JP2001147544A - Electrophotographic photoreceptor, process cartridge with same and electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor excellent in the toner releasability of the surface layer, having high toner transfer efficiency and excellent also in cleaning characteristics and electrical characteristics and to provide a process cartridge with the photoreceptor and an electrophotographic device. SOLUTION: The electrophotographic photoreceptor contains a high molecular weight polycarbonate containing repeating units of formula 1, e.g. formula 3 and repeating units of formula 2, e.g. formula 4 in the surface layer or contains a high molecular weight polycarbonate containing repeating units of the formula 1 and repeating units of formula 5, e.g. formula 6 in the surface layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic photoreceptor,
The present invention relates to a process cartridge and an electrophotographic apparatus having the same, and more particularly, to an electrophotographic photosensitive member using a polymer having a specific structure as a binder resin.

[0002]

2. Description of the Related Art In recent years, electrophotographic photoreceptors (hereinafter sometimes simply referred to as "photoreceptors") have the advantages of high speed and high printing quality. Has been used significantly in the field. The electrophotographic photoreceptor used in these electrophotographic devices is less expensive and more manufacturable than conventional electrophotographic photoreceptors using inorganic photoconductive materials such as selenium, selenium-tellurium alloy, selenium-arsenic alloy, and cadmium sulfide. Electrophotographic photoreceptors using an organic photoconductive material having an excellent advantage in terms of disposability are becoming mainstream.
Above all, a function-separated type organic photoconductor in which a charge generation layer that generates charges by exposure and a charge transport layer that transports charges are laminated is excellent in electrophotographic properties such as sensitivity, chargeability and its repetition stability. Various proposals have been made and put to practical use.

[0003] However, the organic photoreceptor is compared with the inorganic photoreceptor.
Generally, the mechanical strength is inferior, and there is a problem that the life of the photosensitive member is short due to abrasion and abrasion caused by mechanical external force of a cleaning blade, a developing brush, paper, and the like. Further, in a system using a contact charging system which has been used in recent years from the viewpoint of ecology, there is also a problem that abrasion of a photoreceptor is greatly increased as compared with a charging system using a corotron. As a result, there has been a problem that the sensitivity of the photoreceptor is reduced to cause fogging in the copy, and the charge potential is reduced to lower the copy density. Therefore, development of a surface layer material that can form a surface layer having sufficient durability has been desired. For example, a photoreceptor using various resins as a binder resin for a surface layer has been proposed (Japanese Patent Laid-Open No. 60-172).
04, JP-A-62-247374, JP-A-63-148263, JP-A-8-110646
JP-A-9-22126). However, it is difficult to say that it has sufficiently responded to the recent demand for improved durability of photoconductors.

On the other hand, the image forming method of the electrophotographic system generally comprises a charging step of uniformly charging the surface of the electrostatic latent image carrier, and exposing the surface of the uniformly charged electrostatic latent image carrier to a latent image. An exposure step of forming, a developing step of forming a toner image by attaching toner to the electrostatic latent image, a transfer step of transferring the toner image to a transfer material, a fixing step of fixing the toner image on the transfer material, And a cleaning step of removing toner remaining on the surface of the electrostatic latent image carrier in the transfer step. In the cleaning process, usually, an elastic rubber blade or a brush is pressed against the surface of the electrostatic latent image carrier to remove and collect the remaining toner, and the collected toner is stored in a collection container and periodically collected. To be discarded. Further, in the transfer step, a primary transfer step of transferring a toner image to the surface of the intermediate transfer member, and a toner image formed on the surface of the intermediate transfer member, in order to more easily register the color image. And an indirect transfer type image forming method having a secondary transfer step of transferring the image onto the second transfer body, can simultaneously realize high-speed output and high image quality.

[0005] In the electrophotographic image forming method,
From the viewpoint of reducing the use of fossil resources, disposal of residual toner generated during transfer has become a problem. In order to avoid the problem of waste toner, it is important to minimize the amount of residual toner, and it is necessary to increase the transfer efficiency of toner. From the viewpoint of not generating waste toner, a cleaner-less method of collecting transfer residual toner in a developing device simultaneously with development without providing a cleaning process,
JP-A-59-133573 and JP-A-59-15766.
No. 1 publication and the like. However, these cleanerless methods do not generate waste toner,
When the residual toner is collected, paper dust and other foreign matter may be simultaneously taken into the developing device, which may adversely affect the life of the developer. On the other hand, in the cleanerless method in which the residual toner is not collected, a positive ghost in which the toner remaining on the surface of the electrostatic latent image carrier is printed out, and a negative ghost due to a light shielding effect of the toner remaining on the surface of the electrostatic latent image carrier. Occurs.

Therefore, increasing the transfer efficiency of toner is important both in the conventional system having a cleaner and in the cleanerless system. As a method for increasing the transfer efficiency of toner, Japanese Patent Application Laid-Open No.
As described in Japanese Patent Publication No. 72-72, there is a method of increasing the area of a bias applying portion of a transfer roller. According to such a method, the transfer efficiency of the toner is improved, but the toner particles directly adhering to the electrostatic latent image carrier cannot be completely transferred. It is enough. In order to increase the transfer efficiency, it is important to efficiently transfer the toner particles directly adhered to the electrostatic latent image carrier, and for that purpose, it is necessary to attach the toner between the toner and the electrostatic latent image carrier. It is effective to lower the contact force.

In the laminated photoreceptor, the surface layer located on the outermost surface of the photoreceptor is required to have excellent surface releasability from toner. On the other hand, when the releasability from the toner is not sufficient, a part of the toner remains in the transfer process, which causes an image defect or a toner component or a component contained in the paper to adhere to the toner filming. Or a phenomenon called "a". Various studies have been made to improve the releasability of the toner as described above. For example, JP-A-61-
Nos. 219049, 62-205357, 50-23231, 61-116362, 61-204633, and 61-27076.
As described in Japanese Patent Application Publication No. 8 (1993) -1994, a silicone-containing resin or a fluorine-containing resin reduces the surface energy of the photoreceptor surface layer to lower the adhesion between the toner and the photoreceptor surface layer, thereby improving the transfer efficiency of the toner. There is a way to raise.

However, these are electrophotographic characteristics such as low sensitivity or an increase in residual potential due to repeated use, and mechanical durability such as deterioration in image quality due to wear and scratches during repeated use and decrease in sensitivity due to film wear. Was still insufficient, and no satisfactory resin was found. In addition, although a solution to the problem by providing a further protective layer on the charge transport layer has been proposed, the sensitivity has decreased and the residual potential has increased.
Also, as described in JP-A-63-221355, there is a method of reducing the surface energy of the photoconductor surface layer by dispersing a fluorine resin powder or a silicone resin powder in the surface layer. However, in this case, there was a problem that the dispersibility in the binder resin was not sufficient, and there was a problem that aggregation was easy, and it was difficult to form a uniform and smooth surface layer.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention has improved abrasion resistance, and even when used repeatedly for a long period of time, the surface layer of the photoreceptor is excellent in releasability from the toner, the transfer efficiency of the toner is high, and the cleaning properties and the electrical properties are excellent. It is an object to provide an electrophotographic photosensitive member, a process cartridge having the same, and an electrophotographic apparatus.

[0010]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a polymer having a specific chemical structure as a binder resin of a photoreceptor surface layer has a problem in that it has an effect on mechanical strength. It has extremely excellent durability and electrical properties, and the photoreceptor using it has excellent surface releasability from toner even after repeated use for a long period of time. It is possible to solve the problems such as blurring, image quality deterioration due to filming, etc.
The present invention has been completed. The means for solving the above problems are as follows. That is, <1> in an electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, a repeating unit represented by the following general formula (1) and the following general formula ( An electrophotographic photoreceptor comprising a high molecular weight polycarbonate polymer containing a repeating unit represented by 2).

[0011]

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(In the general formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkane group, an aryl group having 6 to 12 carbon atoms, or fluorine substitution. R _{3 to} R ₁₀ each independently represent a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkane group, an aryl group having 6 to 12 carbon atoms, a fluorine atom,
Represents a bromine atom or a chlorine atom. )

[0013]

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(In the general formula (2), R _{21 to} R ₂₄ each independently represent a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkane group, an aryl group having 6 to 12 carbon atoms, a fluorine atom, Represents a bromine atom or a chlorine atom.) <2> At least one selected from the group consisting of terminal groups represented by the following general formulas (I) to (III) at the polymer chain terminal of the high molecular weight polycarbonate polymer. The electrophotographic photosensitive member according to <1>, wherein the electrophotographic photosensitive member has a seed.

[0015]

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(In the general formulas (I) to (III), R _{101 to} R
₁₀₃ each independently represents an alkyl group having 1 to 30 carbon atoms, a cycloalkane group, a perfluoroalkyl group, a substituted perfluoroalkyl group, or an aryl group having 6 to 12 carbon atoms, and Y _{1 to} Y ₃ are Each independently represents a single bond,-
Represents —, —CO—, —COO—, or —C (CH ₃ ) ₂ —. <3> The high-molecular-weight polycarbonate polymer further contains a repeating unit represented by the following general formula (3) and / or a repeating unit represented by the following general formula (4).
> Or <2>.

[0017]

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(In the general formula (3), A represents a single bond, a linear, branched or aryl-substituted alkylidene group having 1 to 15 carbon atoms, an arylenedialkylidene group, -O-, -S
-, - CO -, - SO- , or -SO ₂ - represents a. R ₃₁
To R ₃₄ each independently represent a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkane group, an aryl group having 6 to 12 carbon atoms, a fluorine atom, a bromine atom, or chlorine atom. )

[0019]

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[0020] (In the general formula (4), R ₄₁ represents a single bond, a hydrogen atom, or an .R ₄₂ to R an alkyl group having 1 to 5 carbon atoms
₄₅ independently represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkane group, an aryl group having 6 to 12 carbon atoms, a fluorine atom, a bromine atom, or a chlorine atom. <4> The ratio of the repeating unit represented by the general formula (1) to the high molecular weight polycarbonate polymer is 0.01 to 1 mol%, and the weight average molecular weight of the high molecular weight polycarbonate polymer Is an electrophotographic photosensitive member according to any one of <1> to <3> above.

<5> In an electrophotographic photoreceptor having at least a photosensitive layer on a conductive support, a surface layer of the electrophotographic photoreceptor includes a repeating unit represented by the above general formula (1) and the following general formula: An electrophotographic photoreceptor comprising a high molecular weight polycarbonate polymer containing a repeating unit represented by (5).

