JP5526082B2 - Electrophotographic photosensitive member and image forming apparatus - Google Patents

Description

  The present invention relates to an electrophotographic photosensitive member and an image forming apparatus including the electrophotographic photosensitive member.

  As an electrophotographic photosensitive member provided in an electrophotographic image forming apparatus, in addition to an inorganic photosensitive member provided with a photosensitive layer made of an inorganic material such as selenium or amorphous silicon, a binder resin, a charge generating agent, a charge transporting agent, etc. An organic photoreceptor having a photosensitive layer containing the organic material as a main component of the photoreceptor material is preferably used. It is known that such an organic photoreceptor is easy to manufacture as compared to an inorganic photoreceptor, and there are various options for the photoreceptor material constituting the photosensitive layer and the degree of freedom in structural design is high.

  In addition, as such an electrophotographic photoreceptor, for example, an electrophotographic photoreceptor using a polycarbonate resin represented by the following formula has been proposed in order to improve the photosensitivity and durability of the photosensitive layer (Patent Document). 1).

〔式中、Ｒ₁，Ｒ₂：水素原子、炭素数１〜６の置換、無置換のアルキル基、置換、無置換アリール基、Ｒ₁，Ｒ₂で形成するＣ₄〜Ｃ₁₀の環状炭化水素残基である。Ｒ₃,Ｒ₄,Ｒ₅及びＲ₆は各々水素原子、ハロゲン原子、炭素数１〜６の置換、無置換のアルキル基、置換、無置換のアリール基を表す。またｌ，ｍ，ｐ,ｑは１〜４の整数である。〕

[Wherein R ₁ and R _{2 are} hydrogen atoms, C 1-6 substituted, unsubstituted alkyl groups, substituted, unsubstituted aryl groups, and C _{4 to} C ₁₀ cyclic carbonization formed by R ₁ and R _2. It is a hydrogen residue. R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group. L, m, p, and q are integers of 1 to 4. ]

JP-A-5-257299

  However, although a photoconductor having a polycarbonate resin containing a biphenyl skeleton as described in Patent Document 1 is slightly superior in wear resistance, higher wear resistance has been accompanied by recent increases in the speed of printers and copiers. At present, there is a demand for a photosensitive member having the property.

  An object of the present invention is to provide an electrophotographic photoreceptor having excellent electrical characteristics and high wear resistance. Another object of the present invention is to provide an image forming apparatus provided with the electrophotographic photosensitive member.

  In view of the above problems, the present inventors have intensively studied and found that an electrophotographic photoreceptor excellent in electrical characteristics and abrasion resistance can be obtained by incorporating the following copolymer polycarbonate resin into the photosensitive layer. It was.

  That is, an electrophotographic photoreceptor according to an aspect of the present invention is an electrophotographic photoreceptor including a conductive substrate and a photosensitive layer formed directly or via an intermediate layer on the conductive substrate, The photosensitive layer contains at least a charge generator, a charge transport agent, and a binder resin, and the binder resin contains a copolymer polycarbonate resin having a repeating unit represented by the following general formula (I). It is characterized by that.

ここで、式（Ｉ）中、Ｒ^１〜Ｒ^６は、同一又は異なって、水素原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、又は炭素数６〜１２のアリール基を示し、Ｘは０．０５〜０．７を示す。また、Ｒ^１およびＲ^２は連結して炭素数５〜８のシクロアルキリデン基であってもよい。

Here, in formula (I), R < ¹ > -R < ⁶ > is the same or different, and is a hydrogen atom, a C1-C8 alkyl group, a C1-C8 alkoxy group, or a C6-C12 aryl. Represents a group, and X represents 0.05 to 0.7. R ¹ and R ² may be connected to each other to form a cycloalkylidene group having 5 to 8 carbon atoms.

  According to such a configuration, it is possible to provide an electrophotographic photosensitive member having excellent electrical characteristics and high wear resistance.

  In the electrophotographic photoreceptor, the charge transport agent is preferably an amine compound represented by any one of the following general formulas (II) to (IV).

［式中、Ｒ^１ａ〜Ｒ^７ａは、同一又は異なって、水素原子、炭素数１〜８のアルキル基、フェニル基又は炭素数１〜８のアルコキシ基を示し、ａは０から５の整数である。］

[Wherein, R ^{1a to} R ^7a are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, or an alkoxy group having 1 to 8 carbon atoms, and a is an integer of 0 to 5. is there. ]

［式中、Ｒ^１ｂ〜Ｒ^８ｂは、同一又は異なって、水素原子、炭素数１〜８のアルキル基又はフェニル基を示し、ａは０〜５の整数、ｂは０〜４の整数、ｋは０または１の整数である。］

[Wherein, R ^{1b to} R ^8b are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, a is an integer of 0 to 5, b is an integer of 0 to 4, k Is an integer of 0 or 1. ]

［式中、Ｒ^１ｃ〜Ｒ^３ｃは、同一又は異なって、炭素数１〜８のアルキル基、フェニル基又は炭素数１〜８のアルコキシ基を示し、ｋは０〜４の整数、ｍ、ｎは０から５の整数である。］

[Wherein, R ^{1c to} R ^3c are the same or different and each represents an alkyl group having 1 to 8 carbon atoms, a phenyl group, or an alkoxy group having 1 to 8 carbon atoms, k is an integer of 0 to 4, m, n Is an integer from 0 to 5. ]

  According to such a configuration, it is possible to provide an electrophotographic photosensitive member with further excellent electrical characteristics. In addition, an electrophotographic photoreceptor excellent in wear resistance can be provided.

  An image forming apparatus according to another aspect of the present invention includes an image carrier, a charging device for charging the surface of the image carrier, and exposing the surface of the charged image carrier, An exposure device for forming an electrostatic latent image on the surface of the image carrier, a developing device for developing the electrostatic latent image as a toner image, and transferring the toner image from the image carrier to a transfer target And the image carrier is the electrophotographic photosensitive member.

  According to such a configuration, it is possible to provide a long-life image forming apparatus capable of forming a high-quality image.

  According to the present invention, it is possible to provide an electrophotographic photoreceptor excellent in electrical characteristics and wear resistance. An image forming apparatus provided with the electrophotographic photosensitive member is also provided.

1 is a schematic cross-sectional view showing the structure of a single-layer type photoreceptor that is an example of an electrophotographic photoreceptor according to an embodiment of the present invention. It is a schematic sectional drawing which shows the structure of the laminated type photoreceptor which is another example of the electrophotographic photoreceptor which concerns on embodiment of this invention. 1 is a schematic diagram illustrating a configuration of an image forming apparatus including an electrophotographic photosensitive member according to an embodiment of the present invention.

  Hereinafter, although the embodiment concerning the present invention is described, the present invention is not limited to these.

  An electrophotographic photoreceptor (hereinafter also simply referred to as “photoreceptor”) according to an embodiment of the present invention includes a conductive substrate and a photosensitive layer formed on the conductive substrate directly or via an intermediate layer. The photosensitive layer comprises at least a charge generator, a charge transport agent, and a binder resin, and the binder resin has a repeating unit represented by the following general formula (I): An electrophotographic photosensitive member characterized by containing a copolymer polycarbonate resin.

