JP4207211B2 - Image forming apparatus and image forming method - Google Patents

Description

  In the present invention, a toner image formed on an electrostatic latent image carrier (hereinafter sometimes referred to as “electrophotographic photosensitive member”, “photosensitive member”, or “photoconductive insulator”) is directly applied to a recording medium. An image forming apparatus to be transferred, wherein the electrophotographic photosensitive member is formed by sequentially laminating a charge generation layer and a charge transport layer containing at least a titanyl phthalocyanine crystal having a specific crystal type and a specific particle size. It relates to a forming method.

  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 is markedly improved in print quality and reliability. This digital recording technique is applied not only to printers but also to ordinary copying machines, and so-called digital copying machines have been developed. In addition, since a variety of information processing functions can be added to a conventional copying machine equipped with this digital recording technology for analog copying, the demand is expected to increase in the future. Further, along with the spread of personal computers and the improvement in performance, the progress of digital color printers for performing color output of images and documents is rapidly progressing.

The printers and copiers are required to have higher speed and higher image quality. In an electrophotographic image forming apparatus, an electrostatic latent image is formed on a photoreceptor by charging and writing, and the electrostatic latent image is developed with toner and visualized. The toner image formed on the photosensitive member is transferred to a recording medium (in most cases, a transfer paper), and the transferred toner image is fixed, thereby fixing the toner image (image) on the recording medium. ) And output.
Among these several processes, there are several processes that influence the improvement in image quality. One is the formation of an electrostatic latent image. The second is faithful development (formation of a toner image) for the electrostatic latent image. The third is faithful transfer of the toner image formed on the photoreceptor. The fourth is faithful fixing of the toner image transferred onto the recording medium. The “faithful” means that the size of the formed electrostatic latent image or toner image is maintained and transferred to the next process.

Regarding the formation of an electrostatic latent image, optical writing is performed on a uniformly charged photoconductor to form a potential contrast on the surface of the photoconductor. At this time, necessary techniques are uniformity of charging and formation of minute dots. The uniformity of charging is almost ensured by the device of the charger and the uniformity of the photoreceptor film thickness. In addition, with regard to the formation of micro dots, the development of optical systems (writing elements, lenses, etc.) and the shortening of the oscillation wavelength of the elements themselves have made it possible to form micro beam systems. It is not.
Regarding the development of the electrostatic latent image, in order to faithfully develop the electrostatic latent image formed on the photoconductor, a sufficient development potential is obtained by appropriately controlling the potential on the photoconductor and the developing bias, and the toner. It is necessary to sufficiently increase the chargeability of the toner itself and to use a sufficiently small developer (toner and carrier) in order to perform finer development. The development potential can be controlled at a level that does not cause an abnormal load on the photoconductor, and the toner chargeability has been fully developed by developing toner materials (base resin and charge control agent). Has been. Also, for high-definition development, a carrier having a small particle diameter (50 μm or less), a toner having a small particle diameter (7 μm or less), and the like have been developed.

  The transfer of the toner image is a process of transferring the toner image formed on the photosensitive member to a recording medium. However, the toner originally transferred to the developing sleeve is transferred to the surface of the photosensitive member. It is tied to the body surface by electrostatic attraction. Since this is transferred onto the recording medium by the action of the electric field, the electric field applied here needs to be a considerably high electric field. At this time, if the transfer electric field strength is low, sufficient toner transfer is not performed, and transfer efficiency is lowered, and residual toner is generated on the photosensitive member, increasing the stress on the cleaning member. In addition, since the image density is reduced, more toner than necessary is used, which causes a problem of environmental load. In order to avoid this, the transfer electric field is set high, but the transfer electric field is basically applied by bias application by the transfer unit, but if it is high, a discharge is generated between the transfer unit and the photosensitive member surface. Cause an effect. This is because an ionization phenomenon occurs due to an electric field applied between the photosensitive member surface and the charger in the minute gap. As a result, the toner image is transferred onto the recording medium originally disposed at the position directly opposite the photoconductor, but the toner image is disturbed by this discharge phenomenon, which is the rate-determining factor for improving the image quality.

The fixing of the toner image is basically a process in which the toner is melted and fixed on the recording medium, and the toner image is enlarged. However, by reducing the particle size of the toner and improving the color density, the amount of toner adhered per unit area (adhesion height) can be reduced, and more heat energy than necessary can be irradiated by advances in the fixing machine. Therefore, the spread or disturbance of the toner image due to fixing is small compared to the transfer process, and at present, it is not a rate-determining process for improving image quality.
As described above, it is no exaggeration to say that the transfer process for transferring the toner image from the surface of the photosensitive member to the recording medium is the rate-determining process for the problem of improving the image quality at present.

  In an image forming apparatus that operates at high speed, from the intention of simplifying the machine design (basically reducing the number of parts) and the intention of reducing the number of transfer processes that cause toner image disturbance as described above, A method of directly transferring the toner image formed on the photoreceptor to a recording medium (transfer paper) is employed. In this method, the recording medium is conveyed by a belt, brought into contact with or close to the surface of the photoconductor, and a sufficient bias is applied from the back side of the recording medium, so that a toner image is transferred from the surface of the photoconductor. Move to a recording medium. Usually, a member that conveys a recording medium, such as a transfer conveyance belt, has a resistance close to conductivity, and a necessary electric field is applied from this member.

In the operation of the image forming apparatus, when the recording medium is continuously fed, it is almost impossible to carry the recording medium without any gap. Accordingly, a gap is formed between the recording medium called the sheet interval and the recording medium. When performing continuous printing, it is possible to operate with the bias applied to the transfer means. However, since a strong electric field acts on the photoconductor between the sheets, the photoconductor is very deteriorated. . For this reason, normally, the transfer bias is applied only when the recording medium is transported and only when the recording medium is covering (facing) the photosensitive member.
However, in the case of a very high-speed image forming apparatus, the system linear speed (hereinafter, sometimes referred to as “photosensitive linear speed” or “process linear speed”) is limited. In order to increase the distance, it is forced to narrow the gap between papers as much as possible. At the same time, a document created by a recent digital image system is required to print an output image of a computer or the like unlike a conventional document. Also, there are originals that are written on the entire surface of the recording medium, such as full-color images, and it is necessary to apply a sufficient electric field to a position corresponding to the entire surface of the recording medium. In particular, in the case of a solid document, the image density at the trailing edge of the transfer paper may be lower even in the original development, and in the transfer process, until the edge of the recording medium is full (in some cases, beyond the edge). It is necessary to apply a transfer bias. For this reason, a very high electric field acts on the photoreceptor facing the both ends (outside) of the recording medium. This is because, in a normal state, the transfer electric field acts on the photoconductor via the recording medium, but there is nothing that blocks the electric field at a location where the recording medium does not exist.

Although the above-mentioned problem is in a direction to be solved by a technique capable of taking the timing of the transfer of the recording medium and applying the transfer bias very accurately, the recording medium has various forms and further has a problem. In general, the length in the longitudinal direction of a photoconductor in an image forming apparatus covers the maximum size of a recording medium output from the image forming apparatus. Therefore, in the case of an A3 compatible image forming apparatus, the image forming apparatus is designed with a length corresponding to the short side length of the A3 sheet. For this reason, when A4 is output, the surface of the photosensitive member can be covered by forming an image with reference to the long side of A4. However, a smaller recording medium (for example, a sheet of B5 or less, a postcard, etc.) can be used. When used for printing, the transfer bias is also applied to the outside of the recording medium, so that a strong electric field acts on the surface of the photoreceptor.
As another form, there is a user who forms an image by using a recording medium in which punch holes are previously formed. In this case, a strong electric field partially acts on the surface of the photoreceptor regardless of the transfer timing.

The electrophotographic photosensitive member used in the image forming apparatus as described above may accelerate fatigue or cause dielectric breakdown due to the action of a strong transfer electric field. As a result, an image defect called background stain may occur in an image output from an image forming apparatus that has been used repeatedly for a long time.
In addition, there is a case where the charge having a bias polarity at the time of transfer remains on the photosensitive member and affects the next charging. When the charging process is started with residual charges remaining on the surface of the photoreceptor, the following problems occur.

In general, since the charger of the high-speed image forming apparatus is charged only with the DC component, if the remaining charge remains, the charging of the portion becomes abnormal and uniform writing is performed on the entire surface. When such a document is printed, the surface potential is not constant, and density unevenness occurs during development. Depending on the polarity of the transfer bias, if a bias having the same polarity as the surface potential of the photoconductor is applied, the surface potential of the toner developing portion of the photoconductor becomes high, and the charge removal means is not sufficient to remove the charge. If it is small, the potential of this portion becomes high, and the history of the previous electrostatic latent image remains (positive remaining, see FIG. 1).
This is more serious when the polarity of the transfer bias is opposite to that of the photosensitive member. In the case of negative and positive development, which is currently the mainstream of digital machines, development is performed on the portion written on the photoconductor, so that the developed portion has a low surface potential. Since a reverse polarity bias is applied here, the surface potential of this portion is charged to a polarity opposite to the original charged polarity of the photoreceptor. As described above, in the case of a high potential with the same polarity, the potential can be canceled by sufficiently performing the photostatic charge, but when the reverse polarity charge is applied, this is canceled by the photostatic charge. It is not possible. This is because current photoconductors generate carriers and can only be transported on one side (usually only holes). As a result, the charging ability becomes insufficient at the time of charging in the next process, and the photosensitive member in this portion is not sufficiently charged, leaving a history of the electrostatic latent image of the previous time (remaining negative, FIG. 2).

In order to avoid these problems, there is a method using a charger that superimposes the AC component. However, when high-speed charging is required, the frequency of the AC component must be increased in accordance with the linear velocity of the photosensitive member. In addition to an increase in the load on the charger or the power source, a chemical hazard on the surface of the photoconductor increases, which causes a fatal problem for high durability that promotes wear of the photoconductor.
This is not the only cause of negatives, but also occurs when the photoconductor is heavily fatigued and enters the charging process with a uniform surface charge after static elimination, especially when the same document is output repeatedly or in a fixed format. When the same manuscript exists at a location (for example, when it is a business manuscript and a company logo mark or the like is present at the same location), it becomes a significant problem.

As described above, the usage of the high-speed image forming apparatus is very diverse including the case where it is colored, and in order to cope with this, the state of the image forming system is always maintained in the same state. In order to realize this concretely, it is all about how to keep the photoconductor in the same state (maintain the initial state) in order to always produce the electrostatic latent image in the same manner.
With current technology, it is very difficult to control the phenomenon of reverse polarity charging, either transfer with reduced transfer capability or charging under strong charging conditions so that no previous history remains. There is only a way. The former is to surely reduce the transfer efficiency and is not allowed for high image quality. Therefore, there is only a method for dealing with the current situation in which the output from the charger is increased.
When such a method is used, a photoreceptor with low pressure resistance may cause dielectric breakdown as described above, or may generate an abnormal image called scumming. I need it.

For the problem of speeding up, a photoconductor having high sensitivity and high speed response has been used. Usually, an LED of 780 nm LD or near 760 nm is used as a light source for a high-speed digital image forming apparatus. It is known to use a titanyl phthalocyanine crystal having a maximum diffraction peak at least 27.2 ° as ± 0.2 °) (see Patent Document 1). This specific crystal type has a very high carrier generation function and can be effectively used as a charge generation material for a photoreceptor for a high-speed image forming apparatus. However, this crystal type has a problem that its stability as a crystal is low, and it is easy to undergo crystal transition against mechanical stress such as dispersion and thermal stress. Compared to the above, the sensitivity is very low, and when a part of the crystal undergoes crystal transition, a sufficient photocarrier generation function cannot be exhibited. Further, when the photoreceptor is used repeatedly, there is a problem that the chargeability is liable to be lowered and the background is likely to be stained.
Furthermore, Patent Document 1 does not include a description of the particle size of a specific crystal type titanyl phthalocyanine crystal and a technology for controlling the particle size, and the particle size is not optimized. It is difficult to make it.

  In light of the process restrictions (requests) that occur in designing a high-speed image forming apparatus, the development of a photoconductor is not sufficient, and photosensitivity for realizing stable high-speed image formation. The fact was that physical development was not enough.

JP 2001-19871 A

  An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention relates to a specific crystal type titanyl in an image forming apparatus adopting a method of transferring a toner image formed on a photoconductor to a recording medium by a direct transfer method in order to form a high-quality image at high speed. By using a photoreceptor containing phthalocyanine crystals, the high sensitivity inherent in titanyl phthalocyanine is maintained, it is highly durable, and when it is used repeatedly at high speed, no abnormal images are generated and images are output in a stable state. An object is to provide a possible image forming apparatus and an image forming method.

  As a result of intensive studies to solve the above problems, the present inventors have made numerous studies in order to form an image with few abnormal images even in repeated use in a high-speed image forming apparatus employing a direct transfer method. As a result, the electrostatic latent image carrier used is an electrophotographic photosensitive member in which at least a charge generation layer and a charge transport layer are sequentially laminated on a support, and CuKα rays (wavelength 1.542 mm) are formed in the charge generation layer. ) With a Bragg angle 2θ diffraction peak (± 0.2 °) having a maximum diffraction peak of at least 27.2 °, and major peaks at 9.4 °, 9.6 °, and 24.0 °. And has a peak at 7.3 ° as the lowest diffraction peak, and has no peak between the 7.3 ° peak and the 9.4 ° peak. .No peak at 3 ° and flatness of primary particles It has been found that the above problems can be solved by including a titanyl phthalocyanine crystal having an average particle size of 0.25 μm or less.