[0022]

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(In the general formula (5), X represents an alkylene group having 2 to 6 carbon atoms, an alkylidene group, an alkylene ether group or an alkylidene ether group. R _{51 to} R
₅₄ is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms,
Represents an aryl group, a fluorine atom, a bromine atom or a chlorine atom. n represents an integer of 0 to 200. <6> The above-mentioned <5>, wherein the polymer chain terminal of the high-molecular-weight polycarbonate polymer has at least one selected from the group consisting of terminal groups represented by the general formulas (I) to (III). Electrophotographic photoreceptor. <7> The high-molecular-weight polycarbonate polymer further includes a repeating unit represented by the general formula (3) and / or a repeating unit represented by the general formula (4).
5> or <6>. <8> The proportion of the repeating unit represented by the general formula (1) with respect to the high molecular weight polycarbonate polymer is 0.01 to 1 mol%, and the weight average molecular weight of the high molecular weight polycarbonate polymer is The electrophotographic photoreceptor according to any one of <5> to <7>, which has a molecular weight of 30,000 or more. <9> integrally supporting the electrophotographic photosensitive member according to any one of <1> to <8>, and at least one unit selected from the group consisting of a charging unit, an image exposing unit, and a cleaning unit; A process cartridge detachable from an electrophotographic apparatus. <10> An electrophotographic apparatus comprising at least the electrophotographic photosensitive member according to any one of <1> to <8> and a contact-type charger.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [Electrophotographic Photoreceptor] -First Invention- In the electrophotographic photoreceptor of the first invention, the repeating unit represented by the general formula (1) and the general formula ( It is characterized by containing a high molecular weight polycarbonate polymer having a repeating unit represented by 2). The surface layer of the photoreceptor, when only a single-layer photosensitive layer is provided on the conductive support, the photosensitive layer is a surface layer, and the charge generation layer and the charge When a transport layer is provided in this order, the charge transport layer becomes a surface layer. Further, when a protective layer is provided on these photosensitive layers, the protective layer becomes a surface layer.

(High molecular weight polycarbonate polymer) The high molecular weight polycarbonate polymer has the following general formula (1)
And a repeating unit represented by the following general formula (2), and if necessary, other repeating units.

[0026]

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In the general formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkane group, an aryl group having 6 to 12 carbon atoms, or a fluorine-substituted type. Represents an alkyl group. R _{3 to} R ₁₀ each independently represent a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkane group, an aryl group having 6 to 12 carbon atoms, a fluorine atom, a bromine atom, or a chlorine atom. These alkyl group, cycloalkane group and aryl group may be further substituted by a substituent.

Specific examples of the repeating unit represented by the general formula (1) are shown in Tables 1 and 2 below, but the present invention is not limited to these specific examples.

[0029]

[Table 1]

[0030]

[Table 2]

Of these, compound 1-1 (the following structural formula) is preferred. The reason is that 4,4 ′, 4 ″, 4 ′ ″-(1,4-phenylenedimethylidene) tetrakisphenol, which is a raw material of the compound 1-1, is easy to produce, has high water solubility, and is crosslinked. This is because the interaction of the main polycarbonate molecular chain is sometimes easily controlled.

[0032]

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Next, the repeating unit represented by the general formula (2) will be described.

[0034]

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In the general formula (2), R _{21 to} R ₂₄ each independently represent a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkane group, an aryl group having 6 to 12 carbon atoms, a fluorine atom, a bromine Represents an atom or a chlorine atom. These alkyl group, cycloalkane group and aryl group may be further substituted by a substituent.

Specific examples of the repeating unit represented by the general formula (2) are shown in Table 3 below, but the present invention is not limited to these specific examples.

[0037]

[Table 3]

Among them, compound 2-1 (the following structural formula) is particularly preferable because of its high mechanical strength and high solubility of bis (4-hydroxyphenyl) ditrifluoromethane as a raw material in a solvent.

[0039]

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In the present invention, the ratio of the repeating unit represented by the general formula (1) to the high molecular weight polycarbonate polymer is extremely important. This ratio is 0.0
1-1 mol% is preferable, and 0.01-0.5 mol% is more preferable. If the ratio is less than 0.01 mol%, the number of molecular chains that cannot form a star shape increases, and the molecular weight distribution may be widened. As a result, high mechanical strength cannot be obtained. On the other hand, if the proportion exceeds 1 mol%, the star-shaped molecular chains also have a large number of crosslinks originating from the repeating unit represented by the general formula (1), so that the entanglement of the molecular chains also increases,
As in the case of the linear high molecular weight product, the solubility in a solvent and the thermal fluidity may be extremely low. In particular, when the ratio exceeds 5 mol%, the entanglement of the molecular chains becomes larger than that of the linear type, and in order to maintain the solubility in a solvent and the heat fluidity, the weight average molecular weight is made extremely low. Must be
High mechanical strength may not be expected.

Further, from the viewpoint of cleaning characteristics, the surface layer of the electrophotographic photoreceptor is required to have a surface property excellent in releasability from toner. Since the characteristics of the photoconductor surface layer depend on the binder resin constituting the photoconductor surface layer, a material having a small surface energy is desired for the binder resin. However, even if it contains a repeating unit having a fluorine atom represented by the general formula (2), in the case of a straight-chain polycarbonate polymer, the surface is initially oriented due to the surface orientation of the surface layer. Although the adhesion of the toner decreases due to the reduction in energy, the surface energy becomes equivalent to that of a normal polycarbonate polymer containing no fluorine atom when the surface layer is scraped off by abrasion. On the other hand, in the case of a high molecular weight polycarbonate polymer containing a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2), since each molecular chain extends in all directions, the surface When a layer is formed, the surface orientation of fluorine atoms is unlikely to occur, and since fluorine atoms are uniformly incorporated as a bulk, there is an advantage that the surface energy can be kept low even after the surface layer is worn.

The weight average molecular weight of the high molecular weight polycarbonate polymer is preferably 30,000 or more,
0 or more is more preferable. The weight average molecular weight is 30,000
If it is less than 3, high mechanical strength may not be expected. The binder resin of the electrophotographic photoreceptor is required to have good solubility in an organic solvent, but when a linear polycarbonate is made to have a high molecular weight of 30,000 or more,
The entanglement between the molecular chains becomes too strong and becomes insoluble in the solvent, and the heat fluidity is lost, so that molding such as coating, casting and injection molding cannot be performed.

In the high molecular weight polycarbonate polymer containing the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) used in the electrophotographic photosensitive member of the present invention, The entanglement is determined by the length of each molecular chain extending from the repeating unit represented by the general formula (1), and the molecular weight of the polymer is four times that of each molecular chain. Therefore, for example, solubility in a solvent and thermal fluidity behave like a polymer having a weight average molecular weight of 20,000,
Regarding mechanical strength, it can satisfy the function as an ultrahigh molecular weight polymer having a weight average molecular weight of 80000. The weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent.

The high molecular weight polycarbonate polymer containing the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) has a high molecular weight on the surface layer of the photoreceptor. Crystallization is likely to occur, and light decay hardly occurs in the crystallized portion, so that the charge remains as a residual potential and may appear as an image quality defect. In addition, during the polymerization, it is difficult to strictly control the molecular weight and the molecular weight distribution, and the viscosity, the solubility and the like change for each polymerization lot, which may cause a problem that the productivity is reduced.

However, at least one terminal group selected from the group consisting of terminal groups represented by the following general formulas (I) to (III) is provided at the terminal of the polymer chain of the high molecular weight polycarbonate polymer.
The presence of seeds prevents crystallization of the surface layer of the photoreceptor, makes it difficult for charges to remain, and provides stable electrical characteristics and image quality. Further, at the time of polymerization, there is an advantage that the control of the molecular weight and the molecular weight distribution becomes easy, and there is no variation in quality among polymerization lots.

[0046]

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In the general formulas (I) to (III), R _{101 to} R ₁₀₃
Each independently represents an alkyl group having 1 to 30 carbon atoms, a cycloalkane group, a perfluoroalkyl group, a substituted perfluoroalkyl group, or an aryl group having 6 to 12 carbon atoms, and Y _{1 to} Y ₃ each represent Independently, a single bond, -O-,
-CO -, - COO-, or -C (CH _{3) 2} - represents a.

In order to introduce at least one of the terminal groups represented by the general formulas (I) to (III) into the terminal of the polymer chain of the high molecular weight polycarbonate polymer, a terminal stopper (molecular weight regulator) is used. Can be used. In the present invention,
Specific examples of the terminal stopper include, for example, phenol, α-naphthol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-
Xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, p-ethylphenol, p-propylphenol,
p-butylphenol, p-pentylphenol, p-
Hexylphenol, p-heptylphenol, p-octylphenol, p-nonylphenol, p-decylphenol, p-undecylphenol, p-dodecylphenol, p-isopropylphenol, p-ter
t-butylphenol, 2,6-dimethyl-p-ter
t-butylphenol, 2-tert-amyl-4-methylphenol, 3-methyl-6-tert-butylphenol, 2-methyl-4,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, , 6-Di-tert-butyl-4-methylphenol, 4-tert-octylphenol, 4-ter
t-aminophenol, 2,4,6-tri-tert-
Butylphenol, p-phenylphenol, 2,6-
Di-tert-butyl-4-phenylphenol,

2,6-di-sec-butyl-4-methylphenol, o-anisole, m-anisole, p-anisole, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-bromophenol, m
-Bromophenol, p-bromophenol, p-ethoxyphenol, o-aminophenol, m-aminophenol, p-aminophenol, p-cyanophenol, p-nitrophenol, 3-methyl-6-isopropylphenol, 2- Methyl-5-isopropylphenol, p- (perfluorononylphenyl) phenol, p- (perfluoroundecylphenyl) phenol, p- (perfluorohexylphenyl) phenol, p-tert- (perfluorobutylphenyl) phenol, 1- (p-hydroxybenzyl) perfluorodecane, p- [2- (1H, 1H-perfluorotridecyloxy) -1,1,1,3,3,3-hexafluoro-2-propyl] phenol, 3,5-bis (perfluorohexyloxy Carbonyl) phenol, p-
Perfluorododecyl hydroxybenzoate, p- (1
H, 1H-perfluorooctyloxy) phenol,
p- (1H, 1H-perfluorodecyloxy) phenol, 2H, 2H-perfluorononane and the like. These may be used alone or in combination of two or more.

Among these terminal stoppers, p-dodecylphenol, p-tert-butylphenol, p-
-Hydroxybenzoic acid-n-dodecyl, p-phenylphenol, p- (1H, 1H-perfluorooctyloxy) phenol, p- (perfluorononylphenyl) phenol, p- (perfluoroundecylphenyl) phenol, p -(Perfluorohexylphenyl) phenol, p-tert-perfluorobutylphenol, p-tert- (perfluorobutylphenyl) phenol, 1- (p-hydroxybenzyl) perfluorodecane, and p- (1H, 1H-per Preferred are fluorodecyloxy) phenol and the like.

The amount of the terminal terminating agent can be appropriately selected according to the amount of the monomer used when synthesizing the high molecular weight polycarbonate polymer.

The high molecular weight polycarbonate polymer is
Further, when a repeating unit represented by the following general formula (3) and / or a repeating unit represented by the following general formula (4) is contained, it is extremely effective for durability and electrical properties related to mechanical strength. Yes and preferred.

[0053]

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In the general formula (3), A is a single bond, having 1 carbon atom.
To 15 linear, branched or aryl-substituted alkylidene groups, arylenedialkylidene groups, -O-, -S-,
-CO -, - SO-, or -SO ₂ - represents a. R _{31 to} R
₃₄ independently represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkane group, an aryl group having 6 to 12 carbon atoms, a fluorine atom, a bromine atom, or a chlorine atom. These alkylidene group, alkyl group, cycloalkane group and aryl group may be further substituted by a substituent.

