JP5300341B2 - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having an excellent effect of suppressing ghost, and to provide a process cartridge and an electrophotographic device having the electrophotographic photoreceptor. <P>SOLUTION: The electrophotographic photoreceptor has a photosensitive layer containing a compound expressed by general formula (1), a polyolefin resin and a charge transporting compound having at least one structure selected from a group consisting of tertiary amine structures and hydrazone structures, wherein when the charge transporting compound has an alkylene chain, the alkylene chain has &le;4C. In formula (1), R<SB>11</SB>represents an alkyl group having 5-20C; X represents O, C=O, COO or a single bond; each of R<SB>12</SB>to R<SB>16</SB>represents a hydrogen atom, alkoxy group, hydroxy group, halogen group, alkyl group, aralkyl group or aryl group. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an electrophotographic photoreceptor containing a specific charge transporting compound, a process cartridge having the electrophotographic photoreceptor, and an electrophotographic apparatus.

  In recent years, demands for higher speed and higher image quality of electrophotographic apparatuses have been further increased. In particular, due to the colorization of output images, there are increasing opportunities to output halftone images and solid images, and the demand for these image quality is increasing year by year. For example, the uniformity of density and color in one output image, and the stability when these papers are continuously fed are the same for color printers and color copiers, for black and white printers and black and white copiers. It is especially emphasized compared to.

  In particular, the phenomenon in which only the portion of the output image irradiated with light (light irradiation portion) becomes darker in the halftone image in the next rotation (positive ghost image), or on the contrary, the phenomenon in which the concentration becomes lighter ( The tolerance range for negative ghost images) is narrowing. These ghost images are considered to be one of the causes that carriers are retained in the electrophotographic photosensitive member, and are particularly prominent when a highly sensitive charge generating substance is used.

As a conventional technique for suppressing a memory phenomenon such as a ghost image, Patent Document 1 discloses a technique in which an acceptor compound is contained in a charge generation layer using oxytitanium phthalocyanine. Patent Document 2 and Patent Document 3 disclose a technique for containing a dithiobenzyl compound in a charge generation layer using phthalocyanine. Patent Documents 4 and 5 disclose a technique in which a charge generation layer contains a naphthalenetetracarboxylic acid diimide compound, a phenanthrene compound, a phenanthroline compound, and an acenaphthoquinone compound, which are electron transport materials.
Japanese Patent Application Laid-Open No. 07-104495 JP 2000-292946 A JP 2002-296817 A JP-A-2005-208618 JP-A-2005-208619

  The level of the ghost image may vary depending on the type of electrophotographic apparatus. This is presumably because the chargeability varies depending on the process speed of the electrophotographic apparatus, the setting of the dark part potential and the bright part potential, and the ability of the charger and the power source.

  Further, when processing the halftone image of the next rotation, the light irradiation portion must be charged from the bright portion potential to the dark portion potential. The ability to charge from the bright part potential to the dark part potential in this case is also considered as one of the causes of the ghost image.

  In addition to the demand for higher speed and higher image quality, the demand for cost reduction and miniaturization is increasing year by year. It is presumed that the chargeability becomes severe as the process proceeds toward cost reduction and miniaturization. Therefore, from now on, it is desired that the ghost image can be suppressed even when the charging property becomes severe.

  An object of the present invention is to provide an electrophotographic photoreceptor excellent in a ghost suppression effect, a process cartridge and an electrophotographic apparatus having the electrophotographic photoreceptor.

According to the present invention, in an electrophotographic photosensitive member having a support and a photosensitive layer provided on the support, the photosensitive layer comprises a compound represented by the following general formula (1), a polycyclic olefin resin, a third A charge transporting compound having at least one structure selected from the group consisting of a secondary amine structure and a hydrazone structure,
When the charge transporting compound has an alkylene chain, an electrophotographic photoreceptor is provided in which the alkylene chain has 4 or less carbon atoms.

（上記式（１）中、Ｒ_１１は炭素数５以上２０以下のアルキル基を示す。Ｒ_１２、Ｒ_１３、Ｒ_１４、Ｒ_１５及びＲ_１６は、それぞれ独立に、水素原子、アルコキシ基、水酸基、ハロゲン基、アミノ基、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基又は置換基を有してもよいアリール基を示す。ＸはＯ、Ｃ＝Ｏ、ＣＯＯ又は単結合を示す。）
また、本発明に従って、前記電荷輸送性化合物が、前記第三級アミン構造及び前記ヒドラゾン構造に、炭素数１以上４以下のアルキル基、炭素数１以上４以下のアルキレン基を有するアラルキル基、置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基及び置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリーレン基からなる群より選択される少なくとも１つを置換基として有する電子写真感光体が提供される。

(In the above formula (1), R ₁₁ represents an alkyl group having 5 to 20 carbon atoms. R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, an alkoxy group, or a hydroxyl group. , A halogen group, an amino group, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or an aryl group that may have a substituent, where X is O, C═O, COO or single bond is indicated.)
Further, according to the present invention, the charge transporting compound comprises an alkyl group having 1 to 4 carbon atoms, an aralkyl group having 1 to 4 carbon atoms in the tertiary amine structure and the hydrazone structure, substituted At least one selected from the group consisting of an aryl group which may have an alkyl group having 1 to 4 carbon atoms as a group and an arylene group which may have an alkoxy group having 1 to 4 carbon atoms as a substituent Is provided as a substituent.

  According to the present invention, the charge transporting compound is at least selected from the group consisting of the following general formulas (2), (3), (4), (6), (7), (8) and (9) One electrophotographic photoreceptor is provided.

（上記式（２）中、Ｒ_２１及びＲ_２２は炭素数１以上４以下のアルキル基、置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基又は炭素数１以上４以下のアルコキシ基を有してもよいアリール基を示す。Ａｒ_２１は置換基として炭素数１以上４以下のアルキル基を有してもよいアリーレン基又は置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリーレン基を示す。Ｒ_２３は置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基、置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基、炭素数１以上４以下のアルキレン基を有するアラルキル基又は水素原子を示す。Ａｒ_２１及びＲ_２３は直接又は他の有機残基を介して環を形成してもよい。）

(In the above formula (2), R ₂₁ and R ₂₂ are each an alkyl group having 1 to 4 carbon atoms, an aryl group which may have an alkyl group having 1 to 4 carbon atoms as a substituent, or 1 to 4 carbon atoms. The aryl group which may have the following alkoxy groups is shown: Ar ₂₁ is an arylene group which may have an alkyl group having 1 to 4 carbon atoms as a substituent or an alkoxy having 1 to 4 carbon atoms as a substituent. R ₂₃ represents an arylene group which may have a group, an aryl group which may have an alkyl group having 1 to 4 carbon atoms as a substituent, and an alkoxy group which has 1 to 4 carbon atoms as a substituent. An aryl group which may be substituted, an aralkyl group having an alkylene group having 1 to 4 carbon atoms, or a hydrogen atom, Ar ₂₁ and R ₂₃ may form a ring directly or through another organic residue. )

（上記式（３）中、Ｒ_３１、Ｒ_３２、Ｒ_３３及びＲ_３４は炭素数１以上４以下のアルキル基、炭素数１以上４以下のアルキレン基を有するアラルキル基、置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基、置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基又は下記一般式（５）で示される置換基を示す。Ａｒ_３１及びＡｒ_３２は置換基として炭素数１以上４以下のアルキル基を有してもよいアリーレン基を示す。）

(In the above formula (3), R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are an alkyl group having 1 to 4 carbon atoms, an aralkyl group having an alkylene group having 1 to 4 carbon atoms, and 1 carbon atom as a substituent. An aryl group which may have an alkyl group having 4 or less or more, an aryl group which may have an alkoxy group having 1 to 4 carbon atoms as a substituent, or a substituent represented by the following general formula (5) is shown. Ar ₃₁ and Ar ₃₂ represent an arylene group which may have an alkyl group having 1 to 4 carbon atoms as a substituent.

（上記式（４）中、Ｒ_４１は置換基を有してもよい炭素数１以上４以下のアルキル基、置換基を有してもよいアリール基又は下記一般式（５）で示される置換基を示す。Ａｒ_４１及びＡｒ_４２は置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基、置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基又は下記一般式（５）で示される置換基を示す。但し、Ａｒ_４１、Ａｒ_４２及びＲ_４１のうち少なくとも１つは下記一般式（５）で示される置換基を１つ以上有する。）

(In the above formula (4), R ₄₁ is an alkyl group having 1 to 4 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a substituent represented by the following general formula (5). Ar ₄₁ and Ar ₄₂ each represent an aryl group that may have an alkyl group having 1 to 4 carbon atoms as a substituent, and an aryl group that may have an alkoxy group having 1 to 4 carbon atoms as a substituent. Or a substituent represented by the following general formula (5), provided that at least one of Ar ₄₁ , Ar ₄₂ and R ₄₁ has one or more substituents represented by the following general formula (5).

（上記式（５）中、Ｒ_５１は炭素数１以上４以下のアルキル基、炭素数１以上４以下のアルキレン基を有するアラルキル基、置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基、置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基又は水素原子を示す。Ａｒ_５１は置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基又は炭素数１以上４以下のアルコキシ基を有してもよいアリール基を示す。Ａｒ_５１及びＲ_５２は直接又は他の有機残基を介して環を形成してもよい。ｎ¹は０〜２の整数を示す。）

(In the above formula (5), R ₅₁ has an alkyl group having 1 to 4 carbon atoms, an aralkyl group having an alkylene group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms as a substituent. An aryl group which may have an aryl group which may have an alkoxy group having 1 to 4 carbon atoms as a substituent or a hydrogen atom Ar ₅₁ has an alkyl group having 1 to 4 carbon atoms as a substituent. An aryl group which may have an aryl group which may have an alkyl group having 1 to 4 carbon atoms, and Ar ₅₁ and R ₅₂ may form a ring directly or via another organic residue; n ¹ represents an integer of 0 to 2.)

