JP4741382B2 - Electrophotographic apparatus and process cartridge - Google Patents

Description

  The present invention relates to an electrophotographic apparatus. More specifically, the present invention relates to a non-contact charging device that is disposed so that at least a gap between a photosensitive member surface and a charging member surface is 100 μm or less, and a specific charge transport material. The present invention relates to an electrophotographic apparatus using a photoconductor including the same.

  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.

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

  As a compact charging method, a contact-type charging member having a roller shape and having a form in contact with the photoreceptor is used as a compact charging method (for example, see Patent Document 1). Compared with the wire method (Corotron, Scorotron), this method can keep the applied voltage to the charging member low, so the capacity of the power pack used for the charging member can be small, which is very effective in reducing the power consumption. This is an advantageous method. In addition, since the potential difference between the charging member and the photoconductor only needs to be small during charging, the amount of oxidizing gas such as ozone and NOx is reduced, reducing the impact on the environment and the electrophotographic photoconductor. Is done. For this reason, generation | occurrence | production of an abnormal image and photoreceptor deterioration can be prevented.

However, the contact charging device has the following problems, which are as follows:
1. Charging roller trace,
2. Charged sound,
3. Deterioration of charging performance due to adhesion of toner on the photosensitive member to the charging member,
4). Adhesion of the material constituting the charging member to the photoreceptor,
5. Permanent deformation of the charging member that occurs when the photoreceptor is stopped for a long time.

  Charging roller traces occur because substances constituting the charging member ooze out from the charging member and adhere to and transfer to the surface of the charged body during the stop period of the charged body. Further, the charging sound is generated because the charging member in contact with the member to be charged vibrates when an AC voltage is applied to the charging member. As a method for solving such a problem, a proximity charging device has been devised in which a charging member is brought close to a photoconductor in a non-contact manner.

  In the proximity charging device, the charging device is opposed so that the distance at the closest part to the photoconductor is 0.005 to 0.3 [mm], and a voltage is applied to the charging member, whereby the photoconductor A charging device that performs charging. In the proximity charging device, since the charging device and the photoconductor are not in contact with each other, there is a problem with the contact charging device such as “adhesion of the substance constituting the charging member to the photoconductor”, “the photoconductor has been stopped for a long time. “Permanent deformation sometimes occurs” is not a problem. Further, with respect to “decrease in charging performance due to adhesion of toner or the like on the photosensitive member to the charging member”, the proximity charging device is superior because less toner adheres to the charging member.

  Such proximity charging is disclosed (for example, see Patent Documents 2 to 11).

  By using the proximity charging device as described above, it is small in size and eliminates the deterioration of the photoconductor due to an oxidizing gas such as ozone, and the problem that the photoconductor and the charging member are in contact with each other, resulting in high durability. An electrophotographic apparatus.

A photoreceptor used in such a highly durable electrophotographic apparatus needs to have stable electrostatic characteristics (chargeability, sensitivity, residual potential, etc.) even after repeated use. 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 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.
JP-A 63-149669 Japanese Patent Laid-Open No. 2-148059 Japanese Patent Application Laid-Open No. 5-127296 JP-A-5-273737 JP-A-5-307279 JP-A-6-308807 JP-A-8-202126 JP-A-9-171282 JP-A-10-288888 JP 2002-148904 A JP 2002-148905 A

  Therefore, the present invention has been made in view of the above, and an object thereof is to provide an electrophotographic apparatus that is compact and can output a high-quality image over a long period of time.

  As a result of intensive studies to solve the above-mentioned problems, the inventors have found that in an electrophotographic apparatus using a non-contact type charging device that is disposed close to each other so that the gap between the surface of the photoreceptor and the surface of the charging member is 100 μm or less. It has been found that an electrophotographic apparatus capable of outputting a high-quality image over a long period of time can be provided by using a photoreceptor containing a specific compound in the photosensitive layer.

  That is, this invention consists of the following aspects.

  (1) At least a photosensitive member, a non-contact type charging device arranged in close proximity so that a gap between the photosensitive member surface and the charging member surface is 100 μm or less, and image exposure after uniform charging to produce an electrostatic latent image In an electrophotographic apparatus having an image exposure device to be formed, a developing device for developing the electrostatic latent image, and a device for transferring the developed image, the photosensitive member has a photosensitive layer at least in the form of a conductive support, An electrophotographic apparatus characterized in that the photosensitive layer contains at least a charge generating material and an electron transport material represented by the following 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す。）
（２）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（１）記載の電子写真装置。

Wherein 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, a substituted or unsubstituted aralkyl group, and R 3 , R4, R5, R6, R7, R8, R9, R10 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group. Represents a group selected from the group consisting of a group, a substituted or unsubstituted aralkyl group.)
(2) The electrophotographic apparatus according to (1), wherein the charge generation material is phthalocyanine.

  (3) The electrophotographic apparatus according to (2), wherein the phthalocyanine is titanyl phthalocyanine.

  (4) 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 CuKα (wavelength 1.542 mm). The electrophotographic apparatus according to the description.

  (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 ray (wavelength 1.542Å), and further 9.4 Major peaks at °, 9.6 °, 24.0 ° and the lowest diffraction peak at 7.3 °, 7.3 ° peak and 9.4 ° The electrophotographic apparatus according to (3) or (4), wherein there is no peak between the peaks.

  (6) The electrophotographic apparatus according to (5), wherein the titanyl phthalocyanine has an average particle size of 0.25 μm or less.

  (7) The electrophotographic apparatus according to any one of (1) to (6), wherein the charging process is performed with positive charging.

