JP4567614B2 - Electrophotographic equipment - Google Patents

Description

  The present invention relates to an electrophotographic apparatus using at least a corona charging device and a photoreceptor containing a specific charge transport material.

  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 technology 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. In addition, 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.

The electrophotographic photosensitive member used in these electrophotographic apparatuses is an organic photoconductive material having superiority in sensitivity, thermal stability, toxicity, and the like with respect to inorganic materials such as Se, CdS, and ZnO conventionally used as photoconductive materials. An electrophotographic photoreceptor using a conductive material has become mainstream. The electrophotographic photosensitive member using the organic photoconductive material mainly includes a function separation type photosensitive layer having a laminated structure including a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material. It is used for.
On the other hand, a single-layer photoconductor including a charge generation material and a charge transport material in a single photosensitive layer can be produced by a simple manufacturing process, and has improved optical characteristics due to fewer layer interfaces. In recent years, it has been attracting attention because of its advantages such as being usable in the charging process.

In general, an electrophotographic apparatus irradiates a uniformly charged photosensitive member with writing light modulated by image data to form an electrostatic latent image on the photosensitive member, and forms this electrostatic latent image. Toner is supplied to the photosensitive member by a developing unit to form a toner image on the photosensitive member and develop.
As a charging method in an electrophotographic apparatus, a corona charging method using a metal wire, a contact charging method in which a charging roller is brought into contact with a photosensitive member, and the like are known.
In the contact charging method, since the photosensitive member and the charging member are in contact with each other, the voltage applied to the charging member can be lowered, and the generation amount of oxidizing gases such as ozone and NOx is smaller than that in the corona charging method. However, because the discharge energy is high, the hazard to the photoconductor is likely to be worn away, the followability of charging is poor when the process line speed is high, and the photoconductor is discharged because a high voltage is directly applied to the photoconductor. There is a fault that it is easy to cause destruction.

The corona charging method is superior to the contact charging method in terms of high-speed tracking and is less advantageous for increasing the speed and durability of the device. There is a disadvantage that the amount of oxidizing gas such as NOx is large (about 100 times that of the contact charging method).
When the photoconductor is exposed to an oxidizing gas such as ozone or NOx, the charge generating material and charge transporting material in the photosensitive layer are subjected to a strong oxidizing action, causing a decrease in chargeability, an increase in residual potential, and a deterioration in sensitivity. As a result, image deterioration such as image density reduction and fogging is caused.

In order to prevent the deterioration due to these oxidizing gases, Patent Document 1 (Japanese Patent Laid-Open No. 57-122444) and the like describe a method of adding an antioxidant to the photosensitive layer. However, when an additive such as an antioxidant is contained in the photosensitive layer, there is a problem that the residual potential is increased or sensitivity is deteriorated from the initial stage or by repeated use, and the durability is still insufficient.
As described above, by using the corona charging method, a high-speed and highly durable electrophotographic apparatus can be obtained, but for that purpose, deterioration such as a decrease in charging is caused even for an oxidizing gas generated in large quantities by corona charging. A photoreceptor that does not wake up is required.

JP 57-122444 A

  An object of the present invention is to provide an electrophotographic apparatus capable of outputting a high-quality image over a long period of time without deterioration of a photoreceptor due to an oxidizing gas even when a corona charging method is used for high speed and high durability. And

  As a result of diligent investigations to solve the above problems, the inventors of the present invention, in an electrophotographic apparatus using a corona charging device, use a photosensitive member containing a specific charge transporting material in the photosensitive layer, thereby forming a photosensitive member using an oxidizing gas. We have found that it is possible to provide an electrophotographic apparatus that can output high-quality images over a long period of time without deterioration.

That is, the said subject is solved by (1)-(9) of this invention shown below.
(1) “At least the photosensitive member, a corona charging device that uniformly charges the surface of the photosensitive member, an image exposure unit that performs image exposure after uniform charging to form an electrostatic latent image, and the electrostatic latent image In the electrophotographic apparatus having the developing means for developing the toner and the transferring means for transferring the developed image, the photosensitive member has at least a photosensitive layer on the conductive support, and at least the charge generating material and the following in the photosensitive layer: An electrophotographic apparatus comprising an electron transport material represented by the general formula (1);

式中、Ｒ１、Ｒ２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、置換又は無置換のアラルキル基からなる群より選ばれる基を表わし、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９、Ｒ１０はそれぞれ独立に水素原子、ハロゲン原子、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、置換又は無置換のアラルキル基からなる群より選ばれる基を表わす。」
（２）「少なくとも感光体と、該感光体の表面を一様に帯電するコロナ帯電装置と、一様帯電後に像露光を行ない静電潜像を形成する像露光手段と、前記静電潜像を現像する現像手段と、現像像を転写する転写手段とを有する電子写真装置において、前記感光体が少なくとも導電性支持体上に感光層を有し、該感光層中に少なくとも電荷発生材料と下記一般式（２）で表わされる電子輸送材料を含むことを特徴とする電子写真装置；

In the formula, R1 and R2 each independently represent a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, R3, R4, R5, R6, R7, R8, R9, R10 are each independently a hydrogen atom, halogen atom, cyano group, nitro group, amino group, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group Represents a group selected from the group consisting of a substituted or unsubstituted aralkyl group. "
(2) “At least the photosensitive member, a corona charging device that uniformly charges the surface of the photosensitive member, an image exposure unit that performs image exposure after uniform charging to form an electrostatic latent image, and the electrostatic latent image In the electrophotographic apparatus having the developing means for developing the toner and the transferring means for transferring the developed image, the photosensitive member has at least a photosensitive layer on the conductive support, and at least the charge generating material and the following in the photosensitive layer: An electrophotographic apparatus comprising an electron transport material represented by the general formula (2);

式中、Ｒ１、Ｒ２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、置換又は無置換のアラルキル基からなる群より選ばれる基を表わす。」
（３）「前記電荷発生材料がフタロシアニンであることを特徴とする前記第（１）項又は第（２）項に記載の電子写真装置」
（４）「前記フタロシアニンがチタニルフタロシアニンであることを特徴とする前記第（３）項記載の電子写真装置」
（５）「前記チタニルフタロシアニンがＣｕ−Ｋα線（波長１．５４２Å）に対するブラッグ角２θの回折ピーク（±０．２゜）として、少なくとも２７．２°に最大回折ピークを有し、更に９．４゜、９．６゜、２４．０゜に主要なピークを有し、かつ最も低角側の回折ピークとして７．３゜にピークを有し、７．３゜のピークと９．４゜のピークの間にピークを有さないことを特徴とする前記第（４）項に記載の電子写真装置」
（６）「前記チタニルフタロシアニンの平均粒子径が０．２５μｍ以下であることを特徴とする前記第（５）項に記載の電子写真装置」
（７）「正帯電で帯電プロセスを行なうことを特徴とする前記第（１）項乃至第（６）項のいずれかに記載の電子写真装置」
（８）「前記電子写真装置が複数の感光体を具備してなり、それぞれの感光体上に現像された単色のトナー画像を順次重ね合わせてカラー画像を形成することを特徴とする前記第（１）項乃至第（７）項のいずれかに記載の電子写真装置」
（９）「プロセス線速が１００ｍｍ／ｓｅｃ以上で動作することを特徴とする前記第（１）項乃至第（８）項のいずれかに記載の電子写真装置」
（１０）「少なくとも感光体を具備してなる電子写真装置用プロセスカートリッジであって、前記第（１）項乃至第（９）項のいずれかに記載の電子写真装置に用いられることを特徴とする電子写真装置用プロセスカートリッジ」

