JP2005148370A - Electrophotographic photoreceptor, and electrophotographic method and electrophotographic apparatus using same, and process cartridge for electrophotographic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor having high durability without impairing electrophotographic properties even to repetitive use over a prolonged period of time and excellent in environment resistance even to oxidizers, etc.; to provide an electrophotographic method and an electrophotographic apparatus in which replacement of a photoreceptor is unnecessary, which achieve high-speed printing or miniaturization of the apparatus by a reduced diameter of a photoreceptor, and by which images of high image quality are stably obtained even in repetitive use, by using the above photoreceptor; and to provide an electrophotographic process cartridge. <P>SOLUTION: The electrophotographic photoreceptor is obtained by forming a photosensitive layer containing at least one of the porphyrin compounds shown by formula (1) on a conductive substrate, wherein R<SP>1</SP>-R<SP>8</SP>are each alkyl or a specified substituent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electrophotographic photosensitive member containing at least one specific porphyrin compound in a photosensitive layer, and an electrophotographic method, an electrophotographic apparatus, and an electrophotographic process cartridge using the electrophotographic photosensitive member.

  In recent years, there has been a remarkable development in information processing system machines using electrophotography. In particular, laser printers and digital copying machines that convert information into digital signals and record information using light have significantly improved print quality and reliability. Furthermore, they have been applied to laser printers or digital copiers capable of full-color printing by fusing with high-speed technology. From such a background, it is particularly important to achieve both high image quality and high durability as a required photoreceptor function.

As photoconductors used in these electrophotographic laser printers, digital copiers, etc., those using organic photosensitive materials (OPC) are generally widely used for reasons such as cost, productivity and non-pollution. Applied. The layer structure of the OPC photoreceptor is roughly divided into a single layer type and a function separation type laminated structure. The first practical OPC, the PVK-TNF charge transfer complex type photoreceptor, was the former single layer type. On the other hand, in 1968, Hayashi and Regensburger independently invented a PVK / a-Se laminated photoconductor, later in 1977 by Melz et al., And in 1978 by Schlosser, an organic pigment dispersion layer and an organic low molecular weight dispersion polymer layer. A layered photoreceptor consisting of organic materials has been announced.
Among them, a photoreceptor using a phthalocyanine compound as a charge generating substance has high sensitivity in the near infrared to visible light region and is practically used as an electrophotographic photoreceptor.

In recent years, increasing the durability of a photoconductor has become an even more important issue due to the reduction in the diameter of the organic photoconductor and the long life requirement accompanying the increase in the speed of the electrophotographic apparatus or the downsizing of the apparatus. Among them, the deterioration of the chargeability and the sensitivity due to the exposure of the phthalocyanine compound due to the oxidization of NOx and ozone mainly generated from the charging portion permeate the photosensitive layer, which are important problems.
As a countermeasure, an additive such as an antioxidant is an effective means. Among them, amine-based antioxidants are used as useful antioxidants. For example, Patent Documents 1 and 2 disclose trialkylamines and aromatic amine additives, Patent Document 3 discloses substituted alkylarylamine compounds, and Patent Document 4 discloses an alkylamino group as an acid scavenger to a photoreceptor. Compounds having the formula are disclosed. However, since general additives are molecularly designed without considering matching with other constituent materials, addition to the photosensitive layer can reduce electrosensitivity and increase the residual potential due to repeated use. It mimics the side effects. In addition, since a large amount of addition is necessary to obtain a sufficient antioxidant effect, it has been difficult to achieve a balance between repeated durability and sensitivity characteristics.

Japanese Unexamined Patent Publication No. 63-4238 Japanese Patent Laid-Open No. 63-216055 JP-A-8-292587 JP 2000-231204 A

  An object of the present invention is to provide an electrophotographic photosensitive member that has high durability without impairing electrophotographic characteristics for repeated use over a long period of time, and is excellent in environmental resistance against oxidizing substances. is there. In addition, by using these photoconductors, it is not necessary to replace the photoconductors, and it is possible to reduce the size of the apparatus accompanying high-speed printing or reducing the diameter of the photoconductor. An electrophotographic method, an electrophotographic apparatus, and an electrophotographic process cartridge are provided.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have made an electrophotography containing a compound in which a porphyrin compound molecule that is a charge generating substance and an alkylamine compound molecule that is an antioxidant are combined as a single molecule by chemical bonding. The present inventors have found that the photosensitive member for use is suitable for the above purpose and have completed the present invention.
Compared to an electrophotographic photosensitive member to which a general antioxidant is added, the electrophotographic photosensitive member to which the porphyrin compound is added has higher durability without impairing the electrophotographic characteristics for long-term repeated use. Furthermore, it is excellent in environmental resistance against oxidizing substances. The reason for this is not clear for now. This is probably because the alkylamine compound having a function of neutralizing oxidizing gas or the like is close to the porphyrin compound through a chemical bond. That is, since an alkylamine compound is always present in the vicinity of the porphyrin compound, the antioxidant efficiency is high, and since it is bonded by a chemical bond, it is necessary to add a large amount of antioxidant to the photosensitive layer (concentration dependence). It is thought to be lost.

  That is, the above-mentioned problem is characterized in that (1) “a photosensitive layer containing at least one porphyrin compound represented by the following general formula (1) as a component is formed on a conductive support of the present invention. Electrophotographic photoreceptor;

〔但し、式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、置換もしくは無置換のアルキル基、もしくは下記一般式Ｙで表わされる置換基、

[In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are substituted or unsubstituted alkyl groups, or substituents represented by the following general formula Y,

（但し、一般式Ｙ中、Ｒ^９は、置換もしくは無置換のアルキレン基である。また、Ｒ^１０、Ｒ^１１は、置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素環基を表わし、同一でも異なっていてもよい。但し、Ｒ^１０、Ｒ^１１のいずれか１つは置換もしくは無置換のアルキル基である。また、Ｒ^１０、Ｒ^１１は、互いに結合し窒素原子を含む置換もしくは無置換の複素環基を形成してもよい。）を表わし、同一でも異なっていてもよい。但し、Ｒ^１〜Ｒ^８の少なくとも１つは置換基Ｙである。Ｘは酸素原子、硫黄原子を表わす。ＭはＨ_２、Ｃｕ、ＴｉＯ、ＧａＣｌ、ＧａＯＨを表わす。〕」、
（２）「導電性支持体上に、下記一般式（２）で示されるポルフィリン化合物の少なくとも一種を含有成分として含有する感光層を形成せしめたことを特徴とする電子写真用感光体；

(In the general formula Y, R ⁹ is a substituted or unsubstituted alkylene group. Also, R ¹⁰ and R ¹¹ are substituted or unsubstituted alkyl groups, substituted or unsubstituted aromatic hydrocarbon ring groups. And each of R ¹⁰ and R ¹¹ is a substituted or unsubstituted alkyl group, and R ¹⁰ and R ¹¹ are bonded to each other and contain a nitrogen atom. A substituted or unsubstituted heterocyclic group may be formed), which may be the same or different. However, at least one of R ^{1 to} R ⁸ is the substituent Y. X represents an oxygen atom or a sulfur atom. M represents _{H 2, Cu, TiO, GaCl} , the GaOH. ]
(2) “An electrophotographic photoreceptor, wherein a photosensitive layer containing at least one porphyrin compound represented by the following general formula (2) as a component is formed on a conductive support;

〔式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、置換もしくは無置換のアルキル基、もしくは下記一般式Ｙで表わされる置換基、

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are a substituted or unsubstituted alkyl group, or a substituent represented by the following general formula Y,

（但し、一般式Ｙ中、Ｒ^９は、置換もしくは無置換のアルキレン基である。Ｒ^１０、Ｒ^１１は、置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素環基を表わし、同一でも異なっていてもよい。但し、Ｒ^１０、Ｒ^１１のいずれか１つは置換もしくは無置換のアルキル基である。また、Ｒ^１０、Ｒ^１１は、互いに結合し窒素原子を含む置換もしくは無置換の複素環基を形成してもよい。）を表わし、同一でも異なっていてもよい。但し、Ｒ^１〜Ｒ^８の少なくとも１つは置換基Ｙである。ＭはＨ_２、Ｃｕ、ＴｉＯ、ＧａＣｌ、ＧａＯＨを表わす。〕」、
（３）「導電性支持体上に、下記一般式（３）で示されるポルフィリン化合物の少なくとも一種を含有成分として含有する感光層を形成せしめたことを特徴とする電子写真用感光体；

(In the general formula Y, R ⁹ represents a substituted or unsubstituted alkylene group. R ¹⁰ and R ¹¹ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon ring group. , Which may be the same or different, provided that any one of R ¹⁰ and R ¹¹ is a substituted or unsubstituted alkyl group, and R ¹⁰ and R ¹¹ are substituted or substituted with each other and containing a nitrogen atom. An unsubstituted heterocyclic group may be formed), which may be the same or different. However, at least one of R ^{1 to} R ⁸ is the substituent Y. M represents _{H 2, Cu, TiO, GaCl} , the GaOH. ]
(3) “An electrophotographic photoreceptor, wherein a photosensitive layer containing at least one porphyrin compound represented by the following general formula (3) as a component is formed on a conductive support;

〔式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、置換もしくは無置換のアルキル基、もしくは下記一般式Ｙで表わされる置換基、

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are a substituted or unsubstituted alkyl group, or a substituent represented by the following general formula Y,

（但し,一般式Y中、Ｒ^９は、置換もしくは無置換のアルキレン基である。Ｒ^１０、Ｒ^１１は、置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素環基を表わし、同一でも異なっていてもよい。但し、Ｒ^１０、Ｒ^１１のいずれか１つは置換もしくは無置換のアルキル基である。また、Ｒ^１０、Ｒ^１１は、互いに結合し窒素原子を含む置換もしくは無置換の複素環基を形成してもよい。）を表わし、同一でも異なっていてもよい。但し、Ｒ^１〜Ｒ^８の少なくとも１つは置換基Ｙである。Ｘは酸素原子、硫黄原子を表わす。ＭはＨ_２、Ｃｕ、ＴｉＯ、ＧａＣｌ、ＧａＯＨを表わす。〕」、
（４）「導電性支持体上に、下記一般式（４）で示されるポルフィリン化合物の少なくとも一種を含有成分として含有する感光層を形成せしめたことを特徴とする電子写真用感光体。

(In the general formula Y, R ⁹ represents a substituted or unsubstituted alkylene group. R ¹⁰ and R ¹¹ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon ring group. , Which may be the same or different, provided that any one of R ¹⁰ and R ¹¹ is a substituted or unsubstituted alkyl group, and R ¹⁰ and R ¹¹ are substituted or substituted with each other and containing a nitrogen atom. An unsubstituted heterocyclic group may be formed), which may be the same or different. However, at least one of R ^{1 to} R ⁸ is the substituent Y. X represents an oxygen atom or a sulfur atom. M represents _{H 2, Cu, TiO, GaCl} , the GaOH. ]
(4) “A photoreceptor for electrophotography, wherein a photosensitive layer containing at least one porphyrin compound represented by the following general formula (4) as a component is formed on a conductive support.