（上記式（６）中、Ａｒ_６１及びＡｒ_６２は置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基又は置換基をとして炭素数１以上４以下のアルコキシ基を有してもよいアリール基を示す。Ｒ_６１は置換基として炭素数１以上４以下のアルキル基を有してもよい縮合環炭化水素若しくは縮合複合環又は置換基として炭素数１以上４以下のアルコキシ基を有してもよい縮合環炭化水素若しくは縮合複合環を示す。）

(In the above formula (6), Ar ₆₁ and Ar ₆₂ have an aryl group which may have an alkyl group having 1 to 4 carbon atoms as a substituent or an alkoxy group having 1 to 4 carbon atoms as a substituent. R ₆₁ represents a condensed ring hydrocarbon or condensed complex ring which may have an alkyl group having 1 to 4 carbon atoms as a substituent, or an alkoxy having 1 to 4 carbon atoms as a substituent. A condensed ring hydrocarbon or condensed complex ring which may have a group.

（上記式（７）中、Ｒ_７１、Ｒ_７２、Ｒ_７３及びＲ_７４は炭素数１以上４以下のアルキル基、炭素数１以上４以下のアルキレン基を有するアラルキル基、置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基又は置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基を示す。Ａｒ_７１は置換基として炭素数１以上４以下のアルキル基を有してもよいアリーレン基又は置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリーレン基を示す。）

(In the above formula (7), R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ are an alkyl group having 1 to 4 carbon atoms, an aralkyl group having 1 to 4 carbon atoms, and a substituent having 1 carbon atom. An aryl group that may have an alkyl group of 4 or less or an aryl group that may have an alkoxy group of 1 to 4 carbon atoms as a substituent, Ar ₇₁ represents 1 to 4 carbon atoms as a substituent. An arylene group which may have an alkyl group of 1 or an arylene group which may have an alkoxy group having 1 to 4 carbon atoms as a substituent.

（上記式（８）中、Ａｒ_８１、Ａｒ_８２、Ａｒ_８３及びＡｒ_８４は置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基又は置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基を示す。）

(In the above formula (8), Ar ₈₁ , Ar ₈₂ , Ar ₈₃ and Ar ₈₄ are each an aryl group which may have an alkyl group having 1 to 4 carbon atoms as a substituent, or 1 to 4 carbon atoms as a substituent. An aryl group which may have an alkoxy group of

（上記式（９）中、Ａｒ_９１、Ａｒ_９２、Ａｒ_９３及びＡｒ_９４は置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基又は置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基を示す。但し、Ａｒ_９１、Ａｒ_９２、Ａｒ_９３及びＡｒ_９４のうち少なくとも１つは下記一般式（１０）で示される置換基を１つ以上有する。）

(In the above formula (9), Ar ₉₁ , Ar ₉₂ , Ar ₉₃ and Ar ₉₄ may have an alkyl group having 1 to 4 carbon atoms as a substituent, or an aryl group or substituent having 1 to 4 carbon atoms. And an aryl group which may have an alkoxy group, provided that at least one of Ar ₉₁ , Ar ₉₂ , Ar ₉₃ and Ar ₉₄ has one or more substituents represented by the following general formula (10). )

（上記式（１０）中、Ｒ_１０１及びＲ_１０２は炭素数１以上４以下のアルキル基、炭素数１以上４以下のアルキレン基を有するアラルキル基又は置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基を示す。）
さらに、本発明に従って、上記電子写真感光体を具備するプロセスカートリッジ及び電子写真装置が提供される。

(In the above formula (10), R ₁₀₁ and R ₁₀₂ are an alkyl group having 1 to 4 carbon atoms, an aralkyl group having an alkylene group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms as a substituent. An aryl group which may have
Furthermore, according to the present invention, there are provided a process cartridge and an electrophotographic apparatus provided with the electrophotographic photosensitive member.

  According to the present invention, it is possible to provide an electrophotographic photoreceptor excellent in ghost suppression effect, a process cartridge and an electrophotographic apparatus having the electrophotographic photoreceptor.

  Hereinafter, the compound represented by the general formula (1) used in the electrophotographic photoreceptor of the present invention will be described.

（式（１）中、Ｒ_１１は炭素数５〜２０のアルキル基を示す。Ｒ_１２、Ｒ_１３、Ｒ_１４、Ｒ_１５及びＲ_１６は、それぞれ独立に、水素原子、アルコキシ基、水酸基、ハロゲン基、アミノ基、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基又は置換基を有してもよいアリール基を示す。ＸはＯ、Ｃ＝Ｏ、ＣＯＯ又は単結合を示す。）
Ｒ_１１で示される炭素数５以上２０以下のアルキル基としては、例えば、直鎖アルキル基、分岐アルキル基、環状アルキル基、環状アルキル基により置換されたアルキル基が挙げられる。

(In the formula (1), R ₁₁ represents an alkyl group having 5 to 20 carbon atoms. R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, an alkoxy group, a hydroxyl group, or a halogen atom. A group, an amino group, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or an aryl group which may have a substituent, X is O, C═O, COO or Indicates a single bond.)
Examples of the alkyl group having 5 to 20 carbon atoms represented by R ₁₁ include a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an alkyl group substituted with a cyclic alkyl group.

  Examples of the linear alkyl group include a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and a tridecyl group.

  Examples of the branched alkyl group include 3-methylbutyl group, 2,2-dimethylpropyl group, 1,1-dimethylpropyl group, 4-methylpentyl group, 5-methylhexyl group, 4,4-dimethylpentyl group, and the like. Can be mentioned.

  Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.

  Examples of the alkyl group substituted with a cyclic alkyl group include the following. Examples thereof include a cyclohexylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cycloheptylmethyl group, a cyclooctylmethyl group, a cyclohexylethyl group, a 2-cyclohexyl-n-propyl group, and a 3-cyclohexyl-n-propyl group.

  Among these, a linear alkyl group is preferable, and an alkyl group having 5 to 12 carbon atoms is preferable.

Examples of the alkoxy group represented by R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  Examples of the halogen group include a fluoro group, a bromo group, a chloro group, and an iodo group.

  Examples of the alkyl group of the alkyl group that may have a substituent include a methyl group, an ethyl group, a propyl group, and a butyl group.

  Examples of the aralkyl group of the aralkyl group that may have a substituent include a benzyl group, a phenethyl group, a naphthylmethyl group, a furfuryl group, and a thienyl group. The following are mentioned as an aryl group of the aryl group which may have the said substituent. For example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a thiophenyl group, a furyl group, and a pyridyl group. Alternatively, a quinolyl group, a benzoquinolyl group, a galazolyl group, a phenothiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group, a dibenzothiophenyl group, and the like.

  Specific examples (exemplary compounds) of the general formula (1) are listed in Table 1.

  X in the general formula (1) represents O, C═O, COO or a single bond, and a single bond is particularly preferable.

  Among the compounds represented by the general formula (1), a compound represented by the following general formula (13) is particularly preferable.

（上記式（１３）中、Ｒ_１３１は炭素数５〜１２のアルキル基を示す。）
上記一般式（１）で示される化合物の分子量は３００以下が好ましい。分子量が３００以上だと、相溶性の効果が十分に得られない場合があった。

(In the above formula (13), R ₁₃₁ represents an alkyl group having 5 to 12 carbon atoms.)
The molecular weight of the compound represented by the general formula (1) is preferably 300 or less. When the molecular weight is 300 or more, the compatibility effect may not be sufficiently obtained.

  Next, the polyolefin resin used in the present invention will be described.

  The polyolefin resin refers to a polymer obtained by polymerizing an olefin. Olefin means a hydrocarbon compound having one or more C═C (double bond between carbons). The polyolefin may be a polymer obtained by polymerizing only an olefin, or may be a polymer obtained by copolymerizing a cyclic olefin and another monomer. Moreover, a cyclic olefin means the cyclic hydrocarbon compound which has 1 or more C = C (double bond between carbon).

  Examples of the polyolefin resin include the following. For example, polyethylene, polypropylene, poly (1-butene), poly (4-methylpentene-1), a copolymer of propylene and ethylene, and a copolymer of ethylene and dicyclopentadiene. Alternatively, a copolymer of ethylene and a norbornene compound, or a ring-opening polymer of a cyclopentadiene derivative. Furthermore, a ring-opening polymer of a cyclohexadiene derivative, a ring-opening copolymer of a cyclopentadiene derivative, a ring-opening copolymer of a cyclohexadiene derivative, and hydrogenated products thereof are also included.

  Below, the specific example of the repeating structural unit which polyolefin resin has is given.

上記のような繰り返し構造単位を誘導することができるモノマーとしては、以下のものが挙げられる。例えば、エチレン、プロピレン、イソブテン、１−ブテン、２−ブテン、４−メチルペンテン−１、スチレン、α−メチルスチレン、ｏ−メチルスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン及びα，β−ジメチルスチレンである。また、ジビニルベンゼン、ビニルナフタレン、ビニルアントラセン、１，１−ジフェニルエチレン、ｍ−ジイソプロペニルベンゼン及びビニルピリジンも挙げられる。更に、メタクリル酸メチル、アクリル酸メチル、アクリロニトリル、メチルビニルケトン、α−シアノアクリル酸メチル、エチレンオキシド、プロピレンオキシド、環状ラクトン、環状ラクタム及び環状シロキサン等又は上述の化合物の誘導体が挙げられる。

Examples of the monomer capable of deriving the repeating structural unit as described above include the following. For example, ethylene, propylene, isobutene, 1-butene, 2-butene, 4-methylpentene-1, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene and α, β -Dimethylstyrene. Also included are divinylbenzene, vinylnaphthalene, vinylanthracene, 1,1-diphenylethylene, m-diisopropenylbenzene and vinylpyridine. Furthermore, methyl methacrylate, methyl acrylate, acrylonitrile, methyl vinyl ketone, methyl α-cyanoacrylate, ethylene oxide, propylene oxide, cyclic lactone, cyclic lactam, cyclic siloxane, etc., or derivatives of the above-mentioned compounds can be mentioned.

