JP2006058866A - Electrophotographic photoreceptor, and image forming apparatus and process cartridge using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor capable of forming stable images even after repeated use, specifically to provide a high durability electrophotographic photoreceptor which makes it possible to suppress a surface stain in repetitive use, to prevent residual potential and to suppress dielectric breakdown in charging with a contact charging member or a charging member disposed near the electrophotographic photoreceptor. <P>SOLUTION: The electrophotographic photoreceptor contains τ type metal-free phthalocyanine and an azo pigment represented by formula (XI) in a photosensitive layer. In the formula, Cp<SB>1</SB>and Cp<SB>2</SB>each represent a coupler residue; and R<SB>201</SB>and R<SB>202</SB>each represent H, halogen, alkyl, alkoxy or cyano and may be the same or different. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electrophotographic photosensitive member in which at least a charge blocking layer, a moire preventing layer, a τ-type metal-free phthalocyanine and a photosensitive layer containing an azo pigment having a specific structure are sequentially laminated, an image forming apparatus using the same, and an image forming apparatus The present invention relates to an apparatus process cartridge.

In recent years, the development of information processing system machines using electrophotography has been remarkable. In particular, an optical printer that converts information into a digital signal and records information by light has significantly improved print quality and reliability. This digital recording technique is applied not only to printers but also to ordinary copying machines, and so-called digital copying machines have been developed. In addition, since a variety of information processing functions are added to a conventional copying machine equipped with this digital recording technology for analog copying, it is expected that its demand will increase further in the future. In addition, with the spread of personal computers and the improvement in performance, the progress of digital color printers for performing color output of images and documents is also rapidly progressing.
Such a digital image forming apparatus is required to improve its function year by year, as well as to have high image quality as well as high durability and high stability. Furthermore, in order to achieve high-speed color, a tandem system using a plurality of image forming elements each having one member necessary for image formation such as charging, exposure, development, cleaning, and charge removal is attached to one photoconductor. Color image forming apparatuses are currently the mainstream. This is usually equipped with image forming elements for yellow, magenta, cyan, and black, and each toner image is made up of four image forming elements in parallel and overlapped on a transfer body (transfer paper) or intermediate transfer body. In this method, a color image is produced at high speed. For this reason, if the photosensitive member and the members around it are not compact, the image forming apparatus becomes very large. Therefore, it is essential to reduce the diameter of the photosensitive member arranged at the center of the image forming element. . Even if the image forming apparatus is made compact by reducing the diameter of the photosensitive member, there is no merit of reducing the diameter when the lifetime is extremely shortened compared to the case of a large diameter. For this reason, it is an issue of this technique to extend the life of the photoconductor as compared with the conventional photoconductor.

  There are two rate-determining processes in the life of the photoreceptor, one is electrostatic fatigue, and the other is surface layer wear. Both are major problems for the current mainstream organic photoreceptors. The former is a change in the surface potential (charge potential and exposed portion potential) of the photoreceptor during repeated use in image formation such as charging and exposure. When organic materials are used, the charged potential decreases or the exposed portion potential increases. (Sometimes called residual potential) is a problem. The latter is a phenomenon in which a layer located on the outermost surface constituting the photosensitive member is mechanically worn by sliding of a cleaning member or the like. When the film thickness of the photoreceptor surface layer decreases due to this wear, scratches on the surface, an increase in electric field strength due to a decrease in the film thickness of the photoreceptor layer, acceleration of electrostatic fatigue, and the like are caused, and the life of the photoreceptor is significantly reduced. It becomes a factor. Therefore, in order to improve the life of the photoreceptor, the above two problems must be solved at the same time.

At present, electrophotographic image forming apparatuses are entering the printing field by realizing high speed, and high image quality and high stability are demanded. Regarding the former, 600 dpi is the lowest quality as the resolution in image writing, and the resolution has been greatly improved. In the latter, taking advantage of the characteristics of electrophotography that can directly print manuscript information, it becomes possible to add various different information one by one to a part of the output manuscript that is good at mass printing. A large amount of processing is performed at the same time, and a wide variety of writing and development is performed in which slightly different information is input one by one, so that stability as a system has been greatly demanded. For these, stability in repeated use of the image forming element is naturally required, and furthermore, it is extremely important that no abnormal image is generated.
The life and stability of such an image forming apparatus is the center of image formation, and a photoreceptor that always performs an associated operation with other members during an image forming operation holds the most important key. With all the energetic development of the photoreceptor so far, several techniques are being completed regarding the electrostatic properties and surface wear of the photoreceptor. For example, with regard to improvement of electrostatic characteristics, development of a charge generation material having a high photocarrier generation efficiency and development of a charge transport material having a high mobility can be mentioned. By combining these, it is possible to obtain a large gain and response in light attenuation. As a whole system, the charging potential is reduced, the amount of writing light is reduced, the developing bias is reduced, the transfer bias is reduced, and the static elimination process is reduced. It creates unnecessaryness and creates a margin in system design. All of these lead to a reduction in the hazard applied to the photoreceptor, and allowance is also created in the photoreceptor itself.
However, as described above, the usage of the photoconductor in the analog type image forming apparatus and the monochrome type image forming apparatus is changed by the advent of a high-speed full-color machine, and various ways of optical writing are used. It became so. In such a case, the biggest problem is that the cause of the abnormal image is the photoconductor. Although there are various cases of occurrence of abnormal images, they can be roughly divided into two. One is an abnormal image due to scratches generated on the surface of the photoconductor, and the other is an abnormal image generated due to electrostatic fatigue of the photoconductor. The former can be dealt with considerably by improving the surface layer of the photosensitive member (for example, using a protective layer) or improving the photosensitive member abutting member. The latter is caused by the deterioration of the photosensitive member itself, but the most serious problem at present is background contamination in negative / positive development.
Causes of scumming include contamination / defects on the conductive support, electrical breakdown of the photosensitive layer, carrier (charge) injection from the support, increased dark decay of the photoconductor, thermal carrier generation in the photosensitive layer, etc. Is mentioned. Of these, the contamination and defects of the support can be dealt with by eliminating such support before applying the photosensitive layer. In a sense, it is caused by an error. is not. Therefore, it is considered that improving the withstand voltage of the photosensitive member, the charge injection property from the support, and the reduction in electrostatic fatigue are fundamental solutions to this problem.

In view of such a point, techniques for providing an undercoat layer or an intermediate layer between a conductive support and a photosensitive layer have been proposed in the past. For example, Patent Document 1 discloses a cellulose nitrate resin intermediate layer, Patent Document 2 includes a nylon resin intermediate layer, Patent Document 3 includes a maleic acid resin intermediate layer, and Patent Document 4 includes a polyvinyl alcohol resin intermediate layer. Are each disclosed.
However, since the intermediate layer of these resins alone (single layer) has a high electric resistance, a residual potential is generated, and image density is lowered in negative / positive development. In addition, since it exhibits ionic conductivity due to impurities and the like, the electrical resistance of the intermediate layer is particularly high under low temperature and low humidity, so that the residual potential is significantly increased. For this reason, it is necessary to reduce the thickness of the intermediate layer, and there is a drawback that the chargeability and charge retention are insufficient in the characteristics after repeated use.
In order to solve these problems, as a technique for controlling the electric resistance of the intermediate layer, a method of adding a conductive additive to the bulk of the intermediate layer has been proposed. For example, Patent Document 5 discloses an intermediate layer in which a carbon or chalcogen-based material is dispersed in a curable resin, and Patent Document 6 includes a thermal polymer intermediate layer using an isocyanate-based curing agent to which a quaternary ammonium salt is added, Patent Document 7 discloses a resin intermediate layer to which a resistance modifier is added, and Patent Document 8 discloses a resin intermediate layer to which an organometallic compound is added. However, these resin intermediate layers alone have a problem that a moire image is generated in an image forming apparatus using coherent light such as laser light in recent years.

Further, for the purpose of simultaneously controlling the moire prevention and the electric resistance of the intermediate layer, a photoconductor containing a filler in the intermediate layer has been proposed. For example, Patent Document 9 includes a resin intermediate layer in which an oxide of aluminum or tin is dispersed, Patent Document 10 includes a resin intermediate layer in which conductive particles are dispersed, and Patent Document 11 includes an intermediate layer in which magnetite is dispersed. In Patent Document 12, a resin intermediate layer in which titanium oxide and tin oxide are dispersed is dispersed. In Patent Documents 13 to 18, borides such as calcium, magnesium, and aluminum, nitrides, fluorides, and oxide powders are dispersed. A resin intermediate layer is disclosed. In the intermediate layer in which such filler is dispersed, the amount of filler in the intermediate layer needs to be increased (that is, the amount of resin needs to be reduced) in order to develop the potential characteristics of the intermediate layer by the dispersed filler. . For this reason, there is a problem in that the adhesiveness with the conductive support decreases with a decrease in the resin amount, and peeling easily occurs between the support and the intermediate layer. In particular, the support is a flexible belt-like structure. This problem is remarkable when
In order to solve such problems, a concept of stacking intermediate layers has been proposed. The structure of lamination is roughly classified into two types. One is a structure in which a resin layer 2 in which filler is dispersed, a resin layer 3 in which filler is not dispersed, and a photosensitive layer 4 are sequentially laminated on a conductive support 1 (see FIG. 1), and the other is the one in which a resin layer 3 in which filler is not dispersed, a resin layer 2 in which filler is dispersed, and a photosensitive layer 4 are sequentially provided on the conductive support 1 (see FIG. 2).

  Describing the former configuration in detail, in order to cover the defects of the support as described above, a conductive layer 2 in which a low-resistance filler is dispersed is provided on the conductive support 1, and the resin layer 3 is provided thereon. Is provided. These are described in Patent Documents 19 to 27, for example. Since the lower conductive layer essentially serves as an electrode in the conductive support 1, the structure of the resin intermediate layer alone and the above-described electrostatic defect of the photosensitive member are not changed. Only, since the conductive layer is composed of a filler dispersion film, a moire prevention function is imparted by scattering of writing light by this layer. In such a configuration, since the lower layer is a conductive layer, the charge opposite to the polarity charged on the surface of the photosensitive member is charged to the interface between the lower layer (conductive layer) and the upper layer (resin intermediate layer). By reaching, the operation of the photoconductor is established. However, when the resistance of the conductive layer is not so low, charge injection from the electrode is not sufficiently performed, and the lower layer becomes a resistance component during repeated use, resulting in a very high residual potential. In particular, in order to cover defects of the conductive support, which is one of the purposes of this configuration, it is essential to make the lower layer sufficiently thick (10 μm or more), and this problem is remarkable.

Patent Documents 28 to 30 disclose a photoreceptor in which a conductive layer, an intermediate layer, and a photosensitive layer containing a titanyl phthalocyanine crystal are stacked. However, unless the crystal form and primary particle size of titanyl phthalocyanine are appropriately controlled, the occurrence of scumming due to the influence of heat carriers cannot be reduced.
On the other hand, as the latter configuration, a hole blocking layer is provided on a conductive support, and a resin layer in which a low resistance filler or an electron conductive filler is dispersed is provided thereon. These are described in Patent Documents 31 and 32, for example. Since this configuration has a hole blocking function as in the former configuration, it effectively acts against soiling. Further, since the filler dispersion film is present in the upper layer, the residual potential is less accumulated than the former configuration. In this configuration, since the charge (hole) injection from the conductive support to the photosensitive layer can be prevented as described above, the scumming phenomenon in the negative / positive development can be considerably reduced. Further, by disposing the charge blocking layer in the lower layer, an increase in the residual potential in repeated use can be reduced as compared with the case of disposing it in the upper layer.

  However, the cause of scumming is not only the injection of charges (holes) from the conductive support to the photosensitive layer, but also the influence of thermal carrier generation in the photosensitive layer cannot be ignored. For this reason, unless the charge generation material used in the charge generation layer and the particle state thereof are controlled, the occurrence of scumming in repeated use cannot be completely controlled.

