machine, or a printer as long as it has an electrophotographic photosensitive member.
As an example of a process cartridge and an electrophotographic apparatus including the electrophotographic photosensitive member of the present invention, a non-magnetic one-component developing type printer will be described below. In FIG. 2, a process cartridge 15 integrally supports the electrophotographic photosensitive member 6, the charging means 8, the developing means 10 and the cleaning means 14 according to the present invention, and is detachable from the main body of the electrophotographic apparatus. The process cartridge 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.
The electrophotographic photosensitive member 6 is rotated around a shaft 7 by a rotating mechanism (not shown), and is charged to a predetermined polarity and potential by a charging unit 8. Furthermore, an electrostatic latent image is formed by irradiating the surface of the charged electrophotographic photosensitive member 6 with exposure light 9 from exposure means (not shown). Then, toner is formed on the electrostatic latent image by the developing unit 10 to form a toner image. The toner image is transferred onto the transfer material 12 by the transfer unit 11, and then the electrophotographic photoreceptor by the cleaning unit 14. The residual toner above 6 is cleaned. A fixing unit 13 for fixing the transferred toner image on the transfer material 12 is disposed on the transfer path of the transfer material 12.

Hereinafter, the present invention will be described specifically by way of examples. In addition, the number of parts in the following composition is part by mass unless otherwise specified.
An electrophotographic photosensitive member was produced by the method described below using a polyolefin resin having the constituent components and mass ratio (%) shown in Table 1 below.
The (A1) type corresponds to the formula (11), the (A2) type corresponds to the formulas (21) and (22), and the (A3) type corresponds to the formulas (31) to (34), respectively. The name of the previous monomer is shown.

<Example 1>
<Preparation of aqueous dispersion containing (B-1)>
When the materials listed in Table 2 were mixed in a sealable pressure-resistant 1-liter capacity glass container equipped with a stirrer and stirred at a rotation speed of the stirring blade of 300 rpm, resin particles were precipitated at the bottom of the container. Was not observed and it was confirmed that it was floating.

  Therefore, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the system temperature was kept at 140 to 145 ° C. and further stirred for 20 minutes. Then, after putting in a water bath and cooling to room temperature (about 25 ° C.) while stirring at a rotational speed of 300 rpm, pressure filtration (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) did. In this way, an aqueous dispersion containing milky white uniform polyolefin resin particles (B-1) was obtained.

<Production of support>
As a support (conductive support), an aluminum base tube (ED tube: JIS-A3003) having an outer diameter of 30.5 mm, an inner diameter of 28.5 mm, and a length of 260.5 mm was prepared by hot extrusion.
A solution made of the materials shown in Table 3 was prepared, and the powder was dispersed using a ball mill for about 20 hours to prepare a coating solution for a conductive layer. The average particle size of the powder dispersed in the coating solution was 0.22 μm.

The conductive layer coating solution is applied onto the aluminum base tube by a dip coating method to form a coating film, and the resulting coating film is heated and cured at a temperature of 140 ° C. for 30 minutes, whereby a conductive film having a thickness of 15 μm is formed. A layer was formed.
Next, 10 parts of copolymer nylon resin (trade name: Amilan CM8000, manufactured by Toray Industries, Inc.) and 30 parts of methoxymethylated nylon (trade name: Toresin EF30T, manufactured by Teikoku Chemical Industry Co., Ltd.) are added to 500 parts by mass of methanol. And it melt | dissolved in the mixed solvent which consists of 250 mass parts of butanol, and prepared the coating liquid for intermediate | middle layers.
The intermediate layer coating solution is applied onto the conductive layer by a dip coating method to form a coating film, and the resulting coating film is dried at a temperature of 120 ° C. for 10 minutes to form an intermediate layer having a thickness of 0.8 μm. Formed.

<Formation of charge generation layer>
Next, the materials shown in Table 4 were mixed and dispersed over 3 hours by a sand mill using glass beads having a diameter of 1 mm. This was diluted with 1200 parts by mass of ethyl acetate to obtain a coating solution for charge generation layer. At this time, the dispersed particle diameter of the charge generation material in the dispersion measured using a natural / centrifugal sedimentation particle size distribution analyzer (CAPA-700, manufactured by Horiba, Ltd.) was 0.15 μm. On the intermediate layer, this charge generation layer coating solution was dip coated and dried at a temperature of 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.2 μm.