  (8) The electrophotographic apparatus includes a plurality of photoconductors, and a color image is formed by sequentially superimposing monochromatic toner images developed on the photoconductors. The electrophotographic apparatus according to any one of (7).

  (9) Used in the electrophotographic apparatus according to any one of (1) to (8), wherein at least charging, image exposure, development, transfer, exposure before cleaning, cleaning, and static elimination are repeated on the electrophotographic photosensitive member. An electrophotographic method, wherein an alternating current component is superimposed on a direct current component and applied to a charging member to charge the photosensitive member.

  (10) An electrophotographic image that is detachable from the apparatus main body and includes at least an electrophotographic photosensitive member, and further includes a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, and a charge eliminating unit. A process cartridge for an apparatus, wherein the process cartridge is used in the electrophotographic apparatus according to any one of (1) to (8).

  Therefore, according to the present invention, it is possible to provide an electrophotographic apparatus that can output a high-quality image over a long period of time.

  First, features of the present invention will be described.

  Specifically, the present invention specifically includes at least a photosensitive member, a non-contact type charging device disposed so that a gap between the photosensitive member surface and the charging member surface is 100 μm or less, and image exposure after uniform charging. In an electrophotographic apparatus having an image exposure device for forming an electrostatic latent image, a developing device for developing the electrostatic latent image, and a device for transferring the developed image, the photoconductor is at least in the form of a conductive support. By using an electrophotographic apparatus having a photosensitive layer and containing at least a charge generating material and the electron transport material represented by the general formula 1 in the photosensitive layer, a compact and high-quality image can be obtained over a long period of time. Can be output.

  In the present invention, as the charging device, a non-contact type charging device is used which is disposed in close proximity so that the gap between the surface of the photoreceptor and the surface of the charging member is 100 μm or less. As the charging member, a roller-shaped member is effectively used because of its operating mechanism and simple apparatus.

  The close contact non-contact method has higher charging efficiency than the wire-type corona charging and generates less oxidizing gas such as ozone, so that deterioration of the photoreceptor due to the oxidizing gas can be reduced.

  Further, in the wire system, in order to obtain a surface potential of 500 to 700 V with the photosensitive member, it is necessary to apply a high voltage of DC 4 kV or more to the wire electrode, and in order to prevent leakage to the shield plate and the apparatus main body. It is necessary to take measures such as maintaining a large distance between the shield plate and the shield plate, and the device itself will be enlarged. However, in the case of the non-contact type arranged in close proximity, this is not necessary, and a compact charging device is obtained. be able to.

  Furthermore, in the non-contact method arranged in the proximity, there is no problem (such as toner on the photosensitive member adhering to the charging member) due to contact between the photosensitive member and the charging member as in the contact method as described above. As a whole, a highly durable electrophotographic apparatus can be obtained.

  In addition, since the electron transport material represented by the general formula 1 used in the present invention exhibits very excellent electron transport properties, a photosensitive layer having a high sensitivity can be obtained by incorporating it into the photosensitive layer as a charge transport material. . Therefore, stable image formation is possible even when the photosensitive member has a small diameter for downsizing the apparatus. In addition, a photoconductor using the electron transport material of the general formula 1 as a charge transport material has not only sensitivity but also good chargeability and a small residual potential accumulation. Further, since the change in characteristics is small even by repeated use, a high-quality image can be output over a long period of time.

  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, a titanyl phthalocyanine having titanium as a central metal as shown in the following structural formula (1) makes it possible to obtain a photosensitive body with particularly high sensitivity, further reducing the size and speed of an electrophotographic apparatus. It is possible to measure.

チタニルフタロシアニンの合成法や電子写真特性に関する文献としては、例えば特開昭５７−１４８７４５号公報、特開昭５９−３６２５４号公報、特開昭５９−４４０５４号公報、特開昭５９−３１９６５号公報、特開昭６１−２３９２４８号公報、特開昭６２−６７０９４号公報などが挙げられる。また、チタニルフタロシアニンには種々の結晶系が知られており、特開昭５９−４９５４４号公報、特開昭５９−１６６９５９号公報、特開昭６１−２３９２４８号公報、特開昭６２−６７０９４号公報、特開昭６３−３６６号公報、特開昭６３−１１６１５８号公報、特開昭６４−１７０６６号公報、特開２００１−１９８７１号公報等に各々結晶形の異なるチタニルフタロシアニンが記載されている。

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. 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, the smaller the average particle size, the higher the sensitivity and the higher the electrophotographic photosensitive member with respect to the background stain. 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.

  It has a maximum diffraction peak at 27.2 °, and further has major peaks at 9.4 °, 9.6 ° and 24.0 °, and 7.3 ° as the lowest diffraction peak. The volume average particle size in a dispersion of titanyl phthalocyanine (charge generating layer coating solution) having a peak at 7.3 ° and no peak between the 7.3 ° peak and the 9.4 ° peak is By setting it to 0.25 μm or less, it has high sensitivity, high stability against scumming, low exposure area potential, and less increase in exposure area potential due to repeated use. Can be output.

  Since the electron transporting material represented by the general formula 1 exhibits electron transporting properties, it becomes a positively charged photoreceptor in a laminated configuration in which the photosensitive layer is provided in the order of the charge generation layer and the charge transport layer from the support side. . 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 in chargeability and is generated. This is preferable because less oxidizing gas is used (about 1/10 of the negative charge).