JP-A-47-6341 JP-A-60-66258 JP 52-10138 A JP 58-105155 A JP 51-65942 A JP 52-82238 A JP-A-55-113045 JP 58-93062 A JP 58-58556 A Japanese Patent Laid-Open No. 60-111255 JP 59-17557 A JP 60-32054 A JP-A 64-68762 JP-A 64-68763 JP-A 64-73352 JP-A 64-73353 JP-A-1-118848 Japanese Patent Laid-Open No. 1-118849 JP 58-95351 A JP 59-93453 A Japanese Patent Laid-Open No. 4-170552 JP-A-6-208238 JP-A-6-222600 Japanese Patent Laid-Open No. 8-184979 JP-A-9-43886 Japanese Patent Laid-Open No. 9-190005 JP-A-9-288367 Japanese Patent Laid-Open No. 5-100461 Japanese Patent Laid-Open No. 5-210260 Japanese Patent Laid-Open No. 7-271072 Japanese Patent Laid-Open No. 5-80572 JP-A-6-19174 Japanese Patent Publication No. 60-29109 Japanese Patent No. 3026645 JP 58-18239 A Japanese Patent No. 3458164 Japanese Patent Laid-Open No. 5-80572 JP-A-6-293769 JP-A-8-110649 Japanese Patent Laid-Open No. 3-191361 Japanese Patent Laid-Open No. 3-141363 Japanese Patent Laid-Open No. 3-101737 JP-A-3-109406 JP 2000-206723 A JP 2001-340001 A JP-A-5-94049 (FIG. 1) Japanese Patent Laid-Open No. 5-113688 (FIG. 1) JP 2002-148904 A JP 2002-148905 A Japan Hardcopy '89 Proceedings p.103 1989

  Accordingly, the present invention has been made in view of the above problems, and an object thereof is to provide an electrophotographic photosensitive member capable of forming a stable image even when used repeatedly. Specifically, a highly durable electrophotographic photosensitive member that can reduce the occurrence of scumming during repeated use, prevent residual potential, and reduce the occurrence of dielectric breakdown during charging by a contact charging member or a charging member disposed in the vicinity. It is to provide.

  It is another object of the present invention to provide an image forming apparatus that generates less abnormal images even when repeated image formation (output) is performed using the photoconductor. Specifically, an object of the present invention is to provide a highly durable and stable image forming apparatus that solves the greatest problems when using negative / positive development such as background contamination and density reduction. It is another object of the present invention to provide a process cartridge that is used in an image forming apparatus that uses the photoconductor and is highly durable and easy to handle.

The features of the present invention, which is a means for solving the above problems, are listed below.
The present inventors have intensively studied a highly durable and highly reliable photoconductor technology for a photoconductor for an image forming apparatus using negative / positive development, and have completed the present invention. The configuration of the present invention is as follows.
(1) The electrophotographic photosensitive member according to the present invention is an electrophotographic photosensitive member in which at least a charge blocking layer, a moire preventing layer, and a photosensitive layer are sequentially laminated on a conductive support. It contains metal-free phthalocyanine and an azo pigment represented by the following formula (XI).
In the formula, Cp ₁ and Cp ₂ represent coupler residues. R ₂₀₁ and R ₂₀₂ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a cyano group, and may be the same or different.

Cp ₁ and Cp ₂ are represented by the following formula (XII):
In the formula, R ₂₀₃ represents a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or an aryl group such as a phenyl group. R ₂₀₄ , R ₂₀₅ , R ₂₀₆ , R ₂₀₇ and R ₂₀₈ are each a hydrogen atom, a nitro group, a cyano group, a halogen atom such as fluorine, chlorine, bromine or iodine, a trifluoromethyl group, a methyl group or an ethyl group. Represents an alkoxy group such as an alkyl group, a methoxy group or an ethoxy group, a dialkylamino group or a hydroxyl group, and Z represents an atom necessary for constituting a substituted or unsubstituted aromatic carbocyclic ring or a substituted or unsubstituted aromatic heterocyclic ring. Represents a group.

(2) The electrophotographic photoreceptor according to the present invention is as described in (1) above, wherein Cp ₁ and Cp ₂ of the azo pigment are different from each other.
(3) In the electrophotographic photoreceptor according to the present invention, the mixing ratio of the τ-type metal-free phthalocyanine and the azo pigment is in the range of 5/1 to 1/5 (weight ratio). ) Or (2).
(4) The electrophotographic photosensitive member according to the present invention is characterized in that the τ-type metal-free phthalocyanine and the azo pigment are simultaneously milled and mixed. Is.
(5) The electrophotographic photosensitive member according to the present invention is the electrophotographic photosensitive member according to any one of (1) to (4), wherein the photosensitive layer has a laminated structure of a charge generation layer and a charge transport layer. is there.
(6) In the electrophotographic photoreceptor according to the present invention, the average particle size of the charge generation material mixed with the τ-type metal-free phthalocyanine and the azo pigment is 0.3 μm or less, and the standard deviation thereof is 0.2 μm or less. Any one of the above (1) to (5), wherein the photosensitive layer or the charge generation layer is coated using a dispersion liquid that has been dispersed until the effective pore size is filtered through a filter having an effective pore size of 5 μm or less. It is a thing of crab.
(7) In the electrophotographic photoreceptor according to the present invention, any one of the above (1) to (6), wherein the charge blocking layer is made of an insulating material and the film thickness is less than 2.0 μm. It is a thing of description.
(8) The electrophotographic photoreceptor according to the present invention is as described in (7) above, wherein the insulating material is made of polyamide.

(9) In the electrophotographic photoreceptor according to the present invention, the moire preventing layer contains an inorganic pigment and a binder resin, and the volume ratio of the two is in the range of 1/1 to 3/1. 1) to any one of (8).
(10) The electrophotographic photosensitive member according to the present invention is as described in (9) above, wherein the binder resin is a thermosetting resin.
(11) The electrophotographic photosensitive member according to the present invention is as described in (10) above, wherein the thermosetting resin is a mixture of alkyd / melamine resin.
(12) In the electrophotographic photosensitive member according to the present invention, the mixing ratio of the alkyd resin and the melamine resin is in the range of 5/5 to 8/2 (weight ratio). belongs to.
(13) The electrophotographic photoreceptor according to the present invention is any one of the above (9) to (12), wherein the inorganic pigment is titanium oxide.
(14) The titanium oxide is two kinds of titanium oxides having different average particle diameters. One titanium oxide (T1) has an average particle diameter (D1), and the other titanium oxide (T2) has an average particle diameter of (D2 ), The relationship of 0.2 <(D2 / D1) ≦ 0.5 is satisfied.
(15) The average particle diameter (D2) of the titanium oxide (T2) is 0.05 μm <D2 <0.2 μm, as described in (14) above.
(16) The above-mentioned (14) or (15), wherein the mixing ratio (weight ratio) of the two types of titanium oxides having different average particle diameters is 0.2 ≦ T2 / (T1 + T2) ≦ 0.8 ).
(17) The electrophotographic photosensitive member according to the present invention is any one of the above (1) to (16), wherein a protective layer is provided on the photosensitive layer.

(18) The electrophotographic photoreceptor according to the present invention is as described in (17) above, wherein the protective layer contains an inorganic pigment or metal oxide having a specific resistance of 10 ¹⁰ Ω · cm or more. .
(19) In the electrophotographic photosensitive member according to the present invention, the metal oxide is any one of alumina, titanium oxide, and silica having a specific resistance of 10 ¹⁰ Ω · cm or more. belongs to.
(20) The electrophotographic photosensitive member according to the present invention is as described in (19) above, wherein the metal oxide is α-alumina having a specific resistance of 10 ¹⁰ Ω · cm or more.
(21) The electrophotographic photosensitive member according to the present invention is as described in any one of (17) to (20) above, wherein the protective layer contains a polymer charge transport material.
(22) The electrophotographic photoreceptor according to the present invention is any one of (17) to (20) above, wherein the binder resin of the protective layer has a cross-linked structure.
(23) The electrophotographic photosensitive member according to the present invention is as described in (22) above, which has a charge transporting site in the structure of the binder resin having the crosslinked structure.
(24) An image forming apparatus according to the present invention is an image forming apparatus comprising at least a charging unit, an exposure unit, a developing unit, a transfer unit, and an electrophotographic photosensitive member. Or (23).
(25) The image forming apparatus according to the present invention is characterized in that a plurality of image forming elements comprising at least a charging unit, an exposure unit, a developing unit, a transfer unit, and an electrophotographic photosensitive member are arranged. belongs to.
(26) The image forming apparatus according to the present invention is as described in (24) or (25) above, wherein a contact charging system is used as a charging unit of the image forming apparatus.
(27) The image forming apparatus according to the present invention is as described in (24) or (25) above, wherein a non-contact proximity arrangement method is used as the charging unit.
(28) The image forming apparatus according to the present invention is as described in (27) above, wherein the gap between the charging member used for the charging unit and the photosensitive member is 100 μm or less.
(29) The image forming apparatus according to the present invention is any one of the above (26) to (28), wherein an AC superimposed voltage is applied as a charging unit of the image forming apparatus.
(30) An image forming apparatus according to the present invention includes an apparatus main body in which a photosensitive member and at least one unit selected from a charging unit, an exposure unit, a developing unit, and a cleaning unit are integrated, and a removable cartridge. Any one of (24) to (29) above, characterized in that
(31) A process cartridge for an image forming apparatus according to the present invention is a process for an image forming apparatus in which at least one means selected from a charging means, an exposure means, a developing means, and a cleaning means and an electrophotographic photosensitive member are integrated. In the cartridge, the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of (1) to (23).

As described above, as is clear from the detailed and specific invention, according to the present invention, there is provided an electrophotographic photoreceptor that does not generate an abnormal image and outputs a stable image when repeatedly used at a high speed. Specifically, a highly durable electrophotographic photosensitive member that can reduce the occurrence of scumming during repeated use, prevent residual potential, and reduce the occurrence of dielectric breakdown during charging by a contact charging member or a charging member disposed in the vicinity. Provided.
In addition, an image forming apparatus is provided that generates less abnormal images even when repeated image formation (output) is performed using the photosensitive member. Specifically, there is provided an image forming apparatus that is capable of high durability and stable operation that solves the greatest problems when using negative / positive development such as background contamination and density reduction.
Furthermore, there is provided a process cartridge for an image forming apparatus that uses the photoconductor and is highly durable and easy to handle.

  The best mode for carrying out the present invention will be described below with reference to the drawings. Note that it is easy for a person skilled in the art to make other embodiments by changing or correcting the present invention within the scope of the claims, and these changes and modifications are included in the scope of the claims. The following description is an example of the best mode of the present invention, and does not limit the scope of the claims.

FIG. 1 is a conceptual cross-sectional view showing one configuration example of lamination in an electrophotographic photosensitive member according to the present invention. FIG. 2 is a conceptual cross-sectional view showing another example of the lamination of the electrophotographic photosensitive member according to the present invention. In the electrophotographic photosensitive member shown in FIG. 1, a resin layer 2 in which a filler is dispersed, a resin layer 3 in which a filler is not dispersed, and a photosensitive layer 4 are sequentially laminated on a conductive support 1, and FIG. An electrophotographic photosensitive member in which a resin layer 3 in which no filler is dispersed, a resin layer 2 in which a filler is dispersed, and a photosensitive layer 4 are sequentially provided.
The electrophotographic photosensitive member of the present invention is an electrophotographic photosensitive member in which at least a charge blocking layer, a moire preventing layer, and a photosensitive layer are sequentially formed on a conductive support, and the τ-type metal-free layer is formed in the photosensitive layer. It contains phthalocyanine and an azo pigment represented by the following formula (XI).
In the formula, Cp ₁ and Cp ₂ represent coupler residues. R ₂₀₁ and R ₂₀₂ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a cyano group, and may be the same or different.

Cp ₁ and Cp ₂ are represented by the following formula (XII):
In the formula, R ₂₀₃ represents a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or an aryl group such as a phenyl group. R ₂₀₄ , R ₂₀₅ , R ₂₀₆ , R ₂₀₇ and R ₂₀₈ are each a hydrogen atom, a nitro group, a cyano group, a halogen atom such as fluorine, chlorine, bromine or iodine, a trifluoromethyl group, a methyl group or an ethyl group. Represents an alkoxy group such as an alkyl group, a methoxy group or an ethoxy group, a dialkylamino group or a hydroxyl group, and Z represents an atom necessary for constituting a substituted or unsubstituted aromatic carbocyclic ring or a substituted or unsubstituted aromatic heterocyclic ring. Represents a group.

The azo pigments represented by the formula (XI) are described in Patent Documents 33 and 34, and the τ-type metal-free phthalocyanine is described in Patent Document 35.
Further, a technique using a mixture of this τ-type metal-free phthalocyanine and an azo pigment having a specific structure is described in Patent Document 36. This technology has yielded a photoreceptor that has a wide flat spectral sensitivity from the visible range to the near infrared range. In addition, by simultaneously milling two kinds of pigments, the τ-type metal-free phthalocyanine was sensitized, and an extremely sensitive photoconductor was produced.
The present inventor has examined the compatibility of a photoreceptor with a digital light source using a mixing technique of a τ-type metal-free phthalocyanine having a high carrier generation efficiency and an azo pigment having a specific structure, and as a result, at a resolution of 600 dpi or more or 1200 dpi or more. It has been found that in the case of being used for a very long time under the circumstances in which it is used, it causes the occurrence of soiling and determines the life of the photoreceptor. As a result of detailed examination of this phenomenon, the present inventor has found that this phenomenon can be controlled by controlling the particle size of the mixed charge generating material. As described above, the photoconductors of the past configuration have not necessarily sufficiently drawn out the capabilities of the materials described in the publication.