Specific examples of the repeating unit represented by the general formula (3) are shown in Tables 4 to 6 below. When A in the general formula (3) represents —C (R ₃₅ ) (R ₃₆ ) —, specific examples of the repeating unit represented by the general formula (3) are shown in Tables 7 to 10 below. Shown in The present invention is not limited to these specific examples.

[0056]

[Table 4]

[0057]

[Table 5]

[0058]

[Table 6]

[0059]

[Table 7]

[0060]

[Table 8]

[0061]

[Table 9]

[0062]

[Table 10]

In the repeating unit represented by the general formula (3), any one of R _{31 to} R ₃₄ is preferably an alkyl group, particularly preferably a methyl group. The reason is that when an alkyl group is substituted ortho to the hydroxy group of the aromatic ring of bisphenol, which is a raw material corresponding to the repeating unit represented by the general formula (3), the reactivity is improved. This makes it advantageous to obtain a high molecular weight polycarbonate polymer. Among these, compound 3-92 (the following structural formula) is particularly preferable because it has high mechanical strength and high solubility of bis (4-hydroxy-3-methylphenyl) methane as a raw material in a solvent.

[0064]

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Next, the repeating unit represented by the general formula (4) will be described.

[0066]

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In the general formula (4), R ₄₁ represents a single bond, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R _{42 to} R ₄₅
Each independently represents a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkane group, an aryl group having 6 to 12 carbon atoms, a fluorine atom, a bromine atom, or a chlorine atom. These alkyl group, cycloalkane group and aryl group may be further substituted by a substituent.

Specific examples of the repeating unit represented by the general formula (4) are shown in Tables 11 and 12 below.
It is not limited to these specific examples.

[0069]

[Table 11]

[0070]

[Table 12]

Regarding the repeating unit represented by the general formula (4), any of R _{42 to} R ₄₅ is an alkyl group, similarly to the case of the repeating unit represented by the general formula (3). Is preferable, and a methyl group is particularly preferable. Among them, compound 4-6 (the following structural formula) has high mechanical strength and bis (4-hydroxy-3) as a raw material.
-Methylphenyl) cyclohexane is particularly preferred because of its high solubility in solvents.

[0072]

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The high molecular weight polycarbonate polymer used in the present invention contains at least one of the repeating units represented by the general formulas (2) to (4), which contains the repeating unit represented by the general formula (2). The proportion of one or more repeating units to the total polymer is preferably 30 mol% or more, and 50 mol% or more.
Mole% or more is more preferable. When the proportion is 30 mol% or more, high mechanical strength of at least one or more kinds of repeating units including the repeating unit represented by the general formula (2),
Solubility is reflected in the high molecular weight polycarbonate polymer. On the other hand, when the proportion is less than 30 mol%, at least one of the repeating units containing the repeating unit represented by the general formula (2) is used.
The high mechanical strength and solubility of more than one kind of repeating unit may not appear in the high molecular weight polycarbonate polymer.

The high-molecular-weight polycarbonate polymer used in the electrophotographic photoreceptor of the present invention has a star-shaped structure which is not substantially linear. Therefore, the high-molecular-weight polycarbonate polymer has a polystyrene equivalent measured by gel permeation chromatography using tetrahydrofuran as a solvent. Even when the weight average molecular weight is as high as 30,000 or more, it can be dissolved in an organic solvent at a rate of 5% by weight or more. For this reason, a coating film can be formed by a method such as casting, coating or dipping, which is suitable for forming an electrophotographic photosensitive member.

In the present invention, as the organic solvent for dissolving the high molecular weight polycarbonate polymer, any one can be used depending on the structure of the polymer. Specific examples thereof include aromatic solvents such as toluene and xylene. Hydrocarbons, chlorinated aromatic hydrocarbons such as monochlorobenzene, chloroaliphatic hydrocarbons such as dichloromethane, chloroform, alcohols such as methanol, ethanol, isopropyl alcohol, and 1-butanol, methyl acetate, ethyl acetate, and propyl acetate Isopropyl acetate, butyl acetate, isobutyl acetate, esters such as amyl acetate, tetrahydrofuran, 1,4-dioxane, ethers such as ethyl ether, acetone, methyl ethyl ketone, ketones such as methyl isobutyl ketone, methyl cellosolve,
Cellosolve, glycol ethers such as butyl cellosolve, alicyclic hydrocarbons such as cyclohexanone, aliphatic hydrocarbons such as n-hexane, etc., among these, tetrahydrofuran is soluble in the high molecular weight polycarbonate polymer Is most preferred.

In the present invention, the high-molecular-weight polycarbonate polymer is used for the purpose of improving compatibility with a charge transporting material and solubility in a solvent, or improving film-forming properties.
It can be used by mixing with other resins. Examples of resins that can be used for the mixing include, for example, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile Copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-
Formaldehyde resin, styrene-alkyd resin, poly-N-vinyl carbazole and the like can be mentioned. These may be used alone or in combination of two or more.

The electrophotographic photoreceptor of the present invention improves the abrasion resistance of the photoreceptor and reduces surface scratches by using the high molecular weight polycarbonate polymer as a binder resin. Excellent maintainability of the cleaning characteristics can be realized even after abrasion of the body surface layer.

-Second Invention- The electrophotographic photoreceptor of the second invention has a surface layer on the photoreceptor,
It is characterized by containing a high molecular weight polycarbonate polymer having a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (5).

(High Molecular Weight Polycarbonate Polymer) The high molecular weight polycarbonate polymer is a repeating unit represented by the general formula (1) and a repeating unit represented by the following general formula (5) already described in the first invention. Unit, and if necessary, other repeating units.

[0080]

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In the general formula (5), X represents an alkylene group having 2 to 6 carbon atoms, an alkylidene group, an alkylene ether group,
Or an alkylidene ether group. R _{51 to} R ₅₄ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Represents an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a fluorine atom, a bromine atom, or a chlorine atom. n
Represents an integer of 0 to 200. These alkyl group, alkoxy group and aryl group may be further substituted by a substituent.

Specific examples of the repeating unit represented by the general formula (5) are shown in Table 13 below, but the present invention is not limited to these specific examples.

[0083]

[Table 13]

Among these, a high molecular weight polycarbonate polymer containing the compound 5-2 (the following structural formula) is particularly preferable because it has excellent electric properties and high mechanical strength.

[0085]

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From the viewpoint of cleaning characteristics, the surface layer of the electrophotographic photoreceptor is required to have a surface property excellent in toner releasability. Since the characteristics of the photoconductor surface layer depend on the binder resin constituting the photoconductor surface layer, a material having a small surface energy is desired for the binder resin. However, even if it contains a repeating unit having a polysiloxane skeleton represented by the general formula (5), in the case of a straight-chain type polycarbonate polymer, when a surface layer is used, the surface orientation of siloxane causes an initial However, when the surface layer is abraded by abrasion, the surface energy has a value equivalent to that of a polycarbonate polymer containing no ordinary siloxane skeleton. On the other hand, in the case of a high molecular weight polycarbonate polymer containing the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (5), each molecular chain extends in all directions, When the layer is formed into a layer, the surface orientation of the siloxane is less likely to occur, and since the siloxane is uniformly incorporated as a bulk, there is an advantage that the surface energy can be kept low even after the abrasion of the surface layer.

In the electrophotographic photoreceptor of the second invention,
Like the electrophotographic photoreceptor of the first invention, the high molecular weight polycarbonate polymer further contains a repeating unit represented by the general formula (3) and / or a repeating unit represented by the general formula (4). Is preferred. Further, the proportion of the repeating unit represented by the general formula (1) to the high molecular weight polycarbonate polymer is preferably 0.01 to 1 mol%, and the weight average molecular weight of the high molecular weight polycarbonate polymer is preferably It is preferable that it is 30,000 or more. That is, the paragraph number [002] described in the first invention.
5] to [0032], [0040], [0042] to
[0077] The description of [0077] also applies to the second invention. Here, in these paragraphs, “general formula (2)” is replaced with “general formula (5)”.

Next, the structure of the electrophotographic photosensitive member according to the first and second aspects of the present invention will be described. The electrophotographic photoreceptors of the first and second inventions have at least a photosensitive layer on a conductive support and, if necessary, other layers.

[Photosensitive Layer] The photosensitive layer may have a single-layer structure or a laminated structure in which a charge generation layer and a charge transport layer are functionally separated. The latter case is advantageous in terms of electrical characteristics (sensitivity, repetition stability). In the case of the photoreceptor having the laminated structure, the order of laminating the charge generation layer and the charge transport layer on the conductive support is not particularly limited, and any of the layers may be an upper layer. The case where the layer is an upper layer is preferred in terms of sensitivity, repetition stability and environmental stability.

When the photosensitive layer has the single-layer structure,
For example, the charge generation material is formed by a coating film of a binder resin containing a charge transport material or both of them. In the case of the laminated structure, the charge generation layer includes, for example, a binder containing a charge generation material. The charge transport layer is formed by a coating film of a resin, for example, a coating film of a binder resin containing a charge transport material. Hereinafter, details of the photosensitive layer having the laminated structure will be described. However, materials such as a binder resin used in the photosensitive layer having the laminated structure can also be used in the photosensitive layer having the single-layer structure.

(Charge Generating Layer) The charge generating layer has, for example, at least a charge generating material and, if necessary, other components such as a binder resin.

-Charge generating material- As the charge generating material, for example, amorphous selenium, crystalline selenium, selenium-tellurium alloy, selenium-arsenic alloy,
Other selenium compounds and selenium alloys, inorganic photoconductors such as zinc oxide and titanium oxide, metal-free phthalocyanine, titanyl phthalocyanine, copper phthalocyanine, tin phthalocyanine, various phthalocyanine pigments such as gallium phthalocyanine, squarium, anthantrone, Various organic pigments and dyes such as perylene-based, azo-based, anthraquinone-based, pyrene-based, pyrylium salts, and thiapyrylium salts are exemplified. In addition, these organic pigments generally have several types of crystal forms. Particularly, in the phthalocyanine pigment, various crystal types such as α-type and β-type are known, but desired sensitivity is obtained. There is no particular problem if it can be obtained, and any crystal type material can be suitably used. These charge generating materials may be used alone or may be used alone.
More than one species may be used in combination. In the present invention, the following compounds (1) to (3) may be mentioned as examples of the charge generation material that can provide particularly excellent performance.

(1) In the measurement of X-ray diffraction spectrum using Cukα ray, Bragg angle (2θ ± 0.2 °)
Chlorogallium phthalocyanine having diffraction peaks at least at 7.4 °, 16.6 °, 25.5 ° and 28.3 °. (2) In the measurement of the X-ray diffraction spectrum using the Cukα ray, at least 7.5 °, 9.9 °, 12.5 °, 16.3 °, at the Bragg angle (2θ ± 0.2 °). 1
Hydroxygallium phthalocyanine having diffraction peaks at 8.6 °, 25.1 ° and 28.1 °. (3) In the measurement of the X-ray diffraction spectrum using the Cukα ray, at least 7.6 °, 18.3 °, 23.2 °, 24.2 ° and the Bragg angle (2θ ± 0.2 °). Hydroxygallium phthalocyanine having a diffraction peak at 27.3 °.