The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
<1> An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to make it visible An image forming apparatus having at least developing means for forming an image, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transfer image transferred to the recording medium, wherein the transfer means The visible image developed on the surface of the electrostatic latent image carrier is directly transferred to a recording medium, and the electrostatic latent image carrier comprises a support, at least a charge generation layer on the support, a charge The transport layer is laminated in this order, and at least 7.0 to 7 as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray (wavelength 1.542 mm) of CuKα in the charge generation layer. Has a maximum diffraction peak at 5 ° and the half-width of the diffraction peak is 1 ° or more. An amorphous or low crystalline titanyl phthalocyanine crystal having an average primary particle size of 0.1 μm or less is crystal-converted using an organic solvent in the presence of water, and the average primary particle size after crystal conversion is It contains a titanyl phthalocyanine crystal after crystal conversion obtained by filtration in a state of 0.25 μm or less , and has a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to CuKα rays (wavelength 1.542Å) in the titanyl phthalocyanine crystal. ) Having a maximum diffraction peak at least 27.2 °, and further having main peaks at 9.4 °, 9.6 °, and 24.0 °, and 7.3 ° as the lowest diffraction peak. In the titanyl phthalocyanine crystal, there is no peak between the 7.3 ° peak and the 9.4 ° peak, no further peak at 26.3 °, and The average particle diameter of primary particles is 0.25 μm or less.
<2> The image forming apparatus according to <1>, wherein the titanyl phthalocyanine crystal is synthesized from a raw material not containing a halogen-containing compound.
<3> Amorphous or low crystalline titanyl phthalocyanine crystal is prepared by the acid paste method, and the obtained amorphous or low crystalline titanyl phthalocyanine crystal is ion-exchanged water until the pH of the ion-exchanged water becomes 6-8. The image forming apparatus according to <1>, wherein the image forming apparatus is cleaned in
<4> Amorphous to low crystalline titanyl phthalocyanine crystal is prepared by the acid paste method, and the obtained amorphous to low crystalline titanyl phthalocyanine crystal has a specific conductivity of ion-exchanged water of 8 μS / cm or less. The image forming apparatus according to <1>, wherein the image forming apparatus is washed with ion-exchanged water.
<5> The amount of the organic solvent used in the crystal conversion of the titanyl phthalocyanine crystal is 10 times or more of the amorphous or low crystalline titanyl phthalocyanine crystal in mass ratio, according to any one of the above <2> to <4> An image forming apparatus.
<6> The image forming apparatus according to any one of <1> to <5>, wherein the charge transport layer contains a polycarbonate resin including a triarylamine structure in at least one of a main chain and a side chain.
<7> The image forming apparatus according to any one of <1> to <6>, wherein a protective layer is provided on the charge transport layer.
<8> The image forming apparatus according to <7>, wherein the protective layer includes at least one selected from an inorganic pigment having a specific resistance of 10 ¹⁰ Ω · cm or more and a metal oxide.
<9> The image forming apparatus according to any one of <7> to <8>, wherein the protective layer further contains a polymer charge transport material.
<10> The image forming apparatus according to any one of <7> to <9>, wherein the protective layer contains a binder resin, and the binder resin has a crosslinked structure.
<11> The image forming apparatus according to <10>, wherein the binder resin having a cross-linked structure has a charge transport site.
<12> The image forming apparatus according to any one of <1> to <11>, wherein the surface of the support in the electrostatic latent image carrier is anodized.
<13> A writing unit and a non-writing unit are formed on the electrostatic latent image carrier by the exposure device, and the absolute value of the surface potential in the non-writing unit of the electrostatic latent image carrier after transfer is 100 V or less. The image forming apparatus according to any one of <1> to <12>.
<14> The image forming apparatus according to <13>, wherein the surface potential in the non-writing portion of the latent electrostatic image bearing member after transfer is a reverse potential of the potential charged by the charger.
<15> The surface potential in the non-writing portion of the latent electrostatic image bearing member after transfer is a reverse potential of the potential charged by the charger, and the absolute value of the surface potential of the non-writing portion is 100 V or less. The image forming apparatus according to any one of <13> to <14>.
<16> The image forming apparatus according to any one of <1> to <15>, wherein the image forming apparatus does not use a light neutralizing unit.
<17> The image forming apparatus according to any one of <1> to <16>, wherein the charger in the electrostatic latent image forming unit applies an AC superimposed voltage to the surface of the electrostatic latent image carrier.
<18> The electrostatic latent image carrier and one or more means selected from an electrostatic latent image forming means, a developing means, and a cleaning means are integrated, and the apparatus main body and a detachable process cartridge are mounted. <1> to <17. The image forming apparatus according to any one of the above.
<19> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, An image forming method comprising at least a transfer step of transferring a visible image to a recording medium and a fixing step of fixing the transferred image transferred to the recording medium, wherein the transfer step includes the surface of the electrostatic latent image carrier The developed latent image is directly transferred onto a recording medium, and the electrostatic latent image carrier is formed by laminating a support, at least a charge generation layer, and a charge transport layer in this order on the support. In addition, the charge generation layer has a maximum diffraction peak at 7.0 to 7.5 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray (wavelength 1.542 mm) of CuKα. And the half width of the diffraction peak is 1 ° or more, and the average particle diameter of the primary particles An amorphous or low crystalline titanyl phthalocyanine crystal having a size of 0.1 μm or less is converted using an organic solvent in the presence of water, and the average primary particle size after the crystal conversion is 0.25 μm or less. Including a titanyl phthalocyanine crystal after crystal conversion obtained by filtration, and at least 27.2 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to CuKα rays (wavelength 1.542Å) in the titanyl phthalocyanine crystal. Has a major diffraction peak at 9.4 °, 9.6 °, and 24.0 °, and has a peak at 7.3 ° as the lowest diffraction peak, There is no peak between the peak at 7.3 ° and the peak at 9.4 °, there is no peak at 26.3 °, and the average particle size of the primary particles in the titanyl phthalocyanine crystal is It is an image forming method characterized by being 0.25 μm or less.

  According to the present invention, it is an image forming apparatus that can solve various problems in the past and uses a direct transfer system to perform high-speed image formation while maintaining high image quality. By using a photoconductor containing titanyl phthalocyanine crystals of a specific particle size, it maintains the high sensitivity inherent in titanyl phthalocyanine, is highly durable, and does not generate abnormal images when used repeatedly at high speed and is stable. An image forming apparatus and an image forming method capable of outputting an image with high resolution are provided.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. Other means, for example, cleaning means, static elimination means, recycling means, control means, etc. are provided.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further, other steps appropriately selected as necessary, for example, a cleaning step, It includes a static elimination process, a recycling process, a control process, and the like.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

  An image forming apparatus according to the present invention includes an electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using toner. A developing unit that develops a visible image by development; a transfer unit that transfers the visible image to a recording medium; and a fixing unit that fixes the transferred image transferred to the recording medium. The visible image developed on the surface of the electrostatic latent image carrier is directly transferred to a recording medium.

-Electrostatic latent image carrier-
The material, shape, structure, size, etc. of the electrostatic latent image carrier are not particularly limited, and can be appropriately selected from known ones. A charge generation layer and a charge transport layer are laminated in this order, and the charge generation layer contains a titanyl phthalocyanine crystal. ± 0.2 °) with a maximum diffraction peak of at least 27.2 °, and further main peaks at 9.4 °, 9.6 ° and 24.0 °, the lowest diffraction peak And having no peak between the 7.3 ° peak and the 9.4 ° peak, and further no peak at 26.3 °, and the titanyl phthalocyanine In crystals The average particle diameter of the primary particles is 0.25 μm or less.
As the support, a conductive support having conductivity is preferable.

  The crystal form of the titanyl phthalocyanine crystal is described in, for example, Japanese Patent Application Laid-Open No. 2001-19871, etc., but by using such a titanyl phthalocyanine crystal, the charging property can be obtained even by repeated use without losing high sensitivity. A stable electrophotographic photosensitive member that does not cause a decrease can be obtained.

As a method for synthesizing the titanyl phthalocyanine crystal, for example, as described in JP-A-6-293769, a method using no titanium halide as a raw material is preferably used. The biggest merit of this method is that the synthesized titanyl phthalocyanine crystal is free of halogenation. When a titanyl phthalocyanine crystal contains a halogenated titanyl phthalocyanine crystal as an impurity, it often has adverse effects such as a decrease in photosensitivity and a decrease in chargeability in the electrostatic characteristics of a photoconductor using the crystal (Japan Hardcopy '89 paper). Collection p.103 1989).
Also in the present invention, halogenated free titanyl phthalocyanine crystals as described in JP-A-2001-19871 are mainly used, and these materials are effectively used.
In order to synthesize the halogenated-free titanyl phthalocyanine, a halogenated material is not used as a raw material in the synthesis of titanyl phthalocyanine. Specifically, the following method is used.

Here, first, a method for synthesizing a titanyl phthalocyanine crystal having the specific crystal type will be described.
First, a synthesis method of a synthetic crude product of titanyl phthalocyanine crystal will be described. Methods for synthesizing phthalocyanines have been known for a long time, and are described, for example, in JP-A-6-293769, “Phthalocyanine Compounds” (1963), “The Phthalineines” (1983), etc. by Moser et al. .

For example, as a first method, a mixture of phthalic anhydrides, metal or metal halide and urea is heated in the presence or absence of a high boiling point solvent. In this case, a catalyst such as ammonium molybdate is used in combination as necessary.
As a second method, phthalonitriles and metal halides are heated in the presence or absence of a high boiling point solvent. This method is used for phthalocyanines that cannot be produced by the first method, such as aluminum phthalocyanines, indium phthalocyanines, oxovanadium phthalocyanines, oxotitanium phthalocyanines, zirconium phthalocyanines, and the like.
The third method is to first react phthalic anhydride or phthalonitrile with ammonia to produce an intermediate such as 1,3-diiminoisoindoline, and then in a metal halide and a high boiling point solvent. This is a reaction method.
The fourth method is a method in which phthalonitriles and a metal alkoxide are reacted in the presence of urea or the like.
Among these, the fourth method does not cause chlorination (halogenation) to the benzene ring, and is an extremely useful method as a method for synthesizing an electrophotographic material, and is used very effectively in the present invention. The

  Next, a method for preparing amorphous titanyl phthalocyanine (low crystalline titanyl phthalocyanine) will be described. This method is a method in which phthalocyanines are dissolved in sulfuric acid, diluted with water and reprecipitated, and an acid paste method or an acid slurry method can be used.

As a specific method, the above synthetic crude product is dissolved in 10-50 times the amount of concentrated sulfuric acid, and if necessary, insoluble matter is removed by filtration or the like, and this is sufficiently cooled to 10-50 times the amount of sulfuric acid. Slowly throw it into water or ice water to reprecipitate titanyl phthalocyanine. The precipitated titanyl phthalocyanine is filtered, washed with ion-exchanged water and filtered, and this operation is sufficiently repeated until the filtrate becomes neutral. Finally, after washing with clean ion-exchanged water, filtration is performed to obtain a water paste having a solid content concentration of about 5 to 15% by mass.
At this time, it is important to thoroughly wash the precipitated titanyl phthalocyanine with ion-exchanged water so as not to leave concentrated sulfuric acid as much as possible. Specifically, it is preferable that the ion-exchanged water after washing exhibits the following physical property values. That is, if the remaining amount of sulfuric acid is expressed quantitatively, it can be expressed by the pH and specific conductivity of ion-exchanged water after washing.
When expressed in terms of pH, the pH is preferably in the range of 6-8. Within this range, it can be determined that the remaining amount of sulfuric acid does not affect the photoreceptor characteristics. This pH value can be easily measured with a commercially available pH meter.
In terms of specific conductivity, it is preferably 8 μS / cm or less, more preferably 5 μS / cm or less, and particularly preferably 3 μS / cm or less. If the specific conductivity is 8 μS / cm or less, it can be determined that the residual amount of sulfuric acid does not affect the photoreceptor characteristics. This specific conductivity can be measured with a commercially available electric conductivity meter. The lower limit of the specific conductivity is the specific conductivity of ion-exchanged water after being used for cleaning. In any measurement, in the range deviating from the above range, the remaining amount of sulfuric acid is large, and the chargeability of the photoconductor may be lowered or the photosensitivity may be deteriorated.
What was produced in this way was the amorphous titanyl phthalocyanine (low crystalline titanyl phthalocyanine) used in the present invention. In this case, the amorphous titanyl phthalocyanine (low crystalline titanyl phthalocyanine) is at least 7.0 to 7 as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray (wavelength 1.542Å) of CuKα. It is preferable to have a maximum diffraction peak at 5 °. In particular, the half width of the diffraction peak is more preferably 1 ° or more. Furthermore, it is preferable that the average particle diameter of the primary particles is 0.1 μm or less.

Next, the crystal conversion method will be described.
Crystal transformation is performed by using the amorphous titanyl phthalocyanine (low crystalline titanyl phthalocyanine) as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray of CuKα (wavelength 1.542１．５). Has a major diffraction peak at 9.4 °, 9.6 °, 24.0 °, and the lowest diffraction peak at 7.3 °, And it is a step of converting into a titanyl phthalocyanine crystal having no peak between the peak at 7.3 ° and the peak at 9.4 ° and not having a peak at 26.3 °.

As a specific method, the crystalline form is obtained by mixing and stirring the amorphous titanyl phthalocyanine (low crystalline titanyl phthalocyanine) with an organic solvent in the presence of water without drying.
In this case, any organic solvent can be used as long as the desired crystal form can be obtained, but tetrahydrofuran, toluene, methylene chloride, carbon disulfide, orthodichlorobenzene, 1,1, Good results are obtained when one selected from 2-trichloroethane is selected. These organic solvents are preferably used alone, but two or more of these organic solvents may be mixed or used in combination with other solvents. The amount of the organic solvent used for crystal conversion is preferably 10 times or more, preferably 30 times or more the mass of amorphous or low crystalline titanyl phthalocyanine. This is because crystal conversion is caused quickly and sufficiently, and an effect of sufficiently removing impurities contained in the amorphous or low crystalline titanyl phthalocyanine is exhibited. The amorphous or low crystalline titanyl phthalocyanine used here is prepared by the acid paste method, but it is preferable to use one obtained by sufficiently washing sulfuric acid as described above. When crystal conversion is performed under conditions where sulfuric acid remains, sulfate ions remain in the crystal particles, and the completed crystals cannot be completely removed even by an operation such as washing with water. When sulfate ions remain, preferable results cannot be obtained, such as a decrease in sensitivity and a decrease in chargeability of the photoreceptor. For example, Japanese Patent Application Laid-Open No. 8-110649 discloses a method for crystal conversion by adding titanyl phthalocyanine dissolved in sulfuric acid into an organic solvent together with ion-exchanged water. At this time, a crystal similar to the X-ray diffraction spectrum of the titanyl phthalocyanine crystal obtained in the present invention can be obtained, but the sulfate ion concentration in titanyl phthalocyanine is high and the light attenuation characteristic (photosensitivity) is poor. The method for producing titanyl phthalocyanine of the present invention is not good.

  The above crystal conversion method is a crystal conversion method according to Japanese Patent Laid-Open No. 2001-19871. On the other hand, in the charge generation material contained in the photoreceptor used in the electrophotographic apparatus of the present invention, the effect is achieved by making the particle diameter of the titanyl phthalocyanine crystal finer (0.25 μm or less). . The following describes a method for synthesizing the titanyl phthalocyanine particle size smaller than the synthesis step.

  In order to make the particle size of the titanyl phthalocyanine crystal finer, the above-mentioned amorphous titanyl phthalocyanine (low crystalline titanyl phthalocyanine) has a primary particle size of 0.1 μm or less (most of which is about 0.01 to 0.05 μm). However (see FIG. 7), it was found that during crystal conversion, the crystal is converted as the crystal grows. Usually, in this type of crystal conversion, a sufficient crystal conversion time is secured because of the risk of remaining raw materials, and after the crystal conversion is sufficiently performed, filtration is performed to obtain a titanyl phthalocyanine crystal having a desired crystal type. Is what you get. For this reason, even though a raw material having sufficiently small primary particles is used as a raw material, a crystal having a large primary particle (approximately 0.3 to 0.5 μm) is obtained as a crystal after crystal conversion. Yes (see FIG. 8). Note that the scale bars in FIGS. 7 and 8 are both 0.2 μm.

  When dispersing the titanyl phthalocyanine crystal produced as shown in FIG. 8, in order to make the particle diameter after dispersion small (0.25 μm or less), dispersion is performed by giving a strong share, and further necessary In response to this, dispersion is performed by giving strong energy to pulverize the primary particles. As a result, as described above, there is a possibility that a part of the particles may be transferred to a crystal type which is not a desired crystal type.

  In this regard, by controlling the primary particle size of the titanyl phthalocyanine crystal from the synthesis stage to obtain a crystal having a small diameter, a method for solving this problem is possible, and the method is effectively used in the present invention. Specifically, the range in which crystal growth hardly occurs during crystal conversion (the range in which the diameter of the amorphous titanyl phthalocyanine particles observed in FIG. 7 is insignificantly small after crystal conversion, generally within 0.25 μm or less. ) Is to obtain a titanyl phthalocyanine crystal having a primary particle size as small as possible by determining when the crystal conversion is completed. The particle size after crystal conversion increases in proportion to the crystal conversion time. For this reason, as described above, it is important to increase the efficiency of crystal conversion and complete it in a short time. There are several important points for this.

FIG. 9 is a TEM image of a titanyl phthalocyanine crystal subjected to crystal conversion in a short time. The scale bar in FIG. 9 is 0.2 μm.
One is to select an appropriate crystal conversion solvent as described above to increase the crystal conversion efficiency. The other is to use strong stirring to bring the solvent and the titanyl phthalocyanine aqueous paste (raw material prepared as described above: amorphous titanyl phthalocyanine) into sufficient contact in order to complete the crystal conversion in a short time. Specifically, it is possible to realize crystal transformation in a short time by using a method such as stirring using a propeller with a very strong stirring force or using a strong stirring (dispersing) means such as a homogenizer (homomixer). is there. Under these conditions, it is possible to obtain a titanyl phthalocyanine crystal in which crystal conversion is sufficiently performed and crystal growth does not occur without the raw material remaining.
At this time, it is preferable to optimize the amount of the organic solvent used for crystal conversion. Specifically, it is preferable to use an organic solvent 10 times or more, preferably 30 times or more the solid content of the amorphous or low crystalline titanyl phthalocyanine. As a result, crystal conversion in a short time can be ensured and impurities contained in the amorphous or low crystalline titanyl phthalocyanine can be surely removed.