On the other hand, the structure of the intermediate layer in which the charge blocking layer and the moire prevention layer are laminated in this order between the conductive support and the photosensitive layer is a technique described in Patent Document 37 and the like as described above. In the combination with the photosensitive layer capable of achieving the above, the influence of generation of heat carriers in the photosensitive layer is large, and the background contamination cannot always be completely prevented. This tendency becomes a significant problem when a charge generating material having high photocarrier generation efficiency as used in the present invention is used.
Therefore, both technologies are unfinished technologies. When an azo pigment having a specific structure as described above is used for a photosensitive layer, and a photoreceptor having an intermediate layer in which a charge blocking layer and a moire preventing layer are laminated in this order is produced. Although high sensitivity and electrostatic stability are manifested, the improvement of the dirt resistance and the prevention of dielectric breakdown by the charging member, which are the objects of the present invention, were not satisfactory.

Therefore, by further combining a technique for controlling the particle size of the charge generation material obtained by mixing the τ-type metal-free phthalocyanine and the azo pigment having a specific structure to 0.25 μm or less by the following method, It has been found that the object of the present invention can be achieved.
In the charge generating material contained in the electrophotographic photosensitive member of the present invention, the effect is expressed by making the particle size finer, and the production method thereof will be described below. The method for controlling the particle size of the azo pigment contained in the photosensitive layer is a method in which coarse particles larger than 0.25 μm are removed after mixing and dispersing the τ-type metal-free phthalocyanine and the azo pigment having a specific structure. .
The average particle size referred to here is a volume average particle size, and is determined with an ultracentrifugal automatic particle size distribution analyzer: CAPA-700 (manufactured by Horiba, Ltd.). At this time, the particle diameter (Median diameter) corresponding to 50% of the cumulative distribution was calculated. However, since this method cannot detect a very small amount of coarse particles, it is important to observe the dispersion directly with an electron microscope and obtain its size in order to obtain more details.
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 size, when an extremely large particle is 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, which makes it difficult to interpret the above-described minute defects.

3 and 4 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. 3. Compared with FIG. 4 having a long dispersion time, it is observed that coarse particles remain. The black particles in FIG. 3 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, CAPA 700). The result is shown in FIG. “A” in FIG. 5 corresponds to the dispersion shown in FIG. 3, 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, there is no difference 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 size), and it is not possible to cope with the recent high-resolution negative / 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.

A method for removing coarse particles after dispersing τ-type metal-free phthalocyanine and an azo pigment having a specific structure will be described.
A general method is used for the preparation of the dispersion, and a τ-type metal-free phthalocyanine and an azo pigment having a specific structure are optionally mixed with a binder resin in a suitable solvent in a ball mill, attritor, sand mill, bead mill, ultrasonic wave, etc. It is obtained by dispersing using.
Here, the τ-type metal-free phthalocyanine and the azo pigment are separately dispersed, and after preparing a dispersion, they may be mixed to form a coating solution for a photosensitive layer (charge generation layer). The pigment is pulverized, mixed, and milled at the same time to prepare a dispersion, and this is used as a coating solution for the photosensitive layer (charge generation layer). It is done. Although the reason for this is not clear, it is considered that interaction between the two types of pigments is likely to occur by simultaneously performing pulverization, mixing, and milling, improving the charge generation efficiency and improving the photosensitivity. It is done.

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.
That is, after preparing a dispersion liquid in which the particles are made as fine as possible without causing crystal transition, it is a method of filtering with a suitable 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 diameter of 5 μm or less, more preferably 3 μm or less, thereby completing the dispersion. Also by this method, a dispersion containing only azo pigment particles having a small particle size (0.25 μm or less, preferably 0.2 μm or less) can be prepared, and a photoconductor using the dispersion can be used in an image forming apparatus. By doing so, the effect of the present application is further enhanced.
At this time, when the particle size of the dispersion to be filtered is too large or the particle size distribution is too wide, the loss due to filtration becomes large or the filtration becomes clogged and filtration becomes impossible. There is a case. For this reason, in the dispersion before filtration, it is desirable to perform dispersion until the average particle size reaches 0.3 μm or less and the standard deviation reaches 0.2 μm or less. When the average particle size is 0.3 μm or more, the loss due to filtration increases, and when the standard deviation is 0.2 μm or more, there may be a problem that the filtration time becomes very long.

The charge generation material used in the present invention has an extremely strong intermolecular hydrogen bonding force, which is a feature of the charge generation material exhibiting highly sensitive characteristics. For this reason, the interaction between the particles of the dispersed charge generating substance particles is very strong. As a result, there is a great possibility that the charge generation material particles dispersed by a disperser etc. are re-aggregated by dilution or the like. Such agglomerates can be removed. At this time, since the dispersion is in a thixotropic state, particles having a size smaller than the effective pore size of the filter to be used are removed. Or the liquid which shows structural viscosity can also be changed into the state close | similar to Newton property by a filter process. Thus, the effect of the present invention is remarkably improved by removing the coarse particles of the charge generating material pigment.
The filter for filtering the dispersion varies depending on the size of coarse particles to be removed, but according to the study by the present inventors, 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 5 μm or less should be used. More preferably, a filter having an effective pore size of 3 μm or less is used. With respect to the effective pore size, the finer the particle, the more effective is the removal of coarse particles. However, if the particle size is too fine, the necessary pigment particles themselves are filtered, and therefore there is an appropriate 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.

FIG. 6 is a cross-sectional view showing a structural example of the electrophotographic photosensitive member used in the present invention. On the conductive support, an azo pigment having a specific structure with a charge blocking layer, a moire preventing layer, a τ-type metal-free phthalocyanine. The photosensitive layer containing is sequentially laminated.
FIG. 7 is a cross-sectional view showing another structural example of the electrophotographic photosensitive member used in the present invention, which has a specific structure with a charge blocking layer, a moire preventing layer, a τ-type metal-free phthalocyanine on a conductive support. A charge generation layer containing an azo pigment and a charge transport layer mainly composed of a charge transport material are sequentially laminated.
FIG. 8 is a cross-sectional view showing still another structural example of the electrophotographic photosensitive member used in the present invention, which has a specific structure with a charge blocking layer, a moire preventing layer, a τ-type metal-free phthalocyanine on a conductive support. A charge generation layer containing an azo pigment, a charge transport layer mainly composed of a charge transport material, and a protective layer are sequentially laminated.

Examples of the conductive support include those having a volume resistance of 10 ¹⁰ Ω · cm or less, such as metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, and platinum, tin oxide, and indium oxide. Metal oxide coated with film or cylindrical plastic or paper by vapor deposition or sputtering, or a plate made of aluminum, aluminum alloy, nickel, stainless steel, etc. After the conversion, a tube subjected to surface treatment such as cutting, superfinishing or polishing can be used. Endless nickel belts and endless stainless steel belts can also be used as the conductive support.
In addition, the conductive support dispersed in a suitable binder resin on the support can be used as the conductive support 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. Is mentioned. The binder resin used at the same time is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, Examples thereof include thermoplastic, thermosetting resins, and photocurable resins such as melamine resin, urethane resin, phenol resin, and alkyd resin. Such a conductive layer can be provided by dispersing and coating these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.
Furthermore, it is electrically conductive by a heat-shrinkable tube in which the conductive powder is contained in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, Teflon (registered trademark) on a suitable cylindrical substrate. Those provided with a conductive layer can also be used favorably as the conductive support of the present invention.

Next, the charge blocking layer 5 will be described.
The charge blocking layer 5 is a layer having a function of preventing reverse polarity charges induced in the electrode (conductive support 1) during charging of the photosensitive member from being injected into the photosensitive layer from the support. In the case of negative charging, it has a function of preventing hole injection, and in the case of positive charging, it has a function of preventing electron injection. As the charge blocking layer, an anodized film typified by an aluminum oxide layer, an inorganic insulating layer typified by SiO, a layer formed from a glassy network of metal oxide as described in Patent Document 40, A layer composed of polyphosphazene as described in Patent Document 41, a layer composed of an aminosilane reaction product as described in Patent Document 42, a layer composed of an insulating binder resin, and a curability And a layer made of a binder resin. In particular, a layer composed of an insulating binder resin or a curable binder resin that can be formed by a wet coating method can be used favorably. Since the charge blocking layer is formed by laminating a moire preventing layer and a photosensitive layer on the charge blocking layer, when these are provided by a wet coating method, the charge blocking layer must be composed of a material or a structure that does not attack the coating film by these coating solvents. Is essential.

Examples of the binder resin that can be used include thermoplastic resins such as polyamide, polyester, vinyl chloride-vinyl acetate copolymer, and thermosetting resins such as active hydrogen (—OH group, —NH ₂ group, —NH group, etc.). And a thermosetting resin obtained by thermally polymerizing a compound containing a plurality of hydrogen groups and a compound containing a plurality of isocyanate groups and / or a compound containing a plurality of epoxy groups. In this case, examples of the compound containing a plurality of active hydrogens include active hydrogens such as polyvinyl butyral, phenoxy resin, phenol resin, polyamide, polyester, polyethylene glycol, polypropylene glycol, polybutylene glycol, and hydroxyethyl methacrylate groups. An acrylic resin etc. are mentioned. Examples of the compound containing a plurality of isocyanate groups include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and prepolymers thereof. Examples of the compound having a plurality of epoxy groups include bisphenol A type epoxy resin. Can be mentioned.

Of these, polyamide is most preferably used from the viewpoints of film formability, environmental stability, and solvent resistance. Further, a thermosetting resin obtained by thermally polymerizing an oil-free alkyd resin and an amino resin such as a butylated melamine resin, a polyurethane having an unsaturated bond, a resin having an unsaturated bond such as an unsaturated polyester, and thioxanthone A photocurable resin such as a combination with a photopolymerization initiator such as a series compound or methylbenzyl formate can also be used as the binder resin.
Further, a conductive polymer having a rectifying property, an acceptor (donor) resin / compound or the like may be added in accordance with the charging polarity, and a function of suppressing charge injection from the substrate may be provided.
The film thickness of the charge blocking layer 5 is not less than 0.1 μm and less than 2.0 μm, preferably about 0.3 μm to 1.0 μm. When the charge blocking layer 5 becomes thicker, the residual potential increases remarkably at low temperatures and low humidity due to repeated charging and exposure, and when the film thickness is too thin, the blocking effect is reduced. Add chemicals, solvents, additives, curing accelerators, etc. necessary for curing (crosslinking) as necessary, and use conventional methods such as blade coating, dip coating, spray coating, beat coating, nozzle coating, etc. Formed on a substrate. After the application, it is dried or cured by a curing process such as drying, heating, or light.

Next, the moire prevention layer 6 will be described.
The moiré prevention layer 6 is a layer having a function of preventing the generation of a moiré image due to optical interference inside the photosensitive layer when writing with coherent light such as laser light. Basically, it has a function of causing light scattering of the writing light. In order to exhibit such a function, it is effective that the anti-moire layer has a material having a large refractive index. In general, it comprises an inorganic pigment and a binder resin, and the inorganic pigment is dispersed in the binder resin. In particular, among inorganic pigments, white pigments are effectively used. For example, titanium oxide, calcium fluoride, calcium oxide, silicon oxide, magnesium oxide, aluminum oxide and the like are favorably used. Among these, titanium oxide having a large hiding power can be most effectively used.
Further, as apparent from FIGS. 6 to 8 described above, in the photoreceptor of the present invention, charge injection from the support 1 is prevented by the charge blocking layer 5, so that at least the photoreceptor in the moire preventing layer 6. From the viewpoint of preventing residual potential, it is preferable to have a function of moving a charge having the same polarity as the charge charged on the surface. For this reason, for example, in the case of a negatively charged photoreceptor, it is desirable to provide the moiré prevention layer 6 with electronic conductivity, and the inorganic pigment to be used is one that has electronic conductivity, or a conductive one. It is desirable to do. Alternatively, the use of an electron conductive material (for example, an acceptor) or the like for the moire prevention layer 6 makes the effect of the present invention more remarkable.

As the binder resin, the same resin as the charge blocking layer 5 can be used. However, considering that the photosensitive layer 4 is laminated on the moire preventing layer 6, it is important that the binder resin is not affected by the coating solvent for the photosensitive layer.
A thermosetting resin is preferably used as the binder resin. In particular, alkyd / melamine resin mixtures are best used. At this time, the mixing ratio of alkyd / melamine resin is an important factor for determining the structure and characteristics of the moire prevention layer. A range where the ratio (weight ratio) between the two is 5/5 to 8/2 can be cited as a good mixing ratio range. If the melamine resin is richer than 5/5, volume shrinkage is increased during thermosetting, and coating film defects are likely to occur, or the residual potential of the photoreceptor is increased. Further, if the alkyd resin is richer than 8/2, it is effective in reducing the residual potential of the photoreceptor, but it is not desirable because the bulk resistance becomes too low and the soiling becomes worse.

