JP2006285119A - Electrophotographic photoreceptor, electrophotographic photoreceptor cartridge, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic photoreceptor, an image forming apparatus, etc., that can suppress the generation of a leak and memory effect during image formation and form images of high quality. <P>SOLUTION: The electrophotographic photoreceptor is constituted by having a layer having a composition containing at least a compound represented by general formula (1), a compound represented by general formula (2), and a compound represented by general formula (3). In general formulas (1) to (3), Ar<SP>1</SP>and Ar<SP>2</SP>denote arylene groups which may have substituents, Ar<SP>3</SP>denotes an aryl group having a substituent, Ar<SP>4</SP>denotes an aryl group which may have a substituent, and Ar<SP>5</SP>and Ar<SP>6</SP>denote aryl groups. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electrophotographic photosensitive member, an electrophotographic photosensitive member cartridge using the same, and an image forming apparatus.

  In recent years, electrophotographic technology has been widely used and applied not only in the field of copying machines but also in the fields of various printers and printing presses because of its excellent immediacy and high quality images.

  For electrophotographic photoreceptors, the core of electrophotographic technology, inorganic photoconductive materials such as amorphous selenium, arsenic-selenium alloys, cadmium sulfide, and zinc oxide have been used as photoconductive materials. However, organic photoconductive materials having advantages such as pollution-free, easy film formation, and easy manufacture of a photoreceptor have been mainly used.

  The layer structure of an electrophotographic photoreceptor using an organic photoconductive material includes a so-called single-layer photoreceptor in which a charge generation material and a charge transport material are contained in the same layer, or a charge generation layer and a charge transport layer. A so-called laminated type photoconductor having been laminated is known. Since the multilayer photoconductor can be combined with an optimal material by dividing the charge generation material and charge transport material with high charge generation efficiency into separate layers, a highly sensitive and stable electrophotographic photoconductor can be obtained. It is often used for reasons such as wide flexibility in material selection and easy adjustment of characteristics.

  On the other hand, the single-layer type photoreceptor is slightly inferior to the laminated type photoreceptor in terms of electrical characteristics and has a low degree of freedom in material selection, but can generate charges near the surface of the photoreceptor, so that high resolution can be achieved. Further, there is an advantage that high printing durability can be achieved by increasing the thickness of the film because the image is not blurred even if the thickness is increased. In addition, the single-layer type photoreceptor requires fewer coating processes, and is advantageous for interference fringes and tube defects derived from a conductive substrate (support), and can use an inexpensive substrate such as a non-cutting tube. For this reason, there is an advantage that the cost can be reduced.

  In addition, since the electrophotographic photosensitive member is repeatedly used in an electrophotographic process, that is, a cycle such as charging, exposure, development, transfer, cleaning, and charge removal, the electrophotographic photosensitive member deteriorates due to various stresses during that time. Among these, as the chemical deterioration, for example, deterioration factors such as strong oxidizing ozone and NOx generated from a corona charger usually used as a charger may damage the photosensitive layer. Such deterioration factors may cause deterioration in electrical stability, such as a decrease in chargeability, an increase in residual potential, and the accompanying image defects when the electrophotographic photoreceptor is repeatedly used. . The occurrence of such a problem is considered to be largely caused by the above-mentioned deterioration factors chemically degrading the charge transport material contained in the photosensitive layer.

  Furthermore, with the recent increase in the speed of the electrophotographic process, an electrophotographic photosensitive member is required to have high sensitivity and high speed response as essential characteristics. Among these, in order to achieve high sensitivity, it is necessary not only to optimize the charge generation material, but also to develop a charge transport material with good matching with it. On the other hand, in order to achieve high-speed response, it is necessary to develop a charge transport material that exhibits high mobility and a sufficiently low residual potential during exposure. In order to solve such a technical problem, various techniques have been developed so far (see, for example, Patent Documents 1 to 5).

Moreover, since it is necessary to dope a polymer with a low molecular weight compound in a high number of parts, the charge transport material may cause problems such as crystallization in the film, but by mixing several kinds of charge transport materials, The solution has been attempted (see, for example, Patent Documents 6 and 7).
JP-A-3-225345 JP-A-6-214409 JP 2000-56490 A JP-A-4-182655 JP-A-1-118141 US Patent Application Publication No. 2004/67427 Japanese Patent Laid-Open No. 2002-40688

  In the mixed photoreceptors reported in the above-mentioned patent documents, the characteristics of the finally obtained photoreceptors are obtained by simply averaging the characteristics of each individual system. In recent years when the improvement of the characteristics of the photoconductor is remarkably required, it is the actual situation that a photoconductor satisfying the recent demand for the improvement of the characteristics has not been obtained yet.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide an electrophotographic photosensitive member that can suppress the occurrence of leakage and memory during image formation and can form a high-quality image. To provide a body. Another object of the present invention is to provide an electrophotographic photosensitive member cartridge and an image forming apparatus using such an electrophotographic photosensitive member.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention by combining three or more specific charge transport materials.

  That is, the gist of the present invention is a composition containing at least a compound represented by the general formula (1), a compound represented by the general formula (2), and a compound represented by the general formula (3). The electrophotographic photosensitive member is provided with a layer having the above (claim 1).

Here, in the general formulas (1) to (3), Ar ¹ and Ar ² represent an arylene group which may have a substituent, Ar ³ represents an aryl group having a substituent, and Ar ⁴ represents a substituted group. Represents an aryl group which may have a group, and Ar ⁵ and Ar ⁶ represent an aryl group.

In the electrophotographic photosensitive member of the present invention, in the general formulas (1) and (2), Ar ³ is preferably a p-tolyl group (claim 2).

  Another gist of the present invention is the above-described electrophotographic photosensitive member, a charging unit that charges the electrophotographic photosensitive member, an exposure unit that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image, and The electrophotographic photosensitive member cartridge is provided with at least one developing unit that develops the electrostatic latent image formed on the electrophotographic photosensitive member.

  Still another gist of the present invention is the above-described electrophotographic photosensitive member, a charging unit that charges the electrophotographic photosensitive member, an exposure unit that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image, and An image forming apparatus comprising: a developing unit that develops an electrostatic latent image formed on the electrophotographic photosensitive member (claim 4).

  According to the electrophotographic photosensitive member of the present invention, since the constituent layer of the single layer type photosensitive member or the multilayer type photosensitive member is formed with the composition containing at least the above three kinds of charge transporting substances, leakage and memory are caused during image formation. Can be suppressed, and a high quality image can be formed.

  In addition, according to the electrophotographic photosensitive member cartridge of the present invention, it is possible to provide an electrophotographic photosensitive member cartridge that exhibits the above effects, and according to the image forming apparatus of the present invention, since such an electrophotographic photosensitive member is provided, A high quality image can be formed.

  Hereinafter, the electrophotographic photosensitive member, the electrophotographic photosensitive member cartridge, and the image forming apparatus of the present invention will be described. However, the present invention is not limited to the following embodiments, and can be arbitrarily set within the scope of the present invention. It can be implemented with deformation.