In the formula, R 1 and R 2 each independently represent a 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. "
(3) “The electrophotographic apparatus according to (1) or (2), wherein the charge generation material is phthalocyanine”
(4) “Electrophotographic apparatus according to item (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 Cu—Kα rays (wavelength 1.542 mm). It has major peaks at 4 °, 9.6 ° and 24.0 °, and has a peak at 7.3 ° as the lowest diffraction peak, a peak at 7.3 ° and 9.4 °. The electrophotographic apparatus according to item (4), wherein there is no peak between the peaks of
(6) “The electrophotographic apparatus according to (5), wherein an average particle diameter of the titanyl phthalocyanine is 0.25 μm or less”
(7) “Electrophotographic apparatus according to any one of items (1) to (6), wherein the charging process is performed with positive charging”
(8) “The electrophotographic apparatus includes a plurality of photoconductors, and a single color toner image developed on each photoconductor is sequentially overlapped to form a color image. The electrophotographic apparatus according to any one of 1) to 7)
(9) "The electrophotographic apparatus according to any one of (1) to (8) above, wherein the process linear velocity is 100 mm / sec or more"
(10) “A process cartridge for an electrophotographic apparatus including at least a photoconductor, wherein the process cartridge is used in the electrophotographic apparatus according to any one of (1) to (9). Process cartridge for electrophotographic device "

  According to the present invention, it is possible to provide an electrophotographic apparatus capable of outputting a high-quality image over a long period of time at high speed and high durability.

  Specifically, at least a photoconductor, a corona charging device that uniformly charges the surface of the photoconductor, an image exposure device that performs image exposure after uniform charging to form an electrostatic latent image, and the electrostatic latent image In the electrophotographic apparatus having a developing device for developing a developing device and a device for transferring a developed image, the photosensitive member has a photosensitive layer on at least a conductive support, and at least the charge generating material and the general material in the photosensitive layer. By using the electrophotographic apparatus including the electron transport material represented by the formula (1) or the general formula (2), a high-quality image can be output at a high speed over a long period of time.

In the present invention, a corona charging device is used as the charging device. Since corona charging is superior in high-speed followability compared to contact charging using a charging roller, it can cope with higher speed of the electrophotographic apparatus. Corona charging has less electrostatic and physical hazards to the photoreceptor.
In contact charging, the discharge energy is high, the electrostatic hazard with respect to the photosensitive member is large, and the charging roller and the photosensitive member are in contact with each other, so that the photosensitive layer wears greatly. Therefore, corona charging can extend the life of the photoreceptor.

On the other hand, since corona charging generates a large amount of oxidizing gas such as ozone and NOx, the generated oxidizing gas deteriorates the photoconductor, causing a problem that the charging property, residual potential, and sensitivity of the photoconductor are deteriorated. .
However, since the electron transport material represented by the general formula (1) or the general formula (2) used in the present invention itself has excellent stability against oxidizing gas, it should be contained in the photosensitive layer. Thus, even if a large amount of oxidizing gas is generated by corona charging, the charging property, residual potential, and sensitivity of the photoreceptor are not deteriorated. This is considered to be resistant to oxidizing gas because of its strong N-basic molecular structure.

  In addition, since the electron transport material represented by the general formula (1) or the general formula (2) used in the present invention exhibits a very excellent electron transport property, it can be contained in the photosensitive layer with respect to the oxidizing gas. In addition to resistance, the photosensitive member is also highly sensitive in terms of electrostatic characteristics. Further, 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 generating material, but among them, a material having a phthalocyanine structure is preferable in combination with the charge transporting material used in the present invention.

  Among them, in particular, by using titanyl phthalocyanine as shown in the following structural formula (1) having titanium as a central metal, a photosensitive layer having particularly high sensitivity can be obtained, and the speed of the electrophotographic apparatus can be further increased. It becomes possible.

（式中、Ｘ_１、Ｘ_２、Ｘ_３、Ｘ_４は各々独立に各種ハロゲン原子を表わし、ｍ、ｎ、ｌ、ｋは各々独立的に０〜４の数字を表わす。）

(In the formula, X ₁ , X ₂ , X ₃ and X ₄ each independently represent various halogen atoms, and m, n, l and k each independently represents a number of 0 to _4. )

  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, and JP-A-59-31965. JP, 61-239248, JP, 62-67094, A, etc. are mentioned. In addition, various crystal systems are known for titanyl phthalocyanine. JP-A 59-49544, JP-A 59-166959, JP-A 61-239248, JP-A 62-67094. JP-A-63-366, JP-A-63-116158, JP-A-64-17066, JP-A-2001-19871, etc. each describe a titanyl phthalocyanine having a different crystal form. .

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 °, In addition, by using titanyl phthalocyanine having a peak at 7.3 ° as the diffraction peak on the lowest angle side and having no peak between the 7.3 ° peak and the 9.4 ° peak, Without losing sensitivity, it is possible to obtain a stable electrophotographic photosensitive member that does not cause a decrease in chargeability even when used repeatedly.
Further, a titanyl phthalocyanine crystal having the above crystal form and having an average primary particle size of 0.25 μm or less at the time of crystal synthesis or by dispersion filtration treatment and free of coarse particles (Japanese Patent Laid-Open No. 2004-83859, No. 2004-78141) is most useful. By using titanyl phthalocyanine crystals having a small average particle size of primary particles, a dispersion having a small average particle size can be prepared. In a normal dispersion, not all particles are present in the form of primary particles, and some aggregated primary particles exist. Therefore, a dispersion liquid having a small average particle diameter can be prepared by setting the average particle size of the primary particles to 0.25 μm or less and using titanyl phthalocyanine crystals having no coarse particles. When the average particle diameter of titanyl phthalocyanine is large, the surface area of the titanyl phthalocyanine particle is decreased, and the amount of contact with the charge transport material is decreased, so that the carrier injection efficiency is decreased. In addition, when the average particle size is large, the probability of coating film defects in the photosensitive layer (charge generation layer) increases, and there is a problem that image defects such as background stains are likely to occur. Therefore, as the average particle size is smaller, an electrophotographic photosensitive member having higher sensitivity and higher stability against soiling can be obtained. This effect is particularly remarkable when the average particle size is 0.25 μm or less.
The average particle diameter here is a volume average particle diameter in the dispersion (coating liquid for charge generation layer), and was determined by an ultracentrifugal automatic particle size distribution analyzer: CAPA-700 (manufactured by Horiba). Is. At this time, the particle size (Median system) corresponding to 50% of the cumulative distribution was calculated. However, this method may not be able to detect a very small amount of coarse particles. Therefore, in order to obtain more details, it is important to observe the titanyl phthalocyanine crystal powder or dispersion directly with an electron microscope and determine its size. It is.