  In the present invention, among the polyolefin resins, a polycyclic olefin having a polymer obtained by polymerizing a cyclic olefin is preferable. The polycyclic olefin may be a polymer obtained by polymerizing only a cyclic olefin, or may be a polymer obtained by copolymerizing a cyclic olefin and another monomer.

  Moreover, the polycyclic olefin resin whose glass transition temperature (Tg) is 100 degreeC or more and 170 degrees C or less is more preferable. In the case of a polyolefin resin and other monomer copolymer, the glass transition temperature (Tg) can be controlled by changing the copolymerization ratio.

  In the present invention, the glass transition temperature of the polyolefin resin was measured using a thermal analyzer (trade name: SSC5200H) manufactured by Seiko Denshi Kogyo Co., Ltd. Specifically, the temperature was measured from 23 ° C. to 280 ° C. at a rate of temperature increase of 5 ° C./min, and the intersection of the solid side tangent of the obtained chart and the tangent at the sharp position of the transition temperature range was defined as the glass transition temperature. did.

  In the present invention, among polycyclic olefin resins, a copolymer having a repeating structural unit represented by the following general formula (11) and a repeating structural unit represented by the following structural formula (12) is particularly preferable.

上記式（１１）中、Ｒ_1１１及びＲ_1１２は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基又は置換基を有してもよいカルボニル基を示す。あるいは、Ｒ^1１1及びＲ^1１２は互いに結合して環を形成してもよい。

In the above formula (11), R ₁₁₁ and R ₁₁₂ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent or a substituent. The carbonyl group which may have is shown. Alternatively, R ^{11 1} and R ¹¹² may be bonded to each other to form a ring.

上記繰り返し構造単位（１１）と上記繰り返し構造単位（１２）との共重合比を変えることで、Ｔｇ（ガラス転移温度）を変える事ができる。

By changing the copolymerization ratio between the repeating structural unit (11) and the repeating structural unit (12), Tg (glass transition temperature) can be changed.

  Examples of commercially available polycyclic olefin resins include “Apel (registered trademark)” manufactured by Mitsui Chemicals, Inc., “Topas (registered trademark)” manufactured by Chicona Corporation, and the like.

  Further, the photosensitive layer of the electrophotographic photoreceptor of the present invention may contain a polyolefin resin and other polymers together. Examples of the resin other than the polyolefin resin include polystyrene, polybutadiene, polyisoprene, polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polyarylate, polyether ketone, polyether ether ketone, and the like.

  Next, the charge transporting compound used in the present invention will be described.

  The charge transporting compound used in the present invention is at least one compound among the compounds represented by the following general formulas (2), (3), (4), (6), (7), (8) and (9) Chosen from.

式（２）中、Ｒ_２１及びＲ_２２は炭素数１以上４以下のアルキル基、置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基又は置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基を示す。Ｒ_２１及びＲ_２２は同一であっても異なっていてもよい。更に、その中でも上記一般式（２）中のＲ_２１及びＲ_２２が置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基又は置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基である場合が好ましい。

In formula (2), R ₂₁ and R ₂₂ are each an alkyl group having 1 to 4 carbon atoms, an aryl group which may have an alkyl group having 1 to 4 carbon atoms as a substituent, or one or more carbon atoms as a substituent. The aryl group which may have 4 or less alkoxy groups is shown. R ₂₁ and R ₂₂ may be the same or different. Furthermore, among them, R ₂₁ and R ₂₂ in the general formula (2) may have an alkyl group having 1 to 4 carbon atoms as a substituent or an alkoxy having 1 to 4 carbon atoms as a substituent. The case where it is an aryl group which may have a group is preferable.

Ar ₂₁ represents an arylene group which may have an alkyl group having 1 to 4 carbon atoms as a substituent or an arylene group which may have an alkoxy group having 1 to 4 carbon atoms as a substituent.

R ₂₃ is an aryl group which may have an alkyl group having 1 to 4 carbon atoms as a substituent, an aryl group which may have an alkoxy group having 1 to 4 carbon atoms as a substituent, and 1 to 4 carbon atoms. An aralkyl group or a hydrogen atom having the following alkylene group is shown. Ar ₂₁ and R ₂₃ may form a ring directly or through another organic residue, and examples of the bonding group include alkylene groups such as methylene group, ethylene group and propylene group, oxygen, nitrogen, sulfur atom and the like. Heteroatoms and the like.

式（３）中、Ｒ_３１、Ｒ_３２、Ｒ_３３及びＲ_３４は炭素数１以上４以下のアルキル基である。又は、炭素数１以上４以下のアルキレン基を有するアラルキル基、置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基、置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基である。又は下記一般式（５）で示される置換基を示す。Ｒ_３１、Ｒ_３２、Ｒ_３３及びＲ_３４はそれぞれ同一であっても異なっていてもよい。更に、その中でも上記一般式（３）中のＲ_３１、Ｒ_３２、Ｒ_３３及びＲ_３４が全て置換基を有してもよいアリール基である場合が好ましい。

In Formula (3), R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are alkyl groups having 1 to 4 carbon atoms. Or an aralkyl group having an alkylene group having 1 to 4 carbon atoms, an aryl group optionally having an alkyl group having 1 to 4 carbon atoms as a substituent, and an alkoxy group having 1 to 4 carbon atoms as a substituent. It is an aryl group that may have. Or the substituent shown by following General formula (5) is shown. R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ may be the same or different. Furthermore, among them, it is preferable that R ₃₁ , R ₃₂ , R ₃₃ and R _{34 in the} general formula (3) are all aryl groups which may have a substituent.

Ar ₃₁ and Ar ₃₂ represent an arylene group which may have an alkyl group having 1 to 4 carbon atoms as a substituent. Ar ₃₁ and Ar ₃₂ may be the same or different.

式（４）中、Ｒ_４１は置換基を有してもよい炭素数１以上４以下のアルキル基、置換基を有してもよいアリール基又は下記一般式（５）で示される置換基を示す。更に、Ｒ_４１はその中でも置換基を有してもよいアリール基又は下記一般式（５）で示される置換基である場合が好ましい。

In formula (4), R ₄₁ represents an alkyl group having 1 to 4 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a substituent represented by the following general formula (5). Show. Furthermore, among these, R ₄₁ is preferably an aryl group which may have a substituent or a substituent represented by the following general formula (5).

Ar ₄₁ and Ar ₄₂ represent an aryl group which may have a substituent, and Ar ₄₁ and Ar ₄₂ may be the same or different. However, at least one of Ar ₄₁ , Ar ₄₂ and R ₄₁ has one or more substituents represented by the following general formula (5). When Ar ₄₁ or Ar ₄₂ does not have a substituent represented by the following general formula (5), Ar ₄₁ and Ar ₄₂ may have an alkyl group having 1 to 4 carbon atoms as a substituent. The aryl group which may have a C1-C4 alkoxy group as a group or a substituent is shown.

式（５）中、Ｒ_５１は炭素数１以上４以下のアルキル基である。又は炭素数１以上４以下のアルキレン基を有するアラルキル基、置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基、置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基である。又は水素原子を示す。Ａｒ_５１は置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基又は置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基を示す。Ａｒ_５１とＲ_５２は直接又は他の有機残基を介して環を形成してもよい。ｎ¹は０〜２の整数を示す。

In formula (5), R ₅₁ is an alkyl group having 1 to 4 carbon atoms. Or an aralkyl group having an alkylene group having 1 to 4 carbon atoms, an aryl group optionally having an alkyl group having 1 to 4 carbon atoms as a substituent, and an alkoxy group having 1 to 4 carbon atoms as a substituent. An aryl group that may be used. Or a hydrogen atom is shown. Ar ₅₁ represents an aryl group which may have an alkyl group having 1 to 4 carbon atoms as a substituent or an aryl group which may have an alkoxy group having 1 to 4 carbon atoms as a substituent. Ar ₅₁ and R ₅₂ may form a ring directly or via another organic residue. n ¹ represents an integer of 0 to 2.

式（６）中、Ａｒ_６１及びＡｒ_６２は置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基又は置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基を示す。Ａｒ_６１及びＡｒ_６２は同一でも異なってもよい。

In formula (6), Ar ₆₁ and Ar ₆₂ may have an aryl group which may have an alkyl group having 1 to 4 carbon atoms as a substituent or an alkoxy group having 1 to 4 carbon atoms as a substituent. A good aryl group is indicated. Ar ₆₁ and Ar ₆₂ may be the same or different.

R ₆₁ is a condensed ring hydrocarbon which may have an alkyl group having 1 to 4 carbon atoms as a substituent. Alternatively, a condensed complex ring, a condensed ring hydrocarbon which may have an alkoxy group having 1 to 4 carbon atoms as a substituent, and a condensed complex ring are shown. Examples of the condensed ring hydrocarbon include naphthalene, anthracene, phenanthrene, pyrene, fluorene, fluoranthene, azulene, indene, perylene, chrysene, coronene and the like. Examples of the fused complex ring include benzofuran, indole, carbazole, benzcarbazole, acridine, phenothiazine, quinoline and the like.

式（７）中、Ｒ_７１、Ｒ_７２、Ｒ_７３及びＲ_７４は炭素数１以上４以下のアルキル基である。又は炭素数１以上４以下のアルキレン基を有するアラルキル基、置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基である。又は置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基を示す。Ｒ_７１、Ｒ_７２、Ｒ_７３及びＲ_７４はそれぞれ同一であっても異なっていてもよい。

In formula (7), R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ are alkyl groups having 1 to 4 carbon atoms. Or an aralkyl group having an alkylene group having 1 to 4 carbon atoms, or an aryl group optionally having an alkyl group having 1 to 4 carbon atoms as a substituent. Or the aryl group which may have a C1-C4 alkoxy group as a substituent is shown. R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ may be the same or different.