  In addition, since the crystal particle diameter and the crystal conversion time are in a proportional relationship as described above, a method of immediately stopping the reaction when a predetermined reaction (crystal conversion) is completed is also an effective means. As the above-mentioned means, a large amount of a solvent that hardly causes crystal conversion is immediately added after crystal conversion as described above. Examples of the solvent that hardly causes crystal transformation include alcohol-based and ester-based solvents. Crystal conversion can be stopped by adding about 10 times these solvents to the crystal conversion solvent.

  The smaller the primary particle diameter produced in this way, the better the results with respect to the problem of the photoreceptor, but the next step for pigment preparation (pigment filtration step), dispersion in dispersion In consideration of stability, side effects may occur even if it is too small. That is, when the primary particles are very fine, there arises a problem that the filtration time becomes very long in the step of filtering the primary particles. In addition, when the primary particles are too fine, the surface area of the pigment particles in the dispersion increases, and the possibility of reaggregation of the particles increases. Therefore, the appropriate particle diameter of the pigment particles is in the range of about 0.05 μm to 0.2 μm.

FIG. 9 shows a TEM image of a titanyl phthalocyanine crystal when crystal conversion is performed in a short time. Unlike the case of FIG. 8, the particle size is small and almost uniform, and no coarse particles as observed in FIG. 8 are observed.
In dispersing the titanyl phthalocyanine crystal produced in a state where the primary particles are small as shown in FIG. 9, the particle diameter after dispersion is made small (0.25 μm or less, more preferably 0.2 μm or less). Can be dispersed by giving a share sufficient to loosen the secondary particles formed by aggregation of the primary particles. As a result, since the energy more than necessary is not given, as described above, it is easy to produce a dispersion having a fine particle size distribution without producing a result that a part of the particles is easily transferred to a crystal type other than the desired crystal type. It is possible.

  An average particle diameter here is a volume average particle diameter, and is calculated | required with the ultracentrifugal automatic particle size distribution measuring apparatus: CAPA-700 (made by Horiba Seisakusho). 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.

  As a result of further observation of the dispersion and examination of micro defects, the above phenomenon was understood as follows. Usually, in the method of measuring the average particle diameter, when extremely large particles are present in several% or more, the presence can be detected, but it is about 1% or less of the whole. When the amount is too small, the measurement is below the detection limit. As a result, the presence of coarse particles is not detected only by measuring the average particle size, making it difficult to interpret the above minute defects.

FIG. 10 and FIG. 11 show photographs observing the state of two types of dispersions in which only the dispersion time is changed while fixing the dispersion conditions. A photograph of the dispersion liquid having a short dispersion time under the same conditions is shown in FIG. 10. Compared with FIG. 11 having a long dispersion time, coarse particles remain. The black particles in FIG. 10 are coarse particles.
The average particle size and particle size distribution of these two types of dispersions were measured by a commercially available particle size distribution measuring device (manufactured by Horiba: Ultracentrifugal automatic particle size distribution measuring device, CAPA700). The result is shown in FIG. “A” in FIG. 13 corresponds to the dispersion shown in FIG. 10, and “B” corresponds to the dispersion shown in FIG. When both are compared, there is almost no difference in the particle size distribution. In addition, the average particle diameter values of the two are “A” of 0.29 μm and “B” of 0.28 μm, and taking into account measurement errors, no difference is recognized between the two.

  Therefore, it is understood that the remaining of a minute amount of coarse particles cannot be detected only by the definition of the known average particle diameter (particle diameter), and it is not possible to cope with the recent high-resolution negative and positive development. The presence of such a minute amount of coarse particles can be recognized for the first time by observing the coating solution at the microscope level.

  In response to such a fact, it is an effective means to make the primary particles produced at the time of crystal conversion as small as possible. For this purpose, in order to complete the crystal conversion in a short time while selecting the appropriate crystal conversion solvent as described above and improving the crystal conversion efficiency, the solvent and titanyl phthalocyanine water paste (the raw material prepared as described above) are used. It can be seen that a technique using strong agitation is effective to sufficiently bring a contact of

  By adopting such a crystal conversion method, a titanyl phthalocyanine crystal having a small primary particle diameter (0.25 μm or less, more preferably 0.2 μm or less) can be obtained. In addition to the technique described in JP-A-2001-19871, it is important in the present invention to use the above-described technique (crystal conversion method for obtaining fine titanyl phthalocyanine crystals) as necessary. Means.

Subsequently, the crystallized titanyl phthalocyanine crystal is immediately filtered to be separated from the crystal conversion solvent. This filtration is performed by using a filter having an appropriate particle size. In this case, it is most appropriate to use vacuum filtration.
Thereafter, the separated titanyl phthalocyanine crystal is heat-dried as necessary. Any known dryer can be used for heat drying, but a blower-type dryer is preferred when the drying is performed in the atmosphere. Furthermore, drying under reduced pressure is also a very effective means in order to increase the drying speed and to exhibit the effects of the present invention more remarkably. In particular, this is an effective means for a material that decomposes at a high temperature or changes its crystal form. It is particularly effective to dry in a state where the degree of vacuum is higher than 10 mmHg.

  The thus obtained titanyl phthalocyanine crystal having a specific crystal type is extremely useful as a charge generating material for an electrophotographic photoreceptor. However, as described above, the crystal form is unstable, and the crystal form is easily transferred when a dispersion is prepared. However, by synthesizing primary particles into infinitely small particles as in the present invention, a dispersion with a small average particle diameter can be prepared without giving an excessive share during the preparation of the dispersion, and the crystal type is also extremely high. It can be produced stably (without changing the synthesized crystal form).

Next, a method for producing the dispersion will be described.
A general method is used for the preparation of the dispersion, and the titanyl phthalocyanine crystal is dispersed in a suitable solvent together with a binder resin as necessary by using a ball mill, an attritor, a sand mill, a bead mill, an ultrasonic wave, or the like. It is obtained. At this time, the binder resin may be selected depending on the electrostatic characteristics of the photoreceptor, and the solvent may be selected depending on the wettability to the pigment, the dispersibility of the pigment, and the like.
As already stated, the titanyl phthalocyanine crystal having a maximum diffraction peak at 27.2 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to CuKα rays (wavelength 1.542 mm) is a thermal energy and mechanical It is known that a crystal transition easily occurs to another crystal type due to a stress such as a dynamic share. This tendency does not change in the titanyl phthalocyanine crystal used in the present invention. That is, in order to produce a dispersion containing fine particles, it is necessary to devise a dispersion method, but the stability of the crystal form and the micronization tend to be in a trade-off relationship. Although there are methods for avoiding this by optimizing the dispersion conditions, all of them make the manufacturing conditions extremely narrow, and a simpler method is desired. In order to solve this problem, the following method is also an effective means.

  That is, it is a method in which a dispersion liquid in which the particles are made as fine as possible is produced within a range where crystal transition does not occur, and then filtered through an appropriate filter. This method is a very effective means in that it can remove a minute amount of coarse particles that cannot be visually observed (or cannot be detected by particle size measurement), and that the particle size distribution is uniform. Specifically, the dispersion prepared as described above is filtered through a filter having an effective pore size of 3 μm or less, more preferably 1 μm or less, thereby completing the dispersion. Also by this method, a dispersion liquid containing only titanyl phthalocyanine crystals having a small particle size (0.25 μm or less, more preferably 0.2 μm or less) can be produced, and a photoreceptor using this is mounted on an image forming apparatus. By using it, the effect of the present invention becomes more remarkable.

  The filter for filtering the dispersion varies depending on the particle size of coarse particles to be removed. As a photoreceptor used in an electrophotographic apparatus that requires a resolution of about 600 dpi, the presence of coarse particles of at least 3 μm affects the image. Therefore, a filter with an effective pore size of less than 3 μm should be used. More preferably, a filter having an effective pore size of 1 μm or less is used. By performing such a filtering process, unnecessary coarse particles can be removed, and a dispersion having a narrow particle size distribution and no coarse particles can be produced.

  As for the effective pore size, the finer the particle, the more effective the removal of coarse particles. However, if the particle size is too fine, the necessary pigment particles themselves are also filtered, and therefore there is an appropriate particle size. In addition, if it is too fine, it takes time for filtration, clogging of the filter, and excessive load is applied when liquid is sent using a pump or the like. As a matter of course, a material having resistance to the solvent used in the dispersion to be filtered is used as the material of the filter used here.

  During filtration, if the amount of coarse particles in the dispersion to be filtered is too large, the amount of pigment to be removed increases, and the solid content concentration of the dispersion after filtration changes, which is not preferable. Therefore, there is an appropriate particle size distribution (particle size, standard deviation) when performing filtration. As in the present invention, there is no pigment loss due to filtration, filter clogging, etc., and in order to perform filtration efficiently, the volume average particle size of the dispersion before filtration is 0.25 μm or less, and its standard deviation is It is preferable to disperse in 0.2 μm or less.

By adding such an operation of filtering the dispersion, coarse particles can be removed, and as a result, background contamination generated on the photoconductor using the dispersion can be reduced. As described above, the finer the filter, the greater the effect (reliable), but the pigment particles themselves may be filtered. In such a case, using the titanyl phthalocyanine primary particles described above in combination with the technique for refining and synthesizing produces a very large effect.
That is, (i) by synthesizing and using refined titanyl phthalocyanine, the dispersion time can be shortened and the dispersion stress can be reduced, and the possibility of crystal transition in dispersion is reduced. (Ii) Since the coarse particle diameter remaining by the dispersion is smaller than that in the case where the fine particles are not refined, a smaller filter can be used, and the effect of removing the coarse particles becomes more reliable. In addition, the amount of titanyl phthalocyanine particles to be removed is reduced, and there is little change in the composition of the dispersion before and after filtration, thus enabling stable production. (Iii) As a result, the manufactured photoconductor is stably produced with high resistance to soiling.

Next, the electrophotographic photosensitive member used in the present invention will be described in detail with reference to the drawings.
FIG. 13 is a cross-sectional view showing one structural example of the electrophotographic photosensitive member used in the present invention. On the support (31), a charge generation layer (35) mainly composed of a titanyl phthalocyanine crystal (charge generation material) having a specific crystal size and a specific particle size, and a charge transport layer mainly composed of a charge transport material (37) has a laminated structure.
FIG. 14 is a cross-sectional view showing another structural example of the electrophotographic photosensitive member used in the present invention. On the support (31), a titanyl phthalocyanine crystal (charge) having a specific crystal type with the specific particle diameter is shown. The charge generation layer (35) mainly composed of the generation material) and the charge transport layer (37) mainly composed of the charge transport material were laminated, and a protective layer (39) was further provided on the charge transport layer. It has a configuration.

As the support (31), a material having a volume resistance of 10 ¹⁰ Ω · cm or less, for example, a metal such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, tin oxide, indium oxide Metal oxide such as film or cylindrical plastic or paper coated by vapor deposition or sputtering, or a plate of aluminum, aluminum alloy, nickel, stainless steel, etc., and methods such as extrusion and drawing After forming the tube, it is possible to use a tube that has been surface-treated by cutting, superfinishing, polishing, or the like. In addition, an endless nickel belt and an endless stainless steel belt disclosed in JP-A-52-36016 can also be used as the support (31).

Of these, a cylindrical support made of aluminum, which can be easily subjected to the anodic oxide film treatment, can be most preferably used. As used herein, aluminum includes both pure aluminum and aluminum alloys. Specifically, JIS 1000 series, 3000 series, and 6000 series aluminum or aluminum alloy is most suitable.
The anodized film is obtained by anodizing various metals and various alloys in an electrolyte solution. Among them, a film called anodized aluminum or an aluminum alloy that has been anodized in an electrolyte solution is used in the present invention. Most suitable for the body. In particular, it is excellent in preventing point defects (black spots, background stains) that occur when used in reversal development (negative and positive development).

The anodizing treatment is performed in an acidic bath such as chromic acid, sulfuric acid, oxalic acid, phosphoric acid, boric acid, sulfamic acid. Of these, treatment with a sulfuric acid bath is most suitable. For example, sulfuric acid concentration: 10 to 20%, bath temperature: 5 to 25 ° C., current density: 1 to 4 A / dm ² , electrolytic voltage: 5 to 30 V, treatment time: treatment in the range of about 5 to 60 minutes However, the present invention is not limited to this. Since the anodic oxide film produced in this way is porous and has high insulation, the surface is very unstable. For this reason, there is a change with time after fabrication, and the physical property value of the anodized film is likely to change. In order to avoid this, it is preferable to further seal the anodized film. Examples of the sealing treatment include a method of immersing the anodized film in an aqueous solution containing nickel fluoride and nickel acetate, a method of immersing the anodized film in boiling water, and a method of treating with pressurized steam. Among these, the method of immersing in the aqueous solution containing nickel acetate is the most preferable. Subsequent to the sealing treatment, the anodic oxide film is washed. The main purpose of this is to remove excess metal salts and the like attached by the sealing treatment. If this remains excessively on the surface of the support (anodized film), it not only adversely affects the quality of the coating film formed on this surface, but also generally low resistance components remain, resulting in the occurrence of soiling. It can also be a cause. Cleaning may be performed with pure water only once, but usually, multistage cleaning is performed. At this time, it is preferable that the final cleaning liquid is as clean (deionized) as possible. Moreover, it is preferable to perform physical rubbing cleaning with a contact member in one of the multi-stage cleaning processes. The thickness of the anodized film formed as described above is preferably about 5 to 15 μm. If it is too thin, the barrier effect as an anodic oxide film is not sufficient, and if it is too thick, the time constant as an electrode becomes too large, resulting in the generation of residual potential and the response of the photoreceptor. There is a case.

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

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

Next, the photosensitive layer will be described. As described above, as the photosensitive layer, a laminated type composed of a charge generation layer (35) and a charge transport layer (37) exhibits excellent characteristics in sensitivity and durability, and is used favorably.
The charge generation layer (35) has, as a charge generation material, a maximum diffraction peak at 27.2 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to CuKα characteristic X-rays (wavelength 1.542 mm). Further, it has major peaks at 9.4 °, 9.6 °, and 24.0 °, and has a peak at 7.3 ° as a diffraction peak at the lowest angle side. There is no peak between the peak at 3 ° and the peak at 9.4 °, and there is no peak at 26.3 °. The average particle size of the primary particles is 0 during crystal synthesis or by dispersion filtration. A layer mainly composed of titanyl phthalocyanine crystal of 25 μm or less (preferably 0.2 μm or less).

In the charge generation layer (35), the pigment is dispersed in a suitable solvent together with a binder resin, if necessary, using a ball mill, attritor, sand mill, ultrasonic wave, etc., and this is coated on a support and dried. Is formed.
As the binder resin used for the charge generation layer (35) as necessary, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate resin, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, polysulfone, Poly-N-vinylcarbazole, polyacrylamide, polyvinyl benzal, polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyphenylene oxide, polyamide, polyvinyl pyridine, cellulosic resin, casein, polyvinyl alcohol, polyvinyl Examples include pyrrolidone and the like.
The addition amount of the binder resin is preferably 0 to 500 parts by mass, and more preferably 10 to 300 parts by mass with respect to 100 parts by mass of the charge generation material.

Examples of the solvent used here include isopropanol, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane, toluene, xylene, ligroin and the like. As a coating method of the coating solution, methods such as dip coating, spray coating, beat coating, nozzle coating, spinner coating, ring coating, and the like can be used.
The film thickness of the charge generation layer 35 is preferably about 0.01 to 5 μm, more preferably 0.1 to 2 μm.
The charge transport layer (37) can be formed by dissolving or dispersing a charge transport material and a binder resin in a suitable solvent, and applying and drying the solution on the charge generation layer. Moreover, a plasticizer, a leveling agent, antioxidant, etc. can also be added as needed.

The charge transport material includes a hole transport material and an electron transport material.
Examples of the electron transporting 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 -Electron-accepting substances such as trinitrodibenzothiophene-5,5-dioxide and benzoquinone derivatives. These may be used alone or in combination of two or more.
Examples of the hole transport material include poly-N-vinylcarbazole or a derivative thereof, poly-γ-carbazolylethyl glutamate or a derivative thereof, pyrene-formaldehyde condensate or a derivative thereof, polyvinylpyrene, polyvinylphenanthrene, polysilane, Oxazole derivatives, oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triarylmethane derivatives, 9-styrylanthracene Derivatives, pyrazoline derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives Other known materials such as body. These may be used alone or in combination of two or more.

