JP4741392B2 - Image forming apparatus and process cartridge - Google Patents

Description

  The present invention relates to an image forming apparatus and a process cartridge.

  In recent years, there has been a remarkable development of information processing system machines using electrophotography. In particular, an optical printer that converts information into a digital signal and records information by light has a remarkable improvement in print quality and reliability. This digital recording technique is applied not only to printers but also to ordinary copying machines, and so-called digital copying machines have been developed. In addition, since a variety of information processing functions are added to a conventional copying machine equipped with this digital recording technology for analog copying, it is expected that its demand will increase further in the future. Further, with the spread of personal computers and the improvement in performance, the progress of digital color printers for performing color output of images and documents is rapidly progressing.

  In recent years, the above-described printers and copiers are desired to be smaller, faster, and higher in image quality.

  There are several problems related to miniaturization and high speed, but one of them is a problem of a writing system. In the case of a semiconductor laser (LD) light source that has been used so far, it is necessary to scan the beam in the longitudinal direction of the photosensitive member, and scanning has been performed by a polygon mirror. In this case, it is necessary to rotate the polygon mirror at a very high speed, and the upper limit of the number of rotations is the rate limiting of the process speed. The high-speed rotation of the polygon mirror not only determines the upper limit of the process speed, but also causes vibrations in the entire apparatus due to the high-speed rotation, which is a major obstacle in improving image quality.

  In response to this problem, a technology that uses multiple optical systems or a technology that multiplies LDs has been developed, but this not only complicates the entire device and increases costs, but also increases the size of the optical system. This is in a direction opposite to the downsizing of the image forming apparatus.

  In recent years, a writing system using LEDs has been used to deal with such problems (see Patent Documents 1 and 2). In such an optical system, the LEDs are formed in an array and arranged in the longitudinal direction of the photoconductor, so that the longitudinal direction of the photoconductor can be simultaneously written in a line and the writing speed is greatly improved. be able to. Further, since writing from the LED head to the photosensitive member can be performed with at least one lens, the optical system itself can be made very compact, which greatly contributes to the development of a compact and high-speed device.

  In addition, when using LEDs, the distance between the light source and the photosensitive member can be arranged at a short distance, so that it is possible to design an optical system that takes advantage of the lens characteristics, and high-density writing is possible. Can be output.

In order to reduce the size of the apparatus, it is indispensable to reduce the diameter of the photoreceptor. When the photosensitive member has a small diameter, the time from the exposure unit to the development unit is shortened in the image forming process. Therefore, the photosensitive member needs to be a highly sensitive photosensitive member that rapidly attenuates light when exposed from a charged state. In addition, in order to continue outputting high-quality images even after repeated use, it is also important that the characteristics (chargeability, sensitivity, residual potential) of the photoreceptor are stably maintained, and abnormal images such as background stains do not occur. It is.
JP 2004-163497 A JP 2001-042554 A

  An object of the present invention is to provide an image forming apparatus and a process cartridge capable of outputting a high-quality image over a long period of time in view of the problems of the above-described conventional technology.

  As a result of intensive studies to solve the above-mentioned problems, the inventors have used a photoconductor containing a specific compound in a photosensitive layer as an exposure unit in an image forming apparatus using an LED, and thereby, for a long period of time, high quality. It has been found that an image forming apparatus capable of outputting a simple image can be provided.

  Specifically, a photoconductor, a charging unit that charges the photoconductor, an exposure unit that exposes the charged photoconductor using a light emitting diode (LED) to form an electrostatic latent image, and An image forming apparatus having at least developing means for developing an electrostatic latent image and transfer means for transferring the developed image, wherein the photoreceptor has at least a photosensitive layer on a conductive support, The photosensitive layer comprises a charge generating material and a general formula (1)

（式中、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子、置換又は無置換のアルキル基、置換又は無置換のシクロアルキル基及び置換又は無置換のアラルキル基からなる群より選択される官能基を表し、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９及びＲ_１０は、それぞれ独立に、水素原子、ハロゲン基、シアノ基、ニトロ基、アミノ基、水酸基、置換又は無置換のアルキル基、置換又は無置換のシクロアルキル基及び置換又は無置換のアラルキル基からなる群より選択される官能基を表す。）
又は一般式（２）

Wherein R ₁ and R ₂ are each independently a functional group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aralkyl group. R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, halogen group, cyano group, nitro group, amino group, hydroxyl group, This represents a functional group selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aralkyl group.
Or general formula (2)

（式中、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子、置換又は無置換のアルキル基、置換又は無置換のシクロアルキル基及び置換又は無置換のアラルキル基からなる群より選択される官能基を表し、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９、Ｒ_１０、Ｒ_１１、Ｒ_１２、Ｒ_１３及びＲ_１４は、それぞれ独立に、水素原子、ハロゲン基、シアノ基、ニトロ基、アミノ基、水酸基、置換又は無置換のアルキル基、置換又は無置換のシクロアルキル基及び置換又は無置換のアラルキル基からなる群より選択される官能基を表し、ｎは、１以上１００以下の整数を表す。）
で表される電子輸送材料を含有することを特徴とする画像形成装置を用いることで、長期に亘り、高品位な画像を出力することができる。

Wherein R ₁ and R ₂ are each independently a functional group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aralkyl group. R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydrogen atom, halogen group And a functional group selected from the group consisting of a cyano group, a nitro group, an amino group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aralkyl group, 1 represents an integer of 1 to 100)
A high-quality image can be output over a long period of time by using an image forming apparatus characterized by containing an electron transport material represented by

  In the present invention, an LED is used as the exposure means. When an LED is used, the optical system can be made smaller and the apparatus can be miniaturized compared to an LD light source that uses a polygon mirror. Also, by arranging the LEDs in an array in the longitudinal direction of the photoconductor, writing can be performed in a line with respect to the rotation of the photoconductor, so that even if the linear velocity of the photoconductor increases, there is a margin for writing. The degree is high. Therefore, by using an LED as the exposure unit, a small and high-speed image forming apparatus can be obtained.

  In addition, since the electron transport material represented by the general formula (1) or (2) used in the present invention exhibits a very excellent electron transport property, it can be contained in the photosensitive layer as a charge transport material. It becomes a highly sensitive photoconductor. Therefore, stable image formation is possible even when the photosensitive member has a small diameter for downsizing the apparatus. In addition, a photoreceptor using an electron transport material represented by the general formula (1) or (2) as a charge transport material has not only sensitivity but also good chargeability and a small residual potential accumulation. Furthermore, since the change in characteristics is small even after repeated use, a high-quality image can be output over a long period of time.

  Furthermore, the characteristics of the charge generation material are improved by using a specific material. In the present invention, a known material can be used as the charge generation material, but among them, a material having a phthalocyanine structure is preferable in view of the combination with the electron transport material used in the present invention.

  Among them, in particular, a general formula having titanium as a central metal

に示すようなチタニルフタロシアニンとすることによって、特に感度が高い感光体とすることができ、画像形成装置として、小型化、高速化をより一層図ることが可能となる。

By using the titanyl phthalocyanine as shown in (2), it is possible to obtain a photosensitive body with particularly high sensitivity, and it is possible to further reduce the size and speed of the image forming apparatus.

  References relating to the synthesis method and electrophotographic properties of titanyl phthalocyanine include, for example, JP-A-57-148745, JP-A-59-36254, JP-A-59-44054, JP-A-59-31965. JP, 61-239248, 62-67094, etc. are mentioned. In addition, various crystal systems are known for titanyl phthalocyanine, such as JP 59-49544, JP 59-166959, JP 61-239248, JP 62-67094. JP, 63-366, JP 63-116158, JP 64-17066, 2001-19871, etc. each describe titanyl phthalocyanine having a different crystal form. Yes.

  Of these crystal forms, titanyl phthalocyanine having a maximum diffraction peak at 27.2 ° with a Bragg angle 2θ exhibits particularly excellent sensitivity characteristics and is used favorably. In particular, it has a maximum diffraction peak at 27.2 ° described in JP-A-2001-19871, and further has main peaks at 9.4 °, 9.6 °, and 24.0 °, High sensitivity is achieved by using titanyl phthalocyanine which has a peak at 7.3 ° as the diffraction peak at the lowest angle and does not have a peak between 7.4 ° and 9.4 °. Thus, it is possible to obtain a stable photoconductor whose chargeability is not easily lowered even when used repeatedly.

  Since the electron transporting material represented by the general formula (1) or (2) exhibits electron transporting properties, the laminated structure in the case where the photosensitive layer is provided in the order of the charge generation layer and the charge transport layer from the support side. Is a positively charged photoconductor. In addition, when the photosensitive layer is used in a single layer configuration, it can be used in both positive and negative charges by using a hole transport material in combination, but the positive charge is more stable in chargeability, This is preferable because less oxidizing gas is generated (about 1/10 of negative charging).

That is, this invention consists of the following aspects.
(1) A photosensitive member, a charging unit that charges the photosensitive member, an exposure unit that exposes the charged photosensitive member using a light emitting diode to form an electrostatic latent image, and the electrostatic latent image An image forming apparatus having at least a developing unit for developing and a transferring unit for transferring the developed image, wherein the photosensitive member has at least a photosensitive layer on a conductive support, and the photosensitive layer has a charge. An image forming apparatus comprising a generating material and an electron transport material represented by the general formula (1).
(2) a photosensitive member, a charging unit that charges the photosensitive member, an exposure unit that exposes the charged photosensitive member using a light emitting diode to form an electrostatic latent image, and the electrostatic latent image An image forming apparatus having at least a developing unit for developing and a transferring unit for transferring the developed image, wherein the photosensitive member has at least a photosensitive layer on a conductive support, and the photosensitive layer has a charge. Generating material and general formula (2)
An image forming apparatus comprising: an electron transport material represented by:
(3) The image forming apparatus according to (1) or (2), wherein the charge generation material is phthalocyanine.
(4) The image forming apparatus according to (3), wherein the phthalocyanine is titanyl phthalocyanine.
(5) The titanyl phthalocyanine has a maximum diffraction peak at 27.2 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray of CuKα, 9.4 °, 9.6 It has a peak at ° and 24.0 °, a peak at the lowest angle side at 7.3 °, and no peak between 7.3 ° and 9.4 ° The image forming apparatus according to (4).
(6) The photosensitive layer has the general formula (3)

