JP6354239B2 - Electrophotographic photosensitive member, electrophotographic photosensitive member cartridge, and image forming apparatus - Google Patents

Description

The present invention relates to an electrophotographic photosensitive member, an image forming apparatus, and a cartridge used for a copying machine, a printer, and the like. More specifically, in the electrophotographic photosensitive member provided as a photosensitive layer by laminating at least a charge generation layer and a charge transport layer, the charge transport layer contains a polyarylate resin, and the charge generation layer has a polyvinyl acetal structure. A resin having a vinyl chloride-vinyl acetate copolymer structure and a resin having a vinyl chloride-vinyl acetate copolymer structure and a resin having a vinyl chloride-vinyl acetate copolymer structure in a specific ratio. The present invention relates to a technique for improving the adhesion of a photosensitive layer, and also relates to an electrophotographic photosensitive member, a cartridge, and an image forming apparatus which are provided with excellent mechanical characteristics.

  The electrophotographic technique is widely used in the fields of copiers, various printers, printing presses and the like because of its excellent immediacy and high quality images. As an electrophotographic photosensitive member that is the core of the electrophotographic technology, an electrophotographic photosensitive member using an organic photoconductive material having advantages such as non-pollution, easy film formation, and easy manufacture (hereinafter simply referred to as “ Also referred to as “photoreceptor”).

  As an electrophotographic photoreceptor using an organic photoconductive material, a so-called dispersion type single-layer photoreceptor in which a photoconductive fine powder is dispersed in a binder resin, a charge generation layer and a charge transport layer are laminated. Multilayer photoreceptors are known. In particular, the multi-layer photoreceptor can obtain charge generating materials with high efficiency and a wide and highly safe photoreceptor, and can be easily formed by coating, has high productivity, and is advantageous in terms of cost. For these reasons, they have been developed and put into practical use.

  In recent years, there has been an increasing demand for further miniaturization of image forming apparatuses from the viewpoint of space saving. In this case, in order to reduce the size of the image forming apparatus, a small-diameter type such as 24 mmφ or 30 mmφ is used as the photoreceptor. As the diameter of the photosensitive member is reduced, the internal stress in the photosensitive layer increases, and as a result, the adhesiveness between the support and the photosensitive layer is deteriorated, and defects such as peeling and cracking are likely to occur. In addition, when the photosensitive layer is made thicker to extend the life of the photoreceptor, the internal stress increases and the adhesiveness deteriorates. In other words, today's electrophotographic photoreceptors are better in addition to the abrasion resistance, which has been cited as the main improvement problem of the mechanical properties of electrophotographic photoreceptors, in addition to the electrical characteristics of electrophotographic photoreceptors. Adhesiveness is required.

  By the way, as a conventional technique whose object is to provide an electrophotographic photosensitive member having high sensitivity and high repetitive stability, a resin having a vinyl chloride-vinyl acetate copolymer structure and a polyvinyl acetal structure in a specific ratio to the charge generation layer Although a technique using both of the resins having a viscosity is known (Patent Document 1), attention has not been paid to the problem of adhesiveness.

Japanese Patent Laid-Open No. 5-142802

In order to improve the durability of the photoreceptor, it is necessary to achieve both stabilization of electrical characteristics such as residual potential, sensitivity and chargeability, and improvement of mechanical characteristics such as wear resistance and adhesion to a conductive support. . In order to improve the adhesion between the conductive support and the photosensitive layer, it is necessary to improve the adhesion between the conductive support, the photosensitive layer, and the photosensitive layer that are in contact with each other. In the case of a sequentially laminated type photoreceptor, a charge generation layer exists between the conductive support or the undercoat layer and the charge transport layer, but a composite component derived from the resin that is a component of each layer and the photosensitive material. Due to physical properties, there may be a problem that sufficient adhesiveness cannot be secured in the case of a specific resin.

  In particular, when a polyarylate resin is used as the binder resin for the charge transport layer, although it has excellent mechanical properties such as wear resistance, it has a problem with respect to adhesion compared to other resins such as polycarbonate resin. .

  In the electrophotographic photosensitive member in which at least a charge generation layer and a charge transport layer are laminated in this order from the conductive support side as a photosensitive layer, the present invention includes a polyarylate resin in the charge transport layer, and The charge generation layer contains both a resin having a polyvinyl acetal structure and a resin having a vinyl chloride-vinyl acetate copolymer structure, and has a vinyl chloride-vinyl acetate copolymer structure for the resin having a polyvinyl acetal structure. It has been found that the adhesiveness is improved by setting the ratio to the resin to a specific ratio, and the present invention has been completed. That is, the gist of the present invention resides in the following five points.

(1) In an electrophotographic photosensitive member provided on a conductive support by laminating at least a charge generation layer and a charge transport layer as a photosensitive layer in this order from the conductive support side.
Containing a polyarylate resin in the charge transport layer, and
The charge generation layer contains at least both a resin having a polyvinyl acetal structure and a resin having a vinyl chloride-vinyl acetate copolymer structure,
The ratio of the resin having the vinyl chloride-vinyl acetate copolymer structure to 1 part by mass of the resin having the polyvinyl acetal structure is 0.01 parts by mass or more and 1.8 parts by mass or less. Photoconductor.

  (2) The electrophotographic photosensitive member according to (1), wherein the polyarylate resin is a polyarylate resin having a repeating structure represented by the following general formula [1].

(In the general formula [1], Ar ^{1 to} Ar ⁴ may be the same or different and each independently represents an arylene group which may have a substituent. X represents a single bond, an oxygen atom, sulfur. 2 represents a divalent organic residue having an atom, a structure represented by Formula [2], or a structure represented by Formula [3], wherein R ¹ and R ^{2 in} Formula [2] are each independently A hydrogen atom, an alkyl group, an aryl group, or a cycloalkylidene group formed by combining R ¹ and R ^2, and R ³ in the formula [3] represents an alkylene group, an arylene group, or a formula a group represented by [4], an alkylene group and ^{R 4} and ^{R 5} are each independently of the formula [4], .k Ar ⁵ is representative of the arylene group is an integer of 0-5. Y has a single bond, a sulfur atom, an oxygen atom, or a structure represented by the formula [5]. That represents a divalent organic residue. Equation [5] R ⁶ and R ⁷ in each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or R ⁶ and R ⁷ and is formed by combining Represents a cycloalkylidene group.)

(3) The electrophotographic photosensitive member according to (1) or (2), wherein the charge generation layer contains a phthalocyanine pigment as a charge generation material.
(4) The electrophotographic photosensitive member according to any one of (1) to (3), a charging unit for charging the electrophotographic photosensitive member, and exposing the charged electrophotographic photosensitive member to form an electrostatic latent image. An electron comprising: an exposure part to be formed; a developing part for developing an electrostatic latent image formed on the electrophotographic photosensitive member; and a cleaning part for cleaning the electrophotographic photosensitive member. Photoconductor cartridge.

  (5) The electrophotographic photosensitive member according to any one of (1) to (3), a charging unit for charging the electrophotographic photosensitive member, and exposing the charged electrophotographic photosensitive member to form an electrostatic latent image. An image forming apparatus comprising: an exposure portion to be formed; and a developing portion for developing an electrostatic latent image formed on the electrophotographic photosensitive member.