〔式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、置換もしくは無置換のアルキル基、もしくは下記一般式Yで表わされる置換基、

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are a substituted or unsubstituted alkyl group, or a substituent represented by the following general formula Y,

（但し、一般式Y中、Ｒ^９は、置換もしくは無置換のアルキレン基である。また、Ｒ^１０、Ｒ^１１は、置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素環基を表わし、同一でも異なっていてもよい。但し、Ｒ^１０、Ｒ^１１のいずれか１つは置換もしくは無置換のアルキル基である。また、Ｒ^１０、Ｒ^１１は、互いに結合し窒素原子を含む置換もしくは無置換の複素環基を形成してもよい。）を表わし、同一でも異なっていてもよい。ＭはＨ_２、Ｃｕ、ＴｉＯ、ＧａＣｌ、ＧａＯＨを表わす。〕」によって解決される。
また、上記課題は本発明の（５）「電子写真感光体に、少なくとも帯電、画像露光、現像、転写が繰り返し行なわれる電子写真方法において、該電子写真感光体が前記第（１）項乃至第（４）項のいずれかに記載の電子写真感光体であることを特徴とする電子写真方法」、
（６）「電子写真感光体に、少なくとも帯電、画像露光、現像、転写を繰り返し行ない、かつ画像露光の際にはＬＤあるいはＬＥＤ等によって感光体上に静電潜像の書き込みが行なわれる、所謂デジタル方式の電子写真方法において、該電子写真感光体が前記第（１）項乃至第（４）項のいずれかに記載の電子写真感光体であることを特徴とする電子写真方法」によって解決される。
ｃ（７）「少なくとも帯電手段、画像露光手段、現像手段、転写手段および電子写真感光体を具備してなる電子写真装置であって、該電子写真感光体が前記第（１）項乃至第（４）項のいずれかに記載の電子写真感光体であることを特徴とする電子写真装置」、
（８）「少なくとも帯電手段、画像露光手段、現像手段、転写手段および電子写真感光体を具備してなる電子写真装置において、画像露光手段にＬＤあるいはＬＥＤ等を使用することによって感光体上に静電潜像の書き込みが行なわれる、所謂デジタル方式の電子写真装置であって、該電子写真感光体が前記第（１）項乃至第（４）項のいずれかに記載の電子写真感光体であることを特徴とする電子写真装置」によって解決される。
また、上記課題は本発明の（９）「少なくとも電子写真感光体を具備してなる電子写真装置用プロセスカートリッジであって、該電子写真感光体が前記第（１）項乃至第（４）項のいずれかに記載の電子写真感光体であることを特徴とする電子写真装置用プロセスカートリッジ」によって解決される。

(In the general formula Y, R ⁹ is a substituted or unsubstituted alkylene group. Also, R ¹⁰ and R ¹¹ are substituted or unsubstituted alkyl groups, substituted or unsubstituted aromatic hydrocarbon ring groups. And each of R ¹⁰ and R ¹¹ is a substituted or unsubstituted alkyl group, and R ¹⁰ and R ¹¹ are bonded to each other and contain a nitrogen atom. A substituted or unsubstituted heterocyclic group may be formed), which may be the same or different. M represents _{H 2, Cu, TiO, GaCl} , the GaOH. ] ”.
Further, the above-mentioned problem is (5) “electrophotographic method wherein at least charging, image exposure, development, and transfer are repeatedly performed on an electrophotographic photosensitive member. The electrophotographic method according to any one of (4), "an electrophotographic method",
(6) “At least charging, image exposure, development, and transfer are repeatedly performed on the electrophotographic photosensitive member, and at the time of image exposure, an electrostatic latent image is written on the photosensitive member by an LD or an LED. In a digital type electrophotographic method, the electrophotographic photosensitive member is an electrophotographic photosensitive member according to any one of the above items (1) to (4). The
c (7) “An electrophotographic apparatus comprising at least a charging means, an image exposing means, a developing means, a transferring means, and an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the item (1) to ( 4) an electrophotographic apparatus characterized by being an electrophotographic photosensitive member according to any one of items
(8) In an electrophotographic apparatus comprising at least a charging means, an image exposing means, a developing means, a transferring means, and an electrophotographic photosensitive member, an LD or LED is used as the image exposing means so that A so-called digital electrophotographic apparatus in which an electrostatic latent image is written, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of (1) to (4). This is solved by an electrophotographic apparatus characterized by the above.
The above-mentioned problem is (9) “process cartridge for an electrophotographic apparatus comprising at least an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the item (1) to (4). The electrophotographic photosensitive member according to any one of the above items is solved by a “process cartridge for an electrophotographic apparatus”.

  According to the present invention, the inclusion of the porphyrin compounds represented by the general formulas (1) to (4) greatly improves the environmental resistance against repeated use and oxidizing gas without causing a decrease in sensitivity. Thus, it is possible to obtain a photoconductor having high durability and capable of obtaining a high-quality image over a long period of time. According to the present invention, an electrophotographic method and an electrophotographic method that do not require replacement of a photoconductor, realize downsizing of an apparatus associated with high-speed printing or a reduction in the diameter of the photoconductor, and can stably obtain a high-quality image even in repeated use. An apparatus and an electrophotographic process cartridge are provided.

Hereinafter, the electrophotographic photosensitive member of the present invention, the electrophotographic method using the same, the electrophotographic apparatus, and the electrophotographic process cartridge will be described in detail.
First, the details of the general formulas (1) to (4) contained in the photosensitive layer in the present invention will be described.

  In the definition of the substituents of the general formulas (1) to (4) of the present invention, specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an undecanyl group. it can. Examples of the aromatic hydrocarbon group include aromatic rings such as benzene, biphenyl, naphthalene, anthracene, fluorene, and pyrene, and heterocyclic groups such as pyridine, quinoline, thiophene, furan, oxazole, oxadiazole, and carbazole. . These substituents include those exemplified in the above specific examples of alkyl groups, alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group, or halogen atoms of fluorine atom, chlorine atom, bromine atom and iodine atom. Atoms, the aromatic hydrocarbon groups, and heterocyclic groups such as pyrrolidine, piperidine, piperazine and the like can be mentioned. Further, when a heterocyclic group containing a nitrogen atom is bonded to each other, the heterocyclic group can include a condensed heterocyclic group in which an aromatic hydrocarbon group is condensed to a pyrrolidino group, piperidino group, piperazino group, or the like. . In addition, examples of the heterocyclic group jointly containing a nitrogen atom include aromatic heterocyclic groups such as N-methylcarbazole, N-ethylcarbazole, N-phenylcarbazole, indole, and quinoline.

  Preferred examples of general formulas (1) to (4) are given below. However, the present invention is not limited to these compounds.

Next, the layer structure of the electrophotographic photosensitive member will be described with reference to FIGS.
FIG. 1 is a cross-sectional view showing an example of the electrophotographic photoreceptor of the present invention. A photosensitive layer (33) mainly comprising a phthalocyanine compound and a charge transport material is provided on a conductive support (31). ing.
The photoreceptor shown in FIG. 2 has a charge generation layer (35) mainly composed of a phthalocyanine compound and a charge transport layer (37) mainly composed of a charge transport material on a conductive support (31). It has a stacked configuration.
In the photoreceptor shown in FIG. 3, a photosensitive layer (33) mainly comprising a phthalocyanine compound and a charge transport material is provided on a conductive support (31), and a protective layer (39) is further provided on the surface of the photosensitive layer. It is provided.
In the photoreceptor shown in FIG. 4, a charge generation layer (35) mainly composed of a phthalocyanine compound and a charge transport layer (37) mainly composed of a charge transport material are laminated on a conductive support (31). The protective layer (39) is further provided on the charge transport layer.
In the photoreceptor shown in FIG. 5, a charge transport layer (37) mainly composed of a charge transport material and a charge generation layer (35) mainly composed of a phthalocyanine compound are laminated on a conductive support (31). Further, a protective layer (39) is provided on the charge generation layer.
The porphyrin compounds represented by the general formulas (1) to (4) of the present invention are preferably contained in the photosensitive layer in the photoreceptor shown in FIGS. 1 to 5, particularly the layer containing a phthalocyanine compound.

As the conductive support (31), a material having a volume resistance of 10 ¹⁰ Ω · cm or less, for example, a metal such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, tin oxide, oxidation A method of extruding and drawing metal oxides such as indium by film deposition or sputtering, or coating a film or cylindrical plastic or paper, or a plate of aluminum, aluminum alloy, nickel, stainless steel, etc. After forming the tube, it is possible to use a tube that has been surface-treated by cutting, superfinishing, polishing, or the like. Further, an endless nickel belt and an endless stainless steel belt disclosed in Japanese Patent Application Laid-Open No. 52-36016 can be used as the conductive support (31).