-Other components such as a binder resin- Examples of the binder resin include polycarbonate resins such as the high molecular weight polycarbonate polymer, polyester polymer, bisphenol A type and bisphenol Z type defined in the present invention; Methacrylic resin, acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer resin,
Examples include vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinyl carbazole and the like. These binder resins may be used alone or in a combination of two or more.

The compounding ratio of the charge generating material to the binder resin (charge generating material: binder resin) was 1 weight%.
0: 1 to 1:10 is preferred. When the compounding ratio of the charge generation material to the binder resin is less than the above numerical range, the sensitivity of the charge generation layer may be insufficient. The thickness of the charge generation layer may not be uniform.

The method for dispersing the charge generating material in the binder resin is not particularly limited, and may be a roll mill,
Known methods using a ball mill, a vibrating ball mill, an attritor, a dyno mill, a sand mill, a colloid mill and the like can be used.

The thickness of the charge generation layer is generally preferably from 0.01 to 5 μm, more preferably from 0.05 to 2.0 μm.
m is more preferred. If the thickness is less than 0.01 μm, the sensitivity of the charge generation layer may be insufficient, while if it exceeds 5 μm, dark decay may increase.

As other components other than the binder resin, ozone and oxidizing gas generated in the electrophotographic apparatus, or antioxidant which can be added for the purpose of preventing deterioration of the photoreceptor due to light and heat. And additives such as light stabilizers, heat stabilizers and the like.

The antioxidant is not particularly limited, and a compound known as an antioxidant can be appropriately selected and used. Examples thereof include a phenol-based antioxidant, a hindered amine-based compound, and an organic sulfur-based oxidant. Antioxidants, organic phosphorus antioxidants and the like are preferably mentioned. The organic sulfur-based antioxidant and the organic phosphorus-based antioxidant,
Since it is a secondary antioxidant, a synergistic effect can be obtained when used in combination with a primary antioxidant such as the phenolic antioxidant or the amine antioxidant.

The light stabilizer is not particularly limited.
As the light stabilizer, a known compound can be appropriately selected and used, and a light stabilizer such as a benzophenone-based, benzotriazole-based, dithiocarbamate-based, or tetramethylpiperidine-based light stabilizer is preferably used.

In addition, as the antioxidant,
2,4, di-t-butylphenyl 3 ′, 5′-di-t-
Butyl-4'-hydroxybenzoate and nickel dibutyl-dithiocarbamate.

Further, one or more kinds of electron accepting substances can be contained for the purpose of improving the sensitivity, reducing the residual potential, and reducing the fatigue when repeatedly used. The electron-accepting substance is not particularly limited and a known electron-accepting positive substance can be appropriately selected and used, for example, succinic anhydride, maleic anhydride, dibromomaleic anhydride,
Phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, tetracyanoquinodimethane, o-dinitrobenzene, m-dinitrobenzene, chloranil, dinitroanthraquinone, trinitrofluorenone, picric acid, o-nitrobenzoic acid, p-nitro Examples include benzoic acid and phthalic acid. Among them, fluorenone,
Quinones and benzene derivatives having electron-withdrawing substituents such as Cl, CN, and NO ₂ are particularly preferred.

As the method of forming the charge generation layer, a method of forming the charge generation material by vacuum evaporation, a method of dispersing and coating the charge generation material together with an organic solvent and the binder resin, and the like are preferable.

(Charge Transport Layer) The charge transport layer contains at least a charge transport material and a binder resin, and further contains other components as necessary.

-Charge transport material- As the charge transport material, for example, 2,5-bis (p
Oxadiazole derivatives such as -diethylaminophenyl) -1,3,4-oxadiazole, 1,3,5-triphenyl-pyrazoline, 1- [pyridyl- (2)]-3
Pyrazoline derivatives such as-(p-diethylaminostyryl) -5- (p-diethylaminostyryl) pyrazoline;
Triphenylamine, tri (p-methyl) phenylamine, N, N-bis (3,4-dimethylphenyl) biphenyl-4-amine, dibenzylaniline, 9,9-dimethyl-N, N-di (p- Aromatic tertiary amino compounds such as tolyl) fluorenone-2-amine, N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,
1-biphenyl] -4,4'-diamine
Grade diamino compound, 3- (4'dimethylaminophenyl) -5,6-di- (4'-methoxyphenyl) -1,
1,2,4-triazine derivatives such as 2,4, -triazine, 4-diethylaminobenzaldehyde-1,1,1
-Diphenylhydrazone, 4-diphenylaminobenzaldehyde-1,1,1-diphenylhydrazone, [p
Hydrazone derivatives such as-(diethylamino) phenyl] (1-naphthyl) phenylhydrazone, 2-phenyl-
Quinazoline derivatives such as 4-styryl-quinazoline,
Benzofuran derivatives such as hydroxy-2,3-di (p-methoxyphenyl) -benzofuran; α such as p- (2,2-diphenylvinyl) -N, N-diphenylaniline
Stilbene derivatives, enamine derivatives, carbazole derivatives such as N-ethylcarbazole, hole transport substances such as poly-N-vinylcarbazole and derivatives thereof, quinone compounds such as chloranyl, bromoanil, anthraquinone, and tetracyanoquinodimethane compounds. , 2,4,7-
Fluorenone compounds such as trinitrofluorenone and 2,4,5,7-tetranitro-9-fluorenone;
(4-biphenyl) -5- (4-t-butylphenyl)
-1,3,4-oxadiazole, 2,5-bis (4-
Naphthyl) -1,3,4-oxadiazole, 2,5-
An oxadiazole-based compound such as bis (4-diethylaminophenyl) 1,3,4oxadiazole; an electron-transporting substance such as a xanthone-based compound; a thiophene compound; a diphenoquinone compound; Alternatively, a polymer having a side chain may be used. These charge transport materials may be used alone or in combination of two or more.

When the photosensitive layer has the laminated structure,
The charge polarity of the photoconductor varies depending on the charge transport polarity of the charge transport material. That is, when a hole transport material is used as the charge transport material, the photoreceptor is used with negative charge, and when the electron transport material is used, the photoreceptor is used with positive charge. When the hole transport material and the electron transport material are mixed, a photoconductor having both charging polarities can be obtained.

Among the charge transporting materials, a benzidine compound represented by the following general formula (6) or a general formula (7) from the viewpoint of obtaining particularly excellent performance in relation to the high molecular weight polycarbonate polymer. )) Are preferred.

[0108]

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(In the general formula (6), R ₆₁ and R ₆₂ may be the same or different and each represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and R ₆₃ and R ₆₄ represent
Which may be the same or different, a hydrogen atom, an alkyl group,
Represents an alkoxy group, a halogen atom or a substituted amino group.
K, l, m and n each represent an integer of 1 or 2. ) Specific examples (compound numbers 6-1 to 6-67) of the benzidine compounds represented by the general formula (6) are shown in Tables 14 to 1 below.
6 is shown.

[0110]

[Table 14]

[0111]

[Table 15]

[0112]

[Table 16]

[0113]

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(In the general formula (7), R ₇₁ and R ₇₂ may be the same or different and each represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and p and q each represent 1 or 2 R ₇₃ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.) Of the triarylamine-based compound represented by the general formula (7), Specific examples (Compound Nos. 7-1 to 7-55) are shown in Table 1 below.
7 to Table 19 show.

[0115]

[Table 17]

[0116]

[Table 18]

[0117]

[Table 19]

In addition to the compounds represented by the above general formulas (6) and (7), charge transporting materials having good properties are represented by the following general formulas (8) to (12). Compounds.

[0119]

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(In the general formula (8), X ₈ represents a divalent hydrocarbon group which may have a substituent, and R _{81 to} R ₈₆ represent
Each represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group, or a substituted amino group, which may be the same or different. R _{87 to} R ₈₁₂ each represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent; May be the same or different from each other. _R88 and _R89 , R
₈₁₁ and R ₈₁₂ may be fused to form a carbocyclic or heterocyclic group. )

[0121]

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(In the general formula (9), X ₉ represents —CH ₂ CH ₂
— Or —CH ＝ CH—, and R _{91 to} R ₉₃ each represent an alkyl group, an aralkyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. , R ₉₄ and R ₉₅ each represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. )

[0123]

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(In the general formula (10), R ₁₀₁ and R ₁₀₂ are
R ₁₀₃ represents a hydrogen atom, an alkyl group,
Represents an alkoxy group or a halogen atom, R ₁₀₄ and R
₁₀₅ represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group which may have a substituent. )

[0125]

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(In the general formula (11), R _{111 to} R ₁₁₇ each represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, which may be the same or different.)

[0127]

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(In the general formula (12), R _{121 to} R ₁₂₄ each represent a hydrogen atom, an alkyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. Represents.)

-Binder Resin-When the charge transport layer is the surface layer, the high molecular weight polycarbonate polymer defined in the present invention is used as the binder resin. When the charge transport layer is not a surface layer, for example, the high molecular weight polycarbonate polymer, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer Copolymer, vinylidene chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole, etc. No. These may be used alone or in combination of two or more.

The ratio of the charge transport material to the binder resin (charge transport material: binder resin) is 10: 1 to 1: 1.
1: 5 is preferred. When the ratio of the charge transport material to the binder resin is less than the numerical range,
Due to insufficient charge transport ability, the residual potential may be increased, while if it exceeds the above numerical range, the charge transporting material may be precipitated or the mechanical strength of the electrophotographic photoreceptor of the present invention may be reduced. May be insufficient.

The charge transport layer is formed by applying a coating solution prepared by mixing the charge transport material and the binder resin in an appropriate solvent on the conductive support and then drying the coating solution. The solvent is not particularly limited and known organic solvents, for example, alcohols such as methanol, ethanol, isopropanol and n-butanol, acetone, methyl ethyl ketone, ketones such as cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, Ethers such as diethyl ether, aliphatic halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride, and trichloroethylene; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; methyl acetate; Esters such as ethyl acetate and n-butyl acetate, and aromatics such as benzene, toluene, xylene, monochlorobenzene and dichlorobenzene are exemplified. These are 1
These may be used alone or in combination of two or more. Also, a trace amount of silicone oil or the like can be added to the coating liquid as a leveling agent for improving smoothness.
These solvents can also be used as a coating solution for the charge generation layer, the undercoat layer and the surface protective layer described below.

The coating method is not particularly limited, and can be appropriately selected from known coating methods according to the shape and use of the photoreceptor. For example, coating methods such as dip coating, ring coating, spray coating, bead coating, blade coating, and roller coating can be used. As the drying method, it is preferable to heat dry after touch drying at room temperature. The temperature of the heating and drying is 30 to
200 ° C. is preferable, and the drying time is 5
Minutes to 2 hours are preferred.