In the moiré prevention layer 6, the volume ratio of the inorganic pigment and the binder resin determines an important characteristic. For this reason, it is important that the volume ratio of the inorganic pigment to the binder resin is in the range of 1/1 to 3/1. When the volume ratio of the two is less than 1/1, not only the moire prevention ability is lowered, but there is a case where the increase of the residual potential in repeated use becomes large. On the other hand, in the region where the volume ratio is 3/1 or more, not only the binding ability of the binder resin is inferior, but also the surface property of the coating film is deteriorated, which may adversely affect the film forming property of the upper photosensitive layer. This effect can be a serious problem when the photosensitive layer is a laminated type and a thin layer such as a charge generation layer is formed. In addition, when the volume ratio is 3/1 or more, there are cases where the binder resin cannot cover the surface of the inorganic pigment, and direct contact with the charge generation material increases the probability of heat carrier generation, resulting in soiling. It may have an adverse effect on it.
Furthermore, the use of two types of titanium oxide having different average particle diameters in the moire prevention layer can improve the concealing power to the conductive substrate and suppress moire, and can cause abnormal images. The hole can be eliminated. For this purpose, it is important that the ratio of the average particle diameters of the two types of titanium oxide used is within a certain range (0.2 <D2 / D1 ≦ 0.5). When the particle size ratio is outside the range specified in the present invention, that is, when the ratio of the average particle size of one titanium oxide (T2) to the average particle size of one titanium oxide (T1) is too small (0.2> D2 / D1) increases the activity on the surface of the titanium oxide, and the electrostatic stability of the electrophotographic photosensitive member is significantly impaired. Further, when the ratio of the average particle diameter of the other titanium oxide (T2) to the average particle diameter of one titanium oxide (T1) is too large (D2 / D1> 0.5), the hiding power to the conductive substrate is lowered. In addition, the suppression of moiré and abnormal images is reduced. The average particle size mentioned here is obtained from a particle size distribution measurement obtained when strong dispersion is performed in an aqueous system.

Further, the average particle size (D2) of titanium oxide (T2) having a smaller particle size is an important factor, and it is important that 0.05 μm <D2 <0.20 μm. When it is smaller than 0.05 μm, the hiding power is reduced, and moire may be generated. On the other hand, when it is larger than 0.20 μm, the filling rate of the titanium oxide in the moire preventing layer is lowered and the effect of suppressing soiling cannot be sufficiently exhibited.
The mixing ratio (weight ratio) of the two types of titanium oxide is also an important factor. When T2 / (T1 + T2) is smaller than 0.2, the filling rate of titanium oxide is not so large and the effect of suppressing scumming cannot be exhibited sufficiently. On the other hand, when it is larger than 0.8, the concealing power is reduced, and moire may be generated. Therefore, it is important that 0.2 ≦ T2 / (T1 + T2) ≦ 0.8.
The film thickness of the moire preventing layer is 1 to 10 μm, preferably 2 to 5 μm. If the film thickness is less than 1 μm, the effect is small, and if it exceeds 10 μm, residual potential is accumulated, which is not desirable.
The inorganic pigment is dispersed together with a solvent and a binder resin by a conventional method, for example, a ball mill, a sand mill, an attrier, etc., and a chemical, a solvent, an additive, a curing accelerator, etc. necessary for curing (crosslinking) as necessary. In addition, it is formed on the substrate by a conventional method such as blade coating, dip coating, spray coating, beat coating, or nozzle coating. After the coating, it is dried or cured by a curing process such as drying, heating, or light.

Next, the photosensitive layer 4 will be described. The photosensitive layer 4 may be a single-layered photosensitive layer 4 including a charge generation material and a charge transport material. However, as described above, the stacked type composed of the charge generation layer 7 and the charge transport layer 8 is sensitive and durable. It exhibits excellent characteristics and is used well. The charge generation layer 7 is a layer mainly composed of the above-described τ-type metal-free phthalocyanine and an azo pigment represented by the formula (XI). In the charge generation layer 7, the pigment is dispersed in a suitable solvent together with a binder resin as necessary using a ball mill, attritor, sand mill, ultrasonic wave, etc., and this is applied onto the conductive support 1 and dried. It is formed by doing. At this time, as described above, the photosensitivity is improved by milling two pigments at the same time. Regarding the mixing ratio of the two, the range of 5/1 to 1/5 (weight ratio) of the τ-type metal-free phthalocyanine and the azo pigment represented by the formula (XI) is desirable. When the τ-type metal-free phthalocyanine is more than 5/1, the photosensitivity in the visible region is insufficient, and when the azo pigment is more than 1/5, the photosensitivity in the near infrared region is insufficient.
As the binder resin used for the charge generation layer 7 as required, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicon 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 pyrrolidone, etc. Can be mentioned. The amount of the binder resin is suitably 0 to 500 parts by weight, preferably 10 to 300 parts by weight with respect to 100 parts by weight of the charge generating material.
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 for the coating solution, a dip coating method, spray coating, beat coating, nozzle coating, spinner coating, ring coating, or the like can be used. The film thickness of the charge generation layer 7 is suitably about 0.01 to 5 μm, preferably 0.1 to 2 μm.

The charge transport layer 8 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.
Charge transport materials include hole transport materials and electron transport materials. Examples of hole transport materials include poly-N-vinylcarbazole and derivatives thereof, poly-γ-carbazolylethyl glutamate and derivatives thereof, pyrene-formaldehyde condensates and derivatives 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, pyrazolines Derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, etc., bisstilbene derivatives, enamine derivatives, etc. Other known materials may be mentioned. These charge transport materials may be used alone or in combination of two or more.
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-tri Examples thereof include electron-accepting substances such as nitrodibenzothiophene-5,5-dioxide and benzoquinone derivatives.
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, polyvinyl acetate, Polyvinylidene chloride, polyarate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, phenol Examples thereof include thermoplastic or thermosetting resins such as resins and alkyd resins.

The amount of the charge transport material is appropriately 20 to 300 parts by weight, preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder resin. The thickness of the charge transport layer is preferably 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. In particular, the use of a non-halogen solvent is desirable for the purpose of reducing environmental burdens. Specifically, cyclic ethers such as tetrahydrofuran, dioxolane and dioxane, aromatic hydrocarbons such as toluene and xylene, and derivatives thereof are preferably used.
For the charge transport layer 8, a polymer charge transport material having a function as a charge transport material and a function of a binder resin is also preferably used. The charge transport layer 8 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 containing a triarylamine structure in the main chain and / or side chain is preferably used. Among these, the polymer charge transport materials represented by the formulas (I) to (X) are favorably used, and these are exemplified below and specific examples are shown.

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

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).

(A represents an integer of 1 to 20, b represents an integer of 1 to 2000, 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. )

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

In the formula, R ₉ and R ₁₀ represent a substituted or unsubstituted aryl group, and Ar ₄ , Ar ₅ , and Ar ₆ represent the same or different arylene groups. X, k, j and n are the same as those in the formula (I). In the formula (III), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

_{Wherein, R 11,} R ₁₂ is a substituted or unsubstituted aryl _{group, Ar 7, Ar 8, Ar} 9 are identical or different arylene group, p is an integer of 1-5. X, k, j and n are the same as those in the formula (I). In the formula (IV), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

In the formula, R ₁₃ and R ₁₄ are substituted or unsubstituted aryl groups, Ar ₁₀ , Ar ₁₁ and Ar ₁₂ are the same or different arylene groups, X ₁ and X ₂ are substituted or unsubstituted ethylene groups, or substituted or unsubstituted Represents a substituted vinylene group. X, k, j and n are the same as those in the formula (VI). In the formula (VI), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

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

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 those in the formula (I). In the formula (VII), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

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 those in the formula (I). In the formula (VIII), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

In the formula, R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ represent a substituted or unsubstituted aryl group, and Ar ₂₄ , Ar ₂₅ , Ar ₂₆ , Ar ₂₇ and Ar ₂₈ represent the same or different arylene groups. X, k, j and n are the same as those in the formula (I). In the formula (IX), two copolymer species are described in the form of an alternating copolymer, but a random copolymer may be used.

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 those in the formula (I). In the 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 for the charge transport layer 8, in addition to the polymer charge transport material described above, the charge transport layer 8 is formed in the state of a monomer or oligomer having an electron donating group at the time of film formation. A polymer having a two-dimensional or three-dimensional crosslinked structure is finally included by performing a curing reaction or a crosslinking reaction after the film.
Further, a charge transport layer having a crosslinked structure is also effectively used as the charge transport 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 the charge transport 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 charge transport layer is formed in a laminated structure, and the charge transport layer of a low molecular weight dispersion polymer is used in the lower layer (charge generation layer side), and the charge transport layer having a crosslinked structure is formed in the upper layer (surface side). You may do it.

The charge transport layer 8 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 charged potential (unexposed portion potential) is constant, if the surface layer of the photoconductor is worn by repeated use, the electric field strength applied to the photoconductor increases accordingly. Since the occurrence frequency of scumming increases with the increase of the electric field strength, the high wear resistance of the photosensitive member is advantageous for scumming. The charge transport layer 8 composed of a polymer having these electron-donating groups is a polymer compound, so that the film transportability is excellent and the charge transport layer 8 is superior to the charge transport layer 8 composed of a low molecular dispersion type polymer. It is possible to construct the parts with high density and to have excellent charge transport ability. For this reason, the photoconductor having the charge transport layer 8 using the polymer charge transport material can be expected to have high-speed response.
Other polymers having an electron-donating group include copolymers of known monomers, block polymers, graft polymers, star polymers, and those disclosed in Patent Documents 43 to 45, for example. It is also possible to use a crosslinked polymer having an electron donating group.
In the present invention, a plasticizer or a leveling agent may be added to the charge transport layer 8. As the plasticizer, those used as general plasticizers such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is suitably about 0 to 30% by weight based on 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 suitable.

  In the above description, the photosensitive layer has a laminated structure. However, in the present invention, the photosensitive layer 4 may have a single layer structure. In order to make the photosensitive layer 4 into a single layer structure, the photosensitive layer is formed by providing a single layer containing at least the above-described charge generating substance and binder resin. As the binder resin, the charge generating layer 7 and the charge transport layer 8 are used. Those described in the explanation of are used well. In addition, when a charge transport material is used in combination with the single-layer photosensitive layer, high photosensitivity, high carrier transport properties, and low residual potential are exhibited, and the single layer photosensitive layer can be used favorably. At this time, as the charge transport material to be used, either a hole transport material or an electron transport material is selected according to the polarity charged on the surface of the photoreceptor. Furthermore, since the above-described polymer charge transporting material also has the functions of a binder resin and a charge transporting material, it is favorably used for a single-layer photosensitive layer.

In the electrophotographic photoreceptor of the present invention, a protective layer 9 may be provided on the photosensitive layer for the purpose of protecting the photosensitive layer 4. 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 the protective layer 9 and improving the durability, the photosensitive member having high sensitivity and no abnormal defects of the present invention can be used effectively.
Materials used for the protective layer 9 include ABS resin, ACS resin, olefin-vinyl monomer copolymer, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone, polybutylene. , Polybutylene terephthalate, polycarbonate, polyarylate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin, polymethylbenten, polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS resin, butadiene-styrene copolymer, polyurethane, poly Examples thereof include resins such as vinyl chloride, polyvinylidene chloride, and epoxy resin. Of these, polycarbonate or polyarylate can be most preferably used.
The protective layer 9 includes other fluorine resins such as polytetrafluoroethylene, silicone resins for the purpose of improving wear resistance, and inorganic fillers such as titanium oxide, tin oxide, potassium titanate, and silica, Moreover, what disperse | distributed the organic filler etc. can be added.

Among the filler materials used for the protective layer 9 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. Materials include metal powders 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, etc. And inorganic materials such as metal oxides and potassium titanate. In particular, it is advantageous to use an inorganic material 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 9 varies depending on the type of filler used and also on the electrophotographic process conditions using the photoreceptor, but the ratio of the filler to the total solid content on the outermost layer side of the protective layer 9 is 5% by weight or more, It is preferably 10% by weight or more and 50% by weight or less, and preferably about 30% by weight or less.
Moreover, the volume average particle diameter of the filler to be 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.
In addition, unless otherwise indicated, the average particle diameter of the filler in this invention 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 diameter (Median diameter) 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. Normally, 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 as the distance from the particle increases, and the potential of a region that is sufficiently away from the particle and electrically neutral is zero. Accordingly, the stability increases as the repulsive force of the particles increases due to the 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. The filler having a high basic pH at the isoelectric point has a higher zeta potential when the system is acidic, so that dispersibility and stability thereof are improved.
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 mix two or more fillers having a dielectric constant of 5 or less and fillers having a dielectric constant of 5 or more. Among these fillers, α-type alumina is a hexagonal close-packed structure that has high insulating properties, high thermal stability, and high wear resistance, and is effective in suppressing image blur and improving wear resistance. Is particularly useful from
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 the measurement apparatus disclosed in Patent Documents 46 and 47, 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 with the upper electrode weight (1 kg) loaded, and the applied voltage is measured at 100V. The area of 10 ⁶ Ω · cm or more was measured with a HIGH RESISTER METER (Yokogawa Hewlett Packard), and the area below it was measured with a digital multimeter (Fluke). The specific resistance value obtained in this way is defined as the specific resistance value according to 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. For the measurement of the capacitance, a dielectric loss measuring device (Ando Electric) was used.