  In addition, the conductive support dispersed in a suitable binder resin and coated on the support can also be used as the conductive support (31) of the present invention. Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc and silver, or metal oxide powder such as conductive tin oxide and ITO. It is done. The binder resin used at the same time is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, Examples thereof include thermoplastic, thermosetting resins, and photocurable resins such as melamine resin, urethane resin, phenol resin, and alkyd resin. Such a conductive layer can be provided by dispersing and coating these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.

  Furthermore, it is electrically conductive by a heat-shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, Teflon (registered trademark) on a suitable cylindrical substrate. Those provided with a conductive layer can also be used favorably as the conductive support (31) of the present invention.

Next, the photosensitive layer will be described. The photosensitive layer may be a single layer or a laminate. For convenience of explanation, the photosensitive layer is first described from the case where it is composed of a charge generation layer (35) and a charge transport layer (37).
The charge generation layer (35) is a layer mainly composed of a phthalocyanine compound. The charge generation layer (35) can be used by mixing with a known charge generation material. As representatives of known charge generation materials, C.I. Pigment Blue 25 (Color Index CI 21180), C.I. Pigment Red 41 ( CI 21200), CI Acid Red 52 (CI 45100), CI Basic Red 3 (CI 45210), azo pigments having a carbazole skeleton (described in JP-A-53-95033), azo pigments having a distyrylbenzene skeleton ( JP-A-53-133445), azo pigments having a triphenylamine skeleton (described in JP-A-53-132347), azo pigments having a dibenzothiophene skeleton (described in JP-A-54-21728) An azo pigment having an oxadiazole skeleton 4-12742), azo pigments having a fluorenone skeleton (described in JP-A No. 54-22834), azo pigments having a bis-stilbene skeleton (described in JP-A No. 54-17733), distyryl An azo pigment having an oxadiazole skeleton (described in JP-A No. 54-2129), an azo pigment having a distyrylcarbazole skeleton (described in JP-A No. 54-14967), an azo pigment having a benzanthrone skeleton, and the like Azo pigments. For example, CI Pigment Blue 16 (CI 74100), Y-type oxotitanium phthalocyanine (Japanese Patent Laid-Open No. 64-17066), A (β) -type oxotitanium phthalocyanine, B (α) -type oxotitanium phthalocyanine, I-type oxotitanium phthalocyanine (Described in JP-A-11-21466), type II chlorogallium phthalocyanine (Iijima et al., Chemical Society of Japan, 67th Spring Annual, 1B4, 04 (1994)), type V hydroxygallium phthalocyanine (Damon et al., Chemical Society of Japan) 67th Spring Annual, 1B4, 05 (1994)), phthalocyanine pigments such as X-type metal-free phthalocyanine (US Pat. No. 3,816,118), C-Ibat Brown 5 (CI 73410), C-Ibat Dye (CI) 7330) and other indigo pigments, Lugo (manufactured by Bayer Co., Ltd.) Scarlet B, such as perylene pigment, such as in-closet Ren Scarlet R (manufactured by Bayer Co., Ltd.) and the like.

  The charge generation layer (35) is obtained by dispersing a phthalocyanine compound in a suitable solvent together with a binder resin as necessary using a ball mill, an attritor, a sand mill, an ultrasonic wave, etc., and applying this onto a conductive support. It is formed by drying.

  The binder resin used for the charge generation layer (35) as necessary may be polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, polysulfone, poly -N-vinyl carbazole, polyacrylamide, polyvinyl benzal, polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyphenylene oxide, polyamide, polyvinyl pyridine, cellulosic resin, casein, polyvinyl alcohol, polyvinyl pyrrolidone Etc. The amount of the binder resin is suitably 0 to 500 parts by weight, preferably 10 to 300 parts by weight with respect to 100 parts by weight of the charge generating material. The binder resin may be added before or after dispersion.

  Examples of the solvent used here include isopropanol, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane, toluene, xylene, and ligroin. In particular, ketone solvents, ester solvents, and ether solvents are preferably used. These may be used alone or in combination of two or more.

The charge generation layer (35) is mainly composed of a phthalocyanine compound, a solvent and a binder resin, and includes any additive such as a sensitizer, a dispersant, a surfactant, and silicone oil. May be.
As a coating method for the coating solution, a dip coating method, spray coating, beat coating, nozzle coating, spinner coating, ring coating, or the like can be used.
The film thickness of the charge generation layer (35) is suitably about 0.01 to 5 μm, preferably 0.1 to 2 μm.

The charge transport layer (37) is a layer mainly composed of a charge transport material.
The charge transport material is divided into a hole transport material, an electron transport material, and a polymer charge transport material, which will be described below.
Examples of the hole transport material include poly-N-carbazole and derivatives thereof, poly-γ-carbazolylethyl glutamate and derivatives thereof, pyrene-formaldehyde condensates and derivatives thereof, polyvinylpyrene, polyvinylphenanthrene, oxazole derivatives, imidazole There are derivatives, triphenylamine derivatives, and compounds represented by the general formula:

（式中、Ｒ^１はメチル基、エチル基、２−ヒドロキシエチル基または２−クロルエチル基を表わし、Ｒ^２はメチル基、エチル基、ベンジル基またはフェニル基を表わし、Ｒ^３は水素原子、塩素原子、臭素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、ジアルキルアミノ基またはニトロ基を表わす。）

(Wherein R ¹ represents a methyl group, an ethyl group, a 2-hydroxyethyl group or a 2-chloroethyl group, R ² represents a methyl group, an ethyl group, a benzyl group or a phenyl group, and R ³ represents a hydrogen atom, chlorine An atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a dialkylamino group, or a nitro group.)

（式中、Ａｒはナフタレン環、アントラセン環、ピレン環及びそれらの置換体あるいはピリジン環、フラン環、チオフェン環を表わし、Ｒはアルキル基、フェニル基またはベンジル基を表わす。）

(In the formula, Ar represents a naphthalene ring, anthracene ring, pyrene ring and a substituted product thereof, or a pyridine ring, a furan ring, and a thiophene ring, and R represents an alkyl group, a phenyl group, or a benzyl group.)

（式中、Ｒ^１はアルキル基、ベンジル基、フェニル基またはナフチル基を表わし、Ｒ^２は水素原子、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、ジアルキルアミノ基、ジアラルキルアミノ基、または置換もしくは無置換のジアリールアミノ基を表わし、ｎは１〜４の整数を表わし、ｎが２以上のときはＲ^２は同じでも異なっていても良い。Ｒ^３は水素原子またはメトキシ基を表わす。）

(Wherein R ¹ represents an alkyl group, a benzyl group, a phenyl group or a naphthyl group, and R ² represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group, a dialkyl group) Represents an aralkylamino group or a substituted or unsubstituted diarylamino group, n represents an integer of 1 to 4, and when n is 2 or more, R ² may be the same or different, and R ³ represents a hydrogen atom or Represents a methoxy group.)

（式中、Ｒ^１は炭素数１〜１１のアルキル基、置換もしくは無置換のフェニル基または複素環基を表わし、Ｒ^２、Ｒ^３はそれぞれ同一でも異なっていてもよく、水素原子、炭素数１〜４のアルキル基、ヒドロキシアルキル基、クロルアルキル基または置換もしくは無置換のアラルキル基を表わし、また、Ｒ^２とＲ^３は互いに結合し窒素を含む複素環を形成していても良い。Ｒ^４は同一でも異なっていてもよく、水素原子、炭素数１〜４のアルキル基、アルコキシ基またはハロゲン原子を表わす。）

(In the formula, R ¹ represents an alkyl group having 1 to 11 carbon atoms, a substituted or unsubstituted phenyl group or a heterocyclic group, and R ² and R ³ may be the same or different, and each represents a hydrogen atom or a carbon number. Represents an alkyl group of 1-4, a hydroxyalkyl group, a chloroalkyl group, or a substituted or unsubstituted aralkyl group, and R ² and R ³ may be bonded to each other to form a nitrogen-containing heterocyclic ring. ⁴ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group or a halogen atom.

（式中、Ｒは水素原子またはハロゲン原子を表わし、Ａｒは置換もしくは無置換のフェニル基、ナフチル基、アントリル基またはカルバゾリル基を表わす。）

(In the formula, R represents a hydrogen atom or a halogen atom, and Ar represents a substituted or unsubstituted phenyl group, naphthyl group, anthryl group or carbazolyl group.)

（式中、Ｒ^１は水素原子、ハロゲン原子、シアノ基、炭素数１〜４のアルコキシ基または炭素数１〜４のアルキル基を表わし、Ａｒは

(Wherein R ¹ represents a hydrogen atom, a halogen atom, a cyano group, an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms;

を表わし、Ｒ^２は炭素数１〜４のアルキル基を表わし、Ｒ^３は水素原子、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基またはジアルキルアミノ基を表わし、ｎは１または２であって、ｎが２のときはＲ^３は同一でも異なっていてもよく、Ｒ^４、Ｒ^５は水素原子、炭素数１〜４の置換もしくは無置換のアルキル基または置換もしくは無置換のベンジル基を表わす。）

R ² represents an alkyl group having 1 to 4 carbon atoms, R ³ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a dialkylamino group, n is 1 or 2, and when n is 2, R ³ may be the same or different, and R ⁴ and R ⁵ are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted group. Alternatively, it represents an unsubstituted benzyl group. )

（式中、Ｒはカルバゾリル基、ピリジル基、チエニル基、インドリル基、フリル基あるいはそれぞれ置換もしくは非置換のフェニル基、スチリル基、ナフチル基、またはアントリル基であって、これらの置換基がジアルキルアミノ基、アルキル基、アルコキシ基、カルボキシ基またはそのエステル、ハロゲン原子、シアノ基、アラルキルアミノ基、Ｎ−アルキル−Ｎ−アラルキルアミノ基、アミノ基、ニトロ基及びアセチルアミノ基からなる群から選ばれた基を表わす。）

Wherein R is a carbazolyl group, pyridyl group, thienyl group, indolyl group, furyl group or a substituted or unsubstituted phenyl group, styryl group, naphthyl group, or anthryl group, and these substituents are dialkylamino Group, alkyl group, alkoxy group, carboxy group or ester thereof, halogen atom, cyano group, aralkylamino group, N-alkyl-N-aralkylamino group, amino group, nitro group, and acetylamino group Represents a group.)