<Formation of charge transport layer>
Next, the materials shown in Table 5 were dissolved in a mixed solvent composed of 50 parts by mass of monochlorobenzene and 10 parts by mass of dichloromethane to prepare a coating solution for a charge transport layer. The charge transport layer coating solution is applied onto the charge generation layer by a dip coating method to form a coating film, and the resulting coating film is dried at a temperature of 110 ° C. for 1 hour to form a charge transport layer having a thickness of 15 μm. Formed.

<Formation of protective layer>
Further, 60 parts of a hole transporting compound represented by the following structural formula (9) is dissolved in a mixed solvent of 60 parts of toluene / 40 parts of IPA, and an aqueous dispersion containing 25% by mass of (B-1) is further prepared. 48 parts was added to prepare a coating solution for a protective layer. This protective layer coating solution (surface layer coating solution) is applied onto the charge transport layer to form a coating film, and the resulting coating film is subjected to an acceleration voltage of 150 KV and an irradiation dose of 4 Mrad in an atmosphere having an oxygen concentration of 10 ppm. The electron beam was irradiated under the conditions of Subsequently, a heat treatment was carried out for 10 minutes under the same atmosphere at a temperature of 100 ° C. to form a protective layer having a thickness of 5 μm to obtain an electrophotographic photoreceptor.

The electrophotographic photosensitive member obtained as described above was mounted on a modified machine of an electrophotographic copying machine GP-40 manufactured by Canon Inc., and tested and evaluated as follows.
First, potential conditions were set so that the dark portion potential (Vd) of the electrophotographic photosensitive member was −700 V and the bright portion potential (Vl) was −200 V, and the initial potential of the electrophotographic photosensitive member was adjusted.
Next, a cleaning blade made of polyurethane rubber was set so that the contact angle with respect to the surface of the electrophotographic photosensitive member was 26 ° and the contact pressure was 30 g / cm.

  Thereafter, a repeated use test for printing 50000 sheets of A4 size paper in the 10-sheet intermittent mode was performed. A test chart having a printing ratio of 5% was used, and only the first of the 10 sheets was intermittent, and the remaining 9 sheets were solid white images. After the repeated use test, test images of solid white, solid black, and halftone images were output, and image defects were observed due to toner slip-through. The above repeated use test was performed in a temperature 23 ° C./humidity 50% RH environment and a temperature 30 ° C./humidity 80% RH environment. The toner slipping state due to poor cleaning was evaluated based on the criteria shown in Table 6 below.

  The potential change after repeated use was evaluated according to Table 7 below.

<Example 2-6 and Comparative Example 1>
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 1 except that the olefin resin listed in Table 11 was used instead of (B-1).
<Example 7>
As a support, an aluminum base tube (ED tube: JIS-A3003) having an outer diameter of 30.5 mm, an inner diameter of 28.5 mm, and a length of 260.5 mm was prepared by hot extrusion.
<Formation of conductive layer>
A solution made of the materials shown in Table 8 was prepared, and the powder was dispersed using a ball mill for about 20 hours to prepare a coating solution for a conductive layer. The average particle size of the powder dispersed in the coating solution was 0.22 μm.

The conductive layer coating solution is applied onto the aluminum base tube by a dip coating method to form a coating film, and the resulting coating film is heated and cured at a temperature of 140 ° C. for 30 minutes, whereby a conductive film having a thickness of 15 μm is formed. A layer was formed.
On this conductive layer, the same intermediate layer coating solution as in Example 1 was applied by a dip coating method and dried at a temperature of 120 ° C. for 10 minutes to form an intermediate layer having a thickness of 0.8 μm.

<Formation of charge generation layer>
Next, the materials shown in Table 9 were mixed and dispersed by a sand mill using glass beads having a diameter of 1 mm over 3 hours. This was diluted with 1200 parts by mass of ethyl acetate to obtain a coating solution for charge generation layer. At this time, the dispersed particle diameter of the charge generation material in the dispersion measured using a natural / centrifugal sedimentation particle size distribution analyzer (CAPA-700, manufactured by Horiba, Ltd.) was 0.15 μm. On the intermediate layer, this charge generation layer coating solution is dip-coated to form a coating film, and the resulting coating film is dried at a temperature of 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.2 μm. Formed.