According to the present invention, the ratio of the resin having a vinyl chloride-vinyl acetate copolymer structure to the resin having a polyvinyl acetal structure contained in the charge generation layer is 0.01 or more and 1.8 or less. It was revealed that the improvement and the stability of the charge generation layer coating solution were good. This ratio is completely different from the quantitative relationship of a resin having a vinyl chloride-vinyl acetate copolymer structure to a resin having a polyvinyl acetal structure known from the prior art.

  The effect of improving the adhesion is particularly remarkable when a polyarylate resin is used in the charge transport layer, because the vinyl chloride-vinyl acetate copolymer is added to the resin having a polyvinyl acetal structure of the charge generation layer. It is considered that by adding a resin having a combined structure at a specific ratio, the compatibility of the charge transport layer with the polyarylate resin is increased, and the adhesive force between both layers is effectively increased.

1 is a schematic diagram illustrating a main configuration of an embodiment of an image forming apparatus of the present invention. The powder X-ray-diffraction spectrum by CuK (alpha) characteristic X-ray of the oxytitanium phthalocyanine used in Example 1 is shown.

Hereinafter, the embodiments of the present invention will be described in detail. However, the present invention is not limited to the following descriptions, and can be appropriately modified and implemented without departing from the gist of the present invention.
[Electrophotographic photoreceptor]
Hereinafter, the electrophotographic photoreceptor of the present invention will be described in detail.

<Conductive support>
As the conductive support used for the photoreceptor, for example, metal materials such as aluminum, aluminum alloy, stainless steel, copper, and nickel, and conductive powders such as metal, carbon, and tin oxide are added to impart conductivity. A resin material, a resin, glass, paper, or the like on which a conductive material such as aluminum, nickel, or ITO (indium tin oxide) is deposited or applied on the surface is mainly used. As a form, a drum shape, a sheet shape, a belt shape or the like is used. A conductive material having an appropriate resistance value may be applied to a conductive support of a metal material in order to control conductivity, surface properties, etc., or to cover defects.

When a metal material such as an aluminum alloy is used as the conductive support, it is preferable to use an anodized film as a blocking layer in order to prevent image black spots and fogging due to leakage from the substrate. When an anodized film is applied, it is desirable to perform a sealing treatment by a known method.
The support surface may be smooth, or may be roughened by using a special cutting method or polishing. Further, it may be roughened by mixing particles having an appropriate particle diameter with the material constituting the support.

<Underlayer>
It is also preferable to provide an undercoat layer as a blocking layer between the conductive support and the photosensitive layer described later in order to improve adhesion and blocking properties. As the undercoat layer, a resin, a resin in which particles such as a metal oxide are dispersed, or the like is used. These may be used alone or in combination with particles of several resins, metal oxides and the like.

  Examples of 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, titanium Examples thereof include metal oxide particles containing a plurality of metal elements such as strontium acid and barium titanate. One kind of these particles may be used alone, or a plurality of kinds of particles may be mixed and used. 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 treated 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 silicon. As the crystal form of the titanium oxide particles, any of rutile, anatase, brookite, and amorphous can be used. Moreover, the thing of a several crystal state may be contained.

In addition, various particle sizes of the metal oxide particles can be used. Among these, from the viewpoint of characteristics and liquid stability, the average primary particle size is usually 1 nm or more, preferably 10 nm or more, and usually 100 nm or less. Preferably it is 50 nm or less.
The undercoat layer is preferably formed in a form in which metal oxide particles are dispersed in a binder resin. As binder resin used for the undercoat layer, epoxy resin, polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, Known binder resins such as polyimide resin, vinylidene chloride resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, polyurethane resin, polyacrylic acid resin and the like can be mentioned. These may be used alone or in combination of two or more in any combination and ratio. Moreover, you may use with the hardening | curing form with the hardening | curing agent. Among these, alcohol-soluble copolymerized polyamides, modified polyamides, and the like are preferable because they exhibit good dispersibility and coatability.

Although the use ratio of the inorganic particles to the resin can be arbitrarily selected, it is usually preferably used in the range of 10% by mass or more and 500% by mass or less from the viewpoint of the stability of the dispersion and coating properties.
The thickness of the undercoat layer is arbitrary as long as the effects of the present invention are not significantly impaired, but the viewpoint of improving the electrical characteristics, strong exposure characteristics, image characteristics, repeat characteristics, and coating properties during production of the electrophotographic photosensitive member. Therefore, it is usually 0.01 μm or more, preferably 0.1 μm or more, more preferably 0.25 μm or more, further preferably 0.5 μm or more, and particularly preferably 0.75 μm or more. Moreover, it is 30 micrometers or less normally, Preferably it is 20 micrometers or less. A known antioxidant or the like may be mixed in the undercoat layer. The undercoat layer may contain pigment particles, resin particles and the like for the purpose of preventing image defects.

<Photosensitive layer>
When the photosensitive layer has a blocking layer such as the above-described undercoat layer on the conductive support, it is formed thereon. The photosensitive layer of the present invention is composed of two or more layers including a charge generation layer in which a charge generation material is dispersed in a binder resin and a charge transport layer in which a charge transport material is dispersed in a binder resin. This is a layer-separated function-separated type (hereinafter referred to as “laminated photosensitive layer” as appropriate). Among them, a “normally laminated photosensitive layer” in which a charge generation layer and a charge transport layer are laminated in this order from the conductive support side. "Layer" is adopted. A “sequentially laminated photosensitive layer” can exhibit balanced photoconductivity.

<Charge generation layer>
<Binder resin>
In the present invention, the binder resin used for the charge generation layer contains at least both a resin having a polyvinyl acetal structure and a resin having a vinyl chloride-vinyl acetate copolymer structure. Specifically, a resin having a polyvinyl acetal structure and a resin having a vinyl chloride-vinyl acetate copolymer structure are mixed and used.

  A resin having a polyvinyl acetal structure is a resin having a condensation structure of vinyl alcohol and aldehyde, and is a partially acetalized polyvinyl butyral in which a part of polyvinyl butyral resin, polyvinyl formal resin or butyral is modified with formal or acetal, etc. Including resin. For example, each brand such as BL-1, BL-5, BX-L, BM-1, BM-5, BH-3, BX-1, BX-5 of S REC B series made by Sekisui Chemical Co., Ltd. Each brand such as KS-1 and KS-5 of S-LEK K series, each brand such as Mobital B16H, B30T, B45M, B60T, B60H, B60HH, B75H, LP BX860 manufactured by Kuraray Co., Ltd. Various types of polyvinyl acetal resins from commercial companies such as Denkabu Chiral # 3000-1, # 3000-4, # 4000-2, # 5000-A, # 6000-C, # 6000-AS, etc. it can. Among them, as the acetal structure, a polyvinyl acetal resin having a condensed structure with acetaldehyde or a condensed structure with butyraldehyde is preferable, and it has both a condensed structure with acetaldehyde and a condensed structure with butyraldehyde. Further preferred.