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

  The synthesis of the electron transport material represented by the general formula (1) or the general formula (2) used in the present invention is not particularly limited, and is synthesized by a known synthesis method. For example, it can be obtained by reacting naphthalenecarboxylic acid or its anhydride with amines to monoimidize, adjusting the pH of naphthalenecarboxylic acid or its anhydride with a buffer and reacting with diamines, and the like. Monoimidization is carried out without solvent or in the presence of a solvent. Although there is no restriction | limiting in particular as a solvent, It does not react with raw materials and products, such as benzene, toluene, xylene, chloronaphthalene, acetic acid, pyridine, methylpyridine, dimethylformamide, dimethylacetamide, dimethylethylene urea, dimethylsulfoxide, and 50 degreeC. It is good to use what can be made to react at the temperature of -250 degreeC. 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. Carboxylic acid derivative dehydration reaction 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 as a solvent, It is good to use what reacts at the temperature of 50 to 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.

Hereinafter, the electrophotographic apparatus of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic view for explaining an electrophotographic apparatus of the present invention, and modifications as will be described later also belong to the category of the present invention.
In FIG. 1, the photoreceptor (11) has at least a photosensitive layer on a conductive support, and at least the charge generating material and the electron transport material represented by the general formula (1) or the general formula (2) in the photosensitive layer. The electron transport material represented by this is included. Although the photoconductor (11) has a drum shape, it may have a sheet shape or an endless belt shape.
As the charging means (charging device) (12), a corona charging device such as corotron or scorotron is used.
In the present invention, the charging polarity can be either positive or negative depending on the structure of the photoconductor, but the positive charging is more stable than the negative charging, and the amount of oxidizing gas such as ozone and NOx is also generated. It is desirable because there are few.
As the transfer means (16), known chargers such as corotron, scorotron, solid state charger, and charging roller can be used, but a combination of transfer charger and separation charger is effective. It is.
Light sources used for the exposure means (13), the charge removal means (1A), etc. include fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light emitting diodes (LEDs), semiconductor lasers (LDs), and electroluminescence (ELs). Examples of luminescent materials such as 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 photoreceptor by the developing means (14) is transferred to the image receiving medium (18), but not all is transferred, and toner remaining on the photoreceptor is also generated. Such toner is removed from the photoreceptor by the cleaning means (17). As the cleaning means, a rubber cleaning blade, a brush such as a fur brush, a mag fur brush, or the like can be used.

FIG. 2 shows another example of an electrophotographic process according to the present invention. In FIG. 2, the photoconductor (11) satisfies the requirements of the present invention and has an endless belt shape.
Driven by drive means (1C), charged by charging means (12), image exposure by exposure means (13), development (not shown), transfer by transfer means (16), cleaning by pre-cleaning exposure means (1B). Pre-exposure, cleaning by the cleaning means (17), and static elimination by the static elimination means (1A) are 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 above electrophotographic process exemplifies an 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 charge-removing exposure. Irradiation can also be performed.

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. There are many shapes and the like of the process cartridge, but general examples include those shown in FIGS. These process cartridges are detachable and easy to maintain.
In the present invention, a plurality of image forming elements in the form of process cartridges as shown in FIG. 3 may be provided. In such a case, a plurality of these image forming apparatuses are used horizontally or diagonally. In the case of FIG. 4 as well, the photoconductor (11) is a photoconductor that satisfies the requirements of the present invention. Although the photoconductor (11) has a drum shape, it may have a sheet shape or an endless belt shape.

  FIG. 5 shows another example of the electrophotographic apparatus according to the present invention. In this electrophotographic apparatus, charging means (charging device) (12), exposure means (13), black (Bk), cyan (C), magenta (M), and yellow (Y) are disposed around the photoreceptor (11). Developing means (14Bk, 14C, 14M, 14Y) for each color toner, an intermediate transfer belt (1F) as an intermediate transfer member, and a cleaning means (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, and are added or omitted as appropriate.

  The photoreceptor (11) is an electrophotographic photoreceptor that satisfies the requirements of the present invention. Each color developing means (14Bk, 14C, 14M, 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 means (1D) disposed inside the intermediate transfer belt (1F). The first transfer means (1D) is arranged so as to be able to come into contact with and separate from the photoreceptor (11), and the intermediate transfer belt (1F) is brought into contact with the photoreceptor (11) only during the transfer operation. The respective color images are 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 means (1E) and then fixed by the fixing means (19). The image is formed by fixing. The second transfer means (1E) is also arranged so as to be able to contact and separate from the intermediate transfer belt (1F), and contacts the intermediate transfer belt (1F) only during the transfer operation.

  In the transfer drum type electrophotographic 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 electrophotographic apparatus has an advantage that the toner images of the respective colors are superimposed on the intermediate transfer body (1F), and thus are not limited by the transfer material. Such an intermediate transfer system is not limited to the apparatus shown in FIG. 5, but is applied to the electrophotographic apparatus shown in FIGS. 1, 2, 3, and 4 and FIG. 6 (a specific example is shown in FIG. 7) described later. can do.

  FIG. 6 shows another example of the electrophotographic apparatus according to the present invention. This electrophotographic 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, 11Bk) for each color are provided. The photoreceptor used in this electrophotographic apparatus is a photoreceptor that satisfies the requirements of the present invention. Around each photoconductor (11Y, 11M, 11C, 11Bk), charging means (12Y, 12M, 12C, 12Bk), exposure means (13Y, 13M, 13C, 13Bk), developing means (14Y, 14M, 14C, 14Bk), cleaning means (17Y, 17M, 17C, 17Bk) and the like are provided. Further, a transfer transfer belt (1G) as a transfer material carrier that comes in contact with and separates from each transfer position of each photoconductor (11Y, 11M, 11C, 11Bk) arranged on a straight line is hung by a driving means (1C). Has been passed. Transfer means (16Y, 16M, 16C, 16Bk) are disposed at transfer positions facing the respective photoconductors (11Y, 11M, 11C, 11Bk) with the conveyance transfer belt (1G) interposed therebetween.

Next, the electrophotographic photosensitive member used in the present invention will be described in detail.
The photosensitive layer of the electrophotographic photoreceptor according to the present invention includes a multilayer photosensitive layer in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are laminated in this order, and a single layer. There is a single-layer type photosensitive layer containing a charge generation material and a charge transport material.

8 and 9 are cross-sectional views schematically showing an example of an electrophotographic photosensitive member used in the electrophotographic apparatus of the present invention. FIG. 8 shows an example of a photosensitive member of a laminated photosensitive layer, and FIG. 9 shows a single layer type. It is an example of the photoreceptor of a photosensitive layer.
First, an example of each layer structure of the laminated photosensitive layer will be described.
In this example, 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). The structure of the photosensitive layer.
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, iron, tin oxide, An oxide such as indium oxide coated with film or cylindrical plastic or paper by vapor deposition or sputtering, or a plate of aluminum, aluminum alloy, nickel, stainless steel, etc., and drawing ironing method or impact ironing method It is possible to use pipes that have been surface-treated by cutting, superfinishing, polishing, etc. after being made into raw pipes by methods such as the Extruded Ironing method, Extruded Drawing method, and cutting method.