[Electrophotographic photoreceptor]
The electrophotographic photosensitive member of the present invention includes a conductive support and a layer having a specific arylamine composition formed on the conductive support. The present invention is characterized in that the specific arylamine composition contains three kinds of compounds (arylamine derivatives) represented by the following general formulas (1), (2) and (3). There is.

(Specific arylamine composition)
In the present invention, the specific arylamine composition contains at least a compound represented by the general formula (1), a compound represented by the general formula (2), and a compound represented by the general formula (3). To do.

In the general formulas (1) to (3), Ar ¹ and Ar ² represent an arylene group which may have a substituent, Ar ³ represents an aryl group having a substituent, and Ar ⁴ represents a substituent. represents an aryl group which may have, Ar ⁵ and Ar ⁶ represents an aryl group.

Examples of the arylene group for Ar ¹ and Ar ² include a phenylene group and a naphthylene group, and among them, a phenylene group is preferable. On the other hand, examples of the aryl group of Ar ³ to Ar ⁶ include a phenyl group and a naphthyl group, and among them, a phenyl group is preferable.

(i) Preferable specific examples of Ar ¹ and Ar ² include a phenylene group and a naphthylene group having no substituent, and among them, a phenylene group having no substituent is preferable. (ii) Preferable specific examples of Ar ³ include a phenyl group (tolyl group) having a methyl group, and a p-tolyl group is particularly preferable. (iii) Preferable specific examples of Ar ⁴ include a phenyl group (tolyl group) having a methyl group, and a p-tolyl group is particularly preferable. (iv) Specific examples of Ar ⁵ and Ar ⁶ include a phenyl group and a naphthyl group, and among them, a phenyl group is preferable.

There is no particular limitation on the substituent to Ar ¹ without replacing the Ar ⁴ each may be a substituent of any group. Preferred examples of such a substituent include an alkyl group, an alkoxy group, an aryl group, and a condensed polycyclic group. Among these, as an alkyl group, a C1-C10 alkyl group is more preferable, a C1-C5 alkyl group is still more preferable, a methyl group is especially preferable, and a phenyl group is preferable as an aryl group. The number of substituents for each of Ar ¹ to Ar ⁴ is generally preferably 1 or more and 3 or less.

Ar ³ and Ar ⁴ may be bonded to each other via a substituent to form a ring, and Ar ¹ and Ar ² may be condensed with each other to form a ring. Ar ⁵ and Ar ⁶ may be directly bonded to each other or bonded via a bonding group to form a ring.

  In addition, the molecular weight of each compound represented by the general formulas (1) to (3) described above is usually 2000 or less, preferably 1000 or less, considering characteristics when a repeated image is formed. Preferably it is 800 or less.

  Moreover, it is preferable that the composition ratio (weight%) of the compound represented by General formula (3) is 0.01% or more and 5% or less with respect to the compound represented by General formula (1). If the composition ratio is less than 0.01%, the solubility in the photosensitive layer may decrease and the photosensitive layer may become cloudy. Even if the composition ratio exceeds 5%, the solubility in the photosensitive layer decreases and the photosensitive layer becomes It may become turbid and electrical characteristics may deteriorate. Moreover, it is preferable that the composition ratio of the compound represented by General formula (2) is 1% or more and 10% or less with respect to the compound represented by General formula (1). When this composition ratio is less than 1% or more than 10%, the solubility in the photosensitive layer may be lowered, the photosensitive layer may become cloudy, or the electrical characteristics may deteriorate.

  Hereinafter, representative examples of the arylamine composition used as the charge transporting material will be shown as the arylamine composition for forming the layer provided in the electrophotographic photoreceptor of the present invention. The representative examples shown below are examples in which the compounds represented by the chemical formulas (1) to (3) are combined as follows. In addition, the representative example shown below is shown for illustration, Comprising: The arylamine composition used for this invention is not limited to the following arylamine compositions. The number at the left end is the number of the arylamine composition configured by combining the compounds represented by the chemical formulas (1) to (3), and is the same as the numbers shown in the table below.

  There is no restriction | limiting in the manufacturing method of such an arylamine composition, It can manufacture by arbitrary methods. For example, a method of synthesizing and mixing each compound (arylamine derivative) separately, or a method of synthesizing a composition containing three kinds of compounds (arylamine derivative) at the time of synthesis can be mentioned. Among these, the latter method is preferable from the viewpoint of cost and ease of production.

Here, the latter method will be described. As shown in the following scheme, an arylamine composition containing three compounds at a time can be synthesized by simultaneously reacting a dihalogen and two or more types of arylamine. Ar ^{1 to} Ar ⁶ are the same as described above.

  The coupling reaction in this method may be performed by a Ullmann reaction using a copper catalyst or an iron catalyst, or by a method using a Pd catalyst. However, it is preferable to carry out by a method using a Pd catalyst from the viewpoint of improving electric characteristics. Moreover, when performing coupling reaction using a Pd catalyst, it is preferable to forcibly discharge | emit the generated alcohol etc. out of the system early from a viewpoint of advancing reaction efficiently.

  A known method can be used as a purification method for the produced composition, and a purification method using silica gel, activated carbon, activated clay, or the like is preferably used.

(Conductive support)
The conductive support constituting the electrophotographic photosensitive member of the present invention can be formed of any material having conductivity. As a constituent material of the conductive support, for example, a metal material such as aluminum, aluminum alloy, stainless steel, copper, or nickel; a resin provided with conductivity by mixing conductive powder such as metal, carbon, or tin oxide Materials: Resin, glass, paper, or the like obtained by depositing or coating a conductive material such as aluminum, nickel, or ITO (indium tin oxide) on the surface of the material. In addition, a conductive support having a suitable resistance value may be used on the surface of a conductive support formed of a metal material for controlling conductivity, surface properties, etc., or for covering defects. .

  Among these, it is preferable to use a metal material such as an aluminum alloy as the conductive support in terms of electrical characteristics, image characteristics, material procurement, cost, and the like. In addition, as the material for the conductive support, one type of material may be used alone, or two or more types of materials may be used in any combination and ratio. Also, the form of the conductive support is arbitrary, and for example, a drum shape, a sheet shape, a belt shape or the like is used.

  Furthermore, it is preferable to subject the conductive support of the present invention to anodizing treatment and sealing treatment from the viewpoint of preventing leakage. As a result, when image formation is performed using the electrophotographic photosensitive member of the present invention, image characteristics can be improved and electrical characteristics can be stabilized.

  The anodizing treatment can be carried out by any method, but is usually carried out by energizing in an acidic bath using the conductive support as an electrode. Although there is no restriction | limiting in particular about an acidic bath, For example, acidic baths, such as chromic acid, a sulfuric acid, an oxalic acid, a boric acid, sulfamic acid, are mentioned. Of these, anodizing in sulfuric acid gives the best results.