ここで、式（Ｉ）中、Ｒ^１〜Ｒ^６は、同一又は異なって、水素原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、又は炭素数６〜１２のアリール基を示し、Ｘは０．０５〜０．７を示す。また、Ｒ^１およびＲ^２は連結して炭素数５〜８のシクロアルキリデン基であってもよい。

Here, in formula (I), R < ¹ > -R < ⁶ > is the same or different, and is a hydrogen atom, a C1-C8 alkyl group, a C1-C8 alkoxy group, or a C6-C12 aryl. Represents a group, and X represents 0.05 to 0.7. R ¹ and R ² may be connected to each other to form a cycloalkylidene group having 5 to 8 carbon atoms.

  Such an electrophotographic photoreceptor is an electrophotographic photoreceptor excellent in electrical characteristics and abrasion resistance. Therefore, an image forming apparatus provided with such an electrophotographic photosensitive member is durable and can form high-quality images over a long period of time.

  The details of the copolymer polycarbonate resin represented by the above formula (I) will be described later.

  If the photoconductor satisfies the above-described configuration, that is, an electrophotographic photoconductor in which the copolymer polycarbonate resin represented by the above formula (I) is contained in the binder resin in the photosensitive layer, the others are particularly It is not limited. Specifically, for example, as shown in FIG. 1, the photosensitive layer is a layer containing a charge generating agent, a charge transporting agent such as a hole transporting agent and an electron transporting agent, and a binder resin in the same layer. It may be a photoreceptor, a so-called single layer type photoreceptor.

  In addition, as shown in FIG. 2, the photosensitive layer includes at least a charge generating layer containing a charge generating agent and a binder resin, and a charge transporting layer containing a charge transporting agent such as a hole transporting agent and a binder resin. A photoconductor obtained by laminating two layers, a so-called laminated photoconductor may be used.

  When a binder resin is used for the charge generation layer, the binder resin is called a base resin, and the binder resin used for the charge transport layer is called a binder resin, similar to the binder resin used for the single-layer photoreceptor described above. . In the photoconductor according to the present embodiment, the copolymer polycarbonate resin represented by the above formula (I) is contained in the above-described binder resin in both the single layer type photoconductor and the laminated type photoconductor.

  FIG. 1 is a schematic cross-sectional view showing the structure of a single-layer type photoreceptor that is an example of an electrophotographic photoreceptor according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing the structure of a multilayer photoconductor as another example of the electrophotographic photoconductor according to the embodiment of the present invention.

  First, as shown in FIG. 1, the single-layer type photoreceptor 10 includes a conductive substrate 12, and a photosensitive layer 14 on the conductive substrate 12, and a charge generating agent, a charge transport agent, and a binder resin are the same. And a layer contained in one layer. The single-layer type photoreceptor 10 is not particularly limited as long as it includes the conductive substrate 12 and the photosensitive layer 14. Specifically, for example, the photosensitive layer 14 may be provided directly on the conductive substrate 12 as shown in FIG. 1A, or the conductive layer 14 as shown in FIG. An intermediate layer 16 as an undercoat layer may be provided between the substrate 12 and the photosensitive layer 14. In addition, as shown in FIGS. 1A and 1B, the photosensitive layer 14 may be exposed as an outermost layer, or as shown in FIG. 1C, the photosensitive layer 14 may be exposed. A protective layer 18 may be provided thereon.

  Next, as shown in FIG. 2, the multilayer photoconductor 20 includes a conductive substrate 12, and a charge generation layer 24 containing a charge generating agent and a base resin as a photosensitive layer on the conductive substrate 12. And a layer obtained by laminating at least two layers including a charge transport layer and a charge transport layer 22 containing a binder resin. The laminated photoreceptor 20 is not particularly limited as long as it includes the conductive substrate 12 and a photosensitive layer in which the charge generation layer 24 and the charge transport layer 22 are laminated. Specifically, as shown in FIG. 2A, the multilayer photoreceptor 20 is formed by laminating the charge generation layer 24 and the charge transport layer 22 in this order on the conductive substrate 12. Alternatively, as shown in FIG. 2B, the charge transport layer 22 and the charge generation layer 24 may be stacked in this order on the conductive substrate 12. Further, as shown in FIGS. 2A and 2B, the photosensitive layer may be provided directly on the conductive substrate 12, or as shown in FIGS. 2C and 2E. As described above, an intermediate layer 16 may be provided between the conductive substrate 12 and the photosensitive layer. Further, as shown in FIG. 2D and FIG. 2F, an intermediate layer 16 as an undercoat layer may be provided between the charge transport layer 22 and the charge generation layer 24. The photosensitive layer may be exposed as an outermost layer, or a protective layer may be provided on the photosensitive layer.

  In addition, if the photoconductor satisfies the above-described configuration, that is, a photoconductor in which a copolymer polycarbonate resin is contained in the binder resin in the photoconductive layer, the photoconductor excellent in electrical characteristics and wear resistance. The body is obtained. Examples of the structure of the photoreceptor include the single-layer photoreceptor and the multilayer photoreceptor as described above.

[Conductive substrate]
The conductive substrate is not particularly limited as long as it can be used as a conductive substrate of an electrophotographic photosensitive member. Specifically, for example, a material having at least a surface portion made of a conductive material can be used. Specifically, for example, it may be made of a conductive material, or may be a plastic material or the like whose surface is covered with a conductive material. Examples of the conductive material include aluminum, iron, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel, and brass. Moreover, as a material which has electroconductivity, the material which has the said electroconductivity may be used by 1 type, and may be used as an alloy etc., for example, combining 2 or more types. Moreover, among the above, the conductive substrate is preferably made of aluminum or an aluminum alloy. By doing so, a photoconductor capable of forming a more suitable image can be provided. This is considered to be due to good charge transfer from the photosensitive layer to the conductive substrate.

  Further, the shape of the conductive substrate is not particularly limited. Specifically, for example, a sheet shape or a drum shape may be used. That is, according to the structure of the image forming apparatus to be applied, it may be a sheet shape or a drum shape, and is not particularly limited.

[Photosensitive layer]
The single-layer photoreceptor has at least one photosensitive layer containing a charge generator, a charge transport agent, and a binder resin. The photosensitive layer of the laminated photoreceptor is a charge generation layer containing at least a charge generator, and at least charge transport. It consists of a charge transport layer containing an agent and a binder resin.

  The copolymer polycarbonate resin represented by the above formula (I) is used as a binder resin for the photosensitive layer. That is, in the present embodiment, in both the single layer type photoreceptor and the laminated type photoreceptor, the above-described binder resin contains the copolymer polycarbonate resin represented by the above formula (I). Further, the layer structure of the photosensitive layer is not particularly limited, and specific examples include the structure of the photosensitive layer shown in FIGS. 1 and 2 as described above.

(Binder resin)
As described above, the binder resin used for the photosensitive member includes a binder resin used for the photosensitive layer of the single-layer photosensitive member or the charge transport layer of the laminated photosensitive member, and a base resin when used for the charge generating layer of the laminated photosensitive member. .

  As described above, the binder resin can be used for a photosensitive layer of a single-layer photoreceptor or a charge transport layer of a laminated photoreceptor, and contains a copolymer polycarbonate resin represented by the above formula (I).

  Next, the base resin is not particularly limited as long as it is a base resin that can be used for the charge generation layer of the laminated photoreceptor as described above.

  The base resin used for the charge generation layer is formed in the order of the charge generation layer and the charge transport layer in the usual multilayer electrophotographic photoreceptor, so that it does not dissolve in the coating solvent for the charge transport layer. Is different from the binder resin.