  The electrophotographic apparatus of the present invention will be described in detail below 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, 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 in the photosensitive layer. The photoconductor 11 has a drum shape, but may have a sheet shape or an endless belt shape.

  As the charging means 12, a non-contact charging member arranged in proximity is used.

  The charging member arranged close here is a type in which the charging member is arranged in a non-contact state so as to have a gap (gap) of 100 μm or less between the surface of the photosensitive member and the surface of the charging member. If this gap is too large, the charging tends to become unstable, and if it is too small, the surface of the charging member may be contaminated when toner remaining on the photoreceptor exists. . Therefore, the gap is suitably 5 to 100 μm, preferably 10 to 50 μm. From the distance of the air gap, it is distinguished from known charging / wire-type chargers such as corotron and scorotron, contact charging members such as contact-type charging rollers, charging brushes and charging blades.

  The adjacently arranged charging member used in the present invention may have any shape as long as it has a mechanism capable of appropriately controlling the gap with the surface of the photoreceptor. For example, the rotation shaft of the photosensitive member and the rotation shaft of the charging member may be mechanically fixed so as to have an appropriate gap. Among them, using a charging member in the shape of a charging roller, a gap forming member is disposed at both ends of the non-image forming portion of the charging member, and only this portion is brought into contact with the surface of the photoreceptor, and the image forming region is disposed in a non-contact manner. Alternatively, the gap forming member at both ends of the non-photosensitive portion of the photoconductor is disposed, and only this portion is brought into contact with the surface of the charging member, and the image forming region is disposed in a non-contact manner, so that the gap can be stably stabilized. It is a method that can be maintained. In particular, the methods described in Patent Documents 10 and 11 can be used satisfactorily. An example of the proximity charging mechanism in which the gap forming member is arranged on the charging member side is shown in FIG.

  Furthermore, as an application method, there is an advantage that uneven charging is less likely to occur by using AC superposition, and it can be used satisfactorily. In particular, in the tandem type full-color image forming apparatus described later, in addition to the problem of uneven density of a halftone image due to uneven charging that occurs in the case of a monochrome image forming apparatus, there is a serious problem of deterioration in color balance (color reproducibility). Connected. The above problem is greatly improved by superimposing the AC component on the DC component, but if the AC component conditions (frequency, peak-to-peak voltage) are too large, the hazard to the photoconductor increases. In some cases, deterioration of the photoconductor may be accelerated. For this reason, superposition of alternating current components should be kept to the minimum necessary.

  The frequency of the AC component varies depending on the linear velocity of the photosensitive member, but 3 kHz or less, preferably 2 kHz or less is appropriate. Regarding the peak-to-peak voltage, when the relationship between the voltage applied to the charging member and the charging potential to the photoconductor is plotted, there is a region where the photoconductor is not charged despite the voltage being applied, and the charging rises from a certain point. Potential is observed. About twice this rising potential is the optimum potential (usually about 1200 to 1500 V) as the peak-to-peak voltage.

  However, when the charging ability of the photosensitive member is low or the linear velocity is very high, the peak-to-peak voltage twice the rising potential as described above may be insufficient. On the other hand, when the chargeability is good, the potential stability may be sufficiently exhibited even when it is twice or less. Therefore, the peak-to-peak voltage is preferably 3 times or less, more preferably 2 times or less of the rising potential. If the peak-to-peak voltage is rewritten as an absolute value, it is desirably used at 3 kV or less, preferably 2 kV or less, more preferably 1.5 kV or less.

  In the present invention, the charging polarity can be either positive or negative depending on the structure of the photoconductor. However, 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.

  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 exposure unit 13 and the charge removal unit 1A include fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light emitting diodes (LEDs), semiconductor lasers (LDs), electroluminescences (ELs) and the like. General. 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 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. 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, a photoconductor 11 satisfies the requirements of the present invention and has an endless belt shape.

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

  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 a general example is shown in FIG. Also in this case, the photoconductor 11 is a photoconductor that satisfies the requirements of the present invention. The photoconductor 11 has a drum shape, but may have a sheet shape or an endless belt shape.

  FIG. 4 shows another example of the electrophotographic apparatus according to the present invention. In this electrophotographic apparatus, a charging unit (12), an exposure unit (13), black (Bk), cyan (C), magenta (M), and yellow (Y) are provided for each color toner around the photoreceptor (11). Developing means (14Bk, 14C, 14M, 14Y), 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 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. Image formation of each color is sequentially performed, 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 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 method is not limited to the apparatus shown in FIG. 4, but can be applied to the electrophotographic apparatus shown in FIGS. 1, 2, and 3 and FIG. 5 (a specific example is shown in FIG. 6) described later. it can.

  FIG. 5 shows another example of the electrophotographic apparatus according to the present invention. This electrophotographic apparatus is of 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, a photoconductor (11Y, 11M, 11C, 11Bk) for each color is provided. The photoreceptor 11 used in this electrophotographic apparatus is a photoreceptor that satisfies the requirements of the present invention. 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. In addition, a transfer transfer belt 1G as a transfer material carrier that is in contact with and separated from each transfer position of each of the photoconductors 11Y, 11M, 11C, and 11Bk arranged on a straight line is stretched by a driving unit 1C. Transfer means 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 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.

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

  First, an example of each layer configuration 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.

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. Oxide such as film or cylindrical plastic or paper coated by vapor deposition or sputtering, or a plate made 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, or the like after being made into a bare pipe by a method such as the Extruded Ironing method, the Extruded Drawing method, or the cutting method.