For example, in the case of anodizing a conductive support made of aluminum in sulfuric acid, the treatment conditions are as follows: the sulfuric acid concentration is 100 g / L to 300 g / L, and the dissolved aluminum concentration is 2 g / L to 15 g / L. L, the liquid temperature is preferably set to 15 ° C. to 30 ° C., the electrolysis voltage is set to 10 V to 20 V, and the current density is preferably set within a range of 0.5 A / dm ^{2 to 2} A / dm ² . However, the processing conditions during the anodizing treatment are not limited to this.

  It is preferable to perform a sealing treatment on the anodic oxide film thus formed. The sealing treatment can be performed by any method, but is usually performed by immersing the conductive support in a sealing agent aqueous solution (sealing solution) containing a sealing agent. A typical example is a low-temperature sealing treatment in which a conductive support is immersed in a sealing agent aqueous solution at a low temperature, or a high-temperature sealing treatment in which a conductive support is immersed in a sealing agent aqueous solution at a high temperature. Is mentioned.

(Underlayer)
An undercoat layer may be provided between the conductive support and the photosensitive layer formed on the conductive support in order to improve adhesion and blocking properties. As the undercoat layer, a resin or a resin in which particles such as a metal oxide are dispersed is used.

  Examples of the metal oxide particles used for the undercoat layer include metal oxide particles containing one metal element such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, iron oxide, calcium titanate, Examples thereof include metal oxide particles containing a plurality of metal elements such as strontium titanate and barium titanate. One type of metal oxide particles may be used alone, or a plurality of types of metal oxide particles may be mixed and used in any combination and ratio.

  Among these metal oxide particles, titanium oxide and aluminum oxide are preferable, and titanium oxide is particularly preferable. The surface of the titanium oxide particles may be subjected to a surface treatment with an inorganic substance such as tin oxide, aluminum oxide, antimony oxide, zirconium oxide, or silicon oxide, or an organic substance such as stearic acid, polyol, or silicone. The treatment applied to the titanium oxide particles may be one type, or two or more types of treatments may be performed in any combination and degree.

  Further, as the crystal form of the titanium oxide particles, any of rutile, anatase, brookite, and amorphous can be used. In addition, the titanium oxide particles may have only one crystal type, or two or more crystal types may be included in any combination and ratio.

  Various metal oxide particle diameters can also be used. Among them, the characteristics of the binder resin, etc., which is the raw material of the undercoat layer, and the stability of the coating liquid used when the undercoat layer is formed by coating. Therefore, the average primary particle size is usually 10 nm or more, preferably 20 nm or more, and usually 100 nm or less, preferably 50 nm or less.

  The undercoat layer is preferably formed in a form in which metal oxide particles are dispersed in a binder resin. Examples of the binder resin used for the undercoat layer include phenoxy, epoxy, polyvinyl pyrrolidone, polyvinyl alcohol, casein, polyacrylic acid, celluloses, gelatin, starch, polyurethane, polyimide, and polyamide. In addition, these may be used independently and may use 2 or more types together by arbitrary combinations and a ratio. Moreover, you may use in the form hardened | cured with the hardening | curing agent. Among these, alcohol-soluble copolymerized polyamide, modified polyamide, and the like are preferable because they exhibit good dispersibility and coatability.

  The mixing ratio of the metal oxide particles to the binder resin used in the undercoat layer can be arbitrarily selected, but it is usually used in the range of 10% by weight to 500% by weight in order to improve the stability of the coating solution and the coating properties. It is preferable in terms of

  Furthermore, the thickness of the undercoat layer can be arbitrarily selected, but it is usually from the viewpoint of improving the electrical characteristics, strong exposure characteristics, image characteristics, and repeat characteristics of the electrophotographic photosensitive member, and coating properties during production. Is 0.1 μm or more, preferably 0.5 μm or more, and usually 20 μm or less, preferably 10 μm or less. Moreover, you may mix a well-known antioxidant etc. in an undercoat layer.

(Photosensitive layer)
Next, the photosensitive layer formed on the conductive support (on the undercoat layer when the above-described undercoat layer is provided) will be described. The photosensitive layer is a layer having, as a charge transport material, an arylamine composition containing the three types of compounds (arylamine derivatives) represented by the general formulas (1), (2) and (3) described above. The type includes a single layer type consisting of the same layer in which the charge generation material and the arylamine composition as the charge transport material are dispersed in the binder resin, the charge generation layer in which the charge generation material is dispersed in the binder resin, and the charge transport. Although a laminate type composed of two layers of a charge transport layer in which an arylamine composition as a substance is dispersed in a binder resin can be mentioned, any form thereof may be used. In general, it is known that the charge transport material exhibits the same performance as a charge transfer function regardless of whether it is a single layer type or a multilayer type.

  In addition, as the laminated photosensitive layer, a forward laminated photosensitive layer in which a charge generation layer and a charge transport layer are laminated in this order from the conductive support side, and conversely, a reverse lamination type in which a charge transport layer and a charge generation layer are laminated in this order There is a photosensitive layer, and any of them can be adopted, but a sequentially laminated photosensitive layer capable of exhibiting the most balanced photoconductivity is preferable. In the following description, a multilayer photoconductor will be described as an example unless otherwise specified.

(Charge generation layer)
In the case of a multilayer photoreceptor, the charge generation layer is prepared by dispersing a charge generation material in a solution obtained by dissolving a binder resin in an organic solvent, or adjusting the coating solution or dispersing the charge generation material in an organic solvent. The liquid is mixed with a binder resin or a liquid obtained by dissolving the binder resin in an organic solvent to prepare a coating liquid, which is coated on a conductive support, and the charge generating substance is bound with various binder resins. It is formed by.

  Any known charge generating substance can be used, and examples thereof include selenium and its alloys, cadmium sulfide, other inorganic photoconductive materials, and organic photoconductive materials such as organic pigments. Among these, organic photoconductive materials are preferable, and organic pigments are particularly preferable. Specific examples of organic pigments include phthalocyanine pigments (hereinafter also referred to as phthalocyanine compounds), azo pigments, dithioketopyrrolopyrrole pigments, squalene pigments, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, anthanthrone. Examples thereof include pigments and benzimidazole pigments.

  Among the above organic pigments, phthalocyanine pigments or azo pigments are particularly preferable as the charge generating substance. The phthalocyanine pigment is a point that a highly sensitive electrophotographic photosensitive member can be obtained with respect to a laser beam having a relatively long wavelength of 600 nm to 900 nm, and the azo pigment is a white light and a relatively short wavelength of 300 nm to 500 nm. Each is excellent in that it has sufficient sensitivity to laser light.

  When a phthalocyanine compound is used as the charge generation material, specifically, metal-free phthalocyanine, copper, indium, gallium, tin, titanium, zinc, vanadium, silicon, germanium, or other metals or oxides, halides, hydroxides thereof Or various crystal forms of coordinated phthalocyanines such as alkoxides. In particular, X-type or τ-type metal-free phthalocyanine, which is a highly sensitive crystal form, titanyl phthalocyanine such as A-type (also known as β-type), B-type (also known as α-type) or D-type (also known as Y-type) Titanium phthalocyanine), vanadyl phthalocyanine, chloroindium phthalocyanine, chlorogallium phthalocyanine such as type II, hydroxygallium phthalocyanine such as type V, μ-oxo-gallium phthalocyanine dimer such as type G and type I, or type II μ-Oxo-aluminum phthalocyanine dimer is preferably used.