（式中、Ｒ_１５及びＲ_１６は、それぞれ独立に、水素原子、置換又は無置換のアルキル基、置換又は無置換のシクロアルキル基及び置換又は無置換のアラルキル基からなる群より選択される官能基を表し、Ｒ_１７、Ｒ_１８、Ｒ_１９及びＲ_２０は、それぞれ独立に水素原子、ハロゲン基、シアノ基、ニトロ基、アミノ基、水酸基、置換又は無置換のアルキル基、置換又は無置換のシクロアルキル基及び置換又は無置換のアラルキル基からなる群より選択される官能基を表す。）
で表される電子輸送材料をさらに含有することを特徴とする（１）乃至（５）のいずれか一項に記載の画像形成装置。
（７）前記帯電手段は、前記感光体を正に帯電することを特徴とする（１）乃至（６）のいずれか一項に記載の画像形成装置。
（８）前記感光体を複数有し、前記転写手段は、該複数の感光体に現像された像を順次転写して重ね合わせることを特徴とする（１）乃至（７）のいずれか一項に記載の画像形成装置。
（９）感光体を少なくとも有し、画像形成装置本体に着脱可能であるプロセスカートリッジにおいて、該画像形成装置は、（１）乃至（８）のいずれか一項に記載の画像形成装置であることを特徴とするプロセスカートリッジ。

Wherein R ₁₅ and R ₁₆ are each independently a functional group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aralkyl group. R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ each independently represents a hydrogen atom, a halogen group, a cyano group, a nitro group, an amino group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group This represents a functional group selected from the group consisting of a cycloalkyl group and a substituted or unsubstituted aralkyl group.)
The image forming apparatus according to any one of (1) to (5), further including an electron transport material represented by:
(7) The image forming apparatus according to any one of (1) to (6), wherein the charging unit charges the photoconductor positively.
(8) There are a plurality of the photoconductors, and the transfer unit sequentially transfers and superimposes the developed images on the plurality of photoconductors. The image forming apparatus described in 1.
(9) In a process cartridge having at least a photoconductor and removable from the main body of the image forming apparatus, the image forming apparatus is the image forming apparatus according to any one of (1) to (8). Process cartridge characterized by.

  According to the present invention, it is possible to provide an image forming apparatus and a process cartridge capable of outputting a high-quality image over a long period of time.

  Next, the best mode for carrying out the present invention will be described.

  Hereinafter, the image forming apparatus of the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a diagram showing an example of an image forming apparatus according to the present invention, and modifications as will be described later also belong to the category of the present invention.

  In FIG. 1, a photoreceptor 11 has at least a photosensitive layer on a conductive support, and includes at least a charge generation material and an electron transport material represented by the general formula (1) or (2) in the photosensitive layer. . The photoconductor 11 has a drum shape, but may be a sheet shape or an endless belt shape.

  An LED is used for the exposure means 13. Since the LEDs can be arranged in an array in the longitudinal direction of the photosensitive member, writing can be performed in a line with respect to the rotation of the photosensitive member. Therefore, even when the linear velocity of the photosensitive member is increased, writing is possible. It has a high margin and is an effective means for speeding up the apparatus. At this time, in order to focus the light emission of the LED on the surface of the photoconductor, writing light is applied to the surface of the photoconductor via a focusing lens array or the like.

  As the charging means 12, known means such as a corotron, a scorotron, a solid state charger (solid state charger), and a charging roller are used.

  The transfer means 16 may be a known charger such as a corotron, scorotron, solid state charger, or charging roller. A combination of a transfer charger and a separation charger is effective. .

  Examples of the light source used for the charge eliminating means 1A include fluorescent materials, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light emitting diodes (LEDs), semiconductor lasers (LDs), electroluminescence (ELs) and the like in general. it can. 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.

  The toner 15 developed on the photoconductor 11 by the developing means 14 is transferred to the image receiving medium 18, but not all is transferred, and some toner remains on the photoconductor 11. Such toner is removed from the photoreceptor 11 by the cleaning means 17. The cleaning means 17 may be a rubber cleaning blade, a brush such as a fur brush, a mag fur brush, or the like.

  FIG. 2 shows another example of the image forming apparatus of the present invention. In FIG. 2, a photoreceptor 11 has at least a photosensitive layer on a conductive support, and includes at least a charge generating material and an electron transport material represented by the general formula (1) or (2) in the photosensitive layer. An endless belt.

  Driven by driving means 1C, charged by charging means 12, image exposure by exposure means 13, development (not shown), transfer by transfer means 16, exposure before cleaning by pre-cleaning exposure means 1B, cleaning by cleaning means 17, and charge removal The charge removal by means 1A is repeated. In FIG. 2, light irradiation for pre-cleaning exposure is performed from the support side of the photoreceptor (in this case, the support is translucent).

  The image forming process described above exemplifies the embodiment of the present invention, and other embodiments are of course possible. For example, in FIG. 2, 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, the pre-transfer exposure, image exposure pre-exposure and other known light irradiation processes are provided to irradiate the photoconductor. Can also be done.

  Further, the image forming means as described above may be fixedly incorporated in a copying machine, 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. Although there are many shapes and the like of the process cartridge, FIG. 3 shows an example of the process cartridge of the present invention. Also in this case, the photoreceptor 11 has at least a photosensitive layer on a conductive support, and includes at least a charge generation material and an electron transport material represented by the general formula (1) or (2) in the photosensitive layer. . The photoconductor 11 has a drum shape, but may be a sheet shape or an endless belt shape.

  FIG. 4 shows another example of the image forming apparatus of the present invention. In this image forming apparatus, around the photosensitive member 11, a charging unit 12, an exposure unit 13, a developing unit 14Bk for each color toner of black (Bk), cyan (C), magenta (M), and yellow (Y), 14C, 14M and 14Y, an intermediate transfer belt 1F which is an intermediate transfer member, and a cleaning unit 17 are arranged in this order. Here, the subscripts Bk, C, M, and Y shown in the figure correspond to the color of the toner described above, and are added as necessary and omitted as appropriate.

  The photoreceptor 11 has at least a photosensitive layer on a conductive support, and includes at least a charge generation material and an electron transport material represented by the general formula (1) or (2) in the photosensitive layer. Each color developing means 14Bk, 14C, 14M and 14Y can be controlled independently, and only the color developing means for image formation is driven. The toner image formed on the photoreceptor 11 is transferred onto the intermediate transfer belt 1F by the first transfer unit 1D disposed inside the intermediate transfer belt 1F. The first transfer unit 1D is disposed so as to be able to come into contact with and separate from the photoconductor 11, and the intermediate transfer belt 1F is brought into contact with the photoconductor 11 only during the transfer operation. Each color image is sequentially formed, and the toner images superimposed on the intermediate transfer belt 1F are collectively transferred to the image receiving medium 18 by the second transfer unit 1E, and then fixed by the fixing unit 19 to form an image. The The second transfer unit 1E is also arranged so as to be able to contact and separate from the intermediate transfer belt 1F, and abuts on the intermediate transfer belt 1F only during the transfer operation.

  In the transfer drum type image forming apparatus, since the toner images of the respective colors are sequentially transferred onto the transfer material electrostatically attracted to the transfer drum, there is a limitation on the transfer material that cannot be printed on cardboard, as shown in FIG. Such an intermediate transfer type image forming apparatus is characterized in that the toner images of the respective colors are superimposed on the intermediate transfer body 1F, so that the transfer material is not limited. Such an intermediate transfer method is not limited to the apparatus shown in FIG. 4, but can be applied to apparatuses shown in FIGS. 1, 2, and 3 and FIG. 5 (a specific example is shown in FIG. 6) described later.

  FIG. 5 shows another example of the image forming apparatus of the present invention. This image forming apparatus is a type that uses four colors of yellow (Y), magenta (M), cyan (C), and black (Bk) as toner, and an image forming unit is provided for each color. In addition, photoconductors 11Y, 11M, 11C, and 11Bk for each color are provided. The photoreceptor 11 used in this image forming apparatus has a photosensitive layer on at least a conductive support, and includes at least a charge generating material in the photosensitive layer and an electron transport represented by the general formula (1) or (2). Contains materials. Around each of the photoconductors 11Y, 11M, 11C, and 11Bk, a charging unit 12, an exposure unit 13, a developing unit 14, a cleaning unit 17, and the like are disposed. Further, a transfer transfer belt 1G as a transfer material carrier that is brought into contact with and separated from the transfer positions of the respective photoconductors 11Y, 11M, 11C, and 11Bk arranged on a straight line is stretched by a driving unit 1C. A transfer unit 16 is disposed at a transfer position facing each of the photoreceptors 1Y, 1M, 1C, and 1Bk with the conveyance transfer belt 1G interposed therebetween.

  Next, the photoconductor used in the present invention will be described in detail.

  The photosensitive layer of the photoreceptor in the present invention is formed by laminating a charge generation layer containing a charge generation material and a charge transport layer containing an electron transport material represented by the general formula (1) or (2) in this order. And a single layer type photosensitive layer containing a charge generating material and an electron transport material represented by the general formula (1) or (2) in a single layer.

  7 and 8 are cross-sectional views showing an example of a photoreceptor used in the image forming apparatus of the present invention. FIG. 7 shows an example of a photoreceptor of a laminated type photosensitive layer, and FIG. 8 shows a monolayer type photosensitive layer. It is an example of a photoreceptor.

  First, an example of each layer configuration of the laminated photosensitive layer will be described.

  FIG. 7 shows a photosensitive layer structure in which an undercoat layer 24 is provided between the conductive support 21 and the charge generation layer 22, and a charge transport layer 23 is provided on the charge generation layer 22.

Examples of the conductive support 21 include those having a volume resistance of 10 ¹⁰ Ω · cm or less, such as metals such as aluminum, nickel, chromium, nichrome, copper, silver, gold, platinum, and iron, tin oxide, and indium oxide. A film or cylindrical plastic, paper or the like coated with oxides such as vapor deposition or sputtering, or a plate made of aluminum, aluminum alloy, nickel, stainless steel, etc., and a drawing ironing method, an impact ironing method, an extracted ironing It is possible to use a tube that has been surface-treated by cutting, super-finishing, polishing, or the like after being made into a raw tube by a method such as a method, an extruded drawing method, or a cutting method.