  Specific examples of the base resin include styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, acrylic copolymer, styrene-acrylic acid copolymer, polyethylene resin, ethylene-acetic acid. Vinyl copolymer, chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, ionomer resin, vinyl chloride-vinyl acetate copolymer, alkyd resin, polyamide resin, polyurethane resin, polysulfone resin, diallyl phthalate resin, ketone resin, polyvinyl Examples include acetal resin, polyvinyl butyral resin, polyether resin, silicone resin, epoxy resin, phenol resin, urea resin, melamine resin, epoxy acrylate resin, and urethane-acrylate resin. The base resin used for the charge generation layer may be used alone or in combination of two or more.

(Copolymer polycarbonate resin)
The copolymer polycarbonate resin used in the present embodiment is not particularly limited as long as it is a copolymer polycarbonate resin represented by the following formula (I).

上記式（Ｉ）中、各置換基は、以下に示すものである。

In the above formula (I), each substituent is as shown below.

R ^{1 to} R ⁶ may be the same or different. That is, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independent.

R ^{1 to} R ⁶ represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

  The alkyl group having 1 to 8 carbon atoms is not particularly limited as long as it is an alkyl group having 1 to 8 carbon atoms, and may be linear or branched. Specifically, methyl group, ethyl group, n-propyl group, sec-propyl group, n-butyl group, t-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, n-heptyl group Group, n-octyl group and the like. The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms.

  Moreover, the C1-C8 alkoxy group here will not be specifically limited if it is C1-C8. Specific alkoxy groups include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, n-hexoxy group, n-heptoxy group Group, n-octoxy group and the like. Carbon number of the said alkoxy group becomes like this. Preferably it is 1-4, More preferably, it is 1-3.

  Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, and an alkyl-substituted phenyl group. The aryl group preferably has 6 to 10 carbon atoms, more preferably 6 carbon atoms.

Further, R ¹ and R ² may be linked to each other to be a cycloalkylidene group having 5 to 8 carbon atoms. Specific examples of the cycloalkylidene group include a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, and a cyclooctylidene group. The cycloalkylidene group preferably has 5 to 6 carbon atoms, more preferably 6 carbon atoms.

  Moreover, in said formula (I), X shows 0.05-0.7.

  The method for synthesizing the copolymer polycarbonate resin is not particularly limited as long as the copolymer polycarbonate resin represented by the above formula (I) can be synthesized.

  Specifically, it can be synthesized using, for example, the methods disclosed in the examples described later.

  In addition, although the said copolymer polycarbonate resin may be used independently for the binder resin in this embodiment, you may add resin other than the said copolymer polycarbonate resin in the range which does not impair the effect of this invention. Other resins that can be blended with the copolymer polycarbonate resin include, for example, styrene resin, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, styrene- Acrylic acid copolymer, acrylic copolymer, polyethylene resin, ethylene-vinyl acetate copolymer, chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, ionomer, vinyl chloride-vinyl acetate copolymer, polyester resin, alkyd Resin, polyamide resin, polyurethane resin, polycarbonate resin, polyarylate resin, polysulfone resin, diallyl phthalate resin, ketone resin, polyvinyl butyral resin, polyether resin, polyester resin, etc., silicone resin, Carboxymethyl resins, phenol resins, urea resins, melamine resins, and other crosslinkable thermosetting resin, further epoxy acrylate resins, urethane - photocurable resins such as acrylate copolymer resin. These may be used alone or in combination of two or more.

(Charge generator)
The charge generator is not particularly limited as long as it can be used as a charge generator for an electrophotographic photosensitive member. Specifically, for example, X-type metal-free phthalocyanine (x-H2Pc), Y-type oxotitanyl phthalocyanine (Y-TiOPc), perylene pigment, bisazo pigment, dithioketopyrrolopyrrole pigment, metal-free naphthalocyanine pigment, metal naphthalocyanine Pigments, squaraine pigments, trisazo pigments, indigo pigments, azurenium pigments, cyanine pigments, powders of inorganic photoconductive materials such as selenium, selenium-tellurium, selenium-arsenic, cadmium sulfide, amorphous silicon, pyrylium salts, ansanthrone pigments, Examples include triphenylmethane pigments, selenium pigments, toluidine pigments, pyrazoline pigments, quinacridone pigments, and the like.

  In addition, each of the charge generating agents may be used alone or in combination of two or more so that the charge generating agent has an absorption wavelength in a desired region. Furthermore, among the above charge generating agents, digital beam image forming apparatuses such as laser beam printers and facsimiles that use a light source such as a semiconductor laser, in particular, require a photoreceptor having sensitivity in a wavelength region of 700 nm or more. Therefore, for example, metal-free phthalocyanines such as X-type metal-free phthalocyanine (x-H2Pc) and phthalocyanine-based pigments such as oxotitanyl phthalocyanine such as Y-type oxotitanyl phthalocyanine (Y-TiOPc) are preferably used. The crystal form of the phthalocyanine pigment is not particularly limited, and various types can be used.

  In the case of an image forming apparatus using a short wavelength laser light source of 350 to 550 nm, an sanslon pigment or a perylene pigment is used as the charge generating agent.

(Charge transport agent)
The charge transfer agent is not particularly limited as long as it can be used as a charge transfer agent contained in the photosensitive layer of the electrophotographic photosensitive member. Moreover, as a charge transport agent, a hole transport agent and an electron transport agent are generally mentioned.

  The hole transport agent is not particularly limited as long as it can be used as a hole transport agent contained in the photosensitive layer of the electrophotographic photoreceptor. Especially, when matching with the said copolymerization polycarbonate resin as binder resin is considered, Preferably, the amine compound shown by either of the following general formula (II)-(IV) is mentioned.

一般式（ＩＩ）中、Ｒ^１ａ〜Ｒ^７ａは、同一又は異なって、水素原子、炭素数１〜８のアルキル基、フェニル基又は炭素数１〜８のアルコキシ基を示し、ａは０から５の整数を示す。

In general formula (II), R ^{1a to} R ^7a are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, or an alkoxy group having 1 to 8 carbon atoms, and a is 0 to 5 Indicates an integer.

  The alkyl group having 1 to 8 carbon atoms is not particularly limited as long as it is an alkyl group having 1 to 8 carbon atoms, and may be linear or branched. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, isopentyl, n-hexyl, 2-methylpentyl, heptyl, octyl and the like. It is done. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

  Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, n -Hetoxy group, n-heptoxy group, n-octoxy group and the like. The number of carbon atoms of the alkoxy group is preferably 1-6, more preferably 1-4.

一般式（ＩＩＩ）中、Ｒ^１ｂ〜Ｒ^８ｂは、同一又は異なって、水素原子、炭素数１〜８のアルキル基又はフェニル基を示し、ａは０〜５の整数、ｂは０〜４の整数、ｋは０または１の整数である。

In General Formula (III), R ^{1b to} R ^8b are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, a is an integer of 0 to 5, and b is 0 to 4. An integer, k is an integer of 0 or 1.

  Examples of the alkyl group having 1 to 8 carbon atoms include the same ones as described above, and the carbon number is preferably 1 to 6, and more preferably 1 to 4.

一般式（ＩＶ）中、Ｒ^１ｃ〜Ｒ^３ｃは、同一又は異なって、炭素数１〜８のアルキル基、フェニル基又は炭素数１〜８のアルコキシ基を示し、ｋは０〜４の整数、ｍ、ｎは０から５の整数である。

In general formula (IV), R ^<1c > -R <^3c> is the same or different, shows a C1-C8 alkyl group, a phenyl group, or a C1-C8 alkoxy group, k is an integer of 0-4, m and n are integers from 0 to 5.