Examples of the binder resin include polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, poly Vinyl acetate, polyvinylidene chloride, polyarate, phenoxy resin, polycarbonate resin, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, Examples thereof include thermoplastic resins such as urethane resins, phenol resins, and alkyd resins, or thermosetting resins.
The amount of the charge transport material added is preferably 20 to 300 parts by weight, and more preferably 40 to 150 parts by weight with respect to 100 parts by weight of the binder resin. The charge transport layer preferably has a thickness of about 5 to 100 μm.

  As the solvent used here, tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone and the like are used. Among them, the use of a non-halogen solvent is preferable for the purpose of reducing the environmental load. Specifically, cyclic ethers such as tetrahydrofuran, dioxolane and dioxane, aromatic hydrocarbons such as toluene and xylene, and derivatives thereof are preferably used.

  In addition, a polymer charge transport material having a function as a charge transport material and a function of a binder resin is also preferably used for the charge transport layer. The charge transport layer composed of these polymer charge transport materials is excellent in wear resistance. As the polymer charge transporting material, known materials can be used, and in particular, a polycarbonate resin having a triarylamine structure including at least one of a main chain and a side chain is preferably used. Among these, polymer charge transport materials represented by the following structural formulas (I) to (X) are favorably used, and these are exemplified below and specific examples are shown.

<Structural Formula (I)>
In the formula, R ₁ , R ₂ and R ₃ are each independently a substituted or unsubstituted alkyl group or a halogen atom, R ₄ is a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₅ and R ₆ are substituted. Or an unsubstituted aryl group, o, p, q are each independently an integer of 0-4, k, j represents a composition, 0.1 ≦ k ≦ 1, 0 ≦ j ≦ 0.9, n is repeated It represents the number of units and is an integer of 5 to 5000. X represents an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following structural formula. In the structural formula (I), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

However, in the formula, R _{101 and} R ₁₀₂ each independently represents a substituted or unsubstituted alkyl group, aryl group or halogen atom. l and m are integers of 0 to 4, Y is a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, —O—, —S—, —SO—, —SO ₂ —. , -CO-, -CO-O-Z-O-CO- (wherein Z represents an aliphatic divalent group) or
(A represents an integer of 1 to 20, b represents an integer of 1 to 2000, and R ₁₀₃ and R ₁₀₄ represent a substituted or unsubstituted alkyl group or aryl group). Here, R ₁₀₁ and R ₁₀₂ , and R ₁₀₃ and R ₁₀₄ may be the same or different. )

<Structural Formula (II)>
However, in the formula, R ₇ and R ₈ represent a substituted or unsubstituted aryl group. Ar ₁ , Ar ₂ , and Ar ₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of structural formula (I). In the structural formula (II), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

<Structural Formula (III)>
In the _formula, R _{9, R 10} represents a substituted or unsubstituted aryl _{group, Ar 4, Ar 5, Ar} 6 independently represent an arylene group. X, k, j and n are the same as in the case of structural formula (I). In the structural formula (III), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

<Structural Formula (IV)>
However, in formula, R <_11> , R < ₁₂ > is a substituted or unsubstituted aryl group, Ar < ₇ >, Ar < ₈ >, Ar < ₉ > is the same or different arylene group, p represents the integer of 1-5. X, k, j and n are the same as in the case of structural formula (I). In the structural formula (IV), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

<Structural Formula (V)>
However, in formula, R <_13> , R < ₁₄ > represents a substituted or unsubstituted aryl group. Ar ₁₀ , Ar ₁₁ and Ar ₁₂ represent the same or different arylene groups. X ₁ and X ₂ represent a substituted or unsubstituted ethylene group or a substituted or unsubstituted vinylene group. X, k, j and n are the same as in the case of structural formula (I). In the structural formula (V), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

<Structural Formula (VI)>
However, in the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are substituted or unsubstituted aryl groups, Ar ₁₃ , Ar ₁₄ , Ar ₁₅ and Ar ₁₆ are the same or different arylene groups, Y ₁ and Y _2. , Y ₃ represents a single bond, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a substituted or unsubstituted alkylene ether group, an oxygen atom, a sulfur atom, or a vinylene group. Also good. X, k, j, and n are the same as in the structural formula (V). In the structural formula (I), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

<Structural Formula (VII)>
However, in the formula, R ₁₉ and R ₂₀ represent a hydrogen atom or a substituted or unsubstituted aryl group, and R ₁₉ and R ₂₀ may form a ring. Ar ₁₇ , Ar ₁₈ and Ar ₁₉ represent the same or different arylene groups. X, k, j and n are the same as in the case of structural formula (I). In the structural formula (VII), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

<Structural Formula (VIII)>
In the formula, R ₂₁ represents a substituted or unsubstituted aryl group, and Ar ₂₀ , Ar ₂₁ , Ar ₂₂ , and Ar ₂₃ represent the same or different arylene groups. X, k, j and n are the same as in the case of structural formula (I). In the structural formula (VIII), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

<Structural Formula (IX)>
In the _{formula, R 22, R 23, R} 24, R 25 represents a substituted or unsubstituted aryl _{group, Ar 24, Ar 25, Ar} 26, Ar 27, Ar 28 may represent an arylene group. X, k, j and n are the same as in the case of structural formula (I). In the structural formula (IX), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

<Structural Formula (X)>
In the formula, R ₂₆ and R ₂₇ represent a substituted or unsubstituted aryl group, and Ar ₂₉ , Ar ₃₀ and Ar ₃₁ represent the same or different arylene groups. X, k, j and n are the same as in the case of structural formula (I). In the structural formula (X), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

  Further, as the polymer charge transport material used in the charge transport layer, in addition to the polymer charge transport material described above, in the state of the monomer or oligomer having an electron donating group at the time of film formation of the charge transport layer, A polymer having a two-dimensional or three-dimensional crosslinked structure is finally included by carrying out a curing reaction or a crosslinking reaction.

  A charge transport layer composed of a polymer having these electron donating groups or a polymer having a crosslinked structure is excellent in wear resistance. Usually, in the electrophotographic process, since the charging potential (unexposed portion potential) is constant, if the surface layer of the photoreceptor is worn by repeated use, the electric field strength applied to the photoreceptor increases accordingly. As the electric field strength increases, the occurrence frequency of scumming increases. Therefore, the high wear resistance of the photosensitive member is advantageous for scumming. The charge transport layer composed of a polymer having these electron donating groups is a polymer compound, so it has excellent film-forming properties and has a charge transport site compared to a charge transport layer composed of a low molecular weight dispersed polymer. It can be configured with high density and has excellent charge transport capability. For this reason, a photoreceptor having a charge transport layer using a polymer charge transport material can be expected to have a high response speed.

  Examples of other polymers having an electron donating group include known monomer copolymers, block polymers, graft polymers, star polymers, and, for example, JP-A-3-109460 and JP-A-2000. It is also possible to use a crosslinked polymer having an electron donating group as disclosed in JP-A-206723 and JP-A No. 2001-34001.

  In the present invention, a plasticizer or a leveling agent may be added to the charge transport layer (37). As the plasticizer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is suitably about 0 to 30% by mass with respect to the binder resin. As the leveling agent, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, polymers or oligomers having a perfluoroalkyl group in the side chain are used, and the amount used is 0 to 0 with respect to the binder resin. 1% by weight is appropriate.

  In the electrophotographic photoreceptor of the present invention, an intermediate layer can be provided between the support (31) and the photosensitive layer. The intermediate layer generally contains a resin as a main component, but these resins are preferably resins having a high solvent resistance with respect to a general organic solvent in consideration of applying a photosensitive layer thereon with a solvent. . Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. Further, fine powder pigments of metal oxides exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the intermediate layer in order to prevent moire and reduce residual potential.

These intermediate layers can be formed by using an appropriate solvent and coating method like the above-mentioned photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the intermediate layer of the present invention. In addition, in the intermediate layer of the present invention, Al ₂ O ₃ is provided by anodic oxidation, organic substances such as polyparaxylylene (parylene), SiO ₂ , SnO ₂ , TiO ₂ , ITO, CeO _2, etc. Those provided with an inorganic material by a vacuum thin film forming method can also be used favorably. In addition, known ones can be used. The thickness of the intermediate layer is suitably from 0 to 5 μm.

  In the electrophotographic photoreceptor of the present invention, a protective layer may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer. In recent years, computers have been used on a daily basis, and there is a demand for miniaturization of devices as well as high-speed output by printers. Therefore, by providing a protective layer and improving the durability, it is possible to use the photosensitive member of the present invention with high sensitivity and no abnormal defects.

  In the photoreceptor of the present invention, a protective layer (39) may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer. Materials used for the protective layer (39) include ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone. , Polybutylene, polybutylene terephthalate, polycarbonate resin, polyarylate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylbenten, polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS resin, butadiene-styrene copolymer, Examples thereof include resins such as polyurethane, polyvinyl chloride, polyvinylidene chloride, and epoxy resin. Among these, polycarbonate resin or polyarylate can be most preferably used.

In addition to the protective layer, a fluorine resin such as polytetrafluoroethylene, a silicone resin, and an inorganic filler such as titanium oxide, tin oxide, potassium titanate, and silica for the purpose of improving wear resistance (inorganic Pigments) or organic fillers (organic pigments) dispersed therein can be added.
Among the filler materials used for the protective layer of the photoreceptor, examples of the organic filler material include fluorine resin powder such as polytetrafluoroethylene, silicone resin powder, a-carbon powder, and the like. Metals such as copper, tin, aluminum and indium, silica, tin oxide, zinc oxide, titanium oxide, indium oxide, antimony oxide, bismuth oxide, tin oxide doped with antimony, tin doped indium oxide and other metals Examples thereof include inorganic materials such as oxides and potassium titanate. In particular, it is advantageous to use an inorganic material among them from the viewpoint of the hardness of the filler. In particular, silica, titanium oxide, and alumina can be used effectively.

The filler concentration in the protective layer varies depending on the type of filler used and also on the electrophotographic process conditions using the photoconductor. 10 mass% or more is more preferable. Moreover, 50 mass% or less is preferable, and 30 mass% or less is more preferable.
Further, the volume average particle size of the filler used is preferably in the range of 0.1 μm to 2 μm, and preferably in the range of 0.3 μm to 1 μm. In this case, if the average particle size is too small, the wear resistance is not sufficiently exhibited, and if it is too large, the surface property of the coating film is deteriorated or the coating film itself cannot be formed.

The average particle diameter of the filler in the present invention is a volume average particle diameter unless otherwise specified, and is determined by an ultracentrifugal automatic particle size distribution analyzer: CAPA-700 (manufactured by Horiba). At this time, the particle size (Median system) corresponding to 50% of the cumulative distribution was calculated. In addition, it is important that the standard deviation of each particle measured simultaneously is 1 μm or less. If the standard deviation is larger than this, the particle size distribution may be too wide, and the effects of the present invention may not be obtained remarkably.
Further, the pH of the filler used in the present invention greatly affects the resolution and the dispersibility of the filler. One possible reason is that hydrochloric acid or the like remains in the filler, particularly the metal oxide, during production. When the remaining amount is large, the occurrence of image blur is unavoidable, and depending on the remaining amount, the dispersibility of the filler may be affected.

  Another reason is due to the difference in chargeability on the surface of the filler, particularly the metal oxide. Usually, particles dispersed in a liquid are charged positively or negatively, and ions having opposite charges gather to try to keep it electrically neutral, and an electric double layer is formed there. The dispersed state of the particles is stabilized. The potential (zeta potential) gradually decreases with increasing distance from the particle, and the potential in a region that is sufficiently away from the particle and electrically neutral is zero. Therefore, the stability increases as the repulsive force of the particles increases due to an increase in the absolute value of the zeta potential, and the particles tend to aggregate and become unstable as they approach zero. On the other hand, the zeta potential varies greatly depending on the pH value of the system, and at a certain pH value, the potential becomes zero and has an isoelectric point. Therefore, the dispersion system is stabilized by increasing the absolute value of the zeta potential as far as possible from the isoelectric point of the system.

  In the configuration of the present invention, the filler having a pH at the isoelectric point of at least 5 is preferably from the viewpoint of image blur suppression, and the more basic the filler, the higher the effect. It was confirmed that there was. A filler exhibiting basicity having a high pH at the isoelectric point has a higher zeta potential when the system is acidic, thereby improving dispersibility and its stability.

Here, the pH of the filler in the present invention is the pH value at the isoelectric point from the zeta potential. At this time, the zeta potential was measured with a laser zeta potentiometer manufactured by Otsuka Electronics Co., Ltd.
Furthermore, as the filler that is less likely to cause image blurring, a filler having high electrical insulation (specific resistance is 10 ¹⁰ Ω · cm or more) is preferable, and the filler having a pH of 5 or more or the filler having a dielectric constant of 5 or more. The ones shown can be used particularly effectively. In addition, a filler having a pH of 5 or more or a filler having a dielectric constant of 5 or more can be used alone, or two or more fillers having a pH of 5 or less and a filler having a pH of 5 or more can be mixed. It is also possible to use a mixture of two or more fillers having a dielectric constant of 5 or less and a filler having a dielectric constant of 5 or more. Among these fillers, α-type alumina, which has high insulation properties, high thermal stability, and high wear resistance, is a hexagonal close-packed structure, from the viewpoint of suppressing image blur and improving wear resistance. It is particularly useful.

The specific resistance of the filler used in the present invention is defined as follows. Since the specific resistance value of a powder such as a filler varies depending on the filling rate, it is necessary to measure under certain conditions. In the present invention, the specific resistance value of the filler was measured using an apparatus having the same configuration as that of the measuring apparatus disclosed in JP-A-5-113688 (FIG. 1), and this value was used. In the measuring device, the electrode area is 4.0 cm ² . Prior to measurement, a load of 4 kg is applied to one electrode for 1 minute, and the sample amount is adjusted so that the distance between the electrodes is 4 mm. At the time of measurement, the measurement is performed under the load condition of the mass (1 kg) of the upper electrode, and the applied voltage is measured at 100V. The area of 10 ⁶ Ω · cm or higher was measured with a HIGH RESISTER METER (manufactured by Yokogawa Hewlett Packard), and the area below it was measured with a digital multimeter (Fluk). The specific resistance value thus obtained is defined as the specific resistance value in the present invention.

The dielectric constant of the filler was measured as follows. Using a cell similar to the measurement of the specific resistance as described above, after applying a load, the capacitance was measured, and the dielectric constant was determined from this. The capacitance was measured using a dielectric loss measuring device (manufactured by Ando Electric).
Further, these fillers can be surface-treated with at least one kind of surface treatment agent, and it is preferable from the viewpoint of dispersibility of the fillers. Decreasing the dispersibility of the filler not only increases the residual potential, but also decreases the transparency of the coating film, causes defects in the coating film, and decreases the wear resistance. It can develop into a big problem. As the surface treatment agent, all conventionally used surface treatment agents can be used, but a surface treatment agent capable of maintaining the insulating properties of the filler is preferable. For example, a titanate coupling agent, an aluminum coupling agent, a zircoaluminate coupling agent, a higher fatty acid, etc., or a mixing treatment of these with a silane coupling agent, Al ₂ O ₃ , TiO ₂ , ZrO ₂ , Silicone, aluminum stearate, or the like, or a mixture thereof is more preferable from the viewpoint of filler dispersibility and image blur. The treatment with the silane coupling agent is strongly influenced by image blur, but the influence may be suppressed by performing a mixing treatment of the surface treatment agent and the silane coupling agent. The surface treatment amount varies depending on the average primary particle size of the filler used, but is preferably 3 to 30% by mass, and more preferably 5 to 20% by mass. If the surface treatment amount is less than this, the filler dispersion effect cannot be obtained, and if it is too much, the residual potential is significantly increased. These filler materials may be used alone or in combination of two or more. The surface treatment amount of the filler is defined by the mass ratio of the surface treatment agent to be used with respect to the filler amount as described above.
These filler materials can be dispersed by using an appropriate disperser. Further, from the viewpoint of the transmittance of the protective layer, it is preferable that the filler used is dispersed to the primary particle level and has less aggregates.