(Charge generation layer)
First, the charge generation layer (22) among the layers in the multilayer photoconductor will be described. 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 a carbazole skeleton, azo pigments having a triphenylamine skeleton, azo pigments having a diphenylamine skeleton, dibenzo An azo pigment having a thiophene skeleton, an azo pigment having a fluorenone skeleton, an azo pigment having an oxadiazole skeleton, an azo pigment having a bisstilbene skeleton, an azo pigment having a distyryl oxadiazole skeleton, an azo pigment 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, Jigoido pigments, bisbenzimidazo - such as Le based 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 preferable from the viewpoint of various properties necessary for the present invention.
Among these, 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 an electrophotographic 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 °, In addition, by using titanyl phthalocyanine having a peak at 7.3 ° as the diffraction peak on the lowest angle side and having no peak between the 7.3 ° peak and the 9.4 ° peak, Without losing sensitivity, it is possible to obtain a stable electrophotographic photosensitive member that does not cause a decrease in chargeability even when used repeatedly.

Such titanyl phthalocyanine can be synthesized as follows. That is,
<Synthesis example>
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 dropwise addition, the temperature was gradually raised to 180 ° C., and the reaction was carried out by stirring for 5 hours while maintaining the reaction temperature between 170 ° C. and 180 ° C. After the completion of the reaction, the mixture was allowed to cool, and then the precipitate was filtered, washed with chloroform until the powder turned blue, then washed several times with methanol, further washed several times with hot water at 80 ° C., and dried. Crude titanyl phthalocyanine was obtained. Dissolve the crude titanyl phthalocyanine in 20 times the amount of concentrated sulfuric acid, add dropwise to 100 times the amount of ice water while stirring, filter the precipitated crystals, and then repeat washing with water until the washing solution becomes neutral. Got.
2 g of the obtained wet cake was put into 20 g of an organic solvent shown in Table 7 and stirred for 4 hours. 100 g of methanol was added to this and stirred for 1 hour, followed by filtration and drying to obtain a titanyl phthalocyanine crystal powder used in the present invention.
The obtained titanyl phthalocyanine crystal powder was subjected to X-ray diffraction spectrum measurement under the following conditions.
X-ray tube: Cu, voltage: 50 kV,
Current: 30 mA
Scanning speed: 2 ° / min,
Scanning range: 3 ° -40 °
Time constant: 2 seconds FIG. 10 shows an X-ray diffraction spectrum of the pigment prepared in the synthesis example.

The binder resin used as necessary for the charge generation layer includes polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, polyarylate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, poly-N-. Examples thereof include vinyl carbazole and polyacrylamide.
These binder resins may be used alone or as a mixture of two or more.
The binder resin is suitably 0 to 500 parts by weight, preferably 10 to 300 parts by weight, per 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 a charge generation layer by a casting method, the above-described charge generation material is dispersed by a ball mill, an attritor, a sand mill, or the like using a solvent such as tetrahydrofuran, cyclohexanone, dioxane, dichloroethane, or butanone together with a binder resin if necessary. What is necessary is just to apply | coat after diluting a dispersion liquid moderately. 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.

(Charge transport layer)
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 , 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 alone or as a mixture of two or more kinds, or as a copolymer comprising two or more kinds of raw material monomers, and further copolymerized with a charge transporting material.

For the purpose of ensuring the stability of the charge transport layer against environmental fluctuations, when an electrically inactive polymer compound is used, for example, polyester, polycarbonate, acrylic resin, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene Fluorine resin, 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 in combination with a binder resin as an additive, the addition amount is preferably 50 wt% or less because of restrictions on light attenuation sensitivity.

  The electron transport material represented by the general formula (1) used in the present invention has a structural skeleton shown below.

式中、Ｒ１、Ｒ２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、置換又は無置換のアラルキル基からなる群より選ばれる基を表わし、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８、Ｒ９、Ｒ１０はそれぞれ独立に水素原子、ハロゲン原子、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、置換又は無置換のアラルキル基からなる群より選ばれる基を表わす。

In the formula, R1 and R2 each independently represent a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, R3, R4, R5, R6, R7, R8, R9, R10 are each independently a hydrogen atom, halogen atom, cyano group, nitro group, amino group, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group Represents a group selected from the group consisting of a substituted or unsubstituted aralkyl group.

  The electron transport material represented by the general formula (2) used in the present invention has a structural skeleton shown below.

式中、Ｒ１、Ｒ２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、置換又は無置換のアラルキル基からなる群より選ばれる基を表わす。

In the formula, R 1 and R 2 each independently represent a 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.

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, i-propyl group, s-butyl group, t -Branched group such as butyl group, methylpropyl group, dimethylpropyl group, ethylpropyl group, diethylpropyl group, methylbutyl group, dimethylbutyl group, methylpentyl group, dimethylpentyl group, methylhexyl group, dimethylhexyl group, alkoxy Alkyl 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 a group in which a part of carbon atoms of the substituted or unsubstituted alkyl group is substituted with a hetero atom (N, O, S, etc.) is also substituted. Included in the alkyl group.

The substituted or unsubstituted cycloalkyl group includes a cycloalkyl ring having 3 to 25 carbon atoms, preferably 3 to 10 carbon atoms, specifically, a homocyclic 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, halogen-substituted alkyl group, alkoxycarbonylalkyl group, carboxyalkyl group, alkanoyloxyalkyl group, aminoalkyl group, halogen atom, amino group, esterified Which may be a carboxyl group, a cycloalkyl group substituted by a cyano group and the like.
The substitution position of these substituents is not particularly limited, and a group in which a part of carbon atoms of the substituted or unsubstituted cycloalkyl group is substituted with a hetero atom (N, O, S, etc.) is also substituted. It is included in the cycloalkyl group.

Examples of the substituted or unsubstituted aralkyl group include groups in which an aromatic ring is substituted on the above-described substituted or unsubstituted alkyl group, and an aralkyl group having 6 to 14 carbon atoms is preferable. More specifically, benzyl group, perfluorophenylethyl group, 1-phenylethyl group, 2-phenylethyl group, terphenylethyl group, dimethylphenylethyl group, diethylphenylethyl group, t-butylphenylethyl group, 3- Examples thereof include a phenylpropyl group, a 4-phenylbutyl group, a 5-phenylpentyl group, a 6-phenylhexyl group, a benzhydryl group, and a trityl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  More specifically, an electron transport material represented by the following formula (1-1), formula (1-2), and formulas (2-1) to (2-5) is obtained, but the image is of high quality. This is preferable. In the formula, Me represents a methyl group.