  Of these phthalocyanine compounds, the A type (β type) shows a clear peak at a diffraction angle 2θ (± 0.2 °) of powder X-ray diffraction at 9.3 °, 10.6 °, and 26.3 ° C. ) Or B-type (α-type) oxytitanium phthalocyanine, D-type (Y-type) oxytitanium phthalocyanine having a clear X-ray diffraction angle 2θ (± 0.2 °) of 27.3 °, Type II chlorogallium phthalocyanine, V type hydroxygallium phthalocyanine, G type μ-oxo-gallium phthalocyanine dimer and the like are particularly preferably used. In particular, from the viewpoint of image improvement, it is preferable to use A-type (β-type), B-type (α-type), or D-type (Y-type) oxytitanium phthalocyanine, or a mixture thereof.

  As the phthalocyanine compound, one kind of compound may be used alone, or plural kinds of compounds may be used in a mixed or mixed crystal state. In addition, phthalocyanine compounds may be used in a mixed state in the crystalline state by mixing the respective constituents later, or a mixed state is produced in the production and processing steps of phthalocyanine compounds such as synthesis, pigmentation, and crystallization. It can also be used. As such treatment, acid paste treatment, grinding treatment, solvent treatment and the like are known. In order to produce a mixed crystal state, as described in JP-A-10-48859, after mixing two types of crystals, they are mechanically ground and made indefinite, and then converted into a specific crystal state by solvent treatment. The method of conversion is mentioned.

  On the other hand, when an azo pigment is used as the charge generation material, various known bisazo pigments or trisazo pigments are preferably used. When an azo pigment is used as the charge generation material, various known bisazo pigments or trisazo pigments are preferably used. Examples of preferred azo pigments are shown below.

  Further, the charge generation materials may be used alone or in combination of two or more in any combination and ratio.

  By the way, when an organic pigment is used as the charge generation material, the fine particles of the organic pigment are used in a form bound with a binder resin. The type of binder resin is not particularly limited. For example, polyvinyl acetate, polyacrylic acid ester, polymethacrylic acid ester, polyester, polycarbonate, polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral, phenoxy resin, epoxy resin, urethane resin, cellulose Examples include esters and cellulose ethers.

  The usage ratio of the charge generating material to the binder resin is usually in the range of 30 to 500 parts by weight of the charge generating material with respect to 100 parts by weight of the binder resin in the case of the multilayer photoreceptor. In the case of a single layer type photoreceptor to be described later, the charge generation material is usually 0.1 parts by weight or more, preferably 1 part by weight or more, and usually 30 parts by weight or less, preferably 10 parts by weight based on 100 parts by weight of the binder resin. Less than parts by weight.

  The thickness of the charge generation layer is usually 0.1 μm or more, preferably 0.15 μm or more, and usually 1 μm or less, preferably 0.6 μm or less.

(Charge transport layer)
In the case of a multilayer photoreceptor, the charge transport layer contains a charge transport material and usually contains a binder resin and other components used as necessary. Specifically, such a charge transport layer is prepared by, for example, preparing a coating solution by dissolving or dispersing a charge transport material and a binder resin in a solvent. In addition, in the case of a reverse lamination type photosensitive layer, it can be obtained by coating and drying on a conductive support (on the undercoat layer when an undercoat layer is provided).

  As the charge transport material, an arylamine composition containing three kinds of compounds (arylamine derivatives) represented by the general formulas (1), (2) and (3) is used.

  In addition to the arylamine composition, other known charge transport materials may be used in combination. When other charge transporting substances are used in combination, the type is not particularly limited, but preferable examples include carbazole derivatives, hydrazone compounds, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, and those in which a plurality of these derivatives are bonded. be able to. More specifically, compounds described in JP-A-2-230255, JP-A-63-225660, JP-A-58-198043, JP-B-58-32372, and JP-B-7-21646 Can be preferably mentioned.

  The binder resin is used to ensure film strength. Usually, the charge transport layer can be obtained by coating and drying a coating solution obtained by dissolving or dispersing a charge transport material and the binder resin in a solvent.

  Examples of the binder resin include polymers and copolymers of vinyl compounds such as butadiene, styrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, vinyl alcohol, and ethyl vinyl ether, polyvinyl butyral, polyvinyl formal, and partial modification. Examples thereof include polyvinyl acetal, polycarbonate, polyester, polyarylate, polyamide, polyurethane, cellulose ether, phenoxy resin, silicon resin, epoxy resin, poly-N-vinylcarbazole resin, and the like. Of these, polycarbonate and polyarylate are particularly preferred. These can also be used after being crosslinked with heat, light or the like using an appropriate curing agent or the like. Moreover, these binders may be used individually by 1 type, and 2 or more types can also be used together by arbitrary combinations and a ratio.

  The ratio of the binder resin to the charge transport material is 20 parts by weight or more of the charge transport material with respect to 100 parts by weight of the binder resin. Among these, 30 parts by weight or more is preferable from the viewpoint of residual potential reduction, and 40 parts by weight or more is more preferable from the viewpoint of stability and charge mobility when repeatedly used. On the other hand, from the viewpoint of thermal stability of the photosensitive layer, the charge transport material is usually used at a ratio of 150 parts by weight or less. Among these, 110 parts by weight or less is preferable from the viewpoint of compatibility between the charge transport material and the binder resin, 80 parts by weight or less is more preferable from the viewpoint of printing durability, and 70 parts by weight or less is most preferable from the viewpoint of scratch resistance.

  In addition, when the arylamine composition of the present invention is used in combination with another charge transport material, the ratio of the arylamine composition and the other charge transport material is arbitrary, but the arylamine composition of the present invention is usually 20%. % By weight or more, preferably 40% by weight or more, and usually 95% by weight or less, preferably 90% by weight or less.

  The thickness of the charge transport layer is not particularly limited, but is usually 5 μm or more, preferably 10 μm or more, and usually 50 μm or less, preferably 45 μm or less from the viewpoint of long life, image stability, and high resolution. Further, the range is 30 μm or less.

(Photosensitive layer of single layer type photoreceptor)
Next, the case of a single layer type photoreceptor will be described. In the case of a single layer type photoreceptor, in addition to the charge generating material and the arylamine composition which is a charge transport material, the photosensitive layer contains a binder resin for securing film strength in the same manner as the charge transport layer of the multilayer photoreceptor. Use to form. Specifically, a coating solution is usually prepared by dissolving or dispersing a charge generating substance, a charge transporting substance, and various binder resins in a solvent, and then on a conductive support (if an undercoat layer is provided, an undercoat layer is provided). It can be obtained by applying and drying the above.

  The types of the arylamine composition and the binder resin, which are charge transport materials, and the usage ratios thereof are the same as those described for the charge transport layer of the multilayer photoreceptor.