(Charge generation layer)
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 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 oxadiazol skeleton, an azo pigment having a bisstilbene skeleton, an azo pigment having a distyryl oxadiazol skeleton, and a distyrylcarbazole skeleton Azo pigments, 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 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 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.

  Binder resins used as necessary for the charge generation layer include 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.

  In addition, 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. The application can be performed by a dip coating method, a spray coating method, a bead coating method, 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.

  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 above general formula (1), but in addition to this, a known charge transport material, that is, An electron transport material (acceptor) and a hole transport material (donor) can also 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, based on 100 parts by weight of the resin component, and is represented by the general formula (1) with respect to the entire charge transport material. The electron transport material 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)
In the electrophotographic photosensitive member 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. 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 photosensitive layer described above.

  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 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 a 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. I can do it.

  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 schematically showing an example of an electrophotographic photosensitive member used in the electrophotographic apparatus of the present invention. The electrophotographic photosensitive member is represented by at least a charge generating material on the conductive support 21 and the general formula 1. A photosensitive layer 25 containing an electron transport material is provided.

  Although not shown, an undercoat layer can 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, known materials can be used as in the case of the laminated structure. However, as described above, the phthalocyanine-based pigment has various aspects necessary for the present invention. Is particularly preferred.

  Among them, as described above, 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 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 transporting material even in a single layer configuration, it is essential to use the electron transporting material represented by the above-mentioned general formula 1, but in addition to this, the known charge transporting as described above. A material, that is, an electron transport material (acceptor) and a hole transport material (donor) can be used in the same manner as in the stacking.

  In the photosensitive layer having a 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, per 100 parts by weight of the binder resin component. However, the electron transport material represented by the general formula (1) 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, per 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, and 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.

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

｛但し、上記一般式中、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す。｝
該置換又は無置換のアルキル基としては、炭素数１乃至２５、好ましくは炭素数１乃至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、ｉ―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、上記置換又は無置換のアルキル基の炭素原子の一部がヘテロ原子（Ｎ、Ｏ、Ｓ等）に置換された基も置換されたアルキル基に含まれる。

{However, in the above general formula, R1 and R2 are each independently 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. R 3, R 4, R 5, R 6, R 7, R 8, R 9, R 10 are each independently a hydrogen atom, halogen atom, cyano group, nitro group, amino group, hydroxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted A group selected from the group consisting of a substituted 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, Carboxymethyl 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, ester 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. Are included in the alkyl 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, electron transport materials represented by the following structural formulas (2) to (8) are preferable in that the obtained image has high quality. In the formula, Me represents a methyl group.

該一般式（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。

Examples of the method for producing the electron transport material represented by the general formula (1) 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を表す。）
本発明に用いる一般式（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若しく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、ナフタレンカルボン酸若しくはその無水物を緩衝液により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、若しくは溶媒存在下でおこなう。溶媒として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原料や生成物と反応せず５０℃乃至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の混合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脱水反応は無溶媒、若しくは溶媒存在下でおこなう。溶媒として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、無水酢酸等原料や生成物と反応せず５０℃乃至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、無触媒若しくは触媒存在下でおこなってよく、特に限定されないが例えばモレキュラーシーブスやベンゼンスルホン酸やp-トルエンスルホン酸等を脱水剤として用いることが例示できる。

(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) used in the present invention is a method of reacting the above naphthalenecarboxylic acid or its anhydride with amines to monoimidize, or using a buffer solution for naphthalenecarboxylic acid or its anhydride. It can be obtained by adjusting pH 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 thru | or 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 in the absence of a 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.

  Hereinafter, the present invention will be described by way of examples. However, this does not limit the scope of the present invention. All parts are parts by weight.

Electron transport material synthesis example 1
First Step: A 200 ml four-necked flask was charged with 5.0 g (18.6 mmol) of 1,4,5,8-naphthalenetetracarboxylic dianhydride and 50 ml of DMF 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 from toluene / hexane to obtain 2.14 g of monoimide A (yield 31.5%).

Second Step A 100 ml four-necked flask was charged with 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 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 from toluene / ethyl acetate to obtain 0.668 g (yield 33.7%) of an electron transport material represented by the structural formula (2). In mass spectrometry (FD-MS) (referred to as electron transporting material 1), a peak of M / z = 726 was observed, so that it was 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.

電子輸送材料合成例２
第一工程
２００ｍｌ４つ口フラスコに、1,4,5,8―ナフタレンテトラカルボン酸二無水物10ｇ（37.3ｍｍｏｌ）とヒドラジン一水和物0.931ｇ（18.6ｍｍｏｌ）、ｐ−トルエンスルホン酸２０ｍｇ、トルエン１００ｍｌを入れ、５時間加熱還流させた。反応終了後、容器を冷却し、減圧濃縮した。残渣をシリカゲルカラムクロマトグラフィーにて精製した。更に回収品をトルエン／酢酸エチルにより再結晶し、二量体Ｃ 2.84g（収率28.7％）を得た。

Electron transport material synthesis example 2
First step In a 200 ml four-necked flask, 10 g (37.3 mmol) of 1,4,5,8-naphthalenetetracarboxylic dianhydride, 0.931 g (18.6 mmol) of hydrazine monohydrate, 20 mg of p-toluenesulfonic acid, 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 In a 100 ml four-necked flask, 2.5 g (4.67 mmol) of both-bodies C and 30 ml of DMF were placed and heated to reflux. To this, a mixture of 0.278 g (4.67 mmol) of 2-aminopropane and 10 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 to obtain 0.556 g (yield 38.5%) of monoimide C.