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

式中、ＲｎはＲ３、Ｒ４、Ｒ７、Ｒ８を表し、ＲｍはＲ５、Ｒ６、Ｒ９、Ｒ１０を表わす。

In the formula, Rn represents R3, R4, R7, and R8, and Rm represents R5, R6, R9, and R10.

  The electron transport material represented by the general formula (1) or the general formula (2) used in the present invention is a method of reacting the naphthalenecarboxylic acid or an anhydride thereof with an amine to monoimidize, an naphthalenecarboxylic acid or an anhydride thereof. It can be obtained by adjusting the pH of the product with a buffer solution and reacting with diamines. Monoimidization is carried out without solvent or in the presence of a solvent. The solvent is not particularly limited, but it does not react with raw materials or products such as benzene, toluene, xylene, chloronaphthalene, acetic acid, pyridine, methylpyridine, dimethylformamide, dimethylacetamide, dimethylethyleneurea, dimethylsulfoxide, and the like. It is good to use what can be made to react at the temperature of -250 degreeC. 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. Carboxylic acid derivative dehydration reaction 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 as a solvent, It is good to use what reacts at the temperature of 50 to 250 degreeC, without reacting with raw materials and products, such as benzene, toluene, chloronaphthalene, bromonaphthalene, and acetic anhydride. Any reaction may be carried out 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.

In the present invention, as a material that can be used for the charge transport material, it is essential to use the electron transport material represented by the general formula (1) or the general formula (2). A charge 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, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-tri Examples thereof include electron accepting substances such as nitrodibenzothiophene-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 addition amount of the charge transport material is suitably 40 to 200 parts by weight, preferably 70 to 150 parts by weight with respect to 100 parts by weight of the resin component, and the general formula (1) or general formula ( The electron transport material represented by 2) is preferably 50 to 100% by weight.

  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.

  If necessary, low-molecular compounds such as antioxidants, plasticizers, lubricants and ultraviolet absorbers and leveling agents described later 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 polymer compound, and the amount of the leveling agent used is 100 parts by weight of the polymer compound. On the other hand, 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 about 15 to 40 μm, preferably about 15 to 30 μm, and when resolution is required, 25 μm or less is appropriate.

(Underlayer)
The electrophotographic photosensitive member used in the present invention is provided with an undercoat layer (24) between the conductive support (21) and the mixed photosensitive layer (25) or the charge generation layer (22). 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. In general, the undercoat layer is mainly composed of a resin. However, considering that the photosensitive layer is applied on the resin using a solvent, the resin is a resin having high resistance to general organic solvents. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin.
In addition, a fine powder such as a metal oxide such as titanium oxide, silica, alumina, zirconium oxide, tin oxide, or indium oxide, or a metal sulfide or metal nitride may be added to the undercoat layer. These undercoat layers can be formed using an appropriate solvent and coating method, as in the case of the above-described 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 this, alumina is provided by anodic oxidation, organic materials such as polyparaxylylene (parylene), and inorganic materials such as silicon oxide, tin oxide, titanium oxide, ITO, ceria are provided by the vacuum thin film manufacturing method. It can be used well as an undercoat 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, a known antioxidant, plasticizer, ultraviolet absorber, low molecular charge transporting material and leveling agent are added to each layer in order to improve the gas barrier property and the environmental resistance of the photoreceptor surface layer. can do.

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. 9 is a cross-sectional view schematically showing an example of an electrophotographic photosensitive member used in the electrophotographic apparatus of the present invention. At least a charge generating material on the conductive support (21) and the general formula (1). Or the photosensitive layer (25) containing the electron transport material represented by General formula (2) is provided.
Although not shown, an undercoat layer may be provided between the conductive support (21) and the photosensitive layer (25).

As the charge generating 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 laminated structure. However, as described above, the phthalocyanine pigment has various characteristics necessary for the present invention. Is particularly preferred.
Among them, as described above, particularly titanyl phthalocyanine having titanium as a central metal makes it possible to obtain a photosensitive layer with particularly high sensitivity, and it is possible to further increase the speed of an electrophotographic apparatus. Further, among various crystal forms as in the case of lamination, 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 °, In addition, by using titanyl phthalocyanine having a peak at 7.3 ° as the diffraction peak on the lowest angle side and having no peak between the 7.3 ° peak and the 9.4 ° peak, Without losing sensitivity, it is possible to obtain a stable electrophotographic photosensitive member that does not cause a decrease in chargeability even when used repeatedly.
These pigments are preferably dispersed in advance by a ball mill, attritor, sand mill or the like using a solvent such as tetrahydrofuran, cyclohexanone, dioxane, dichloroethane or butanone. 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 the case of a single layer structure, it is essential to use the electron transport material represented by the general formula (1) or the general formula (2), but in addition to this, A known charge transporting material as described above, that is, an electron transporting material (acceptor) and a hole transporting material (donor) can be used in the same manner as in the lamination.
In the photosensitive layer having the single layer structure, the charge generating material is suitably 0.1 to 30% by weight, preferably 0.5 to 10% by weight, based on the entire photosensitive layer. The electron transport material is suitably 5 to 300 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight of the binder resin component. However, the electron transport material represented by the general formula (1) or the general formula (2) is preferably 50 to 100% by weight with respect to the entire electron transport material. The hole transport material is suitably 5 to 300 parts by weight, preferably 20 to 150 parts by weight with respect to 100 parts by weight of the binder resin component. When the electron transport material and the hole transport material are used in combination, the total 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.

  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 polymer compound such as a binder resin. The amount of the leveling agent used is the polymer compound. About 0.001 to 5 parts by weight is appropriate for 100 parts by weight.
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 about 10 to 45 μm, preferably about 15 to 32 μm, and when resolution is required, 25 μm or less is appropriate.

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. Further, the recovered product was recrystallized from toluene / hexane to obtain 2.14 g of monoimide A (yield 31.5%).
<Second step>
Into 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 were heated and refluxed 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. Furthermore, the recovered product was recrystallized from toluene / ethyl acetate to obtain 0.668 g (yield 33.7%) of an electron transport material represented by the structural formula (I). (Referred to as electron transport material 1)
In mass spectrometry (FD-MS), a peak of M / z = 726 was observed and identified as a target product. In the elemental analysis, calculated values were 69.41% carbon, 5.27% hydrogen, and 7.71% nitrogen, and the measured values were 69.52% carbon, 5.09% hydrogen, and 7.93% nitrogen.

(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. The recovered product was recrystallized from toluene / ethyl acetate to obtain 2.84 g of dimer C (yield 28.7%).
<Second step>
A 100 ml four-necked flask was charged with 2.5 g (4.67 mmol) of both-bodies C and 30 ml of DMF 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 the residue was purified by silica gel column chromatography to obtain 0.556 g of monoimide C (yield 38.5%).
<Third step>
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. Further, the recovered product was recrystallized from toluene / hexane to obtain 0.243 g (yield 22.4%) of an electron transport material represented by the structural formula (II). (Referred to as electron transport material 2)
In mass spectrometry (FD-MS), the peak was identified as M / z = 670, and the product was identified as the target product. In the elemental analysis, the calculated values were 68.05% carbon, 4.51% hydrogen, and 8.35% nitrogen, and the measured values were 68.29% carbon, 4.72% hydrogen, and 8.33% nitrogen.