  The charge generation layer 22 will be described first among the layers in the multilayer photoconductor. The charge generation layer is a layer mainly composed of a charge generation material, and a binder resin may be used as necessary. As the charge generation material used in the present invention, a known material can be used. For example, phthalocyanine pigments such as metal phthalocyanine and metal-free phthalocyanine, azulenium salt pigments, squaric acid methine pigments, azo pigments having carbazole skeleton, azo pigments having triphenylamine skeleton, azo pigments having diphenylamine skeleton, dibenzothiophene skeleton Azo pigments having a fluorenone skeleton, azo pigments having an oxadiazole skeleton, azo pigments having a bis-stilbene skeleton, azo pigments having a distyryl oxadiazole skeleton, azo pigments having a distyrylcarbazole skeleton, perylene Pigments, anthraquinone or polycyclic quinone pigments, quinoneimine pigments, diphenylmethane and triphenylmethane pigments, benzoquinone and naphthoquinone pigments, cyanine and azomethine pigments, indigo Id based pigments, bisbenzimidazole pigments. These charge generation materials can be used alone or as a mixture of two or more.

  In the present invention, phthalocyanine pigments are particularly preferred from the viewpoint of various properties required for the present invention. Among them, in particular, titanyl phthalocyanine having titanium as a central metal makes it possible to obtain a photosensitive layer having particularly high sensitivity, and it is possible to further increase the speed of the image forming apparatus. Further, among various crystal forms, titanyl phthalocyanine having a maximum diffraction peak at 27.2 ° with a Bragg angle 2θ exhibits particularly excellent sensitivity characteristics and is used favorably. In particular, it has a maximum diffraction peak at 27.2 ° described in JP-A-2001-19871, and further has main peaks at 9.4 °, 9.6 °, and 24.0 °. As the lowest diffraction angle diffraction peak, titanyl phthalocyanine having a peak at 7.3 ° and no peak between the 7.4 ° peak and the 9.4 ° peak is used. Without losing high sensitivity, it is possible to obtain a stable photoconductor in which the chargeability is unlikely to deteriorate even after repeated use.

  Examples of the binder resin used in the charge generation layer as needed include polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, polyarylate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly (N- Vinylcarbazole), polyacrylamide and the like.

  These binder resins may be used alone or as a mixture of two or more.

  The content of the binder resin is usually 0 to 500 parts by weight, and preferably 10 to 300 parts by weight with respect to 100 parts by weight of the charge generating material.

  Further, a polymer charge transport material can be used as the binder resin of the charge generation layer. Furthermore, a charge transport material may be added as necessary.

  As a method for forming the charge generation layer, a casting method from a solution dispersion system is preferable. In order to provide the charge generation layer by the casting method, the charge generation material is dispersed by a ball mill, an attritor, a sand mill or the like using a binder resin and a solvent such as tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, or butanone as necessary. The dispersion may be applied after being diluted appropriately. Application can be performed by dip coating, spray coating, bead coating, or the like.

  The film thickness of the charge generation layer provided as described above is usually 0.01 μm to 5 μm, preferably 0.1 μm to 2 μm.

  Next, the charge transport layer 23 will be described.

  The charge transport layer is formed by dissolving or dispersing a mixture or copolymer containing a charge transport component and a binder component as main components in a suitable solvent, and applying and drying the mixture.

  Examples of the polymer compound that can be used as the binder component of the charge transport layer include 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, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, acrylic resin, silicone resin, fluororesin, epoxy resin And thermoplastic or thermosetting resins such as melamine resin, urethane resin, phenol resin, alkyd resin, etc., but are not limited thereto.

  These polymer compounds can be used singly or as a mixture of two or more kinds, as a copolymer composed of two or more raw material monomers, and further as a copolymer of the raw material monomer and the charge transport material.

  For the purpose of ensuring the stability of the charge transport layer against environmental fluctuations, when using an electrically inactive polymer compound, for example, polyester, polycarbonate, acrylic resin, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyethylene, Polypropylene, fluororesin, polyacrylonitrile, acrylonitrile-styrene-butadiene copolymer, styrene-acrylonitrile copolymer, ethylene-vinyl acetate copolymer and the like are effective.

  Here, the electrically inactive polymer compound refers to a polymer compound that does not include a chemical structure exhibiting photoconductivity such as a triarylamine structure.

  When these resins are used as an additive in combination with a binder resin, the amount added is preferably 50% by weight or less because of limitations on light attenuation sensitivity.

  In the present invention, it is essential to use an electron transport material represented by the general formula (1) or (2) as a material that can be used for the charge transport material. A transport material, that is, an electron transport material (acceptor) and a hole transport material (donor) can be used in combination.

  Examples of the electron transport material include chloroanil, bromanyl, 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-4H-indeno [1,2-b] thiophen-4-one, 1,3,7- Examples thereof include electron accepting substances such as trinitrodibenzothiophene-5,5-dioxide. These electron transport materials may be used alone or as a mixture of two or more.

  As the hole transport material, an electron donating substance is preferably used.

  Examples thereof include oxazole derivatives, oxadiazole derivatives, imidazole derivatives, triphenylamine derivatives, 9- (p-diethylaminostyrylanthracene), 1,1-bis- (4-dibenzylaminophenyl) propane, styrylanthracene, Examples include styrylpyrazolines, phenylhydrazones, α-phenylstilbene derivatives, thiazole derivatives, triazole derivatives, phenazine derivatives, acridine derivatives, benzofuran derivatives, benzimidazole derivatives, and thiophene derivatives. These hole transport materials may be used alone or as a mixture of two or more.

  The amount of the charge transport material added is suitably 40 to 200 parts by weight, preferably 70 to 150 parts by weight, based on 100 parts by weight of the resin component, and the general formula (1) or It is preferable to contain 50 to 100% by weight of the electron transport material represented by (2).

  Examples of the dispersion solvent that can be used in preparing the charge transport layer coating solution include ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone, ethers such as dioxane, tetrahydrofuran, and ethyl cellosolve, toluene, xylene, and the like. Examples include aromatics, halogens such as chlorobenzene and dichloromethane, and esters such as ethyl acetate and butyl acetate. These solvents can be used alone or in combination. Further, if necessary, a low molecular compound such as an antioxidant, a plasticizer, a lubricant, and an ultraviolet absorber and a leveling agent can be added to the charge transport layer. These compounds can be used alone or as a mixture of two or more. The amount of the low molecular compound used is 0.1 to 50 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the resin component, and the amount of the leveling agent used is 100 parts by weight of the resin component. Thus, about 0.001 to 5 parts by weight is appropriate.

  As the coating method, a dipping method, a spray coating method, a ring coating method, a roll coater method, a gravure coating method, a nozzle coating method, a screen printing method, or the like is employed.

  The thickness of the charge transport layer is suitably 15 to 40 μm, preferably 15 to 30 μm, and when resolution is required, 25 μm or less is appropriate.

  In the photoreceptor used in the present invention, an undercoat layer 24 may be provided between the conductive support and the mixed photosensitive layer or the charge generation layer. The undercoat layer is provided for the purpose of improving adhesiveness, preventing moire, improving coatability of the upper layer, reducing residual potential, and preventing charge injection from the conductive support. The undercoat layer generally contains a resin as a main component, but these resins are resins having a high solubility resistance to a general organic solvent in consideration of applying a photosensitive layer thereon using a solvent. Desirably, 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 resins, and alkyd-melamine resins. And a curable resin that forms a three-dimensional network structure such as an epoxy resin.

  Further, fine powders such as metal oxides such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, and indium oxide, metal sulfides, and metal nitrides may be added to the undercoat layer. These undercoat layers can be formed using an appropriate solvent and a coating method in the same manner as the photosensitive layer.

  Further, as the undercoat layer, a metal oxide layer formed by using, for example, a sol-gel method using a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like is also useful. In addition to these, alumina provided by anodic oxidation, organic substances such as polyparaxylylene (parylene), and inorganic substances such as silicon oxide, tin oxide, titanium oxide, ITO, and ceria were provided by the vacuum thin film manufacturing method. It can be used well as a pulling layer.

  The thickness of the undercoat layer is suitably from 0.1 to 10 μm, more preferably from 1 to 5 μm.

  In the present invention, in order to improve the gas barrier property and environmental resistance of the surface layer of the photoreceptor, known antioxidants, plasticizers, ultraviolet absorbers, low molecular charge transport materials and leveling agents are added to each layer. can do.

  Further, in the present invention, by adding an electron transport material represented by the general formula (3) to the photosensitive layer, the photosensitive layer can be made dense, so that the gas barrier property is improved and generated by a charger or the like. It is possible to suppress deterioration of the photoreceptor due to the oxidizing gas. In addition, since shrinkage during film formation is relieved, when a flexible sheet such as an aluminum-deposited PET sheet or nickel belt is used as a support, it is possible to reduce warpage generally referred to as curl, cracks, etc. The occurrence of defects in the photoconductor can be suppressed.

  This is because the electron transport material represented by the general formula (3) has a low molecular weight, and thus acts as a plasticizer in the photosensitive layer, but the electron transport represented by the general formula (3). The material has electron transporting ability and is a monomer of the electron transporting material represented by the general formulas (1) and (2). Can be reduced.

  The electron transport material represented by the general formula (3) is suitably added in an amount of 1 to 50% by weight with respect to the electron transport material represented by the general formula (1) or (2). If the amount added is less than 1% by weight, the effect may not be obtained. Moreover, since the electron transport material represented by General formula (3) is inferior to the electron transport material represented by General formula (1) and (2), when an addition amount is more than 50 weight% Sensitivity may decrease.

  Next, an example of a single-layer type photosensitive layer containing a charge generation material and a charge transport material in a single layer will be described.

  FIG. 8 is a cross-sectional view showing another example of a photoreceptor used in the image forming apparatus of the present invention. At least a charge generating material and a general formula (1) or (2) are formed on a conductive support 21. A photosensitive layer 25 containing the electron transport material represented is provided. Although not shown, it is also possible to provide an undercoat layer between the conductive support 21 and the photosensitive layer 25.

  As the charge generation material that can be used for the photosensitive layer having a single layer structure, a known material can be used as in the case of the layered structure. However, as described above, the phthalocyanine pigment has various characteristics necessary for the present invention. Particularly preferred from the viewpoint.

  Among them, in particular, titanyl phthalocyanine having titanium as a central metal makes it possible to obtain a photosensitive layer having particularly high sensitivity, and it is possible to further increase the speed of the image forming apparatus. Further, like the multilayer photosensitive layer, among various crystal forms, titanyl phthalocyanine having a maximum diffraction peak at 27.2 ° with a Bragg angle 2θ exhibits particularly excellent sensitivity characteristics and is used favorably. In particular, it has a maximum diffraction peak at 27.2 ° described in JP-A-2001-19871, and further has main peaks at 9.4 °, 9.6 °, and 24.0 °. And, as the lowest diffraction angle diffraction peak, by using titanyl phthalocyanine having a peak at 7.3 ° and no peak between the 7.4 ° peak and the 9.4 ° peak, Without losing high sensitivity, it is possible to obtain a stable photoconductor in which chargeability is unlikely to deteriorate even after repeated use.