In addition, as a resin having a polyvinyl acetal structure, a suitable quantitative ratio exists for the acetal structure and the remaining hydroxyl groups. The ratio of the acetal structure such as the acetaldehyde condensed structure and the butyraldehyde condensed structure to the whole resin having the polyvinyl acetal structure is at least 60 mol%, preferably 63 mol%, at most 80 mol%, preferably 77 mol% or less. It is. Further, the ratio of the remaining hydroxyl group to the entire resin having a polyvinyl acetal structure is at least 17 mol% or more, preferably 20 mol% or more, at most 40 mol% or less, preferably 37 mol% or less. If the quantity ratio of the acetal structure such as acetaldehyde condensation structure or butyraldehyde condensation structure is too small and the hydroxyl group quantity ratio is too large, the solubility of the resin component itself becomes poor, and the acetal structure such as acetaldehyde condensation structure or butyraldehyde condensation structure If the amount ratio is too large and the amount ratio of the hydroxyl group is too small, the stability of the coating solution deteriorates.

  Examples of the resin having a vinyl chloride-vinyl acetate copolymer structure include vinyl chloride-vinyl acetate copolymer, hydroxy-modified vinyl chloride-vinyl acetate copolymer, carboxyl-modified vinyl chloride-vinyl acetate copolymer, etc. And vinyl acetate copolymer. For example, commercially available chlorides such as Dow Chemical's VMCH, VMCC, VAGH, VAGF, etc., Nissin Chemical Industry's Solveine A, Solvein AL, Solvein C, Solvein TA2, Solvein TAO, Solvein M5, etc. A vinyl-vinyl acetate copolymer can be used. In particular, in the present invention, a copolymer having a vinyl chloride / vinyl acetate polymerization ratio of 50/50 or more and 95/5 or less is preferably used.

In addition to vinyl chloride and vinyl acetate, a third component may be included, and examples include vinyl alcohol, maleic acid, maleic anhydride, and the like. Examples of the composition of the vinyl chloride-vinyl acetate polymer containing the third component include vinyl chloride-vinyl acetate-vinyl alcohol copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, vinyl chloride-vinyl acetate. -Vinyl alcohol-maleic anhydride copolymer, vinyl chloride-vinyl acetate-maleic acid-maleic anhydride copolymer, vinyl chloride-vinyl acetate-vinyl alcohol-maleic acid-maleic anhydride copolymer, and the like. The ratio of the third component other than vinyl chloride and vinyl acetate is preferably 10% by mass or less based on the entire copolymer. The molecular weight of the vinyl chloride-vinyl acetate copolymer used is preferably in the range of 3,000 to 80,000.

  The use ratio of the resin having a vinyl chloride-vinyl acetate copolymer structure in the present invention to 1 part by mass of the resin having a polyvinyl acetal structure is 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably. 0.2 parts by mass or more. When this ratio is too small, the effect of improving adhesiveness cannot be sufficiently exhibited. On the other hand, the maximum use ratio is 1.8 parts by mass or less, preferably 1.5 parts by mass or less, and more preferably 1.0 parts by mass or less. When this ratio is too large, the stability of the coating solution for charge generation layer is poor, and there is a problem in practical use.

  As binder resins other than the above resins used for the charge generation layer, polyarylate resin, polycarbonate resin, polyester resin, modified ether-based polyester resin, phenoxy resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin , Polystyrene resin, acrylic resin, methacrylic resin, polyacrylamide resin, polyamide resin, polyvinyl pyridine resin, cellulosic resin, polyurethane resin, epoxy resin, silicone resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, casein and hydroxy-modified vinyl chloride Vinyl acetate copolymer, carboxyl-modified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer such as vinyl chloride-vinyl acetate-maleic anhydride copolymer, styrene-butadiene Insulating resins such as copolymers, vinylidene chloride-acrylonitrile copolymers, styrene-alkyd resins, silicon-alkyd resins, phenol-formaldehyde resins, and organic photoconductive materials such as poly-N-vinylcarbazole, polyvinyl anthracene, and polyvinyl perylene. Can be selected and used in combination. These binder resins may be used alone or in combination of two or more.

  The total amount of the resin having the polyvinyl acetal structure of the present invention and the resin having a vinyl chloride-vinyl acetate copolymer structure in the binder resin is at least 70% by mass, preferably 100% by mass. This is preferable.

<Charge generating material>
The charge generating material may be used alone or in a mixed state with several dyes and pigments.
Examples of the charge generation material include inorganic photoconductive materials such as selenium and its alloys, cadmium sulfide, and organic photoconductive materials such as organic pigments. Organic photoconductive materials are preferred, and organic photoconductive materials are particularly preferable. Pigments are preferred. Examples of organic pigments include phthalocyanine pigments, azo pigments, dithioketopyrrolopyrrole pigments, squalene (squarylium) pigments, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, anthanthrone pigments, and benzimidazole pigments. . Among these, phthalocyanine pigments or azo pigments are particularly preferable as dyes used in the mixed state from the viewpoint of photosensitivity. When organic pigments are used as the charge generation material, usually, fine particles of these organic pigments are used in the form of a dispersion layer bound by the binder resin.

  When a phthalocyanine pigment is used as the charge generation material, specifically, metal-free phthalocyanine and metal-containing phthalocyanine are used. Specific examples of metal-containing phthalocyanines include metals such as copper, indium, gallium, tin, titanium, zinc, vanadium, silicon, germanium, or their oxides, halides, hydroxides, alkoxides, and the like. Various crystal forms of phthalocyanines are used. In particular, oxytitanium phthalocyanines such as A type (also known as β type), B type (also known as α type), and D type (also known as Y type), which are highly sensitive crystal types, chloro such as vanadyl phthalocyanine, chloroindium phthalocyanine, and type II Preferable use is gallium phthalocyanine, hydroxygallium phthalocyanine such as V type, μ-oxo-gallium phthalocyanine dimer such as G type and I type, μ-oxo-aluminum phthalocyanine dimer such as type II, and metal-free phthalocyanine It is done.

  Among these phthalocyanines, A type (β type), B type (α type), D type (Y type) oxytitanium phthalocyanine, II type chlorogallium phthalocyanine, V type hydroxygallium phthalocyanine, G type μ-oxo- Gallium phthalocyanine dimer and the like are preferable. Particularly, oxytitanium phthalocyanine is preferably D-type (Y-type) having a clear diffraction peak mainly at a Bragg angle (2θ ± 0.2 °) of 27.2 ° in a powder X-ray diffraction spectrum by CuKα characteristic X-ray. .

These crystalline forms are mainly produced by crystal conversion from amorphous or low crystalline oxytitanium phthalocyanine. These crystal types are metastable crystal types, exhibit various crystal types and particle shapes depending on the manufacturing method, and have characteristics as an electrophotographic photosensitive member such as charge generation ability, charging property, and dark decay. It is known to depend on
As a method for producing the aforementioned D-type (Y-type) oxytitanium phthalocyanine, an amorphous oxytitanium phthalocyanine or a low crystalline oxytitanium phthalocyanine is obtained by chemical treatment or mechanical grinding treatment of a phthalocyanine crystal precursor, Obtained upon contact with an organic solvent.

  The chemical treatment is a treatment method for adjusting amorphous or low crystalline oxytitanium phthalocyanine using chemical phenomena such as dissolution and reaction. On the other hand, when an azo pigment is used as a charge generation material, various known azo pigments can be used as long as they have sensitivity to a light source for light input. Trisazo pigments are preferably used.