(Electron Transport Material Synthesis Example 3)
<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 1.10 g (18.6 mmol) of 2-aminopropane 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 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 from toluene / hexane to obtain 2.08 g of monoimide B (yield 36.1%).
<Second step>
In a 100 ml four-necked flask, 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 are heated and refluxed 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 from toluene / ethyl acetate to obtain 0.810 g (yield 37.4%) of an electron transport material represented by the following structural formula (III). (Referred to as electron transport material 3)
In mass spectrometry (FD-MS), the peak of M / z = 614 was observed and identified as the target product. In the elemental analysis, the calculated values were 66.45% carbon, 3.61% hydrogen, and 9.12% nitrogen, and the measured values were 66.28% carbon, 3.45% hydrogen, and 9.33% nitrogen.

-Synthesis of titanyl phthalocyanine crystals-
(Pigment synthesis example 1)
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 dropwise addition, the temperature was gradually raised to 180 ° C., and the reaction was carried out by stirring for 5 hours while maintaining the reaction temperature between 170 ° C. and 180 ° C. After the reaction is completed, the mixture is allowed to cool, and then the precipitate is filtered, washed with chloroform until the powder turns blue, then washed several times with methanol, then washed several times with hot water at 80 ° C. and dried. Crude titanyl phthalocyanine was obtained. Crude titanyl phthalocyanine is dissolved in 20 times the amount of concentrated sulfuric acid, added dropwise to 100 times the amount of ice water with stirring, the precipitated crystals are filtered, and then ion-exchanged water (pH: 7. 0, specific conductivity: 1.0 μS / cm) Repeated washing with water (pH value of ion-exchanged water after washing was 6.8, specific conductivity was 2.6 μS / cm), wet of titanyl phthalocyanine pigment A cake (water paste) was obtained. 40 g of the obtained wet cake (water paste) was put into 200 g of tetrahydrofuran, stirred for 4 hours, filtered and dried to obtain titanyl phthalocyanine powder. This is designated as Pigment 1.
The solid content concentration of the wet cake was 15% by mass. The crystal conversion solvent was used in a mass ratio of 33 times that of the wet cake. In addition, the halogen-containing compound is not used for the raw material of the pigment synthesis example 1.
The obtained titanyl phthalocyanine powder was subjected to X-ray diffraction spectrum measurement under the following conditions. As a result, the Bragg angle 2θ with respect to Cu-Kα ray (wavelength 1.542Å) was 27.2 ± 0.2 °, and the maximum peak and minimum angle 7 .3 ± 0.2 ° peak, 9.4 °, 9.6 °, 24.0 ° main peaks, 7.3 ° peak and 9.4 ° peak A titanyl phthalocyanine powder having no peak in between was obtained. The result is shown in FIG.

<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)
-Synthesis of titanyl phthalocyanine crystals-
An aqueous paste of titanyl phthalocyanine pigment was synthesized according to the method of Pigment Synthesis Example 1, and crystal conversion was performed as follows to obtain phthalocyanine crystals having smaller primary particles than in Pigment Synthesis Example 1.
According to JP 2004-83859 A and Example 1, 400 parts by mass of tetrahydrofuran was added to 60 parts by mass of the water paste before crystal conversion obtained in Pigment Synthesis Example 1, and a homomixer (Kennis, MARK IIf model at room temperature) was added. ) Was vigorously stirred (2000 rpm), and when the dark blue color of the paste changed to light blue (20 minutes after the start of stirring), the stirring was stopped and immediately filtered under reduced pressure. The crystals obtained on the filter were washed with tetrahydrofuran to obtain a pigment wet cake. This was dried under reduced pressure (5 mmHg) at 70 ° C. for 2 days to obtain 8.5 parts by mass of titanyl phthalocyanine crystals. This is designated as Pigment 2. The raw material of Pigment Synthesis Example 1 does not use a halogen-containing compound. The solid content concentration of the wet cake was 15% by mass. The crystal conversion solvent was used in a mass ratio of 44 times that of the wet cake.
A portion of titanyl phthalocyanine (water paste) before crystal conversion prepared in Pigment Synthesis Example 1 was diluted with ion-exchanged water to approximately 1% by mass, and the surface was scooped with a copper net having been subjected to conductive treatment. The particle diameter of phthalocyanine was observed with a transmission electron microscope (TEM, Hitachi: H-9000NAR) at a magnification of 75000 times. The average particle size was determined as follows.

The TEM image observed as described above is taken as a TEM photograph, and 30 titanyl phthalocyanine particles (a shape close to a needle shape) projected are arbitrarily selected, and the size of each major axis is measured. An arithmetic average of the major diameters of the measured 30 individuals was determined and used as the average particle size of the primary particles. The average particle size of the primary particles in the water paste in Pigment Synthesis Example 1 determined by the above method was 0.06 μm.
In addition, the titanyl phthalocyanine crystal after crystal conversion just before filtration in Pigment Synthesis Example 1 and Pigment Synthesis Example 2 was diluted with tetrahydrofuran so as to be about 1% by mass, and observed in the same manner as the above method. Table 1 shows the average particle size of the primary particles obtained as described above. In addition, the titanyl phthalocyanine crystals produced in Pigment Synthesis Example 1 and Pigment Synthesis Example 2 did not necessarily have the same shape of all crystals (a shape close to a triangle, a shape close to a square, etc.). For this reason, the calculation was performed with the length of the largest diagonal line of the crystal as the major axis.

顔料合成例２で作製した顔料２は、先程と同様の方法でＸ線回折スペクトルを測定した。その結果、顔料合成例２で作製した顔料２のＸ線回折スペクトルは、顔料合成例１で作製した顔料１のスペクトルと一致した。

Pigment 2 prepared in Pigment Synthesis Example 2 was measured for an X-ray diffraction spectrum by the same method as described above. As a result, the X-ray diffraction spectrum of Pigment 2 prepared in Pigment Synthesis Example 2 matched the spectrum of Pigment 1 prepared in Pigment Synthesis Example 1.

(Pigment synthesis example 3)
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 dropping, the temperature was gradually raised to 200 ° C., and the reaction was carried out by stirring for 3 hours while maintaining the reaction temperature between 200 ° C. and 220 ° C. After completion of the reaction, the mixture was allowed to cool to 130 ° C. and filtered while hot, then washed with 1-chloronaphthalene until the powder turned blue, then washed several times with methanol, and further with hot water at 80 ° C. After washing twice, it was dried to obtain a pigment. This is designated as Pigment 3.
The obtained titanyl phthalocyanine powder was subjected to X-ray diffraction spectrum measurement under the above conditions, and confirmed to be the same as the spectrum described in the publication.

<Photoconductor 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: Beccosol M-6401-50): 60 parts Melamine resin (Dainippon Ink: Super Becamine L-121-60): 40 parts 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 φ10 mm alumina balls as media) for 5 days to obtain an undercoat layer coating solution.