  Examples of the alkyl group having 1 to 8 carbon atoms include the same ones as described above, and the carbon number is preferably 1 to 6, and more preferably 1 to 4.

  Moreover, as a C1-C8 alkoxy group here, the thing similar to the above is mentioned, The carbon number becomes like this. Preferably, it is 1-6, More preferably, it is 1-4.

  The amine compounds represented by the general formulas (II) to (IV) can be produced by various conventionally known production methods. For example, the amine compound represented by the general formula (II) is based on the description in JP 2005-289877 A and the like, and the amine compound represented by the general formula (III) is disclosed in JP 2006-008670 A. Based on the description of the gazette and the like, the amine compound represented by the general formula (IV) can be produced based on the description of JP 2000-239236 A and the like.

  In addition to the amine compound, the hole transport agent may contain other hole transport agents. Specific examples of other hole transporting agents include benzidine derivatives, oxadiazole compounds such as 2,5-di (4-methylaminophenyl) -1,3,4-oxadiazole, 9 Styryl compounds such as-(4-diethylaminostyryl) anthracene, carbazole compounds such as polyvinylcarbazole, organic polysilane compounds, pyrazoline compounds such as 1-phenyl-3- (p-dimethylaminophenyl) pyrazoline, hydrazone compounds, Nitrogen-containing cyclic compounds such as triphenylamine compounds, indole compounds, oxazole compounds, isoxazole compounds, thiazole compounds, thiadiazole compounds, imidazole compounds, pyrazole compounds, triazole compounds, condensed polycyclic compounds Compounds and the like. Among these, triphenylamine compounds and benzidine derivatives are preferable, and benzidine derivatives are more preferable. Moreover, these may be used independently and may be used in combination of 2 or more type.

  The electron transport agent is not particularly limited as long as it can be used as an electron transport agent contained in the photosensitive layer of the electrophotographic photosensitive member. Specifically, for example, quinone derivatives, naphthoquinone derivatives, anthraquinone derivatives, malononitrile derivatives, thiopyran derivatives, trinitrothioxanthone derivatives, 3,4,5,7-tetranitro-9-fluorenone derivatives, dinitroanthracene derivatives, dinitroacridine derivatives, Nitroantharaquinone derivatives, dinitroanthraquinone derivatives, tetracyanoethylene, 2,4,8-trinitrothioxanthone, dinitrobenzene, dinitroanthracene, dinitroacridine, nitroanthraquinone, dinitroanthraquinone, succinic anhydride, maleic anhydride, dibromoanhydride maleic An acid etc. are mentioned. Moreover, as said electron transport agent, each said electron transport agent may be used independently, and may be used in combination of 2 or more type.

(Additive)
The photoreceptor may contain various additives other than the charge generating agent, the charge transporting agent, and the binder resin as long as the electrophotographic characteristics and abrasion resistance are not adversely affected. Specific examples of the additive include, for example, antioxidants, radical scavengers, singlet quenchers, deterioration inhibitors such as ultraviolet absorbers, softeners, plasticizers, surface modifiers, extenders, Examples include thickeners, dispersion stabilizers, waxes, acceptors, donors, surfactants, and leveling agents. In order to improve the sensitivity of the photosensitive layer, a known sensitizer such as terphenyl, halonaphthoquinones, and acenaphthylene may be used in combination with the charge generator.

[Method for producing electrophotographic photosensitive member]
Next, a method for producing an electrophotographic photoreceptor will be described.

  First, a method for producing the single layer type photoreceptor will be described.

  The single-layer photoreceptor is a coating in which the charge generator, the charge transport agent (hole transport agent, electron transport agent), the binder resin, and various additives as necessary are dissolved or dispersed in a solvent. It can be produced by applying the liquid onto the conductive substrate by coating or the like and drying it. The coating method is not particularly limited, and examples thereof include a dip coating method.

  In the single-layer photoreceptor, the contents of the charge generator, the charge transport agent, and the binder resin are appropriately selected and are not particularly limited. Specifically, for example, the content of the charge generating agent is preferably 0.1 to 50 parts by mass and more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the binder resin. preferable. Moreover, it is preferable that it is 5-100 mass parts with respect to 100 mass parts of binder resins, and, as for content of the said electron transport agent, it is more preferable that it is 10-80 mass parts. Moreover, it is preferable that it is 5-500 mass parts with respect to 100 mass parts of binder resins, and, as for content of the said hole transport agent, it is more preferable that it is 25-200 mass parts. Furthermore, the total amount of the hole transporting agent and the electron transporting agent, that is, the content of the charge transporting agent is preferably 20 to 500 parts by weight with respect to 100 parts by weight of the binder resin, and 30 to 200 parts by weight. It is more preferable that

  The thickness of the photosensitive layer of the single-layer type photoreceptor is not particularly limited as long as it can sufficiently function as a photosensitive layer. Specifically, for example, 5 to 100 μm is preferable, and 10 to 50 μm is preferable.

  Next, a method for producing the multilayer photoconductor will be described.

  The multilayer photoconductor can be manufactured by the following method.

  Specifically, for example, first, the charge generating layer, the base resin, and, if necessary, a coating solution for forming a charge generating layer in which various additives are dissolved or dispersed in a solvent, the charge transport agent, and the binder resin. A charge transport layer forming coating solution in which various additives and the like are dissolved or dispersed in a solvent as required is prepared. Then, the charge generation layer is formed by coating one of the coating liquid for forming the charge generation layer and the coating liquid for forming the charge transport layer on the conductive substrate by coating or the like, and drying. And any one of the charge transport layers. Thereafter, the other coating solution is applied onto the conductive substrate on which the charge generation layer or the charge transport layer is formed and dried to form the other layer. By doing so, the multilayer photoreceptor can be manufactured. The coating method is not particularly limited, and examples thereof include a dip coating method.

  In the multilayer photoconductor, the contents of the charge generator, the charge transport agent, the base resin, and the binder resin are appropriately selected and are not particularly limited. Specifically, for example, the content of the charge generation agent is preferably 5 to 1000 parts by mass, and 30 to 500 parts by mass with respect to 100 parts by mass of the base resin constituting the charge generation layer. It is more preferable.

  Moreover, it is preferable that it is 10-500 mass parts with respect to 100 mass parts of binder resin which comprises the said charge transport layer, and, as for content of the said charge transport agent, it is more preferable that it is 25-100 mass parts.

  Moreover, the thickness of each layer of the charge generation layer and the charge transport layer is not particularly limited as long as it can sufficiently function as each layer. Specifically, the thickness of the charge generation layer is, for example, preferably 0.01 to 5 μm, and more preferably 0.1 to 3 μm. Further, specifically, the thickness of the charge transport layer is preferably, for example, 2 to 100 μm, and more preferably 5 to 50 μm.

  Further, the solvent contained in the coating solution is not particularly limited as long as each component can be dissolved or dispersed. Specifically, for example, alcohols such as methanol, ethanol, isopropanol and butanol, aliphatic hydrocarbons such as n-hexane, octane and cyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, dichloromethane, dichloroethane, Halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate and methyl acetate, Examples include dimethylformaldehyde, dimethylformamide, dimethyl sulfoxide and the like. These solvents may be used alone or in combination of two or more.

  The electrophotographic photosensitive member can be used as an image carrier of an electrophotographic image forming apparatus. The image forming apparatus is not particularly limited as long as it is an electrophotographic system. Specifically, the electrophotographic photoreceptor can be used, for example, as an image carrier of an image forming apparatus described later.