（式中、Ｒ^１は低級アルキル基、置換もしくは無置換のフェニル基、またはベンジル基を表わし、Ｒ^２、Ｒ^３は水素原子、低級アルキル基、低級アルコキシ基、ハロゲン原子、ニトロ基、アミノ基あるいは低級アルキル基またはベンジル基で置換されたアミノ基を表わし、ｎは１または２の整数を表わす。）

(In the formula, R ¹ represents a lower alkyl group, a substituted or unsubstituted phenyl group, or a benzyl group, and R ² and R ³ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a nitro group, and an amino group. Alternatively, it represents an amino group substituted with a lower alkyl group or a benzyl group, and n represents an integer of 1 or 2.)

（式中、Ｒ^１は水素原子、アルキル基、アルコキシ基またはハロゲン原子を表わし、Ｒ^２およびＲ^３は置換もしくは無置換のアリール基を表わし、Ｒ^４は水素原子、低級アルキル基または置換もしくは無置換のフェニル基を表わし、また、Ａｒは置換もしくは無置換のフェニル基またはナフチル基を表わす。）

(In the formula, R ¹ represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom, R ² and R ³ represent a substituted or unsubstituted aryl group, and R ⁴ represents a hydrogen atom, a lower alkyl group or a substituted or unsubstituted group. Represents a substituted phenyl group, and Ar represents a substituted or unsubstituted phenyl group or a naphthyl group.)

（式中、ｎは０または１の整数、Ｒ^１は水素原子、アルキル基または置換もしくは無置換のフェニル基を表わし、Ａｒ^１は置換もしくは未置換のアリール基を表わし、Ｒ^５は置換アルキル基を含むアルキル基、あるいは置換もしくは無置換のアリール基を表わし、Ａは

(Wherein n represents an integer of 0 or 1, R ¹ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted phenyl group, Ar ¹ represents a substituted or unsubstituted aryl group, and R ⁵ represents a substituted alkyl group. Represents an alkyl group containing or a substituted or unsubstituted aryl group, and A represents

、９−アントリル基または置換もしくは無置換のカルバゾリル基を表わし、ここでＲ^２は水素原子、アルキル基、アルコキシ基、ハロゲン原子または

, 9-anthryl group or substituted or unsubstituted carbazolyl group, wherein R ² is a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or

（ただし、Ｒ^３およびＲ^４は置換もしくは無置換のアリール基を示し、Ｒ^３およびＲ^４は同じでも異なっていてもよく、Ｒ^４は環を形成しても良い）を表わし、ｍが２以上のとき、Ｒ^２は同一でも異なっても良い。また、ｎが０のとき、ＡとＲ^１は共同で環を形成しても良い。）

Wherein R ³ and R ⁴ represent a substituted or unsubstituted aryl group, R ³ and R ⁴ may be the same or different, and R ⁴ may form a ring, and m is 2 In the above, R ² may be the same or different. When n is 0, A and R ¹ may form a ring together. )

（式中、Ｒ^１、Ｒ^２およびＲ^３は水素原子、低級アルキル基、低級アルコキシ基、ハロゲン原子またはジアルキルアミノ基を表わし、ｎは０または１を表わす。）

(Wherein R ¹ , R ² and R ³ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom or a dialkylamino group, and n represents 0 or 1)

（式中、Ｒ^１およびＲ^２は置換アルキル基を含むアルキル基、または置換もしくは未置換のアリール基を表わし、Ａは置換アミノ基、置換もしくは未置換のアリール基またはアリル基を表わす。）

(Wherein R ¹ and R ² represent an alkyl group including a substituted alkyl group, or a substituted or unsubstituted aryl group, and A represents a substituted amino group, a substituted or unsubstituted aryl group, or an allyl group.)

（式中、Ｘは水素原子、低級アルキル基またはハロゲン原子を表わし、Ｒは置換アルキル基を含むアルキル基、または置換もしくは無置換のアリール基を表わし、Ａは置換アミノ基または置換もしくは無置換のアリール基を表わす。）

(In the formula, X represents a hydrogen atom, a lower alkyl group or a halogen atom, R represents an alkyl group containing a substituted alkyl group, or a substituted or unsubstituted aryl group, and A represents a substituted amino group or a substituted or unsubstituted aryl group. Represents an aryl group.)

（式中、Ｒ^１は低級アルキル基、低級アルコキシ基またはハロゲン原子を表わし、Ｒ^２、Ｒ^３は同じでも異なっていてもよく、水素原子、低級アルキル基、低級アルコキシ基またはハロゲン原子を表わし、ｌ、ｍ、ｎは０〜４の整数を表わす。）

(Wherein R ¹ represents a lower alkyl group, a lower alkoxy group or a halogen atom, R ² and R ³ may be the same or different, and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom; l, m, and n represent an integer of 0 to 4.)

（式中、Ｒ^１、Ｒ^３およびＲ^４は水素原子、アミノ基、アルコキシ基、チオアルコキシ基、アリールオキシ基、メチレンジオキシ基、置換もしくは無置換のアルキル基、ハロゲン原子または置換もしくは無置換のアリール基を、Ｒ^２は水素原子、アルコキシ基、置換もしくは無置換のアルキル基またはハロゲン原子を表わす。ただし、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４はすべて水素原子である場合は除く。また、ｋ，ｌ，ｍおよびｎは１、２、３または４の整数であり、それぞれが２、３または４の整数の時は、前記Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は同じでも異なっていても良い。）

(Wherein R ¹ , R ³ and R ⁴ are a hydrogen atom, an amino group, an alkoxy group, a thioalkoxy group, an aryloxy group, a methylenedioxy group, a substituted or unsubstituted alkyl group, a halogen atom, or a substituted or unsubstituted group. R ² represents a hydrogen atom, an alkoxy group, a substituted or unsubstituted alkyl group or a halogen atom, except that R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms. K, l, m and n are integers of ¹ , ² , 3 or 4, and when each is an integer of 2, 3 or 4, R ¹ , R ² , R ³ and R ⁴ may be the same May be different.)

（式中、Ａｒは置換基を有してもよい炭素数１８個以下の縮合多環式炭化水素基を表わし、また、Ｒ^１およびＲ^２は水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、アルコキシ基、置換もしくは無置換のフェニル基を表わし、それぞれ同じでも異なっていても良い。ｎは１もしくは２の整数を表わす。）

(In the formula, Ar represents a condensed polycyclic hydrocarbon group having 18 or less carbon atoms which may have a substituent, and R ¹ and R ² are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group. A group, an alkoxy group, a substituted or unsubstituted phenyl group, which may be the same or different, and n represents an integer of 1 or 2.)

（式中、Ａｒは置換もしくは無置換の芳香族炭化水素基を表わし、Ａは

(In the formula, Ar represents a substituted or unsubstituted aromatic hydrocarbon group, and A represents

（ただし、Ａｒ'は置換もしくは無置換の芳香族炭化水素基を表わし、Ｒ^１およびＲ^２は置換もしくは無置換のアルキル基、または置換もしくは無置換のアリール基である。）を表わす。）

(Wherein Ar ′ represents a substituted or unsubstituted aromatic hydrocarbon group, and R ¹ and R ² represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group). )

（式中、Ａｒは置換もしくは無置換の芳香族炭化水素基を、Ｒは水素原子、置換もしくは無置換のアルキル基、または置換もしくは無置換のアリール基を表わす。ｎは０または１、ｍは１または２であって、ｎ＝０、ｍ＝１の場合、ＡｒとＲは共同で環を形成しても良い。）

(In the formula, Ar represents a substituted or unsubstituted aromatic hydrocarbon group, R represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. N is 0 or 1, m is When 1 or 2 and n = 0 and m = 1, Ar and R may form a ring together.)