(Coating solution for charge generation layer)
Metal-free phthalocyanine pigment (Dainippon Ink Industries, Ltd .: Fastogen Blue8120B): 12 parts Polyvinyl butyral resin (Sekisui Chemical Co., Ltd .: ESREC BX-1): 5 parts 2-butanone: 200 parts cyclohexanone: 400 parts A PSZ ball having a diameter of 0.5 mm was used for the glass pot, and dispersion was performed at a rotation 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 These are stirred and dissolved Thus, a charge transport layer coating solution was obtained.

Next, on the 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 immersed in the dip coating method. And dried to form a 4.5 μm subbing layer, a 0.15 μm charge generation layer, and a 25 μm charge transport layer (referred to as “photoreceptor 1”).
The drying temperature of each layer was 135 ° C. for 20 minutes, 80 ° C. for 15 minutes, and 120 ° C. for 20 minutes.

<Photoconductor Preparation Example 2>
Metal-free phthalocyanine was dispersed under the following composition and conditions to prepare a pigment dispersion.
Metal-free phthalocyanine pigment (Dainippon Ink and Chemicals Co., Ltd .: Fastogen Blue 8120B): 3 parts Cyclohexanone: 97 parts Dispersion was carried out at a rotation speed of 100 rpm for 5 hours using a PSZ ball of φ0.5 mm in a glass pot of φ9 cm.
A photoconductor coating solution having the following composition was prepared using the dispersion.
Dispersion liquid: 60 parts Hole transport material of structural formula (IV): 25 parts Electron transport material 1: 25 parts Z-type polycarbonate resin (manufactured by Teijin Chemicals: Panlite TS-2050): 50 parts Silicone oil (Shin-Etsu Chemical Co., Ltd.) Manufactured by KF50): 0.01 parts Tetrahydrofuran: 350 parts

こうして得られた感光層用塗工液をφ３０ｍｍ、長さ３４０ｍｍアルミニウムドラム上に、浸漬塗工法にて塗布、１２０℃で２０分間乾燥し、２５μｍの感光層を形成し、感光体を作製した（感光体２とする）。

The photosensitive layer coating solution thus obtained was applied onto 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 photosensitive layer of 25 μm, thereby producing a photoreceptor ( Photoconductor 2).

<Photoreceptor Preparation Example 3>
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that titanyl phthalocyanine of Pigment 1 was used instead of X-type metal-free phthalocyanine (Fastogen Blue 8120B) in Photoconductor Preparation Example 1 (Photoconductor) 3).
The average particle diameter in the coating solution for charge generation layer using pigment 1 titanyl phthalocyanine was measured by CAPA-700 manufactured by Horiba, Ltd. and found to be 0.31 μm.

<Photoreceptor Preparation Example 4>
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 2 except that titanyl phthalocyanine of Pigment 1 was used instead of X-type metal-free phthalocyanine (Fastogen Blue 8120B) in Photoconductor Preparation Example 2 (Photoconductor) 4).
The average particle size in the pigment dispersion using the titanyl phthalocyanine of Pigment 1 was measured by CAPA-700 manufactured by Horiba, Ltd. and found to be 0.35 μm.

<Photoreceptor Preparation Example 5>
A photoconductor was prepared in exactly the same manner as in Photoconductor Preparation Example 1 except that titanyl phthalocyanine of pigment 2 was used instead of X-type metal-free phthalocyanine (Fastogen Blue 8120B) in Photoconductor Preparation Example 1 (Photoconductor) 5).
In addition, when the average particle diameter in the coating solution for charge generation layers using the titanyl phthalocyanine of the pigment 2 was measured with CAPA-700 made from Horiba, it was 0.19 micrometer.

<Photoconductor Preparation Example 6>
A photoconductor was prepared in exactly the same manner as in Photoconductor Preparation Example 2 except that titanyl phthalocyanine of Pigment 2 was used instead of X-type metal-free phthalocyanine (Fastogen Blue 8120B) in Photoconductor Preparation Example 2 (Photoconductor) 6).
In addition, when the average particle diameter in the pigment dispersion using the titanyl phthalocyanine of the pigment 2 was measured by CAPA-700 manufactured by Horiba, it was 0.20 μm.

<Photoconductor Preparation Example 7>
A photoconductor was prepared in exactly the same manner as in Photoconductor Preparation Example 1 except that titanyl phthalocyanine of pigment 3 was used instead of X-type metal-free phthalocyanine (Fastogen Blue 8120B) in Photoconductor Preparation Example 1 (Photoconductor) 7).

<Photoreceptor Preparation Example 8>
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 2 except that titanyl phthalocyanine of pigment 3 was used instead of X-type metal-free phthalocyanine (Fastogen Blue 8120B) in Photoconductor Preparation Example 2 (Photoconductor) 8).

<Photoconductor Preparation Example 9>
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the electron transport material 2 was used instead of the electron transport material 1 in Photoconductor Preparation Example 3 (referred to as Photoconductor 9).

<Photoreceptor Preparation Example 10>
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 2 except that the electron transport material 2 was used instead of the electron transport material 1 in Photoconductor Preparation Example 4 (referred to as Photoconductor 10).

<Photoreceptor Preparation Example 11>
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the electron transport material 3 was used instead of the electron transport material 1 in Photoconductor Preparation Example 3 (referred to as Photoconductor 11).

<Photoconductor Preparation Example 12>
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 2 except that the electron transport material 3 was used instead of the electron transport material 1 in Photoconductor Preparation Example 4 (referred to as Photoconductor 12).

<Photoreceptor Preparation Example 13>
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that a compound of the following structural formula (V) was used in place of the electron transport material 1 in Photoconductor Preparation Example 3 (referred to as Photoconductor 13).

<Photoreceptor Preparation Example 14>
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 2 except that the compound of the structural formula (V) was used in place of the electron transport material 1 in Photoconductor Preparation Example 4 (referred to as Photoconductor 14).

<Photoreceptor Preparation Example 15>
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that a compound of the following structural formula (VI) was used in place of the electron transport material 1 in Photoconductor Preparation Example 3 (referred to as Photoconductor 15).

<Photoreceptor Preparation Example 16>
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 2 except that the compound of the structural formula (VI) was used in place of the electron transport material 1 in Photoconductor Preparation Example 4 (referred to as Photoconductor 16).

Examples 1-12 and Comparative Examples 1-4
After mounting the photoconductors 1 to 16 produced as described above, an electrophotographic apparatus (Imgio Neo 270 remodeling machine manufactured by Ricoh, the charging member is replaced with a scorotron, and the power pack is further replaced so as to be positively charged. The printing durability test was performed to print 10,000 sheets in total using a 5% writing rate chart (characters equivalent to 5% of the image area are written on the entire A4 surface). .
The toner and developer used were exchanged for toner and developer having polarity reversed from those dedicated to imgio Neo 270.
As a charging condition, a bias was set so that the charged potential of the photosensitive member at the start of the test was +500 V, and the test was performed under this charging condition until the end of the test. The developing bias was + 350V. The test environment is 23 ° C. and 55% RH.