  As the charge generation material, the same materials as those described for the charge generation layer of the multilayer photoreceptor can be used. However, in the case of a photosensitive layer of a single-layer type photoreceptor, it is desirable to sufficiently reduce the particle size of the charge generating material. Specifically, the range is usually 1 μm or less, preferably 0.5 μm or less.

  If the amount of the charge generating material dispersed in the photosensitive layer is too small, sufficient sensitivity cannot be obtained.If the amount is too large, there are adverse effects such as a decrease in chargeability and a decrease in sensitivity. On the other hand, it is used in the range of usually 0.5% by weight or more, preferably 1% by weight or more, and usually 50% by weight or less, preferably 20% by weight or less.

  Further, the film thickness of the photosensitive layer is usually 5 μm or more, preferably 10 μm or more, and usually 100 μm or less, preferably 50 μm or less.

  For the photosensitive layer, well-known antioxidants, plasticizers, ultraviolet absorbers, electron-withdrawing compounds are used for the purpose of improving film forming properties, flexibility, coating properties, stain resistance, gas resistance, light resistance, etc. Further, additives such as a leveling agent and a visible light shielding agent may be contained. The same applies to the case of each layer constituting the multilayer photoconductor.

(Other layers)
In both the multilayer type photoreceptor and the single-layer type photoreceptor, the photosensitive layer formed by the above-mentioned procedure may be the uppermost layer, that is, the surface layer, but another layer may be provided on the photosensitive layer, and this may be used as the surface layer. . For example, a protective layer may be provided for the purpose of preventing wear of the photosensitive layer or preventing or reducing deterioration of the photosensitive layer due to discharge products generated from a charger or the like.

  Further, for the purpose of reducing frictional resistance and wear on the surface of the electrophotographic photosensitive member, a resin such as a fluorine-based resin or a silicone resin, or particles made of these resins or particles of an inorganic compound may be included in the surface layer. . Alternatively, a layer containing these resins and particles may be newly formed as a surface layer.

(Method for forming each layer)
Each of the above layers constituting the electrophotographic photosensitive member is formed by immersing, coating, spraying, nozzle coating, bar coating, roll coating, blade coating a coating solution obtained by dissolving or dispersing a substance to be contained in a solvent. These are formed by sequentially coating by a known method.

  There is no particular limitation on the solvent used for preparing the coating solution, that is, the solvent or the dispersion medium. Specific examples include alcohols such as methanol, ethanol, propanol, and 2-methoxyethanol, tetrahydrofuran, 1,4-dioxane, Ethers such as dimethoxyethane, esters such as methyl formate and ethyl acetate, ketones such as acetone, methyl ethyl ketone, cyclohexanone and 4-methoxy-4-methyl-2-pentanone, and aromatic hydrocarbons such as benzene, toluene and xylene , Chlorinated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2 trichloroethane, 1,1,1-trichloroethane, tetrachloroethane, 1,2-dichloropropane, trichloroethylene, n-butylamine, Isopropanol amino , Diethylamine, triethanolamine, ethylenediamine, nitrogen-containing compounds such as triethylenediamine, acetonitrile, N- methylpyrrolidone, N, N- dimethylformamide, aprotic polar solvents such as dimethyl sulfoxide and the like. Moreover, these may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and kinds.

  In addition, the amount of solvent used is not particularly limited, but considering the purpose of each layer and the properties of the selected solvent, it may be appropriately adjusted so that the physical properties such as the solid content concentration and viscosity of the coating solution are within a desired range. preferable.

  For example, in the case of a photosensitive layer of a single layer type photoreceptor and a charge transport layer of a laminated type photoreceptor, the solid content concentration of the coating liquid or dispersion is usually 10% by weight or more, preferably 15% by weight or more. The range is usually 40% by weight or less, preferably 35% by weight or less. Further, the viscosity of the coating liquid or dispersion is usually 50 cps or more, preferably 100 cps or more, and usually 500 cps or less, preferably 400 cps or less.

  In the case of a charge generating layer of a multilayer photoreceptor, the solid content concentration of the coating liquid or dispersion is usually 1% by weight or more, preferably 2% by weight or more, and usually 15% by weight or less, preferably 10%. The range is not more than wt%. Further, the viscosity of the coating liquid or dispersion is usually in the range of 0.1 cps or more, preferably 0.5 cps or more, and usually 10 cps or less, preferably 8 cps or less.

  The coating solution is preferably dried at room temperature, after being statically dried at room temperature, usually in a temperature range of 30 ° C. or higher and 200 ° C. or lower for 1 minute to 2 hours, statically or under air blowing. The heating temperature may be constant or the heating may be performed while changing the temperature during drying.

[Image forming apparatus]
Next, an embodiment of an image forming apparatus using the electrophotographic photosensitive member of the present invention (an image forming apparatus of the present invention) will be described with reference to FIG. However, the embodiment is not limited to the following description, and can be arbitrarily modified without departing from the gist of the present invention.

  As shown in FIG. 1, the image forming apparatus includes an electrophotographic photosensitive member 1, a charging device (charging unit) 2, an exposure device (exposure unit) 3, and a developing device (developing unit) 4. Accordingly, a transfer device 5, a cleaning device 6, and a fixing device 7 are provided.

  The electrophotographic photoreceptor 1 is not particularly limited as long as it is the above-described electrophotographic photoreceptor of the present invention, but in FIG. 1, as an example, a drum in which the above-described photosensitive layer is formed on the surface of a cylindrical conductive support. The electrophotographic photosensitive member is shown. A charging device 2, an exposure device 3, a developing device 4, a transfer device 5, and a cleaning device 6 are arranged along the outer peripheral surface of the electrophotographic photoreceptor 1.

  The charging device 2 charges the electrophotographic photosensitive member 1 and uniformly charges the surface of the electrophotographic photosensitive member 1 to a predetermined potential. In FIG. 1, a roller-type charging device (charging roller) is shown as an example of the charging device 2, but other corona charging devices such as corotron and scorotron, contact-type charging devices such as charging brushes and charging films, etc. are often used. Used.

  In many cases, the electrophotographic photosensitive member 1 and the charging device 2 are cartridges having both of them (the electrophotographic photosensitive member cartridge of the present invention; hereinafter referred to as “photosensitive cartridge” as appropriate), and the main body of the image forming apparatus. Designed to be removable from. However, the charging device 2 may be provided separately from the cartridge, for example, in the main body of the image forming apparatus. For example, when the electrophotographic photoreceptor 1 or the charging device 2 is deteriorated, the photoreceptor cartridge can be detached from the image forming apparatus main body, and another new photoreceptor cartridge can be mounted on the image forming apparatus main body. It has become. Also, the toner described later is often stored in the toner cartridge and designed to be removable from the main body of the image forming apparatus. When the toner in the used toner cartridge runs out, this toner cartridge is removed. It can be removed from the main body of the image forming apparatus and another new toner cartridge can be mounted. Further, a cartridge equipped with all of the electrophotographic photosensitive member 1, the charging device 2, and the toner may be used.