Examples of the compound represented by the general formula (11) include 9-ethylcarbazole-3-carbaldehyde-1-methyl-1-phenylhydrazone, 9-ethylcarbazole-3-carbaldehyde-1-benzyl-1- Examples include phenylhydrazone and 9-ethylcarbazole-3-carbaldehyde-1,1-diphenylhydrazone.
Examples of the compound represented by the general formula (12) include 4-diethylaminostyryl-β-carbaldehyde-1-methyl-1-phenylhydrazone, 4-methoxynaphthalene-1-carbaldehyde-1-benzyl- 1-phenylhydrazone and the like.
Examples of the compound represented by the general formula (13) include 4-methoxybenzaldehyde-1-methyl-1-phenylhydrazone, 2,4-dimethoxybenzaldehyde-1-benzyl-1-phenylhydrazone, 4-diethylaminobenzaldehyde- 1,1-diphenylhydrazone, 4-methoxybenzaldehyde-1- (4-methoxy) phenylhydrazone, 4-diphenylaminobenzaldehyde-1-benzyl-1-phenylhydrazone, 4-dibenzylaminobenzaldehyde-1,1-diphenylhydrazone and so on.
Examples of the compound represented by the general formula (14) include 1,1-bis (4-dibenzylaminophenyl) propane, tris (4-diethylaminophenyl) methane, 1,1-bis (4-di-). Benzylaminophenyl) propane, 2,2′-dimethyl-4,4′-bis (diethylamino) -triphenylmethane, and the like.
Examples of the compound represented by the general formula (15) include 9- (4-diethylaminostyryl) anthracene and 9-bromo-10- (4-diethylaminostyryl) anthracene.
Examples of the compound represented by the general formula (16) include 9- (4-dimethylaminobenzylidene) fluorene and 3- (9-fluorenylidene) -9-ethylcarbazole.
Examples of the compound represented by the general formula (17) include 1,2-bis (4-diethylaminostyryl) benzene and 1,2-bis (2,4-dimethoxystyryl) benzene.
Examples of the compound represented by the general formula (18) include 3-styryl-9-ethylcarbazole and 3- (4-methoxystyryl) -9-ethylcarbazole.
Examples of the compound represented by the general formula (19) include 4-diphenylaminostilbene, 4-dibenzylaminostilbene, 4-ditolylaminostilbene, 1- (4-diphenylaminostyryl) naphthalene, 1- (4 -Diphenylaminostyryl) naphthalene.
Examples of the compound represented by the general formula (20) include 4′-diphenylamino-α-phenylstilbene and 4′-bis (4-methylphenyl) amino-α-phenylstilbene.
Examples of the compound represented by the general formula (21) include 1-phenyl-3- (4-diethylaminostyryl) -5- (4-diethylaminophenyl) pyrazoline.
Examples of the compound represented by the general formula (22) include 2,5-bis (4-diethylaminophenyl) -1,3,4-oxadiazole, 2-N, N-diphenylamino-5- (4 -Diethylaminophenyl) -1,3,4-oxadiazole, 2- (4-dimethylaminophenyl) -5- (4-diethylaminophenyl) -1,3,4-oxadiazole and the like.
Examples of the compound represented by the general formula (23) include 2-N, N-diphenylamino-5- (N-ethylcarbazol-3-yl) -1,3,4-oxadiazole, 2- ( 4-diethylaminophenyl) -5- (N-ethylcarbazol-3-yl) -1,3,4-oxadiazole.
Examples of the benzidine compound represented by the general formula (24) include N, N′-diphenyl-N, N′-bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-. Examples include diamine, 3,3′-dimethyl-N, N, N ′, N′-tetrakis (4-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine.
Examples of the biphenylylamine compound represented by the general formula (25) include 4′-methoxy-N, N-diphenyl- [1,1′-biphenyl] -4-amine and 4′-methyl-N. , N-bis (4-methylphenyl)-[1,1′-biphenyl] -4-amine, 4′-methoxy-N, N-bis (4-methylphenyl)-[1,1′-biphenyl]- 4-amine, N, N-bis (3,4-dimethylphenyl)-[1,1′-biphenyl] -4-amine and the like.
Examples of the triarylamine compound represented by the general formula (26) include N, N-diphenyl-pyrene-1-amine, N, N-di-p-tolyl-pyrene-1-amine, N, N-di-p-tolyl-1-naphthylamine, N, N-di (p-tolyl) -1-phenanthrylamine, 9,9-dimethyl-2- (di-p-tolylamino) fluorene, N, N , N ′, N′-tetrakis (4-methylphenyl) -phenanthrene-9,10-diamine, N, N, N ′, N′-tetrakis (3-methylphenyl) -m-phenylenediamine, and the like.
Examples of the diolefin aromatic compound represented by the general formula (27) include 1,4-bis (4-diphenylaminostyryl) benzene and 1,4-bis [4-di (p-tolyl) amino. Styryl] benzene.
Examples of the styrylpyrene compound represented by the general formula (28) include 1- (4-diphenylaminostyryl) pyrene and 1- (N, N-di-p-tolyl-4-aminostyryl) pyrene. .

  Examples of the electron transport material include chloroanil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4,5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-indeno4H-indeno [1,2-b] thiophen-4-one, 1,3 , 7-trinitrodibenzothiophene-5,5-dioxide and the like, and the electron transport materials listed in the following general formulas (29), (30) and (31) can be preferably used. These charge transport materials may be used alone or in combination of two or more.

（式中Ｒ^１、Ｒ^２およびＲ^３は水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、アルコキシ基、置換もしくは無置換のフェニル基を表わし、それぞれ同じでも異なっていても良い。）

(Wherein R ¹ , R ² and R ³ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or a substituted or unsubstituted phenyl group, and may be the same or different.)

（式中Ｒ^１、Ｒ^２は水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のフェニル基を表わし、それぞれ同じでも異なっていても良い。）

(Wherein R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group, and may be the same or different.)

（式中Ｒ^１、Ｒ^２およびＲ^３は水素原子、ハロゲン原子、置換もしくは無置換のアルキル基、アルコキシ基、置換もしくは無置換のフェニル基を表わし、それぞれ同じでも異なっていても良い。）

(Wherein R ¹ , R ² and R ³ represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or a substituted or unsubstituted phenyl group, and may be the same or different.)

  As the binder resin, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, Polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin And thermoplastic or thermosetting resins such as phenol resins and alkyd resins.

  The thickness of the charge transport layer is preferably 25 μm or less from the viewpoint of resolution and responsiveness. Regarding the lower limit, although it differs depending on the system to be used (particularly the charging potential), it is preferably 5 μm or more.

  As the solvent used here, tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone and the like are used. The charge transport materials may be used alone or in combination of two or more.

  As the antioxidant that can be used in the present invention, a general antioxidant described later can be used, and (c) hydroquinone-based compounds and (f) hindered amine-based compounds are particularly effective. However, the antioxidant used here differs from the purpose described later and is used only for the protection of alteration of the phthalocyanine compound used in the present invention. For this reason, these antioxidants are preferably contained in the coating solution in the step before containing the phthalocyanine compound of the present invention, and the addition amount is 0.1 to 200 wt% with respect to the phthalocyanine compound. Can produce a sufficient effect.

  For the charge transport layer, a polymer charge transport material having a function as a charge transport material and a function as a binder resin is also preferably used. The charge transport layer composed of these polymer charge transport materials is excellent in wear resistance. As the polymer charge transport material, known materials can be used, and in particular, a polycarbonate containing a triarylamine structure in the main chain and / or side chain is preferably used. Among these, polymer charge transport materials represented by the formulas (I) to (XI) are preferably used. These are illustrated below and specific examples are shown.

式中、Ｒ_１，Ｒ_２，Ｒ_３はそれぞれ独立して置換もしくは無置換のアルキル基又はハロゲン原子、Ｒ_４は水素原子又は置換もしくは無置換のアルキル基、Ｒ_５，Ｒ_６は置換もしくは無置換のアリール基、ｏ，ｐ，ｑはそれぞれ独立して０〜４の整数、ｋ，ｊは組成を表わし、０．１≦ｋ≦１、０≦ｊ≦０．９、ｎは繰り返し単位数を表わし５〜５０００の整数である。Ｘは脂肪族の２価基、環状脂肪族の２価基、または下記一般式で表わされる２価基を表わす。

In the formula, R ₁ , R ₂ and R ₃ are each independently a substituted or unsubstituted alkyl group or a halogen atom, R ₄ is a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₅ and R ₆ are substituted or unsubstituted. Substituted aryl group, o, p, q are each independently an integer of 0-4, k, j are compositions, 0.1 ≦ k ≦ 1, 0 ≦ j ≦ 0.9, n is the number of repeating units Represents an integer of 5 to 5000. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula.

式中、Ｒ_１０１，Ｒ_１０２は各々独立して置換もしくは無置換のアルキル基、アリール基またはハロゲン原子を表わす。ｌ、ｍは０〜４の整数、Ｙは単結合、炭素原子数１〜１２の直鎖状、分岐状もしくは環状のアルキレン基、−Ｏ−，−Ｓ−，−ＳＯ−，−ＳＯ_２−，−ＣＯ−，−ＣＯ−Ｏ−Ｚ−Ｏ−ＣＯ−（式中Ｚは脂肪族の２価基を表わす。）または、

In the formula, R ₁₀₁ and R ₁₀₂ each independently represents a substituted or unsubstituted alkyl group, aryl group or halogen atom. l and m are integers of 0 to 4, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, —O—, —S—, —SO—, —SO ₂ —. , -CO-, -CO-O-Z-O-CO- (wherein Z represents an aliphatic divalent group), or

（式中、ａは１〜２０の整数、ｂは１〜２０００の整数、Ｒ_１０３、Ｒ_１０４は置換または無置換のアルキル基又はアリール基を表わす。）を表わす。ここで、Ｒ_１０１とＲ_１０２，Ｒ_１０３とＲ_１０４は、それぞれ同一でも異なってもよい。

(Wherein, a represents an integer of 1 to 20, b represents an integer of 1 to 2000, and R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or an aryl group). Here, R ₁₀₁ and R ₁₀₂ , R ₁₀₃ and R ₁₀₄ may be the same or different.

式中、Ｒ_７，Ｒ_８は置換もしくは無置換のアリール基、Ａｒ_１，Ａｒ_２，Ａｒ_３は同一あるいは異なるアリレン基を表わす。Ｘ，ｋ，ｊおよびｎは、（Ｉ）式の場合と同じである。

In the formula, R ₇ and R ₈ represent a substituted or unsubstituted aryl group, and Ar ₁ , Ar ₂ , and Ar ₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of formula (I).

式中、Ｒ_９，Ｒ_１０は置換もしくは無置換のアリール基、Ａｒ_４，Ａｒ_５，Ａｒ_６は同一あるいは異なるアリレン基を表わす。Ｘ，ｋ，ｊおよびｎは、（Ｉ）式の場合と同じである。

In the formula, R ₉ and R ₁₀ represent a substituted or unsubstituted aryl group, and Ar ₄ , Ar ₅ , and Ar ₆ represent the same or different arylene groups. X, k, j and n are the same as in the case of formula (I).

式中、Ｒ_１１，Ｒ_１２は置換もしくは無置換のアリール基、Ａｒ_７，Ａｒ_８，Ａｒ_９は同一あるいは異なるアリレン基、ｐは１〜５の整数を表わす。Ｘ，ｋ，ｊおよびｎは、（Ｉ）式の場合と同じである。

In the formula, R ₁₁ and R ₁₂ are substituted or unsubstituted aryl groups, Ar ₇ , Ar ₈ and Ar ₉ are the same or different arylene groups, and p represents an integer of 1 to 5. X, k, j and n are the same as in the case of formula (I).