Ar ₇₁ represents an arylene group which may have an alkyl group having 1 to 4 carbon atoms as a substituent or an arylene group which may have an alkoxy group having 1 to 4 carbon atoms as a substituent.

式（８）中、Ａｒ_８１、Ａｒ_８２、Ａｒ_８３及びＡｒ_８４は置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基又は置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基を示す。Ａｒ_８１、Ａｒ_８２、Ａｒ_８３及びＡｒ_８４はそれぞれ同一であっても異なっていてもよい。

In formula (8), Ar ₈₁ , Ar ₈₂ , Ar ₈₃ and Ar ₈₄ are an aryl group which may have an alkyl group having 1 to 4 carbon atoms as a substituent, or an alkoxy having 1 to 4 carbon atoms as a substituent. The aryl group which may have a group is shown. Ar ₈₁ , Ar ₈₂ , Ar ₈₃ and Ar ₈₄ may be the same or different.

式（９）中、Ａｒ_９１、Ａｒ_９２、Ａｒ_９３及びＡｒ_９４は置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基又は置換基として炭素数１以上４以下のアルコキシ基を有してもよいアリール基を示す。但し、Ａｒ_９１、Ａｒ_９２、Ａｒ_９３及びＡｒ_９４のうち少なくとも１つは下記一般式（１０）で示される置換基を１つ以上有する。Ａｒ_９１、Ａｒ_９２、Ａｒ_９３及びＡｒ_９４はそれぞれ同一であっても異なっていてもよい。

In formula (9), Ar ₉₁ , Ar ₉₂ , Ar ₉₃ and Ar ₉₄ are an aryl group which may have an alkyl group having 1 to 4 carbon atoms as a substituent, or an alkoxy having 1 to 4 carbon atoms as a substituent. The aryl group which may have a group is shown. However, at least one of Ar ₉₁ , Ar ₉₂ , Ar ₉₃ and Ar ₉₄ has one or more substituents represented by the following general formula (10). Ar ₉₁ , Ar ₉₂ , Ar ₉₃ and Ar ₉₄ may be the same or different.

式（１０）中、Ｒ_１０１及びＲ_１０２は炭素数１以上４以下のアルキル基、炭素数１以上４以下のアルキレン基を有するアラルキル基又は置換基として炭素数１以上４以下のアルキル基を有してもよいアリール基を示す。Ｒ_１０１及びＲ_１０２はそれぞれ同一であっても異なっていてもよい。

In Formula (10), R ₁₀₁ and R ₁₀₂ have an alkyl group having 1 to 4 carbon atoms, an aralkyl group having an alkylene group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms as a substituent. An aryl group which may be substituted is shown. R ₁₀₁ and R ₁₀₂ may be the same or different.

  In the above formulas (2), (3), (4), (5), (6), (7), (8), (9) and (10), alkyl having 1 to 4 carbon atoms Specific examples of the group include a methyl group, an ethyl group, a propyl group, and a butyl group.

  Specific examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  Specific examples of the aralkyl group having an alkylene group having 1 to 4 carbon atoms include benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, naphthylmethyl group, and furfuryl group.

  Specific examples of the aryl group include the following. For example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, and a thiophenyl group. Or a furyl group, a pyridyl group, a quinolyl group, a benzoquinolyl group, a carbazolyl group, a phenothiazinyl group, a benzofuryl group, a benzothiophenyl group, a dibenzofuryl group, a dibenzothiophenyl group, and the like.

  Moreover, the following are mentioned as a specific example of an arylene group. For example, benzene, naphthalene, anthracene, phenanthrene, pyrene, and benzothiophene. Alternatively, it is a divalent group in which two hydrogen atoms are removed from pyridine, quinoline, benzoquinoline, carbazole, phenothiazine, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, or the like.

  Next, specific examples (example compounds) of the charge transporting compound are listed in Table 2.

  Only one type of charge transporting compound of the present invention may be used, or two or more types may be used. Further, other charge transporting compounds may be used in combination.

  The details of the reason why the ghost suppression effect is manifested by incorporating a charge transport compound, a polycyclic olefin resin and a compound having the structure of the general formula (1) into the photosensitive layer are unknown, but the outline is considered as follows. .

  In order to suppress a ghost image, it is effective to suppress memory due to charge trapping. When forming the halftone image of the next rotation, it is necessary to charge the light irradiated part from the bright part potential to the dark part potential, and the ability to charge (chargeability) is also high. This is effective for image suppression.

  The present inventors have found that the dielectric relaxation phenomenon of the electrophotographic photosensitive member is involved in the ghost image while proceeding with the study on the charging property from the bright part potential to the dark part potential. Specifically, when the dielectric loss tangent of the electrophotographic photosensitive member is small, the charging property is improved.

  Here, as a method for obtaining an electrophotographic photosensitive member having a small dielectric loss tangent, it is conceivable to reduce the dielectric loss tangent of the photosensitive layer of the electrophotographic photosensitive member. One method for realizing a photosensitive layer having a low dielectric loss tangent is to use a resin having a low dielectric loss tangent as the binder resin for the photosensitive layer. A polyolefin-based resin is known as a resin having a small dielectric loss tangent.

  In the case of using a polyolefin-based resin and a conventionally used charge transport material, an improvement in chargeability was observed. However, on the other hand, the amount of memory that has been suppressed with binder resins that have been used frequently, such as polycarbonate, has increased, and the suppression of memory and the improvement of chargeability have not been compatible.

  As a result of intensive studies on this problem, the present inventors have considered that there is a problem in the compatibility between the polyolefin resin and the charge transport material. The reason for this is thought to be that, since many charge transport materials that have been conventionally used do not have long alkylene chains, the compatibility with long alkylene chains, which are constituents of polyolefin resins, is poor.

  In order to improve compatibility with a polyolefin resin even for a charge transport material having no long alkylene chain, the present invention has been achieved by using a compound having a specific structure having a long alkylene chain. . A compound having a structure represented by the general formula (1) using a charge transport material that does not have a group having an alkylene chain of 5 or more carbon atoms and a polyolefin resin as a binder resin having a small dielectric loss tangent (tan δ). The effect of suppressing ghost images has been dramatically improved.

  The photosensitive layer of the electrophotographic photoreceptor of the present invention may be a layered type (functional separation type) in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are laminated. A single layer type in which the charge transport material is dispersed in the same layer may be used. From the viewpoint of electrophotographic characteristics, a multilayer photosensitive layer is preferable, and in particular, a multilayer photosensitive layer having a structure in which a charge generation layer and a charge transport layer are stacked in this order from the support side is preferable.

  The support used in the electrophotographic photosensitive member of the present invention may be a conductive one (conductive support), and examples thereof include those made of metals or alloys such as aluminum, nickel, copper, gold and iron. . Alternatively, a thin film of a metal such as aluminum, silver, or gold, or a conductive material such as indium oxide or tin oxide may be formed on an insulating support such as polyester, polycarbonate, polyimide, or glass. Further, a support obtained by dispersing carbon and a conductive filler in a resin and imparting conductivity may be used.

  The surface of the support may be subjected to an electrochemical treatment such as anodization in order to improve electrical characteristics and adhesion. Further, the surface of the support may be subjected to chemical treatment with a solution obtained by dissolving a metal salt compound or a fluorine compound metal salt in an acidic aqueous solution mainly composed of alkali phosphate or phosphoric acid or tannic acid. .

  In addition, when the electrophotographic photosensitive member of the present invention is used in an electrophotographic apparatus using single-wavelength light such as laser light as exposure light (image exposure light), the surface of the support is moderately used to suppress interference fringes. It is preferable to roughen the surface. Specifically, it is preferable that the surface of the support is subjected to honing, blasting, cutting, and electropolishing, or a conductive film containing a conductive metal oxide and a binder resin is provided on the support.

  The honing process includes a dry process and a wet process, either of which may be adopted. The wet honing treatment is a method in which a suspension obtained by suspending a powdery abrasive in a liquid such as water is sprayed on the surface of a support at a high speed to roughen the surface. In the case of wet honing treatment, the surface roughness of the support can be controlled by the spraying pressure of the suspension, the speed, the amount of abrasive, the type, shape, size, hardness, specific gravity, suspension temperature, and the like. The dry honing treatment is a method in which an abrasive is sprayed onto the surface of a support with air at a high speed to roughen the surface. Also in the case of the dry honing treatment, the surface roughness of the support can be controlled in the same manner as the wet honing treatment. Examples of the abrasive used for the honing treatment include particles such as silicon carbide, alumina, iron, and glass beads.

  A conductive layer may be provided between the support and the photosensitive layer or an intermediate layer described later for the purpose of suppressing interference fringes due to scattering of laser light or the like and covering the scratches on the support.

The conductive layer can be formed by dispersing conductive particles such as carbon black, metal particles, and metal oxide particles in a binder resin. Examples of the metal oxide particles include zinc oxide and titanium oxide particles. Further, barium sulfate particles coated with oxygen-deficient SnO ₂ can also be used as the conductive particles.

  Examples of the binder resin used for the conductive layer include a phenol resin, a polyurethane resin, and a polyamide resin. These have good adhesion to the support, improve the dispersibility of the conductive particles, and have good solvent resistance after film formation.

  Further, a leveling agent may be added to the conductive layer in order to improve the surface property of the conductive layer.

  An intermediate layer having functions such as a barrier function and an adhesive function may be provided between the support or the conductive layer and the photosensitive layer. The intermediate layer can be formed of, for example, casein, polyvinyl alcohol, nitrocellulose, polyamide (nylon 6, nylon 66, nylon 610, copolymer nylon, alkoxymethylated nylon, etc.), polyurethane, aluminum oxide, or the like.

  When the photosensitive layer is a laminated photosensitive layer, the charge generation layer is formed by applying a charge generation layer coating solution obtained by dispersing a charge generation material together with a binder resin and a solvent, and drying it. Can do.