  When a metal-free phthalocyanine compound or a metal-containing phthalocyanine compound is used as the charge generation material, a highly sensitive photoreceptor can be obtained with respect to a laser beam having a relatively long wavelength, for example, a laser beam having a wavelength around 780 nm. Further, when an azo pigment such as monoazo, diazo, or trisazo is used, white light, laser light having a wavelength around 660 nm, or laser light having a relatively short wavelength (for example, a wavelength in the range of 380 nm to 500 nm). It is possible to obtain a photoreceptor having sufficient sensitivity to the laser beam).

  When the organic pigments exemplified above are used as the charge generation material, one kind may be used alone, or two or more kinds of pigments may be mixed and used. In this case, as described above, by using a combination of two or more types of charge generating materials having spectral sensitivity characteristics in different spectral regions in the visible region and the near red region, the spectral sensitivity in different spectral regions in the visible region and the near red region is used. It is possible to have characteristics, which is preferable.

<Formation method>
Specifically, the charge generation layer in the functional separation type photoconductor is prepared by dissolving the binder resin in a solvent and dispersing the charge generation material and the metal complex or metal salt of the aromatic carboxylic acid described above to prepare a coating solution. And it forms by apply | coating this on an electroconductive support body (when providing an undercoat layer on an undercoat layer).

  Solvents used for the preparation of coating solutions and dispersion media for dissolving the binder resin include, for example, saturated aliphatic solvents such as pentane, hexane, octane and nonane, aromatic solvents such as toluene, xylene and anisole, chlorobenzene, Halogenated aromatic solvents such as dichlorobenzene and chloronaphthalene, amide solvents such as dimethylformamide and N-methyl-2-pyrrolidone, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol and benzyl alcohol, glycerin, Aliphatic polyhydric alcohols such as polyethylene glycol, chain solvents such as acetone, cyclohexanone, methyl ethyl ketone, and cyclic ketone solvents, ester solvents such as methyl formate, ethyl acetate, n-butyl acetate, methylene chloride, chloroform, 1, 2-Dichro Halogenated hydrocarbon solvents such as ethane, linear ether solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, 1,4-dioxane, methylcellosolve, ethylcellosolve, acetonitrile, dimethylsulfoxide, sulfolane, hexa Examples include aprotic polar solvents such as methyl phosphate triamide, and those that do not dissolve the undercoat layer described above are preferably used. These can be used alone or in combination of two or more.

  In the charge generation layer of the function-separated type photoreceptor, the compounding ratio (mass) of the binder resin and the charge generation material is 10 parts by mass or more, preferably 30 parts by mass or more, 1000 masses with respect to 100 parts by mass of the binder resin. The film thickness is usually 0.1 μm to 10 μm, preferably 0.15 μm to 0.6 μm. If the ratio of the charge generation material is too high, the stability of the coating solution may be reduced due to aggregation of the charge generation material. On the other hand, if the ratio of the charge generating substance is too low, the sensitivity as a photoreceptor may be reduced.

  As a method for dispersing the charge generation material, a known dispersion method such as a ball mill dispersion method, an attritor dispersion method, or a sand mill dispersion method can be used. In this case, it is effective to refine the particles to a particle size of 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less.

<Charge transport layer>
<Binder resin>
For the charge transport layer, a binder resin is used to ensure film strength. The charge transport layer can be obtained by applying and drying a coating solution obtained by dissolving or dispersing a charge transport material and various binder resins in a solvent.

  Polyarylate resin is contained as a binder resin. As the polyarylate resin used here, a resin containing a repeating structure represented by the following general formula [1] is particularly preferable. The polyarylate resin can be produced by a known method, for example, with a divalent hydroxyaryl component and a dicarboxylic acid component.

In the general formula [1], Ar ^{1 to} Ar ⁴ may be the same or different, and each independently represents an arylene group which may have a substituent. The arylene group is not particularly limited, but is preferably an arylene group having 6 to 20 carbon atoms, and examples thereof include a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, and a pyrenylene group. Among these, a phenylene group and a naphthylene group are particularly preferable from the viewpoint of production cost. Further, when a phenylene group and a naphthylene group are compared, a phenylene group is more preferable in terms of ease of synthesis in addition to manufacturing cost.

The substituent that may be independently present in the arylene group is not particularly limited, and preferred examples include a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a condensed polycyclic group, and a halogen group. Considering the mechanical properties as the binder resin for the photosensitive layer and the solubility in the coating solution for forming the photosensitive layer, the aryl group is preferably a phenyl group or a naphthyl group, and the halogen group is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The alkoxy group is preferably a methoxy group, an ethoxy group, or a butoxy group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and 1 to 2 carbon atoms. Are particularly preferable, and specifically, a methyl group is most preferable. The number of substituents for each of Ar ^{1 to} Ar ⁴ is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and particularly preferably 1 or less.

Further, in the general formula [1], Ar ¹ and Ar ² are preferably the same arylene group having the same substituent, and particularly preferably an unsubstituted phenylene group. Ar ³ and Ar ⁴ are preferably the same arylene group, and particularly preferably a phenylene group having a methyl group.

In General Formula [1], X represents a divalent organic residue having a single bond, an oxygen atom, a sulfur atom, a structure represented by Formula [2], or a structure represented by Formula [3]. R ¹ and R ² in the formula [2] each independently represent a hydrogen atom, an alkyl group, or an aryl group, or a cycloalkylidene group formed by combining R ¹ and R ² . Examples of the alkyl group of R ¹ and R ² in the formula [2] include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the aryl group include a phenyl group and a naphthyl group. In addition, examples of the cycloalkylidene group formed by combining R ¹ and R ² in the formula [2] include a cyclopentylidene group, a cyclohexylidene group, and a cycloheptylidene group. Furthermore, R ³ in the formula [3] is an alkylene group, an arylene group, or a group represented by the formula [4], and R ⁴ and R ⁵ in the formula [4] are each independently an alkylene group. And Ar ⁵ represents an arylene group. Examples of the alkylene group represented by R ³ in the formula [3] include a methylene group, an ethylene group, and a propylene group. Examples of the arylene group represented by R ³ in the formula [3] include a phenylene group and a terphenylene group. It is done. Specific examples of the group represented by the formula [4] include a group represented by the following formula [6]. Among these, X is preferably an oxygen atom from the viewpoint of wear resistance.

In general formula [1], k is an integer of 0 to 5, preferably an integer of 0 to 1, and most preferably 1 from the viewpoint of wear resistance.
In general formula [1], Y represents a single bond, a sulfur atom, an oxygen atom, or a divalent organic residue having a structure represented by formula [5]. R ⁶ and R ⁷ in the formula [5] each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a cycloalkylidene group formed by combining R ⁶ and R ⁷ . Considering the mechanical properties as the binder resin for the photosensitive layer and the solubility in the coating solution for forming the photosensitive layer, the aryl group is preferably a phenyl group or a naphthyl group, and the alkoxy group is preferably a methoxy group, an ethoxy group, or a butoxy group. preferable. Moreover, as an alkyl group, a C1-C10 alkyl group is preferable, More preferably, it is C1-C8, Most preferably, it is C1-2. Considering the simplicity of production of the divalent hydroxyaryl component used in producing the polyarylate resin, Y is a single bond, —O—, —S—, —CH ₂ —, —CH (CH ₃ ) —. , —C (CH ₃ ) ₂ — and cyclohexylidene are preferable, and —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ — and cyclohexylidene are particularly preferable. Is —CH ₂ —, —CH (CH ₃ ) —.