  These pigments are preferably dispersed in advance in a solvent such as tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, or butanone by a ball mill, an attritor, a sand mill, or the like. Moreover, you may disperse | distribute with binder resin as needed at the time of dispersion | distribution.

  As a material that can be used for the charge transport material even in a single layer configuration, it is essential to use the electron transport material represented by the general formula (1) or (2). Such a known charge transporting material, that is, an electron transporting material (acceptor) and a hole transporting material (donor) can be used in the same manner as in the laminated photosensitive layer.

  In the photosensitive layer having the single layer structure, the charge generating material is added in an amount of 0.1 to 30% by weight, preferably 0.5 to 10% by weight, based on the entire photosensitive layer. The electron transport material is added in an amount of 5 to 300 parts by weight, preferably 10 to 150 parts by weight, per 100 parts by weight of the binder resin component. However, it is preferable that the electron transport material represented by the general formula (1) or (2) is contained in an amount of 50 to 100% by weight with respect to the entire electron transport material. The hole transport material is added in an amount of 5 to 300 parts by weight, preferably 20 to 150 parts by weight, based on 100 parts by weight of the binder resin component. When the electron transport material and the hole transport material are used in combination, the addition amount of the electron transport material and the hole transport material is 20 to 300 parts by weight, preferably 30 to 200 parts by weight with respect to 100 parts by weight of the binder resin component. It is appropriate that

  Examples of the solvent that can be used in preparing the photosensitive layer coating solution include ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone, ethers such as dioxane, tetrahydrofuran, and ethyl cellosolve, and aromatics such as toluene and xylene. , Halogens such as chlorobenzene and dichloromethane, and esters such as ethyl acetate and butyl acetate. These solvents can be used alone or in combination.

  Further, if necessary, low-molecular compounds such as antioxidants, plasticizers, lubricants and ultraviolet absorbers and leveling agents can be added to the photosensitive layer. These compounds can be used alone or as a mixture of two or more. The amount of the low molecular compound used is 0.1 to 50 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the resin component such as a binder resin. 0.001 to 5 parts by weight is appropriate with respect to parts by weight.

  Even in the case of a single layer structure, by adding an electron transport material represented by the general formula (3) to the photosensitive layer, the photosensitive layer can be made dense, so that the gas barrier property is improved, Deterioration of the photoreceptor due to the generated oxidizing gas can be suppressed. In addition, since shrinkage during film formation is relieved, when a flexible sheet such as an aluminum-deposited PET sheet or nickel belt is used as a support, it is possible to reduce warpage generally referred to as curl, cracks, etc. The occurrence of defects in the photoconductor can be suppressed.

  In the photosensitive layer having a single layer structure, the electron transport material represented by the general formula (3) should be added in an amount of 1 to 50% by weight based on the electron transport material represented by the general formula (1) or (2). Is appropriate. If the amount added is less than 1% by weight, the effect may not be obtained. Moreover, since the electron transport material represented by the general formula (3) is inferior to the electron transport material represented by the general formulas (1) and (2), the addition amount is more than 50% by weight. The sensitivity may decrease.

  As the coating method, a dipping method, a spray coating method, a ring coating method, a roll coater method, a gravure coating method, a nozzle coating method, a screen printing method, or the like is employed.

  The film thickness of the photosensitive layer is suitably 10 to 45 μm, preferably 15 to 32 μm, and when resolution is required, 25 μm or less is appropriate.

  The electron transport materials represented by the general formulas (1), (2) and (3) used in the present invention each have the following structural skeleton.

（式中、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子、置換又は無置換のアルキル基、置換又は無置換のシクロアルキル基及び置換又は無置換のアラルキル基からなる群より選択される官能基を表し、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９及びＲ_１０は、それぞれ独立に、水素原子、ハロゲン基、シアノ基、ニトロ基、アミノ基、水酸基、置換又は無置換のアルキル基、置換又は無置換のシクロアルキル基及び置換又は無置換のアラルキル基からなる群より選択される官能基を表す。）

Wherein R ₁ and R ₂ are each independently a functional group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aralkyl group. R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, halogen group, cyano group, nitro group, amino group, hydroxyl group, This represents a functional group selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aralkyl group.

（式中、Ｒ_１及びＲ_２は、それぞれ独立に、水素原子、置換又は無置換のアルキル基、置換又は無置換のシクロアルキル基及び置換又は無置換のアラルキル基からなる群より選択される官能基を表し、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９、Ｒ_１０、Ｒ_１１、Ｒ_１２、Ｒ_１３及びＲ_１４は、それぞれ独立に、水素原子、ハロゲン基、シアノ基、ニトロ基、アミノ基、水酸基、置換又は無置換のアルキル基、置換又は無置換のシクロアルキル基及び置換又は無置換のアラルキル基からなる群より選択される官能基を表し、ｎは、１以上１００以下の整数を表す。）

Wherein R ₁ and R ₂ are each independently a functional group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aralkyl group. R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently a hydrogen atom, halogen group And a functional group selected from the group consisting of a cyano group, a nitro group, an amino group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aralkyl group, 1 represents an integer of 1 to 100)

（式中、Ｒ_１５及びＲ_１６は、それぞれ独立に、水素原子、置換又は無置換のアルキル基、置換又は無置換のシクロアルキル基及び置換又は無置換のアラルキル基からなる群より選択される官能基を表し、Ｒ_１７、Ｒ_１８、Ｒ_１９及びＲ_２０は、それぞれ独立に水素原子、ハロゲン基、シアノ基、ニトロ基、アミノ基、水酸基、置換又は無置換のアルキル基、置換又は無置換のシクロアルキル基及び置換又は無置換のアラルキル基からなる群より選択される官能基を表す。）
置換又は無置換のアルキル基としては、炭素数１〜２５、好ましくは、炭素数１〜１０の炭素原子を有するアルキル基、具体的には、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ペプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基といった直鎖状のもの、イソプロピル基、ｓ−ブチル基、ｔ−ブチル基、メチルプロピル基、ジメチルプロピル基、エチルプロピル基、ジエチルプロピル基、メチルブチル基、ジメチルブチル基、メチルペンチル基、ジメチルペンチル基、メチルヘキシル基、ジメチルヘキシル基等の分岐状のもの、アルコキシアルキル基、モノアルキルアミノアルキル基、ジアルキルアミノアルキル基、ハロゲン置換アルキル基、アルキルカルボニルアルキル基、カルボキシアルキル基、アルカノイルオキシアルキル基、アミノアルキル基、エステル化されていてもよいカルボキシル基で置換されたアルキル基、シアノ基で置換されたアルキル基等が例示できる。なお、これらの置換基の置換位置については特に限定されず、アルキル基の炭素原子の一部がヘテロ原子（Ｎ、Ｏ、Ｓ等）に置換された官能基も置換されたアルキル基に含まれる。

Wherein R ₁₅ and R ₁₆ are each independently a functional group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aralkyl group. R ₁₇ , R ₁₈ , R ₁₉ and R ₂₀ each independently represents a hydrogen atom, a halogen group, a cyano group, a nitro group, an amino group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group This represents a functional group selected from the group consisting of a cycloalkyl group and a substituted or unsubstituted aralkyl group.)
The substituted or unsubstituted alkyl group is an alkyl group having 1 to 25 carbon atoms, preferably 1 to 10 carbon atoms, specifically a methyl group, an ethyl group, an n-propyl group, an n- Straight chain such as butyl group, n-pentyl group, n-hexyl group, n-peptyl group, n-octyl group, n-nonyl group, n-decyl group, isopropyl group, s-butyl group, t-butyl Group, branched group such as methylpropyl group, dimethylpropyl group, ethylpropyl group, diethylpropyl group, methylbutyl group, dimethylbutyl group, methylpentyl group, dimethylpentyl group, methylhexyl group, dimethylhexyl group, alkoxyalkyl group Monoalkylaminoalkyl group, dialkylaminoalkyl group, halogen-substituted alkyl group, alkylcarbonylalkyl group, Kishiarukiru group, alkanoyloxy group, an aminoalkyl group, esterified optionally alkyl group substituted with a carboxyl group which have an alkyl group substituted by a cyano group are exemplified. The substitution position of these substituents is not particularly limited, and functional groups in which some of the carbon atoms of the alkyl group are substituted with heteroatoms (N, O, S, etc.) are also included in the substituted alkyl group. .

  As the substituted or unsubstituted cycloalkyl group, a cycloalkyl ring having 3 to 25 carbon atoms, preferably 3 to 10 carbon atoms, specifically, a homogenous ring from cyclopropane to cyclodecane, methylcyclo Those having an alkyl substituent such as pentane, dimethylcyclopentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, tetramethylcyclohexane, ethylcyclohexane, diethylcyclohexane, t-butylcyclohexane, alkoxyalkyl groups, monoalkylaminoalkyl groups, dialkylamino Alkyl group, halogenated alkyl group, alkoxycarbonylalkyl group, carboxyalkyl group, alkanoyloxyalkyl group, aminoalkyl group, halogen group, amino group, esterified A carboxyl group which may, cycloalkyl group substituted by a cyano group and the like. In addition, the substitution position of these substituents is not particularly limited, and a cycloalkyl group in which a functional group in which a part of carbon atoms of the cycloalkyl group is substituted with a hetero atom (N, O, S, etc.) is also substituted. include.

  Examples of the substituted or unsubstituted aralkyl group include groups in which an aromatic ring is substituted on a substituted or unsubstituted alkyl group, and an aralkyl group having 6 to 14 carbon atoms is preferable. Specifically, benzyl group, perfluorophenylethyl group, 1-phenylethyl group, 2-phenylethyl group, terphenylethyl group, dimethylphenylethyl group, diethylphenylethyl group, t-butylphenylethyl group, 3-phenylpropylene. Illustrative examples include a sulfur group, a 4-phenylbutyl group, a 5-phenylpentyl group, a 6-phenylhexyl group, a benzhydryl group, and a trityl group.

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

  The electron transport material represented by the general formula (1) is preferably an electron transport material represented by the structural formulas (1-1) to (1-7) in that a high-quality image can be obtained.