式中、Ｒ_１３，Ｒ_１４は置換もしくは無置換のアリール基、Ａｒ_１０，Ａｒ_１１，Ａｒ_１２は同一あるいは異なるアリレン基、Ｘ_１，Ｘ_２は置換もしくは無置換のエチレン基、又は置換もしくは無置換のビニレン基を表わす。Ｘ，ｋ，ｊおよびｎは、（Ｉ）式の場合と同じである。

In the formula, R ₁₃ and R ₁₄ are substituted or unsubstituted aryl groups, Ar ₁₀ , Ar ₁₁ and Ar ₁₂ are the same or different arylene groups, X ₁ and X ₂ are substituted or unsubstituted ethylene groups, or substituted or unsubstituted Represents a substituted vinylene group. X, k, j and n are the same as in the case of formula (I).

式中、Ｒ_１５，Ｒ_１６，Ｒ_１７，Ｒ_１８は置換もしくは無置換のアリール基、Ａｒ_１３，Ａｒ_１４，Ａｒ_１５，Ａｒ_１６は同一あるいは異なるアリレン基、Ｙ_１，Ｙ_２，Ｙ_３は単結合、置換もしくは無置換のアルキレン基、置換もしくは無置換のシクロアルキレン基、置換もしくは無置換のアルキレンエーテル基、酸素原子、硫黄原子、ビニレン基を表わし同一であっても異なってもよい。Ｘ，ｋ，ｊおよびｎは、（Ｉ）式の場合と同じである。

In the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are substituted or unsubstituted aryl groups, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆ are the same or different arylene groups, and Y ₁ , Y ₂ and Y ₃ are A single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group may be the same or different. X, k, j and n are the same as in the case of formula (I).

式中、Ｒ_１９，Ｒ_２０は水素原子、置換もしくは無置換のアリール基を表わし，Ｒ_１９とＲ_２０は環を形成していてもよい。Ａｒ_１７，Ａｒ_１８，Ａｒ_１９は同一あるいは異なるアリレン基を表わす。Ｘ，ｋ，ｊおよびｎは、（Ｉ）式の場合と同じである。

In the formula, R ₁₉ and R _{20 each} represent a hydrogen atom or a substituted or unsubstituted aryl group, and R ₁₉ and R ₂₀ may form a ring. Ar ₁₇ , Ar ₁₈ and Ar ₁₉ represent the same or different arylene groups. X, k, j and n are the same as in the case of formula (I).

式中、Ｒ_２１は置換もしくは無置換のアリール基、Ａｒ_２０，Ａｒ_２１，Ａｒ_２２，Ａｒ_２３は同一あるいは異なるアリレン基を表わす。Ｘ，ｋ，ｊおよびｎは、（Ｉ）式の場合と同じである。

In the formula, R ₂₁ represents a substituted or unsubstituted aryl group, and Ar ₂₀ , Ar ₂₁ , Ar ₂₂ , and Ar ₂₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of formula (I).

式中、Ｒ_２２，Ｒ_２３，Ｒ_２４，Ｒ_２５は置換もしくは無置換のアリール基、Ａｒ_２４，Ａｒ_２５，Ａｒ_２６，Ａｒ_２７，Ａｒ_２８は同一あるいは又は異なるアリレン基を表わす。Ｘ，ｋ，ｊおよびｎは、（Ｉ）式の場合と同じである。

In the formula, R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ represent a substituted or unsubstituted aryl group, and Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ and Ar ₂₈ represent the same or different arylene groups. X, k, j and n are the same as in the case of formula (I).

式中、Ｒ_２６，Ｒ_２７は置換もしくは無置換のアリール基、Ａｒ_２９，Ａｒ_３０，Ａｒ_３１は同一あるいは異なるアリレン基を表わす。Ｘ，ｋ，ｊおよびｎは、（Ｉ）式の場合と同じである。

In the formula, R ₂₆ and R ₂₇ represent a substituted or unsubstituted aryl group, and Ar ₂₉ , Ar ₃₀ and Ar ₃₁ represent the same or different arylene groups. X, k, j and n are the same as in the case of formula (I).

（式中、Ａｒ_１、Ａｒ_２、Ａｒ_３、Ａｒ_４およびＡｒ_５は置換もしくは無置換の芳香環基、Ｚは芳香環基または―Ａｒ_６―Ｚａ―Ａｒ_６―を表わし、Ａｒ_６は置換もしくは無置換の芳香環基、ＺａはＯ、Ｓまたはアルキレン基、ＲおよびＲ'は直鎖又は分岐鎖のアルキレン基を表わす。ｍは０または１を表わす。Ｘ，ｋ，ｊおよびｎは、（Ｉ）式の場合と同じである。）

(In the formula, Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ and Ar ₅ represent a substituted or unsubstituted aromatic ring group, Z represents an aromatic ring group or —Ar ₆ —Za—Ar ₆ —, and Ar ₆ represents a substituted group. Or an unsubstituted aromatic ring group, Za represents O, S or an alkylene group, R and R ′ represent a linear or branched alkylene group, m represents 0 or 1, and X, k, j and n represent (Same as in formula (I).)

  The charge transport layer (37) can be formed by dissolving or dispersing the charge transport material alone or in a binder resin and an appropriate solvent, and applying and drying the solution on the charge generation layer. Further, if necessary, two or more kinds of plasticizers, leveling agents, antioxidants and the like can be added.

  As a coating method of the coating liquid obtained as described above, conventional coating methods such as dip coating, spray coating, beat coating, nozzle coating, spinner coating, ring coating, and the like can be used.

  Next, the case where the photosensitive layer has a single layer structure (33) will be described. A photoreceptor in which the above-described charge generating material is dispersed in a binder resin can be used. The photosensitive layer can be formed by dissolving or dispersing a charge generating substance, a charge transporting substance, and a binder resin in a suitable solvent, and applying and drying them. Moreover, a plasticizer, a leveling agent, antioxidant, etc. can also be added as needed.

  As the binder resin, in addition to the binder resin previously mentioned in the charge transport layer (37), the binder resin mentioned in the charge generation layer (35) may be mixed and used. Of course, the polymer charge transport materials mentioned above can also be used favorably. The amount of the phthalocyanine compound with respect to 100 parts by weight of the binder resin is preferably 5 to 40 parts by weight, and the amount of the charge transport material is preferably 0 to 190 parts by weight, and more preferably 50 to 150 parts by weight. The photosensitive layer is formed by dip coating, spray coating, bead coating, a coating solution in which a charge generating material and a binder resin are dispersed together with a charge transporting material using a solvent such as tetrahydrofuran, dioxane, dichloroethane, and cyclohexane. It can be formed by coating with a ring coat or the like. The film thickness of the photosensitive layer is suitably about 5 to 25 μm.

  In the photoreceptor of the present invention, an undercoat layer can be provided between the conductive support (31) and the photosensitive layer. In general, the undercoat layer is mainly composed of a resin. However, considering that the photosensitive layer is coated with a solvent on these resins, the resin may be a resin having high solvent resistance with respect to a general organic solvent. desirable. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. Further, a metal oxide fine powder pigment exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the undercoat layer in order to prevent moire and reduce residual potential.

These undercoat layers can be formed using an appropriate solvent and a coating method like the above-mentioned photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the undercoat layer of the present invention. In addition, in the undercoat layer of the present invention, Al ₂ O ₃ is provided by anodization, organic substances such as polyparaxylylene (parylene), SiO ₂ , SnO ₂ , TiO ₂ , ITO, CeO ₂ A material provided with an inorganic material such as a vacuum thin film can also be used favorably. In addition, known ones can be used. The thickness of the undercoat layer is suitably from 0 to 5 μm.

  In the photoreceptor of the present invention, a protective layer (39) may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer. Materials used for the protective layer (39) include ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether, aryl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone. , Polybutylene, polybutylene terephthalate, polycarbonate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylbenten, polypropylene, polyphenylene oxide, polysulfone, polystyrene, polyarylate, AS resin, butadiene-styrene copolymer, polyurethane , Resins such as polyvinyl chloride, polyvinylidene chloride, and epoxy resin. From the viewpoint of filler dispersibility, residual potential, and coating film defects, polycarbonate or polyarylate is particularly effective and useful.

A filler material is added to the protective layer of the photoreceptor for the purpose of improving the wear resistance.
As a solvent to be used, a solvent used in the charge transport layer (37) such as tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, and acetone can be used. However, a solvent having a high viscosity is preferable at the time of dispersion, but a solvent having high volatility is preferable at the time of coating. When there is no solvent satisfying these conditions, it is possible to use a mixture of two or more solvents having respective physical properties, which may have a great effect on filler dispersibility and residual potential. .

  As a method for forming the protective layer, conventional methods such as dip coating, spray coating, beat coating, nozzle coating, spinner coating, ring coating, etc. can be used. preferable.

  In the photoreceptor of the present invention, an intermediate layer can be provided between the photosensitive layer and the protective layer. In the intermediate layer, a binder resin is generally used as a main component. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As a method for forming the intermediate layer, a generally used coating method as described above is employed. In addition, about 0.05-2 micrometers is suitable for the thickness of an intermediate | middle layer.

In the present invention, in order to improve environmental resistance, in order to prevent a decrease in sensitivity and an increase in residual potential, oxidation is performed on each layer such as a charge generation layer, a charge transport layer, an undercoat layer, a protective layer, and an intermediate layer. Inhibitors, plasticizers, lubricants, UV absorbers and leveling agents can be added. Representative materials of these compounds are described below.
Examples of the antioxidant that can be added to each layer include, but are not limited to, the following.
(A) Phenolic compounds 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, n-octadecyl-3- (4′- Hydroxy-3 ′, 5′-di-t-butylphenol), 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis- (4-ethyl-) 6-t-butylphenol), 4,4′-thiobis- (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), 1,1,3 -Tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxy Benzyl) benzene, te Lakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis (4′-hydroxy-3′-t-butyl) Phenyl) butyric acid] cricol ester, tocopherols and the like.
(B) Paraphenylenediamines N-phenyl-N′-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylene Diamine, N, N′-di-isopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine and the like.
(C) Hydroquinones 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, 2 -(2-octadecenyl) -5-methylhydroquinone and the like.
(D) Organic sulfur compounds Dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like.
(E) Organic phosphorus compounds Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine and the like.