  The type of the exposure apparatus 3 is not particularly limited as long as it can expose the electrophotographic photoreceptor 1 to form an electrostatic latent image on the photosensitive surface of the electrophotographic photoreceptor 1. Specific examples include halogen lamps, fluorescent lamps, lasers such as semiconductor lasers and He—Ne lasers, LEDs, and the like. Further, exposure may be performed by a photoreceptor internal exposure method. The light used for the exposure is arbitrary, but monochromatic light is generally preferable. For example, monochromatic light having a wavelength of 780 nm, monochromatic light having a wavelength of 600 nm to 700 nm, slightly short wavelength, and monochromatic light having a wavelength of 380 nm to 500 nm. For example, exposure may be performed.

  The type of the developing device 4 is not particularly limited as long as it can develop the exposed electrostatic latent image on the electrophotographic photosensitive member 1 into a visible image. Specific examples include dry development methods such as cascade development, one-component conductive toner development, and two-component magnetic brush development, and wet development methods. In FIG. 1, the developing device 4 includes a developing tank 41, an agitator 42, a supply roller 43, a developing roller 44, and a regulating member 45, and has a configuration in which toner T is stored inside the developing tank 41. . Further, a replenishing device (not shown) for replenishing the toner T may be attached to the developing device 4 as necessary. This replenishing device is configured to be able to replenish toner T from a container such as a bottle or a cartridge.

  The supply roller 43 is formed from a conductive sponge or the like. The developing roller 44 is made of a metal roll such as iron, stainless steel, aluminum, or nickel, or a resin roll obtained by coating such a metal roll with a silicon resin, a urethane resin, a fluorine resin, or the like. The surface of the developing roller 44 may be smoothed or roughened as necessary.

  The developing roller 44 is disposed between the electrophotographic photoreceptor 1 and the supply roller 43 and is in contact with the electrophotographic photoreceptor 1 and the supply roller 43, respectively. However, the developing roller 44 and the electrophotographic photosensitive member 1 may not be in contact with each other but may be close to each other. The supply roller 43 and the developing roller 44 are rotated by a rotation drive mechanism (not shown). The supply roller 43 carries the stored toner T and supplies it to the developing roller 44. The developing roller 44 carries the toner T supplied by the supply roller 43 and contacts the surface of the electrophotographic photosensitive member 1.

  The regulating member 45 is formed of a resin blade such as silicon resin or urethane resin, a metal blade such as stainless steel, aluminum, copper, brass, phosphor bronze, or a blade obtained by coating such a metal blade with a resin. This regulating member 45 normally abuts against the developing roller 44 and is pressed against the developing roller 44 side with a predetermined force by a spring or the like (a general blade linear pressure is 5 to 500 g / cm). If necessary, the regulating member 45 may be provided with a function of imparting charging to the toner T by frictional charging with the toner T.

  The agitator 42 is provided as necessary, and is rotated by a rotation driving mechanism, and agitates the toner T and conveys the toner T to the supply roller 43 side. A plurality of agitators 42 may be provided with different blade shapes and sizes.

  The type of the toner T is arbitrary, and besides the pulverized toner, a polymerized toner using a suspension polymerization method, an emulsion polymerization method, or the like can be used. In particular, when a polymerized toner is used, a toner having a small particle diameter of about 4 μm to 8 μm is preferable, and the toner particles are used in a variety of shapes from a nearly spherical shape to a shape outside the potato-like spherical shape. be able to. The polymerized toner is excellent in charging uniformity and transferability and is suitably used for high image quality.

  The type of the transfer device 5 is not particularly limited, and an apparatus using an arbitrary system such as an electrostatic transfer method such as corona transfer, roller transfer, or belt transfer, a pressure transfer method, or an adhesive transfer method can be used. . Here, it is assumed that the transfer device 5 includes a transfer charger, a transfer roller, a transfer belt, and the like disposed so as to face the electrophotographic photoreceptor 1. The transfer device 5 applies a predetermined voltage value (transfer voltage) having a polarity opposite to the charging potential of the toner T, and transfers the toner image formed on the electrophotographic photosensitive member 1 to a recording paper (paper, medium) P. Is.

  There is no restriction | limiting in particular about the cleaning apparatus 6, Arbitrary cleaning apparatuses, such as a brush cleaner, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, can be used. The cleaning device 6 scrapes the residual toner adhering to the electrophotographic photosensitive member 1 with a cleaning member and collects the residual toner. If there is little or almost no residual toner, the cleaning device 6 may be omitted.

  The fixing device 7 includes an upper fixing member (fixing roller) 71 and a lower fixing member (fixing roller) 72, and a heating device 73 is provided inside the fixing member 71 or 72. FIG. 1 shows an example in which a heating device 73 is provided inside the upper fixing member 71. The upper and lower fixing members 71 and 72 include a fixing roll in which a metal base tube made of stainless steel, aluminum, or the like is coated with silicon rubber, a fixing roll in which Teflon (registered trademark) resin is coated, a fixing sheet, or the like. A member can be used. Further, each of the fixing members 71 and 72 may be configured to supply a release agent such as silicone oil in order to improve releasability, or may be configured to forcibly apply pressure to each other by a spring or the like.

  When the toner transferred onto the recording paper P passes between the upper fixing member 71 and the lower fixing member 72 heated to a predetermined temperature, the toner is heated to a molten state and cooled after passing through the recording paper. Toner is fixed on P.

  The type of the fixing device is not particularly limited, and a fixing device of an arbitrary method such as heat roller fixing, flash fixing, oven fixing, pressure fixing, or the like can be provided.

  In the image forming apparatus configured as described above, an image is recorded as follows. That is, first, the surface (photosensitive surface) of the electrophotographic photosensitive member 1 is charged to a predetermined potential (for example, −600 V) by the charging device 2. At this time, charging may be performed with a DC voltage, or charging may be performed by superimposing an AC voltage on the DC voltage.

  Subsequently, the photosensitive surface of the charged electrophotographic photosensitive member 1 is exposed by the exposure device 3 according to the image to be recorded, and an electrostatic latent image is formed on the photosensitive surface. Then, development of the electrostatic latent image formed on the photosensitive surface of the electrophotographic photoreceptor 1 is performed by the developing device 4.

  The developing device 4 thins the toner T supplied by the supply roller 43 with a regulating member (developing blade) 45 and has a predetermined polarity (here, the same polarity as the charging potential of the electrophotographic photosensitive member 1). Negatively charged) and conveyed while being carried on the developing roller 44 and brought into contact with the surface of the electrophotographic photosensitive member 1.

  When the charged toner T carried on the developing roller 44 contacts the surface of the electrophotographic photoreceptor 1, a toner image corresponding to the electrostatic latent image is formed on the photosensitive surface of the electrophotographic photoreceptor 1. This toner image is transferred onto the recording paper P by the transfer device 5. Thereafter, the toner remaining on the photosensitive surface of the electrophotographic photosensitive member 1 without being transferred is removed by the cleaning device 6.

  After the transfer of the toner image onto the recording paper P, the final image is obtained by passing the fixing device 7 and thermally fixing the toner image onto the recording paper P.