In the present invention, the polyarylate resin is preferably a polyarylate resin having a repeating structure represented by the following general formula [7]. In the following general formula [7], Ar ^{16 to} Ar ¹⁹ each independently represent an arylene group which may have a substituent, and R ⁸ represents a hydrogen atom or an alkyl group.

In the general formula [7], Ar ^{16 to} Ar ¹⁹ respectively correspond to the Ar ^{1 to} Ar ⁴ and particularly preferably a phenylene group which may have a substituent. Moreover, as a preferable substituent, it is a hydrogen atom or an alkyl group, Most preferably, it is a methyl group. Further, in the general formula [7], Ar ¹⁸ and Ar ¹⁹ are the same phenylene group having a methyl group, and Ar ¹⁶ and Ar ¹⁷ are particularly preferably phenylene groups having no substituent. R ⁸ represents a hydrogen atom or an alkyl group, and the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably a methyl group. .

  The divalent hydroxyaryl component to be a divalent hydroxyaryl residue in the polyarylate resin is represented by the following general formula [8], but is preferably represented by the following general formula [9].

Ar ³ , Ar ⁴ and Y in the general formula [8] are as described above.

Ar ¹⁸ and Ar ¹⁹ in the general formula [9] independently represent a phenylene group which may have a substituent, and R ⁸ represents a hydrogen atom or a methyl group.
Among these, when R ⁸ in the general formula [9] is a hydrogen atom, bis (4-hydroxyphenyl) methane and (2-hydroxyphenyl) are considered in consideration of the ease of production of the divalent hydroxyaryl component. ) (4-hydroxyphenyl) methane, bis (2-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) methane, bis (4-hydroxy-3-ethylphenyl) methane are preferred, It is also possible to use a combination of a plurality of hydroxyaryl components.

In addition, when R ⁸ in the general formula [9] is a methyl group, 1,1-bis (4-hydroxyphenyl) ethane, 1- (2-hydroxyphenyl) -1- (4-hydroxyphenyl) ethane 1,1-bis (2-hydroxyphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 1,1-bis (4-hydroxy-3-ethylphenyl) ethane are preferred, A combination of a plurality of these divalent hydroxyaryl components can also be used.

  Although the general formula [9] is included in the general formula [8], the divalent hydroxyaryl component represented by the general formula [8] is bis (4-hydroxy-3, 5-dimethylphenyl) methane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, or bis (4 -Hydroxyphenyl) ether, (2-hydroxyphenyl) (4-hydroxyphenyl) ether, bis (2-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, bis (4-hydroxy-3-) Ethylphenyl) ether is preferred, and a combination of a plurality of these divalent hydroxyaryl components can be used.

  The dicarboxylic acid component which is a dicarboxylic acid residue in the polyarylate resin is represented by the following general formula [10].

Ar ¹ , Ar ² , X, and k in the general formula [10] are as described above, and are preferably represented by the following general formula [11].

Ar ¹⁶ and Ar ¹⁷ in the general formula [11] are also as described above, and are preferably phenylene groups which may have a substituent.
Specific examples of the preferred dicarboxylic acid residue include diphenyl ether-2,2′-dicarboxylic acid residue, diphenyl ether-2,3′-dicarboxylic acid residue, diphenyl ether-
Examples include 2,4′-dicarboxylic acid residue, diphenyl ether-3,3′-dicarboxylic acid residue, diphenyl ether-3,4′-dicarboxylic acid residue, diphenyl ether-4,4′-dicarboxylic acid residue. Among these, considering the simplicity of production of the dicarboxylic acid component, diphenyl ether-2,2′-dicarboxylic acid residue, diphenyl ether-2,4′-dicarboxylic acid residue, diphenyl ether-4,4′-dicarboxylic acid Residues are more preferred, and diphenyl ether-4,4′-dicarboxylic acid residues are particularly preferred.

The viscosity average molecular weight of the polyarylate resin is not particularly limited, but is usually 10,000 or more, preferably 15,000 or more, more preferably 20,000 or more, but usually 300,000 or less, preferably 200, 000 or less, more preferably 100,000 or less. If the viscosity average molecular weight is excessively small, the mechanical strength of the photosensitive layer is lowered, which is not practical. On the other hand, if the viscosity average molecular weight is excessively large, it is difficult to apply and form the photosensitive layer to an appropriate film thickness.

  Polyarylate resin is used as the binder resin, but other resins can be blended and used. Examples of resins that can be used in combination include polymers and copolymers of vinyl compounds such as butadiene resins, styrene resins, vinyl acetate resins, vinyl chloride resins, acrylic ester resins, methacrylic ester resins, vinyl alcohol resins, and ethyl vinyl ethers. , Polyvinyl butyral resin, polyvinyl formal resin, partially modified polyvinyl acetal, polycarbonate resin, polyester resin, polyamide resin, polyurethane resin, cellulose ester resin, phenoxy resin, silicone resin, silicon-alkyd resin, poly-N-vinylcarbazole resin, etc. Polycarbonate resin is particularly preferable. These resins may be modified with a silicon reagent or the like. These can also be used by crosslinking with an appropriate curing agent by heat, light or the like.

<Charge transport material>
The charge transport material is not particularly limited, and any material can be used. Examples of known charge transport materials include aromatic nitro compounds such as 2,4,7-trinitrofluorenone, cyano compounds such as tetracyanoquinodimethane, electron withdrawing materials such as quinone compounds such as diphenoquinone, and carbazole derivatives. , Indole derivatives, imidazole derivatives, oxazole derivatives, pyrazole derivatives, thiadiazole derivatives, heterocyclic compounds such as benzofuran derivatives, aniline derivatives, hydrazone derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine derivatives, and a plurality of these compounds Examples thereof include an electron donating substance such as a polymer in which a species is bonded, or a polymer having a group composed of these compounds in the main chain or side chain. Among these, carbazole derivatives, aromatic amine derivatives, stilbene derivatives, butadiene derivatives, enamine derivatives, and those in which a plurality of these compounds are bonded are preferable.

Any one of these charge transport materials may be used alone, or two or more thereof may be used in any combination.
Preferred specific examples of the charge transport material are shown below. In the following compounds, R represents the same or different substituents. Specifically, a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group, an arylalkyl and the like are preferable. Particularly preferred is a methyl group, an ethyl group or a benzyl group. N is an integer of 0 or more and 2 or less.

  The following exemplary compounds are specific examples of charge transport materials that can be used, and are not limited thereto.

<Formation method>
The ratio of the binder resin to the charge transport material is usually 10 parts by mass or more with respect to 100 parts by mass of the binder resin, and preferably 30 parts by mass or more from the viewpoint of reducing the residual potential. From a viewpoint, 35 mass parts or more is more preferable. On the other hand, from the viewpoint of thermal stability of the photosensitive layer, it is usually 150 parts by mass or less, preferably 120 parts by mass or less from the viewpoint of compatibility between the charge transport material and the binder resin, and from the viewpoint of printing durability. 100 mass parts or less are more preferable, and 80 mass parts or less are especially preferable from a viewpoint of scratch resistance.