Examples of the plasticizer that can be added to each layer include, but are not limited to, the following.
(A) Phosphate ester plasticizer Triphenyl phosphate, tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, trichloroethyl phosphate, cresyl diphenyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, Triphenyl phosphate etc.
(B) Phthalate ester plasticizers Dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, phthalate Dinonyl acid, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, butyl benzyl phthalate, butyl lauryl phthalate, methyl oleyl phthalate, octyl decyl phthalate, dibutyl fumarate, dioctyl fumarate Such.
(C) Aromatic carboxylic acid ester plasticizers Trioctyl trimellitic acid, tri-n-octyl trimellitic acid, octyl oxybenzoate, and the like.
(D) Aliphatic dibasic ester plasticizer dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, di-n-octyl adipate, adipic acid n-octyl-n-decyl , Diisodecyl adipate, dicapryl adipate, di-2-ethylhexyl azelate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate, di-n-octyl sebacate, di-2-ethylhexyl sebacate, di-2 sebacate -Ethoxyethyl, dioctyl succinate, diisodecyl succinate, dioctyl tetrahydrophthalate, di-n-octyl tetrahydrophthalate and the like.
(E) Fatty acid ester derivatives butyl oleate, glycerin monooleate, methyl acetylricinoleate, pentaerythritol ester, dipentaerythritol hexaester, triacetin, tributyrin and the like.
(F) Oxyacid ester plasticizers Methyl acetyl ricinoleate, butyl acetyl ricinoleate, butyl phthalyl butyl glycolate, tributyl acetyl citrate and the like.
(G) Epoxy plasticizer Epoxidized soybean oil, epoxidized linseed oil, epoxy butyl stearate, decyl epoxy stearate, octyl epoxy stearate, benzyl epoxy stearate, dioctyl epoxy hexahydrophthalate, didecyl epoxy hexahydrophthalate, etc. .
(H) Dihydric alcohol ester plasticizers such as diethylene glycol dibenzoate and triethylene glycol di-2-ethylbutyrate.
(I) Chlorine-containing plasticizer Chlorinated paraffin, chlorinated diphenyl, chlorinated fatty acid methyl, methoxychlorinated fatty acid methyl and the like.
(J) Polyester plasticizer Polypropylene adipate, polypropylene sebacate, polyester, acetylated polyester and the like.
(K) Sulfonic acid derivatives p-toluenesulfonamide, o-toluenesulfonamide, p-toluenesulfoneethylamide, o-toluenesulfoneethylamide, toluenesulfone-N-ethylamide, p-toluenesulfone-N-cyclohexylamide and the like.
(L) Citric acid derivatives Triethyl citrate, triethyl acetyl citrate, tributyl citrate, tributyl acetyl citrate, tri-2-ethylhexyl acetyl citrate, n-octyl decyl acetyl citrate and the like.
(M) Others Terphenyl, partially hydrogenated terphenyl, camphor, 2-nitrodiphenyl, dinonylnaphthalene, methyl abietate and the like.

Examples of the lubricant that can be added to each layer include, but are not limited to, the following.
(A) Hydrocarbon compound Liquid paraffin, paraffin wax, microwax, low-polymerized polyethylene and the like.
(B) Fatty acid compounds Lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and the like.
(C) Fatty acid amide compounds Stearylamide, palmitylamide, oleinamide, methylenebisstearamide, ethylenebisstearamide and the like.
(D) Ester compounds Lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, fatty acid polyglycol esters, and the like.
(E) Alcohol compounds Cetyl alcohol, stearyl alcohol, ethylene glycol, polyethylene glycol, polyglycerol and the like.
(F) Metal soap Lead stearate, cadmium stearate, barium stearate, calcium stearate, zinc stearate, magnesium stearate and the like.
(G) Natural wax Carnauba wax, candelilla wax, beeswax, whale wax, ibotarou, montan wax and the like.
(H) Others Silicone compounds, fluorine compounds, etc.

Examples of the ultraviolet absorber that can be added to each layer include, but are not limited to, the following.
(A) Benzophenone series 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ', 4-trihydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4- Such as methoxybenzophenone.
(B) Salsylate type Phenyl salsylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like.
(C) Benzotriazole series (2′-hydroxyphenyl) benzotriazole, (2′-hydroxy5′-methylphenyl) benzotriazole, (2′-hydroxy5′-methylphenyl) benzotriazole, (2′-hydroxy3) '-Tert-butyl-5'-methylphenyl) 5-chlorobenzotriazole (d) cyanoacrylate series ethyl-2-cyano-3,3-diphenyl acrylate, methyl 2-carbomethoxy 3 (paramethoxy) acrylate, and the like.
(E) Quencher (metal complex)
Nickel (2,2′thiobis (4-t-octyl) phenolate) normal butylamine, nickel dibutyldithiocarbamate, nickel dibutyldithiocarbamate, cobalt dicyclohexyldithiophosphate and the like.
(F) HALS (hindered amine)
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6 6-tetramethylpyridine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy- 2,2,6,6-tetramethylpiperidine and the like.

Next, the electrophotographic method and the electrophotographic apparatus of the present invention will be described in detail with reference to the drawings.
FIG. 6 is a schematic diagram for explaining the electrophotographic process and the electrophotographic apparatus of the present invention, and the following examples also belong to the category of the present invention.
In FIG. 6, the photoreceptor (1) is provided with at least a photosensitive layer, and the outermost surface layer contains a filler. The photosensitive member (1) has a drum shape, but may be a sheet or an endless belt. The charging charger (3), pre-transfer charger (7), transfer charger (10), separation charger (11), and pre-cleaning charger (13) include corotron, scorotron, solid state charger, and charging. A roller etc. are used and a well-known means can be used.
As the transfer means, the above charger can be generally used. However, as shown in the figure, a combination of the transfer charger (10) and the separation charger (11) is effective.
Further, light sources such as an image exposure unit (5) and a charge removal lamp (2) include fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light emitting diodes (LEDs), semiconductor lasers (LD), and electroluminescence (EL). ) And other luminescent materials can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
In addition to the steps shown in FIG. 6, the light source and the like are provided with a transfer step, a static elimination step, a cleaning step, a pre-exposure step, and the like using light irradiation, so that the photosensitive member is irradiated with light.

  The toner developed on the photoconductor (1) by the developing unit (6) is transferred to the transfer paper (9), but not all is transferred and remains on the photoconductor (1). Toner is also produced. Such toner is removed from the photoreceptor by the fur brush (14) and the cleaning blade (15). Cleaning may be performed only with a cleaning brush, and a known brush such as a fur brush or a mag fur brush is used as the cleaning brush.

When the electrophotographic photosensitive member is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner.
A known method is applied to the developing unit, and a known method is also used for the charge eliminating unit.

  FIG. 7 shows another example of the electrophotographic process according to the present invention. The photosensitive member (21) has at least a photosensitive layer, and further contains a filler on the outermost surface layer. The photosensitive member (21) is driven by driving rollers (22a) and (22b) and charged by a charger (23), and a light source (24). Image exposure, development (not shown), transfer using a charger (25), pre-cleaning exposure using a light source (26), cleaning using a brush (27), and static elimination using a light source (28) are repeated. In FIG. 7, the photoconductor (21) (of course, the support is translucent in this case) is irradiated with pre-cleaning exposure light from the support side.

  The above illustrated electrophotographic process is illustrative of an embodiment of the present invention, and of course other embodiments are possible. For example, in FIG. 7, the pre-cleaning exposure is performed from the support side, but this may be performed from the photosensitive layer side, or image exposure and neutralization light irradiation may be performed from the support side.

  On the other hand, the light irradiation process is illustrated as image exposure, pre-cleaning exposure, and static elimination exposure. In addition, a pre-transfer exposure, a pre-exposure of image exposure, and other known light irradiation processes are provided to light the photosensitive member. Irradiation can also be performed.

  The image forming means as described above may be fixedly incorporated in a copying apparatus, a facsimile, or a printer, but may be incorporated in these apparatuses in the form of a process cartridge. A process cartridge is a single device (part) that contains a photosensitive member and includes a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, and a charge eliminating unit. There are many shapes and the like of the process cartridge, but a general example is shown in FIG. The photoreceptor (16) has at least a photosensitive layer on a conductive support and contains a filler in the outermost surface layer.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not restrict | limited by an Example. All parts are parts by weight.
Example 1
An undercoat layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following composition are sequentially applied onto an aluminum cylinder by dip coating and dried to obtain a 3.5 μm undercoat layer, 0. A 2 μm charge generation layer and a 23 μm charge transport layer were formed (photoreceptor 1).
◎ Undercoat layer coating solution Titanium dioxide powder: 400 parts Melamine resin: 65 parts Alkyd resin: 120 parts 2-butanone: 400 parts ◎ Charge generation layer coating solution Compound No. 1-1 porphyrin compound: 12 parts Polyvinyl butyral: 5 parts 2-butanone: 200 parts Cyclohexanone: 400 parts Charge transport layer coating solution Polycarbonate resin (Z Polyca, manufactured by Teijin Chemicals): 10 parts Charge transport of the following structural formula Substance: 100 parts

テトラヒドロフラン：１００部

Tetrahydrofuran: 100 parts

  The electrophotographic photosensitive member produced as described above is mounted on an electrophotographic process cartridge, the charging method is a corona charging method (scorotron type), and the image exposure light source is a 780 nm semiconductor laser (LD) manufactured by Ricoh imgio MF2200. After setting the dark part potential to 800 (-V) with a remodeling machine, repeated tests corresponding to printing of 100,000 sheets in total were performed. The dark portion potential and the light portion potential after the printing equivalent to 100,000 sheets printing were evaluated. The results are shown in Table 5.

Examples 2-8
In Example 1, Exemplified Compound No. Except having used the compound shown in Table 5 as the porphyrin compound of 1-1, it carried out similarly to Example 1, and produced and evaluated the electrophotographic photoreceptors 2-8. The results are also shown in Table 5.