In general, the thickness of the charge transport layer is preferably 5 to 50 μm, more preferably 10 to 30 μm. When the thickness is less than 5 μm, leakage is likely to occur, and the thickness of the layer decreases during use, which may shorten the life of the electrophotographic photoreceptor of the present invention. In some cases, the residual potential increases, and the thickness of the charge transport layer becomes non-uniform.

-Other components- As the other components, those described in the charge generation layer are used.
Components similar to other components other than the binder resin are preferably exemplified.

[Conductive Support] The conductive support is not particularly limited as long as it is generally used as a conductive support of an electrophotographic photosensitive member.
For example, aluminum, copper, iron, zinc, metals such as nickel, by evaporation, aluminum, copper, gold, silver, platinum,
Laminate paper, plastic or glass, metal foil, or carbon black, indium oxide, tin oxide-oxidized with thin film of palladium, titanium, nickel-chromium, stainless steel, copper-indium, indium oxide, tin oxide, etc. Various types of supports obtained by applying a coating liquid in which antimony powder, metal powder, copper iodide, or the like is dispersed in a binder resin, and conducting a conductive treatment are preferably exemplified.

The shape of the conductive support is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a drum shape, a sheet shape, a plate shape, and a pipe shape.

The conductive support may be subjected to mirror cutting, etching, anodic oxidation, rough cutting,
Various surface treatments such as centerless grinding, sand blasting, and wet honing can be performed. By the surface treatment, by roughening the surface of the support, it is possible to prevent grain-shaped density unevenness due to interference light in the photoconductor that can occur when using a coherent light source such as a laser beam. . In particular, it is effective when the conductive support uses a metal pipe base material.

[Other layers] As the other layers,
Examples include an undercoat layer and a surface protective layer. (Undercoat layer) As the undercoat layer, an acetal resin such as polyvinyl butyral, a polyvinyl alcohol resin,
Casein, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, silicone-alkyd resin, Examples include a high molecular compound such as a phenol-formaldehyde resin and a melamine resin, and an organic metal compound such as a zirconium, titanium, aluminum, manganese or silicon compound. Among them, silicone compounds, organic zirconium compounds, organic titanium compounds, and organic aluminum compounds are preferably exemplified. These compounds may be used alone or in combination of two or more, and may be used as a polycondensate of a plurality of compounds. Furthermore, among these compounds, when an organometallic compound containing zirconium or silicon is used, the residual potential can be reduced, so that the potential change due to the environment is small and the potential change due to repeated use is small. ,
Excellent performance can be obtained.

In the undercoat layer, various organic or inorganic fine powders can be contained, if necessary, for the purpose of improving electric characteristics and light scattering. The organic or inorganic fine powder is not particularly limited and can be appropriately selected from known organic or inorganic fine powders. In particular, among the inorganic fine powders, titanium oxide, zinc oxide, and zinc oxide And white pigments such as zinc sulfide, lead white and lithopone, and inorganic pigments as extenders such as alumina, calcium carbonate and barium sulfate. Further, among the organic fine powders, Teflon resin particles, benzoguanamine resin particles, styrene resin particles and the like are preferable. The organic or inorganic fine powder preferably has a particle size of 0.01 to 2 μm. The amount of the inorganic fine powder to be added is preferably from 10 to 80% by weight, more preferably from 30 to 70% by weight, based on the solid content of the undercoat layer.

To disperse and contain the organic or inorganic fine powder in the undercoat layer, the organic or inorganic fine powder is
After adding to the solution in which the resin component and the like are dissolved, the dispersion is performed. The dispersion treatment is performed using a roll mill, a ball mill, a vibration ball mill, an attritor, a sand mill, a colloid mill, a paint shaker, or the like.

The thickness of the undercoat layer is 0.1 to 1
0 μm is preferred. When the thickness is 0.1 μm or less, the conductive support is insufficiently concealed, so that black spots and white spots may be generated. On the other hand, when the thickness exceeds 10 μm, the residual potential increases. May be.

(Surface Protective Layer) As the surface protective layer,
Examples include an insulating resin protective layer and a low-resistance protective layer. Examples of the low resistance protective layer include a protective layer in which a resistance adjuster such as conductive fine particles is dispersed in an insulating resin. The conductive fine particles have an electric resistance of 10 ⁹ Ω
-Fine particles exhibiting white, gray or bluish white with a size of not more than cm are preferred. The average particle size of the conductive fine particles is 0.3 μm.
m or less, more preferably 0.1 μm or less. As the conductive fine particles, for example, molybdenum oxide, tungsten oxide, antimony oxide, tin oxide, titanium oxide,
A solid solution carrier of indium oxide, tin oxide and antimony or antimony oxide or a mixture thereof, or a mixture of these metal oxides in a single particle, or a coated particle thereof may be used. Among them, tin oxide, a solid solution of tin oxide and antimony or antimony oxide can appropriately adjust electric resistance, and can make the surface protective layer substantially transparent. (Japanese Patent Application Laid-Open Nos. Sho 57-30847 and 57
-128344).

As the insulating resin used for the insulating resin protective layer and the low resistance protective layer, the high molecular weight polycarbonate polymer specified in the present invention is used, and a resin which can be used for the mixing is used in combination. be able to.

Next, the structure of the electrophotographic photosensitive member of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view illustrating the configuration of the electrophotographic photosensitive member according to the first embodiment. This electrophotographic photoreceptor has a charge generation layer 3-a on a conductive support 1.
Is provided, and the charge transport layer 3-b is provided thereon. FIG. 2 is a schematic cross-sectional view illustrating the configuration of the electrophotographic photosensitive member according to the second embodiment. This electrophotographic photosensitive member is different from the first embodiment in that an undercoat layer 2 is provided between a conductive support 1 and a charge generation layer 3-a. FIG. 3 is a schematic sectional view illustrating the configuration of the electrophotographic photosensitive member according to the third embodiment. This electrophotographic photosensitive member is different from the first embodiment in that a protective layer 4 is provided on the charge transport layer 3-b. FIG.
FIG. 4 is a schematic sectional view illustrating a configuration of an electrophotographic photosensitive member according to a fourth embodiment. This electrophotographic photoreceptor is different from the third embodiment in that a conductive support 1 and a charge generation layer 3-a are provided between the conductive support 1 and the charge generation layer 3-a.
An undercoat layer 2 is provided. FIG. 5 is a schematic sectional view showing the configuration of the electrophotographic photosensitive member according to the fifth embodiment. The electrophotographic photoreceptor has a single photosensitive layer 3 on a conductive support 1.
-C is provided. FIG. 6 is a schematic cross-sectional view illustrating the configuration of the electrophotographic photosensitive member according to the sixth embodiment. The electrophotographic photosensitive member is different from the fifth embodiment in that an undercoat layer 2 is provided between a conductive support 1 and a single photosensitive layer 3-c. FIG. 7 is a schematic sectional view showing the configuration of the electrophotographic photosensitive member according to the seventh embodiment. This electrophotographic photosensitive member is different from the sixth embodiment in that a protective layer 4 is provided on a single-layer photosensitive layer 3-c.

The electrophotographic photoreceptor of the present invention may be an electrophotographic apparatus such as a light lens type copier, a laser beam printer emitting near-infrared light or visible light, a digital copier, an LED printer, a laser facsimile, or the like. It can be suitably used for a process cartridge provided in an electrophotographic apparatus. The electrophotographic photoreceptor of the present invention can be used in combination with a one-component or two-component regular developer or a reversal developer. Furthermore, the electrophotographic photoreceptor of the present invention can be used for an electrophotographic apparatus provided with a contact charger having a charging roller and a charging brush, with less occurrence of current leakage, and can easily obtain good image quality. .

[Electrophotographic Apparatus] Next, an electrophotographic apparatus having the electrophotographic photosensitive member of the present invention will be described. FIG. 8 is a schematic explanatory view showing a first embodiment of an electrophotographic apparatus provided with the electrophotographic photosensitive member of the present invention. The electrophotographic apparatus includes an electrophotographic photoreceptor 10, a charger 11, a power supply 1
2, an image input device 13, a developing device 14, and a transfer device 15
, A cleaning device 16, a static eliminator 17, and a fixing device 18
And A charger 11 of a corona discharge type (non-contact charging type) is arranged on the electrophotographic photoreceptor 10, and the charger 11 is operated by a voltage supplied from a power supply 12. FIG. 9 is a schematic explanatory view showing a second embodiment of the electrophotographic apparatus provided with the electrophotographic photosensitive member of the present invention. 9, the same reference numerals as those in FIG. 8 indicate the same members and configurations as those in FIG. In this electrophotographic apparatus, unlike the electrophotographic apparatus of the first embodiment, a charger 11 ′ of a contact charging system is in contact with the electrophotographic photoreceptor 10. Charger 1
1 'operates with the voltage supplied from the power supply 12.
Some contact-type electrophotographic apparatuses do not include the static eliminator 17.

FIG. 10 is a schematic explanatory view showing a third embodiment of the electrophotographic apparatus provided with the electrophotographic photosensitive member of the present invention. 10, the same reference numerals as those in FIG. 8 indicate the same members and configurations as those in FIG. In the electrophotographic apparatus, unlike the electrophotographic apparatus according to the first embodiment, the electrophotographic photoreceptor 10, the charger 11, the image input unit 13, the developing unit 14, the cleaning unit 16, and the charge removing unit 17 include a cartridge 19.
Are integrally supported by As shown in FIG. 10, the electrophotographic photoreceptor of the present invention, a charging unit, an image exposure unit,
By using an electrophotographic process cartridge which is integrally supported with at least one means selected from the group consisting of cleaning means and cleaning means and is detachable from the electrophotographic apparatus, the user can be prevented from soiling his hands and clothes with toner. It has the advantage that it can be done.

[0148]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. The high molecular weight polycarbonate polymers shown in the following compound examples were synthesized. (Compound Example A) As a raw material 4-functional phenol derivative,
4 ′, 4 ″, 4 ′ ″-(1,4-phenylenedimethylidene) tetrakisphenol 0.02 mmol, and 2,2-bis (4-hydroxyphenyl) as a diol
2.5 mmol of ditrifluoromethylmethane, 23.7 mmol of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane and 23.7 mmol of bis (4-hydroxy-3-methylphenyl) methane are put into a 1-liter flask. did. Further, 165 mmol of sodium hydroxide was used as a sodium phenoxide agent, and 0.5 m of benzyltriethylammonium chloride was used as a catalyst.
mol, and add 220 ml of ion-exchanged water to this,
Stir to dissolve the contents. At this time, the inside of the system was maintained at 17 ° C. using a cool bath. Methylene chloride 200m
was added, and the capillary tip of the dropping funnel with cavities was attached so as to enter the methylene chloride layer. A solution in which 17.5 mmol of triphosgene was dissolved in 50 ml of methylene chloride was dropped into the system over 10 minutes from a dropping funnel.