Further, these fillers can be surface-treated with at least one kind of surface treatment agent, and it is preferable from the viewpoint of filler dispersibility. Lowering the dispersibility of the filler not only increases the residual potential, but also lowers the transparency of the coating, causes defects in the coating, and lowers 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 titanate coupling agents, aluminum coupling agents, zircoaluminate coupling agents, higher fatty acids, etc. Alternatively or mixed processing thereof 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 wt%, more preferably 5 to 20 wt%. 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 weight 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 9 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 8 can be used. When a low molecular charge transport material is used as the charge transport material, a concentration gradient in the protective layer 9 may be provided. In order to improve wear resistance, it is an effective means to reduce the concentration of the surface side. The concentration referred to here represents the ratio of the weight of the low-molecular charge transporting substance to the total weight of all the materials constituting the protective layer 9, and the concentration gradient is a gradient that decreases the concentration on the surface side in the above weight ratio. It shows that it is provided. 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 9, a normal coating method is employed. The thickness of the protective layer 9 is suitably about 0.1 to 10 μm. 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 9.

Next, the image forming apparatus of the present invention will be described in detail with reference to the drawings.
FIG. 9 is a schematic diagram for explaining the image forming process and the image forming apparatus of the present invention, and the following modifications also belong to the category of the present invention.
In FIG. 9, the photoreceptor 11 is provided with at least a charge blocking layer, a moire preventing layer, and a photosensitive layer on a conductive support, and the photosensitive layer is represented by the τ-type metal-free phthalocyanine and the formula (XI). It contains an azo pigment. The photoconductor 11 has a drum shape, but may have a sheet shape or an endless belt shape.
The image forming apparatus in FIG. 9 operates as follows. A predetermined charge is applied to the photoconductor 11 from the charging roller 13, writing light corresponding to the input signal is applied from the image exposure unit 15, the charge on the surface of the cheering body where writing is performed is erased, and an electrostatic latent image is formed. It is formed. The electrostatic latent image is developed with toner by the developing unit 16 to form a toner image.
The toner image developed on the photoreceptor is transferred to the transfer paper 19. That is, a bias is applied to the transfer paper 19 sent to the transfer portion by the registration roller 18 from the back side of the transfer paper 19 (opposite side of the photoconductor) by the transfer charger 20, and the toner is transferred to the transfer paper 19 from the surface of the photoconductor. Is done. At this time, the pre-transfer charger 17 may be used together as necessary. Further, the transfer paper 19 is separated from the surface of the photosensitive member by the separation charger 21 and the separation claw 22, and is sent to a fixing unit (not shown) to fix the toner image on the transfer paper.
On the other hand, the toner remaining on the surface of the photoconductor without being transferred is separated from the surface of the photoconductor by the fur brush 24 and / or the cleaning blade 25 (the surface of the photoconductor is cleaned). At this time, the pre-cleaning charger 23 is used together as necessary.
Finally, the charge on the photosensitive member is erased by the charge eliminating lamp 12. Thereafter, the process proceeds to the next process.
For the charging roller 13, the pre-transfer charger 17, the transfer charger 20, the separation charger 21, and the pre-cleaning charger 23, known devices such as a corotron, a scorotron, a solid state charger, a charging roller, and a transfer roller are known. Means are used.
Of these charging methods, a contact charging method or a non-contact proximity arrangement method is particularly desirable. The contact charging method has advantages such as high charging efficiency, a small amount of ozone generation, and downsizing of the apparatus.
The contact-type charging member here is a type in which the surface of the charging member is in contact with the surface of the photosensitive member, and includes a charging roller, a charging blade and a charging brush. Of these, charging rollers and charging brushes are used favorably.

Further, the charging member arranged in the proximity is a type in which the charging member is arranged in a non-contact state so as to have a gap (gap) of 100 μm or less between the surface of the photosensitive member and the surface of the charging member. It is distinguished from known chargers typified by corotron and scorotron from the distance of the gap. The adjacently arranged charging member used in the present invention may have any shape as long as it has a mechanism capable of appropriately controlling the gap with the surface of the photoreceptor. For example, the rotation shaft of the photosensitive member and the rotation shaft of the charging member may be mechanically fixed so as to have an appropriate gap. In particular, a charging member in the shape of a charging roller is used, gap forming members are arranged at both ends of the non-image forming portion of the charging member, and only this portion is brought into contact with the surface of the photosensitive member, and the image forming region is arranged in a non-contact manner. Alternatively, a method in which a gap forming member at both ends of the photosensitive member non-image forming portion is arranged, and only this portion is brought into contact with the surface of the charging member, and the image forming region is arranged in a non-contact manner can stabilize the gap with a simple method. It is a method that can be maintained. In particular, the methods described in Patent Documents 48 and 49 can be used satisfactorily. An example of the proximity charging mechanism in which the gap forming member is arranged on the charging member side is shown in FIG.
The proximity charging mechanism shown in FIG. 10 operates as follows. In order to give an appropriate charging potential to the image forming area 33 of the photoreceptor 11, the charging roller 13 in which a roller member is formed on the metal shaft 32 with a conductive rubber or the like is used. At this time, the gap forming member 31 is provided on the surface of the charging roller in contact with the non-image forming area 34 of the photoconductor 11 so that the surface of the charging roller and the surface of the photoconductor have an appropriate gap. The gap forming member 31 abuts on the non-image forming area 34, so that an appropriate gap between the surface of the photoreceptor and the charging roller surface in the image forming area 33 is maintained. In this state, by applying an appropriate bias to the charging roller 13, the surface of the photoreceptor is appropriately charged.

The non-contact method has advantages such as high charging efficiency, low ozone generation, miniaturization of the apparatus, no contamination with toner, and no mechanical wear due to contact. Therefore, it is used well. Furthermore, as an application method, there is an advantage that uneven charging is less likely to occur by using AC superposition, and it can be used satisfactorily.
As described above, when a contact-type charging member or a non-contact charging-type charging member is used, there is a drawback that dielectric breakdown of the photosensitive member is likely to occur. However, the photoconductor used in the present invention has an intermediate layer composed of a laminate structure of a charge blocking layer and a moire preventing layer, and further, the photoconductive layer does not contain coarse particles of a charge generating material, so that Extremely high pressure resistance. For this reason, the resistance against the dielectric breakdown of the photosensitive member is high, and the merit (prevention of uneven charging) of the charging member can be utilized.
Although the photosensitive member is charged by such a charging member, in a normal image forming apparatus, scumming due to the photosensitive member is likely to occur, so that the electric field strength applied to the photosensitive member is set low (40 V). / Μm or less, preferably 30 V / μm or less). This is because the occurrence of soiling depends on the electric field strength, and the probability of soiling increases as the electric field strength increases. However, reducing the electric field strength applied to the photoreceptor reduces the efficiency of photocarrier generation and reduces the photosensitivity. In addition, since the electric field strength applied between the surface of the photoreceptor and the conductive support is reduced, the straightness of the photocarrier generated in the photosensitive layer is reduced, and diffusion due to clone repulsion is increased, resulting in a decrease in resolution. Arise. On the other hand, by using the electrophotographic photosensitive member of the present invention, it is possible to extremely reduce the probability of background contamination, so there is no need to reduce the electric field intensity more than necessary, and it can be used even under an electric field intensity of 40 V / μm or more. become able to. For this reason, a sufficient amount of gain in the attenuation of the photoreceptor light can be ensured, a large margin can be created for the later-described development (potential), and development can be performed without reducing the resolution.

The image exposure unit 15 uses a light source capable of ensuring high luminance such as a light emitting diode (LED), a semiconductor laser (LD), and electroluminescence (EL).
As a light source such as the static elimination lamp 12, all luminescent 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.
Among these light sources, light emitting diodes and semiconductor lasers have high irradiation energy and long wavelength light of 600 to 800 nm. Therefore, the above-mentioned charge generation material mixture of τ-type metal-free phthalocyanine and azo pigment is highly sensitive. It is used favorably from showing.
Such a light source or the like irradiates the photosensitive member with light by providing a transfer step, a static elimination step, a cleaning step, or a pre-exposure step in combination with light irradiation in addition to the steps shown in FIG.

The toner developed on the photoconductor 11 by the developing unit 16 is transferred to the transfer paper 19, but not all is transferred, and some toner remains on the photoconductor 11. Such toner is removed from the photoreceptor by the fur brush 24 and the cleaning brush 25. The cleaning may be performed only with the cleaning brush 25, and a known brush or a mag fur brush is used as the cleaning brush 25.
When the electrophotographic photosensitive member is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member.
If this is developed with toner of negative (positive) polarity (electrodetection fine particles), a positive image is obtained, and if developed with toner of positive (negative) polarity, a negative image is obtained.
A known method is applied to the developing unit, and a known method is also used for the charge eliminating unit.

FIG. 11 shows another example of the electrophotographic process according to the present invention. The photoreceptor 41 is provided with at least a charge blocking layer, a moire preventing layer, and a photosensitive layer on a conductive support, and contains a τ-type metal-free phthalocyanine and an azo pigment represented by the formula (XI).
The electrophotographic process shown in FIG. 11 operates as follows. The photoconductor 41 is driven by driving rollers 42a and 42b, and is charged by a charging charger 43, image exposure by an image exposure source 44, development (not shown), transfer using a transfer charger 45, and pre-cleaning exposure by pre-cleaning exposure 46. Then, cleaning with the cleaning brush 47 and static elimination with the static elimination light source 48 are repeated. In FIG. 11, light exposure for image exposure is performed on the photoconductor 41 (of course, the support is translucent) from the support side.
The above electrophotographic process exemplifies an embodiment of the present invention, and other embodiments are of course possible. For example, in FIG. 11, the pre-cleaning exposure is performed from the photosensitive layer side, but this may be performed from the translucent support side, or irradiation with static elimination light may be performed from the support side.
On the other hand, the light irradiation process is illustrated as image exposure, pre-cleaning exposure, and charge-removing exposure. Irradiation can also be performed.

  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. The process cartridge is a single device (part) that contains a photosensitive member, and further includes a charging unit, 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 the one shown in FIG. The photoreceptor 51 is provided with at least a charge blocking layer, a moire preventing layer, and a photosensitive layer on a conductive support, and the photosensitive layer contains a τ-type metal-free phthalocyanine and an azo pigment represented by the formula (XI). Do it.

FIG. 13 is a schematic diagram for explaining the tandem-type full-color electrophotographic apparatus of the present invention, and the following modifications also belong to the category of the present invention.
In FIG. 13, reference numerals 61C, 61M, 61Y, and 61K denote drum-shaped photoconductors. The photoconductor 61 has at least a charge blocking layer, a moire preventing layer, and a photoconductive layer provided on a conductive support. Τ-type metal-free phthalocyanine and an azo pigment represented by the formula (XI).
The photoreceptors 61C, 61M, 61Y, and 61K rotate in the direction of the arrow in the figure, and around the charging members 62C, 62M, 62Y, and 62K, the developing members 64C, 64M, 64Y, and 64K, the cleaning member 65C, at least in the order of rotation. 65M, 65Y, and 65K are arranged. The charging members 62C, 62M, 62Y, and 62K are charging members that constitute a charging device for uniformly charging the surface of the photoreceptor. Laser light 63C, 63M, 63Y, and 63K from an exposure member (not shown) is irradiated from the back side of the photosensitive member between the charging members 62C, 62M, 62Y, and 62K and the developing members 64C, 64M, 64Y, and 64K. Electrostatic latent images are formed on 61C, 61M, 61Y, and 61K. Then, four image forming elements 66C, 66M, 66Y, and 66K centering on the photoreceptors 61C, 61M, 61Y, and 61K are juxtaposed along the transfer conveyance belt 70 that is a transfer material conveyance unit. The transfer / conveying belt 70 is arranged between the developing members 64C, 64M, 64Y, and 64K of the image forming units 66C, 66M, 66Y, and 66K and the cleaning members 65C, 65M, 65Y, and 65K to the photoreceptors 61C, 61M, 61Y, and 61K. Transfer brushes 71 </ b> C, 71 </ b> M, 71 </ b> Y, and 71 </ b> K for applying a transfer bias are disposed on the surface (back surface) that is in contact with and contacts the back side of the transfer conveyor belt 70 on the photoconductor side. Each of the image forming elements 66C, 66M, 66Y, and 66K has a different toner color inside the developing device, and the other components have the same configuration.