一般式（１）で表される電子輸送材料の製造方法としては、下記の方法が例示できる。なお、ナフタレンカルボン酸は、公知の合成方法（例えば、米国特許６７９４１０２号公報、Ｉｎｄｕｓｔｒｉａｌ Ｏｒｇａｎｉｃ Ｐｉｇｍｅｎｔｓ ２ｎｄ ｅｄｉｔｉｏｎ，ＶＣＨ，４８５（１９９７）等）に従い、下記反応により合成される。

Examples of the method for producing the electron transport material represented by the general formula (1) include the following methods. Naphthalenecarboxylic acid is synthesized by the following reaction according to a known synthesis method (for example, US Pat. No. 6,794,102, Industrial Organic Pigments 2nd edition, VCH, 485 (1997)).

（式中、Ｒ_ｎは、Ｒ_３、Ｒ_４、Ｒ_７、Ｒ_８を表し、Ｒ_ｍは、Ｒ_５、Ｒ_６、Ｒ_９、Ｒ_１０を表す。）
一般式（１）で表される電子輸送材料は、上記のナフタレンカルボン酸又はその無水物をアミン類と反応させ、モノイミド化する方法、緩衝液を用いて、ナフタレンカルボン酸又はその無水物をｐＨ調整してジアミン類と反応させる方法等により得られる。モノイミド化は、無溶媒又は溶媒存在下で行う。溶媒は、特に制限はないが、ベンゼン、トルエン、キシレン、クロロナフタレン、酢酸、ピリジン、メチルピリジン、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルエチレンウレア、ジメチルスルホキサイド等の原料や生成物と反応せず、５０〜２５０℃の温度で反応させられるものを用いるとよい。ｐＨ調整には、水酸化リチウム、水酸化カリウム等の塩基性水溶液をリン酸等の酸と混合することにより作製した緩衝液を用いる。カルボン酸と、アミン類やジアミン類とを反応させて得られたカルボン酸誘導体の脱水反応は、無溶媒又は溶媒存在下で行う。溶媒は、特に制限は無いが、ベンゼン、トルエン、クロロナフタレン、ブロモナフタレン、無水酢酸等の原料や生成物と反応せず、５０〜２５０℃の温度で反応させられるものを用いるとよい。いずれの反応も、無触媒又は触媒存在下で行ってよく、特に限定されないが、例えば、脱水剤として、モレキュラーシーブス、ベンゼンスルホン酸、ｐ−トルエンスルホン酸等を用いることが例示できる。

(Wherein, _{R n represents R 3, R 4, R 7} , R 8, R m _{represents R 5, R 6, R 9} , R 10.)
The electron transport material represented by the general formula (1) is prepared by reacting the above naphthalenecarboxylic acid or its anhydride with amines to monoimidize, using a buffer solution, and converting the naphthalenecarboxylic acid or its anhydride to pH. It is obtained by a method of adjusting and reacting with diamines. Monoimidization is carried out without solvent or in the presence of a solvent. The solvent is not particularly limited, but does not react with raw materials and products such as benzene, toluene, xylene, chloronaphthalene, acetic acid, pyridine, methylpyridine, dimethylformamide, dimethylacetamide, dimethylethyleneurea, dimethylsulfoxide, What is made to react at the temperature of 50-250 degreeC is good to be used. For pH adjustment, a buffer solution prepared by mixing a basic aqueous solution such as lithium hydroxide or potassium hydroxide with an acid such as phosphoric acid is used. The dehydration reaction of the carboxylic acid derivative obtained by reacting carboxylic acid with amines or diamines is carried out without solvent or in the presence of a solvent. Although there is no restriction | limiting in particular in a solvent, It is good to use what is made to react at the temperature of 50-250 degreeC, without reacting with raw materials and products, such as benzene, toluene, chloronaphthalene, bromonaphthalene, and acetic anhydride. Any reaction may be performed without a catalyst or in the presence of a catalyst, and is not particularly limited. For example, molecular sieves, benzenesulfonic acid, p-toluenesulfonic acid and the like can be used as a dehydrating agent.

The electron transport material represented by the structural formula (1-3) can be manufactured by the following method.
(First step)
In a 200 ml four-necked flask, 5.0 g (18.6 mmol) of 1,4,5,8-naphthalenetetracarboxylic dianhydride and 50 ml of DMF are added and heated to reflux. To this, a mixture of 1.10 g (18.6 mmol) of 2-aminopropane and 25 ml of DMF is added dropwise with stirring. After completion of dropping, the mixture is heated to reflux for 6 hours. After completion of the reaction, the reaction vessel is cooled and concentrated under reduced pressure. Toluene is added to the residue and the residue is purified by silica gel column chromatography. Furthermore, the recovered product is recrystallized with a toluene / hexane mixed solvent to obtain 2.08 g (yield: 36.1%) of monoimide B.
(Second step)
In a 100 ml four-necked flask, add 2.0 g (6.47 mmol) of monoimide B, 0.162 g (3.23 mmol) of hydrazine monohydrate, 10 mg of p-toluenesulfonic acid, and 50 ml of toluene, and heat to reflux for 5 hours. . After completion of the reaction, the vessel is cooled and concentrated under reduced pressure. The residue is purified by silica gel column chromatography. Further, the recovered product is recrystallized with a mixed solvent of toluene / ethyl acetate to obtain 0.810 g (yield 37.4%) of an electron transport material represented by the structural formula (1-3). In addition, in mass spectrometry (FD-MS), when the peak of M / z = 614 is observed, it identifies with the target object. In the elemental analysis, the calculated values are 66.45% carbon, 3.61% hydrogen, and 9.12% nitrogen, whereas the measured values are 66.28% carbon, 3.45% hydrogen, and 9.33 nitrogen. % Is obtained.

The electron transport material represented by Structural Formula (1-5) can be produced by the following method.
(First step)
In a 200 ml four-necked flask, 1,4,5,8-naphthalenetetracarboxylic dianhydride 10 g (37.3 mmol), hydrazine monohydrate 0.931 g (18.6 mmol), p-toluenesulfonic acid 20 mg, toluene Add 100 ml and heat to reflux for 5 hours. After completion of the reaction, the vessel is cooled and concentrated under reduced pressure. The residue is purified by silica gel column chromatography. Furthermore, the recovered product is recrystallized with a toluene / ethyl acetate mixed solvent to obtain 2.84 g of dimer C (yield: 28.7%).
(Second step)
In a 200 ml four-necked flask, 5.0 g (9.39 mmol) of Dimer C and 50 ml of DMF are placed and heated to reflux. To this, a mixture of 1.08 g (9.39 mmol) of 2-aminoheptane and 25 ml of DMF is added dropwise with stirring. After completion of dropping, the mixture is heated to reflux for 6 hours. After completion of the reaction, the reaction vessel is cooled and concentrated under reduced pressure. Toluene is added to the residue and purified by silica gel column chromatography to obtain 1.66 g (yield 28.1%) of monoimide D.
(Third process)
In a 100 ml four-necked flask, 1.5 g (2.38 mmol) of monoimide D and 50 ml of DMF are placed and heated to reflux. To this, a mixture of 0.408 g (2.38 mmol) of 6-aminoundecane and 10 ml of DMF is added dropwise with stirring. After completion of dropping, the mixture is heated to reflux for 6 hours. After completion of the reaction, the reaction vessel is cooled and concentrated under reduced pressure. Toluene is added to the residue and the residue is purified by silica gel column chromatography. Furthermore, the recovered product is recrystallized with a toluene / hexane mixed solvent to obtain 0.276 g (yield: 14.8%) of an electron transport material represented by the structural formula (1-5). In addition, in mass spectrometry (FD-MS), the peak of M / z = 782 is observed, so that it is identified as the target product. In the elemental analysis, calculated values are 70.57% carbon, 5.92% hydrogen, and 7.16% nitrogen, whereas measured values are 70.77% carbon, 6.11% hydrogen, and 7.02 nitrogen. % Is obtained.

  The following method can be illustrated as a manufacturing method of the electron transport material represented by General formula (2).

一般式（２）で表される電子輸送材料の繰り返し単位ｎは、１〜１００の整数である。ｎは、数平均分子量から求められる。ｎが１００を超えると、化合物の分子量が大きくなり、各種溶媒に対する溶解性が低下することがある。一方、ｎが１の場合は、ナフタレンカルボン酸の三量体であるが、Ｒ_１及びＲ_２の置換基を適切に選択することにより、オリゴマーでも優れた電子移動特性が得られる。このようにｎを変化させるにより、オリゴマーからポリマーまで幅広い範囲のナフタレンカルボン酸誘導体が合成される。分子量が小さいオリゴマー領域では、段階的に合成することで、単分散の化合物を得ることができる。また、分子量が大きいポリマー領域では、分子量に分布を有する化合物が得られる。

The repeating unit n of the electron transport material represented by the general formula (2) is an integer of 1 to 100. n is determined from the number average molecular weight. When n exceeds 100, the molecular weight of the compound increases and the solubility in various solvents may decrease. On the other hand, when n is 1, it is a trimer of naphthalene carboxylic acid, but excellent electron transfer characteristics can be obtained even with oligomers by appropriately selecting substituents for R ₁ and R ₂ . By changing n in this way, a wide range of naphthalenecarboxylic acid derivatives from oligomers to polymers are synthesized. In an oligomer region having a small molecular weight, a monodispersed compound can be obtained by stepwise synthesis. In the polymer region having a large molecular weight, a compound having a distribution in molecular weight is obtained.

  Examples of the electron transport material represented by the general formula (2) include electron transport materials represented by the structural formulas (2-1) to (2-3).

一般式（３）で表される電子輸送材料としては、構造式（３−１）〜（３−３）で表される電子輸送材料が例示できる。

Examples of the electron transport material represented by the general formula (3) include electron transport materials represented by the structural formulas (3-1) to (3-3).