After stirring and cooling were maintained for 10 minutes after completion of the dropwise addition, 0.25 ml of tributylamine was added to the system as a polymerization catalyst. While cooling, stirring was continued for 1 hour and 20 minutes. Thereafter, 100 ml of methylene chloride was added, and the stirring was stopped. Transfer the contents to a separatory funnel and add ion-exchanged water 30
0 ml was added and the mixture was allowed to stand overnight. Separate the methylene chloride layer,
Washing was performed three times with 500 ml of ion-exchanged water. The separated methylene chloride layer was dropped into 1.5 liter of methanol,
Solidified and filtered. The polymer obtained after drying was dissolved in 300 ml of chloroform, dropped into 1.5 liter of methanol, solidified, and filtered to obtain 11 g of a target high molecular weight polycarbonate polymer.

It was confirmed that the obtained polymer had a star-shaped structure by comparing a linear polycarbonate having a main skeleton with the same structure and the same molecular weight with 1% by weight in tetrahydrofuran.
The solution viscosities at the time of dissolution were compared, and CV = (solution viscosity of the obtained polymer) / (solution viscosity of the linear polymer) ≦ 0.
When the value of 5 was satisfied, the obtained polymer was judged to be star-shaped. With respect to the obtained high molecular weight polycarbonate polymer, a weight average molecular weight in terms of polystyrene was measured by gel permeation chromatography (GPC) HLC8020 (manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent. The weight average molecular weight was 180,000. The glass transition temperature was 128 ° C. as measured by DSC3110 (manufactured by Material Analysis and Characterization Co., Ltd.).

(Compound Example B) As a starting material 4-functional phenol derivative, 4,4 ′, 4 ″, 4 ′ ″-(1,4-phenylenedimethylidene) tetrakisphenol 0.02 mmol
1, and 2.5 mmol of 2,2-bis (4-hydroxyphenyl) ditrifluoromethylmethane as a diol
And 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane and 23.7 mmol of bis (4-hydroxy-3-methylphenyl) methane
Was charged into a 1 liter flask. Further, 165 mmol of sodium hydroxide is used as a sodium phenoxide agent.
l, and 0.5 mmol of benzyltriethylammonium chloride as a catalyst.
0 ml was added and stirred to dissolve the contents. At this time, the inside of the system was maintained at 17 ° C. using a cool bath. To this, 200 ml of methylene chloride was added, and 6 g of phosgene was blown in while stirring for about 1 minute. 1 after phosgene injection
After maintaining stirring and cooling for 0 minutes, 0.25 ml of tributylamine was added as a polymerization catalyst into the system. While cooling, stirring was continued for 1 hour and 20 minutes. Thereafter, 100 ml of methylene chloride was added, and the stirring was stopped. The contents were transferred to a separatory funnel, and 200 ml of ion-exchanged water was added and left overnight. Separate the methylene chloride layer and add 500 ml of ion-exchanged water.
And washed three times. The separated methylene chloride layer was dropped into 1.5 liter of methanol, solidified and filtered. The polymer obtained after drying was dissolved in 300 ml of chloroform, and 3
It was dropped into 1 liter of methanol, solidified, and filtered to obtain 11 g of the desired high molecular weight polycarbonate polymer. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example C) In the synthesis of Compound Example A, 4,4 ′,
A high molecular weight polycarbonate polymer was obtained in the same manner as in the synthesis of Compound Example A except that 0.2 mmol of 4 ″, 4 ′ ″-(1,4-phenylenedimethylidene) tetrakisphenol was used. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example D) In the synthesis of Compound Example A, 4,4 ',
A high molecular weight polycarbonate polymer was obtained in the same manner as in the synthesis of Compound Example A except that 0.002 mmol of 4 ″, 4 ′ ″-(1,4-phenylenedimethylidene) tetrakisphenol was used. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example E) In the synthesis of Compound Example A, 2,2-bis (4-hydroxyphenyl) ditrifluoromethylmethane was used as a raw material diol at 15.0 mm.
ol and 17.5 mmol of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane and bis (4-
17.5 m of hydroxy-3-methylphenyl) methane
A high molecular weight polycarbonate polymer was obtained in the same manner as in Compound Example A except that mol was used. Further, with respect to the high molecular weight polycarbonate polymer, the compound example A
Various measurements were performed in the same manner as described above.

(Compound Example F) In the synthesis of Compound Example A, instead of bis (4-hydroxy-3-methylphenyl) methane as the raw material diol, 2,2-bis (4-
A high molecular weight polycarbonate polymer was obtained in the same manner as in Compound Example A, except that (hydroxy-3-methylphenyl) propane was used. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example G) In the synthesis of Compound Example A, instead of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane as a raw material diol,
2,2-bis (4-hydroxy-3-methylphenyl)
A high molecular weight polycarbonate polymer was obtained in the same manner as in Compound Example A except that propane was used. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example H) In the synthesis of Compound Example A, 2,2-bis (4-hydroxyphenyl) ditrifluoromethylmethane was used as a starting material diol in an amount of 2.5 mmol.
1 and 47.4 mmol of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane were used.
A high molecular weight polycarbonate polymer was obtained in the same manner as in Compound Example A. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example I) In the synthesis of Compound Example A, 2,2-bis (4-hydroxyphenyl) ditrifluoromethylmethane was used as a starting material diol in an amount of 2.5 mmol.
A high molecular weight polycarbonate polymer was obtained in the same manner as in Compound Example A, except that 1 and 47.4 mmol of 2,2-bis (4-hydroxy-3-methylphenyl) propane were used. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example J) In the synthesis of Compound Example A, the tetrafunctional phenol derivative 4,4 ′, 4 ″, 4 ′ ″-
A polycarbonate polymer was obtained in the same manner as in Compound Example A, except that (1,4-phenylenedimethylidene) tetrakisphenol was not used. Various measurements were performed on the polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example K) In the synthesis of Compound Example A, except that 2,2-bis (4-hydroxyphenyl) ditrifluoromethylmethane was not used.
In the same manner as in the above, a polycarbonate polymer was obtained. Also,
About this polycarbonate polymer, the said compound example A
Various measurements were performed in the same manner as described above.

The measurement results of Compound Example A to Compound Example K are shown in Table 20 below.

[0162]

[Table 20]

(Compound Example a) In the synthesis of Compound Example A, p-hydroxybenzoic acid-n was used as a terminal stopper (molecular weight regulator) when a sodium phenoxide agent was added.
A high molecular weight polycarbonate polymer was obtained in the same manner as in the synthesis of Compound Example A except that 0.2 g of -dodecyl was added. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example b) In the synthesis of Compound Example B, p-hydroxybenzoic acid-n-dodecyl was added as a terminal terminator at the time of addition of a sodium phenoxide agent.
Except for adding 2 g, the same as in the synthesis of Compound Example B,
A high molecular weight polycarbonate polymer was obtained. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example c) In the synthesis of Compound Example C, p-hydroxybenzoic acid-n-dodecyl was added as a terminal terminator to a sodium terminating agent at the time of addition of sodium phenoxide agent.
Except for adding 2 g, the same as in the synthesis of Compound Example C,
A high molecular weight polycarbonate polymer was obtained. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example d) In the synthesis of Compound Example D, n-dodecyl p-hydroxybenzoate-n-dodecyl was added as a terminal stopper at the time of adding a sodium phenoxide agent.
Except for adding 2 g, the same as in the synthesis of Compound Example D,
A high molecular weight polycarbonate polymer was obtained. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example e) In the synthesis of Compound Example E, the procedure of Synthesis of Compound Example E was repeated except that 0.2 g of p-dodecylphenol was added as a terminal stopper when the sodium phenoxide agent was added. Thus, a high molecular weight polycarbonate polymer was obtained. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example f) In the synthesis of Compound Example F, 0.2 g of p-tert-butylphenol was used as a terminal stopper when adding a sodium phenoxide agent.
Except for the addition, a high molecular weight polycarbonate polymer was obtained in the same manner as in the synthesis of Compound Example F. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example g) In the synthesis of Compound Example G, except that 0.2 g of p-phenylphenol was added as a terminal terminator when the sodium phenoxide agent was added, the procedure was the same as in the synthesis of Compound Example G. Thus, a high molecular weight polycarbonate polymer was obtained. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example h) In the synthesis of Compound Example H, except that 0.2 g of p- (1H, 1H-perfluorooctyloxy) phenol was added as a terminal terminator when the sodium phenoxide agent was added. A high molecular weight polycarbonate polymer was obtained in the same manner as in the synthesis of Compound Example H. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example i) In the synthesis of Compound Example I, except that 0.2 g of p- (1H, 1H-perfluorodecyloxy) phenol was added as a terminal stopper at the time of adding the sodium phenoxide agent. , Compound Example I
A high molecular weight polycarbonate polymer was obtained in the same manner as in the synthesis of. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example j) In the synthesis of Compound Example J, p-hydroxybenzoic acid-n-dodecyl was added as a terminal terminator at the time of adding a sodium phenoxide agent.
Except for adding 2 g, the same as in the synthesis of Compound Example J,
A high molecular weight polycarbonate polymer was obtained. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

(Compound Example k) In the synthesis of Compound Example K, p-hydroxybenzoic acid-n-dodecyl was added as a terminal stopper at the time of addition of a sodium phenoxide agent.
Except for adding 2 g, the same as in the synthesis of Compound Example K,
A high molecular weight polycarbonate polymer was obtained. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example A.

Table 21 below shows the measurement results of the above-mentioned Compound Examples a to k.

[0175]

[Table 21]

(Compound Example L) As a starting material 4-functional phenol derivative, 4,4 ′, 4 ″, 4 ′ ″-(1,4-phenylenedimethylidene) tetrakisphenol 0.02 mmol
l and phenol-modified silicone oil X-22-1821 (manufactured by Shin-Etsu Silicone) 2.5 mm as a diol
ol, 23.7 mmol of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane and 23.7 mmol of bis (4-hydroxy-3-methylphenyl) methane
was charged into a 1 liter flask. Further, as a sodium phenoxide agent, sodium hydroxide 165 mm
ol, and 0.5 mmol of benzyltriethylammonium chloride as a catalyst.
20 ml was added and stirred to dissolve the contents. At this time, the inside of the system was maintained at 17 ° C. using a cool bath. To this was added 200 ml of methylene chloride, and the tip of the capillary of the dropping funnel with cavities was attached so as to enter the methylene chloride layer. A solution in which 17.5 mmol of triphosgene was dissolved in 50 ml of methylene chloride was dropped into the system over 10 minutes from a dropping funnel.

After completion of the dropwise addition, stirring and cooling were maintained for 10 minutes, 0.25 ml of tributylamine was added as a polymerization catalyst into the system. While cooling, stirring was continued for 1 hour and 20 minutes. Thereafter, 100 ml of methylene chloride was added, and the stirring was stopped. Transfer the contents to a separatory funnel and add ion-exchanged water 30
0 ml was added and the mixture was allowed to stand overnight. Separate the methylene chloride layer,
Washing was performed three times with 500 ml of ion-exchanged water. The separated methylene chloride layer was dropped into 1.5 liter of methanol,
Solidified and filtered. The polymer obtained after drying was dissolved in 300 ml of chloroform, dropped into 1.5 liter of methanol, solidified, and filtered to obtain 11 g of a target high molecular weight polycarbonate polymer.