<Formation of charge transport layer>
Next, the material described in Table 10 is dissolved in a mixed solvent composed of 50 parts by mass of toluene and 20 parts by mass of IPA, and an aqueous dispersion containing 25% by mass of (B-3) as an olefin resin is added to 14. Four parts were added to prepare a charge transport layer coating solution (surface layer coating solution).

  The charge transport layer coating solution is applied onto the charge generation layer by a dip coating method to form a coating film, and the resulting coating film is dried at a temperature of 110 ° C. for 1 hour to form a charge transport layer having a thickness of 20 μm. To obtain an electrophotographic photosensitive member.

<Example 8>
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 7 except that (B-5) was used as the olefin resin used for the charge transport layer coating solution.
<Example 9>
Instead of the polyarylate resin used in the coating solution for the charge transport layer, bisphenol Z type polycarbonate resin (trade name: Iupilon, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) was used, and the olefin resin was changed to (B-7). An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 7.

<Example 10>
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 9 except that (B-8) was used as the olefin resin used in the charge transport layer coating solution.
<Example 11>
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 9 except that (B-9) was used as the olefin resin used in the charge transport layer coating solution.

<Example 12-19>
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 9 except that the olefin resins listed in Table 11 were used.
<Example 20>
The hole transporting compound used in the coating liquid for the protective layer is a compound represented by the following structural formula (11), and an aqueous dispersion 2.4 containing 25% by mass of (B-16) as an olefin resin to be added. An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 1 except that the parts were changed.

<Example 21>
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 20 except that the amount of the aqueous dispersion containing the olefin resin added to the protective layer coating solution was 7.2 parts.
<Example 22>
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 20 except that the amount of the aqueous dispersion containing the olefin resin added to the protective layer coating solution was 24 parts.

<Example 23>
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 20 except that the amount of the aqueous dispersion containing the olefin resin added to the protective layer coating solution was 48 parts.
<Example 24>
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 20 except that the amount of the aqueous dispersion containing the olefin resin added to the protective layer coating solution was 72 parts.
<Example 25>
An electrophotographic photoreceptor was prepared and evaluated in the same manner as in Example 20 except that the amount of the aqueous dispersion containing the olefin resin added to the protective layer coating solution was 96 parts.

<Comparative example 2>
In the same manner as in Example 1, except that 12 parts of SG2000 (manufactured by Lead City Co., Ltd.), which is an aqueous solution of ethylene and acrylic acid copolymer resin, was added to the protective layer coating liquid instead of the aqueous dispersion containing the olefin resin. Photoconductors were prepared and evaluated.
<Comparative Example 3>
In the same manner as in Example 1 except that 12 parts of EVAflex 4260 (manufactured by Mitsui DuPont), which is a copolymer resin of ethylene and vinyl acetate, was added to the coating liquid for the protective layer instead of the aqueous dispersion containing the olefin resin. Photoconductors were prepared and evaluated.

<Comparative Example 4>
An electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that 12 parts of super cron (manufactured by Nippon Paper Industries Co., Ltd.), a chlorinated ethylene resin, was added to the protective layer coating solution instead of the aqueous dispersion containing the olefin resin. And evaluated.
<Comparative Example 5>
In place of the aqueous dispersion containing the olefin resin, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that 12 parts of Acrylift (manufactured by Sumitomo Chemical Co.), which is a copolymer of ethylene and methyl methacrylate, was added to the coating solution for the protective layer. Were prepared and evaluated.
<Comparative Example 6>
Instead of the aqueous dispersion containing the olefin resin, the same electron as in Example 1 except that 12 parts of Yukalon A-200K (Mitsubishi Chemical Co., Ltd.), which is a copolymer resin of ethylene and acrylic acid, was added to the coating solution for the protective layer. Photoconductors were prepared and evaluated.
<Comparative Example 7>
In place of the aqueous dispersion containing the olefin resin, an electrophotographic photosensitive member was prepared in the same manner as in Example 1 except that 12 parts of MIPERON XM330 (manufactured by Mitsui Chemicals), which is a crosslinked ethylene particle, was added to the protective layer coating solution. evaluated.
<Comparative Example 8>
An electrophotographic photosensitive member was prepared and evaluated in the same manner as in Example 11 except that the binder resin was replaced with polystyrene by replacing the bisphenol Z-type polycarbonate resin which is an ester group-containing polymer.
Evaluation of Examples 1 to 25 and Comparative Examples 1 to 8 is shown in Table 11 below.