As the charge generation material used in the present invention,
(1) Azo pigments such as monoazo, disazo and trisazo (2) Phthalocyanine pigments such as metal phthalocyanine and non-metal phthalocyanine (3) Indigo pigments such as indigo and thioindigo (4) Perylene pigments such as perylene acid anhydride and perylene acid imide (5) Polycyclic quinone pigments such as anthraquinone and pyrenequinone (6) squarylium dyes (7) pyrylium salts, thiapyrylium salts (8) triphenylmethane dyes (9) inorganic substances such as selenium, selenium-tellurium, amorphous silicon (10 Quinacridone pigment (11) azurenium salt pigment (12) cyanine dye (13) xanthene dye (14) quinoneimine dye (15) styryl dye (16) cadmium sulfide (17) zinc oxide and the like. Among these, metal phthalocyanine pigments are particularly preferable. Among these, oxytitanium phthalocyanine, chlorogallium phthalocyanine, dichlorotin phthalocyanine, and hydroxygallium phthalocyanine are preferable, and among these, hydroxygallium phthalocyanine is particularly preferable.

  As oxytitanium phthalocyanine, oxytitanium phthalocyanine having strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction Crystals are preferred. Or 9.5 °, 9.7 °, 11.7 °, 15.0 °, 23.5 °, 24.1 ° and 27 of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction. Also preferred is an oxytitanium phthalocyanine crystal having a strong peak at 3 °.

  As chlorogallium phthalocyanine, a chlorogallium phthalocyanine crystal having strong peaks at 7.4 °, 16.6 °, 25.5 and 28.2 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction Is preferred. Alternatively, chlorogallium phthalocyanine crystals having strong peaks at 6.8 °, 17.3 °, 23.6 °, and 26.9 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction are also preferable. Furthermore, the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction is 8.7 ° to 9.2 °, 17.6 °, 24.0 °, 27.4 ° and 28.8 °. A chlorogallium phthalocyanine crystal having a strong peak is likewise preferred.

  As dichlorotin phthalocyanine, Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction are 8.3 °, 12.2 °, 13.7 °, 15.9 °, 18.9 ° and 28. Dichlorotin phthalocyanine crystals having a strong peak at 2 ° are preferred. Alternatively, dichlorotin phthalocyanine crystals having strong peaks at 8.5 °, 11.2 °, 14.5 °, and 27.2 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction are also preferable. Or 8.7 °, 9.9 °, 10.9 °, 13.1 °, 15.2 °, 16.3 °, 17 of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction Also preferred are dichlorotin phthalocyanine crystals having strong peaks at .4 °, 21.9 ° and 25.5 °. Furthermore, the Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction are 9.2 °, 12.2 °, 13.4 °, 14.6 °, 17.0 ° and 25.3 °. Likewise preferred are dichlorotin phthalocyanine crystals having a strong peak.

  The hydroxygallium phthalocyanine is preferably a hydroxygallium phthalocyanine crystal having strong peaks at 7.3 °, 24.9 ° and 28.1 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction. Or strong peaks at Bragg angles (2θ ± 0.2 °) of 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° Also preferred are hydroxygallium phthalocyanine crystals having:

  Examples of the binder resin for the charge generation layer include the following. Examples thereof include butyral resin, polyester resin, polycarbonate resin, polyarylate resin, polystyrene resin, polyvinyl methacrylate resin, polyvinyl acrylate resin, polyvinyl acetate resin, and polyvinyl chloride resin. Moreover, a polyamide resin, a polyurethane resin, a silicone resin, an alkyd resin, an epoxy resin, a cellulose resin, a melamine resin, etc. are also mentioned. Among these, a butyral resin is preferable.

  The dispersed particle diameter of the charge generation material in the charge generation layer is preferably 0.5 μm or less, more preferably 0.3 μm or less, and more preferably 0.01 μm or more and 0.2 μm or less.

  The film thickness of the charge generation layer is preferably from 0.01 μm to 2 μm, more preferably from 0.05 μm to 0.3 μm.

  When the photosensitive layer is a laminated photosensitive layer, the charge transport layer is for a charge transport layer obtained by dissolving a charge transport compound, a polyolefin resin, and the compound represented by the general formula (1) together in a solvent. It can be formed by applying a coating liquid and drying it. The weight of the charge transporting compound is preferably 30% or more and 80% or less with respect to the total weight of the charge transporting physical compound and the binder resin. If the amount of the charge transporting compound is too small, the charge transporting ability is lowered, and problems such as a reduction in sensitivity and an increase in residual potential may occur.

  The content of the compound represented by the general formula (1) is preferably 5% or more and 30% or less with respect to the total weight of the charge transporting compound and the polyolefin resin.

  If the content of the compound represented by the general formula (1) is too small, the compatibility effect may not be sufficiently obtained. If the content is too large, the original charge transport ability is lowered, the sensitivity is lowered, and the residual potential is raised. Such problems may occur.

  Moreover, it is preferable that content of the compound of the said General formula (1) is 20% or more and 80% or less with respect to each weight of the said charge transport compound and the said polyolefin resin. If the content of the compound represented by the general formula (1) is too small relative to the charge transporting compound, the compatibility effect may not be sufficiently obtained. If the content is too large, the original charge transporting ability is lowered. In some cases, problems such as a decrease in sensitivity and an increase in residual potential may occur.

  In addition, if the content of the compound represented by the general formula (1) is too small with respect to the polyolefin resin, the compatibility effect may not be sufficiently obtained. If the content is too large, the original wear resistance is sufficiently obtained. In some cases, the life of the photoconductor may be shortened.

  The thickness of the charge transport layer is preferably 1 μm or more and 30 μm or less, and more preferably 5 μm or more and 20 μm or less.

  When the photosensitive layer is a single-layer type photosensitive layer, it is obtained by dispersing the charge generating substance, the charge transporting compound, the polyolefin resin, and the compound represented by the general formula (1) together with the solvent. A single layer type photosensitive layer coating solution is applied. By drying this, the single-layer type photosensitive layer can be formed.

  The film thickness of the single-layer type photosensitive layer is preferably 8 μm or more and 40 μm or less, and more preferably 12 μm or more and 30 μm or less. The content of the charge generating substance and the charge transporting substance in the single layer type photosensitive layer is preferably 10% by mass to 80% by mass, and preferably 30% by mass to 80% by mass with respect to the total mass of the single layer type photosensitive layer. % Or less is more preferable.

  In the present invention, a protective layer is provided on the photosensitive layer for the purpose of protecting the surface of the photosensitive layer from mechanical external force, chemical external force, etc., and for the purpose of improving transferability and cleaning properties. You can also.

  The various resins described above can be used as the binder resin for the protective layer. It can be formed by applying a protective layer coating solution obtained by dissolving the resin alone or the resin and the above-described charge transporting substance in a solvent, and drying the coating solution. Further, the protective layer may be formed by curing a monomer having charge transporting ability or a polymer type charge transporting substance using various crosslinking reactions. Examples of the curing reaction include radical polymerization, ionic polymerization, thermal polymerization, photopolymerization, and radiation polymerization (electron beam polymerization).

  Further, the protective layer may contain conductive particles and a lubricant.

  Examples of the conductive particles used for the protective layer include metals, metal oxides, and carbon black. Examples of the metal include aluminum, zinc, copper, chromium, nickel, silver, and stainless steel. Moreover, what vapor-deposited these metals on the surface of the particle | grains of a plastic can also be used as electroconductive particle. Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony and tantalum-doped tin oxide, and antimony-doped zirconium oxide. .

  Examples of the lubricant used in the protective layer include fluorine atom-containing resin particles, silica particles, and silicone particles. Among them, fluorine atom-containing resin particles are particularly preferable. Fluorine atom-containing resin particles include tetrafluoroethylene resin, trifluoroethylene chloride resin, hexafluoroethylene propylene resin, vinyl fluoride resin, vinylidene fluoride resin, ethylene difluoride dichloride resin, and their co-polymers. Coalesce is mentioned. Among these, a tetrafluoroethylene resin and a vinylidene fluoride resin are particularly preferable. These may be used alone or in combination of two or more.

  The thickness of the protective layer is preferably from 0.5 μm to 5 μm, more preferably from 1 μm to 3 μm.

  When applying the coating liquid for each of the above layers, for example, methods such as dip coating, spray coating, spinner coating, bead coating, blade coating, extrusion coating, and beam coating can be employed. . Among these, the dip coating method is preferable from the viewpoint of mass productivity.

  FIG. 1 shows a schematic configuration of an electrophotographic apparatus provided with a process cartridge having the electrophotographic photosensitive member of the present invention.

  In FIG. 1, reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven around a shaft 2 in a direction indicated by an arrow with a predetermined peripheral speed (process speed). In the rotation process, the electrophotographic photosensitive member 1 is first subjected to uniform charging with a predetermined positive or negative potential on its peripheral surface by a charging unit (primary charging unit) 3. Next, the electrophotographic photoreceptor 1 receives exposure light 4 from exposure means (not shown). Thus, electrostatic latent images corresponding to the target image information are sequentially formed on the peripheral surface of the electrophotographic photosensitive member 1.

  The formed electrostatic latent image is developed as a toner image with the toner in the developing means 5 of the normal or reversal developing system. Next, the transfer material 7 (paper, film, or the like) taken out from a paper supply unit (not shown) in synchronization with the rotation of the electrophotographic photosensitive member 1 and fed between the electrophotographic photosensitive member 1 and the transfer unit 6 is used. The toner images formed on the peripheral surface of the electrophotographic photosensitive member 1 are sequentially transferred by the transfer unit 6. At this time, a voltage having a polarity opposite to the charge of the toner is applied to the transfer means 6 from a power source (not shown). The transfer method may be an intermediate transfer method.