[Image forming apparatus]
The image forming apparatus for providing the electrophotographic photosensitive member is not particularly limited as long as it is an electrophotographic image forming apparatus. Specifically, for example, the image bearing member, a charging device for charging the surface of the image bearing member, and the surface of the charged image bearing member are exposed to form an electrostatic latent image on the surface of the image bearing member. An exposure device for forming an image, a developing device for developing the electrostatic latent image as a toner image, and a transfer device for transferring the toner image from the image carrier to a transfer target, Examples include an image forming apparatus in which the image carrier is the electrophotographic photosensitive member.

  Further, a tandem color image forming apparatus using a plurality of color toners, which will be described later, is preferable. More specifically, for example, a tandem color image forming apparatus using a plurality of colors of toner as described later can be given. Here, a tandem color image forming apparatus will be described.

  The image forming apparatus provided with the electrophotographic photosensitive member according to the present embodiment includes a plurality of image carriers arranged in parallel in a predetermined direction so as to form toner images with toners of different colors on the respective surfaces. A plurality of developing units each provided with a developing roller disposed opposite to each image carrier and carrying the toner carried on the surface and supplying the carried toner to the surface of each image carrier. And the electrophotographic photosensitive member is used as the image carrier.

  FIG. 3 is a schematic diagram showing a configuration of an image forming apparatus including the electrophotographic photosensitive member according to the embodiment of the present invention. Here, as the image forming apparatus 1, a color printer 1 will be described as an example.

  As shown in FIG. 3, the color printer 1 has a box-shaped device main body 1a. In the apparatus main body 1a, a toner image based on image data and the like is transferred to the paper P while feeding the paper P fed from the paper feeding unit 2 and the paper P fed from the paper feeding unit 2. An image forming unit 3 and a fixing unit 4 for performing a fixing process for fixing the unfixed toner image transferred onto the paper P by the image forming unit 3 to the paper P are provided. Further, on the upper surface of the apparatus main body 1a, a paper discharge unit 5 for discharging the paper P subjected to the fixing process by the fixing unit 4 is provided.

  The paper feed unit 2 includes a paper feed cassette 121, a pickup roller 122, paper feed rollers 123, 124 and 125, and a registration roller 126. The paper feed cassette 121 is provided so as to be detachable from the apparatus main body 1a, and stores the paper P of each size. The pickup roller 122 is provided at the upper left position of the paper feed cassette 121 shown in FIG. 3 and takes out the paper P stored in the paper feed cassette 121 one by one. The paper feed rollers 123, 124, and 125 send out the paper P picked up by the pickup roller 122 to the paper transport path. The registration roller 126 temporarily waits for the paper P sent to the paper transport path by the paper feed rollers 123, 124, 125, and then supplies the paper P to the image forming unit 3 at a predetermined timing.

  In addition, the paper feeding unit 2 further includes a manual feed tray (not shown) and a pickup roller 127 that are attached to the left side surface of the device main body 1a shown in FIG. The pickup roller 127 takes out the paper P placed on the manual feed tray. The paper P taken out by the pickup roller 127 is sent out to the paper transport path by the paper feed rollers 123 and 125, and is supplied to the image forming unit 3 by the registration roller 126 at a predetermined timing.

  The image forming unit 3 includes an image forming unit 7, an intermediate transfer belt 31 on which a toner image based on image data transmitted from a computer or the like to the surface (contact surface) of the image forming unit 7 is primarily transferred, A secondary transfer roller 32 for secondarily transferring the toner image on the intermediate transfer belt 31 onto the paper P fed from the paper feed cassette 121 is provided.

  The image forming unit 7 includes a black toner supply unit 7K, a yellow toner supply unit 7Y, a cyan toner supply unit 7C, which are sequentially arranged from the upstream side (right side in FIG. 3) to the downstream side. And a magenta toner supply unit 7M. In each of the units 7K, 7Y, 7C, and 7M, a photosensitive drum 37 as an image carrier is disposed at the center position so as to be rotatable in the arrow (clockwise) direction. Around each photosensitive drum 37, a charger 39, an exposure device 38, a developing device 71, a cleaning device (not shown), a static eliminator as a static eliminator, and the like are sequentially arranged from the upstream side in the rotation direction. . As the photosensitive drum 37, the electrophotographic photosensitive member is used. Further, the electrophotographic photosensitive member according to the present embodiment can also be applied to an image forming apparatus (printer) from which a static eliminator as a static eliminator is removed.

  The charger 39 uniformly charges the peripheral surface of the photosensitive drum 37 rotated in the direction of the arrow. Examples of the charger 39 include a non-contact discharge type corotron type and scorotron type charger, a contact type charging roller and a charging brush. The exposure device 38 is a so-called laser scanning unit. Laser light based on image data input from a personal computer (PC) as a host device is applied to the peripheral surface of the photosensitive drum 37 uniformly charged by the charger 39. Irradiation forms an electrostatic latent image on the photosensitive drum 37 based on the image data. The developing device 71 supplies toner to the peripheral surface of the photosensitive drum 37 on which the electrostatic latent image is formed, thereby forming a toner image based on the image data. The toner image is primarily transferred to the intermediate transfer belt 31. The cleaning device cleans the toner remaining on the peripheral surface of the photosensitive drum 37 after the primary transfer of the toner image to the intermediate transfer belt 31 is completed. The static eliminator neutralizes the peripheral surface of the photosensitive drum 37 after the primary transfer is completed. The peripheral surface of the photosensitive drum 37 cleaned by the cleaning device and the static eliminator is directed to the charger for a new charging process, and a new charging process is performed.

  The intermediate transfer belt 31 is an endless belt-like rotating body, and includes a driving roller 33, a driven roller 34, a backup roller 35, and a surface (contact surface) side so as to be in contact with the peripheral surface of each photosensitive drum 37. It is spanned across a plurality of rollers such as the primary transfer roller 36. The intermediate transfer belt 31 is configured to rotate endlessly by the plurality of rollers in a state in which the intermediate transfer belt 31 is pressed against the photosensitive drum 37 by a primary transfer roller 36 disposed to face each photosensitive drum 37. The driving roller 33 is rotationally driven by a driving source such as a stepping motor, and gives a driving force for rotating the intermediate transfer belt 31 endlessly. The driven roller 34, the backup roller 35, and the primary transfer roller 36 are rotatably provided, and are driven to rotate with the endless rotation of the intermediate transfer belt 31 by the driving roller 33. These rollers 34, 35, and 36 are driven to rotate via the intermediate transfer belt 31 in accordance with the main rotation of the drive roller 33 and support the intermediate transfer belt 31.

  The primary transfer roller 36 applies a primary transfer bias (a polarity opposite to the toner charging polarity) to the intermediate transfer belt 31. By doing so, the toner image formed on each photosensitive drum 37 is moved in the direction of the arrow (counterclockwise) by driving the driving roller 33 between each photosensitive drum 37 and the primary transfer roller 36. The images are sequentially transferred (primary transfer) to the rotating intermediate transfer belt 31 in an overcoated state.

  The secondary transfer roller 32 applies a secondary transfer bias having a polarity opposite to that of the toner image to the paper P. By doing so, the toner image primarily transferred onto the intermediate transfer belt 31 is transferred to the paper P between the secondary transfer roller 32 and the backup roller 35, and thereby, a color transfer image ( An unfixed toner image) is transferred.