In the case of a multilayer photoreceptor, 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 from the viewpoint of long life, image stability, and high resolution. , Preferably 45 μm or less, more preferably 40 μm or less.
It should be noted that each layer constituting the laminated type has a well-known antioxidant, plasticizer, UV absorption for the purpose of improving film forming properties, flexibility, coating properties, stain resistance, gas resistance, light resistance, etc. An agent, an electron-withdrawing compound, a leveling agent, a visible light shielding agent, and the like may be included.

  Examples of the antioxidant include hindered phenol compounds and hindered amine compounds. Examples of the leveling agent include silicone oil and fluorine oil.

<Other functional layers>
In the order laminated type photoreceptor, a protective layer may be provided on the outermost layer for the purpose of preventing the photosensitive layer from being worn and preventing or reducing the deterioration of the photosensitive layer due to a discharge substance or the like generated from a charger or the like. The protective layer is formed by containing a conductive material in an appropriate binder resin, or charge transporting ability such as a triphenylamine skeleton as described in JP-A-9-190004 and JP-A-10-252377. The copolymer using the compound which has can be used.

Examples of the conductive material used for the protective layer include aromatic amino compounds such as TPD (N, N′-diphenyl-N, N′-bis- (m-tolyl) benzidine), antimony oxide, indium oxide, tin oxide, and oxide. Metal oxides such as titanium, tin oxide-antimony oxide, aluminum oxide, and zinc oxide can be used, but are not limited thereto.
As the binder resin used for the protective layer, known resins such as polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polyvinyl ketone resin, polystyrene resin, polyacrylamide resin, and siloxane resin can be used. Further, a copolymer of the above resin with a skeleton having a charge transporting ability such as a triphenylamine skeleton as described in JP-A-9-190004 can also be used.

  Further, for the purpose of reducing the frictional resistance and wear on the surface of the photoconductor, and increasing the transfer efficiency of the toner from the photoconductor to the transfer belt and paper, etc., the surface layer is made of a fluororesin, silicone resin, polyethylene resin, or the like. You may contain the particle | grains which consist of these resin, and the particle | grains of an inorganic compound. Alternatively, a layer containing these resins and particles may be newly formed as a surface layer.

<Method for forming each layer>
Each layer constituting the above-described photoreceptor is formed by dip coating, spray coating, nozzle coating, bar coating, roll coating, blade coating on a conductive support obtained by dissolving or dispersing a substance to be contained in a solvent. It is formed by repeating a coating / drying step sequentially for each layer by a known method such as coating.

There are no particular restrictions on the solvent or dispersion medium used for the preparation of the coating solution, but specific examples include alcohols such as methanol, ethanol, propanol and 2-methoxyethanol, tetrahydrofuran, 1,4-dioxane, dimethoxyethane and the like. Ethers, esters such as methyl formate and ethyl acetate, acetone, methyl ethyl ketone, cyclohexanone, ketones such as 4-methoxy-4-methyl-2-pentanone, aromatic hydrocarbons such as benzene, toluene, xylene, dichloromethane, Chlorinated hydrocarbons such as chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, tetrachloroethane, 1,2-dichloropropane, trichloroethylene, n-butylamine, isopropanolamine, Diethyl Min, 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.

The amount of the solvent or the dispersion medium used is not particularly limited, but considering the purpose of each layer and the properties of the selected solvent / dispersion medium, it is appropriately determined so that the physical properties such as the solid content concentration and viscosity of the coating liquid are within a desired range. It is preferable to adjust.
For example, in the case of the charge transport layer, the solid content concentration of the coating solution is usually 5% by mass or more, preferably 10% by mass or more, and usually 40% by mass or less, preferably 35% by mass or less. Further, the viscosity of the coating solution is usually 10 mPa · s or higher, preferably 50 mPa · s or higher, and usually 2000 mPa · s or lower, preferably 1000 mPa · s or lower, at the temperature during use.

  In the case of the charge generation layer, the solid content concentration of the coating solution is usually 0.1% by mass or more, preferably 1% by mass or more, and usually 15% by mass or less, preferably 10% by mass or less. To do. Further, the viscosity of the coating solution is usually in the range of 0.1 mPa · s or more, preferably 0.5 mPa · s or more, and usually 20 mPa · s or less, preferably 10 mPa · s or less, at the temperature during use.

  Each layer constituting these photoconductors is formed by applying the coating solution obtained by the above-described method on a support using a known coating method, repeating the coating and drying steps for each layer, and sequentially coating the layers. The Examples of the coating method include a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a wire bar coating method, a blade coating method, a roller coating method, an air knife coating method, and a curtain coating method. Other known coating methods can also be used. Among them, the dip coating method is particularly preferable.

  The coating solution is preferably dried by touching at room temperature, followed by heating or drying in a temperature range of usually 30 ° C. or more and 200 ° C. or less for 1 minute to 2 hours, while still or blowing. Further, the heating temperature may be constant, or heating may be performed while changing the temperature during drying.

[Cartridge, image forming device]
Next, a drum cartridge and an image forming apparatus using the electrophotographic photosensitive member of the present invention will be described with reference to FIG.

As shown in FIG. 1, the image forming apparatus includes an electrophotographic photoreceptor 1, a charging device (charging means) 2, an exposure device (exposure means; image exposure means) 3, and a developing device (developing means) 4. Furthermore, a transfer device (transfer means) 5, a cleaning unit 6, and a fixing device (fixing means) 7 are provided as necessary.
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 photoconductor is shown. A charging device 2, an exposure device 3, a developing device 4, a transfer device 5 and a cleaning unit 6 are arranged along the outer peripheral surface of the electrophotographic photosensitive member 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, and contact-type charging devices such as charging brushes are often used.

In many cases, the electrophotographic photosensitive member 1, the charging device 2, and the cleaning unit 6 are cartridges (process cartridges including the electrophotographic photosensitive member of the present invention; hereinafter referred to as “process cartridge” as appropriate) as image forming apparatuses. Designed to be removable from the main body and replaceable. For example, when the electrophotographic photosensitive member 1, the charging device 2, and the cleaning unit 6 are deteriorated, the process cartridge can be removed from the image forming apparatus main body, and another new process cartridge can be mounted on the image forming apparatus main body. It has become. Further, a process cartridge equipped with all of the electrophotographic photosensitive member 1, the charging device 2, the cleaning unit 6, and the toner may be used.

  The type of exposure apparatus 3 is not particularly limited as long as it can form an electrostatic latent image on the photosensitive surface of the electrophotographic photosensitive member 1 by performing exposure (image exposure) on the electrophotographic photosensitive member 1. Absent. Specific examples include halogen lamps, fluorescent lamps, lasers such as semiconductor lasers and He—Ne lasers, and LEDs (light emitting diodes). Further, exposure may be performed by a photoreceptor internal exposure method.

  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. As a specific example, an arbitrary apparatus such as a dry development system such as cascade development, one-component conductive toner development, or two-component magnetic brush development, or a wet development system (liquid development system) can be used. FIG. 1 shows a configuration related to the dry development method. 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 is configured to store toner T 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. The 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 silicone 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 silicone resin or urethane resin, a metal blade such as stainless steel, aluminum, copper, brass, phosphor bronze, or a blade obtained by coating such metal blade with resin. The regulating member 45 normally abuts on 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 0.05 to 5 N / 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.
On the other hand, with regard to the liquid development method, the liquid developer used is a dispersion of a toner made of pigment or resin imparted with chargeability in an organic solvent having a high insulation property such as a hydrocarbon organic solvent. . This is a mechanism in which the toner charged in the liquid is electrophoresed in accordance with the developing electric field, and therefore, the mobility of the toner in the organic solvent having viscosity is related. As an example, development is performed with a low-concentration developer, and then excess developer solvent is squeezed with a squeeze roller adjacent to the photoreceptor to form a thin, uniform and high-density toner image on the photoreceptor. Can do.