  The transfer material 7 that has received the transfer of the toner image is separated from the peripheral surface of the electrophotographic photosensitive member, conveyed to the fixing means 8, and subjected to a fixing process of the toner image, and as a formed image (print, copy) outside the apparatus. Printed out.

  The peripheral surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by the removal of adhering matters such as transfer residual toner by the cleaning means 9. In recent years, a cleaner-less system has also been studied, and it is possible to configure such that the transfer residual toner is directly collected by a developing device or the like.

  Thereafter, the charge is removed by pre-exposure light 10 from a pre-exposure unit (not shown), and is repeatedly used for image formation. When the charging unit 3 is a contact charging unit using a charging roller or the like, pre-exposure is not always necessary.

  In the present invention, among the components such as the electrophotographic photosensitive member 1, the charging unit 3, the developing unit 5, and the cleaning unit 9, a plurality of components are housed in a container and integrally formed as a process cartridge. It may be configured to be detachable from the photographic apparatus main body. For example, at least one of the charging unit 3, the developing unit 5, and the cleaning unit 9 is integrally supported together with the electrophotographic photosensitive member 1 to form a cartridge, and is detachable from the apparatus main body using a guide unit 12 such as a rail of the apparatus main body. Process cartridge 11.

  Further, when the electrophotographic apparatus is a copying machine or a printer, the original is read by a reflected light or transmitted light from the original or a sensor and converted into a signal. The exposure light 4 is light irradiated by scanning of a laser beam performed according to this signal, driving of an LED array, driving of a liquid crystal shutter array, or the like.

  The electrophotographic photosensitive member of the present invention can be applied to general electrophotographic apparatuses such as copying machines, laser beam printers, LED printers, FAX, and liquid crystal shutter printers. Furthermore, the present invention can be widely applied to apparatuses such as a display, recording, light printing, plate making and facsimile using an electrophotographic technology.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. In the examples, “part” means “part by mass”.

Example 1
An aluminum cylinder having a diameter of 30 mm and a length of 260.5 mm was ultrasonically washed with water as a support.

Next, barium sulfate particles coated with oxygen-deficient SnO ₂ (powder resistivity: 200 Ω · cm, SnO ₂ coverage (mass ratio: 60%), 40 parts, titanium oxide (trade name: TITANIX JR, Takeka Co., Ltd.) ) Made 8 parts. Furthermore, 25 parts of phenol resin (trade name: Pryofen J-325, manufactured by Dainippon Ink & Chemicals, Inc., resin solid content 60%) as a binder resin are prepared. These, 30 parts of methoxypropanol, and 30 parts of methanol were dispersed in a sand mill apparatus for 2 hours using glass beads having a diameter of 1 mm to prepare a dispersion for the conductive layer.

  3.9 parts of silicone resin particles (trade name: Tospearl 120, manufactured by GE Toshiba Silicone Co., Ltd., average particle size 2 μm) as a surface roughening agent are prepared. 0.002 part of silicone oil (trade name: SH28PA, manufactured by Toray Dow Corning Silicone Co., Ltd.) as a leveling agent is prepared. These were added to the above dispersion and stirred to prepare a coating solution for a conductive layer.

  This conductive layer coating solution is dip-coated on a support in a 23 ° C./60% RH environment, and dried and cured (heat cured) at 140 ° C. for 30 minutes, whereby a conductive film having a thickness of 20 μm is obtained. A layer was formed.

  Next, 5 parts of N-methoxymethylated 6 nylon was dissolved in 95 parts of methanol to prepare an intermediate layer coating material.

  This intermediate layer coating solution was dip coated on the conductive layer and dried at 100 ° C. for 20 minutes to form an intermediate layer having a thickness of 0.5 μm.

  Next, the Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction are 7.5 °, 9.9 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 °. Prepare 10 parts of hydroxygallium phthalocyanine crystal with strong peak. 0.1 parts of a compound represented by the following structural formula (14) and 5 parts of a polyvinyl butyral resin (trade name: ESREC BX-1, manufactured by Sekisui Chemical Co., Ltd.) are prepared. These were added to 250 parts of cyclohexanone and dispersed for 4 hours in a sand mill using glass beads having a diameter of 1 mm.

その後、下記構造式（１５）で示される化合物３部を加え溶解し、これに２５０部の酢酸エチルを加えて希釈することによって、電荷発生層用塗布液を調製した。

Thereafter, 3 parts of a compound represented by the following structural formula (15) was added and dissolved, and 250 parts of ethyl acetate was added thereto and diluted to prepare a charge generation layer coating solution.

この電荷発生層用塗布液を中間層上に浸漬塗布し、これを１０分間１００℃で乾燥させることによって、膜厚が０．１６μｍの電荷発生層を形成した。

This charge generation layer coating solution was dip coated on the intermediate layer and dried at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of 0.16 μm.

  Next, Exemplified Compound No. 2-21 10 parts, polycyclic olefin (trade name: TOPAS-5013, manufactured by Ticona, Tg: 130 ° C.) 10 parts, Exemplified Compound No. Prepare 5 copies of 1-2. These were dissolved in a mixed solvent of 50 parts of monochlorobenzene and 30 parts of tetrahydrofuran (THF) to prepare a coating solution for a charge transport layer.

  The charge transport layer coating solution was dip-coated on the charge generation layer and dried at 120 ° C. for 1 hour to form a charge transport layer having a thickness of 18 μm.

  Thus, an electrophotographic photoreceptor 1 having a charge transport layer as a surface layer was produced.

The polycyclic olefin (trade name: TOPAS-5013, manufactured by Ticona, Tg: 130 ° C.) is a repeating structural unit represented by the above general formula (11) (R ₁₁₁ : hydrogen atom, R ₁₁₂ : hydrogen atom) and the above structure. It is a copolymer having a repeating structural unit represented by the formula (12).

  The electrophotographic photosensitive member 1 according to this example was allowed to stand for 24 hours in a low-temperature and low-humidity (15 ° C./10% RH) environment, and then the output image and the surface potential were evaluated in the same environment.

  For the evaluation of the output image, a modified machine (process speed: 94.2 mm / s) of a laser beam printer (trade name: Color Laser Jet 4600) manufactured by Hewlett-Packard Company was used. The charging means of this laser beam printer is a contact charging means provided with a charging roller, and a voltage of only DC voltage is applied to the charging roller. Further, this laser beam printer does not have a static eliminating unit at a position upstream of the charging unit and downstream of the transfer unit in the rotation direction of the electrophotographic photosensitive member. As a modification, the amount of exposure light (image exposure light) is variable.

  The electrophotographic photosensitive member 1 was mounted on a cyan process cartridge, the developing cartridge was removed from the apparatus, and a potential measuring device was inserted therein. This was mounted in a cyan process cartridge station of the printer, and the amount of exposure light was set so that the bright portion potential (Vl) was −150V. The potential measuring apparatus is configured by arranging a potential measuring probe at the developing position of the developing cartridge, and the position of the potential measuring probe with respect to the electrophotographic photosensitive member is set at the center in the drum axis direction.

  Thereafter, the potential measuring device was removed, the developing cartridge was returned to the original state, and an initial ghost image evaluation was performed.

  As an image for ghost evaluation, as shown in FIG. 2, a halftone image printed with a 1-dot Keima pattern after a black square image was output at the head of the image was used.

  For evaluation of the ghost image, a spectral densitometer (trade name: X-Rite 504/508) manufactured by X-Rite Co., Ltd. was used. In the output image, the density of the portion that is not the ghost portion is subtracted from the density of the ghost portion, and this is used as the ghost image density. This was performed 10 points on one output image, and the average value of 10 points was obtained.

  In this experiment, the ghost image density is at a level that has a clear difference when it is 0.05 or more, and when it is less than 0.05, there is no apparent difference at the level. Moreover, the ghost image evaluated the 1st sheet | seat (initial stage) and after 15000th sheet passing.

  At the time of paper feeding, a full color printing operation was performed in an intermittent mode in which a character image with a printing rate of 2% for each color was output one sheet of letter paper every 20 seconds, and 15,000 sheets were passed. Immediately thereafter, ghost images were evaluated. Thereafter, the developing cartridge was taken out from the apparatus, and a potential measuring device was inserted therein to evaluate the light portion potential (Vl). The results are shown in Table 4.

(Examples 2 to 16)
In Example 1, the exemplified compound No. 1 used in the charge transport layer was used. Electrophotographic photoreceptors 2 to 16 were produced in the same manner as in Example 1 except that 1-2 was changed to those shown in Table 3, respectively. The electrophotographic photoreceptors 2 to 16 were evaluated in the same manner as the electrophotographic photoreceptor 1. The results are shown in Table 4.

(Examples 17 to 32)
In Example 1, the exemplified compound No. 1 used in the charge transport layer was used. 2-21, polycyclic olefin, Exemplified Compound No. 2 Electrophotographic photosensitive members 17 to 32 were produced in the same manner as in Example 1 except that the amount of 1-2 was changed to the amount shown in Table 3, respectively. The electrophotographic photoreceptors 17 to 32 were evaluated in the same manner as the electrophotographic photoreceptor 1. The results are shown in Table 4.

(Examples 33-53)
In Example 1, the exemplified compound No. 1 used in the charge transport layer was used. Electrophotographic photosensitive members 33 to 53 were produced in the same manner as in Example 1 except that 2-21 was changed to those shown in Table 3 respectively. In addition, the electrophotographic photoreceptors 33 to 53 were evaluated in the same manner as the electrophotographic photoreceptor 1. The results are shown in Table 4.

(Examples 54 to 56)
Example 1 is the same as Example 1 except that the polycyclic olefin resin (trade name: TOPAS-5013, manufactured by Ticona, Tg = 130 ° C.) used in the charge transport layer is changed to that shown in Table 3. Thus, electrophotographic photoreceptors 13 to 15 were produced. The electrophotographic photoreceptors 54 to 56 were evaluated in the same manner as the electrophotographic photoreceptor 1. The results are shown in Table 4.