  In addition to the above-described configuration, the image forming apparatus may be configured to perform, for example, a static elimination process. The neutralization step is a step of neutralizing the electrophotographic photosensitive member by exposing the electrophotographic photosensitive member, and a fluorescent lamp, an LED, or the like is used as the neutralizing device. In addition, the light used in the static elimination process is often light having an exposure energy that is at least three times that of the exposure light.

  The image forming apparatus may be further modified. For example, the image forming apparatus may be configured to perform a pre-exposure process, an auxiliary charging process, or the like, or may be configured to perform offset printing. A full-color tandem system configuration using toner may be used.

  However, an image forming apparatus using reversal development is particularly effective in the characteristics of the photoreceptor of the present invention.

  In this embodiment, the electrophotographic photosensitive member cartridge of the present invention has been described by exemplifying the photosensitive member cartridge including the electrophotographic photosensitive member 1 and the charging device 2. However, the electrophotographic photosensitive member cartridge of the present invention is electrophotographic. The photosensitive member 1 may be provided with at least one of a charging device (charging unit) 2, an exposure device (exposure unit) 3, and a developing device (developing unit) 4. Specifically, for example, the electrophotographic photosensitive member cartridge of the present invention includes all of the electrophotographic photosensitive member 1, the charging device (charging unit) 2, the exposure device (exposure unit) 3, and the developing device (developing unit) 4. You may comprise as a cartridge.

  Hereinafter, the present invention will be described in more detail with reference to production examples, examples and comparative examples. In addition, this invention is not limited to the Example shown here, In the range which does not deviate from the summary of this invention, it can change arbitrarily and can implement.

<Manufacture of charge transport materials>
(Production Example A: Composition 1)
In a 500 ml four-necked flask under nitrogen atmosphere, 200 ml of xylene, 40.6 g of 4,4′-diiodobiphenyl, 37.9 g of di (p-tolyl) amine, 1.9 g of diphenylamine, and sodium-tert-butoxide 21 0.1 g was added and 20 ml of a xylene solution containing 18 mg of palladium acetate and 64 mg of tri-tert-butylphosphine was added with stirring. Thereafter, the reactor was heated to 120 ° C. and continued to be heated at that temperature for 2 to 3 hours to be reacted. After completion of the reaction, the reaction mixture was cooled, and 200 ml of toluene and 200 ml of water were added for liquid separation. The organic layer was washed with 100 mL / time of water three times, dried over magnesium sulfate, and concentrated under reduced pressure. The obtained crude product was dissolved in 50 mL of a toluene / hexane (1/1) mixed solution, and then passed through column chromatography (silica gel 1 kg, developing solvent: toluene / hexane = 1/1) to give composition 1 Obtained (yield 38 g). From the results of LC and NMR, the molar ratio of the compounds represented by the general formulas (1) to (3) is (1) :( 2) :( 3) = 92.2: 7.7: 0.1. It turned out to be.

(Production Example B: Composition 11)
Composition 11 was obtained in the same manner as in Production Example A except that N-phenyl-N- (m-tolyl) amine was used instead of di (p-tolyl) amine (yield 35 g).

(Production Example C: Composition 6)
Composition 6 was obtained in the same manner as in Production Example A except that N-phenyl-N- (1-naphthyl) amine was used instead of diphenylamine (yield 36 g).

<Production of photoconductor>
Example 1
In X-ray diffraction, 10 parts by weight of A-type oxytitanium phthalocyanine having diffraction peaks at 9.3 °, 10.6 °, and 26.3 ° at a Bragg angle (2θ ± 0.2) of In addition to -2-pentanone (150 parts by weight), pulverization and dispersion treatment was performed for 1 hour in a sand grind mill.

  After the pulverization and dispersion treatment, 100 parts by weight of a 5% 1,2-dimethoxyethane solution of polyvinyl butyral (“Denka Butyral # 6000C” manufactured by Denki Kagaku Kogyo Co., Ltd.) as a binder resin and phenoxy resin (Union Carbide) A coating solution for a charge generation layer was prepared by adding 100 parts by weight of a 5 wt% 1,2-dimethoxyethane solution of “PKHH” manufactured by the company.

  This coating solution was anodized in an aqueous sulfuric acid solution to anodize the surface, and an aluminum tube having a diameter of 30 mm and a length of 254 mm subjected to low-temperature sealing at 90 ° C. in an aqueous nickel acetate solution (conductive support) The charge generation layer was formed by dip coating on the body) so that the film thickness after drying was 0.4 μm and drying.

  Separately, 1.40 parts by weight of the composition obtained in Production Example 1 as a charge transport material, and 1,1-bis (4-hydroxyphenyl) -1-phenylethane shown below as a binder resin as an aromatic diol component The repeating unit A comprising 49 mol% and 2,2-bis (4-hydroxy-3-methylphenyl) propane as an aromatic diol component comprises 51 mol%, and is derived from pt-butylphenol. 100 parts by weight of a polycarbonate resin having a terminal structure (viscosity average molecular weight 30,000) and 0.03 parts by weight of silicone oil as a leveling agent are dissolved in 640 parts by weight of a tetrahydrofuran / toluene (weight ratio 8/2) mixed solvent. Thus, a charge transport layer coating solution was prepared.

  The coating solution is dip-coated on the charge generation layer so that the film thickness after drying is 20 μm, and dried to form a charge transport layer, whereby an electrophotographic photosensitive member having a laminated photosensitive layer is obtained. Manufactured.

(Evaluation of electrophotographic photoreceptor)
An electrophotographic characteristic evaluation apparatus produced according to the standard of the Electrophotographic Society of the obtained electrophotographic photosensitive member ["Basics and Applications of Secondary Electrophotographic Technology" (Edited by the Electrophotographic Society, published by Corona, page 404-405) The electrical characteristics were evaluated by charging, exposure, potential measurement, and static elimination cycles, and the results are shown in Table 1.

(Evaluation of electrical characteristics)
When the charged surface of the photosensitive member is charged so that the initial surface potential becomes −700 V, and the light of the halogen lamp is irradiated with monochromatic light of 780 nm by the interference filter, the surface potential becomes − (minus) 350 V. Irradiation energy (μJ / cm ² ) was taken as sensitivity. Further, the residual potential Vr (−V) after irradiation was measured using LED light of 660 nm as the static elimination light.

(Evaluation of image characteristics)
When this electrophotographic photosensitive member was mounted on a laser printer manufactured by Hewlett-Packard Co., a laser jet 4 (LJ4) remodeling machine, and an image formation test for 10,000 sheets was performed, image defects and noise were observed after the 10,000 sheets were formed. A good image with no image was obtained. Subsequently, 10,000 sheets were continuously printed, but no image deterioration such as memory and fog was observed, and the image density was good and stable. These results are shown in Table 1. In Table 1, “◯” means “cannot be confirmed”, “Δ” means “barely recognized”, and “x” means “clearly recognized”.