  Further, the protective layer (39) may contain a charge transport material for reducing residual potential and improving responsiveness. As the charge transport material, the materials described in the description of the charge transport layer can be used. When a low molecular charge transport material is used as the charge transport material, a concentration gradient in the protective layer may be provided. In order to improve wear resistance, it is an effective means to reduce the concentration of the surface side. The concentration here means the ratio of the mass of the low-molecular charge transporting substance to the total mass of all the materials constituting the protective layer, and the concentration gradient is a gradient in which the concentration decreases on the surface side in the mass ratio. It shows that. The use of a polymer charge transport material is very advantageous in terms of enhancing the durability of the photoreceptor.

As a method for forming the protective layer, a normal coating method is employed. In addition, about 0.1-10 micrometers is suitable for the thickness of a protective layer. In addition to the above, a known material such as a-C or a-SiC formed by a vacuum thin film forming method can be used as the protective layer.
In addition, the polymer charge transport material described in the section of the charge transport layer can be used as the binder resin for the protective layer. As the effect when this is used, the effect of improving the wear resistance and the high-speed charge transport can be obtained as described in the section of the charge transport layer.
Moreover, the protective layer which consists of a crosslinked structure is also used effectively as binder resin of a protective layer. Regarding the formation of a cross-linked structure, a reactive monomer having a plurality of cross-linkable functional groups in one molecule is used to cause a cross-linking reaction using light or thermal energy to form a three-dimensional network structure. is there. This network structure functions as a binder resin and exhibits high wear resistance.

Moreover, it is a very effective means to use a monomer having a charge transporting ability in whole or in part as the reactive monomer. By using such a monomer, a charge transport site is formed in the network structure, and the function as a protective layer can be sufficiently expressed. A reactive monomer having a triarylamine structure is effectively used as the monomer having charge transporting ability.
The charge transport layer having such a network structure has high wear resistance, but has a large volume shrinkage during the crosslinking reaction, and if it is too thick, cracks may occur. In such a case, the protective layer may be a laminated structure, a low molecular dispersion polymer protective layer may be used for the lower layer (photosensitive layer side), and a protective layer having a crosslinked structure may be formed on the upper layer (surface side). good.

  As described above, the use of a polymer charge transport material for the photosensitive layer (charge transport layer) or the provision of a protective layer on the surface of the photoreceptor increases the durability (wear resistance) of each photoreceptor. In addition, when used in a tandem type full-color image forming apparatus as described later, a new effect not found in the monochrome image forming apparatus is also produced.

  In the case of a full-color image, various types of images are input, but on the contrary, a typical image may also be input. For example, the presence of a seal in a Japanese document or the like. Something like indicia is usually located towards the edge of the image area, and the colors used are also limited. In a state in which a random image is always written, image writing, development, and transfer are performed on the photoconductor in the image forming element on average. When many image formations are repeated or only a specific image forming element is used, the durability balance is lost. In such a state, when a photoreceptor having a low surface durability (physical, chemical, mechanical) is used, this difference becomes significant, and an image problem is likely to occur. On the other hand, when the photoconductor is made highly durable, the amount of such local change is small, and as a result, it becomes difficult to appear as a defect on the image, so that high durability is achieved and the stability of the output image is improved. This is very effective.

-Electrostatic latent image forming means-
The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. , Non-contact chargers using corona discharge such as corotron and scorotron (including proximity type non-contact chargers having a gap of several tens to several hundreds of μm between the surface of the photoreceptor and the charger), etc. Can be mentioned.
The charger charges the photoconductor and applies electric field strength. The electric field strength applied to the photoconductor is preferably 30 V / μm or higher. The higher the electric field strength, the more the above-mentioned simultaneous exposure by multibeam, line image by sequential exposure, reduction of dot image non-uniformity, dot image density, sharpness, etc. The property becomes good. However, there is a possibility that problems such as dielectric breakdown of the photosensitive member and carrier adhesion during development occur, and the upper limit is approximately 60 V / μm or less, more preferably 50 V / μm or less.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The type of the exposure device is not particularly limited and may be appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system. Is mentioned.
In the present invention, a back light system in which imagewise exposure is performed from the back surface side of the electrostatic latent image carrier may be adopted.

  As a light source of the exposure device, a light source capable of ensuring high brightness such as a light emitting diode (LED), a semiconductor laser (LD), and electroluminescence (EL) and capable of writing with high resolution (600 dpi or higher resolution) can be used. .

-Development means-
The development can be performed by developing the electrostatic latent image with toner to form a visible image.
The developing unit is not particularly limited as long as it can be developed using toner, and can be appropriately selected from known ones. For example, the developing unit accommodates toner and contacts the electrostatic latent image with the toner. Alternatively, those having at least a developing device that can be applied in a non-contact manner are preferable.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

The toner can be used for both regular development and reversal development depending on the charging polarity of the toner used. When a toner having a polarity opposite to the charged polarity of the photoreceptor is used, normal development is used. When a toner having the same polarity is used, the electrostatic latent image is developed by reversal development.
Although it depends on the light source used in the exposure device, considering the life of the light source and the like, in the case of a digital light source used in recent years, the toner development in the writing part generally corresponds to the low image area ratio. A reversal development method is advantageous. There are two methods, a one-component method in which development is performed with toner alone and a two-component method in which a two-component developer comprising a toner and a carrier is used. Either method can be used favorably.

-Transfer means-
The transfer means is a means for transferring the visible image onto a recording medium. There is a method in which a visual image is first transferred and then the visible image is secondarily transferred onto the recording medium. Either aspect can be used satisfactorily, but the former (direct transfer) method with a small number of transfers is preferred when the adverse effect of the transfer is great when the image quality is improved.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer unit is not particularly limited and may be appropriately selected from known transfer units according to the purpose. For example, a transfer conveyance belt that can simultaneously convey a recording medium may be mentioned. It is done.

The transfer means (the primary transfer means, the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

  The transfer charger can be a transfer belt or a transfer roller, but it is desirable to use a contact type such as a transfer belt or a transfer roller that generates less ozone. As a voltage / current application method at the time of transfer, either a constant voltage method or a constant current method can be used, but the transfer charge amount can be kept constant, and a constant voltage with excellent stability can be used. The current method is more desirable. As such a transfer unit, a known unit can be used as long as the configuration of the present invention can be satisfied.

-Fixing means-
The fixing may be performed each time the visible image transferred to the recording medium is fixed using a fixing device, and the toner of each color is transferred to the recording medium, or the toner is stacked on the toner of each color. May be performed simultaneously at the same time.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.
As a light source such as a static elimination lamp, general light emitting materials such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electroluminescence (EL) can be used. Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.

  This neutralization mechanism can be omitted when the AC component is used in a superposed manner in the previous charging method, or when the residual potential of the photoreceptor is small. Further, instead of optical static elimination, an electrostatic static elimination mechanism (for example, a static elimination brush with a reverse bias applied or grounded) can be used. As described above, a document with a small writing rate has a large effect of light neutralization, and it is preferable not to use light neutralization as long as there is no influence of afterimage or the like in the next image forming cycle.

  The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

  The recycling unit is a step of recycling the electrophotographic color toner removed by the cleaning unit to the developing unit, and examples thereof include a known conveyance unit.

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

Here, an aspect of the image forming apparatus of the present invention will be described with reference to FIG.
FIG. 3 is a schematic diagram for explaining the image forming apparatus of the present invention, and modifications as described later also belong to the category of the present invention.
In FIG. 3, a photoreceptor (1) as an electrostatic latent image carrier is provided with a photosensitive layer including at least a charge generation layer and a charge transport layer on a support, and CuKα rays (wavelength 1) are provided on the charge generation layer. As a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to .542 Å), it has a maximum diffraction peak at least 27.2 ° and is further dominant at 9.4 °, 9.6 °, and 24.0 °. Having a peak and having a peak at 7.3 ° as the lowest diffraction peak, and having no peak between the 7.3 ° peak and the 9.4 ° peak, Furthermore, it contains a titanyl phthalocyanine crystal having no peak at 26.3 ° and having an average primary particle diameter of 0.25 μm or less. The photosensitive member (1) has a drum shape, but may be a sheet or an endless belt.

As the transfer means of the apparatus shown in FIG. 3, a direct transfer system is used in which the toner image formed on the surface of the photoreceptor is directly transferred to a recording medium.
As the charger (3), a wire type charger or a roller-type charger is used. In particular, a scorotron charger is preferably used for high-speed charging as in the present invention. Although this charging device charges the photoconductor, the higher the electric field strength applied to the photoconductor, the better the dot reproducibility. Therefore, it is desirable to apply an electric field strength of 30 V / μm or more. . However, there is a possibility that problems such as dielectric breakdown of the photoreceptor and carrier adhesion during development occur, and the upper limit is approximately 60 V / μm or less, more preferably 50 V / μm or less.

  In addition, the image exposure unit (5) can ensure high brightness such as a light emitting diode (LED), a semiconductor laser (LD), and electroluminescence (EL), and can be written at a resolution of 600 dpi or more (preferably 1200 dpi or more). A possible light source is used. Depending on the resolution of the light source (writing light), the resolution of the formed electrostatic latent image, and thus the toner image, is determined. The higher the resolution, the clearer the image. However, if writing is performed at a higher resolution, writing takes longer, so writing with one writing light source is limited by the drum linear speed (process speed). Therefore, when there is one writing light source, a resolution of about 1200 dpi is the upper limit. When there are a plurality of write light sources, each of them only has to bear a write area, and the upper limit is substantially “1200 dpi × number of write light sources”. The writing light source here refers to one LD element or one LED element. For example, LEDs arranged in an array are handled as a plurality of light sources.

  The developing unit (6) can handle both normal development and reversal development depending on the charging polarity of the toner used. When toner having a polarity opposite to the charged polarity of the photoreceptor is used, normal development is used. When toner having the same polarity is used, the electrostatic latent image is developed by reversal development. Depending on the light source used in the previous image exposure unit, in the case of a digital light source used in recent years, there is generally a reversal development method in which toner development is performed on the writing portion in response to a low image area ratio. This is advantageous in view of the life of the light source. There are two methods, a one-component method in which development is performed with toner alone and a two-component method in which a two-component developer comprising a toner and a carrier is used. Either method can be used favorably.

As the transfer means, a member of a type in which a toner image formed on a photoreceptor is directly transferred to a recording medium such as paper on which the toner image is output is used.
Although FIG. 3 shows a transfer charger (10) as a transfer means, a transfer charger and a transfer roller can also be used. Among them, it is desirable to use a contact type such as a transfer belt or a transfer roller that generates less ozone. Any such transfer means can be used as long as it can satisfy the structure of the present invention.

  As a voltage / current application method at the time of transfer, either a constant voltage method or a constant current method can be used, but the transfer charge amount can be kept constant, and a constant voltage with excellent stability can be used. The current method is more desirable. In particular, by subtracting the current that flows from the power supply member (high-voltage power supply) that supplies electric charge to the transfer means and does not flow into the photoconductor, the current to the photoconductor is subtracted. A method of controlling the value is preferred. Specifically, in order to obtain the current flowing through the roller holding the transfer belt, the related member such as the roller is not directly dropped to the ground, but the current flowing through the related member is returned to the high voltage power source. It is desirable to obtain a difference from the output of the power supply and perform constant current control using a high voltage power supply having a feedback function so that the difference becomes a constant value. An example of a circuit configuration diagram that can take such a form is shown in FIG.

  The transfer current is a current based on the amount of charge required to peel off the toner electrostatically attached to the photosensitive member and transfer it to a recording medium (transfer paper or intermediate transfer member). In order to avoid transfer defects such as transfer residue, it is only necessary to increase the transfer current. However, in the case of using negative and positive development, charging with a polarity opposite to the charging polarity of the photosensitive member is given. As a result, the electrostatic fatigue of the photoconductor becomes remarkable. For this reason, in the electrophotographic apparatus so far, the deterioration of the electrostatic fatigue characteristics due to the reverse charging applied to the photoconductor is rate-limiting and it is difficult to increase the transfer current, but the titanyl phthalocyanine crystal having a specific crystal type is This problem can be solved by using the photoconductor used.

The larger the transfer current, the more advantageous it is because the amount of charge exceeding the electrostatic adhesion force between the photoconductor and the toner can be given, but if a certain threshold value is exceeded, a discharge phenomenon will occur between the transfer means and the photoconductor, and it will be fine. As a result, the developed toner image is scattered. For this reason, the upper limit is a range in which this discharge phenomenon does not occur. This threshold value varies depending on the gap (distance) between the transfer means and the photoconductor, the material constituting the both, and the like, but the discharge phenomenon can be avoided by using it at about 200 μA or less. Therefore, the upper limit value of the transfer current is about 200 μA.
At this time, the surface potential of the photoreceptor after transfer has a great influence on the electrostatic fatigue of the photoreceptor in repeated use. That is, the electrostatic fatigue of the photoreceptor is greatly influenced by the amount of charge passing through the photoreceptor. This passing charge amount corresponds to the amount of charge flowing in the film thickness direction of the photoreceptor. As an operation in the image forming apparatus of the photoconductor, the main charger is charged to a desired charging potential (in most cases, negatively charged), and optical writing is performed based on an input signal corresponding to the document. At this time, photocarriers are generated in the portion where writing is performed, and the surface charge is neutralized (potential decay). At this time, the amount of charge depending on the amount of generated photocarriers flows in the direction of the photoreceptor film thickness.
On the other hand, the area where the optical writing is not performed (non-writing portion) proceeds to the charge removal process through the development process and the transfer process (a cleaning process is performed before that if necessary). Here, when the surface potential of the photoconductor is close to the potential applied by main charging (excluding dark decay), the amount of charge is almost the same as that in the area where optical writing is performed. Will flow into. In general, since current writing is low in writing, if this method is used, the amount of charge passing through the photoreceptor in repeated use is almost the current that flows in the static elimination process (the writing rate is 10%). Then, the current flowing in the static elimination process occupies 90% of the total).
This passing charge greatly affects the electrostatic characteristics of the photoconductor, for example, causing deterioration of the material constituting the photoconductor. As a result, the residual potential of the photosensitive member is raised, depending on the amount of passing charge. When the residual potential of the photoconductor is increased, the image density is lowered in the negative and positive development used in the present invention, which is a serious problem. Therefore, there is a problem of how to reduce the passing charge amount of the photoconductor in order to increase the lifetime (high durability) of the photoconductor in the image forming apparatus.
On the other hand, there is a way of thinking that the photostatic discharge is not performed, but if the main charger is not large in charging ability, the charging cannot be stabilized and a problem such as an afterimage may occur.
The passing charge of the photoconductor is generated by the movement of the generated optical carrier by light irradiation by the electric potential (the electric field generated thereby) charged on the surface of the photoconductor. Therefore, if the photoreceptor surface potential can be attenuated by means other than light, the amount of passing charge per rotation of the photoreceptor (one cycle of image formation) can be reduced.
For this purpose, it is effective to adjust the charge passing through the photosensitive member by adjusting the transfer bias in the transfer process. That is, a non-writing portion that is charged by main charging and does not perform writing enters the transfer process in a state close to the charged potential except for the dark attenuation amount. At this time, the absolute value on the polarity side charged by the main charger is reduced to 100 V or less, so that almost no photocarrier is generated even when the subsequent charge removal process is entered, and no passing charge is generated. This value is preferably closer to 0V.
Furthermore, by adjusting the transfer bias, by applying a transfer bias so that the surface potential of the photosensitive member is charged to a polarity opposite to the charging polarity applied by the main charging, it is more preferable because no optical carrier is generated. . However, under transfer conditions that charge to the opposite polarity, there are cases where a large amount of transfer dust occurs or the main charge of the next image forming process (cycle) cannot catch up. In that case, since a problem such as an afterimage may occur, the absolute value of the reverse polarity is preferably 100 V or less.