  The fixing unit 4 performs a fixing process on the transfer image transferred to the paper P by the image forming unit 3. The fixing unit 4 is disposed opposite to the heating roller 41 heated by the energized heating element and the heating roller 41. And a pressure roller 42 whose surface is pressed against the peripheral surface of the heating roller 41.

  The transferred image transferred to the paper P by the secondary transfer roller 32 in the image forming unit 3 is subjected to a fixing process by heating when the paper P passes between the heating roller 41 and the pressure roller 42. Fixed to P. The paper P subjected to the fixing process is discharged to the paper discharge unit 5. Further, in the color printer 1 of the present embodiment, a transport roller 6 is disposed at an appropriate position between the fixing unit 4 and the paper discharge unit 5.

  The paper discharge unit 5 is formed by recessing the top of the apparatus main body 1a of the color printer 1, and a paper discharge tray 51 for receiving the discharged paper P is formed at the bottom of the concave portion. .

  The image forming apparatus 1 forms an image on the paper P by the image forming operation as described above. In the tandem image forming apparatus as described above, since the electrophotographic photosensitive member is provided as the image carrier, a high-quality image can be formed.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited at all by the Example.

[Synthesis of copolymer polycarbonate resin]
First, the synthesis of the copolymer polycarbonate resin used in each example will be described.

(Synthesis Example 1)
A copolymer polycarbonate resin represented by the following formula (R-1) was synthesized as follows.

（２，７−ブロモ−９，１０−ジヒドロフェナンスレンの合成）
９，１０−ジヒドロフェナンスレン１００ｇ（０．５５５ｍｏｌ）をリン酸トリメチル６００ｍｌに溶解し、３２〜３５℃で臭素を２４８．２５ｇ（１．５５ｍｏｌ）を添加し、同温度で２７時間反応させた。１０℃に冷却後、析出した結晶を濾過し、１０℃のメタノール２００ｍｌで４回洗浄した。その後、クロロホルムにて再結晶し、２，７−ブロモ−９，１０−ジヒドロフェナンスレン１１６．２ｇ（０．３４３６ｍｏｌ）を得た。収率は６１．９％であった。

(Synthesis of 2,7-bromo-9,10-dihydrophenanthrene)
100 g (0.555 mol) of 9,10-dihydrophenanthrene was dissolved in 600 ml of trimethyl phosphate, 248.25 g (1.55 mol) of bromine was added at 32-35 ° C., and the mixture was reacted at the same temperature for 27 hours. . After cooling to 10 ° C., the precipitated crystals were filtered and washed 4 times with 200 ml of 10 ° C. methanol. Then, it recrystallized with chloroform, and 116.2 g (0.3436 mol) of 2,7-bromo-9,10-dihydrophenanthrene was obtained. The yield was 61.9%.

(Synthesis of 2,7-dihydroxy-9,10-dihydrophenanthrene)
In a 3 L SUS-316 autoclave, 79.44 g (0.235 mol) 2,7-dibromo-9,10-dihydrophenanthrene, 184 g (4.7 mol) sodium hydroxide, 450 ml ethanol, 1 L water and 1st oxide Copper (1,9 g, 0.0235 mol) was charged, and the air was replaced with nitrogen. Then, the mixture was heated to 200 ° C. with stirring and held for 6 hours. Next, after the autoclave was cooled to room temperature, the reaction product was taken out and the inside of the autoclave was washed with ethanol and water. 200 ml of toluene was added to this solution, and unreacted raw materials and neutral by-products were extracted and removed into the toluene phase, and then the alkaline aqueous solution was filtered to remove the copper catalyst. Subsequently, the alkaline aqueous solution was acidified with concentrated sulfuric acid, and the precipitated crystals were separated by a centrifugal separator to obtain 36.41 g of white powder (2,7-dihydroxy-9,10-dihydrophenanthrene). The yield was 73%.

(R-1 synthesis example)
A solution prepared by dissolving 134.18 g (0.50 mol) of bisphenol Z in 680 mL of a 6 wt% aqueous sodium hydroxide solution and 310 mL of methylene chloride was mixed and stirred, and phosgene gas was added to the solution for 1. sec. It was blown at a rate of 0 L for 20 minutes. Subsequently, this reaction liquid was left and separated, and an methylene chloride solution of an oligomer having a degree of polymerization of 2 to 4 in the organic layer and having a chloroformate group at the molecular end was obtained. Methylene chloride was added to the resulting methylene chloride solution of the oligomer to make a total volume of 560 mL. Thereafter, 21.22 g (0.10 mol) of 2,7-dihydroxy-9,10-dihydrophenanthrene synthesized above was mixed with a solution of 120 wt. P-tert-butylphenol 2.0 g (0.013 mol) was added. Next, 3 ml of a 6 wt% triethylamine aqueous solution was added as a catalyst while vigorously stirring the mixed solution, and a reaction was performed at 30 ° C. with stirring for 2.0 hours. After completion of the reaction, the reactive organism is diluted with 1.5 L of methylene chloride, then washed twice with 2.0 L of water and 3 times with 1 L of 0.01N hydrochloric acid, and the organic layer is poured into methanol for reprecipitation. It refine | purified and obtained resin (PC-A conversion molecular weight 50,200) shown by general formula (R-1).

(Synthesis Example 2)
A copolymer polycarbonate resin represented by the following formula (R-2) was synthesized as follows.

ビスフェノールＺに替えて、ビスフェノールＣ １２８．１７ｇ（０．５０ｍｏｌ）を使用した以外は、合成例１と同様にしてＲ−２を得た。

R-2 was obtained in the same manner as in Synthesis Example 1 except that 128.17 g (0.50 mol) of bisphenol C was used instead of bisphenol Z.

(Synthesis Example 3)
A copolymer polycarbonate resin represented by the following formula (R-3) was synthesized as follows.

ビスフェノールＺに替えて、ビスフェノールＢ １２１．１６ｇ（０．５０ｍｏｌ）を使用した以外は合成例１と同様にしてＲ−３を得た。
（合成例４）
下記式（Ｒ−４）（式中、Ｘ＝０．０５）で表される共重合ポリカーボネート樹脂を、以下のようにして合成した。なお、以下の（Ｒ−５）〜（Ｒ−７）も同様の式で表される共重合ポリカーボネート樹脂である。

R-3 was obtained in the same manner as in Synthesis Example 1 except that 121.16 g (0.50 mol) of bisphenol B was used instead of bisphenol Z.
(Synthesis Example 4)
A copolymer polycarbonate resin represented by the following formula (R-4) (wherein X = 0.05) was synthesized as follows. The following (R-5) to (R-7) are also copolymer polycarbonate resins represented by the same formula.

２，７−ジヒドロキシ−９，１０−ジヒドロフェナンスレンの配合量を５．３１ｇ（０．２５ｍｏｌ）に変更した以外は合成例１と同様にしてＲ−４を得た。

R-4 was obtained in the same manner as in Synthesis Example 1 except that the amount of 2,7-dihydroxy-9,10-dihydrophenanthrene was changed to 5.31 g (0.25 mol).

(Synthesis Examples 5-7)
A copolymer polycarbonate resin represented by the above formula (R-5) (where X = 0.1), a copolymer polycarbonate resin represented by (R-6) (where X = 0.4), The copolymer polycarbonate resin represented by (R-7) (where X = 0.7) is the same as that of Synthesis Example 4 except that the amount of 2,7-dihydroxy-9,10-dihydrophenanthrene added is By adjusting 10.62 g (0.050 mol) (R-5), 63.72 g (0.300 mol) (R-6), 233.67 g (1.100 mol) (R-7), R- 5-7 were synthesized.