Hereinafter, the present invention will be described by way of examples. Note that this does not limit the scope of the present invention. All parts are parts by weight.
(Electron Transport Material Synthesis Example 1)
(First step)
In a 200 ml four-necked flask, 5.0 g (18.6 mmol) of 1,4,5,8-naphthalenetetracarboxylic dianhydride and 50 ml of DMF were placed and heated to reflux. To this, a mixture of 2.14 g (18.6 mmol) of 2-aminoheptane and 25 ml of DMF was added dropwise with stirring. After completion of dropping, the mixture was heated to reflux for 6 hours. After completion of the reaction, the container was cooled and concentrated under reduced pressure. Toluene was added to the residue, and the residue was purified by silica gel column chromatography. Furthermore, the recovered product was recrystallized with a toluene / hexane mixed solvent to obtain 2.14 g (yield: 31.5%) of monoimide A.
(Second step)
In a 100 ml four-necked flask, 2.0 g (5.47 mmol) of monoimide A, 0.137 g (2.73 mmol) of hydrazine monohydrate, 10 mg of p-toluenesulfonic acid, and 50 ml of toluene are placed and heated to reflux for 5 hours. It was. After completion of the reaction, the container was cooled and concentrated under reduced pressure. The residue was purified by silica gel column chromatography. Further, the recovered product was recrystallized with a mixed solvent of toluene / ethyl acetate to obtain 0.668 g (yield 33.7%) of the electron transport material 1 represented by the structural formula (1-1). In addition, in mass spectrometry (FD-MS), when the peak of M / z = 726 was observed, it identified with the target object. In the elemental analysis, the calculated values are 69.41% carbon, 5.27% hydrogen, and 7.71% nitrogen, whereas the measured values are 69.52% carbon, 5.09% hydrogen, and 7.93 nitrogen. %Met.
(Electron transport material synthesis example 2)
(First step)
In a 200 ml four-necked flask, 1,4,5,8-naphthalenetetracarboxylic dianhydride 10 g (37.3 mmol), hydrazine monohydrate 0.931 g (18.6 mmol), p-toluenesulfonic acid 20 mg, toluene 100 ml was added and heated to reflux for 5 hours. After completion of the reaction, the container was cooled and concentrated under reduced pressure. The residue was purified by silica gel column chromatography. Furthermore, the recovered product was recrystallized with a mixed solvent of toluene / ethyl acetate to obtain 2.84 g of dimer C (yield 28.7%).
(Second step)
In a 100 ml four-necked flask, 2.5 g (4.67 mmol) of Dimer C and 30 ml of DMF were placed and heated to reflux. To this, a mixture of 2-aminopropane 0.278 g (4.67 mmol) and DMF 10 ml was added dropwise with stirring. After completion of dropping, the mixture was heated to reflux for 6 hours. After completion of the reaction, the reaction vessel was cooled and concentrated under reduced pressure. Toluene was added to the residue and purified by silica gel column chromatography to obtain 0.556 g (yield 38.5%) of monoimide C.
(Third process)
In a 50 ml four-necked flask, 0.50 g (1.62 mmol) of monoimide C and 10 ml of DMF were placed and heated to reflux. To this, a mixture of 2-aminoheptane 0.186 g (1.62 mmol) and DMF 5 ml was added dropwise with stirring. After completion of dropping, the mixture was heated to reflux for 6 hours. After completion of the reaction, the reaction vessel was cooled and concentrated under reduced pressure. Toluene was added to the residue, and the residue was purified by silica gel column chromatography. Furthermore, the recovered product was recrystallized with a toluene / hexane mixed solvent to obtain 0.243 g (yield 22.4%) of the electron transport material 2 represented by the structural formula (1-2). In addition, in mass spectrometry (FD-MS), when the peak of M / z = 670 was observed, it identified with the target object. In the elemental analysis, the calculated values are 68.05% carbon, 4.51% hydrogen, and 8.35% nitrogen, while the measured values are 68.29% carbon, 4.72% hydrogen, and 8.33 nitrogen. %Met.
(Electron Transport Material Synthesis Example 3)
(First step)
In a 200 ml four-necked flask, 5.0 g (9.39 mmol) of dimer C and 50 ml of DMF were placed and heated to reflux. To this, a mixture of 2-aminoheptane 1.08 g (9.39 mmol) and DMF 25 ml was added dropwise with stirring. After completion of dropping, the mixture was heated to reflux for 6 hours. After completion of the reaction, the reaction vessel was cooled and concentrated under reduced pressure. Toluene was added to the residue and purified by silica gel column chromatography to obtain 1.66 g (yield 28.1%) of monoimide D.
(Second step)
In a 100 ml four-necked flask, 1.5 g (2.38 mmol) of monoimide D and 50 ml of DMF were placed and heated to reflux. To this, a mixture of 2-aminooctane 0.308 g (2.38 mmol) and DMF 10 ml was added dropwise with stirring. After completion of dropping, the mixture was heated to reflux for 6 hours. After completion of the reaction, the reaction vessel was cooled and concentrated under reduced pressure. Toluene was added to the residue, and the residue was purified by silica gel column chromatography. Furthermore, the recovered product was recrystallized with a toluene / hexane mixed solvent to obtain 0.328 g (yield 18.6%) of the electron transport material 3 represented by the structural formula (1-4). In addition, in mass spectrometry (FD-MS), when the peak of M / z = 740 was observed, it identified with the target object. In the elemental analysis, the calculated values are 69.72% carbon, 5.44% hydrogen, and 7.56% nitrogen, whereas the measured values are 69.55% carbon, 5.26% hydrogen, and 7.33 nitrogen. %Met.
(Electron transport material synthesis example 4)
(First step)
In a 200 ml four-necked flask, 5.0 g (18.6 mmol) of 1,4,5,8-naphthalenetetracarboxylic dianhydride and 50 ml of DMF were placed and heated to reflux. To this, a mixture of 1.62 g (18.6 mmol) of 2-aminopentane and 25 ml of DMF was added dropwise with stirring. After completion of dropping, the mixture was heated to reflux for 6 hours. After completion of the reaction, the container was cooled and concentrated under reduced pressure. Toluene was added to the residue, and the residue was purified by silica gel column chromatography. Furthermore, the recovered product was recrystallized with a toluene / hexane mixed solvent to obtain 3.49 g (yield: 45.8%) of monoimide E.
(Second step)
In a 100 ml four-necked flask, 3.0 g (7.33 mmol) of monoimide E, 0.983 g (3.66 mmol) of 1,4,5,8-naphthalenetetracarboxylic dianhydride, hydrazine monohydrate 368 g (7.33 mmol), p-toluenesulfonic acid 10 mg, and toluene 50 ml were added and heated to reflux for 5 hours. After completion of the reaction, the container was cooled and concentrated under reduced pressure. The residue was purified twice by silica gel column chromatography. Further, the recovered product was recrystallized with a mixed solvent of toluene / ethyl acetate to obtain 0.939 g (yield 13.7%) of the electron transport material 4 represented by the structural formula (2-1). In addition, in mass spectrometry (FD-MS), when the peak of M / z = 934 was observed, it identified with the target object. In the elemental analysis, the calculated values are 66.81% carbon, 3.67% hydrogen, and 8.99% nitrogen, whereas the measured values are 66.92% carbon, 3.74% hydrogen, and 9.05 nitrogen. %Met.
(Pigment synthesis example 1)
A pigment was produced according to the method described in the production example of JP-A-2-8256 (Japanese Patent Publication No. 7-91486). That is, 9.8 g of phthalodinitrile and 75 ml of 1-chloronaphthalene are stirred and mixed, and 2.2 ml of titanium tetrachloride is added dropwise under a nitrogen stream. After completion of the dropwise addition, the temperature was gradually raised to 200 ° C., and the reaction was carried out by stirring for 3 hours while maintaining the reaction temperature at 200 to 220 ° C. After completion of the reaction, the mixture was allowed to cool and filtered when it reached 130 ° C. Next, the powder is washed with 1-chloronaphthalene until the powder turns blue, washed several times with methanol, further washed several times with hot water at 80 ° C., and dried to obtain titanyl phthalocyanine powder (Pigment 1). It was.

Under the following conditions, the X-ray diffraction spectrum of Pigment 1 was measured and confirmed to be the same as the spectrum described in the publication.
(X-ray diffraction spectrum measurement conditions)
X-ray tube: Cu
Voltage: 50kV
Current: 30mA
Scanning speed: 2 ° / min Scanning range: 3-40 °
Time constant: 2 seconds (Pigment synthesis example 2)
A pigment was prepared according to Japanese Patent Application Laid-Open No. 2001-19871. That is, 29.2 g of 1,3-diiminoisoindoline and 200 ml of sulfolane are mixed, and 20.4 g of titanium tetrabutoxide is added dropwise under a nitrogen stream. After completion of the dropping, the temperature was gradually raised to 180 ° C., and the reaction was carried out by stirring for 5 hours while maintaining the reaction temperature at 170 to 180 ° C. After completion of the reaction, the mixture was allowed to cool and the precipitate was filtered, and washed with chloroform until the powder turned blue. Next, it was washed several times with methanol, further washed several times with hot water at 80 ° C., and dried to obtain crude titanyl phthalocyanine. Crude titanyl phthalocyanine was dissolved in 20 times the amount of concentrated sulfuric acid and added dropwise to 100 times the amount of ice water with stirring, and the precipitated crystals were filtered. Next, washing with water was repeated until the washing solution became neutral, and a titanyl phthalocyanine pigment wet cake (water paste) was obtained. 2 g of the obtained wet cake was put into 20 g of tetrahydrofuran, stirred for 4 hours, filtered and dried to obtain titanyl phthalocyanine powder (pigment 2).

Under the conditions of Pigment Synthesis Example 1, the X-ray diffraction spectrum of Pigment 2 was measured, and the diffraction peak (± 0.2 °) of Bragg angle 2θ with respect to Cu-Kα ray (wavelength 1.542 mm) described in the publication was as follows: It has a maximum diffraction peak at least 27.2 °, and further has main peaks at 9.4 °, 9.6 °, and 24.0 °, and 7.3 as the lowest diffraction peak. It was confirmed that it was titanyl phthalocyanine having a peak at ° and no peak between the peak at 7.3 ° and the peak at 9.4 °.
(Photoreceptor Preparation Example 1)
An undercoat layer coating solution, a charge generation layer coating solution and a charge transport layer coating solution having the following composition were prepared.
(Coating liquid for undercoat layer)
Alkyd resin (Dainippon Ink Industries, Ltd .: Beccosol M-6401-50): 60 parts Melamine resin: 40 parts (Dainippon Ink Industries, Ltd .: Super Becamine L-121-60)
Titanium oxide (Ishihara Sangyo Co., Ltd .: CR-EL): 400 parts Methyl ethyl ketone: 500 parts These were ball milled with a ball mill apparatus (using 10 mm diameter alumina balls as media) for 5 days, did.
(Coating solution for charge generation layer)
Metal-free phthalocyanine pigment: 12 parts (Dainippon Ink Industries, Ltd .: Fastogen Blue 8120B)
Polyvinyl butyral resin: (manufactured by Sekisui Chemical Co., Ltd .: ESREC BX-1): 5 parts 2-butanone: 200 parts cyclohexanone: 400 parts These were put into a glass pot having a diameter of 9 cm, and a PSZ ball having a diameter of 0.5 mm was used. Dispersion was carried out at a rotational speed of 100 rpm for 5 hours to obtain a charge generation layer coating solution.
(Coating liquid for charge transport layer)
Electron transport material 1: 10 parts Z-type polycarbonate resin (manufactured by Teijin Chemicals: Panlite TS-2050): 10 parts Silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: KF50): 0.01 parts Tetrahydrofuran: 80 parts It melt | dissolved and it was set as the coating liquid for charge transport layers.