  Use light sources such as fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light-emitting diodes (LEDs), semiconductor lasers (LDs), and electroluminescence (ELs) as light sources such as static elimination lamps (2). Can do. 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.

Such a light source or the like irradiates the photosensitive member with light by providing a process such as a transfer process, a charge eliminating process, a cleaning process, or a pre-exposure using light irradiation in addition to the process shown in FIG.
This neutralization mechanism can be omitted when the AC component is superposed and used in the previous charging method, or when the residual potential of the photoreceptor is small. Further, instead of optical static elimination, an electrostatic static elimination mechanism (for example, a static elimination brush applied with a reverse bias or grounded) can be used. As described above, a document with a small writing rate has a large effect of light neutralization, and it is preferable not to use a light neutralization unit unless there is an effect of afterimage or the like in the next image forming cycle. In FIG. 3, 8 is a registration roller, 11 is a separation charger, and 12 is a separation claw.

  In addition, the toner developed on the photoreceptor (1) by the developing unit (6) is transferred to the transfer paper (9), but when toner remaining on the photoreceptor (1) is generated, a fur brush ( 14) and the blade (15). Cleaning may be performed only with a cleaning brush, and a known brush such as a fur brush or a mag fur brush is used as the cleaning brush.

Next, FIG. 5 is a schematic diagram for explaining the tandem-type full-color image forming apparatus of the present invention, and the following modifications also belong to the category of the present invention.
In FIG. 5, reference numerals (16Y), (16M), (16C), and (16K) denote drum-shaped photoconductors, and the photoconductors include at least a charge generation layer and a charge transport layer on a conductive support. The charge generation layer has a maximum diffraction peak at 27.2 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to CuKα rays (wavelength 1.542 mm), and further 9 .4 °, 9.6 °, 24.0 °, the peak at 7.3 ° as the lowest diffraction peak, and the 7.3 ° peak. It contains titanyl phthalocyanine crystals having no peak between the 9.4 ° peaks, no peak at 26.3 °, and an average primary particle size of 0.25 μm or less.

The photoconductors (16Y), (16M), (16C), and (16K) rotate in the direction of the arrow in the figure, and the chargers (17Y), (17M), (17C), (17K) at least in the order of rotation therearound. ), Developing means (19Y), (19M), (19C), (19K), cleaning member (20Y), (20M), (20C), (20K), neutralizing means (27Y), ( 27M), (27C), and (27K) are arranged, and the distance between the charge eliminating means and the charger is set to 0.15 seconds or less as the time required for a certain point of the photoconductor to move between the centers. The chargers (17Y), (17M), (17C), and (17K) are chargers that constitute a charging device for uniformly charging the surface of the photoreceptor. From the surface of the photosensitive member between the chargers (17Y), (17M), (17C), (17K) and the developing means (19Y), (19M), (19C), (19K), an exposure unit (not shown) Laser beams (18Y), (18M), (18C), and (18K) are irradiated so that an electrostatic latent image is formed on the photoconductors (16Y), (16M), (16C), and (16K). It has become. Then, the four image forming elements (25Y), (25M), (25C), and (25K) centering on such photoconductors (16Y), (16M), (16C), and (16K) serve as transfer materials. They are juxtaposed along the transfer conveyance belt (22) which is a conveyance means.
The transfer conveyance belt (22) is a means for directly transferring the toner image on the photosensitive member to the recording medium (26). Each of the image forming units (25Y), (25M), (25C), (25K) Photoconductors (16Y), (16M), (16C) between the developing means (19Y), (19M), (19C), (19K) and the cleaning members (20Y), (20M), (20C), (20K) ), (16K), and transfer brushes (21Y), (21M), (21C), 21B, 21C, 21C, 21C, 21C, 21C, 21C, and 16C for applying a transfer bias to the back surface (back surface) of the transfer conveyance belt (22). (21K) is arranged. Each of the image forming elements (25Y), (25M), (25C), and (25K) is different in the color of the toner inside the developing device, and the others are the same in configuration.

In the full-color image forming apparatus having the configuration shown in FIG. 5, the image forming operation is performed as follows. First, in each of the image forming elements (25Y), (25M), (25C), and (25K), an electrostatic latent image is formed on the photoconductors (16Y), (16M), (16C), and (16K). It has become. Then, the photoreceptors (16Y), (16M), (16C), and (16K) rotate, and the photoreceptors are charged by the chargers (17Y), (17M), (17C), and (17K). The At this time, in order to form a high-definition latent image, charging is performed so that the electric field strength of the photoreceptor is 30 V / μm or more (60 V μm or less, preferably 50 V / μm or less).
Next, writing is performed at a resolution of 600 dpi or more (preferably 1200 dpi or more) with laser light (18Y), (18M), (18C), and (18K) at an exposure unit (not shown) arranged outside the photoreceptor. The electrostatic latent image corresponding to each color image to be created is formed. Also in this case, 1200 dpi writing is generally the upper limit for one writing light source.

Next, the latent image is developed by developing means (19Y), (19M), (19C), and (19K) to form a toner image. Developing means (19Y), (19M), (19C), and (19K) are developing means for developing with toners of Y (yellow), M (magenta), C (cyan), and K (black), respectively. The toner images of the respective colors formed on the two photoconductors (16Y), (16M), (16C), and (16K) are superimposed on the transfer paper. The transfer paper (26) is fed from the tray by a paper feed roller (not shown), temporarily stopped by a pair of registration rollers (23), and transferred and conveyed (22) in synchronization with image formation on the photosensitive member. ). The recording medium (26) held on the transfer conveyance belt (22) is conveyed, and each color at the contact position (transfer section) with each photoconductor (16Y), (16M), (16C), (16K). The toner image is transferred.
The toner image on the photoconductor includes transfer bias applied to the transfer brushes (21Y), (21M), (21C), and (21K) and the photoconductors (16Y), (16M), (16C), and (16K). The image is directly transferred onto the recording medium (26) by an electric field formed from the potential difference of. The recording medium (26) on which the toner images of four colors are superimposed through the four transfer sections is conveyed to the fixing device (24), where the toner is fixed, and is discharged to a discharge section (not shown).
Further, residual toner remaining on each of the photoconductors (16Y), (16M), (16C), and (16K) without being transferred by the transfer unit is removed from the cleaning devices (20Y), (20M), (20C), ( 20K).
Subsequently, excess residual charges on the photosensitive member are removed by the charge eliminating units (27Y), (27M), (27C), and (27K). Thereafter, charging is performed uniformly by the charger, and the next image formation is performed.
In the example of FIG. 5, the image forming elements are arranged in the order of Y (yellow), M (magenta), C (cyan), and K (black) from the upstream side to the downstream side in the transfer paper conveyance direction. However, it is not limited to this order, and the color order is arbitrarily set. Further, when creating a black-only document, it is particularly effective to use the present invention to provide a mechanism that stops image forming elements other than black ((25Y), (25M), (25C)). .
Further, as described above, the surface of the photoreceptor after transfer is preferably charged to 100 V or less on the polarity side charged by the main charger, more preferably charged to the reverse polarity side, and to the reverse polarity side. It is particularly preferable to charge to 100 V or less. As a result, an increase in residual potential due to repeated use of the photoreceptor can be reduced.

  The image forming means as described above may be fixedly incorporated in a copying apparatus, a facsimile, or a printer, but may be incorporated in these apparatuses in the form of a process cartridge. A process cartridge is a single device (part) that contains a photoconductor, and further includes a charger, an exposure unit, a developing unit, a transfer unit, a cleaning unit, a neutralizing unit, and the like. There are many shapes and the like of the process cartridge, but a general example is shown in FIG. The photoreceptor (101) is provided with a photosensitive layer including at least a charge generation layer and a charge transport layer on a support. The charge generation layer has a diffraction peak (± 0.2 °) and has a maximum diffraction peak at least 27.2 °, and further has major peaks at 9.4 °, 9.6 °, and 24.0 °, and the diffraction at the lowest angle. There is a peak at 7.3 ° as a peak, and there is no peak between the peak at 7.3 ° and the peak at 9.4 °, and no peak at 26.3 °. And it contains a titanyl phthalocyanine crystal having an average primary particle size of 0.25 μm or less.

  As described above, a light source capable of performing writing with a resolution of 600 dpi or higher is preferably used for the image exposure unit (103), and an optional charger (preferably scorotron charging) is used for the charger (102). Used. In FIG. 6, reference numeral 104 denotes a developing means having two developing sleeves, 105 denotes a recording medium, 106 denotes a transfer means, and 107 denotes a cleaning means.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example at all.

(Comparative Synthesis Example 1)
-Synthesis of titanyl phthalocyanine crystals-
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.) until the washing solution becomes neutral. 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 this 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 amount of the crystal conversion solvent used was 33 times the mass ratio of the wet cake. In addition, the halogen-containing compound is not used for the raw material of the comparative 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 A titanyl phthalocyanine powder having a peak at .3 ± 0.2 ° and no peak between the peak at 7.3 ° and the peak at 9.4 ° and no peak at 26.3 ° Was obtained. The result is shown in FIG.

  A part of the water paste obtained in Comparative Synthesis Example 1 was dried at 80 ° C. under reduced pressure (5 mmHg) for 2 days to obtain a low crystalline titanyl phthalocyanine powder. The X-ray diffraction spectrum of the dry powder of water paste 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

(Comparative Synthesis Example 2)
-Synthesis of titanyl phthalocyanine crystals-
A pigment was produced according to the method described in Example 1 of JP-A-1-299874 (Patent No. 2512081). That is, the wet cake produced in the previous Comparative Synthesis Example 1 was dried, 1 g of the dried product was added to 50 g of polyethylene glycol, and sand milling was performed with 100 g of glass beads. After the crystal transition, the mixture was washed successively with dilute sulfuric acid and aqueous ammonium hydroxide and dried to obtain a pigment. This is designated as Pigment 2. The raw material of Comparative Synthesis Example 2 does not use a halogen-containing compound.

(Comparative Synthesis Example 3)
-Synthesis of titanyl phthalocyanine crystals-
A pigment was produced according to the method described in Production Example 1 of JP-A-3-269064 (Patent No. 2854682). That is, the wet cake prepared in Comparative Synthesis Example 1 was dried, and 1 g of the dried product was stirred in a mixed solvent of 10 g of ion-exchanged water and 1 g of monochlorobenzene for 1 hour (50 ° C.), and then methanol and ion-exchanged water. The pigment was obtained by washing and drying. This is designated as Pigment 3. The raw material of Comparative Synthesis Example 3 does not use a halogen-containing compound.

(Comparative Synthesis Example 4)
-Synthesis of titanyl phthalocyanine crystals-
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 the completion of the reaction, the mixture was allowed to cool to 130 ° C. and filtered while hot. Next, the powder was washed with 1-chloronaphthalene until the powder turned blue. Next, it was washed several times with methanol, further washed several times with hot water at 80 ° C., and dried to obtain a pigment. This is designated as Pigment 4. The raw material of Comparative Synthesis Example 4 uses a halogen-containing compound.

(Comparative Synthesis Example 5)
-Synthesis of titanyl phthalocyanine crystals-
A pigment was prepared according to the method described in Synthesis Example 1 of JP-A No. 64-17066 (Japanese Patent Publication No. 7-97221). That is, 5 parts by mass of α-type TiOPc was subjected to crystal conversion treatment at 100 ° C. for 10 hours with a sand grinder together with 10 g of sodium chloride and 5 g of acetophenone. This was washed with ion-exchanged water and methanol, purified with dilute sulfuric acid aqueous solution, washed with ion-exchanged water until the acid content disappeared, and dried to obtain a pigment. This is designated as Pigment 5. As the raw material of Comparative Synthesis Example 5, a halogen-containing compound is used.

(Comparative Synthesis Example 6)
-Synthesis of titanyl phthalocyanine crystals-
A pigment was prepared according to the method described in Example 1 of JP-A-11-5919 (Japanese Patent No. 3003664). That is, 20.4 parts by mass of O-phthalodinitrile and 7.6 parts by mass of titanium tetrachloride were heated at 200 ° C. for 2 hours in 50 parts by mass of quinoline, the solvent was removed by steam distillation, 2% hydrochloric acid, The product was purified with 2% aqueous sodium hydroxide solution, washed with methanol and N, N-dimethylformamide, and dried to obtain titanyl phthalocyanine. 2 parts by mass of this titanyl phthalocyanine is dissolved little by little in 40 parts by mass of 98% by mass sulfuric acid at 5 ° C., and the mixture is stirred for about 1 hour while maintaining the temperature at 5 ° C. or less. Subsequently, the sulfuric acid solution is slowly poured into 400 parts by mass of ice water stirred at high speed, and the precipitated crystals are filtered. The crystals are washed with distilled water until no acid remains, and a wet cake is obtained. The cake was stirred in 100 parts by mass of THF for about 5 hours, filtered, washed with THF and dried to obtain a pigment. This is designated as Pigment 6. The raw material of Comparative Synthesis Example 6 uses a halogen-containing compound.

(Comparative Synthesis Example 7)
-Synthesis of titanyl phthalocyanine crystals-
A pigment was produced according to the method described in Synthesis Example 2 of JP-A-3-255456 (Patent No. 3005052). That is, 10 parts by weight of the wet cake prepared in Comparative Synthesis Example 1 was mixed with 15 parts by weight of sodium chloride and 7 parts by weight of diethylene glycol, and milled for 60 hours with an automatic mortar under heating at 80 ° C. Next, sufficient washing was performed to completely remove sodium chloride and diethylene glycol contained in the treated product. After drying this under reduced pressure, 200 parts by mass of cyclohexanone and glass beads having a diameter of 1 mm were added, and the mixture was treated with a sand mill for 30 minutes to obtain a pigment. This is designated as Pigment 7. The raw material of Comparative Synthesis Example 7 does not use a halogen-containing compound.

(Comparative Synthesis Example 8)
-Synthesis of titanyl phthalocyanine crystals-
A pigment was prepared according to the method for producing a titanyl phthalocyanine crystal of JP-A-8-110649. That is, 58 g of 1,3-diiminoisoindoline and 51 g of tetrabutoxy titanium were reacted in 210 mL of α-chloronaphthalene at 210 ° C. for 5 hours, and then washed in the order of α-chloronaphthalene and dimethylformamide (DMF). Thereafter, it was washed with hot DMF, hot water and methanol and dried to obtain 50 g of titanyl phthalocyanine. 4 g of titanyl phthalocyanine was added to 400 g of concentrated sulfuric acid cooled to 0 ° C., followed by stirring at 0 ° C. for 1 hour. After confirming that phthalocyanine was completely dissolved, it was added to a 800 mL water / 800 mL toluene mixture cooled to 0 ° C. After stirring at room temperature for 2 hours, the precipitated phthalocyanine mixed crystal was separated from the mixed solution and washed with methanol and water in this order. After confirming the neutrality of the washing water, the phthalocyanine mixed crystal was filtered from the washing water and dried to obtain 2.9 g of titanyl phthalocyanine mixed crystal. This is designated as Pigment 8. The raw material of Comparative Synthesis Example 8 does not use a halogen-containing compound.

(Synthesis Example 1)
-Synthesis of titanyl phthalocyanine crystals-
According to the method of Comparative Synthesis Example 1, an aqueous paste of titanyl phthalocyanine pigment was synthesized, and crystal conversion was performed as follows to obtain phthalocyanine crystals having smaller primary particles than Comparative Synthesis Example 1.
400 parts by mass of tetrahydrofuran was added to 60 parts by mass of the water paste before crystal conversion obtained in Comparative Synthesis Example 1, and the mixture was stirred vigorously (2000 rpm) with a homomixer (Kennis, MARKIIf model) at room temperature. When the color changed to light blue (20 minutes after the start of stirring), stirring was stopped and filtration under reduced pressure was immediately performed. The crystals obtained on the filter were washed with tetrahydrofuran to obtain a wet pigment cake. This was dried under reduced pressure (5 mmHg) at 70 ° C. for 2 days to obtain 8.5 parts by mass of titanyl phthalocyanine crystals. This is designated as Pigment 9. The raw material of 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 an amount of 44 times by mass ratio with respect to the wet cake.