In the color electrophotographic apparatus having the configuration shown in FIG. 13, the image forming operation is performed as follows. First, in each of the image forming elements 66C, 66M, 66Y, and 66K, the photoconductors 61C, 61M, 61Y, and 61K are charged by the charging members 62C, 62M, 62Y, and 62K that rotate in the direction of the arrow (the direction along with the photoconductor). Then, an electrostatic latent image corresponding to each color image to be created is formed by laser beams 63C, 63M, 63Y, and 63K by an exposure unit (not shown) disposed inside the photoconductor. Next, the latent image is developed by the developing members 64C, 64M, 64Y, and 64K to form a toner image. The developing members 64C, 64M, 64Y, and 64K are developing members that perform development with toners of C (cyan), M (magenta), Y (yellow), and K (black), respectively, and the four photosensitive members 61C, 61M, and 61Y. , 61K toner images of each color are superimposed on the transfer paper. The transfer paper 67 is sent out from the tray by a paper feed roller 68, temporarily stopped by a pair of registration rollers 69, and sent to the transfer conveyance belt 70 in synchronism with the image formation on the photosensitive member. The transfer paper 67 held on the transfer conveyance belt 70 is conveyed, and each color toner image is transferred at the contact positions (transfer portions) with the respective photoreceptors 61C, 61M, 61Y, 61K. The toner image on the photoconductor is transferred onto the transfer paper 67 by an electric field formed by a potential difference between the transfer bias applied to the transfer brushes 71C, 71M, 71Y, and 71K and the photoconductors 61C, 61M, 61Y, and 61K. The Then, the transfer paper 67 on which the four color toner images are superimposed through the four transfer portions is conveyed to the fixing device 72, where the toner is fixed, and is discharged to a paper discharge portion (not shown). Further, the residual toner remaining on the photosensitive members 61C, 61M, 61Y, and 61K without being transferred by the transfer unit is collected by the cleaning devices 65C, 65M, 65Y, and 65K. In the example of FIG. 13, the image forming elements are arranged in the order of C (cyan), M (magenta), Y (yellow), 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 a black-only document is created, it is particularly effective to use the present invention to provide a mechanism that stops the image forming elements (66C, 66M, 66Y) other than black. Further, although the charging member is in contact with the photosensitive member in FIG. 13, by using a charging mechanism as shown in FIG. 13, an appropriate gap (about 10-200 μm) is provided between them. In addition, the wear amount of the both can be reduced, and toner filming on the charging member can be reduced and the toner can be used satisfactorily.
The image forming means as described above may be fixedly incorporated in a copying apparatus, facsimile, or printer, but each electrophotographic element may be incorporated in the apparatus in the form of a process cartridge. . A process cartridge is a single device (part) that contains a photoconductor and further includes a charging unit, an exposure unit, a developing unit, a transfer unit, a cleaning unit, a neutralizing unit, and the like.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not restrict | limited by an Example. All parts are parts by weight.
(Dispersion Preparation Example 1)
Dispersion was carried out under the conditions shown below with a formulation having the following composition to prepare a dispersion (referred to as dispersion A).
τ-type metal-free phthalocyanine 5 parts Polyvinyl butyral (manufactured by Sekisui Chemical: BX-1) 2 parts Cyclohexanone 250 parts 2-butanone 100 parts A solvent in which polyvinyl butyral is dissolved in a ball mill disperser using 10 mm diameter PSZ balls All of the metal phthalocyanine was charged and dispersed at a rotational speed of 85 rpm for 7 days to prepare a dispersion.
Dispersion was carried out under the following composition with the following composition to prepare a dispersion (referred to as Dispersion B).
5 parts of azo pigment with the following structure
Polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd .: BX-1) 2 parts Cyclohexanone 250 parts 2-butanone 100 parts Using a PSZ ball having a diameter of 10 mm in a ball mill disperser, all of the solvent in which polyvinyl butyral is dissolved and an azo pigment are added, and the rotational speed is 85 rpm. Was dispersed for 7 days to prepare a dispersion.
Dispersion A and Dispersion B produced as described above were all mixed to obtain a charge generation layer coating solution (referred to as Dispersion 1). In the above composition, the weight ratio of the τ-type metal-free phthalocyanine and the azo pigment is 1/1.

(Dispersion preparation example 2)
Dispersion was carried out under the following composition with the following composition to prepare a dispersion (referred to as Dispersion C).
τ-type metal-free phthalocyanine 5 parts Polyvinyl butyral (manufactured by Sekisui Chemical: BX-1) 2 parts Cyclohexanone 250 parts 2-butanone 100 parts A solvent in which polyvinyl butyral is dissolved in a ball mill disperser using 10 mm diameter PSZ balls All of the metal phthalocyanine was charged and dispersed at a rotational speed of 85 rpm for 7 days to prepare a dispersion.
Dispersion was carried out under the following composition with the following composition to prepare a dispersion (referred to as Dispersion D).
5 parts of azo pigment with the following structure
Polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd .: BX-1) 2 parts Cyclohexanone 250 parts 2-butanone 100 parts Using a PSZ ball having a diameter of 10 mm in a ball mill disperser, all of the solvent in which polyvinyl butyral is dissolved and an azo pigment are added, and the rotational speed is 85 rpm. Was dispersed for 7 days to prepare a dispersion.
Dispersion C and Dispersion D produced as described above were all mixed to obtain a charge generation layer coating solution (referred to as Dispersion 1). In the above composition, the weight ratio of the τ-type metal-free phthalocyanine and the azo pigment is 1/1.

(Dispersion preparation example 3)
Dispersion was carried out under the conditions shown below with a formulation having the following composition to prepare a dispersion as a charge generation layer coating solution.
τ-type metal-free phthalocyanine 5 parts Azo pigment of the following structure 5 parts
Polyvinyl butyral (manufactured by Sekisui Chemical: BX-1) 4 parts Cyclohexanone 500 parts 2-butanone 200 parts A PSZ ball having a diameter of 10 mm was used in a ball mill disperser, and all the solvent, azo pigment and τ-type metal-free phthalocyanine in which polyvinyl butyral was dissolved Then, dispersion was performed for 7 days at a rotational speed of 85 rpm to prepare a dispersion liquid (referred to as dispersion liquid 3). In the above composition, the weight ratio of the τ-type metal-free phthalocyanine and the azo pigment is 1/1.

(Dispersion preparation example 4)
A dispersion was prepared in the same manner as dispersion preparation example 3 except that the azo pigment used in dispersion preparation example 3 was changed to one having the following structure (referred to as dispersion liquid 4).
In the above composition, the weight ratio of the τ-type metal-free phthalocyanine and the azo pigment is 1/1.

(Dispersion preparation example 5)
In Dispersion Preparation Example 4, a dispersion was prepared in the same manner as Dispersion Preparation Example 2 except that the formulation of the dispersion was changed as follows (referred to as Dispersion 5).
τ-type metal-free phthalocyanine 8 parts Azo pigment with the following structure 2 parts
Polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd .: BX-1) 4 parts Cyclohexanone 500 parts 2-butanone 200 parts In the above composition, the weight ratio of τ-type metal-free phthalocyanine and azo pigment is 4/1.

(Dispersion Preparation Example 6)
In Dispersion Preparation Example 4, a dispersion was prepared in the same manner as Dispersion Preparation Example 4 except that the dispersion formulation was changed as follows (referred to as Dispersion 6).
τ-type metal-free phthalocyanine 2 parts Azo pigment of the following structure 8 parts
Polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd .: BX-1) 4 parts Cyclohexanone 500 parts 2-Butanone 200 parts In the above composition, the weight ratio of τ-type metal-free phthalocyanine and azo pigment is 1/4.

(Dispersion Preparation Example 7)
In Dispersion Preparation Example 4, a dispersion was prepared in the same manner as Dispersion Preparation Example 4 except that the dispersion formulation was changed as follows (referred to as Dispersion 7).
τ-type metal-free phthalocyanine 6 parts Azo pigment of the following structure 1 part
Polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd .: BX-1) 3 parts Cyclohexanone 400 parts 2-butanone 150 parts In the above composition, the weight ratio of τ-type metal-free phthalocyanine and azo pigment is 6/1.

(Dispersion Preparation Example 8)
In Dispersion Preparation Example 4, a dispersion was prepared in the same manner as Dispersion Preparation Example 4 except that the dispersion formulation was changed as follows (referred to as Dispersion 8).
τ-type metal-free phthalocyanine 1 part Azo pigment with the following structure 6 parts
Polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd .: BX-1) 3 parts Cyclohexanone 400 parts 2-butanone 150 parts In the above composition, the weight ratio of τ-type metal-free phthalocyanine and azo pigment is 1/6.

(Dispersion Preparation Example 9)
A dispersion was prepared in the same manner as dispersion preparation example 4 except that the azo pigment used in dispersion preparation example 4 was changed to one having the following structure (referred to as dispersion liquid 9).

(Dispersion Preparation Example 10)
The dispersion 2 prepared in Dispersion Production Example 4 was filtered using a cotton wind cartridge filter, TCW-3-CS (effective pore size 3 μm) manufactured by Advantech. During filtration, filtration was performed using a pump in a pressurized state (referred to as dispersion 10).

(Dispersion Preparation Example 11)
Except for changing the filter used in Dispersion Preparation Example 4 to Advantech Co., Ltd., Cotton Wind Cartridge Filter, TCW-5-CS (effective pore diameter 5 μm), pressure filtration is performed in the same manner as Dispersion Preparation Example 4, A dispersion was prepared (referred to as dispersion 11).

(Dispersion Preparation Example 12)
Dispersion was performed by changing the dispersion conditions in Dispersion Preparation Example 4 as follows (referred to as Dispersion 12). Dispersion was performed for 2 days at a rotational speed of 85 rpm.

(Dispersion Preparation Example 13)
The dispersion prepared in Dispersion Preparation Example 12 was filtered using a cotton wind cartridge filter, TCW-5-CS (effective pore size 5 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 it was not possible to filter all the dispersions. Therefore, the following evaluation has not been conducted.

The particle size distribution of the pigment particles in the dispersion prepared as described above was measured using Horiba: CAPA-700. The results are shown in Table 1.

Example 1
A 60 mm diameter aluminum cylinder (JIS 1050) was coated with a charge blocking layer coating solution, a moire prevention layer coating solution, a charge generation layer coating solution, and a charge transport layer coating solution having the following composition in sequence and dried. A multilayer photoreceptor was prepared by forming a 0.5 μm charge blocking layer, a 3.5 μm moire prevention layer, a 0.3 μm charge generation layer, and a 23 μm charge transport layer.
<Charge blocking layer>
Alcohol-soluble nylon (Toray: Amilan CM8000) 4 parts Methanol 70 parts n-Butanol 30 parts <Moire prevention layer coating solution>
Titanium oxide (CR-EL: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm) 84 parts Alkyd resin 33.6 parts [Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Melamine resin 18.7 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 100 parts In the above composition, the volume ratio of the inorganic pigment to the binder resin is 1/1.
The ratio of alkyd resin to melamine resin is a 6/4 weight ratio.
<Charge generation layer coating solution>
The previously prepared dispersion 1 was used.
<Charge transport layer coating solution>
Polycarbonate (TS2050: manufactured by Teijin Chemicals Ltd.) 10 parts 7 parts of charge transport material having the following structural formula
80 parts of methylene chloride

(Examples 2-11 and Comparative Examples 1-4)
A photoconductor was prepared in the same manner as in Example 1 except that the charge generation layer coating solution (dispersion 1) used in Example 1 was changed to Dispersions 2 to 12 and Dispersions A, B, and D, respectively. . Table 2 shows the correspondence between the example numbers and the dispersions used.

(Examples 12 to 22 and Comparative Examples 5 to 8)
The electrophotographic photoreceptors of Examples 1 to 11 and Comparative Examples 1 to 4 manufactured as described above are mounted on the electrophotographic apparatus shown in FIG. 9, and an image exposure light source is a semiconductor laser of 780 nm (image writing by a polygon mirror). Using a contact type charging roller as the charging member and a transfer belt as the transfer member, an image was output using a chart with a writing rate of 6% under the following charging conditions, and the image density was confirmed (the test environment was 22). ° C / 55% RH). The results are shown in Table 2.
<Charging conditions>
DC bias: -950V
AC bias: 2.0 kV (peak to peak), frequency: 1.5 kHz

(Examples 23 to 33 and Comparative Examples 9 to 12)
The electrophotographic photosensitive members of Examples 1 to 11 and Comparative Examples 1 to 4 manufactured as described above are mounted on the electrophotographic apparatus shown in FIG. 9, and an image exposure light source is a 655 nm semiconductor laser (image writing by a polygon mirror). Using a contact type charging roller as the charging member and a transfer belt as the transfer member, an image was output using a chart with a writing rate of 6% under the following charging conditions, and the image density was confirmed (the test environment was 22). ° C / 55% RH). The results are shown in Table 3.
<Charging conditions>
DC bias: -950V
AC bias: 2.0 kV (peak to peak), frequency: 1.5 kHz

(Comparative Example 13)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the charge blocking layer was not provided.

(Comparative Example 14)
In Example 9, a photoreceptor was prepared in the same manner as in Example 9 except that the moire preventing layer was not provided.

(Comparative Example 15)
A photoconductor was prepared in the same manner as in Example 9 except that the coating order of the charge blocking layer and the moire preventing layer was changed.