The polycyclic olefin (trade name: TOPAS-6015, manufactured by Ticona, Tg: 160 ° C.) is composed of the repeating structural unit (R ₁₁₁ : hydrogen atom, R ₁₁₂ : hydrogen atom) of the general formula (11) and the structural formula ( 12) A copolymer having a repeating structural unit.

The polycyclic olefin (trade name: TOPAS-8007, manufactured by Ticona, Tg: 75 ° C.) is composed of the repeating structural unit (R ₁₁₁ : hydrogen atom, R ₁₁₂ : hydrogen atom) of the above general formula (11) and the above structural formula ( 12) A copolymer having a repeating structural unit.

The polycyclic olefin (trade name: APL-6509T, manufactured by Mitsui Chemicals, Tg: 80 ° C.) is composed of the repeating structural unit (R ₁₁₁ : hydrogen atom, R ₁₁₂ : hydrogen atom) of the above general formula (11) and the above. It is a copolymer having a repeating structural unit of the structural formula (12).

(Example 57)
The polycyclic olefin resin of Example 1 (trade name: TOPAS-5013, manufactured by Ticona, Tg = 130 ° C.) and the polycyclic olefin resin having a repeating structural unit of the following structural formula (16) (trade name: ZEONEX-480) , Manufactured by Nippon Zeon Co., Ltd., Tg = 138 ° C.). Except for this, an electrophotographic photosensitive member 57 was produced in the same manner as in Example 1. The electrophotographic photoreceptor 57 was evaluated in the same manner as the electrophotographic photoreceptor 1. The results are shown in Table 4.

(Example 58)
The polycyclic olefin resin of Example 1 (trade name: TOPAS-5013, manufactured by Ticona, Tg = 130 ° C.) was converted to a cyclopentane-based polycyclic olefin resin (trade name: ZEONOR-1060, manufactured by Nippon Zeon Co., Ltd.) Tg = 100 ° C.) Except for this, an electrophotographic photosensitive member 58 was produced in the same manner as in Example 1. Further, the electrophotographic photoreceptor 58 was evaluated in the same manner as the electrophotographic photoreceptor 1. The results are shown in Table 4.

(Example 59)
The polycyclic olefin resin of Example 1 (trade name “TOPAS (registered trademark) -5013” manufactured by Ticona Co., Ltd., Tg = 130 ° C.) and a polycyclic olefin resin having a repeating structural unit of the following structural formula (17) (trade name: Changed to ARTON, manufactured by JSR Corporation, Tg = 170 ° C. Except for this, an electrophotographic photosensitive member 59 was produced in the same manner as in Example 1. Further, the electrophotographic photoreceptor 59 was evaluated in the same manner as the electrophotographic photoreceptor 1. The results are shown in Table 4.

(Example 60)
In Example 1, an electrophotographic photoreceptor 60 was produced and evaluated in the same manner as in Example 1 except that the charge transport layer was produced as follows. The results are shown in Table 4.

  First, 10 parts of polyethylene (trade name: UBEC150, manufactured by Ube Maruzen Polyethylene Co., Ltd.) was dissolved by heating at 120 ° C. in a solvent of 80 parts of xylene. In the heated and dissolved solution, Exemplified Compound No. 10 to 21 parts of Exemplified Compound No. 2-21. 5 parts of 1-5 was added to prepare a coating solution for charge transport layer.

  The charge transport layer coating solution was dip coated on the charge generation layer in a state heated to 120 ° C., and dried at 120 ° C. for 1 hour to form a charge transport layer having a thickness of 18 μm.

(Example 61)
In Example 1, an electrophotographic photosensitive member 61 was produced and evaluated in the same manner as in Example 1 except that the charge transport layer was produced as follows. The results are shown in Table 4.

  First, 10 parts of polypropylene (trade name: Sumitomo Noblen, manufactured by Sumitomo Chemical Co., Ltd.) was heated and melted at 180 ° C. To the heated and melted solution, Exemplified Compound No. 10 to 21 parts of Exemplified Compound No. 2-21. 5 parts of 1-5 was added and melted to prepare a charge transport layer coating solution.

  The charge transport layer coating solution is heated to 180 ° C. and coated on the charge generation layer using an extrusion type coating apparatus, and dried at 120 ° C. for 1 hour, whereby a charge having a thickness of 25 μm is obtained. A transport layer was formed.

(Examples 62 to 106)
In Examples 1 to 16 and 33 to 61, Example 1 was performed except that the thickness of the charge transport layer was changed to 15 μm and the following protective layer (second charge transport layer) was provided on the charge transport layer. To 16 and 33 to 61, electrophotographic photosensitive members 62 to 106 were produced. The electrophotographic photoreceptors 62 to 106 were evaluated in the same manner as the electrophotographic photoreceptor 1. The results are shown in Table 5.

  In Examples 62 to 106, a protective layer is provided as follows.

  First, 0.45 part of a fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) as a dispersant was added to 1,1,2,2,3,3,4-heptafluorocyclopentane 35. Part and 35 parts of 1-propanol.

Thereafter, 9 parts of tetrafluoroethylene resin powder (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) as a lubricant was added. Furthermore, the dispersion process was performed three times at a pressure of 59 MPa (600 kgf / cm ² ) using a high-pressure disperser (trade name: Microfluidizer M-110EH, manufactured by Microfluidics, USA). Thereby, the tetrafluoroethylene resin powder was uniformly dispersed.

  Further, this was pressure filtered through a 10 μm PTFE membrane filter to prepare a lubricant dispersion.

  Next, 21 parts of the charge transporting compound represented by the following structural formula (18) is added to the lubricant dispersion, and this is filtered under pressure with a 5 μm membrane filter made of PTFE (tetrafluoroethylene resin). A coating solution for protective layer was prepared.

この保護層用塗布液を電荷輸送層上に浸漬塗布し、これに、窒素中において加速電圧１５０ｋＶ、線量１．５×１０^４Ｇｙの条件で電子線を照射し、引き続いて被照射体の温度が１２０℃になる条件で９０秒間加熱処理を行った。このときの酸素濃度は１０ｐｐｍであった。更に、大気中で１００℃に調製された熱風乾燥機中で、２０分間加熱処理を行うことによって、膜厚３μｍの保護層を形成した。

This protective layer coating solution is dip-coated on the charge transport layer, and this is irradiated with an electron beam in nitrogen under the conditions of an acceleration voltage of 150 kV and a dose of 1.5 × 10 ⁴ Gy, followed by the temperature of the irradiated object. Was subjected to heat treatment for 90 seconds under the condition of 120.degree. The oxygen concentration at this time was 10 ppm. Furthermore, a protective layer having a thickness of 3 μm was formed by performing heat treatment for 20 minutes in a hot air dryer adjusted to 100 ° C. in the atmosphere.

(Example 107)
In Example 1, the thickness of the charge transport layer was changed to 15 μm, and the following protective layer (second charge transport layer) was provided on the charge transport layer. A photoreceptor 41 was produced. The electrophotographic photoreceptor 41 was evaluated in the same manner as the electrophotographic photoreceptor 1. The results are shown in Table 5.

  In Example 107, a protective layer is provided as follows.

  Fluorine atom-containing resin (trade name: GF-300, manufactured by Toagosei Co., Ltd.) 0.45 part as a dispersant was replaced with 35 parts of 1,1,2,2,3,3,4-heptafluorocyclopentane. Dissolved in 35 parts of 1-propanol.

Thereafter, 9 parts of tetrafluoroethylene resin powder (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) as a lubricant was added. Furthermore, the dispersion process was performed three times at a pressure of 59 MPa (600 kgf / cm ² ) using a high-pressure disperser (trade name: Microfluidizer M-110EH, manufactured by Microfluidics, USA). Thereby, the tetrafluoroethylene resin powder was uniformly dispersed.

  Further, this was pressure filtered through a 10 μm PTFE membrane filter to prepare a lubricant dispersion.

  Next, 10 parts of a charge transporting compound represented by the following structural formula (19) and 10 parts of a polycarbonate resin having a repeating structural unit represented by the following structural formula (20) were added to the lubricant dispersion. This was pressure filtered with a PTFE 5 μm membrane filter to prepare a protective layer coating solution.

この保護層用塗布液を電荷輸送層上にスプレーコーティングし、これを３０分間１２０℃で乾燥させることによって、膜厚が３μｍの保護層を形成した。

This protective layer coating solution was spray-coated on the charge transport layer and dried at 120 ° C. for 30 minutes to form a protective layer having a thickness of 3 μm.

(Comparative Example 1)
In Example 1, a polycyclic olefin resin (trade name: TOPAS-5013, manufactured by Ticona, Tg = 130 ° C.) used for the charge transport layer is a polyarylate resin having a repeating structural unit represented by the following structural formula (21) (weight) The average molecular weight was changed to 115000). Except for this, an electrophotographic photosensitive member C1 was produced in the same manner as in Example 1. The electrophotographic photoreceptor C1 was evaluated in the same manner as the electrophotographic photoreceptor 1. The results are shown in Table 6.

  In Comparative Example 1, a charge transport layer coating solution was prepared by dissolving a polyarylate resin having a repeating structural unit of the following structural formula (21) in a mixed solvent of 50 parts of monochlorobenzene and 30 parts of tetrahydrofuran.

この電荷輸送層用塗布液を電荷発生層上に浸漬塗布し、１時間１２０℃で乾燥させることによって、膜厚が１８μｍの電荷輸送層を形成した。

This charge transport layer coating solution was dip coated on the charge generation layer and dried at 120 ° C. for 1 hour to form a charge transport layer having a thickness of 18 μm.

(Comparative Examples 2 to 4)
In Comparative Example 1, Exemplified Compound No. 1 used for the charge transport layer was used. 2-21, No. 2 respectively. 3-6, no. 4-3, no. Electrophotographic photosensitive members C2 to C4 were produced in the same manner as in Comparative Example 1 except that the number of photoconductors was changed to 6-6. The electrophotographic photoreceptors C2 to C4 were evaluated in the same manner as the electrophotographic photoreceptor 1. The results are shown in Table 6.