(Reference Synthesis Example 8)
A copolymer polycarbonate resin represented by the following formula (R-8) was synthesized as follows.

２，７−ジヒドロキシ−９，１０−ジヒドロフェナンスレンに替えて、４，４’−ビフェノールを１８．６２ｇ（０．１ｍｏｌ）使用した以外は合成例１と同様にしてＲ−８を得た。

R-8 was obtained in the same manner as in Synthesis Example 1 except that 18.62 g (0.1 mol) of 4,4′-biphenol was used instead of 2,7-dihydroxy-9,10-dihydrophenanthrene. .

[Example 1]
(Manufacture of photoconductor)
After surface treatment with alumina and silica, 2 parts by mass of titanium oxide (Taca prototype SMT-A (number average primary particle size 10 nm), which was surface-treated with methyl hydrogen polysiloxane while being wet-dispersed, and 6,12,66 , 610 quaternary copolymerized polyamide resin (1 part by mass of Amilan CM8000 manufactured by Toray, 10 parts by mass of methanol, 1 part by mass of butanol, and 1 part by mass of toluene were dispersed for 5 hours using a bead mill, and an intermediate layer (undercoat layer) A coating solution was prepared.

  After filtering the obtained intermediate layer coating solution with a 5 micron filter, an aluminum drum-shaped support having a diameter of 30 mm and a total length of 246 mm was applied as a conductive support by a dip coating method at 130 ° C. for 30 minutes. Heat treatment was performed to form an intermediate layer having a thickness of 2 μm.

  Next, 1.5 parts by mass of titanyl phthalocyanine, 1 part by mass of a polyvinyl acetal resin (Sekisui Chemical Co., Ltd., SREC BX-5) as a binder resin, 40 parts by mass of propylene glycol monomethyl ether and 40 parts by mass of tetrahydrofuran as a dispersion medium are mixed, and mixed in a bead mill. For 2 hours to prepare a coating solution for the charge generation layer. The obtained coating solution is filtered through a 3 micron filter, applied to the intermediate layer prepared above by dip coating, dried at 50 ° C. for 5 minutes, and a charge generation layer having a thickness of 0.3 μm. Formed.

  Next, 50 parts by mass of a hole transporting agent (CTM-1) represented by the following formula (C-1) as a hole transporting agent, 2 parts by mass of Irganox 1010 as an additive, and Synthesis Example 1 as a binder resin 100 parts by weight of the polycarbonate resin synthesized in (R-1, viscosity average molecular weight 50,500), 350 parts by weight of tetrahydrofuran as a solvent and 350 parts of toluene were mixed and dissolved to prepare a coating solution for a charge transport layer.

  The prepared charge transport layer coating solution is applied onto the charge generation layer in the same manner as the charge generation layer coating solution, and dried at 120 ° C. for 40 minutes to form a 20 μm-thick charge transport layer. A photographic photoreceptor was prepared.

［実施例２］
正孔輸送剤として上記式（Ｃ−１）で表されるＣＴＭ−１の代わりに、下記式（Ｃ−２）で表される正孔輸送剤（ＣＴＭ−２）を用いたこと以外、実施例１と同様である。

[Example 2]
Implemented except that the hole transport agent (CTM-2) represented by the following formula (C-2) was used instead of CTM-1 represented by the above formula (C-1) as the hole transport agent. Similar to Example 1.

［実施例３］
正孔輸送剤として上記式（Ｃ−１）で表されるＣＴＭ−１の代わりに、下記式（Ｃ−３）で表される正孔輸送剤（ＣＴＭ−３）を用いたこと以外、実施例１と同様である。

[Example 3]
Implementation other than using the hole transport agent (CTM-3) represented by the following formula (C-3) instead of CTM-1 represented by the above formula (C-1) as the hole transport agent. Similar to Example 1.

［実施例４］
正孔輸送剤として上記式（Ｃ−１）で表されるＣＴＭ−１の代わりに、下記式（Ｃ−４）で表される正孔輸送剤（ＣＴＭ−４）を用いたこと以外、実施例１と同様である。

[Example 4]
Implemented except that the hole transporting agent (CTM-4) represented by the following formula (C-4) was used as the hole transporting agent instead of CTM-1 represented by the above formula (C-1). Similar to Example 1.

［実施例５］
正孔輸送剤として上記式（Ｃ−１）で表されるＣＴＭ−１の代わりに、下記式（Ｃ−５）で表される正孔輸送剤（ＣＴＭ−５）を用いたこと以外、実施例１と同様である。

[Example 5]
Implemented except that the hole transport agent (CTM-5) represented by the following formula (C-5) was used instead of CTM-1 represented by the above formula (C-1) as the hole transport agent. Similar to Example 1.

［実施例６］
正孔輸送剤として上記式（Ｃ−１）で表されるＣＴＭ−１の代わりに、下記式（Ｃ−６）で表される正孔輸送剤（ＣＴＭ−６）を用いたこと以外、実施例１と同様である。

[Example 6]
Implemented except that the hole transporting agent (CTM-6) represented by the following formula (C-6) was used instead of CTM-1 represented by the above formula (C-1) as the hole transporting agent. Similar to Example 1.

［実施例７］
正孔輸送剤として上記式（Ｃ−１）で表されるＣＴＭ−１の代わりに、下記式（Ｃ−７）で表される正孔輸送剤（ＣＴＭ−７）を用いたこと以外、実施例１と同様である。

[Example 7]
Implemented except that the hole transporting agent (CTM-7) represented by the following formula (C-7) was used instead of CTM-1 represented by the above formula (C-1) as the hole transporting agent. Similar to Example 1.

［実施例８］
正孔輸送剤として上記式（Ｃ−１）で表されるＣＴＭ−１の代わりに、下記式（Ｃ−８）で表される正孔輸送剤（ＣＴＭ−８）を用いたこと以外、実施例１と同様である。

[Example 8]
Implemented except that the hole transporting agent (CTM-8) represented by the following formula (C-8) was used instead of CTM-1 represented by the above formula (C-1) as the hole transporting agent. Similar to Example 1.

［実施例９］
正孔輸送剤として上記式（Ｃ−１）で表されるＣＴＭ−１の代わりに、下記式（Ｃ−９）で表される正孔輸送剤（ＣＴＭ−９）を用いたこと以外、実施例１と同様である。

[Example 9]
Implemented except that the hole transport agent (CTM-9) represented by the following formula (C-9) was used instead of CTM-1 represented by the above formula (C-1) as the hole transport agent. Similar to Example 1.

［実施例１０］
正孔輸送剤として上記式（Ｃ−１）で表されるＣＴＭ−１の代わりに、下記式（Ｃ−１０）で表される正孔輸送剤（ＣＴＭ−１０）を用いたこと以外、実施例１と同様である。

[Example 10]
Implemented except that the hole transporting agent (CTM-10) represented by the following formula (C-10) was used as the hole transporting agent instead of CTM-1 represented by the above formula (C-1). Similar to Example 1.

［実施例１１］
正孔輸送剤として上記式（Ｃ−１）で表されるＣＴＭ−１の代わりに、下記式（Ｃ−１１）で表される正孔輸送剤（ＣＴＭ−１１）を用いたこと以外、実施例１と同様である。

[Example 11]
Implemented except that the hole transporting agent (CTM-11) represented by the following formula (C-11) was used as the hole transporting agent instead of CTM-1 represented by the above formula (C-1). Similar to Example 1.