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. Furthermore, 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 (3). In mass spectrometry (FD-MS) (referred to as electron transporting material 2), a peak of M / z = 670 was observed, so that it was identified as a 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.

電子輸送材料合成例３
第一工程
２００ｍｌ４つ口フラスコに、上述した二量体Ｃ 5.0g（9.39ｍｍｏｌ）、ＤＭＦ５０ｍｌを入れ、加熱還流させた。これに、2−アミノヘプタン 1.08ｇ（9.39ｍｍｏｌ）ＤＭＦ２５ｍｌの混合物を攪拌しながら滴下した。滴下終了後、６時間加熱還流させた。反応終了後、反応容器を冷却し、減圧濃縮した。残渣にトルエンを加え、シリカゲルカラムクロマトグラフィーにて精製し、モノイミド体Ｄ 1.66ｇ（収率28.1％）を得た。

Electron transport material synthesis example 3
First Step In a 200 ml four-necked flask, 5.0 g (9.39 mmol) of the dimer C described above and 50 ml of DMF were placed and heated to reflux. To this, a mixture of 1.08 g (9.39 mmol) DMF 25 ml 2-aminoheptane 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 of monoimide D (yield 28.1%).

Second Step A 100 ml four-necked flask was charged with 1.5 g (2.38 mmol) of monoimide D and 50 ml of DMF 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. Further, the recovered product was recrystallized from toluene / hexane to obtain 0.328 g (yield 18.6%) of an electron transport material represented by the structural formula (5). In mass spectrometry (FD-MS) (referred to as electron transporting material 3), a peak of M / z = 740 was observed, so that it was identified as a target product. In the elemental analysis, the calculated values were 69.72% carbon, 5.44% hydrogen, and 7.56% nitrogen, and the measured values were 69.55% carbon, 5.26% hydrogen, and 7.33% nitrogen.

−チタニルフタロシアニン結晶の合成−
（顔料合成例１）
特開２００１−１９８７１号公報に準じて、顔料を作製した。即ち、１，３−ジイミノイソインドリン２９．２ｇとスルホラン２００ｍｌを混合し、窒素気流下でチタニウムテトラブトキシド２０．４ｇを滴下する。滴下終了後、徐々に１８０℃まで昇温し、反応温度を１７０℃乃至１８０℃の間に保ちながら５時間撹拌して反応を行った。反応終了後、放冷した後、析出物を濾過し、クロロホルムで粉体が青色になるまで洗浄し、次にメタノールで数回洗浄し、更に８０℃の熱水で数回洗浄した後乾燥し、粗チタニルフタロシアニンを得た。粗チタニルフタロシアニンを２０倍量の濃硫酸に溶解し、１００倍量の氷水に撹拌しながら滴下し、析出した結晶を濾過し、次いで、洗浄液が中性になるまでイオン交換水（ｐＨ：７．０、比伝導度：１．０μＳ／ｃｍ）により水洗いを繰り返し（洗浄後のイオン交換水のｐＨ値は６．８、比伝導度は２．６μＳ／ｃｍであった）、チタニルフタロシアニン顔料のウェットケーキ（水ペースト）を得た。得られたこのウェットケーキ（水ペースト）４０ｇをテトラヒドロフラン２００ｇに投入し、４時間攪拌を行った後、濾過を行い、乾燥して、チタニルフタロシアニン粉末を得た。これを顔料１とする。

-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 complete, 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 It has a peak at .3 ± 0.2 °, and further has main peaks at 9.4 °, 9.6 °, and 24.0 °, and a peak at 7.3 ° and a peak at 9.4 °. 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)
According to the method of Pigment Synthesis Example 1, a titanyl phthalocyanine pigment water paste was synthesized, and crystal conversion was performed as follows to obtain phthalocyanine crystals having smaller primary particles than 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 filtration was immediately performed under reduced pressure. The crystals obtained on the filtration device were washed with tetrahydrofuran to obtain a wet cake of pigment. 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 size 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 diameter. The average particle size 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. The average particle size obtained as described above is shown in Table 1. 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 carried out 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 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 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 for 5 days with a ball mill apparatus (using φ10 mm alumina balls as the media) to prepare 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 Using a PSZ ball of φ0.5 mm in a φ9 cm glass pot for 5 hours at a rotation speed of 100 rpm Dispersion was performed to obtain a charge generation layer coating solution.

(Coating liquid for charge transport layer)
Electron transport material 1: 10 parts
Z-type polycarbonate resin (Teijin Chemicals: Panlite TS-2050): 10 parts Silicone oil (Shin-Etsu Chemical Co., Ltd .: KF50): 0.01 parts Tetrahydrofuran: 80 parts did.

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 to produce a photoreceptor. (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 Industries, Ltd .: Fastogen Blue8120B): 3 parts Cyclohexanone: 97 parts A PSZ ball of φ0.5 mm was used in a φ9 cm glass pot and dispersed at a rotation speed of 100 rpm for 5 hours.