It was confirmed that the obtained polymer had a star-shaped structure by comparing a linear polycarbonate having the same main skeleton with the same molecular weight with 1% by weight of tetrahydrofuran in tetrahydrofuran.
The solution viscosities at the time of dissolution were compared, and CV = (solution viscosity of the obtained polymer) / (solution viscosity of the linear polymer) ≦ 0.
When the value of 5 was satisfied, the obtained polymer was judged to be star-shaped. With respect to the obtained high molecular weight polycarbonate polymer, a weight average molecular weight in terms of polystyrene was measured by gel permeation chromatography (GPC) HLC8020 (manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent. The weight average molecular weight was 180,000. The glass transition temperature measured by DSC3110 (manufactured by Material Analysis and Characterization Co., Ltd.) was 118 ° C.

(Compound Example M) As a starting material 4-functional phenol derivative, 4,4 ', 4 ", 4'"-(1,4-phenylenedimethylidene) tetrakisphenol 0.02 mmol
1 and 2.5 m of phenol-modified silicone oil X-22-1821 (manufactured by Shin-Etsu Silicone) as a diol
mol, 2,3-mmol of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane and bis (4-
(Hydroxy-3-methylphenyl) methane 23.7 mm
was charged into a 1 liter flask. Further, 165m of sodium hydroxide is used as a sodium phenoxide agent.
mol and 0.5 mmol of benzyltriethylammonium chloride as a catalyst, and 220 ml of ion-exchanged water was added thereto, followed by stirring to dissolve the contents. At this time, the inside of the system was maintained at 17 ° C. using a cool bath. To this, 200 ml of methylene chloride was added, and while stirring, 1.2 liter of phosgene gas was blown in for about 5 minutes. After stirring and cooling for 10 minutes after the completion of the injection of the phosgene gas, 0.25 ml of tributylamine was added to the system as a polymerization catalyst. While cooling, stirring was continued for 1 hour and 20 minutes. Thereafter, 100 ml of methylene chloride was added, and the stirring was stopped. Transfer the contents to a separatory funnel and add 300 parts of ion-exchanged water.
ml was added and left to stand overnight. The methylene chloride layer was separated and washed three times with 500 ml of ion-exchanged water. The separated methylene chloride layer was dropped into 1.5 liter of methanol, solidified and filtered. After drying, the polymer obtained is mixed with chloroform 3
The resultant was dissolved in 00 ml, dropped into 1.5 liters of methanol, solidified and filtered to obtain 11 g of the desired high molecular weight polycarbonate polymer. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example L.

(Compound Example N) In the synthesis of Compound Example L, 4,4 ′,
A high molecular weight polycarbonate polymer was obtained in the same manner as in Compound Example L except that 0.2 mmol of 4 ″, 4 ′ ″-(1,4-phenylenedimethylidene) tetrakisphenol was used. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example L.

(Compound Example O) In the synthesis of Compound Example L, 4,4 ′,
A high molecular weight polycarbonate polymer was obtained in the same manner as in Compound Example L except that 0.002 mmol of 4 ″, 4 ′ ″-(1,4-phenylenedimethylidene) tetrakisphenol was used. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example L.

(Compound Example P) In the synthesis of Compound Example L, phenol-modified silicone oil X-22-1821 (manufactured by Shin-Etsu Silicone) was used as a raw material diol.
0 mmol, 17.5 mmol of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane and 1 mmol of bis (4-hydroxy-3-methylphenyl) methane
A high molecular weight polycarbonate polymer was obtained in the same manner as in Compound Example L, except that 7.5 mmol was used. Also,
Various measurements were performed on this high molecular weight polycarbonate polymer in the same manner as in Compound Example L described above.

(Compound Example Q) In the synthesis of Compound Example L, instead of bis (4-hydroxy-3-methylphenyl) methane as a raw material diol, 2,2-bis (4-
A high molecular weight polycarbonate polymer was obtained in the same manner as in Compound Example L, except that (hydroxy-3-methylphenyl) propane was used. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example L.

(Compound Example R) In the synthesis of Compound Example L, instead of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane as a raw material diol,
2,2-bis (4-hydroxy-3-methylphenyl)
A high molecular weight polycarbonate polymer was obtained in the same manner as in Compound Example L except that propane was used. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example L.

(Compound Example S) In the synthesis of Compound Example L, phenol-modified silicone oil X-22-1821 (manufactured by Shin-Etsu Silicone) was used as a raw material diol in an amount of 2.5%.
A high molecular weight polycarbonate polymer was obtained in the same manner as in Compound Example L except that 47.4 mmol of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane and 47.4 mmol of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane were used. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example L.

(Compound Example T) In the synthesis of Compound Example L, phenol-modified silicone oil X-22-1821 (manufactured by Shin-Etsu Silicone) was used as a raw material diol in an amount of 2.5%.
mmol and 47.4 mmol of 2,2-bis (4-hydroxy-3-methylphenyl) propane,
A high molecular weight polycarbonate polymer was obtained in the same manner as in Compound Example L. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example L.

(Compound Example U) In the synthesis of Compound Example L, the tetrafunctional phenol derivative 4,4 ′, 4 ″, 4 ′ ″-
A polycarbonate polymer was obtained in the same manner as in Compound Example L except that (1,4-phenylenedimethylidene) tetrakisphenol was not used. Various measurements were performed on this polycarbonate polymer in the same manner as in Compound Example L.

(Compound Example V) In the synthesis of Compound Example L, a phenol-modified silicone oil X-22-182 was used.
A polycarbonate polymer was obtained in the same manner as in Compound Example L, except that No. 1 (made by Shin-Etsu Silicone) was not used. Various measurements were performed on this polycarbonate polymer in the same manner as in Compound Example L.

The measurement results of Compound Example L to Compound Example V are shown in Table 22 below.

[0190]

[Table 22]

(Compound Example 1) In the synthesis of Compound Example L, p-hydroxybenzoic acid-n-dodecyl was added as a terminal terminator to a sodium phenoxydating agent.
Except for adding 2 g, the same as in the synthesis of Compound Example L,
A high molecular weight polycarbonate polymer was obtained. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example L.

(Compound Example m) In the synthesis of Compound Example 1, except that p-phenylphenol was added instead of p-hydroxybenzoic acid-n-dodecyl as a terminal stopper, the synthesis was performed in the same manner as in the synthesis of Compound Example 1. Thus, a high molecular weight polycarbonate polymer was obtained. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example L.

(Compound Example n) In the synthesis of Compound Example 1, except that p- (1H, 1H-perfluorooctyloxy) phenol was added instead of p-hydroxybenzoic acid-n-dodecyl as a terminal terminator, A high molecular weight polycarbonate polymer was obtained in the same manner as in the synthesis of Compound Example 1. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example L.

(Compound Example o) In the synthesis of Compound Example P, except that 0.2 g of p- (1H, 1H-perfluorodecyloxy) phenol was added as a terminal terminator when the sodium phenoxide agent was added. , Compound Example P
A high molecular weight polycarbonate polymer was obtained in the same manner as in the synthesis of. Various measurements were performed on the high molecular weight polycarbonate polymer in the same manner as in Compound Example L.

Table 23 below shows the measurement results of the above compound examples 1 to o.

[0196]

[Table 23]

Next, examples of the electrophotographic photosensitive member will be described. (Example 1) The surface of an ED tube aluminum (30 mmφ) was coated on a conductive support with alumina spherical fine powder (D ₅₀ =
(30 μm) and a surface roughened to a center line average roughness Ra = 0.18 μm by a liquid honing method. Polyvinyl butyral resin (Eslec BM-S,
4 parts by weight of Sekisui Chemical Co., Ltd. dissolved in 170 parts by weight of n-butyl alcohol, 30 parts by weight of an organic zirconium compound (acetylacetone zirconium butyrate) and 3 parts by weight of a mixture of organic silane compounds (γ-aminopropyltrimethoxysilane) Parts were mixed and stirred, and the resulting undercoat layer-forming coating liquid was applied on the conductive support by dip coating using the obtained coating liquid, and subjected to a curing treatment at 150 ° C. for 1 hour.
An undercoat layer having a thickness of 1.2 μm was formed.

Next, in the case of the Bragg angle (2θ ± 0.2 °) of the X-ray diffraction spectrum using Cukα ray, the following condition was obtained.
3 parts by weight of chlorgallium phthalocyanine having diffraction peaks at 4 °, 16.6 °, 25.5 ° and 28.3 °, 2 parts by weight of a vinyl chloride-vinyl acetate copolymer (VMCH, manufactured by Nippon Unicar) And a mixture consisting of 180 parts by weight of butyl acetate and butyl acetate was subjected to a dispersion treatment for 4 hours by a sand mill, and the resulting dispersion was applied on the undercoat layer by a dip coating method. A 2 μm charge generation layer was formed. Next, 4 parts by weight of N, N-bis (3,4-dimethylphenyl) biphenyl-4-amine represented by the compound number (7-33) as a charge transporting material and the above compound example (A) as a binder resin 6 parts by weight of a high molecular weight polycarbonate polymer were dissolved in 60 parts by weight of tetrahydrofuran and 0.2 parts by weight of 2,6-di-t-butyl-4-methylphenol. Using the obtained coating solution, coating was performed on the charge generation layer,
For 40 minutes to form a charge transport layer having a thickness of 25 μm, thereby producing an electrophotographic photosensitive member having three layers.

The obtained electrophotographic photoreceptor was mounted on a color copying machine (Acolor 935, manufactured by Fuji Xerox Co., Ltd.), and the light amount was adjusted to perform a print test of 50,000 sheets. Was evaluated, and the residual potential, charged potential and abrasion amount of the photoreceptor after printing 50,000 sheets were measured and evaluated. A scorotron charger was used for charging, and the grid voltage was -650 V. After exposure (760 nm, 20 mJ / m ² ), 0.5
After a lapse of seconds, the surface potential was measured and defined as a residual potential. The evaluation results are shown in Table 24 below. Note that the transfer efficiency was evaluated by measuring a fixed area toner image (toner amount: W ₁ +) on the surface of the electrostatic latent image carrier.
W ₂ ) is formed and the toner image (toner amount: W ₂ ) on the transfer material immediately after the transfer step and the toner image (toner amount: W ₁ ) remaining on the surface of the electrostatic latent image carrier are calculated according to the following formula. The transfer efficiency was calculated. Transfer efficiency (%) = W ₂ / (W ₁ + W ₂ ) × 100

(Examples 2 to 9) In Example 1, the high-molecular-weight polycarbonate polymer of the compound example (A) used as the binder resin of the charge transport layer was replaced with the compound examples (B) to (I). Example 2 was repeated in the same manner as in Example 1 except that the high molecular weight polycarbonate polymer was used.
To 9 were prepared. Evaluation was performed in the same manner as in Example 1 using each of the obtained electrophotographic photosensitive members. The evaluation results are shown in Table 24 below.

(Comparative Examples 1-2) In Example 1, the high molecular weight polycarbonate polymer of the compound example (A) used as the binder resin of the charge transport layer was replaced with the above-mentioned compound examples (J) to (K). Electrophotographic photoreceptors of Comparative Examples 1 and 2 were produced in the same manner as in Example 1 except that the polycarbonate polymer was used. Evaluation was performed in the same manner as in Example 1 using each of the obtained electrophotographic photosensitive members. The evaluation results are shown in Table 24 below.