  Next, on an aluminum drum having a diameter of 30 mm and a length of 340 mm, the coating liquid for the undercoat layer, the coating liquid for the charge generation layer, and the coating liquid for the charge transport layer are sequentially applied by a dip coating method. Coating and drying were performed to form an undercoat layer of 4.5 μm, a charge generation layer of 0.15 μm, and a charge transport layer of 25 μm.

The drying temperature of each layer was set at 135 ° C. for 20 minutes, 80 ° C. for 15 minutes, and 120 ° C. for 20 minutes.
(Photoreceptor preparation example 2)
Metal-free phthalocyanine was dispersed under the following composition and conditions to prepare a pigment dispersion.

Metal-free phthalocyanine pigment: 3 parts (Dainippon Ink Industries, Ltd .: Fastogen Blue 8120B)
Cyclohexanone: 97 parts These were put into a glass pot having a diameter of 9 cm and dispersed using a PSZ ball having a diameter of 0.5 mm at a rotation speed of 100 rpm for 5 hours to obtain a pigment dispersion.

  A photoreceptor coating solution having the following composition was prepared using the pigment dispersion.

Pigment dispersion: 60 parts Structural formula

で表される正孔輸送材料：２５部
電子輸送材料１：２５部
Ｚ型ポリカーボネート樹脂（帝人化成社製：パンライトＴＳ−２０５０）：５０部
シリコーンオイル（信越化学工業社製：ＫＦ５０）：０．０１部
テトラヒドロフラン：３５０部
こうして得られた感光層用塗工液を直径３０ｍｍ、長さ３４０ｍｍアルミニウムドラム上に、浸漬塗工法により塗布、１２０℃で２０分間乾燥し、２５μｍの感光層を形成し、感光体２を作製した。
（感光体作製例３）
電荷発生材料として、無金属フタロシアニン顔料（Ｆａｓｔｏｇｅｎ Ｂｌｕｅ８１２０Ｂ）の代わりに、顔料１を用いた以外は、感光体作製例１と同様にして感光体３を作製した。
（感光体作製例４）
電荷発生材料として、無金属フタロシアニン顔料（Ｆａｓｔｏｇｅｎ Ｂｌｕｅ８１２０Ｂ）の代わりに、顔料１を用いた以外は、感光体作製例２と同様にして感光体４を作製した。
（感光体作製例５）
電荷発生材料として、無金属フタロシアニン（Ｆａｓｔｏｇｅｎ Ｂｌｕｅ８１２０Ｂ）の代わりに、顔料２を用いた以外は、感光体作製例１と同様にして感光体５を作製した。
（感光体作製例６）
電荷発生材料として、無金属フタロシアニン（Ｆａｓｔｏｇｅｎ Ｂｌｕｅ８１２０Ｂ）の代わりに、顔料２を用いた以外は、感光体作製例２と同様にして感光体６を作製した。
（感光体作製例７）
電子輸送材料１の代わりに、電子輸送材料２を用いた以外は、感光体作製例５と同様にして感光体７を作製した。
（感光体作製例８）
電子輸送材料１の代わりに、電子輸送材料２を用いた以外は、感光体作製例６と同様にして感光体８を作製した。
（感光体作製例９）
電子輸送材料１の代わりに、電子輸送材料３を用いた以外は、感光体作製例５と同様にして感光体９を作製した。
（感光体作製例１０）
電子輸送材料１の代わりに、電子輸送材料３を用いた以外は、感光体作製例６と同様にして感光体１０を作製した。
（感光体作製例１１）
電子輸送材料１の代わりに、構造式（Ａ）

Hole transport material represented by: 25 parts Electron transport material 1: 25 parts Z-type polycarbonate resin (manufactured by Teijin Chemicals: Panlite TS-2050): 50 parts Silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: KF50): 0 0.01 parts Tetrahydrofuran: 350 parts The photosensitive layer coating solution thus obtained was applied on an aluminum drum having a diameter of 30 mm and a length of 340 mm by a dip coating method and dried at 120 ° C. for 20 minutes to form a 25 μm photosensitive layer. A photoreceptor 2 was prepared.
(Photoreceptor Preparation Example 3)
Photoreceptor 3 was produced in the same manner as Photoreceptor Production Example 1 except that pigment 1 was used instead of the metal-free phthalocyanine pigment (Fastogen Blue 8120B) as the charge generation material.
(Photosensitive member production example 4)
Photoreceptor 4 was produced in the same manner as Photoreceptor Production Example 2, except that pigment 1 was used instead of the metal-free phthalocyanine pigment (Fastogen Blue 8120B) as the charge generation material.
(Photoreceptor Preparation Example 5)
Photoreceptor 5 was produced in the same manner as Photoreceptor Production Example 1 except that pigment 2 was used instead of metal-free phthalocyanine (Fastogen Blue 8120B) as the charge generation material.
(Photosensitive member preparation example 6)
Photoreceptor 6 was produced in the same manner as Photoreceptor Production Example 2, except that pigment 2 was used instead of metal-free phthalocyanine (Fastogen Blue 8120B) as the charge generation material.
(Photoreceptor Preparation Example 7)
Photoreceptor 7 was produced in the same manner as Photoreceptor Production Example 5, except that electron transport material 2 was used instead of electron transport material 1.
(Photoreceptor Preparation Example 8)
A photoconductor 8 was prepared in the same manner as in Photoconductor Preparation Example 6 except that the electron transport material 2 was used instead of the electron transport material 1.
(Photoreceptor Preparation Example 9)
A photoconductor 9 was prepared in the same manner as in Photoconductor Preparation Example 5 except that the electron transport material 3 was used instead of the electron transport material 1.
(Photoreceptor Preparation Example 10)
A photoconductor 10 was produced in the same manner as in Photoconductor Production Example 6 except that the electron transport material 3 was used instead of the electron transport material 1.
(Photoreceptor Preparation Example 11)
Instead of the electron transport material 1, the structural formula (A)

で表される化合物を用いた以外は、感光体作製例５と同様にして感光体１１を作製した。
（感光体作製例１２）
電子輸送材料１の代わりに、構造式（Ａ）で表される化合物を用いた以外は、感光体作製例６と同様にして感光体１２を作製した。
（感光体作製例１３）
電子輸送材料１の代わりに、構造式（Ｂ）

Photoreceptor 11 was produced in the same manner as Photoreceptor Production Example 5 except that the compound represented by formula (1) was used.
(Photoconductor Preparation Example 12)
A photoconductor 12 was produced in the same manner as in Photoconductor Production Example 6 except that the compound represented by the structural formula (A) was used instead of the electron transport material 1.
(Photoreceptor Preparation Example 13)
Instead of the electron transport material 1, the structural formula (B)

で表される化合物を用いた以外は、感光体作製例５と同様にして感光体１３を作製した。
（感光体作製例１４）
電子輸送材料１の代わりに、構造式（Ｂ）であらわされる化合物を用いた以外は、感光体作製例６と同様にして感光体１４を作製した。
（感光体作製例１５）
電子輸送材料１の代わりに、電子輸送材料４を用いた以外は、感光体作製例５と同様にして感光体１５を作製した。
（感光体作製例１６）
電子輸送材料１の代わりに、電子輸送材料４を用いた以外は、感光体作製例６と同様にして感光体１６を作製した。
（感光体作製例１７）
１０部の電子輸送材料１を、８部の電子輸送材料１及び２部の構造式（３−１）で表される電子輸送材料５に変更した以外は、感光体作製例５と同様にして感光体１７を作製した。
（感光体作製例１８）
１０部の電子輸送材料１を、８部の電子輸送材料１及び２部の電子輸送材料５に変更した以外は、感光体作製例６と同様にして感光体１８を作製した。
（実施例１〜１０、１３、１４、参考例１１、１２及び比較例１〜４）
感光体１〜１８を実装用にした後、画像形成装置ｉｍｇｉｏ Ｎｅｏ ２７０（リコー社製）の改造機（パワーパックを交換し、正帯電となるように改造し、露光光源をＬＥＤに換装した装置）に搭載し、書き込み率が５％のチャート（Ａ４全面に対して、画像面積として５％相当の文字が平均的に書かれている）を用い、通算１万枚印刷する耐刷試験を行った。

Photoconductor 13 was prepared in the same manner as in Photoconductor Preparation Example 5 except that the compound represented by formula (1) was used.
(Photoreceptor Preparation Example 14)
A photoconductor 14 was produced in the same manner as in Photoconductor Production Example 6 except that a compound represented by the structural formula (B) was used instead of the electron transport material 1.
(Photoreceptor Preparation Example 15)
A photoconductor 15 was produced in the same manner as in Photoconductor Production Example 5 except that the electron transport material 4 was used instead of the electron transport material 1.
(Photoreceptor Preparation Example 16)
A photoconductor 16 was produced in the same manner as in Photoconductor Production Example 6 except that the electron transport material 4 was used instead of the electron transport material 1.
(Photoreceptor Preparation Example 17)
Except for changing 10 parts of the electron transport material 1 to 8 parts of the electron transport material 1 and 2 parts of the electron transport material 5 represented by the structural formula (3-1), the same procedure as in Photoconductor Preparation Example 5 was performed. A photoreceptor 17 was produced.
(Photoreceptor Preparation Example 18)
A photoconductor 18 was prepared in the same manner as in Photoconductor Preparation Example 6 except that 10 parts of the electron transport material 1 were changed to 8 parts of the electron transport material 1 and 2 parts of the electron transport material 5.
(Examples 1 to 10, 13, 14 , Reference Examples 11 and 12 and Comparative Examples 1 to 4)
After the photoconductors 1 to 18 are mounted, the image forming apparatus imgio Neo 270 (manufactured by Ricoh) is remodeled (the power pack is replaced and remodeled to be positively charged, and the exposure light source is replaced with an LED. ) And a printing test that prints 10,000 sheets in total using a chart with a writing rate of 5% (characters equivalent to 5% of the image area are written on the entire A4 surface). It was.

  An LED having a wavelength of 780 nm was used, which was arranged in an array on a glass substrate so that writing could be performed on the surface of the photoreceptor through a focusing lens array.

  The toner and developer used were changed from a dedicated toner for imgio Neo 270 to a toner and developer having opposite polarities.