(Example 34)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the thickness of the charge blocking layer was 0.3 μm.

(Example 35)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the thickness of the charge blocking layer was 1.0 μm.

(Example 36)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the thickness of the charge blocking layer was 2.0 μm.

(Example 37)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the thickness of the charge blocking layer was 0.1 μm.

(Example 38)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Moire prevention layer coating solution>
Titanium oxide (CR-EL: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm) 252 parts Alkyd resin 33.6 parts [Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Melamine resin 18.7 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 300 parts In the above composition, the volume ratio of the inorganic pigment to the binder resin is 3/1. The ratio of alkyd resin to melamine resin is a 6/4 weight ratio.

(Example 39)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Moire prevention layer coating solution>
Titanium oxide (CR-EL: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm) 120 parts Alkyd resin 33.6 parts [Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Melamine resin 18.7 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 150 parts In the above composition, the volume ratio of the inorganic pigment to the binder resin is 0.7 / 1. The ratio of alkyd resin to melamine resin is a 6/4 weight ratio.

(Example 40)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Moire prevention layer coating solution>
Titanium oxide (CR-EL: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm) 336 parts Alkyd resin 33.6 parts [Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Melamine resin 18.7 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 350 parts In the above composition, the volume ratio of the inorganic pigment to the binder resin is 4/1. The ratio of alkyd resin to melamine resin is a 6/4 weight ratio.

(Example 41)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Charge blocking layer coating solution>
Alkyd resin 33.6 parts [Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Melamine resin 18.7 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 500 parts

(Example 42)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Moire prevention layer coating solution>
Zinc oxide (SAZEX 4000: manufactured by Sakai Chemical) 110 parts Alkyd resin 33.6 parts [Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Melamine resin 18.7 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 120 parts In the above composition, the volume ratio of the inorganic pigment to the binder resin is 1/1. The ratio of alkyd resin to melamine resin is a 6/4 weight ratio.

(Example 43)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Moire prevention layer coating solution>
Titanium oxide (CR-EL: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm) 84 parts Alkyd resin 22.4 parts [Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Melamine resin 28 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 100 parts In the above composition, the volume ratio of the inorganic pigment to the binder resin is 1/1. The ratio of alkyd resin to melamine resin is 4/6 weight ratio.

(Example 44)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Moire prevention layer coating solution>
Titanium oxide (CR-EL: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm) 84 parts Alkyd resin 28 parts [Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Melamine resin 23.3 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 100 parts In the above composition, the volume ratio of the inorganic pigment to the binder resin is 1/1. The ratio of alkyd resin to melamine resin is 5/5 weight ratio.

(Example 45)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Moire prevention layer coating solution>
Titanium oxide (CR-EL: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm) 84 parts Alkyd resin 39.2 parts [Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Melamine resin 14 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 100 parts In the above composition, the volume ratio of the inorganic pigment to the binder resin is 1/1. The ratio of alkyd resin to melamine resin is a 7/3 weight ratio.

(Example 46)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Moire prevention layer coating solution>
Titanium oxide (CR-EL: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm) 84 parts Alkyd resin 44.8 parts [Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Melamine resin 9.3 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 100 parts In the above composition, the volume ratio of the inorganic pigment to the binder resin is 1/1.
The ratio of alkyd resin to melamine resin is 8/2 weight ratio.

(Example 47)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Moire prevention layer coating solution>
Titanium oxide (CR-EL: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm) 84 parts Alkyd resin 50.4 parts [Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Melamine resin 4.7 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 100 parts In the above composition, the volume ratio of the inorganic pigment to the binder resin is 1/1. The ratio of alkyd resin to melamine resin is 9/1 weight ratio.

(Example 48)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Moire prevention layer coating solution>
Titanium oxide (CR-EL: Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm) 84 parts Alcohol-soluble nylon (Toray: Amilan CM8000) 24 parts Methanol 300 parts n-Butanol 130 parts In the above composition, inorganic pigment and binder resin The volume ratio is 1/1.

(Example 49)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Moire prevention layer coating solution>
Titanium oxide (CR-EL: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm) 42 parts Titanium oxide (PT-401M: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.07 μm) 42 parts [Beckolite M6401-50 -S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Alkyd resin 33.6 parts Melamine resin 18.7 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 100 parts In the above composition, the volume ratio of the inorganic pigment to the binder resin is 1/1. The ratio of alkyd resin to melamine resin is a 6/4 weight ratio. The ratio of the average particle diameter is 0.28, and the mixing ratio of both is 0.5.

(Example 50)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Moire prevention layer coating solution>
Titanium oxide (CR-EL: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm) 75.6 parts Titanium oxide (PT-401M: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.07 μm) 8.4 parts Alkyd resin 33.6 parts [Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Melamine resin 18.7 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 100 parts In the above composition, the volume ratio of the inorganic pigment to the binder resin is 1/1. The ratio of alkyd resin to melamine resin is a 6/4 weight ratio. The average particle size ratio is 0.28, and the mixing ratio of both is 0.1.

(Example 51)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Moire prevention layer coating solution>
Titanium oxide (CR-EL: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm) 8.4 parts Titanium oxide (PT-401M: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.07 μm) 75.6 parts Alkyd resin 33.6 parts [Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Melamine resin 18.7 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 100 parts In the above composition, the volume ratio of the inorganic pigment to the binder resin is 1/1. The ratio of alkyd resin to melamine resin is a 6/4 weight ratio. The ratio of the average particle diameter is 0.28, and the mixing ratio of both is 0.9.

(Example 52)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Moire prevention layer coating solution>
Titanium oxide (CR-EL: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm) 42 parts Titanium oxide (TTO-F1: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.04 μm) 42 parts Alkyd resin 33.6 parts [Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Melamine resin 18.7 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 100 parts In the above composition, the volume ratio of the inorganic pigment to the binder resin is 1/1. The ratio of alkyd resin to melamine resin is a 6/4 weight ratio. The ratio of the average particle diameter is 0.16, and the mixing ratio of both is 0.5.

(Example 53)
In Example 9, a photoconductor was prepared in the same manner as in Example 9 except that the moiré preventing layer coating solution was changed to one having the following composition.
<Moire prevention layer coating solution>
Titanium oxide (CR-EL: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm) 42 parts Titanium oxide (A-100: manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.15 μm) 42 parts Alkyd resin 33.6 parts [Beckolite M6401-50-S (solid content 50%), manufactured by Dainippon Ink & Chemicals, Inc.]
Melamine resin 18.7 parts [Super Becamine L-121-60 (solid content 60%), manufactured by Dainippon Ink & Chemicals, Inc.]
2-butanone 100 parts In the above composition, the volume ratio of the inorganic pigment to the binder resin is 1/1. The ratio of alkyd resin to melamine resin is a 6/4 weight ratio. The ratio of the average particle diameter is 0.6, and the mixing ratio of both is 0.5.

(Examples 54 to 84 and Comparative Examples 16 to 20)
The electrophotographic photoreceptors of Examples 1 to 11, 34 to 53 and Comparative Examples 1 to 2 and 13 to 15 produced as described above are mounted on the electrophotographic apparatus shown in FIG. 9, and the image exposure light source is a semiconductor laser having a wavelength of 780 nm. (Image writing by polygon mirror) Using a contact type charging roller as a charging member and a transfer belt as a transfer member, continuous 200,000 sheets were printed using a chart with a writing rate of 6% under the following charging conditions. . Subsequent white solid and halftone images were output and evaluated, and the presence or absence of background stains, the presence or absence of moire, and the image density were confirmed (the test environment was 22 ° C./55% RH). The background image evaluation was carried out in 4 stages. Very good ones were indicated by 、, good ones were indicated by ○, slightly inferior ones were indicated by Δ, and very bad ones were indicated by ×. The results are shown in Table 4.
<Charging conditions>
DC bias: -950V
AC bias: 2.0 kV (peak to peak), frequency: 1.5 kHz

(Example 85)
A photoconductor was prepared in the same manner as in Example 9 except that the charge transport layer coating solution in Example 9 was changed to one having the following composition.
<Charge transport layer coating solution>
Polymer charge transport material having the following composition (weight average molecular weight: about 135,000) 10 parts

0.5 parts of additive with the following structure
100 parts methylene chloride

(Example 86)
The photoconductor as in Example 9 except that the thickness of the charge transport layer in Example 9 was 18 μm, and a protective layer coating solution having the following composition was applied and dried on the charge transport layer to provide a 5 μm protective layer. Was made.
<Protective layer coating solution>
10 parts of polycarbonate (TS2050: manufactured by Teijin Chemicals Ltd., viscosity average molecular weight: 50,000)
7 parts of charge transport material with the following structural formula
4 parts of alumina fine particles (specific resistance: 2.5 × 10 ¹² Ω · cm, average primary particle size: 0.4 μm)
Cyclohexanone 500 parts Tetrahydrofuran 150 parts

(Example 87)
A photoconductor was prepared in the same manner as in Example 86 except that the alumina fine particles in the protective layer coating solution in Example 86 were changed to the following.
4 parts of titanium oxide fine particles (specific resistance: 1.5 × 10 ¹⁰ Ω · cm, average primary particle size: 0.5 μm)

(Example 88)
A photoconductor was prepared in the same manner as in Example 86 except that the alumina fine particles in the protective layer coating solution in Example 86 were changed to the following.
4 parts of tin oxide-antimony oxide powder (specific resistance: 10 ⁶ Ω · cm, average primary particle size 0.4 μm)

Example 89
The photoconductor as in Example 9 except that the thickness of the charge transport layer in Example 9 was 18 μm, and a protective layer coating solution having the following composition was applied and dried on the charge transport layer to provide a 5 μm protective layer. Was made.
<Protective layer coating solution>
Methyltrimethoxysilane 100 parts 3% acetic acid 20 parts 35 parts of a charge transporting compound having the following structure
Antioxidant (Sanol LS2626: Sankyo Chemical Co., Ltd.) 1 part Curing agent (dibutyltin acetate) 1 part 2-propanol 200 parts

(Example 90)
The photoconductor as in Example 9 except that the thickness of the charge transport layer in Example 9 was 18 μm, and a protective layer coating solution having the following composition was applied and dried on the charge transport layer to provide a 5 μm protective layer. Was made.
<Protective layer coating solution>
Methyltrimethoxysilane 100 parts 3% acetic acid 20 parts 35 parts of a charge transporting compound having the following structure
α-alumina particles (Sumicorundum AA-03: manufactured by Sumitomo Chemical Co., Ltd.) 15 parts Antioxidant (Sanol LS2626: manufactured by Sankyo Chemical Co., Ltd.) 1 part Polycarboxylic acid compound BYK P104: manufactured by BYK Chemie 0.4 part Curing agent (dibutyl) Tin acetate) 1 part 2-propanol 200 parts

(Examples 91-97)
The electrophotographic photosensitive member of Examples 9 and 85 to 90 produced as described above is mounted on the electrophotographic apparatus shown in FIG. 1, and an image exposure light source is a semiconductor laser of 780 nm (image writing by a polygon mirror), and a charging member As a charging member, a charging member for close placement in which an insulating tape having a thickness of 50 μm is wound around both ends of a charging roller as shown in FIG. 10 (the space between the photoreceptor and the surface of the charging member is 50 μm) Under the conditions, continuous printing of 200,000 sheets was performed using a chart with a writing rate of 6%. Thereafter, solid white and halftone images were output, and the presence or absence of background stains, the presence or absence of moire, and the image density were confirmed (the test environment was 22 ° C./55% RH). In addition, the evaluation of the background stain was performed in 4 stages, and an extremely good one was indicated by ◎, a good one by ○, a slightly inferior by Δ, and a very bad one by ×. Further, the amount of abrasion of the photosensitive layer after printing 200,000 sheets (when the protective layer is provided, the amount of abrasion of the protective layer) was measured. The results are shown in Table 5.
<Charging conditions>
DC bias: -900V
AC bias: 2.0 kV (peak to peak), frequency: 2.0 kHz

(Example 98)
In Example 91, after a paper feeding test of 200,000 sheets, a halftone image was output in a 30 ° C./90% RH environment, and image evaluation was performed.

Example 99
The charging member in Example 91 was changed from a charging member for close placement to a scorotron charger, and the surface potential of the non-image portion of the photosensitive member was set to be the same (−900 V) as in Example 91. 200,000 sheets were tested in the same manner as Example 91 without changing other conditions. After the paper passing test, a halftone image was output in a 30 ° C./90% RH environment in the same manner as in Example 98, and image evaluation was performed.

(Example 100)
The charging member in Example 91 was changed from the charging member for close placement to the charging member for contact (no gap), and the charging conditions were set to the same conditions as in Example 91. 200,000 sheets were tested in the same manner as in Example 65 without changing other conditions. After the paper passing test, a halftone image was output in a 30 ° C./90% RH environment in the same manner as in Example 98, and image evaluation was performed.