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

Dispersion liquid: 60 parts Hole transport material of structural formula 9: 25 parts Electron transport material 1: 25 parts
Z-type polycarbonate resin (Teijin Chemicals: Panlite TS-2050): 50 parts Silicone oil (Shin-Etsu Chemical Co., Ltd .: 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、感光体を作成した。（感光体２とする）
感光体作製例３
感光体作製例１において電荷発生材料をＸ型無金属フタロシアニン(Fastogen Blue8120B)に代えて顔料１のチタニルフタロシアニンを用いた以外は感光体作製例１と全く同様にして感光体を作製した。（感光体３とする）
なお、顔料１のチタニルフタロシアニンを用いた電荷発生層用塗工液中での体積平均粒径を堀場製作所製CAPA-700で測定したところ0.31μｍであった。

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, followed by drying at 120 ° C. for 20 minutes to form a 25 μm photosensitive layer to prepare a photoreceptor. (Referred to as photoreceptor 2)
Photoconductor Preparation Example 3
A photoconductor was prepared in exactly the same manner as in Photoconductor Preparation Example 1 except that the charge generating material in Example 1 was replaced with X-type metal-free phthalocyanine (Fastogen Blue 8120B) and titanyl phthalocyanine of Pigment 1 was used. (Referred to as photoreceptor 3)
The volume average particle diameter in the coating solution for charge generation layer using the titanyl phthalocyanine of Pigment 1 was measured by CAPA-700 manufactured by Horiba, Ltd. and found to be 0.31 μm.

Photoconductor Preparation Example 4
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 2, except that the charge generating material in Example 2 was replaced with X-type metal-free phthalocyanine (Fastogen Blue 8120B) and titanyl phthalocyanine of Pigment 1 was used. (Referred to as photoreceptor 4)
The volume 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.

Photoconductor Preparation Example 5
A photoconductor was prepared in exactly the same manner as in Photoconductor Preparation Example 1 except that the charge generating material in Example 1 was changed to X-type metal-free phthalocyanine (Fastogen Blue 8120B) and titanyl phthalocyanine of Pigment 2 was used. (Referred to as photoreceptor 5)
The volume average particle diameter in the coating solution for charge generation layer using the titanyl phthalocyanine of Pigment 2 was measured by CAPA-700 manufactured by Horiba, Ltd. and found to be 0.19 μm.

Photoconductor Preparation Example 6
A photoconductor was prepared in exactly the same manner as in Photoconductor Preparation Example 2, except that the charge generating material in Example 2 was replaced with X-type metal-free phthalocyanine (Fastogen Blue 8120B) and titanyl phthalocyanine of Pigment 2 was used. (Referred to as photoreceptor 6)
The volume average particle size of the pigment 2 in the pigment dispersion using titanyl phthalocyanine of the pigment 2 was 0.20 μm as measured with CAPA-700 manufactured by Horiba.

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. (Referred to as photoreceptor 7)
Photoconductor Preparation Example 8
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 2 except that the charge generating material in Example 2 was replaced with X-type metal-free phthalocyanine (Fastogen Blue 8120B) and titanyl phthalocyanine of Pigment 3 was used. (Referred to as photoreceptor 8)
Photoconductor Preparation Example 9
A photoconductor was prepared in exactly the same manner as in Photoconductor Preparation Example 1 except that the electron transport material 2 was used in place of the electron transport material 1 in Photoconductor Preparation Example 3. (Referred to as photoreceptor 9)
Photoconductor Preparation Example 10
A photoconductor was prepared in exactly 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 photoreceptor 10)
Photoconductor Preparation Example 11
A photoconductor was prepared in exactly 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 photoreceptor 11)
Photoconductor Preparation Example 12
A photoconductor was prepared in exactly 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 photoreceptor 12)
Photoconductor 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 10 was used in place of the electron transport material 1 in Photoconductor Preparation Example 3. (Referred to as photoreceptor 13)

感光体作製例１４
感光体作製例４において電子輸送材料１に代えて上記構造式１０の化合物を用いた以外は感光体作製例２と全く同様にして感光体を作製した。（感光体１４とする）
感光体作製例１５
感光体作製例３において電子輸送材料１に代えて下記構造式１１の化合物を用いた以外は感光体作製例１と全く同様にして感光体を作製した。（感光体１５とする）

Photoconductor 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 10 was used instead of the electron transport material 1 in Photoconductor Preparation Example 4. (Referred to as photoreceptor 14)
Photoconductor 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 11 was used in place of the electron transport material 1 in Photoconductor Preparation Example 3. (Referred to as photoreceptor 15)

感光体作製例１６
感光体作製例４において電子輸送材料１に代えて上記構造式１１の化合物を用いた以外は感光体作製例２と全く同様にして感光体を作製した。（感光体１６とする）
実施例１乃至１２及び比較例１乃至４
以上のように作製した感光体１乃至１６を実装用にした後、電子写真装置（リコー製ｉｍｇｉｏ Ｎｅｏ ２７０改造機、パワーパックを交換し正帯電となるよう改造し、帯電部材を図９に示すような非接触帯電ローラに交換した装置）に搭載し、書き込み率５％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 Preparation Example 16
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 2 except that the compound of Structural Formula 11 was used instead of the electron transport material 1 in Photoconductor Preparation Example 4. (Referred to as photoreceptor 16)
Examples 1 to 12 and Comparative Examples 1 to 4
After the photoconductors 1 to 16 produced as described above are mounted, the electrophotographic apparatus (Imgio Neo 270 remodeling machine manufactured by Ricoh, the power pack is replaced and remodeled to be positively charged, and the charging member is shown in FIG. (Equipment replaced with such a non-contact charging roller) and 10,000 sheets using a 5% writing rate chart (characters equivalent to 5% as the image area are written on the entire A4 surface) A printing durability test for printing was performed.

  The gap between the photoreceptor and the charging member was 50 μm.

  The toner and developer used were exchanged for toner and developer having polarity reversed from those dedicated to imgio Neo 270.

  The charging means of the electrophotographic apparatus 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 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.

  Image evaluation, dark part potential, and light part 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, etc. were comprehensively evaluated. The evaluation rank is as follows.