  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 a toner image formed on the electrophotographic photosensitive member 1 to a recording paper (paper, medium, transfer target). Transfer to P.

  The cleaning unit 6 collects residual toner adhering to the photoreceptor 1 by scraping it off with a cleaning blade, a cleaning brush or the like and storing it in a recovery container. The cleaning blade includes an elastic rubber member and a support member, and an edge member may be further provided on the photosensitive member contact portion of the elastic rubber member as necessary. Further, from the viewpoint of improving the cleaning property, it is preferable that the cleaning blade counter-contacts the photoconductor.

  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. Each of the upper and lower fixing members 71 and 72 includes a fixing roll in which a metal base tube such as stainless steel or aluminum is coated with silicon rubber, a fixing roll in which Teflon (registered trademark) resin is coated, and a fixing sheet. 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 any type such as heat roller fixing, flash fixing, oven fixing, pressure fixing, etc. can be provided including those used here.

  In the electrophotographic apparatus configured as described above, a charging step for charging the photosensitive member, an exposure step for exposing the charged photosensitive member to form an electrostatic latent image, and developing the electrostatic latent image with toner. An image is recorded by performing a developing process and a transferring process for transferring the toner to the transfer target. That is, first, the surface (photosensitive surface) of the photoreceptor 1 is charged to a predetermined potential by the charging device 2 (charging process). At this time, charging may be performed by a DC voltage, or charging may be performed by superimposing an AC voltage on the DC voltage.

Subsequently, the photosensitive member is exposed to form an electrostatic latent image (exposure process). That is, the photosensitive surface of the charged photoreceptor 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 photoreceptor 1 is performed by the developing device 4 (developing process). The developing device 4 thins the toner T supplied by the supply roller 43 by a regulating member (developing blade) 45 and has a predetermined polarity (here, the same polarity as the charging potential of the photosensitive member 1) and positive polarity. ), And conveyed while being carried on the developing roller 44 to be brought into contact with the surface of the photoreceptor 1. When the charged toner T carried on the developing roller 44 comes into contact with the surface of the photoreceptor 1, a toner image corresponding to the electrostatic latent image is formed on the photosensitive surface of the photoreceptor 1.

The toner image is transferred to the recording paper P by the transfer device 5 (transfer process). Thereafter, the toner remaining on the photosensitive surface of the photoreceptor 1 without being transferred is removed by the cleaning unit 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 have a configuration capable of performing, 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 wavelength of the light used for static elimination is not particularly limited as long as the photoconductor generates a charge, and any wavelength of 400 to 800 nm can be selected, and general-purpose LEDs such as a red LED and a blue LED can also be used.

  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.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, the following examples are shown in order to explain the present invention in detail, and the present invention is not limited to the following examples unless it is contrary to the gist thereof. In the following examples, “parts” means “parts by mass”.

[Example 1]
<Method for preparing photoconductor sample for adhesion test>
The Bragg angle (2θ ± 0.2) is 27 in the X-ray diffraction by CuKα ray obtained by making it amorphous by mechanical treatment by the same method as in Comparative Synthesis Example 1 of JP 2007-148387 A and contacting with the solvent. Add 10 parts by mass of D-type oxytitanium phthalocyanine having a strong diffraction peak at 3 ° and having the powder X-ray diffraction spectrum shown in FIG. 2 to 150 parts by mass of 1,2-dimethoxyethane, and pulverize and disperse with a sand grind mill To prepare a pigment dispersion. 160 parts by mass of the pigment dispersion thus obtained and a resin having a polyvinyl acetal structure (trade name # 6000C, acetal structure ratio 66 mol%, polyvinyl alcohol structure ratio 30 mol%, vinyl acetate structure 4 mol%, manufactured by Denki Kagaku Kogyo Co., Ltd.) A resin having a vinyl chloride-vinyl acetate copolymer structure (trade name VAGH vinyl chloride 90% by mass, vinyl acetate 4% by Dow Chemical Co., Ltd.) in 5% by mass of 1,2-dimethoxyethane solution. 1 part by weight, and 6 parts by weight of vinyl alcohol), and an appropriate amount of 1,2-dimethoxyethane is added to finally form a coating solution for forming a charge generation layer having a solid content concentration of 4.0% by weight. Produced.

The charge generation layer was formed by coating this on an aluminum substrate using a wire bar so that the film thickness was 0.4 μm. Subsequently, CTM (1) represented by the following structural formula was used as a charge transport material. 40 parts by weight, 4 parts by weight of an antioxidant (1) represented by the following formula as an antioxidant, 100 parts by weight of polyarylate A (PAR-A, viscosity average molecular weight 41,000) having the following repeating structure, and leveling As an agent, 0.05 part by mass of silicone oil was mixed with 640 parts by mass of a mixed solvent of tetrahydrofuran and toluene (80% by mass of tetrahydrofuran, 20% by mass of toluene) to prepare a coating solution for forming a charge transport layer.

  This charge transport layer-forming coating solution is dip-coated on the above-described charge generation layer so that the film thickness after drying is 18 μm, and dried at 125 ° C. for 20 minutes to obtain a laminated photoreceptor sample for adhesive evaluation. It was created.

[Example 2]
A laminated photoreceptor sample for evaluating adhesiveness was prepared in the same manner as in Example 1 except that the amount of the resin having a vinyl chloride-vinyl acetate copolymer structure used in the coating solution for forming the charge generation layer was 2.5 parts. Created.

Example 3
A laminated photoreceptor sample for evaluating adhesiveness was prepared in the same manner as in Example 1 except that the amount of the resin having a vinyl chloride-vinyl acetate copolymer structure used in the coating solution for forming the charge generation layer was 0.5 part. Created.

[Comparative Example 1]
Instead of adding 1 part of a resin having a vinyl chloride-vinyl acetate copolymer structure in Example 1, 1 part of a resin having a polyvinyl acetal structure was added to make a total of 6 parts in the same manner as in Example 1. Thus, a laminated photoreceptor sample for adhesion evaluation was prepared.

[Comparative Example 2]
Instead of adding 2.5 parts of a resin having a vinyl chloride-vinyl acetate copolymer structure in Example 2 and adding 2.5 parts of a resin having a polyvinyl acetal structure to make a total of 7.5 parts, In the same manner as in Example 1, a laminated photoreceptor sample for adhesive evaluation was prepared.

[Comparative Example 3]
A laminate type photoreceptor sample for adhesive evaluation was prepared in the same manner as in Example 1 except that the resin having a vinyl chloride-vinyl acetate copolymer structure was not added in Example 1.

[Comparative Example 4]
In Example 1, 5 parts by mass of a resin having a vinyl chloride-vinyl acetate copolymer structure was mixed with 50 parts by mass of a 1,2-dimethoxyethane solution containing 5% by mass of a resin having a polyvinyl acetal structure, and an appropriate amount. 1 and 2-dimethoxyethane were added, and a coating composition for forming a charge generation layer having a solid content concentration of 4.0% by mass was finally prepared. A body sample was created.