Next, a portion of the pre-crystallized titanyl phthalocyanine (water paste) prepared in Comparative Synthesis Example 1 was diluted with ion-exchanged water to approximately 1% by mass, and the surface was scooped with a copper net having a conductive treatment. The particle diameter of titanyl 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. The arithmetic average of the major axis of the measured 30 individuals was determined and used as the average particle size.
The average particle size in the water paste in Synthesis Example 1 determined by the above method was 0.06 μm.

  In addition, the titanyl phthalocyanine crystal after crystal conversion immediately before filtration in Comparative Synthesis Example 1 and Synthesis Example 1 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 diameter determined as described above is shown in Table 1. In addition, the titanyl phthalocyanine crystal produced in Comparative Synthesis Example 1 and Synthesis Example 1 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.

  The pigments 2 to 8 prepared in the above Comparative Synthesis Examples 2 to 8 were measured for X-ray diffraction spectra by the same method as described above, and confirmed to be the same as the spectra described in the respective publications. Further, the X-ray diffraction spectrum of the pigment 9 produced in Synthesis Example 1 was identical to the spectrum of the pigment 1 produced in Comparative Synthesis Example 1. Table 2 shows the characteristics of each X-ray diffraction spectrum and the peak position of the X-ray diffraction spectrum of the pigment obtained in Comparative Synthesis Example 1.

(Dispersion Preparation Example 1)
Pigment 1 prepared in Comparative Synthesis Example 1 was dispersed under the following composition under the following conditions to prepare a dispersion as a charge generation layer coating solution.
Titanyl phthalocyanine pigment (Pigment 1) 15 parts by weight Polyvinyl butyral (manufactured by Sekisui Chemical: BX-1) 10 parts by weight 2-butanone 280 parts by weight A commercially available bead mill disperser was used to dissolve polyvinyl butyral using a PSZ ball having a diameter of 0.5 mm. All of 2-butanone and pigment were added, and the rotor rotation speed was 1200 r. p. m. For 30 minutes to prepare a dispersion. This was designated as Dispersion Liquid 1.

(Dispersion preparation examples 2 to 9)
In place of pigment 1 used in dispersion preparation example 1, pigments 2 to 9 prepared in comparative synthesis examples 2 to 8 and synthesis example 1 were used, respectively. Produced. These were designated as dispersions 2 to 9, corresponding to the pigment numbers.

(Dispersion Preparation Example 10)
Dispersion 1 prepared in Dispersion Preparation Example 1 was filtered using a cotton wind cartridge filter, TCW-1-CS (effective pore size 1 μm) manufactured by Advantech. During filtration, a pump was used and filtration was performed in a pressurized state. This was designated as Dispersion Liquid 10.

(Dispersion Preparation Example 11)
Dispersion was performed by pressure filtration in the same manner as in Dispersion Preparation Example 10, except that the filter used in Dispersion Preparation Example 10 was changed to Advantech's Cotton Wind Cartridge Filter and TCW-3-CS (effective pore size 3 μm). A liquid was prepared. This was designated as Dispersion Liquid 11.

(Dispersion Preparation Example 12)
Dispersion was carried out by pressure filtration in the same manner as in Dispersion Preparation Example 10, except that the filter used in Dispersion Preparation Example 10 was changed to an Advantech Co., Ltd. cotton wind cartridge filter, TCW-5-CS (effective pore size 5 μm). A liquid was prepared. This was designated as Dispersion Liquid 12.

(Dispersion Preparation Example 13)
Dispersion was performed by changing the dispersion conditions in Dispersion Preparation Example 1 as follows. This was designated as Dispersion Liquid 13.
Rotor rotation speed: 1000 r. p. m. For 20 minutes.

(Dispersion Preparation Example 14)
The dispersion prepared in Dispersion Preparation Example 13 was filtered using a cotton wind cartridge filter, TCW-1-CS (effective pore size 1 μm) manufactured by Advantech. During filtration, a pump was used and filtration was performed in a pressurized state. During the filtration, the filter was clogged, and all of the dispersion liquid could not be filtered. For this reason, the following evaluation was not implemented.

  The particle size distribution of the pigment particles in the dispersion prepared as described above was measured with CAPA-700 from Horiba. The results are shown in Table 3.

(Photoreceptor Preparation Example 1)
An undercoating layer coating solution, a charge generation layer coating solution, and a charge transporting layer coating solution having the following composition are sequentially applied to an aluminum cylinder (JIS 1050) having a diameter of 100 mm, dried, and dried under 3.5 μm. A pulling layer, a charge generation layer, and a 28 μm charge transport layer were formed to produce a laminated photoreceptor. This is a photoreceptor 1. The film thickness of the charge generation layer was adjusted so that the transmittance of the charge generation layer at 780 nm was 20%. The transmittance of the charge generation layer was determined by applying a charge generation layer coating solution having the following composition to an aluminum cylinder wrapped with a polyethylene terephthalate film under the same conditions as the preparation of the photoreceptor, and applying the charge generation layer as a comparative control. The transmittance of 780 nm was evaluated with a commercially available spectrophotometer (manufactured by Shimadzu Corporation: UV-3100).

-Undercoat layer coating solution-
Titanium oxide (CR-EL: Ishihara Sangyo Co., Ltd.) 70 parts by mass Alkyd resin 15 parts by mass (Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.)
Melamine resin 10 parts by mass (Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.)
2-butanone 100 parts by mass

-Charge generation layer coating solution-
The previously prepared dispersion 1 was used.
-Charge transport layer coating solution-
Polycarbonate resin (TS2050: manufactured by Teijin Chemicals Ltd.) 10 parts by mass Charge transport material having the following structural formula: 7 parts by mass
80 parts by mass of methylene chloride

(Photosensitive member production examples 2 to 13)
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 1 except that the charge generation layer coating solution (dispersion 1) used in Photoconductor Preparation Example 1 was changed to dispersions 2 to 13, respectively. In addition, the film thickness of the charge generation layer was adjusted so that the transmittance at 780 nm was 20% when all the coating liquids were used, as in Photoreceptor Preparation Example 1.

( Example 1 and Comparative Examples 1 to 23)
The prepared electrophotographic photosensitive members of Preparation Examples 1 to 13 are mounted on the image forming apparatus shown in FIG. 3 (photosensitive linear velocity is 360 mm / sec), and the surface of the photosensitive member is −900 V using a scorotron charger. The image exposure light source is a semiconductor laser of 780 nm (image writing by a polygon mirror, resolution 600 dpi), the development is a two-component development, and a toner image is directly formed on the transfer paper using a transfer conveyance belt as a transfer means. Transfer was performed (control was performed using the circuit shown in FIG. 4 so that the transfer current was constant). A 780 nm LED was used as the charge eliminating light, and the entire surface of the photoconductor was irradiated with light to eliminate the charge. Using a chart with a writing rate of 6%, 100,000 sheets were continuously printed at a speed of 65 sheets per minute (the test environment was 22 ° C.-55% RH).

<Image evaluation>
The following two evaluations were performed after printing 100,000 sheets of images.
(I) Evaluation of background stain A solid white image was output, and rank evaluation was performed from the number and size of black spots generated on the background.
The dirt rank evaluation was carried out in 4 stages. Very good ones were indicated by 、, good ones by 、, slightly inferior ones by Δ, and very bad ones by x.
(Ii) Evaluation of dot formation state Using the test chart shown in FIG. 17, a halftone image (one dot image having a diameter of 60 μm) is formed immediately after the white solid portion, the character portion, and the black solid portion, and the dot formation state is determined. Observed.
The results are shown in Table 4.

(Photoconductor Preparation Examples 14 to 26)
Photoconductors were prepared in the same manner as in Photoconductor preparation examples 1 to 13, except that the aluminum cylinder used in Photoconductor preparation examples 1 to 13 was changed to one having a diameter of 60 mm.

( Example 4 and Comparative Examples 11-20)
The produced electrophotographic photosensitive members of Preparation Examples 14 to 26 are mounted on the image forming apparatus shown in FIG. 3 (photosensitive member linear velocity is 250 mm / sec), and a contact-type charger (charging roller having a diameter of 20 mm) is used. The surface of the photosensitive member is charged to −900 V under the following charging conditions, the image exposure light source is a semiconductor laser of 780 nm (image writing by a polygon mirror, resolution 600 dpi), and development is performed by two-component development. The toner image was directly transferred onto the transfer paper using a transfer belt (control was performed using the circuit shown in FIG. 4 so that the transfer current was constant). An 780 nm LED was used for the charge removal light, and the entire surface of the photoconductor was irradiated with light to remove the charge. Using a chart with a writing rate of 6%, continuous printing of 50,000 sheets was performed at a rate of 45 sheets per minute (the test environment is 22 ° C.-55% RH).

<Charging conditions>
DC bias: -1600V

<Image evaluation>
The following two evaluations were performed after printing 100,000 sheets of images.
(I) Evaluation of background stain A solid white image was output, and rank evaluation was performed from the number and size of black spots generated on the background.
The dirt rank evaluation was carried out in 4 stages. Very good ones were indicated by 、, good ones by 、, slightly inferior ones by Δ, and very bad ones by x.
(Ii) Evaluation of dot formation state Using the test chart shown in FIG. 17, a halftone image (one dot image having a diameter of 60 μm) is formed immediately after the white solid portion, the character portion, and the black solid portion, and the dot formation state is determined. Observed.
The results are shown in Table 5.

(Example 7)
In Example 1, the chart used for the printing test was changed to a chart with a writing rate of 1%, and a continuous 100,000 sheet printing test was performed. At this time, in order to measure the surface potential of the photoconductor at the development site of the image forming apparatus shown in FIG.
Before and after the printing test, the potential of the exposed portion of the photoreceptor at the development site was measured. At this time, in order to measure the surface potential of the exposed portion, the optical writing was performed on the entire surface of the photosensitive member.
In the printing test in Example 7, the transfer bias was adjusted so that the potential of the non-written portion of the photoreceptor after transfer was −150V. In this measurement, optical writing was not performed, and the potential after transfer of the photosensitive member was measured. The results are shown in Table 6.

(Example 8)
In Example 7, a printing test was performed in the same manner as in Example 7 except that the potential of the non-written portion of the photoconductor after transfer was adjusted to −80V. The results are shown in Table 6.

Example 9
In Example 7, a printing test was performed in the same manner as in Example 7 except that the potential of the non-written portion of the photoconductor after transfer was adjusted to 0V. The results are shown in Table 6.

(Example 10)
In Example 7, a printing test was performed in the same manner as in Example 7 except that the potential of the non-written portion of the photoconductor after transfer was adjusted to + 70V. The results are shown in Table 6.

(Example 11)
In Example 7, a printing test was conducted in the same manner as in Example 7 except that the potential of the non-written portion of the photoreceptor after transfer was adjusted to + 150V. The results are shown in Table 6.

Example 12
In Example 7, a printing test was conducted in the same manner as in Example 7 except that the static eliminating means was changed from the static eliminating lamp to a conductive brush (connected to ground). The results are shown in Table 6.

(Photoconductor Preparation Example 27)
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 9 except that the charge transport layer coating solution in Photoconductor Preparation Example 9 was changed to the following composition.
-Charge transport layer coating solution-
10 parts by mass of polymeric charge transport material having the following composition (weight average molecular weight: about 135,000)
0.5 parts by mass of additives having the following structure
100 parts by mass of methylene chloride

(Photoreceptor Preparation Example 28)
Except that the film thickness of the charge transport layer in Photoreceptor Preparation Example 9 was 22 μm, a protective layer coating solution having the following composition was applied on the charge transport layer, dried, and a protective layer having a film thickness of 5 μm was provided. A photoconductor was prepared in the same manner as the photoconductor production example 9.
-Protective layer coating liquid-
Polycarbonate resin (TS2050: manufactured by Teijin Chemicals Ltd.) 10 parts by mass Charge transport material having the following structural formula: 7 parts by mass
4 parts by mass of alumina fine particles (specific resistance: 2.5 × 10 ¹² Ω · cm, average primary particle size: 0.4 μm)
Cyclohexanone 500 parts by mass Tetrahydrofuran 150 parts by mass

(Photoconductor Preparation Example 29)
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 28 except that the alumina fine particles in the protective layer coating solution in Photoconductor Preparation Example 28 were changed to the following.
Titanium oxide fine particles 4 parts by mass (specific resistance: 1.5 × 10 ¹⁰ Ω · cm, average primary particle size: 0.5 μm)

(Photoreceptor Preparation Example 30)
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 28 except that the alumina fine particles in the protective layer coating solution in Photoconductor Preparation Example 28 were changed to the following.
4 parts by mass of tin oxide-antimony oxide powder (specific resistance: 10 ⁶ Ω · cm, average primary particle size 0.4 μm)

(Photoreceptor Preparation Example 31)
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 28 except that the protective layer coating solution in Photoconductor Preparation Example 28 was changed to one having the following composition.
-Protective layer coating liquid-
17 parts by mass of polymer charge transport material having the following structural formula (n was about 250 as measured by GPC)
4 parts by mass of alumina fine particles (specific resistance: 2.5 × 10 ¹² Ω · cm, average primary particle size: 0.4 μm)
Cyclohexanone 500 parts by mass Tetrahydrofuran 150 parts by mass

(Photoconductor Preparation Example 32)
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 28 except that the protective layer coating solution in Photoconductor Preparation Example 28 was changed to the following composition.
-Protective layer coating liquid-
Methyltrimethoxysilane 100 parts by weight 3% acetic acid 20 parts by weight Charge transporting compound having the following structure 35 parts by weight
Antioxidant (Sanol LS2626: Sankyo Chemical Co., Ltd.) 1 part by mass Curing agent (dibutyltin acetate) 1 part by mass 2-propanol 200 parts by mass

(Photoconductor Preparation Example 33)
A photoconductor was prepared in the same manner as in Photoconductor Preparation Example 28 except that the protective layer coating solution in Photoconductor Preparation Example 28 was changed to the following composition.
-Protective layer coating liquid-
Methyltrimethoxysilane 100 parts by weight 3% acetic acid 20 parts by weight Charge transporting compound having the following structure 35 parts by weight
α-alumina particles (Sumicorundum AA-03: manufactured by Sumitomo Chemical Co., Ltd.) 15 parts by mass Antioxidant (Sanol LS2626: manufactured by Sankyo Chemical Co., Ltd.) 1 part by mass Polycarboxylic acid compound (BYK P104: manufactured by BYK Chemie) 0.4 mass Part Curing agent (dibutyltin acetate) 1 part by mass 2-propanol 200 parts by mass

(Photoconductor Preparation Example 34)
The aluminum cylinder (JIS 1050) in Photoconductor Preparation Example 9 was subjected to the following anodized film treatment. Then, without providing an undercoat layer, a charge generation layer and a charge transport layer were provided in the same manner as in Photoconductor Preparation Example 1 to prepare a photoconductor.
-Anodized film treatment-
The surface of the support was mirror-polished, degreased and washed with water, and then immersed in an electrolytic bath with a liquid temperature of 20 ° C. and sulfuric acid of 15 vol%, and an anodized film treatment was performed at an electrolysis voltage of 15 V for 30 minutes. Further, after washing with water, sealing treatment was performed with a 7% nickel acetate aqueous solution (50 ° C.). Then, the support body in which the 7-micrometer-thick anodic oxide film was formed was obtained through the washing | cleaning by a pure water.

(Examples 13 to 20)
The electrophotographic photoreceptors produced in photoreceptor preparation examples 27 to 34 are mounted on the image forming apparatus shown in FIG. 3 (photoconductor linear velocity is 360 mm / sec), and the surface of the photoreceptor is −900 V using a scorotron charger. The image exposure light source is a semiconductor laser of 780 nm (image writing by a polygon mirror, resolution is 600 dpi), development is performed by two-component development, and a toner image is directly transferred onto a transfer paper using a transfer belt as a transfer means. (The circuit shown in FIG. 4 was used to control the transfer current to be constant). An 780 nm LED was used for the charge removal light, and the entire surface of the photoconductor was irradiated with light to remove the charge. Using a chart with a writing rate of 6%, 100,000 sheets were continuously printed at a speed of 65 sheets per minute (the test environment was 22 ° C.-55% RH).