◎: Very good ○: Good △: Slightly inferior ×: Very bad Dark area potential: The surface potential of the photoconductor when it moves to the development position after primary charging, and the initial charge is + 600V. The applied voltage was adjusted, and thereafter, the applied voltage was kept constant until after the test was completed. The developing bias was + 450V.

  Bright portion potential: The surface potential of the photosensitive member when the image is exposed to the image (full exposure) and moved to the developing portion position after primary charging.

Example 13
In Example 1, evaluation was performed in the same manner as in Example 1 except that the gap between the photosensitive member and the charging member was changed to 80 μm.

Comparative Example 5
In Example 1, evaluation was performed in the same manner as in Example 1 except that the gap between the photosensitive member and the charging member was changed to 120 μm.

  The results of Examples 1 to 13 and Comparative Examples 1 to 5 are shown in Table 2.

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感光体特性が安定しており、良好な画像が出力できる。また感光体と帯電部材間の空隙が大きくなると帯電ムラによる画像ムラが見られ、空隙が１００μｍを超えると実使用には耐えないと判断される。

In the embodiment satisfying the requirements of the present invention, the photoreceptor characteristics are stable even after repeated use, and a good image can be output. Further, when the gap between the photosensitive member and the charging member becomes large, image unevenness due to charging unevenness is seen, and when the gap exceeds 100 μm, it is determined that the actual use is not durable.

Examples 14 to 19
After the photoreceptors 2, 4, 6, 8, 10, 12 are mounted, an electrophotographic apparatus (Ricoh's imgio Neo 270 remodeling machine, an apparatus in which the charging member is replaced with a non-contact charging roller as shown in FIG. 9) The printing durability test was performed to print 10,000 sheets in total using a 5% writing rate chart (characters equivalent to 5% as the image area are written on the entire A4 surface).

  The gap between the photoreceptor and the charging member was 50 μm.

  The charging means of the electrophotographic apparatus used an external power supply, 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 so 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.

  Image evaluation, dark part potential, and light part 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, etc. were comprehensively evaluated. The evaluation ranks are as follows: ◎: Very good ○: Good △: Slightly inferior ×: Very bad Dark portion potential: The surface potential of the photosensitive member when moved to the developing portion position after primary charging, and initially − The applied voltage of the charger was adjusted to 600 V, and thereafter, the applied voltage was constant until after the test was completed. The developing bias was −450V.

  Bright portion potential: The surface potential of the photosensitive member when the image is exposed to the image (full exposure) and moved to the developing portion position after primary charging.

  The results of Examples 14 to 19 are shown in Table 3.

実施例２０乃至３１及び比較例６乃至９
作製した感光体１乃至１６を実装用にした後、タンデム機構を有し、図９のような非接触帯電ローラを有するフルカラー電子写真装置（リコー製ＩＰＳｉＯ Ｃｏｌｏｒ８１００改造機、パワーパックを交換し正帯電となるよう改造し、さらに書込みに用いるＬＤの波長を780nmのものに換装した装置）に搭載し、書き込み率５％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 20 to 31 and Comparative Examples 6 to 9
After the produced photoreceptors 1 to 16 are mounted, a full-color electrophotographic apparatus having a tandem mechanism and a non-contact charging roller as shown in FIG. 9 (Ricoh's IPSiO Color 8100 remodeling machine, replacing the power pack and positively charging. In addition, it is mounted on a device in which the LD wavelength used for writing is changed to one with a wavelength of 780 nm, and a writing rate 5% chart (on the whole surface of A4, characters equivalent to 5% as an image area on average) A printing durability test was performed to print 10,000 sheets in total.

  The gap between the photoreceptor and the charging member was 50 μm.

  The toner and developer used were changed from a dedicated one for IPSiO Color 8100 to a toner and developer having opposite polarity.

  The charging means of the electrophotographic apparatus used an external power source, 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 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 color reproducibility were evaluated.

  Image evaluation: An image for evaluation was output, and rank evaluation was performed comprehensively for background stains, fogging, image density, and the like.

  Color reproducibility: An ISO / JIS-SCID image N1 (portrait) was output and the color reproducibility was evaluated.

In any case, the evaluation ranks are as follows: ◎: Very good ○: Good △: Somewhat inferior ×: Very bad The results of Examples 20 to 31 and Comparative Examples 6 to 9 are shown in Table 4.

上述のように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感光体特性が安定しており、良好な画像が出力できる。

As described above, in the example satisfying the requirements of the present invention, the photoreceptor characteristics are stable even after repeated use, and a good image can be output.

  As described above, as is clear from the detailed and specific invention, at least the photosensitive member, a non-contact charging device that is disposed in close proximity so that the gap between the photosensitive member surface and the charging member surface is 100 μm or less, and uniform In an electrophotographic apparatus comprising: an image exposure device that exposes an image after charging to form an electrostatic latent image; a developing device that develops the electrostatic latent image; and a device that transfers the developed image. By using an electrophotographic apparatus characterized by having a photosensitive layer in the form of a conductive support and containing at least a charge generating material and an electron transport material represented by the general formula 1 in the photosensitive layer, A high-quality image can be output.

  In the present invention, as the charging device, a non-contact type charging device is used which is disposed in close proximity so that the gap between the surface of the photoreceptor and the surface of the charging member is 100 μm or less. As the charging member, a roller-shaped member is effectively used because of its operating mechanism and simple apparatus.