(Comparative Example 5)
In Comparative Example 1, Exemplified Compound No. 1 used for the charge transport layer was used. An electrophotographic photoreceptor C5 was produced in the same manner as in Comparative Example 1 except that 1-2 was omitted. Further, the electrophotographic photoreceptor C5 was evaluated in the same manner as the electrophotographic photoreceptor 1. The results are shown in Table 6.

(Comparative Example 6)
In Example 1, the exemplified compound No. 1 used in the charge transport layer was used. An electrophotographic photoreceptor C6 was produced in the same manner as in Example 1 except that 1-2 was omitted. Further, the electrophotographic photoreceptor C6 was evaluated in the same manner as the electrophotographic photoreceptor 1. The results are shown in Table 6.

(Comparative Examples 7-9)
In Comparative Example 6, Exemplified Compound No. 1 used for the charge transport layer was used. 2-21, No. 2 respectively. 3-6, no. 4-3, no. Electrophotographic photosensitive members C7 to C9 were produced in the same manner as in Comparative Example 6 except that the number of photoconductors was changed to 6-6. The electrophotographic photoreceptors C7 to C9 were evaluated in the same manner as the electrophotographic photoreceptor 1. The results are shown in Table 6.

1 is a diagram illustrating an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having the electrophotographic photosensitive member of the present invention. It is a figure which shows the image for evaluation used in the Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 2 Axis 3 Charging means 4 Exposure light 5 Developing means 6 Transfer means 7 Transfer material 8 Fixing means 9 Cleaning means 10 Pre-exposure light 11 Process cartridge 12 Guide means

Claims (12)

In an electrophotographic photosensitive member having a support and a photosensitive layer provided on the support,
The photosensitive layer is
A compound represented by the following general formula (1):
A polycyclic olefin resin;
A charge transporting compound having at least one structure selected from the group consisting of a tertiary amine structure and a hydrazone structure;
Containing
An electrophotographic photoreceptor, wherein when the charge transporting compound has an alkylene chain, the alkylene chain has 4 or less carbon atoms.

(In the above formula (1), R ₁₁ represents an alkyl group having 5 to 20 carbon atoms. R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently a hydrogen atom, an alkoxy group, or a hydroxyl group. , A halogen atom, an amino group, an optionally substituted alkyl group, an optionally substituted aralkyl group or an optionally substituted aryl group, X is O, C═O, COO or single bond is indicated.) The electrophotographic photosensitive member according to claim 1, wherein in the compound represented by the general formula (1), X is O, C═O, or a single bond .   In the charge transporting compound, the tertiary amine structure and the hydrazone structure have an alkyl group having 1 to 4 carbon atoms, an aralkyl group having an alkylene group having 1 to 4 carbon atoms, and a substituent having 1 or more carbon atoms. Claims having at least one selected from the group consisting of an aryl group optionally having 4 or less alkyl groups and an arylene group optionally having an alkoxy group having 1 to 4 carbon atoms as a substituent. Item 3. The electrophotographic photosensitive member according to Item 1 or 2. The charge transporting compound is at least one selected from the group consisting of the following general formulas (2), (3), (4), (6), (7), (8) and (9). 3. The electrophotographic photosensitive member according to 3.

(In the above formula (2), R ₂₁ and R ₂₂ are each an alkyl group having 1 to 4 carbon atoms, an aryl group which may have an alkyl group having 1 to 4 carbon atoms as a substituent, or 1 to 4 carbon atoms. The aryl group which may have the following alkoxy groups is shown: Ar ₂₁ is an arylene group which may have an alkyl group having 1 to 4 carbon atoms as a substituent or an alkoxy having 1 to 4 carbon atoms as a substituent. R ₂₃ represents an arylene group which may have a group, an aryl group which may have an alkyl group having 1 to 4 carbon atoms as a substituent, and an alkoxy group which has 1 to 4 carbon atoms as a substituent. An aryl group which may be substituted, an aralkyl group having an alkylene group having 1 to 4 carbon atoms, or a hydrogen atom, Ar ₂₁ and R ₂₃ may form a ring directly or through another organic residue. )

(In the above formula (3), R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are an alkyl group having 1 to 4 carbon atoms, an aralkyl group having an alkylene group having 1 to 4 carbon atoms, and 1 carbon atom as a substituent. An aryl group which may have an alkyl group having 4 or less or more, an aryl group which may have an alkoxy group having 1 to 4 carbon atoms as a substituent, or a substituent represented by the following general formula (5) is shown. Ar ₃₁ and Ar ₃₂ represent an arylene group which may have an alkyl group having 1 to 4 carbon atoms as a substituent.

(In the above formula (4), R ₄₁ is an alkyl group having 1 to 4 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a substituent represented by the following general formula (5). Ar ₄₁ and Ar ₄₂ each represent an aryl group that may have an alkyl group having 1 to 4 carbon atoms as a substituent, and an aryl group that may have an alkoxy group having 1 to 4 carbon atoms as a substituent. Or a substituent represented by the following general formula (5), provided that at least one of Ar ₄₁ , Ar ₄₂ and R ₄₁ has one or more substituents represented by the following general formula (5).

(In the above formula (5), R ₅₁ has an alkyl group having 1 to 4 carbon atoms, an aralkyl group having an alkylene group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms as a substituent. An aryl group which may have an aryl group which may have an alkoxy group having 1 to 4 carbon atoms as a substituent or a hydrogen atom Ar ₅₁ has an alkyl group having 1 to 4 carbon atoms as a substituent. An aryl group which may have an aryl group which may have an alkyl group having 1 to 4 carbon atoms, and Ar ₅₁ and R ₅₂ may form a ring directly or via another organic residue. n ¹ represents an integer of 0 to 2.)

(In the above formula (6), Ar ₆₁ and Ar ₆₂ have an aryl group which may have an alkyl group having 1 to 4 carbon atoms as a substituent or an alkoxy group having 1 to 4 carbon atoms as a substituent. R ₆₁ represents a condensed ring hydrocarbon or condensed complex ring which may have an alkyl group having 1 to 4 carbon atoms as a substituent, or an alkoxy having 1 to 4 carbon atoms as a substituent. A condensed ring hydrocarbon or condensed complex ring which may have a group.

(In the above formula (7), R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ are an alkyl group having 1 to 4 carbon atoms, an aralkyl group having 1 to 4 carbon atoms, and a substituent having 1 carbon atom. An aryl group that may have an alkyl group of 4 or less or an aryl group that may have an alkoxy group of 1 to 4 carbon atoms as a substituent, Ar ₇₁ represents 1 to 4 carbon atoms as a substituent. An arylene group which may have an alkyl group of 1 or an arylene group which may have an alkoxy group having 1 to 4 carbon atoms as a substituent.

(In the above formula (8), Ar ₈₁ , Ar ₈₂ , Ar ₈₃ and Ar ₈₄ are each an aryl group which may have an alkyl group having 1 to 4 carbon atoms as a substituent, or 1 to 4 carbon atoms as a substituent. An aryl group which may have an alkoxy group of

(In the above formula (9), Ar ₉₁ , Ar ₉₂ , Ar ₉₃ and Ar ₉₄ may have an alkyl group having 1 to 4 carbon atoms as a substituent, or an aryl group or substituent having 1 to 4 carbon atoms. And an aryl group which may have an alkoxy group, provided that at least one of Ar ₉₁ , Ar ₉₂ , Ar ₉₃ and Ar ₉₄ has one or more substituents represented by the following general formula (10). )

(In the above formula (10), R ₁₀₁ and R ₁₀₂ are an alkyl group having 1 to 4 carbon atoms, an aralkyl group having an alkylene group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms as a substituent. An aryl group which may have   The electrophotographic photosensitive member according to claim 1, wherein the electrophotographic photosensitive member has a protective layer on the photosensitive layer. The electrophotographic photosensitive member according to any one of the polycycloolefin glass transition temperature (Tg) of the resin is claims 1 to 5 is 170 ° C. or less 100 ° C. or higher. The polycycloolefin resin of claims 1 to 6, characterized in that a copolymer having a repeating structural unit represented by the repeating structural units and the following general formula represented by the following general formula (11) (12) The electrophotographic photosensitive member according to any one of the above.

(In Formula (11), R ₁₁₁ and R ₁₁₂ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. And R ₁₁₁ and R ₁₁₂ may be bonded to each other to form a ring.

The content of the compound having the structure of the general formula (1) is 20% or more and 80% or less with respect to the respective weights of the charge transporting compound and the polycyclic olefin resin. The electrophotographic photosensitive member according to any one of 1 to 7 . The electrophotographic photosensitive member according to any one of claims 1 to 8 , wherein the compound having the structure of the general formula (1) has a molecular weight of 300 or less. The electrophotographic photosensitive member according to any one of claims 1 to 9 , wherein the compound having the structure of the general formula (1) is the following general formula (13).

(In the above formula (13), R ₁₃₁ represents an alkyl group having 5 to 12 carbon atoms.) An electrophotographic photosensitive member according to any one of claims 1 to 10 , a charging unit for charging the electrophotographic photosensitive member, a developing unit for developing the electrophotographic photosensitive member on which an electrostatic latent image is formed with toner, Together with at least one means selected from the group consisting of a transfer means for transferring a toner image on the electrophotographic photosensitive member onto a transfer material and a cleaning means for recovering toner remaining on the electrophotographic photosensitive member after the transfer step. A process cartridge that is integrally supported and detachable from the main body of the electrophotographic apparatus. The electrophotographic photosensitive member according to any one of claims 1 to 10, charging means for charging the electrophotographic photosensitive member, a developing means and electrophotographic developing the electrophotographic photoreceptor formed electrostatic latent image with toner An electrophotographic apparatus comprising transfer means for transferring a toner image on a photographic photosensitive member onto a transfer material.

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