<Image evaluation>
The following two evaluations were performed after printing 100,000 sheets of images.
(I) Evaluation of background stain A solid white image was output, and rank evaluation was performed from the number and size of black spots generated on the background.
The dirt rank evaluation was carried out in 4 stages. Very good ones were indicated by 、, good ones by 、, slightly inferior ones by Δ, and very bad ones by x.
(Ii) Evaluation of dot formation state Using the test chart shown in FIG. 17, a halftone image (one dot image having a diameter of 60 μm) is formed immediately after the white solid portion, the character portion, and the black solid portion, and the dot formation state is determined. Observed.
In addition, the amount of abrasion of the photosensitive layer after printing 100,000 sheets (the amount of abrasion of the protective layer when a protective layer is provided) was measured. The above results are shown in Table 7 together with the case of Example 1.

(Photoconductor Preparation Example 35)
The aluminum cylinder of the photoreceptor preparation example 1 was changed to one having a diameter of 60 mm to prepare a photoreceptor having the same composition as the photoreceptor preparation example 1.

(Photoconductor Preparation Example 36)
The aluminum cylinder of the photoreceptor preparation example 4 was changed to one having a diameter of 60 mm, and a photoreceptor having the same composition as that of the photoreceptor preparation example 4 was prepared.

(Photoconductor Preparation Example 37)
A photoconductor having the same composition as that of photoconductor preparation example 5 was prepared by changing the aluminum cylinder of photoconductor preparation example 5 to one having a diameter of 60 mm.

(Photoconductor Preparation Example 38)
The aluminum cylinder of the photoreceptor preparation example 8 was changed to one having a diameter of 60 mm, and a photoreceptor having the same composition as that of the photoreceptor preparation example 8 was prepared.

(Photoconductor Preparation Example 39)
The aluminum cylinder of the photoreceptor preparation example 9 was changed to one having a diameter of 60 mm, and a photoreceptor having the same composition as that of the photoreceptor preparation example 9 was prepared.

(Photoconductor Preparation Example 40)
The aluminum cylinder of the photoreceptor preparation example 10 was changed to one having a diameter of 60 mm to prepare a photoreceptor having the same composition as that of the photoreceptor preparation example 10.

(Examples 20 to 21 and Comparative Examples 21 to 24)
The photoconductors of Examples 35 to 40 manufactured as described above are mounted on a single process cartridge for an image forming apparatus as shown in FIG. 6 together with a charger (scorotron charging), and further, as shown in FIG. It was mounted on an image forming apparatus (photosensitive linear velocity is 250 mm / sec). In the four image forming elements, charging is performed by a scorotron charger as a charger so that the surface potential of the photoreceptor becomes −900 V, and an image exposure light source is a semiconductor laser of 780 nm (image writing by a polygon mirror, resolution 600 dpi), The toner image was directly transferred onto transfer paper using a transfer belt as transfer means (control was performed using the circuit shown in FIG. 4 so that the transfer current was constant). Using a chart with a writing rate of 6%, continuous 50,000 sheets were printed at a rate of 40 sheets per minute (the test environment is 22 ° C.-55% RH).

<Image evaluation>
The following three evaluations were carried out after printing 50,000 sheets.
(I) Evaluation of background stain A solid white image was output, and rank evaluation was performed from the number and size of black spots generated on the background.
The dirt rank evaluation was carried out in 4 stages. Very good ones were indicated by 、, good ones by 、, slightly inferior ones by Δ, and very bad ones by x.
(Ii) Evaluation of dot formation state Using the test chart shown in FIG. 17, a halftone image (one dot image having a diameter of 60 μm) is formed immediately after a white solid portion, a character portion, and a black (color) solid portion. The formation state was observed.
(Iii) Evaluation of color reproducibility The same full-color image was output after initial printing of the photoreceptor and 100,000 sheets, and an attempt was made to evaluate color reproducibility.
In any case, the rank evaluation was performed in four stages, and very good ones were indicated by ◎, good ones by ○, slightly inferior by Δ, and very bad by x. In addition, the amount of abrasion of the photosensitive layer after printing 100,000 sheets (the amount of abrasion of the protective layer when a protective layer is provided) was measured.
Table 8 shows the above results.

(Comparative Examples 25-30)
The full color image forming apparatus shown in FIG. 5 is modified to provide an intermediate transfer member, and in Examples 20 to 21 and Comparative Examples 21 to 24, the toner images formed on the photosensitive member are once transferred to the intermediate transfer member. Then, evaluation was performed in the same manner as in Examples 20 to 21 and Comparative Examples 21 to 24 except that the transfer paper was changed so as to be transferred to the transfer paper.
In the evaluation, 1-dot images were enlarged and observed with an optical microscope, and compared with the corresponding Examples 20 to 21 and Comparative Examples 21 to 24. The results are shown in Table 8.

  Finally, 7.3 ° which is the lowest angle peak of the Bragg angle θ, which is a feature of the titanyl phthalocyanine crystal used in the present invention, will be verified as to whether or not it is the same as the lowest angle 7.5 ° of known materials.

(Comparative Synthesis Example 9)
A titanyl phthalocyanine crystal was obtained in the same manner as in Comparative Synthesis Example 1 except that the crystal conversion solvent in Comparative Synthesis Example 1 was changed from methylene chloride to 2-butanone.
As in Comparative Synthesis Example 1, the XD spectrum of the titanyl phthalocyanine crystal produced in Comparative Synthesis Example 9 was measured. This is shown in FIG. From FIG. 18, the lowest angle in the XD spectrum of the titanyl phthalocyanine crystal produced in Comparative Synthesis Example 9 is 7.5 °, which is different from the lowest angle (7.3 °) of the titanyl phthalocyanine produced in Comparative Synthesis Example 1. It can be seen that it exists.

(Measurement Example 1)
A pigment prepared in the same manner as the pigment described in JP-A-61-239248 (having a maximum diffraction peak at 7.5 °) was used as the pigment obtained in Comparative Synthesis Example 1 (minimum angle 7.3 °). Mass% was added and mixed in a mortar, and the X-ray diffraction spectrum was measured as before. The X-ray diffraction spectrum of Measurement Example 1 is shown in FIG.

(Measurement example 2)
3 was prepared in the same manner as the pigment described in JP-A-61-239248 (having a maximum diffraction peak at 7.5 °) as the pigment obtained in Comparative Synthesis Example 9 (minimum angle 7.5 °). Mass% was added and mixed in a mortar, and the X-ray diffraction spectrum was measured as before. The X-ray diffraction spectrum of Measurement Example 2 is shown in FIG.

In the spectrum of FIG. 19, it can be seen that there are two independent peaks at 7.3 ° and 7.5 ° on the lower angle side, and at least the peaks at 7.3 ° and 7.5 ° are different. It was. On the other hand, in the spectrum of FIG. 20, the low angle side peak exists only at 7.5 °, which is clearly different from the spectrum of FIG.
From the above, it was found that the minimum angle peak of 7.3 ° in the titanyl phthalocyanine crystal of the present invention is different from the 7.5 ° peak in the known titanyl phthalocyanine crystal.

  The image forming apparatus of the present invention is a specific crystal type in an image forming apparatus that employs a system that transfers a toner image formed on a photoconductor to a recording medium by a direct transfer system in order to form a high-quality image at high speed. By using a photoconductor containing the titanyl phthalocyanine crystal, it maintains the high sensitivity inherent in titanyl phthalocyanine, is highly durable, has no abnormal images when it is used repeatedly at high speed, and is stable. Is suitably used for an image forming apparatus capable of outputting the image.

FIG. 1 is a schematic diagram for explaining a positive afterimage. FIG. 2 is a schematic diagram for explaining a negative afterimage. FIG. 3 is a schematic view for explaining an example of the electrophotographic process and the image forming apparatus of the present invention. FIG. 4 is a diagram showing a transfer circuit capable of constant current control. FIG. 5 is a schematic diagram for explaining an example of the tandem full-color image forming apparatus of the present invention. FIG. 6 is a view for explaining an example of a process cartridge for an image forming apparatus according to the present invention. FIG. 7 is a TEM image of amorphous titanyl phthalocyanine. The scale bar in the figure is 0.2 μm. FIG. 8 is a TEM image of titanyl phthalocyanine after crystal conversion. The scale bar in the figure is 0.2 μm. FIG. 9 is a TEM image of a titanyl phthalocyanine crystal that has been crystallized in a short time. The scale bar in the figure is 0.2 μm. FIG. 10 is a diagram showing the state of the dispersion when the dispersion time is short. FIG. 11 is a diagram showing the state of the dispersion when the dispersion time is long. FIG. 12 is a diagram showing an average particle size and a particle size distribution for the dispersions of FIGS. 10 and 11. FIG. 13 is a diagram showing an example of the layer structure of the electrophotographic photosensitive member used in the present invention. FIG. 14 is a diagram showing an example of the layer structure of another electrophotographic photosensitive member used in the present invention. FIG. 15 is a diagram showing an XD spectrum of titanyl phthalocyanine synthesized in Comparative Synthesis Example 1. FIG. 16 is a diagram showing an XD spectrum of a dry powder of water paste. FIG. 17 shows a test chart used in Example 1. FIG. 18 is a diagram showing an XD spectrum of titanyl phthalocyanine synthesized in Comparative Synthesis Example 9. FIG. 19 is a diagram showing an XD spectrum of titanyl phthalocyanine used in Measurement Example 1. FIG. 20 is a diagram showing an XD spectrum of titanyl phthalocyanine used in Measurement Example 2.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Static elimination lamp 3 Charger charger 5 Image exposure part 6 Developing unit 8 Registration roller 9 Transfer paper 10 Transfer charger 11 Separation charger 12 Separation claw 14 Fur brush 15 Cleaning blade 16Y, 16M, 16C, 16K Photoconductor 17Y, 17M, 17C, 17K Charger 18Y, 18M, 18C, 18K Laser light 19Y, 19M, 19C, 19K Developing means 20Y, 20M, 20C, 20K Cleaning member 21Y, 21M, 21C, 21K Transfer brush 22 Transfer conveyance belt 23 Registration roller 24 Fixing Apparatus 25Y, 25M, 25C, 25K Image forming element 26 Transfer paper

Claims (19)

An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a visible image An image forming apparatus including at least a developing unit that transfers the visible image onto a recording medium, and a fixing unit that fixes the transferred image transferred onto the recording medium. The visible image developed on the surface of the electrostatic latent image carrier is directly transferred to a recording medium, and the electrostatic latent image carrier comprises a support, at least a charge generation layer on the support, a charge transport layer, Are stacked in this order, and at least 7.0 to 7.5 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray of CuKα (wavelength 1.542 mm) in the charge generation layer. Having a maximum diffraction peak and a half-width of the diffraction peak of 1 ° or more, An amorphous or low crystalline titanyl phthalocyanine crystal having an average particle diameter of 0.1 μm or less is converted using an organic solvent in the presence of water, and the average particle diameter of primary particles after the crystal conversion is 0 A diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to CuKα rays (wavelength 1.542 mm) in the titanyl phthalocyanine crystal, including titanyl phthalocyanine crystal after crystal conversion obtained by filtration in a state of .25 μm or less As a diffraction peak on the lowest angle side at 7.3 °, with a maximum diffraction peak at least 27.2 °, and major peaks at 9.4 °, 9.6 °, and 24.0 °. A primary grain in the titanyl phthalocyanine crystal having a peak, no peak between the peak at 7.3 ° and the peak at 9.4 °, no peak at 26.3 °, and An image forming apparatus, wherein the average particle size of the child is 0.25 μm or less. The image forming apparatus according to claim 1, wherein the titanyl phthalocyanine crystal is synthesized from a raw material not containing a halogen-containing compound . An amorphous or low crystalline titanyl phthalocyanine crystal is prepared by the acid paste method, and the obtained amorphous or low crystalline titanyl phthalocyanine crystal is washed with ion exchange water until the pH of the ion exchange water is 6-8. The image forming apparatus according to claim 1 . Amorphous or low crystalline titanyl phthalocyanine crystal was prepared by the acid paste method, and the obtained amorphous or low crystalline titanyl phthalocyanine crystal was ion-exchanged water until the specific conductivity of ion-exchanged water became 8 μS / cm or less. The image forming apparatus according to claim 1, wherein the image forming apparatus is washed with The image forming apparatus according to any one of claims 2 to 4, wherein the amount of the organic solvent used in the crystal conversion of the titanyl phthalocyanine crystal is 10 times or more that of the amorphous or low crystalline titanyl phthalocyanine crystal in terms of mass ratio . The image forming apparatus according to claim 1, wherein the charge transport layer contains a polycarbonate resin containing a triarylamine structure in at least one of a main chain and a side chain . The image forming apparatus according to claim 1, further comprising a protective layer on the charge transport layer . The protective layer has a specific resistance of 10 ¹⁰ The image forming apparatus according to claim 7, comprising at least one selected from inorganic pigments and metal oxides of Ω · cm or more. The image forming apparatus according to claim 7, wherein the protective layer further contains a polymer charge transport material . The image forming apparatus according to claim 7, wherein the protective layer contains a binder resin, and the binder resin has a crosslinked structure . The image forming apparatus according to claim 10, wherein the structure of the binder resin having a crosslinked structure has a charge transport site . The image forming apparatus according to claim 1, wherein the surface of the support in the electrostatic latent image carrier is anodized . The writing unit and the non-writing unit are formed on the electrostatic latent image carrier by the exposure device, and the absolute value of the surface potential in the non-writing unit of the electrostatic latent image carrier after transfer is 100 V or less. 13. The image forming apparatus according to any one of items 1 to 12 . The image forming apparatus according to claim 13, wherein the surface potential in the non-writing portion of the electrostatic latent image carrier after the transfer is a reverse potential of the potential charged by the charger . The surface potential at the non-writing portion of the latent electrostatic image bearing member after transfer is a reverse potential of the potential charged by the charger, and the absolute value of the surface potential of the non-writing portion is 100 V or less. The image forming apparatus according to any one of claims 14 to 14. The image forming apparatus according to claim 1, wherein the image forming apparatus does not use a light neutralizing unit . The image forming apparatus according to claim 1, wherein the charger in the electrostatic latent image forming unit applies an AC superimposed voltage to the surface of the electrostatic latent image carrier. 2. The electrostatic latent image carrier and at least one means selected from an electrostatic latent image forming means, a developing means, and a cleaning means are integrated, and a process cartridge that is detachable from the apparatus main body is mounted. 18. The image forming apparatus according to any one of items 1 to 17. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, and the visible image An image forming method including at least a transfer step for transferring the image to a recording medium and a fixing step for fixing the transferred image transferred to the recording medium, wherein the transfer step is developed on the surface of the electrostatic latent image carrier. The latent electrostatic image bearing member is formed by laminating a support, at least a charge generation layer, and a charge transport layer in this order on the support. The charge generation layer has a maximum diffraction peak at 7.0 to 7.5 ° as a diffraction peak (± 0.2 °) with a Bragg angle 2θ with respect to the characteristic X-ray (wavelength 1.542１．５) of CuKα, and The half width of the diffraction peak is 1 ° or more, and the average primary particle diameter is 0.1. An amorphous or low crystalline titanyl phthalocyanine crystal having a particle size of m or less is subjected to crystal conversion using an organic solvent in the presence of water, and filtered in a state where the average primary particle size after the crystal conversion is 0.25 μm or less. And a titanyl phthalocyanine crystal after crystal conversion obtained by this method, and a diffraction peak (± 0.2 °) of Bragg angle 2θ with respect to CuKα ray (wavelength 1.542Å) in the titanyl phthalocyanine crystal is at least 27.2 ° It has a diffraction peak, and further has main peaks at 9.4 °, 9.6 °, and 24.0 °, and has a peak at 7.3 ° as the lowest diffraction peak. There is no peak between the peak at 3 ° and the peak at 9.4 °, there is no peak at 26.3 °, and the average particle size of the primary particles in the titanyl phthalocyanine crystal is 0.25. An image forming method, wherein the image forming method is μm or less .