[0202]

[Table 24]

(Examples 10 to 18) In Example 1,
Example 1 was the same as Example 1 except that the high molecular weight polycarbonate polymer of the compound example (A) used as the binder resin of the charge transport layer was replaced with the high molecular weight polycarbonate polymer of the above compound examples (a) to (i). In the same manner, the electrophotographic photosensitive members of Examples 10 to 18 were produced. Evaluation was performed in the same manner as in Example 1 using each of the obtained electrophotographic photosensitive members. The evaluation results are shown in Table 25 below.

(Comparative Examples 3 and 4) In Example 1, the high molecular weight polycarbonate polymer of the compound example (A) used as the binder resin of the charge transport layer was replaced with the above compound examples (j) to (k). Electrophotographic photoreceptors of Comparative Examples 3 and 4 were produced in the same manner as in Example 1 except that the polycarbonate polymer was used. Evaluation was performed in the same manner as in Example 1 using each of the obtained electrophotographic photosensitive members. The evaluation results are shown in Table 25 below.

[0205]

[Table 25]

From the results in Tables 24 and 25, Examples 1 to
Regarding the electrophotographic photoreceptor No. 18, even when a print test was performed using a printer of a type in which charging was performed by a contact charging device, no image quality abnormality due to leak discharge of the photoreceptor was observed in any case. These photoreceptors have less wear,
Transfer efficiency did not decrease over a long period of time. In addition, it had stable electric characteristics without a decrease in chargeability and a rise in residual potential. However, in the electrophotographic photoreceptors of Comparative Examples 1 and 3, abrasion was large, dark decay increased, chargeability decreased, and fogging was observed in low density portions. Further, the electrophotographic photosensitive members of Comparative Examples 2 and 4 had low transfer efficiencies.

(Examples 19 to 27)
Example 1 was the same as Example 1 except that the high molecular weight polycarbonate polymer of the compound example (A) used as the binder resin of the charge transport layer was replaced with the high molecular weight polycarbonate polymer of each of the above compound examples (L) to (T). Similarly, the electrophotographic photosensitive members of Examples 19 to 27 were produced. Evaluation was performed in the same manner as in Example 1 using each of the obtained electrophotographic photosensitive members. The evaluation results are shown in Table 26 below.

(Comparative Examples 5 to 6) In Example 1, the high molecular weight polycarbonate polymer of the compound example (A) used as the binder resin of the charge transport layer was replaced with the compound examples (U) to (V). Electrophotographic photoreceptors of Comparative Examples 5 to 6 were produced in the same manner as in Example 1 except that the polycarbonate polymer was used. Evaluation was performed in the same manner as in Example 1 using each of the obtained electrophotographic photosensitive members. The evaluation results are shown in Table 26 below.

[0209]

[Table 26]

(Examples 28 to 31)
Example 1 was the same as Example 1 except that the high molecular weight polycarbonate polymer of the compound example (A) used as the binder resin of the charge transport layer was replaced with the high molecular weight polycarbonate polymer of each of the above compound examples (l) to (o). Similarly, the electrophotographic photosensitive members of Examples 28 to 31 were produced. Evaluation was performed in the same manner as in Example 1 using each of the obtained electrophotographic photosensitive members. The evaluation results are shown in Table 27 below.

[0211]

[Table 27]

From the results shown in Tables 26 and 27, Example 19 was obtained.
In all of the electrophotographic photoreceptors No. to No. 31, even when a print test was performed using a printer of a type which is charged by a contact charging device, no image quality abnormality caused by leak discharge of the photoreceptor was observed. These photoreceptors have less wear,
Transfer efficiency did not decrease over a long period of time. In addition, it had stable electric characteristics without a decrease in chargeability and a rise in residual potential. However, in the electrophotographic photoreceptor of Comparative Example 5, abrasion was large, dark decay increased, chargeability decreased, and fogging was observed in a low density portion. In the electrophotographic photosensitive member of Comparative Example 6, the transfer efficiency was low.

[0213]

According to the present invention, the abrasion resistance is improved, and even when used repeatedly for a long period of time, the surface layer of the photoreceptor has excellent releasability from the toner, the transfer efficiency of the toner is high, and the cleaning properties and It is possible to provide an electrophotographic photosensitive member having excellent electrical characteristics, a process cartridge having the same, and an electrophotographic apparatus.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view illustrating a configuration of an electrophotographic photosensitive member according to a first embodiment.

FIG. 2 is a schematic cross-sectional view illustrating a configuration of an electrophotographic photosensitive member according to a second embodiment.

FIG. 3 is a schematic cross-sectional view illustrating a configuration of an electrophotographic photosensitive member according to a third embodiment.

FIG. 4 is a schematic sectional view illustrating a configuration of an electrophotographic photosensitive member according to a fourth embodiment.

FIG. 5 is a schematic cross-sectional view illustrating a configuration of an electrophotographic photosensitive member according to a fifth embodiment.

FIG. 6 is a schematic sectional view illustrating a configuration of an electrophotographic photosensitive member according to a sixth embodiment.

FIG. 7 is a schematic sectional view illustrating a configuration of an electrophotographic photosensitive member according to a seventh embodiment.

FIG. 8 is a schematic explanatory view showing the electrophotographic apparatus of the first embodiment.

FIG. 9 is a schematic explanatory view illustrating an electrophotographic apparatus according to a second embodiment.

FIG. 10 is a schematic explanatory view showing an electrophotographic apparatus according to a third embodiment.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Conductive support 2 Undercoat layer 3-a photosensitive layer (charge generation layer) 3-b photosensitive layer (charge transport layer) 3-c photosensitive layer (single layer) 4 protective layer 10 electrophotographic photosensitive member 11 charger ( Non-contact charging system) 11 'charger (contact charging system) 12 power supply 13 image input device 14 developing device 15 transfer device 16 cleaning device 17 static eliminator 18 fixing device 19 cartridge

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masahiko Miyamoto 1600 Takematsu, Minami Ashigara City, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. (72) Inventor Hiroshi Nakamura 1600 Takematsu, Minami Ashigara City, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. (72) Inventor Ichiro Takekawa 1600 Takematsu, Minami Ashigara, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. (72) Inventor Masahiko Hozumi 1600 Takematsu, Minami Ashigara City, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. Address Fuji Xerox Co., Ltd. F-term (Reference) 2H068 AA03 AA13 BB20 BB26 BB52 BB53 FA03 FA04 FA27 4J029 AA09 AA10 AB02 AB07 AC02 AD01 AD07 AE04 BB18 BD09A BD09B BE05A BE05B BF14A BF14B BG08H01 DB01 FA08

Claims (10)

[Claims] 1. An electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, wherein a repeating unit represented by the following general formula (1) and a general formula (1) An electrophotographic photosensitive member comprising a high molecular weight polycarbonate polymer containing a repeating unit represented by 2). Embedded image (In the general formula (1), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkane group, an aryl group having 6 to 12 carbon atoms, or a fluorine-substituted alkyl group R _{3 to} R ₁₀ are each independently a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkane group,
An aryl group having 6 to 12 carbon atoms, a fluorine atom, a bromine atom,
Or a chlorine atom. ) (In the general formula (2), R _{21 to} R ₂₄ each independently represent a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkane group, an aryl group having 6 to 12 carbon atoms, a fluorine atom, a bromine atom, Or represents a chlorine atom.) 2. The polymer according to claim 1, wherein the high molecular weight polycarbonate polymer has at least one terminal selected from the group consisting of terminal groups represented by the following general formulas (I) to (III) at the terminal of the polymer chain. Electrophotographic photoreceptor. Embedded image (In the general formulas (I) to (III), R _{101 to} R ₁₀₃ each independently represent an alkyl group having 1 to 30 carbon atoms, a cycloalkane group, a perfluoroalkyl group, a substituted perfluoroalkyl group, or a carbon number. Represents an aryl group of 6 to 12, and represents Y ₁
To Y ₃ are each independently a single bond, -O-, -CO
—, —COO—, or —C (CH ₃ ) ₂ —. ) 3. The high-molecular-weight polycarbonate polymer according to claim 1, further comprising a repeating unit represented by the following general formula (3) and / or a repeating unit represented by the following general formula (4). Electrophotographic photoreceptor. Embedded image (In the general formula (3), A is a single bond, a linear, branched or aryl-substituted alkylidene group having 1 to 15 carbon atoms, an arylenedialkylidene group, -O-, -S-, -CO-,
-SO-, or -SO ₂ - represents a. R _{31 to} R ₃₄ each independently represent a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, a cycloalkane group, an aryl group having 6 to 12 carbon atoms, a fluorine atom, a bromine atom, or a chlorine atom. ) (In the general formula (4), R ₄₁ represents a single bond, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms. R _{42 to} R ₄₅ each independently represent a hydrogen atom, a 1 to 7 carbon atom. Represents an alkyl group, a cycloalkane group, an aryl group having 6 to 12 carbon atoms, a fluorine atom, a bromine atom, or a chlorine atom.) 4. The ratio of the repeating unit represented by the general formula (1) to the high molecular weight polycarbonate polymer is 0.01 to 1 mol%, and the weight average of the high molecular weight polycarbonate polymer is Molecular weight 30,000
4. The electrophotographic photoreceptor according to claim 1, which is as described above. 5. An electrophotographic photosensitive member having at least a photosensitive layer on a conductive support, wherein the repeating unit represented by the general formula (1) and the following general formula ( An electrophotographic photosensitive member comprising a high-molecular-weight polycarbonate polymer containing a repeating unit represented by 5). Embedded image (In the general formula (5), X represents an alkylene group having 2 to 6 carbon atoms, an alkylidene group, an alkylene ether group, or an alkylidene ether group. R _{51 to} R ₅₄ each independently represent a hydrogen atom or a carbon atom. Alkyl group of 1 to 6, 1 carbon atom
Represents an alkoxy group having 6 to 6, an aryl group having 6 to 12 carbon atoms, a fluorine atom, a bromine atom, or a chlorine atom. n is 0-2
Represents an integer of 00. ) 6. The polymer chain terminal of the high molecular weight polycarbonate polymer has at least one selected from the group consisting of terminal groups represented by the general formulas (I) to (III). Electrophotographic photoreceptor. 7. The high molecular weight polycarbonate polymer according to claim 5, further comprising a repeating unit represented by the general formula (3) and / or a repeating unit represented by the general formula (4). Electrophotographic photoreceptor. 8. The ratio of the repeating unit represented by the general formula (1) to the high molecular weight polycarbonate polymer is 0.01 to 1 mol%, and the weight average of the high molecular weight polycarbonate polymer is Molecular weight 30,000
The electrophotographic photosensitive member according to any one of claims 5 to 7, which is as described above. 9. An electrophotographic photosensitive member according to claim 1 and at least one unit selected from the group consisting of a charging unit, an image exposing unit and a cleaning unit. A process cartridge detachable from a photographic device. 10. An electrophotographic apparatus comprising at least the electrophotographic photosensitive member according to claim 1 and a contact-type charger.