［実施例１２］
バインダー樹脂として上記ポリカーボネート樹脂（Ｒ−１）の代わりに、上記合成例２で合成したポリカーボネート樹脂（Ｒ−２、粘度平均分子量４８，０００）を用いたこと以外、実施例１と同様である。

[Example 12]
It is the same as that of Example 1 except having used the polycarbonate resin (R-2, viscosity average molecular weight 48,000) synthesize | combined in the said synthesis example 2 instead of the said polycarbonate resin (R-1) as binder resin.

[Example 13]
It is the same as Example 1 except having used the polycarbonate resin (R-3, viscosity average molecular weight 53,200) synthesize | combined in the said synthesis example 3 instead of the said polycarbonate resin (R-1) as binder resin.

[Example 14]
It is the same as that of Example 1 except having used the polycarbonate resin (R-4, viscosity average molecular weight 45,000) synthesize | combined in the said synthesis example 4 instead of the said polycarbonate resin (R-1) as binder resin.

[Example 15]
It is the same as that of Example 1 except having used the polycarbonate resin (R-5, viscosity average molecular weight 46,200) synthesize | combined in the said synthesis example 5 instead of the said polycarbonate resin (R-1) as binder resin.

[Example 16]
It is the same as that of Example 1 except having used the polycarbonate resin (R-6, viscosity average molecular weight 48,000) synthesize | combined in the said synthesis example 6 instead of the said polycarbonate resin (R-1) as binder resin.

[Example 17]
It is the same as that of Example 1 except having used the polycarbonate resin (R-7, viscosity average molecular weight 55,200) synthesize | combined in the said synthesis example 7 instead of the said polycarbonate resin (R-1) as binder resin.

[Comparative Example 1]
It is the same as that of Example 1 except having used the polycarbonate resin (R-8, viscosity average molecular weight 40,500) synthesize | combined in the said reference synthesis example 8 instead of the said polycarbonate resin (R-1) as binder resin. .

[Comparative Example 2]
Implemented except that Teijin Panlite TS2050 (R-9, viscosity average molecular weight 50, 200) represented by the following chemical formula (R-9) was used as the binder resin instead of the polycarbonate resin (R-1). Similar to Example 1.

［評価］
実施例１〜１７及び比較例１〜２に係る電子写真感光体を、以下の方法により評価した。

[Evaluation]
The electrophotographic photoreceptors according to Examples 1 to 17 and Comparative Examples 1 and 2 were evaluated by the following methods.

(Electrical characteristics evaluation)
The electrophotographic photosensitive member was measured for chargeability (surface potential V0) and sensitivity (post-exposure potential V1) under the following conditions using an electrical property tester manufactured by GENTEC.
Charging: Number of rotations: 31 rpm Drum inflow current: Surface potential sensitivity at -10 μA: Charging at 600 V Exposure wavelength: 780 nm Exposure amount: 0.8 μJ / cm ² Post exposure time Surface potential after 80 msec

(Abrasion evaluation test)
In Examples 1 to 17 and Comparative Examples 1 and 2, the wear evaluation was performed using the charge transport layer coating solution prepared for the electrophotographic photosensitive member.

  First, the prepared charge transport layer coating solution was applied to a PP (polypropylene) sheet (thickness 0.3 mm) wound around a φ78 aluminum pipe, dried at 120 ° C. for 40 minutes, and evaluated for wear with a film thickness of 30 μm. A sheet was prepared.

  The charge transport layer was peeled off from this PP sheet and attached to Wheel S-36 (manufactured by Taber) to prepare a sample. Using a rotary abrasion tester (manufactured by Toyo Seiki Co., Ltd.), a 1000 wheel wear test was performed at a wear wheel C-10 (Taber), a load of 500 gf, and a rotation speed of 60 rpm. The amount of wear was evaluated by the change in weight.

  The results of the electrical property evaluation and the wear evaluation test are shown in Table 1 together with the materials of the photosensitive layer.

表１からわかるように、バインダー樹脂として一般式（Ｉ）で示される繰り返し単位を有する共重合ポリカーボネート樹脂を含有している電子写真感光体（実施例１〜１７）は、前記ポリカーボネート樹脂以外の樹脂をバインダー樹脂として用いた場合（比較例１、２）と比較して、耐摩耗性に優れることがわかった。さらに、一般式（ＩＩ）〜（ＩＶ）で示されるアミン系化合物を正孔輸送剤として含有する電子写真感光体（実施例１〜９および実施例１２〜１７）は、前記アミン系化合物以外の化合物を正孔輸送剤として用いた場合（実施例１０および１１）と比較して、電気特性により優れることがわかった。

As can be seen from Table 1, the electrophotographic photosensitive member (Examples 1 to 17) containing the copolymer polycarbonate resin having the repeating unit represented by the general formula (I) as the binder resin is a resin other than the polycarbonate resin. As compared with the case where is used as a binder resin (Comparative Examples 1 and 2), it was found that the wear resistance is excellent. Furthermore, the electrophotographic photoreceptors (Examples 1 to 9 and Examples 12 to 17) containing the amine compounds represented by the general formulas (II) to (IV) as hole transporting agents are other than the amine compounds. It was found that the electrical characteristics were superior as compared with the case where the compound was used as a hole transporting agent (Examples 10 and 11).

DESCRIPTION OF SYMBOLS 10 Single layer type electrophotographic photoconductor 12 Conductive base | substrate 14 Photosensitive layer 16 Intermediate layer 18 Protective layer 20 Laminated type electrophotographic photoconductor 22 Charge transport layer 24 Charge generation layer

Claims (3)

An electrophotographic photoreceptor comprising a conductive substrate and a photosensitive layer formed directly or via an intermediate layer on the conductive substrate,
The photosensitive layer contains at least a charge generating agent, a charge transporting agent, and a binder resin,
The electrophotographic photosensitive member, wherein the binder resin contains a copolymer polycarbonate resin having a repeating unit represented by the following general formula (I).

[In Formula (I), R ^{1 to} R ⁶ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. X represents 0.05 to 0.7. R ¹ and R ² may be connected to each other to form a cycloalkylidene group having 5 to 8 carbon atoms. ] The electrophotographic photoreceptor according to claim 1, wherein the charge transfer agent is an amine compound represented by any one of the following general formulas (II) to (IV).

[In formula (II), R < ^1a > -R < ^7a > is the same or different, and shows a hydrogen atom, a C1-C8 alkyl group, a phenyl group, or a C1-C8 alkoxy group, a is 0-5. Is an integer. ]

[In formula (III), R ^<1b > -R < ^8b > is the same or different and shows a hydrogen atom, a C1-C8 alkyl group, or a phenyl group, a is an integer of 0-5, b is 0-4. An integer, k is an integer of 0 or 1. ]

[In formula (IV), R ^<1c > -R < ^3c > is the same or different, shows a C1-C8 alkyl group, a phenyl group, or a C1-C8 alkoxy group, k is an integer of 0-4, m and n are integers from 0 to 5. ] An image carrier;
A charging device for charging the surface of the image carrier;
An exposure device for exposing the surface of the charged image carrier to form an electrostatic latent image on the surface of the image carrier;
A developing device for developing the electrostatic latent image as a toner image;
A transfer device for transferring the toner image from the image carrier to a transfer target,
The image forming apparatus according to claim 1, wherein the image bearing member is the electrophotographic photosensitive member according to claim 1.

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