(Example 2)
An electrophotographic photoreceptor was produced and evaluated in the same manner as in Example 1 except that the composition 11 obtained in Production Example B was used in place of the composition 1 obtained in Production Example A. The results are shown in Table 1.

(Example 3)
An electrophotographic photoreceptor was produced and evaluated in the same manner as in Example 1 except that the composition 6 obtained in Production Example C was used in place of the composition 1 obtained in Production Example A. The results are shown in Table 1.

(Comparative Example 1)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the following compounds were used in place of the composition 1 obtained in Production Example A. The results are shown in Table 1.

(Comparative Example 2)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the following compounds were used in place of the composition 1 obtained in Production Example A. The results are shown in Table 1.

(Comparative Example 3)
Instead of the composition 1 obtained in Production Example A, an attempt was made to produce an electrophotographic photosensitive member in the same manner as in Example 1 except that the following compound was used. Could not be created.

(Comparative Example 4)
Instead of the composition 1 obtained in Production Example A, an attempt was made to produce an electrophotographic photosensitive member in the same manner as in Example 1 except that the following compound was used. Could not be created.

(Comparative Example 5)
It replaced with the composition 1 obtained by manufacture example A, and carried out similarly to Example 1 except having used the following composition (Compound 1: Compound 2: Compound 3 = 92.2: 7.7: 0.1). An electrophotographic photoreceptor was manufactured and evaluated. The results are shown in Table 1.

(Comparative Example 6)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the following compound was used instead of the exemplified compound 1 obtained in Production Example A. The results are shown in Table 1.

(Comparative Example 7)
An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the following compound was used instead of the exemplified compound 1 obtained in Production Example A. The results are shown in Table 1.

  As described above, the composition system of the present invention not only inhibits crystallization by mixing, but also obtains good results by mixing in electrical characteristics and image evaluation.

Example 4
The surface of a cylinder made of an aluminum alloy having an outer diameter of 30 mm, a length of 351 mm, and a wall thickness of 1.0 mm, which has a mirror-finished surface, is anodized and then sealed with a sealant mainly composed of nickel acetate. As a result, an anodic oxide coating (alumite coating) of about 6 μm was formed. This cylinder was dip-coated in the charge generation layer coating solution prepared in Example 1 to form a charge generation layer so that the film thickness after drying was about 0.4 μm. The charge generation layer coating liquid was highly uniform and could form a good charge generation layer without unevenness.

  Next, the cylinder on which this charge generation layer was formed was dip-coated in the charge transport layer coating solution prepared in Example 1, and the film thickness after drying was 18 μm, and there was no unevenness, twist, film thickness fluctuation, etc. A charge transport layer was formed. The photoreceptor thus obtained is referred to as a photoreceptor drum A.

(Comparative Example 8)
A photosensitive drum was prepared in the same manner as in Example 4 except that the polycarbonate resin was a polycarbonate resin composed of repeating units represented by the following formula. The obtained photosensitive drum is designated as B.

(Image evaluation by image forming device)
The photosensitive drums A and B are mounted on a cartridge of a commercially available laser printer (manufactured by Oki Data Corporation, ML9300), and 14,000 intermittent image formations are performed in an LL (5 ° C., 10% RH) environment. It was. A solid image and a memory confirmation image were printed every 1000 sheets printed from the beginning of image formation.

  To evaluate the fog on the drum, apply a cellophane tape on the surface of the photoconductive drum after printing a solid white image, and apply it so that there are no air bubbles between the tape and the photoconductive drum. Put on. Next, the density | concentration was measured for the affixed tape using the Macbeth densitometer (Macbeth company make, RD920). This difference was defined as a fog value on the drum.

  For the fog value on the drum, the above operation was performed every 1000 sheets printed from the initial stage of image formation, and this operation was performed until after 14,000 sheets were printed.

  The evaluation of the memory image is performed by measuring the density (hereinafter referred to as H1) after forming the halftone image, and then the memory confirmation image (the black solid circle is at the top of the image and the background is the halftone). The density at the drum cycle (94.2 mm) position (hereinafter referred to as H2) was measured using the black solid circle as the starting point, and the absolute value of the difference between H1 and H2 was used as the memory value. Similarly to the fogging value, the memory value was measured from the initial image formation until every 1000 sheets were printed and after a maximum of 14,000 sheets were printed. The larger the fog value and the memory value, the worse the image. Further, when the numerical value (difference between H1 and H2) shown here exceeds 0.05, it can be recognized as a visually apparent difference. Further, when evaluating the fog value and the memory value, the following polymerized toner was used.

(Method for producing polymerized toner)
1000 parts by weight of a cyan base toner mainly composed of a styrene-acrylic acid-n-butyl acrylate copolymer (peak molecular weight of 30,000) produced by an emulsion polymerization aggregation method, and silica 1 ( 20 parts by weight of hexamethyldisilazane treatment (primary particle size of about 30 nm) and 5 parts by weight of silica 2 (dimethylpolysiloxane treatment, about 7 nm of primary particle size) were added to a Mitsui Mining Co., Ltd. Henschel mixer. Were mixed to prepare a toner for this evaluation. The results are shown in Tables 2 and 3.

  The present invention can be carried out in any field that requires an electrophotographic photosensitive member, and is suitable for use in, for example, a copying machine, a printer, a printing machine, and the like.

1 is a schematic diagram illustrating a main configuration of an embodiment of an image forming apparatus of the present invention.

Explanation of symbols

1 Photoconductor (Electrophotographic photoconductor)
2 Charging device (charging roller; charging unit)
3 Exposure equipment (exposure section)
4 Development device (development unit)
DESCRIPTION OF SYMBOLS 5 Transfer device 6 Cleaning device 7 Fixing device 41 Developing tank 42 Agitator 43 Supply roller 44 Developing roller 45 Restriction member 71 Upper fixing member (pressure roller)
72 Lower fixing member (fixing roller)
73 Heating device T Toner P Recording paper (paper, medium)

Claims (4)

A layer having a composition containing at least a compound represented by the general formula (1), a compound represented by the general formula (2), and a compound represented by the general formula (3) is provided. An electrophotographic photoreceptor.

(In General Formulas (1) to (3), Ar ¹ and Ar ² represent an arylene group which may have a substituent, Ar ³ represents an aryl group having a substituent, and Ar ⁴ represents a substituent. Represents an aryl group which may have, Ar ⁵ and Ar ⁶ represent an aryl group.) 2. The electrophotographic photosensitive member according to claim 1, wherein Ar ³ in the general formulas (1) to (2) is a p-tolyl group.   The electrophotographic photosensitive member according to claim 1, a charging unit that charges the electrophotographic photosensitive member, an exposure unit that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image, and An electrophotographic photosensitive member cartridge comprising: at least one developing unit that develops an electrostatic latent image formed on the electrophotographic photosensitive member. 3. The electrophotographic photosensitive member according to claim 1; a charging unit that charges the electrophotographic photosensitive member; and an exposure unit that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image; An image forming apparatus comprising: a developing unit that develops an electrostatic latent image formed on the electrophotographic photosensitive member.

Images