  The close contact non-contact method has higher charging efficiency than the wire-type corona charging and generates less oxidizing gas such as ozone, so that deterioration of the photoreceptor due to the oxidizing gas can be reduced.

  Further, in the wire system, in order to obtain a surface potential of 500 to 700 V with the photosensitive member, it is necessary to apply a high voltage of DC 4 kV or more to the wire electrode, and in order to prevent leakage to the shield plate and the apparatus main body. It is necessary to take measures such as maintaining a large distance between the shield plate and the shield plate, and the device itself will be enlarged. However, in the case of the non-contact type arranged in close proximity, this is not necessary, and a compact charging device is obtained. be able to.

  Furthermore, in the non-contact method arranged in the proximity, there is no problem (such as toner on the photosensitive member adhering to the charging member) due to contact between the photosensitive member and the charging member as in the contact method as described above. As a whole, a highly durable electrophotographic apparatus can be obtained.

  In addition, since the electron transport material represented by the general formula 1 used in the present invention exhibits very excellent electron transport properties, a photosensitive layer having a high sensitivity can be obtained by incorporating it into the photosensitive layer as a charge transport material. . Therefore, stable image formation is possible even when the photosensitive member has a small diameter for downsizing the apparatus. In addition, a photoconductor using the electron transport material of the general formula 1 as a charge transport material has not only sensitivity but also good chargeability and a small residual potential accumulation. Further, since the change in characteristics is small even by repeated use, a high-quality image can be output over a long period of time.

  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, a titanyl phthalocyanine as shown in the above structural formula (1) having titanium as a central metal makes it possible to obtain a photosensitive body with particularly high sensitivity, and to further reduce the size and speed of an electrophotographic apparatus. It becomes possible to do more.

  Various crystal systems are known for titanyl phthalocyanine, and there are titanyl phthalocyanines having different crystal forms.

  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.

  The volume average particle size in the dispersion of titanyl phthalocyanine having the above crystal form (coating solution for charge generation layer) is 0.25 μm or less, so it is highly sensitive and highly stable against background stains. Since the potential is low and the exposure portion potential is not increased by repeated use, a good image can be output stably over a long period of time.

  Since the electron transporting material represented by the general formula 1 exhibits electron transporting properties, it becomes a positively charged photoreceptor in a laminated configuration in which the photosensitive layer is provided in the order of the charge generation layer and the charge transport layer from the support side. . 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 charge).

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to such specific embodiments, and various modifications and changes can be made within the scope of the gist of the present invention described in the claims. It can be changed.

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 sectional drawing which shows the layer structure of the electrophotographic photoreceptor which concerns on this invention. It is sectional drawing which shows another example of the electrophotographic photoreceptor which concerns on this invention. It is a schematic diagram which shows the example of the electrical-resistance member arrange | positioned closely based 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 Discharge means 1B Pre-cleaning exposure means 1C Driving 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 26 Charging roller 27 Gap forming member 28 Metal shaft 29 Non-image forming area 30 Image forming area

Claims (10)

A sensitive light body, the gap between the surface of the charging member surface and the non-contact type of the photosensitive member are placed so as to 100μm or less, a charging device for charging the photosensitive member, the charged photoreceptor in and image exposure, the image exposure device for forming an electrostatic latent image, a developing device for forming a toner image an electrostatic latent image formed on the photoreceptor is developed with toner, is formed on the photosensitive body the toner image image possess a transfer device for transferring to the image receiving medium,
The photosensitive member has a photosensitive layer formed on a conductive support,
Photosensitive layer, viewed contains a charge generating material and 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 electrophotographic apparatus , which is a compound represented by the formula: The electrophotographic apparatus according to claim 1 , wherein the charge generation material is phthalocyanine. The electrophotographic apparatus according to claim 2 , wherein the phthalocyanine is titanyl phthalocyanine. The titanyl phthalocyanine, a CuKα diffraction peak of Bragg angle 2θ for (wavelength 1.542 Å) (± 0.2 °), electrons according to claim 3, characterized in that it has a 27.2 maximum peak Photo equipment. The titanyl phthalocyanine, a diffraction peak of Bragg angle 2 [Theta] (± 0.2 °) with respect to CuKα rays (wavelength 1.542 Å), 9. 4 °, further comprising a peak 9.6 °, 24.0 °, 7. 5. The electrophotographic apparatus according to claim 4 , wherein the electrophotographic apparatus has a peak at the lowest angle at 3 °, and has no peak between the peak at 7.3 ° and the peak at 9.4 °. . The electrophotographic apparatus according to claim 5, wherein the titanyl phthalocyanine has an average particle size of 0.25 μm or less. The charging device, an electrophotographic apparatus according to any one of claims 1 to 6, characterized in that makes charging the photosensitive member positively. Having said photoconductor multiple,
The transfer apparatus, each of the monochromatic toner images formed on the photosensitive member by overlapping and sequentially transferred to the intermediate transfer member to form a color image, the image receiving medium a color image formed on the intermediate transfer member The electrophotographic apparatus according to claim 1, wherein the electrophotographic apparatus is transferred to the electrophotographic apparatus. The charging device, an electrophotographic apparatus according to any one of claims 1 to 8, characterized in that a voltage obtained by superposing an AC component on a DC component to the charging member. A process cartridge Ru detachable der to the main body of an electrophotographic apparatus,
The photosensitive member is disposed so that a gap between the surface of the photosensitive member and the surface of the non-contact charging member is 100 μm or less, and has a charging device for charging the photosensitive member,
The photosensitive member has a photosensitive layer formed on a conductive support,
The photosensitive layer includes 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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