(Example 101)
Evaluation was performed in the same manner as in Example 100 except that the charging conditions in Example 100 were changed as follows.
<Charging conditions>
DC bias: −1600 V (surface potential of the non-image portion of the photoreceptor in the initial state is −900 V)
AC bias: None

(Example 102)
Evaluation was performed in the same manner as in Example 91 except that the charging conditions in Example 91 were changed as follows. After a paper feeding test of 200,000 sheets, a halftone image was output in a 30 ° C./90% RH environment in the same manner as in Example 98, and image evaluation was performed.
<Charging conditions>
DC bias: −1600 V (surface potential of the non-image portion of the photoreceptor in the initial state is −900 V)
AC bias: None

(Example 103)
Evaluation was performed in the same manner as in Example 91 except that the gap of the charging member (proximity charging roller) used in Example 91 was changed to 70 μm. After a paper feeding test of 200,000 sheets, a halftone image was output in a 30 ° C./90% RH environment in the same manner as in Example 98, and image evaluation was performed.

(Example 104)
Evaluation was performed in the same manner as in Example 91 except that the gap of the charging member (proximity charging roller) used in Example 91 was changed to 100 μm. After a paper feeding test of 200,000 sheets, a halftone image was output in a 30 ° C./90% RH environment in the same manner as in Example 98, and image evaluation was performed.

(Example 105)
Evaluation was performed in the same manner as in Example 91 except that the gap of the charging member (proximity charging roller) used in Example 91 was changed to 150 μm. After a paper feeding test of 200,000 sheets, a halftone image was output in a 30 ° C./90% RH environment in the same manner as in Example 98, and image evaluation was performed.

(Example 106)
In Example 92, after a paper feeding test of 200,000 sheets, a halftone image was output in a 30 ° C./90% RH environment, and image evaluation was performed.

(Example 107)
In Example 93, after a paper passing test of 200,000 sheets, a halftone image was output in a 30 ° C./90% RH environment, and image evaluation was performed.
Table 6 shows the evaluation results in Examples 98 to 107 described above.
In Examples 98 to 107 in Table 6, in any case, there was no problem in practical use.

(Example 108)
A photoconductor having the same composition as in Example 1 was produced by replacing the aluminum cylinder of Example 1 with one having a diameter of 30 mm.

(Example 109)
The aluminum cylinder of Example 4 was changed to one having a diameter of 30 mm, and a photoconductor having the same composition as that of Example 4 was produced.

(Example 110)
The aluminum cylinder of Example 9 was changed to one having a diameter of 30 mm, and a photoconductor having the same composition as that of Example 9 was produced.

(Comparative Example 21)
A photoconductor having the same composition as that of Comparative Example 1 was prepared by changing the aluminum cylinder of Comparative Example 1 to one having a diameter of 30 mm.

(Comparative Example 22)
A photoconductor having the same composition as that of Comparative Example 3 was prepared by changing the aluminum cylinder of Comparative Example 3 to one having a diameter of 30 mm.

(Comparative Example 23)
The aluminum cylinder of Comparative Example 13 was changed to one having a diameter of 30 mm, and a photoconductor having the same composition as Comparative Example 13 was produced.

(Comparative Example 24)
The aluminum cylinder of Comparative Example 14 was changed to one having a diameter of 30 mm, and a photoconductor having the same composition as Comparative Example 14 was produced.

(Comparative Example 25)
The aluminum cylinder of Comparative Example 15 was changed to one having a diameter of 30 mm, and a photoconductor having the same composition as Comparative Example 15 was produced.

(Examples 111 to 113 and Comparative Examples 21 to 25)
The electrophotographic photoreceptors of Examples 108 to 111 and Comparative Examples 21 to 25 manufactured as described above are mounted on one electrophotographic apparatus process cartridge together with the charging member, and further mounted on the full-color electrophotographic apparatus shown in FIG. did. The four image forming elements were subjected to a 200,000 full-color image passing test under the process conditions shown below. Thereafter, confirmation of the presence or absence of soiling and halftone image evaluation were performed (the test environment is 22 ° C./55% RH). In addition, character omission and background stain evaluation were performed in four stages, and very good ones were indicated by ◎, good ones were indicated by ○, slightly inferior ones by Δ, and very bad ones by x. The results are shown in Table 7.
<Charging conditions>
DC bias -800V,
AC bias 1.8kV (peak to peak), frequency 2.0kHz
<Charging member> Same as used in Example 65 <Writing> 655 nm LD (using polygon mirror)
<Transfer conditions> 75 μA

It is a cross-sectional conceptual diagram which shows the structural example of lamination | stacking in a well-known electrophotographic photoreceptor. It is a cross-sectional conceptual diagram which shows the structural example of lamination | stacking in a well-known electrophotographic photoreceptor. It is a photograph which shows the state of a dispersion liquid. It is a photograph which shows the state of a dispersion liquid. It is a graph which shows the particle size and particle size distribution of a dispersion liquid. FIG. 3 is a conceptual cross-sectional view showing a configuration example of an electrophotographic photosensitive member used in the present invention. It is a cross-sectional conceptual diagram which shows the other structural example of the electrophotographic photosensitive member used for this invention. It is a cross-sectional conceptual diagram which shows the other structural example of the electrophotographic photosensitive member used for this invention. 1 is a schematic diagram illustrating an example of an image forming apparatus according to the present invention. It is a perspective conceptual diagram which shows the charging means of a non-contact proximity | contact arrangement | positioning mechanism. It is the schematic which shows an example of another electrophotographic process which concerns on this invention. FIG. 2 is a schematic diagram illustrating an example of a process cartridge for an image forming apparatus according to the present invention. 1 is a schematic diagram illustrating an example of a tandem full-color electrophotographic apparatus according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Conductive support body 2 Filler dispersion layer 3 Resin layer 4 Photosensitive layer 5 Charge blocking layer 6 Moire prevention layer 7 Charge generation layer 8 Charge transport layer 9 Protective layer 11, 41, 51, 61C, 61M, 61Y, 61K Photoconductor 12 Static elimination lamp 13, 53 Charging roller 15, 54 Image exposure unit 16 Development unit 17 Pre-transfer charger 18, 69 Registration roller 19, 67 Transfer paper 20, 45 Transfer charger 21 Separation charger 22 Separation claw 23 Pre-cleaning charger 24 Fur brush 25 Cleaning Blade 31 Gap forming member 32 Metal shaft 33 Image forming area 34 Non-image forming area 42a, 42b Driving roller
43 Charger 44 Image exposure source 46 Exposure before cleaning 47, 55 Cleaning brush 48 Static elimination light source 56 Development roller 57 Transfer roller 62C, 62M, 62Y, 62K Charging member 63C, 63M, 63Y, 63K Laser beam 64C, 64M, 64Y, 64K Developing member 65C, 65M, 65Y, 65K Cleaning member 66C, 66M, 66Y, 66K Image forming element 68 Paper feed roller 70 Transfer conveyor belt 71C, 71M, 71Y, 71K Transfer brush 72 Fixing device

Claims (31)

In the electrophotographic photosensitive member in which at least a charge blocking layer, a moire preventing layer, and a photosensitive layer are sequentially laminated on a conductive support, the electrophotographic photosensitive member includes τ-type metal-free phthalocyanine and the following (XI) And an azo pigment represented by the formula:
In the formula, Cp ₁ and Cp ₂ represent coupler residues. R ₂₀₁ and R ₂₀₂ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a cyano group, and may be the same or different. Cp ₁ and Cp ₂ are represented by the following formula (XII):
In the formula, R ₂₀₃ represents a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, or an aryl group such as a phenyl group. R ₂₀₄ , R ₂₀₅ , R ₂₀₆ , R ₂₀₇ and R ₂₀₈ are each a hydrogen atom, a nitro group, a cyano group, a halogen atom such as fluorine, chlorine, bromine or iodine, a trifluoromethyl group, a methyl group or an ethyl group. Represents an alkoxy group such as an alkyl group, a methoxy group or an ethoxy group, a dialkylamino group or a hydroxyl group, and Z represents an atom necessary for constituting a substituted or unsubstituted aromatic carbocyclic ring or a substituted or unsubstituted aromatic heterocyclic ring. Represents a group. It said electrophotographic photosensitive member is an electrophotographic photosensitive member according to claim 1, wherein the coupler residue Cp ₁ and coupler residue Cp ₂ of the azo pigment are different from each other. The electrophotographic photosensitive member according to claim 1, wherein a mixing ratio of the τ-type metal-free phthalocyanine and the azo pigment is in a range of 5/1 to 1/5 (weight ratio). The electrophotographic photosensitive member according to any one of claims 1 to 3, wherein the τ-type metal-free phthalocyanine and the azo pigment are simultaneously milled and mixed. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer has a laminated structure of a charge generation layer and a charge transport layer. A filter in which the average particle size of the charge generation material mixed with the τ-type metal-free phthalocyanine and the azo pigment is 0.3 μm or less and the standard deviation is 0.2 μm or less, and then the effective pore size is 5 μm or less. The electrophotographic photosensitive member according to claim 1, wherein the photosensitive layer or the charge generation layer is coated using a dispersion liquid filtered through the above. The electrophotographic photosensitive member according to claim 1, wherein the charge blocking layer is made of an insulating material and has a thickness of less than 2.0 μm. The electrophotographic photosensitive member according to claim 7, wherein the insulating material is polyamide. The electrophotographic photoreceptor according to any one of claims 1 to 8, wherein the moire preventing layer contains an inorganic pigment and a binder resin, and the volume ratio of the two is in the range of 1/1 to 3/1. . The electrophotographic photosensitive member according to claim 9, wherein the binder resin is a thermosetting resin. The electrophotographic photosensitive member according to claim 10, wherein the thermosetting resin is a mixture of alkyd / melamine resin. The electrophotographic photosensitive member according to claim 11, wherein a mixing ratio of the alkyd resin and the melamine resin is in a range of 5/5 to 8/2 (weight ratio). The electrophotographic photosensitive member according to claim 9, wherein the inorganic pigment is titanium oxide. The titanium oxide is two types of titanium oxides having different average particle diameters, and the average particle diameter (D1) of one titanium oxide (T1) and the average particle diameter of the other titanium oxide (T2) are (D2). The electrophotographic photosensitive member according to claim 13, wherein 0.2 <(D2 / D1) ≦ 0.5 is satisfied. The electrophotographic photosensitive member according to claim 14, wherein an average particle diameter (D2) of the titanium oxide (T2) is 0.05 μm <D2 <0.2 μm. The electrophotography according to claim 14 or 15, wherein a mixing ratio (weight ratio) of the two types of titanium oxides having different average particle diameters is 0.2≤T2 / (T1 + T2) ≤0.8. Photoconductor. The electrophotographic photosensitive member according to claim 1, further comprising a protective layer on the photosensitive layer. The electrophotographic photosensitive member according to claim 17, wherein the protective layer contains an inorganic pigment or metal oxide having a specific resistance of 10 ¹⁰ Ω · cm or more. The electrophotographic photoreceptor according to claim 18, wherein the metal oxide is any one of alumina, titanium oxide, and silica having a specific resistance of 10 ¹⁰ Ω · cm or more. The electrophotographic photosensitive member according to claim 19, wherein the metal oxide is α-alumina having a specific resistance of 10 ¹⁰ Ω · cm or more. 21. The electrophotographic photosensitive member according to claim 17, wherein the protective layer contains a polymer charge transport material. 21. The electrophotographic photosensitive member according to claim 17, wherein the binder resin of the protective layer has a crosslinked structure. The electrophotographic photosensitive member according to claim 22, wherein the structure of the binder resin having a crosslinked structure has a charge transporting site. In an image forming apparatus comprising at least a charging unit, an exposure unit, a developing unit, a transfer unit, and an electrophotographic photosensitive member,
24. The image forming apparatus according to claim 1, wherein the electrophotographic photosensitive member is one according to any one of claims 1 to 23. The image forming apparatus according to claim 24, wherein the image forming apparatus includes a plurality of image forming elements including at least a charging unit, an exposure unit, a developing unit, a transfer unit, and an electrophotographic photosensitive member. 26. The image forming apparatus according to claim 24, wherein a contact charging method is used as a charging unit of the image forming apparatus. 26. The image forming apparatus according to claim 24, wherein a non-contact proximity arrangement method is used as a charging unit of the image forming apparatus. 28. The image forming apparatus according to claim 27, wherein a gap between a charging member used for the charging unit and the photosensitive member is 100 μm or less. 29. The image forming apparatus according to claim 26, wherein an AC superimposed voltage is applied as charging means of the image forming apparatus. The image forming apparatus includes an apparatus main body in which a photosensitive member and at least one unit selected from a charging unit, an exposure unit, a developing unit, and a cleaning unit are integrated, and a detachable cartridge. 30. The image forming apparatus according to claim 24. In a process cartridge for an image forming apparatus in which at least one unit selected from a charging unit, an exposure unit, a developing unit, and a cleaning unit and an electrophotographic photosensitive member are integrated,
24. The process cartridge for an image forming apparatus, wherein the electrophotographic photosensitive member is the electrophotographic photosensitive member according to any one of claims 1 to 23.