Image evaluation, dark portion potential, and light portion potential were evaluated before and after the printing durability test.
(Image evaluation)
An image for evaluation was output, and the background contamination, fogging, image density, and the like were evaluated comprehensively. The evaluation rank is as follows.
◎: Very good ○: Good △: Slightly inferior ×: Very bad (dark part potential)
After the primary charging, the photosensitive member surface potential when moved to the developing unit position was adjusted, and the applied voltage of the charger was adjusted to +500 V in the initial stage, and thereafter, the applied voltage was constant until the end of the test. The developing bias was + 350V.
(Bright part potential)
Photoreceptor surface potential when the image is exposed (entire exposure) after primary charging and moved to the development position.
The results of Examples 1 to 12 and Comparative Examples 1 to 4 are shown in Table 2.

Examples 13-24 and Comparative Examples 5-8
The produced photoreceptors 1 to 16 were subjected to an ozone exposure test in which they were left in an environment having an ozone concentration of 10 ppm for 5 days. Image evaluation, dark part potential, and light part potential were evaluated before and after the ozone exposure test. The evaluation method is the same as in Examples 1-12 and Comparative Examples 1-4.
The results of Examples 13 to 24 and Comparative Examples 5 to 8 are shown in Table 3 above.

From the results in Table 2, it can be seen that in Examples 1 to 12 that satisfy the requirements of the present invention, the characteristics of the photoreceptor are stable even when used repeatedly, and a good image can be output. Moreover, it turns out that the dark part electric potential hardly changes with ozone exposure in Examples 13-24 which satisfy | fill the requirement of this invention from the result of Table 3, and the stability with respect to oxidizing gas is excellent.
On the other hand, in Comparative Examples 1 to 4 that do not satisfy the requirements of the present invention, the dark part potential of the photoreceptor is lowered by repeated use, and an abnormal image is generated. The results of the ozone exposure test in Table 3 also show that the dark part potential decreases and an abnormal image is generated. Therefore, it can be seen that the results in Table 2 are caused by the deterioration of the photoconductor by the oxidizing gas generated in large quantities by corona charging. .

Examples 25-36 and Comparative Examples 9-12
After the produced photoconductors 1 to 16 are mounted, a full-color electrophotographic apparatus having a tandem mechanism (Ricoh's IPSiO Color 8100 remodeling machine, the charging member is replaced with a scorotron, and the power pack is replaced to be positively charged. Furthermore, it is mounted on a device in which the wavelength of the LD used for writing is replaced with one having a wavelength of 780 nm), and a writing rate 5% chart (characters equivalent to 5% as an image area are written on the entire A4 surface) A press life test was performed to print 10,000 sheets in total.
The toner and developer used were changed from a dedicated one for IPSiO Color 8100 to a toner and developer having opposite polarity.
As a charging condition, a bias was set so that the charged potential of the photosensitive member at the start of the test was +500 V, and the test was performed under this charging condition until the test was completed. The developing bias was + 350V. 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 ranks are as follows: ◎: Very good ○: Good △: Somewhat inferior ×: Very bad The results of Examples 25 to 36 and Comparative Examples 9 to 12 are shown in Table 4.

1 is a schematic cross-sectional view illustrating an example of an electrophotographic apparatus according to the present invention. It is a schematic cross section which shows another example of the electrophotographic apparatus which concerns on this invention. It is a schematic cross section which shows another example of the electrophotographic apparatus which concerns on this invention. It is a schematic cross section which shows another example of the electrophotographic apparatus which concerns on this invention. It is a schematic cross section which shows another example of the electrophotographic apparatus which concerns on this invention. It is a schematic cross section which shows another example of the electrophotographic apparatus which concerns on this invention. It is a schematic cross section which shows another example of the electrophotographic apparatus which concerns on this invention. It is sectional drawing which shows the example of the layer structure of the electrophotographic photoreceptor which concerns on this invention. It is sectional drawing which shows the example of another layer structure of the electrophotographic photoreceptor which concerns on this invention. It is a X-ray diffraction spectrum figure of the titanyl phthalocyanine synthesize | combined by the synthesis example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 ... Electrophotographic photoreceptor 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 ... Charging means 1B ... Pre-cleaning exposure means 1C ... Drive means 1D ... First transfer means 1E ... Second transfer means 1F ... Intermediate transfer member 1G: image receiving medium carrier 21 ... conductive support 22 ... charge generation layer 23 ... charge transport layer 24 ... undercoat layer 25 ... photosensitive layer

Claims (10)

At least a photoconductor, a corona charging device that uniformly charges the surface of the photoconductor, an image exposure unit that performs image exposure after uniform charging to form an electrostatic latent image, and development that develops the electrostatic latent image In the electrophotographic apparatus having a transfer means for transferring a developed image, the photosensitive member has at least a photosensitive layer on a conductive support, and at least the charge generating material and the following general formula (1) are included in the photosensitive layer. An electrophotographic apparatus comprising an electron transport material represented by:

In the formula, R1 and R2 each independently represent a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aralkyl group, R3, R4, R5, R6, R7, R8, R9, R10 are each independently a hydrogen atom, halogen atom, cyano group, nitro group, amino group, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group Represents a group selected from the group consisting of a substituted or unsubstituted aralkyl group. At least a photoconductor, a corona charging device that uniformly charges the surface of the photoconductor, an image exposure unit that performs image exposure after uniform charging to form an electrostatic latent image, and development that develops the electrostatic latent image In the electrophotographic apparatus having a transfer means for transferring a developed image, the photosensitive member has at least a photosensitive layer on a conductive support, and at least the charge generating material and the following general formula (2) are included in the photosensitive layer. An electrophotographic apparatus comprising an electron transport material represented by:

In the formula, R 1 and R 2 each independently represent a 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. The electrophotographic apparatus according to claim 1, wherein the charge generation material is phthalocyanine. 4. The electrophotographic apparatus according to claim 3, wherein the phthalocyanine is titanyl phthalocyanine. 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 Cu-Kα ray (wavelength 1.542Å), and further 9.4 °, 9 It has major peaks at .6 ° and 24.0 °, and has a peak at 7.3 ° as the lowest angle diffraction peak, between the 7.3 ° peak and the 9.4 ° peak. The electrophotographic apparatus according to claim 4, wherein the apparatus has no peak. The electrophotographic apparatus according to claim 5, wherein the titanyl phthalocyanine has an average particle size of 0.25 μm or less. The electrophotographic apparatus according to claim 1, wherein the charging process is performed with positive charging. 7. The electrophotographic apparatus according to claim 1, wherein the electrophotographic apparatus includes a plurality of photoconductors, and a single color toner image developed on each photoconductor is sequentially superimposed to form a color image. An electrophotographic apparatus according to claim 1. The electrophotographic apparatus according to claim 1, wherein the electrophotographic apparatus operates at a process linear velocity of 100 mm / sec or more. An electrophotographic apparatus process cartridge comprising at least a photoconductor, wherein the electrophotographic apparatus process cartridge is used in the electrophotographic apparatus according to claim 1.

Images