DESCRIPTION OF SYMBOLS 1 Conductive support body 2 Charge generation layer 3 Charge transport layer 4 Single photosensitive layer 5 Protective layer 6 Electrophotographic photoreceptor 7 Axis 8 Charging means 9 Exposure light 10 Developing means 11 Transfer means 12 Transfer material 13 Fixing means 14 Cleaning means 15 Process cartridge 16 rail

Claims (9)

An electrophotographic photosensitive member having a support and a photosensitive layer provided on the support,
The electrophotographic photoreceptor has a surface layer containing an ester group-containing polymer having an ester group represented by the following chemical formula 1 and a polyolefin resin.
The polyolefin resin is
(A1) a repeating structural unit represented by the following formula (11):
(A2) at least one structural unit selected from the group consisting of a repeating structural unit represented by the following formula (21) and a repeating structural unit represented by the following formula (22); and (a3) in the following formula (31) At least one selected from the group consisting of the repeating structural unit shown, the repeating structural unit represented by the following formula (32), the repeating structural unit represented by the following formula (33), and the repeating structural unit represented by the following formula (34). Has a structural unit of species,
The mass ratio (%) of (a1) is (A1), the mass ratio (%) of (a2) is (A2), and the mass ratio (%) of (a3) is (A3). ), (A2) and (A3) satisfy the following formulas (I) and (II).
Formula (I) 55 ≦ (A1) / {(A1) + (A2) + (A3)} × 100 ≦ 93
Formula (II) 0.01 ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 10

(In formula (11), R ^{11 to} R ¹⁴ each independently represent a hydrogen atom or an alkyl group.)

(In formulas (21) and (22), R ^{21 to} R ²⁴ each independently represents a hydrogen atom, an alkyl group, a phenyl group, or Y ²¹ COOH (Y ²¹ represents a single bond, an alkylene group, or an arylene group). R ²⁵ and R ²⁶ each independently represents a hydrogen atom, an alkyl group or a phenyl group, and X ²¹ represents —Y ²² COOCOY ²³ — (Y ²² and Y ²³ represent Each independently represents a single bond, an alkylene group or an arylene group.) However, at least one of R ^{21 to} R ²⁴ is a monovalent group represented by —Y ²¹ COOH. Group.)

(In formulas (31) to (34), R ^{31 to} R ³⁵ each independently represent a hydrogen atom or a methyl group, and R ^{41 to} R ⁴³ each independently represents an alkyl group having 1 to 10 carbon atoms. R ^{51 to} R ⁵³ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) The electrophotographic photosensitive member according to claim 1, wherein the (A1), the (A2), and the (A3) satisfy the following formula (II-2) and formula (III).
Formula (II-2) 0.01 ≦ (A2) / {(A1) + (A2) + (A3)} × 100 ≦ 5
Formula (III) 55/42 ≦ (A1) / (A3) ≦ 99/1   The electrophotographic photosensitive member according to claim 1, wherein the polyolefin resin is an ethylene-maleic anhydride-acrylic acid ester terpolymer or an ethylene-maleic anhydride-methacrylic acid ester terpolymer.   The electrophotographic photoreceptor according to claim 1, wherein the polyolefin resin has a molecular weight of 20,000 or more.   5. The electrophotographic photosensitive member according to claim 1, wherein the ester group-containing polymer is a polycarbonate resin, a polyarylate resin, or a crosslinked polymer in which an acryloyloxy group or a methacryloyloxy group is polymerized.   The electrophotographic photosensitive member according to claim 1, wherein a mass ratio of the polyolefin resin in the surface layer is 1% or more and 40% or less. An electrophotographic photosensitive member manufacturing method for manufacturing the electrophotographic photosensitive member according to any one of claims 1 to 6,
An electrophotographic photosensitive member comprising a step of forming a coating film of a coating solution for a surface layer having the ester group-containing polymer and the polyolefin resin, and forming the surface layer by heating the coating film. Manufacturing method.   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 that is detachable from the main unit.   An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an exposure unit, a developing unit, and a transfer unit.

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