[Comparative Example 5]
In Example 1, a resin having a polyvinyl acetal structure was not used, and only 6 parts by mass of a resin having a vinyl chloride-vinyl acetate copolymer structure was used to prepare a charge generation layer forming coating solution. However, shortly after the preparation, the charge generation material aggregated and settled, so that a photoconductor sample for evaluating adhesion could not be successfully produced.

[Examples 4 to 6, Comparative Example 6]
Resin having a polyvinyl acetal structure in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 5 except that CTM (2) having the following structure was used instead of the charge transport material CTM (1), and chloride By changing the ratio of the resin having a vinyl-vinyl acetate copolymer structure, a laminate type photoreceptor sample for adhesive evaluation was prepared.
The contents and mass ratios of the resin having a polyvinyl acetal structure and the resin having a vinyl chloride-vinyl acetate copolymer structure in each Example and Comparative Example are shown in Table 1.

[Examples 7-8, Comparative Examples 7-8]
Resins having a polyvinyl acetal structure in the same manner as in Examples 4 to 6 and Comparative Example 6, except that polyarylate B having the following structure (PAR-B, viscosity average molecular weight 40,000) was used instead of polyarylate A. And the ratio of the resin having a vinyl chloride-vinyl acetate copolymer structure was changed to prepare a laminate type photoreceptor sample for adhesive evaluation.
The contents and mass ratios of the resin having a polyvinyl acetal structure and the resin having a vinyl chloride-vinyl acetate copolymer structure in each Example and Comparative Example are shown in Table 1.

[Examples 9 to 12]
Resin having a polyvinyl acetal structure in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 5 except that CTM (3) having the following structure was used instead of the charge transport material CTM (1), and chloride By changing the ratio of the resin having a vinyl-vinyl acetate copolymer structure, a laminate type photoreceptor sample for adhesive evaluation was prepared.
The contents and mass ratios of the resin having a polyvinyl acetal structure and the resin having a vinyl chloride-vinyl acetate copolymer structure in each example are shown in Table 1.

<Adhesion test>
On the obtained sample for evaluation of adhesiveness, an NT cutter was used to cut 6 pieces in the vertical direction and 6 pieces in the horizontal direction at intervals of 2 mm to produce 5 × 5 25 squares. Cellotape (registered trademark) (manufactured by Nichiban Co., Ltd.) was applied from above, and the adhesion of the photosensitive layer was tested by pulling it up to 90 ° with respect to the adhesion surface. This test was performed four times, and the total number of photosensitive layer squares that remained without being peeled in 100 squares was evaluated as an adhesion rate. The larger the number, the better the adhesion.

<Evaluation of electrical characteristics of photoconductor>
Examples 1 to 3 and comparison using an electrophotographic characteristic evaluation device (basic and applied electrophotographic technology, edited by Electrophotographic Society, Corona, pages 404-405) prepared according to the Electrophotographic Society measurement standard The photoconductor produced in Example 3 was attached to an aluminum drum to form a cylindrical shape, and the aluminum drum and the aluminum substrate of the photoconductor were connected to each other, and then the drum was rotated at a constant rotational speed to charge, expose, The electrical characteristic evaluation test by the cycle of potential measurement and static elimination was performed in Examples 1 to 3 and Comparative Example 3.

At that time, the initial surface potential was −700 V, exposure was 780 nm, and charge removal was monochromatic light of 660 nm. The surface potential (VL) when 780 nm light was irradiated at 1.0 μJ / cm ² was measured. In the VL measurement, the time required for the exposure-potential measurement was 100 ms. The measurement environment was a temperature of 25 ° C. and a relative humidity of 50%. The smaller the absolute value of the VL value, the better the electrical characteristics.

  These results are shown in Table-1.

(In the table, “PVA” represents a resin having a polyvinyl acetal structure, and “vinyl chloride-vinyl acetate copolymer” represents a resin having a vinyl chloride-vinyl acetate copolymer structure.)

  From the above table, it can be seen that the adhesiveness is good when the charge generation layer contains a resin having a polyvinyl acetal structure and a resin having a vinyl chloride-vinyl acetate copolymer structure in a specific ratio. Furthermore, in terms of electrical characteristics, the same performance is maintained as compared with the case where only a resin having a polyvinyl acetal structure is used.

1 Photoconductor (Electrophotographic photoconductor)
2 Charging device (charging roller; charging unit)
3 Exposure equipment (exposure section)
4 Development device (development unit)
5 Transfer device 6 Cleaning device (cleaning part)
7 Fixing Device 41 Developing Tank 42 Agitator 43 Supply Roller 44 Developing Roller 45 Regulating 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)

In the electrophotographic photosensitive member provided on the conductive support by laminating at least a charge generation layer and a charge transport layer as a photosensitive layer in this order from the conductive support side,
The charge transport layer contains a polyarylate resin having a repeating structure represented by the following general formula [1] , and
The charge generation layer contains at least both a resin having a polyvinyl acetal structure and a resin having a vinyl chloride-vinyl acetate copolymer structure,
The ratio of the resin having the vinyl chloride-vinyl acetate copolymer structure to 1 part by mass of the resin having the polyvinyl acetal structure is 0.01 parts by mass or more and 1.8 parts by mass or less. Photoconductor.

(In the general formula [1], Ar ^{1 to} Ar ⁴ may be the same or different,
An arylene group optionally having a substituent is represented. X is a single bond, oxygen atom, sulfur atom
, A divalent organic residue having a structure represented by the formula [2] or a structure represented by the formula [3]
. R ¹ and R ² in the formula [2] are each independently a hydrogen atom, an alkyl group, or an ant
Or a cycloalkylidene group formed by combining R ¹ and R ² . further,
R ³ in the formula [3] is an alkylene group, an arylene group, or a group represented by the formula [4]
In the formula [4], R ⁴ and R ⁵ each independently represent an alkylene group, and Ar ⁵ represents arylene.
Represents a group. k represents an integer of 0 to 5. Y is a single bond, a sulfur atom, an oxygen atom, or the formula [5]
The bivalent organic residue which has a structure represented by these is shown. In the formula [5], R ⁶ is a hydrogen atom, R ⁷ is water
Represents an elementary atom or a methyl group. )

The electrophotographic photosensitive member according to claim 1, wherein the charge generation layer contains a phthalocyanine pigment as a charge generation material. The electrophotographic photosensitive member according to claim 1 or 2 , and a charging unit for charging the electrophotographic photosensitive member,
An exposure unit for exposing the charged electrophotographic photosensitive member to form an electrostatic latent image, a developing unit for developing the electrostatic latent image formed on the electrophotographic photosensitive member, and a cleaning for cleaning the electrophotographic photosensitive member An electrophotographic photosensitive member cartridge comprising at least one of the units. The electrophotographic photosensitive member according to claim 1 or 2 , and a charging unit for charging the electrophotographic photosensitive member,
An image forming apparatus comprising: an exposure unit that exposes the charged electrophotographic photosensitive member to form an electrostatic latent image; and a developing unit that develops the electrostatic latent image formed on the electrophotographic photosensitive member. apparatus.

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