  As the charging means, an external power source was used, and the voltage applied to the charging roller was selected as an AC component with a peak-to-peak voltage of 1.9 kV and a frequency of 1.35 kHz. For the DC component, a bias was set so that the charging potential of the photosensitive member at the start of the test was +600 V, and the test was performed under this charging condition until the end of the test. The developing bias was + 450V. The test environment is 23 ° C. and 55% RH.

After the printing durability test, image evaluation and resolution evaluation were performed.
(Image evaluation)
An image for evaluation was output, and the rank was evaluated comprehensively with respect to background dirt, fogging, image density, and the like.
(resolution)
A halftone image was output, and the dot formation state (dot dispersion and dot reproducibility) was observed.

  In any case, the evaluation rank is as follows.

◎: Very good ○: Good Δ: Slightly inferior ×: Very bad As mentioned above, the evaluation results of Examples 1 to 10, 13, 14 , Reference Examples 11 and 12 and Comparative Examples 1 to 4 are shown in Table 1.

（実施例１５〜１９、２１及び参考例２０）
感光体２、４、６、８、１０、１６、１８を実装用にした後、接触方式の帯電ローラを用いた画像形成装置ｉｍｇｉｏ Ｎｅｏ ２７０（リコー社製）の改造機（露光光源をＬＥＤに換装した装置）に搭載し、書き込み率が５％のチャート（Ａ４全面に対して、画像面積として５％相当の文字が平均的に書かれている）を用い、通算１万枚印刷する耐刷試験を行った。

(Examples 15 to 19, 21 and Reference Example 20 )
After the photoreceptors 2, 4, 6, 8, 10, 16, 18 are mounted, the image forming apparatus imgio Neo 270 (manufactured by Ricoh) using a contact-type charging roller is modified (the exposure light source is an LED). Printed on a refurbished device), printing a total of 10,000 sheets using a chart with a writing rate of 5% (characters equivalent to 5% of the image area are written on the entire A4 surface) A test was conducted.

  An LED having a wavelength of 780 nm was used, which was arranged in an array on a glass substrate so that writing could be performed on the surface of the photoreceptor through a focusing lens array.

  The charging means used an external power source, and the voltage applied to the charging roller was an AC component with a peak-to-peak voltage of 1.9 kV and a frequency of 1.35 kHz. For the DC component, a bias was set such that the charged potential of the photosensitive member at the start of the test was −600 V, and the test was performed under this charging condition until the end of the test. The developing bias was −450V. The test environment is 23 ° C. and 55% RH.

After the printing durability test, image evaluation and resolution evaluation were performed.
(Image evaluation)
An image for evaluation was output, and the rank was evaluated comprehensively with respect to background dirt, fogging, image density, and the like.
(resolution)
A halftone image was output, and the dot formation state (dot dispersion and dot reproducibility) was observed.

  In any case, the evaluation rank is as follows.

：: Very good ○: Good △: Slightly inferior ×: Very bad As described above, the evaluation results of Examples 15 to 19, 21 and Reference Example 20 are shown in Table 2.

（実施例２２〜３１、３４、３５、参考例３２、３３及び比較例５〜８）
感光体１〜１８を実装用にした後、タンデム機構を有するフルカラー画像形成装置ＩＰＳｉＯ
Ｃｏｌｏｒ８１００（リコー社製）の改造機（パワーパックを交換し、正帯電となるよう改造し、さらに露光光源をＬＥＤに換装した装置）に搭載し、書き込み率が５％のチャート（Ａ４全面に対して、画像面積として５％相当の文字が平均的に書かれている）を用い、通算１万枚印刷する耐刷試験を行った。

(Examples 22 to 31, 34 , 35 , Reference Examples 32 and 33, and Comparative Examples 5 to 8)
Full-color image forming apparatus IPSiO having a tandem mechanism after the photoreceptors 1 to 18 are mounted.
Color 8100 (manufactured by Ricoh Co., Ltd.) chart (with a replacement of the power pack, remodeled to be positively charged, and further replaced the exposure light source with an LED) and a writing rate of 5% (on the entire A4 chart) In addition, a printing durability test for printing 10,000 sheets in total was performed using 5% of characters as an image area.

  An LED having a wavelength of 780 nm was used, which was arranged in an array on a glass substrate so that writing could be performed on the surface of the photoreceptor through a focusing lens array.

  The toner and developer used were changed from those dedicated to IPSiO Color 8100 to toner and developer having opposite polarities.

  As the charging means, an external power source was used, and the voltage applied to the charging roller was selected as an AC component with a peak-to-peak voltage of 1.9 kV and a frequency of 1.35 kHz. For the DC component, a bias was set so that the charging potential of the photosensitive member at the start of the test was +600 V, and the test was performed under this charging condition until the end of the test. The developing bias was + 450V. The test environment is 23 ° C. and 55% RH.

After the printing durability test, image evaluation and color reproducibility were evaluated.
(Image evaluation)
An image for evaluation was output, and the rank was evaluated comprehensively with respect to background dirt, fogging, image density, and the like.
(Color reproducibility)
An ISO / JIS-SCID image N1 (portrait) was output and the color color reproducibility was evaluated.

  In any case, the evaluation rank is as follows.

◎: Very good ○: Good Δ: Slightly inferior ×: Very bad As described above, the evaluation results of Examples 22 to 31, 34 , 35 , Reference Examples 32 and 33 and Comparative Examples 5 to 8 are shown in Table 3.

表１、表２及び表３の結果から、本発明の要件を満たす実施例では、繰り返し使用によっても異常画像が無く、また高精細な画像が出力できることがわかる。
（実施例３６〜３９）
感光体５、６、１７、１８について、オゾン濃度１０ｐｐｍの環境に５日間放置するオゾン暴露試験を行った。オゾン暴露試験後に画像評価及び解像度の評価を行った。評価は、（実施例１〜１０、１３、１４、参考例１１、１２及び比較例１〜４）で用いた画像形成装置を用いて行った。
（画像評価）
評価用画像を出力し、目視で地汚れ、かぶり、画像濃度等を総合的にランク評価した。
（解像度）
ハーフトーン画像を出力し、ドット形成状態（ドットの散り具合やドット再現性）を観察した。

From the results of Tables 1, 2 and 3, it can be seen that in the examples satisfying the requirements of the present invention, there is no abnormal image even when used repeatedly, and a high-definition image can be output.
(Examples 36 to 39)
The photoreceptors 5, 6, 17, and 18 were subjected to an ozone exposure test in which they were left in an environment with an ozone concentration of 10 ppm for 5 days. Image evaluation and resolution evaluation were performed after the ozone exposure test. Evaluation was performed using the image forming apparatus used in (Examples 1 to 10, 13, 14 , Reference Examples 11 and 12 and Comparative Examples 1 to 4).
(Image evaluation)
An image for evaluation was output, and the rank was evaluated comprehensively with respect to background dirt, fogging, image density, and the like.
(resolution)
A halftone image was output, and the dot formation state (dot dispersion and dot reproducibility) was observed.

  In any case, the evaluation rank is as follows.

A: Very good B: Good B: Somewhat inferior X: Very bad The evaluation results of Examples 36 to 39 are shown in Table 4.

It is a figure which shows an example of the image forming apparatus of this invention. It is a figure which shows the other example of the image forming apparatus of this invention. It is a figure which shows an example of the process cartridge of this invention. It is a figure which shows the other example of the image forming apparatus of this invention. It is a figure which shows the other example of the image forming apparatus of this invention. It is a figure which shows the other example of the image forming apparatus of this invention. 2 is a cross-sectional view showing an example of a photoreceptor used in the image forming apparatus of the present invention. FIG. It is sectional drawing which shows the other example of the photoreceptor used for the image forming apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Photoconductor 12 Charging means 13 Exposure means 14 Developing means 15 Toner 16 Transfer means 17 Cleaning means 18 Image receiving medium 19 Fixing means 1A Discharge means 1B Pre-cleaning exposure means 1C Driving means 1D First transfer means 1E Second transfer means 1F Intermediate transfer body 1G Image receiving medium carrier 21 Conductive support 22 Charge generation layer 23 Charge transport layer 24 Subbing layer 25 Photosensitive layer

Claims (7)

A photosensitive member, a charging unit that Ru charges the photosensitive body, and exposed using a light-emitting diode on the photosensitive member that the charging and exposure means for forming an electrostatic latent image, the electrostatic formed on the photoreceptor an image forming apparatus for chromatic developing means for forming a toner image by developing the latent image with toner, a transfer means for transferring the image receiving medium the toner image formed on said photosensitive member,
Photoreceptor is sensitive light layer is formed on the conductive support,
Photosensitive layer contains a charge generating material及beauty electron transport material,
The electron transport material has the chemical formula

A compound represented by the chemical formula

A compound represented by the chemical formula

A compound represented by the chemical formula

A compound represented by the chemical formula

A compound represented by the chemical formula

Or a chemical formula represented by

An image forming apparatus, wherein the compound is represented by the formula: The image forming apparatus according to claim 1, wherein the charge generation material is phthalocyanine. The image forming apparatus according to claim 2 , wherein the phthalocyanine is titanyl phthalocyanine. The titanyl phthalocyanine, a diffraction peak of Bragg angle 2θ with respect to characteristic X-ray of CuKa (± 0.2 °) has two 7.2 ° maximum peak, 9.4 °, 9.6 °, and 24 have a .0 ° peak has a peak of 7.3 ° lowest angle side, characterized in that no peak between peak and the 9.4 ° peak of the 7.3 ° The image forming apparatus according to claim 3 . It said charging means, an image forming apparatus according to any one of claims 1 to 4, characterized in Rukoto is positively charging the photosensitive member. A plurality of the photoreceptors;
The transfer unit sequentially transfers toner images formed on the plurality of photosensitive members to an intermediate transfer member and superimposes them, and transfers the toner images transferred and superimposed on the intermediate transfer member to the image receiving medium. the image forming apparatus according to any one of claims 1 to 5, characterized in that it has a secondary transfer means for. A photoreceptor, charged by exposure using a light-emitting diode on the photosensitive body, have a exposing means for forming an electrostatic latent image, a process cartridge is detachably mountable to the main body of the image forming apparatus,
The photoreceptor has a photosensitive layer formed on a conductive support,
The photosensitive layer contains a charge generation material and an electron transport material,
The electron transport material has the chemical formula

A compound represented by the chemical formula

A compound represented by the chemical formula

A compound represented by the chemical formula

A compound represented by the chemical formula

A compound represented by the chemical formula

Or a chemical formula represented by

A process cartridge , which is a compound represented by the formula:

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