Examples 9-16
Electrophotographic photoreceptors 9 to 16 were prepared and evaluated in the same manner as in Example 1 except that the charge transport layer coating solution in Example 1 was changed to the following composition. The results are also shown in Table 6.
Charge transport layer coating solution Polycarbonate resin (A-Polyca, Teijin Chemicals): 10 parts Charge transport material of the following structural formula: 9 parts

テトラヒドロフラン：１００部

Tetrahydrofuran: 100 parts

Example 17
An electrophotographic photosensitive member 17 was prepared and evaluated in the same manner as in Example 1 except that the charge generation layer coating solution in Example 1 was changed to one having the following composition. The results are also shown in Table 7.
Charge generation layer coating solution Compound No. 1-8 porphyrin compound: 7 parts Oxotitanium phthalocyanine having the powder XD spectrum shown in FIG. 9: 5 parts Polyvinyl butyral: 5 parts 2-butanone: 200 parts Cyclohexanone: 400 parts

Example 18
No. 17 in Example 17. No. 1-8 porphyrin compound No. An electrophotographic photoreceptor 18 was prepared and evaluated in the same manner as in Example 17 except that the porphyrin compound was changed to 2-8. The results are also shown in Table 7.

Example 19
No. 17 in Example 17. No. 1-8 porphyrin compound No. An electrophotographic photoreceptor 19 was prepared and evaluated in the same manner as in Example 17 except that the porphyrin compound was changed to 3-8. The results are also shown in Table 7.

Example 20
No. 17 in Example 17. No. 1-8 porphyrin compound No. An electrophotographic photoreceptor 20 was produced and evaluated in the same manner as in Example 17 except that the porphyrin compound was changed to 4-8. The results are also shown in Table 7.

Example 21
In Example 1, the electrophotographic photosensitive member 21 was prepared and evaluated in the same manner as in Example 1 except that the charge transport material and binder resin contained in the charge transport layer were changed to the following materials. The results are also shown in Table 7.
Polymer charge transport material of the following structural formula: 19 parts

Comparative Example 1
A comparative electrophotographic photosensitive member 1 was prepared and evaluated in the same manner as in Example 1 except that the porphyrin compound in Example 1 was changed to the oxo titanyl phthalocyanine compound having the powder XD spectrum shown in FIG. The results are shown in Table 8.

Comparative Example 2
In Example 17, compound no. A comparative electrophotographic photoreceptor 2 was prepared and evaluated in the same manner as in Example 17 except that the 1-8 porphyrin compound was changed to the following hindered amine antioxidant. The results are shown in Table 8.

  From the above evaluation results, it was confirmed that the photoreceptor containing the porphyrin compound of the present invention has little decrease in dark portion potential and increase in bright portion potential even after printing 100,000 sheets. On the other hand, the comparative photoreceptor 1 had no problem at the initial stage, but the dark portion potential was remarkably lowered after printing 100,000 sheets. Further, it can be seen that the comparative photosensitive member 2 has a high bright portion potential from the beginning, and the light attenuation characteristic (sensitivity characteristic) is extremely poor.

Examples 22 to 24, Comparative Example 3
Further, the electrophotographic photoreceptors 1, 17, 21 and the comparative photoreceptor 1 of the present invention were left in a desiccator adjusted to a nitrogen oxide (NOx) gas concentration of 50 ppm for 4 days, and the dark portion potential evaluation before and after was performed. It was.

  From the evaluation results shown in Table 9, it can be seen that the resistance to oxidizing gas, that is, the suppression of dark portion potential reduction is greatly improved by incorporating the porphyrin compound of the present invention in the photoreceptor. On the other hand, it can be seen that the comparative photosensitive member 1 has a significant dark potential drop due to the oxidizing gas.

1 is an example of a cross-sectional view of an electrophotographic photosensitive member of the present invention. It is another example of sectional drawing of the electrophotographic photosensitive member of this invention. It is another example of sectional drawing of the electrophotographic photosensitive member of this invention. It is another example of sectional drawing of the electrophotographic photosensitive member of this invention. It is another example of sectional drawing of the electrophotographic photosensitive member of this invention. It is the schematic which shows an example of the electrophotographic process and electrophotographic apparatus of this invention. It is the schematic which shows the other example of the electrophotographic process and electrophotographic apparatus of this invention. FIG. 2 is a schematic diagram illustrating an example of a process cartridge for an image forming apparatus according to the present invention. It is a figure which shows the XD spectrum of the oxotitanium phthalocyanine used in the Example. It is a figure which shows the XD spectrum of the oxo titanyl phthalocyanine used by the comparative example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Static elimination lamp 3 Charger 4 Eraser 5 Image exposure part 6 Developing unit 7 Pre-transfer charger 8 Registration roller 9 Transfer paper 10 Transfer charger 11 Separation charger 12 Separation claw 13 Pre-cleaning charger 14 Fur brush 15 Cleaning blade 16 Photoconductor 17 Charging Charger 18 Cleaning Brush 19 Image Exposure Unit 20 Developing Roller 21 Photoconductor 22a Driving Roller 22b Driving Roller 23 Charging Charger 24 Image Exposure Source 25 Transfer Charger 26 Pre-Cleaning Exposure 27 Cleaning Brush 28 Static Discharge Light Source 31 Conductive Support 33 Photosensitive Layer 35 charge generation layer 37 charge transport layer 39 protective layer

Claims (9)

An electrophotographic photoreceptor, wherein a photosensitive layer containing at least one porphyrin compound represented by the following general formula (1) as a component is formed on a conductive support.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are substituted or unsubstituted alkyl groups, or substituents represented by the following general formula Y,

(In the general formula Y, R ⁹ is a substituted or unsubstituted alkylene group. Also, R ¹⁰ and R ¹¹ are substituted or unsubstituted alkyl groups, substituted or unsubstituted aromatic hydrocarbon ring groups. And each of R ¹⁰ and R ¹¹ is a substituted or unsubstituted alkyl group, and R ¹⁰ and R ¹¹ are bonded to each other and contain a nitrogen atom. A substituted or unsubstituted heterocyclic group may be formed), which may be the same or different. However, at least one of R ^{1 to} R ⁸ is the substituent Y. X represents an oxygen atom or a sulfur atom. M represents _{H 2, Cu, TiO, GaCl} , the GaOH. ] 1. An electrophotographic photoreceptor, wherein a photosensitive layer containing at least one porphyrin compound represented by the following general formula (2) as a component is formed on a conductive support.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are a substituted or unsubstituted alkyl group, or a substituent represented by the following general formula Y,

(In the general formula Y, R ⁹ represents a substituted or unsubstituted alkylene group. R ¹⁰ and R ¹¹ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon ring group. May be the same or different, provided that any one of R ¹⁰ and R ¹¹ is a substituted or unsubstituted alkyl group, and R ¹⁰ and R ¹¹ are substituted or substituted with each other and containing a nitrogen atom. An unsubstituted heterocyclic group may be formed), which may be the same or different. However, at least one of R ^{1 to} R ⁸ is the substituent Y. M represents _{H 2, Cu, TiO, GaCl} , the GaOH. ] A photosensitive member for electrophotography, wherein a photosensitive layer containing at least one porphyrin compound represented by the following general formula (3) as a component is formed on a conductive support.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are a substituted or unsubstituted alkyl group, or a substituent represented by the following general formula Y,

(In the general formula Y, R ⁹ represents a substituted or unsubstituted alkylene group. R ¹⁰ and R ¹¹ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic hydrocarbon ring group. , Which may be the same or different, provided that any one of R ¹⁰ and R ¹¹ is a substituted or unsubstituted alkyl group, and R ¹⁰ and R ¹¹ are substituted or substituted with each other and containing a nitrogen atom. An unsubstituted heterocyclic group may be formed), which may be the same or different. However, at least one of R ^{1 to} R ⁸ is the substituent Y. X represents an oxygen atom or a sulfur atom. M represents _{H 2, Cu, TiO, GaCl} , the GaOH. ] A photosensitive member for electrophotography, wherein a photosensitive layer containing at least one porphyrin compound represented by the following general formula (4) as a component is formed on a conductive support.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are a substituted or unsubstituted alkyl group, or a substituent represented by the following general formula Y,

(In the general formula Y, R ⁹ is a substituted or unsubstituted alkylene group. Also, R ¹⁰ and R ¹¹ are substituted or unsubstituted alkyl groups, substituted or unsubstituted aromatic hydrocarbon ring groups. And each of R ¹⁰ and R ¹¹ is a substituted or unsubstituted alkyl group, and R ¹⁰ and R ¹¹ are bonded to each other and contain a nitrogen atom. A substituted or unsubstituted heterocyclic group may be formed), which may be the same or different. M represents _{H 2, Cu, TiO, GaCl} , the GaOH. ] 5. The electrophotographic photosensitive member according to claim 1, wherein at least charging, image exposure, development, and transfer are repeatedly performed on the electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to claim 1. And an electrophotographic method. A so-called digital electronic device in which at least charging, image exposure, development, and transfer are repeatedly performed on an electrophotographic photosensitive member, and an electrostatic latent image is written on the photosensitive member by an LD or LED during image exposure. 5. An electrophotographic method according to claim 1, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 1 to 4. 5. An electrophotographic apparatus comprising at least a charging unit, an image exposing unit, a developing unit, a transferring unit, and an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is any one of claims 1 to 4. An electrophotographic apparatus characterized by being a body. In an electrophotographic apparatus comprising at least a charging unit, an image exposing unit, a developing unit, a transferring unit, and an electrophotographic photosensitive member, an electrostatic latent image is formed on the photosensitive member by using an LD or an LED as the image exposing unit. 5. A so-called digital electrophotographic apparatus in which writing is performed, wherein the electrophotographic photoreceptor is the electrophotographic photoreceptor according to any one of claims 1 to 4. An electrophotographic photosensitive member comprising at least an electrophotographic photosensitive member, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 1 to 4. Process cartridge for equipment.

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